AWWA Adsorbent Treatment Technologies For Arsenic Removal

Arsenic
Research
Partnership
Adsorbent Treatment
Technologies for
Arsenic Removal
Subject Area:
High-Quality Water
Adsorbent Treatment
Technologies for
Arsenic Removal
2005 AwwaRF. All rights reserved.
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Adsorbent Treatment
Technologies for
Arsenic Removal
Prepared by:
Gary Amy, Hsiao-wen Chen, and Aleksandra Drizo
University of Colorado (CU), Boulder, Colorado, United States
Urs von Gunten
Swiss Federal Institute of Aquatic Science and Technology (EAWAG), Dubendorf, Switzerland
Phil Brandhuber and Ruth Hund
McGuire Environmental Consultants (MEC), Denver, Colorado, United States
Zaid Chowdhury, Sunil Kommineni, and Shahnawaz Sinha
Malcolm Pirnie Inc. (MPI), Phoenix, Arizona, United States
Martin Jekel
Technical University of Berlin (TUB), Berlin, Germany
and
Kashi Banerjee
Vivendi Water/U.S. Filter (USF), Pittsburgh, Pennsylvania, United States
Sponsored by:
Arsenic Research Partnership
Jointly funded by:
Awwa Research Foundation
6666 West Quincy Avenue, Denver, CO 80235-3098
and
United States Environmental Protection Agency
Washington, D.C., 20460
Published by:
and
DISCLAIMER
This study was sponsored by the Arsenic Research Partnership. The Arsenic Research Partnership consisted of
the Awwa Research Foundation (AwwaRF), the U.S. Environmental Protection Agency (USEPA), and the
Association of California Water Agencies (ACWA). The study was jointly funded by AwwaRF and USEPA
under Cooperative Agreement No. CR 828216-01. AwwaRF, USEPA, and ACWA assume no responsibility for
the content of the research study reported in this publication or for the opinions or statements of fact expressed
in the report. The mention of trade names for commercial products does not represent or imply the approval or
endorsement of AwwaRF, USEPA, or ACWA. This report is presented solely for informational purposes.
Copyright 2005
by Awwa Research Foundation
All Rights Reserved
Printed in the U.S.A.
ISBN 1-58321-399-6
CONTENTS
LIST OF TABLES....................................................................................................................
vii
LIST OF FIGURES ..................................................................................................................
ix
FOREWORD ............................................................................................................................ xiii

ACKNOWLEDGMENTS ........................................................................................................
xv
EXECUTIVE SUMMARY ...................................................................................................... xvii

CHAPTER 1: INTRODUCTION AND BACKGROUND .....................................................
Background ...................................................................................................................
Adsorbents and Arsenic Removal.................................................................................
Objectives .....................................................................................................................
Research Approach .......................................................................................................
1
1
1
2
2
CHAPTER 2: LITERATURE SURVEY SUMMARY...........................................................
CHAPTER 3: VENDOR AND MANUFACTURER SURVEY.............................................
15
CHAPTER 4: ARSENIC OCCURRENCE AND CO-OCCURRENCE ANALYSIS ............

Objectives of the Arsenic Co-Occurrence Analysis .....................................................
Source Data...................................................................................................................
Creation of the Groundwater Arsenic Co-Occurrence Database..................................
Characteristics of Arsenic Occurrence..........................................................................
Characteristics of Arsenic Speciation ...........................................................................
Characteristics of Arsenic Co-Occurrence ...................................................................
General Water Quality Characteristics .............................................................
Are Waters That Contain Arsenic Different From Those That Do Not?..........
Direct Correlation Between Arsenic and Other Parameters .............................
Alternative Water Quality Testing Matrices.................................................................
Summary .......................................................................................................................
19
19
19
20
22
26
26
27
27
32
33
35
CHAPTER 5: EXPERIMENTAL PROTOCOLS AND ANALYTICAL METHODS ..........

Introduction...................................................................................................................
Batch Testing Protocols ................................................................................................
Preliminary Screening Tests .............................................................................
Intensive Testing of Select Adsorbents.............................................................
Column Testing Protocols.............................................................................................
TCLP/Wet Testing Protocols .......................................................................................
37
37
37
37
38
40
40
v
Analytical Methods.......................................................................................................
Total Arsenic and Interferant Measurements....................................................
Arsenic Speciation ............................................................................................
QA/QC for Arsenic Analysis ........................................................................................
41
41
41
41
CHAPTER 6: BENCH TESTING ...........................................................................................

Batch Testing ................................................................................................................
Preliminary Screening Experiments .................................................................
Intensive Testing of Selected Adsorbents.........................................................
43
43
43
52
CHAPTER 7: ARSENIC ADSORBENT DESIGN AND COSTING TOOL.........................

Introduction...................................................................................................................
Single Parameter and Multiple Regression Models......................................................
Single Parameter Model....................................................................................
Multiple Regression Model...............................................................................
Description of Tool Algorithms and Calculations ........................................................
Instructions for Using the Tool .....................................................................................
Basis of Cost Opinions .................................................................................................
81
81
86
86
86
90
94
95
CHAPTER 8: CONCLUSIONS ..............................................................................................
97
APPENDIX A: LITERATURE SURVEY ............................................................................... 101

APPENDIX B: ADSORBENTS TESTED FOR ARSENIC REMOVAL:
SYNTHESIS OF LITERATURE AND VENDOR/MANUFACTURER SURVEYS ............ 117
REFERENCES ......................................................................................................................... 131
ABBREVIATIONS .................................................................................................................. 137
vi
TABLES
2.1 Adsorbents tested: description, water quality parameters and references .................
2.2 Batch isotherm studies: reported adsorption capacities and protocols used ..............
10
3.1 Adsorbents tested for arsenic removal: synthesis of literature review and
vendor/manufacturer survey.......................................................................................
16
4.1 Database parameters and data acceptance criteria .....................................................
21
4.2 Summary of arsenic occurrence by physiographic region .........................................
25
4.3 Summary of occurrence of co-occurring parameters in national groundwater

arsenic database .........................................................................................................
28
4.4 Pearson correlation coefficients at 95% confidence level measuring the

degree of correlation between arsenic and co-occurring parameters.........................
34
4.5 Alternate water quality testing matrixes for waters containing moderate or
high levels of arsenic..................................................................................................
35
5.1 Summary of quality assurance and quality control procedures for arsenic
analysis.......................................................................................................................
41
6.1 Physical/chemical properties of adsorbents ...............................................................
53
6.2 Concentrations of interferents based on the co-occurrence survey............................
55
6.3 Ionic composition of NSF challenge water (pH = 7.5)..............................................
55
6.4 Water quality summary of utility-supplied waters.....................................................
56
6.5 CV values (%) for isotherm constants and Freundlich predictions ...........................
59
6.6 Values of Freundlich isotherm fitting parameters (KF and 1/n) for adsorption
of arsenic onto tested media and predicted adsorption capacity when As(V)
concentration in solution is 10 g/L or 50 g/L ........................................................
60
6.7 Values of Langmuir isotherm fitting parameters (KL and Qmax) for adsorption
of arsenic onto tested media.......................................................................................
61
6.8 Summary of SMI results ............................................................................................
75
vii
6.9 Monomeric versus polymeric silica concentrations...................................................
77
6.10 Experimental conditions employed in column tests ..................................................
78
6.11 TCLP and WET results for spent arsenic sorptive media ..........................................
80
7.1 Design and operating criteria used in sizing and costing of arsenic
adsorption systems .....................................................................................................
82
7.2 Single parameter and multiple regression models .....................................................
87
viii
FIGURES
1.1 Research approach .....................................................................................................
4.1 Database development flow chart ..............................................................................
20
4.2 Distribution of groundwater arsenic sites by state .....................................................
23
4.3 Physiographic zones of the United States..................................................................
23
4.4 National cumulative probability distribution for arsenic occurrence for

9867 stations extracted from NWIS...........................................................................
24
4.5 Cumulative probability distribution for arsenic occurrence by physiographic

zone. ...........................................................................................................................
25
4.6 Comparison of cumulative probability distributions of pH for waters

containing low, moderate, and high concentrations of arsenic ..................................
30
4.7 Comparison of cumulative probability distributions of silica for waters

30
4.8 Comparison of cumulative probability distributions of fluoride for waters

31
4.9 Comparison of cumulative probability distributions of alkalinity for waters

31
4.10 Comparison of cumulative probability distributions of phosphate for waters

32
4.11 Comparison of cumulative probability distributions of iron for waters

32
4.12 Comparison of cumulative probability distributions of sulfate for waters

33
6.1 (a) pH fluctuation and (b) arsenic removal in the absence or presence of a
pH buffer: initial pH of 7.0 with GFH and As(V) = 100 g/L...................................
45
6.2 As(V) removal (100 g/L) at pH 7 as a function of time by (a) AA-400G,

(b) AA-FS50, (c) ARM 100, (d) Bayoxide E33, (e) GFH, (f) MetSorb,
(g) MIEX, (h) Z33 Rev. B, (i) Geothite, and (j) pyrolusite........................................
46
6.3 Isotherms for candidate adsorbents: As(V) at a pH of 7.0 and 24 hours ...................
51
ix
6.4 Percent removal of As(V) by candidate adsorbents: As(V) = 100 g/L;

pH = 7.0, 24 hours ....................................................................................................
51
6.5 Percent removal of As(III) by candidate adsorbents: media dose = 100 mg/L;
As(III) = 100 g/L; pH = 7.0, 24 hours .....................................................................
52
6.6 Zeta potential versus pH for adsorbents.....................................................................
54
6.7 Isotherm replicate (triplicate) series for Metsorb G with As(V) at a pH of

7.0 and 24 hours.........................................................................................................
58
6.8 Isotherm replicate (triplicate) series for SMI-III with As(V) at a pH of

7.0 and 24 hours.......................................................................................................
58
6.9 Single-solute isotherms for As(V) at pH 6.0: in the absence of interferents .............
62
62
63
6.12 Summary of interference factors: ratio of As(V) capacity to that at pH 6.0

in the absence of interferents .....................................................................................
63
6.13 Adsorption capacity, Q10, for As(V) as a function of pH: absence of interferants ....
64
6.14 Adsorption capacity, Q10, for As(V) as a function of pH: presence of

phosphate at 50% occurrence level ............................................................................
64

phosphate at 75% occurrence level ............................................................................
65

silica at 50% occurrence level....................................................................................
65

silica at 75% occurrence level....................................................................................
66

vanadium at 75% occurrence level ............................................................................
66
6.19 Isotherms for As(III) at a pH of 7.0: absence of interferants .....................................
67
6.20 Adsorption capacity, Q10, for As(III) as a pH of 7.0: absence of interferants ...........
67
6.21 Isotherms for As(V) in NSF challenge water.............................................................
70
x
6.22 Adsorption capacity, Q10, for As(V) in NSF challenge water ...................................
70
6.23
Isotherm for As(III) in NSF challenge water ............................................................
71
6.24 Adsorption capacity, Q10, for As(III) in NSF challenge water ..................................
71
6.25 Isotherms for utility-supplied water: Tucson, AZ groundwater.................................
72
6.26 Isotherms for utility-supplied water: LADWP, CA surface water .............................
72
6.27 Isotherms for utility-supplied water: El Paso, TX groundwater ................................
73
6.28 Isotherms for utility-supplied water: Alamosa, CO groundwater ..............................
73
6.29 Isotherms for GFH with As(V) at varying pH levels and silica concentrations.........
78
6.30 Breakthrough curves for column tests with NSF challenge water.............................
79
7.1 Cost flowchart ............................................................................................................
91
7.2 Media replacement flowchart.....................................................................................
92
7.3 Backwash calculation flowchart.................................................................................
92
7.4 Plant footprint calculation flowchart..........................................................................
93
xi
FOREWORD
The Awwa Research Foundation (AwwaRF) is a nonprofit corporation that is dedicated to
the implementation of a research effort to help utilities respond to regulatory requirements and
traditional high-priority concerns of the industry. The research agenda is developed through a process of consultation with subscribers and drinking water professionals. Under the umbrella of a
Strategic Research Plan, the Research Advisory Council prioritizes the suggested projects based
upon current and future needs, applicability, and past work; the recommendations are forwarded
to the Board of Trustees for final selection. The foundation also sponsors research projects
through an unsolicited proposal process; the Collaborative Research, Research Applications, and
Tailored Collaboration programs; and various joint research efforts with organizations such as the
U.S. Environmental Protection Agency, the U.S. Bureau of Reclamation, and the Association of
California Water Agencies.
This publication is a result of one of these sponsored studies, and it is hoped that its findings will be applied in communities throughout the world. The following report serves not only as
a means of communicating the results of the water industrys centralized research program but
also as a tool to enlist the further support of the nonmember utilities and individuals.
Projects are managed closely from their inception to the final report by the foundations
staff and large cadre of volunteers who willingly contribute their time and expertise. The foundation serves a planning and management function and awards contracts to other institutions such as
water utilities, universities, and engineering firms. The funding for this research effort comes primarily from the Subscription Program, through which water utilities subscribe to the research program and make an annual payment proportionate to the volume of water they deliver and
consultants and manufacturers subscribe based on their annual billings. The program offers a costeffective and fair method for funding research in the public interest.
A broad spectrum of water supply issues is addressed by the foundations research agenda:
resources, treatment and operations, distribution and storage, water quality and analysis, toxicology, economics, and management. The ultimate purpose of the coordinated effort is to assist water
suppliers to provide the highest possible quality of water economically and reliably. The true benefits are realized when the results are implemented at the utility level. The foundations trustees
are pleased to offer this publication as a contribution toward that end.
The focus of this study was a comparative assessment of different adsorbent treatment
technologies for arsenic (As) removal from drinking water supplies. The studied evaluated a large
number commercially available and developmental adsorbents of different properties. These
adsorbents were tested under a wide range of water quality conditions, including inhibitory species (e.g., phosphate) reducing the adsorbent capacity for arsenic. The evaluation encompassed
arsenic in its two principal oxidation states: arsenate, As(V); and arsenite, As(III). The (leaching)
stability of spent adsorbents was assessed to promote their use as throwaway materials after highcapacity arsenic adsorption. A decision framework (e.g., an algorithm-like procedure), in the form
of a software package, was developed for helping utilities determine the most appropriate adsorbent based on cost and performance in terms of known water quality parameters.
Walter J. Bishop
Chair, Board of Trustees
Robert C. Renner
Executive Director
xiii
ACKNOWLEDGMENTS
PROJECT ADVISORY COMMITTEE (PAC)
The advice and help provided by the Project Advisory Committee (PAC) and AwwaRF
project officer, Traci Case, are sincerely appreciated. The PAC consisted of Tom Sorg, David
Hand, Michelle DeHaan, and Jason Wen.
PARTICIPATING UTILITIES
We acknowledge the participation of utilities that supplied water for testing and associated
water quality data: Tucson (AZ), El Paso (TX), Los Angeles Department of Water and Power
(LADWP), and Alamosa (CO).
xv
EXECUTIVE SUMMARY
STUDY OBJECTIVES
The objective of this study were: (i) to identify the inhibitory impacts of water quality on
the performance of a range of adsorbents (commercially available and experimental) for the
removal of arsenate and arsenite; (ii) to define adsorbent properties that will minimize the effects
of water quality and/or maximize arsenic adsorption capacity; (iii) to investigate the applicability
of various adsorbents to arsenite (As(III)) removal as opposed to a need for pre-oxidation to arsenate (As(V)); (iv) to assess the (leaching) stability of spent adsorbents to promote their use as
throwaway materials; and (v) to develop a decision framework (e.g., an algorithm-like procedure)
for helping utilities determine the most appropriate adsorbent based on cost and performance in
terms of known water quality parameters.
RESEARCH APPROACH
The research approach was performed in two phases comprising a total of five tasks. The
first phase, embodying the first and second tasks, was intended to complete a preliminary identification of candidate media and to define the experimental water quality matrix. The second phase,
embodying the last three tasks, represented the experimental efforts, data analysis, comparative
assessment, and selection framework.
LITERATURE AND VENDOR SURVEYS
Extensive literature and vendor surveys revealed that there are a large number of commercial and experimental adsorbents, available for arsenic removal. Some of the commercially available materials are mature products (e.g., activated alumina) that have been widely tested,
revealing both their attributes and limitations, while others are more recent products that have not
been as rigorously tested (e.g., various iron oxides). Based on their predominant adsorption mechanism as well as material composition, these adsorbents fall into several categories: (i) ion
exchange media (e.g., MIEX); (ii) metal oxides (e.g., activated alumina and iron oxides); and (iii)
redox-reactive media (e.g., MnO2). In this study, we have chosen to highlight the second category
in the forms of both pure minerals and amended/impregnated materials. The literature review also
revealed that adsorption capacities were influenced by arsenic speciation, arsenate (As(V)) versus
arsenite (As(III)), and water quality in terms of pH conditions and the presence on interfering species competing with arsenic for adsorption sites. Influential interferants were revealed to include
silica, phosphate, fluoride, sulfate, carbonate, and others. Based on the literature and vendor surveys, a total of 12 adsorbents, 10 commercially available and 2 experimental, were identified for
experimental evaluation. Besides pH as an important water quality condition, phosphate and silica
were identified for intensive interferant testing, later supplemented by vanadium and fluoride for
less intensive assessment.
xvii
ARSENIC OCCURRENCE AND CO-OCCURRENCE SURVEY

An arsenic occurrence and co-occurrence survey was conducted to indicate national
(USA) occurrence levels of total arsenic, arsenic species domination, and co-occurrence trends
between arsenic and interferants. Based on statistical analysis of an integrated national database
for groundwater, the mean total arsenic concentration was determined to be 4.5 g/L, with a
90 percentile value of about 10 g/L. Geographically, the highest national levels were found in the
Intermontane region encompassing states west of the continental divide (e.g., Arizona and New
Mexico) except for Washington, western Oregon, and northern California; lowest levels were
found in the Atlantic Plain region. Binning of data showed that about 5% of all groundwater sites
contained 20 g/L, about 5% contained between 10 to 20 g/L, and about 5% between 5 to
10 g/L. While a rigorous study of arsenic speciation in groundwater was not found, several limited studies suggested that As(V) is the predominant species in U.S. groundwaters although, in
other global settings such as Bangladesh, As(III) is known to dominate in more anoxic groundwaters. There were semi-quantitative trends to indicate that groundwaters with arsenic 5 g/L
tended to be higher in pH, silica, fluoride, alkalinity, and phosphate than those with <5 g/L; however, at a 95% confidence level, no statistically significant correlations were found between
arsenic and the various co-occurring parameters according to the binning classifications. A decision was made to define a typical water and a difficult to treat water in terms of 50 and 75 percentile levels of interferants. For pH, levels of 6.0, 7.0, and 8.0 were specified for testing,
corresponding to roughly 10, 25, and 75 percentile levels; a lower pH (e.g., 6.0) than typical (i.e.,
50 percentile) is of interest because of observations on enhanced performance of many adsorbents
at lower pH conditions, suggesting the possibility of pH depression as a pre-treatment step.
BATCH AND COLUMN EXPERIMENTS
Preliminary batch experiments were performed to screen twelve candidate adsorbents:
AA-400G (activated alumina (AA)); AA-FS50 (iron impregnated AA); MIEX (amagnetized ion
exchange resin); Bayoxide E33 (granular ferric oxide (GFO)); Granular Ferric Hydroxide (GFH);
Metsorb (titanium dioxide); Z33-Revision B (iron modified zeolyte); ARM 100 (alumina based,
with proprietary promoters); Sulfur Modified Iron Version III (SMI); ViroClear Bauxsol F3
(Bauxite Clay); Geothite (-FeOOH); and Pyrolusite (-MnO2). An initial set of preliminary
experiments indicated that pseudo equilibrium conditions could be established within a 24 hour
time frame, a basis for isotherm development. Additional preliminary experiments were performed to approximate As(V) and As(III) adsorption capacities as a basis to reduce the number of
adsorbents to five select adsorbents for intensive batch testing of water quality effects: AA-FS50,
Bayoxide E33, GFH, Metsorb G, and Z33. Four of these adsorbents (AA-FS50, Bayoxide E33,
GFH, and Metsorb G) were further evaluated in continuous-flow column tests. Another of the candidate adsorbents, SMI, was the focus of a special study because of interest in its high As(V)
capacity but with significant concerns about experimental reproducibility.
Based on batch testing results with synthetic waters at each of the three pH conditions and
the presence or absence of an individual interferant, a number of trends were discerned. First, in
addressing the performance of each adsorbent independently, the following observations were
made. The AA-FS50 showed a moderate deterioration in performance as pH increased, a significant decrease in capacity in the presence of fluoride, and only a small effect exerted by phosphate.
The Bayoxide E33 media showed only a slight pH effect but exhibited significant impacts by
phosphate and vanadium with some silica effects. GFH showed a decrease in performance as pH
xviii
increased, with phosphate, silica, and vanadium exhibiting adverse effects. MetSorb G showed a
decrease in performance as pH increased, with phosphate, silica, and vanadium exhibiting effects,
although the interferent effects were less at lower pH. Z33 performance decreased as pH increased
and phosphate had a significant effect.
Second, in addressing adsorbent comparisons, the following observations were made. The
two iron oxide media (Bayoxide E33 and GFH) and Metsorb G generally showed comparable
weight-based capacities although GFH performance dropped sharply at the highest pH; interferant effects were lowest for Metsorb G. The iron-modified activated alumina (AA-FS50) showed a
higher capacity than the two iron oxide media and Metsorb G at lower pH, but a lower capacity at
higher pH, indicating more of a pH dependency. The iron-modified zeolite (Z33) generally exhibited the lowest capacities.
Differences in physical/chemical properties of the adsorbents helped to explain some of
the differences. The order of pHZPC (high to low) was Bayoxide E33 > GFH > AA-FS50 > Z33 ~
Metsorb G. The higher pHZPC of the Bayoxide E33 versus GFH helped explain the better performance of the former iron oxide at higher pH conditions. The order of surface area (high to low)
was AA-FS50 ~ GFH > Metsorb G > Bayoxide E33 > Z33. The very low surface area of the Z33
was manifested in a lower number of adsorption sites per unit mass. The material composition differed significantly: aluminum and iron content for AA-FS50, titanium dioxide for Metsorb G, clay
content for Z33, and iron oxides for GFH and Bayoxide E33. The high capacity exhibited by the
Metsorb E33 may involve a more complicated mechanism than simply surface complexation or
ligand exchange.
Three of the adsorbents; Bayoxide E33, Metsorb G, and GFH; were tested for arsenite
removal; while all three adsorbents demonstrated a significant potential for As(III) removal, their
As(III) capacities were significantly less than their As(V) capacities; the order of performance
was Bayoxide E33 > Metsorb G > GFH.
Three adsorbents (Bayoxide E33, Metsorb G, and GFH) were tested in a NSF challenge
water containing As(V) or As(III) with multiple interferants at a constant pH (7.5) as well as several utility-supplied natural waters containing multiple interferants and variable pH. The order of
capacities for As(V) in the NSF challenge water was Metsorb G > Bayoxide E33 > GFH, while
the order of capacities for As(III) was Metsorb G >GFH > Bayoxide E33. The general order of
capacities for the natural waters was Metsorb G > Bayoxide E33 > GFH.
Results from a special batch study on SMI revealed a higher As(V) capacity than that of
the other adsorbents; however, its performance was substantially reduced at higher pH conditions
and/or in the presence of interferants. Moreover, its As(III) capacity was much lower than its
As(V) capacity.
Another special batch study was performed to more closely study the effects different
forms of silica, monomeric versus polymeric. It was found that at higher silica concentrations,
polymeric silica can form and potentially foul porous adsorbents, thus reducing their capacity.
Four of the adsorbents (Metsorb G, AA-FS50, Bayoxide E33, and GFH) were tested in
dynamic column tests employing the NSF challenge water spiked with As(V) at concentrations of
250 g/L (for Metsorb G) to 1,000 g/L (for the other three adsorbents); the purpose of the high
initial concentration was to facilitate breakthrough. Based on an empty bed contact time (EBCT)
of 5 minutes, the AA-FS50 and GFH showed similar results with breakthrough at about 4,000 to
5,000 bed volumes (BVs). The Metsorb G and Bayoxide E33 were run for longer periods of about
8,000 and 12,000 BVs, respectively. The Metsorb G experiment was terminated before a clear
breakthrough trend was observed, however, this result is consistent with the lower initial As(V)
xix
concentration employed in this test. The residuals from these column tests were subjected to
TCLP and WET tests which indicated that all would not be classified as hazardous, permitting
their disposal as throwaway adsorbents.
ARSENIC ADSORBENT DESIGN AND COSTING TOOL
An arsenic adsorbent design and costing tool was developed based on seven adsorbents:
AA-FS50, Bayoxide E-33, GFH, Metsorb G, Z-33, SMI, and AA-400G (conventional, granular
activated alumina). The software is an interactive tool which contains input and output forms. The
user enters information in the input form, and the tool calculates design and cost parameters and
displays the results in an output form. The type of input parameters that the user is required to
enter includes system parameters (e.g., average flow), water quality (e.g., influent arsenic, phosphate, and silica concentrations), target water quality (e.g., treated-water arsenic), operational
preferences (e.g., pH adjustment) and cost parameters (e.g., interest). The user has the option
instructing the use of either Freundlich or Langmuir isotherm models to predict adsorption capacity. The tool generates outputs that include the calculated Freundlich or Langmuir coefficients,
adsorption capacities, capital costs, operations and maintenance (O&M) costs, plant footprint,
residuals quantities and water quality interference warnings. The outputs are calculated based on
the water quality and system information that the user enters in the input form.
xx
CHAPTER 1
INTRODUCTION AND BACKGROUND
BACKGROUND
Arsenic is a metalloid or oxyanion found in both ground and surface water sources. It
occurs in both dissolved and colloidal/particulate forms. In drinking water supplies, dissolved
arsenic occurs as either arsenate, As(V), or arsenite, As(III). In the pH range of drinking waters,
the anionic arsenate (pKa1, pKa2, pKa3 = 2.2, 7.0, 11.5, respectively) dominates as either a monoor di-valent oxyanion (H2AsO4 or HAsO42) whereas arsenite, the reduced form, is a nonionic
species (H3AsO3; pKa1, pKa2, pKa3 = 9.2, 12.1, 13.4, respectively). The colloidal/particulate
forms of arsenic found in drinking water supplies are thought to occur primarily as arsenic species
adsorbed to naturally-occurring metal (e.g., iron) oxide surfaces and, to a lesser extent, derived
from arsenic-bearing minerals (e.g., arsenic trioxide, As2O3 and arsenopyrite, FeAsS) subjected to
geochemical weathering reactions.
ADSORBENTS AND ARSENIC REMOVAL
The applicability of conventional adsorbents, including activated alumina (AA) and ion
exchange (IX), for the removal of arsenic has been established along with associated water quality
constraints (e.g., SO42 for IX) and regeneration requirements (Amy, et al., 2000). However,
conventional adsorbents either require that arsenic be in the form of arsenate (in the case of IX) or
exhibit a much higher capacity for arsenate over arsenite (in the case of AA). While oxidation of
As(III) to As(V) can be easily achieved by oxidants such as ozone, chlorine, or permanganate, this
practice adds operational complexity and may embody secondary impacts such as the formation
of disinfection by-products and possibly biodegradable organic matter (BOM). Recent work has
involved the development of new adsorbents with less water quality constraints, higher capacities,
and/or increased removals of arsenite. Moreover, the development of these high capacity adsorbents (discussed in later literature and vendor surveys) has been accompanied by a change in
philosophy in which many are now considered to be throwaway materials that can be disposed of
in a landfill if an appropriate leaching (e.g., TCLP) test can be passed. This approach eliminates
the need for regeneration and associated problems with the regenerant stream.
Besides the form of arsenic, water quality affects arsenic adsorption. The main water
quality constraints for adsorbents are pH, affecting the charge of arsenate (mono- vs. di-valent) as
well as the surface charge of the adsorbent (pHZPC), and competing anions, some which are
affected by pH (e.g., silicate, phosphate, and natural organic matter (NOM) in the form of
humic/fulvic acids) and others which are unaffected by pH (sulfate, nitrate and fluoride). The
beneficial presence of iron as a precipitating adsorption surface has been recognized, largely
through assessment of enhancing the performance of Fe/Mn removal and ferric coagulation plants
in removing arsenic by promoting the formation of amorphous ferric hydroxide, Fe(OH)3 (Amy
et al., 2000). Given that arsenate (and arsenite) embody both metal (As) and ligand (O) properties,
the mechanisms of arsenate (and arsenate) adsorption onto metal (e.g., iron) oxide surfaces can
occur through surface complexation or ligand exchange:
1
Surface Complexation:
Ligand (L) Exchange:
>XOH + HAsO42 XOHAsO42 + H+

>XOH + L >XL + OH
(L = HAsO42)
Adsorbents potentially applicable to arsenic removal can be classified into three general
categories: (i) established commercially available adsorbents which are known to effectively
remove arsenic and are well-characterized with respect to their operational characterisitics and
behavior under various water quality conditions (e.g., activated alumina, AA); (ii) emerging
commercially available adsorbents which have been developed and demonstrated to effectively
remove arsenic but whose performance in various water quality matrices have not been studied in
detail (e.g., granular ferric hydroxide, GFH); and (iii) experimental media that often represent
pure mineral materials that have only been studied in more narrowly focused research projects
(e.g., pyrolusite). While most adsorbents are available in a granular form applicable to use in
fixed-bed columns, some are available in a powdered form for other uses such as hybrid (coupled)
adsorbent-membrane systems (e.g., powdered AA + microfiltration (MF) or ultrafiltration (UF)).
OBJECTIVES
The objective of this study were
to identify the inhibitory impacts of water quality on the performance of a range of

adsorbents (commercially available and experimental) for the removal of arsenate and
arsenite;
to define adsorbent properties that will minimize the effects of water quality and/or
maximize arsenic adsorption capacity (e.g., specific surface area, pHZPC);
to investigate the applicability of various adsorbents to As(III) removal as opposed to a
need for pre-oxidation to As(V);
to assess the (leaching) stability of spent adsorbents to promote their use as throwaway
materials;
to develop a procedure (e.g., an algorithm-like procedure) for helping utilities
determine the most appropriate adsorbent based on cost and performance in terms of
known water quality parameters.
RESEARCH APPROACH
The research approach was divided into two phases comprising a total of five tasks. The
first phase, embodying the first and second tasks, was intended to complete a preliminary identification of candidate media and to define the experimental water quality matrix. The second phase,
embodying the last three tasks, represented the experimental efforts, data analysis, comparative
assessment, and selection framework.
Since the number of adsorbents that have been developed and potential water quality
matrices in which to test these adsorbents are virtually unlimited, it was imperative that the experimental combinations of adsorbents and water quality matrices be selected to benefit the greatest
number of drinking water utilities. Therefore, the first task was to review the international literature and to contact vendors as a basis for identifying a list of candidate adsorbents. The second
2
Figure 1.1 Research approach
task involved the use of arsenic occurrence databases to help determine which ions and other
water quality conditions (e.g., phosphate, pH) most commonly occur with arsenic. This information helped the research team identify water quality matrices that would most likely affect
drinking water utilities. By combining the information gathered from the first two tasks, the
project team was able to proceed to the experimental phase of the project with the knowledge that
the select media were representative of the range of materials available and the test water quality
conditions were representative of conditions that utilities will encounter.
After identification of available adsorbents appropriate water quality conditions, candidate
adsorbents were first studied in a set of preliminary experiments (Task 3) to assess kinetics and
capacities, with results used to screen potential adsorbents and help identify a reduced number of
select adsorbents to be subjected to intensive bench-scale testing (Task 4). These select adsorbents
were characterized according to important physical/chemical properties influencing arsenic and
competing anion adsorption. Batch and continuous-flow column tests were performed in the
fourth task to define arsenic removal trends which, upon data analysis and isotherm modeling,
indicated performance within various water quality matrices. Finally, once influential parameters
were defined for each adsorbent tested, the research team developed an algorithm-like procedure
in the fifth task for helping utilities select the most appropriate adsorbent type based on cost, water
quality, and other factors. A summary of our research approach is shown in Figure 1.1.
3
CHAPTER 2
LITERATURE SURVEY SUMMARY
The literature survey was completed with a total of over 400 articles and papers assembled
from numerous journals, of which the most valuable sources were Journal of American Water
Works Association, Environmental Science and Technology, Water Research, Desalination,
Journal of Environmental Engineering, and Water Science and Technology, containing about onefourth of the articles. Relevant papers were also found in a number of other journals including:
Separation Science and Technology, Environmental Technology, Environmental Engineering
Science, Water, Air, and Soil Pollution, Chemosphere, Journal of Hazardous Materials, Journal
Water Pollution Control Federation, Water Quality Research Journal of Canada, Colloidal
Surface, Journal of Analytical Atomic Spectrometry, Journal of Water Chemistry and Technology,
Powder Technology, Journal of Environmental Science and Health, Journal of Radioanalytical
and Nuclear Chemistry, Soil Science, Water Environment Research, Chemical Engineering and
Technology, International Journal of Water, Waste Management, Environmental Technology, Environmental Geology, and Geochim. Cosmochim Acta. The detailed literature survey is presented in
Appendix A. Based on the detailed literature survey, two summary tables have been derived and
are presented to summarize adsorbents tested (Table 2.1) and reported isotherm capacities
(Table 2.2).
The literature survey largely confirmed our original notions about influential interferants
and types of adsorbent materials that have or might have merit for adsorption of oxyanions and
metalloids such as arsenate (or arsenite). While a significant number of commercially available
materials have been tested, many of the adsorbents tested are experimental or pure minerals.
Many fall within the general category of metal (hydro)xides, with various iron oxides being very
common. Some function as simple ion exchange media. Another common group of materials is
surface-modified natural materials. The major interferants have been shown to be phosphate,
silica, carbonate, sulfate, and fluoride. pH has been shown in many cases to exhibit a major effect
on media performance.
5
Table 2.1
Adsorbents tested: description, water quality parameters and references
Adsorbents tested
Basis (adsorbent description)
Magnetic ion-exchange
(iron-oxide, magnetite)
Magnetically impregnated ion-exchange

resins (MIEX)
Water quality
parameter(s)
studied
Sulfate
NOM
pH
Hydrous iron oxide particles (HIOPs)
Non-compressible and semicrystalline structure

(hematite)
Sulfur-modified iron (SMI)
Metallic iron and elemental

sulfur comp.
Granular ferric hydroxide (GFH)

(Prepared by neutralizing &
precipitating FeCl3 with NaOH)
-FeOOH
Akaganeit
Ferrihydrite (FH)
Geothite (-FeOOH)
Haematite
pH, temperature
Iron oxide coated sands (IOCS) or iron

oxide coated microsands (IOC-M)
Copper, chromate
Sulfate
NOM
Limiting parameter/
limiting level
References
Increasing
(0100 mg/L)
Increasing DOC
(04 mg/L)
more effective at
lower values (5.5)
Chang et al. (2004); Amy et al. (2002)
DOC (04 mg/L)

pH wider range

Sulfate
Phosphate
Phosphate
Chang et al. (2004);

Driehaus et al. (1998);
Pal (2001);
Selvin et al. (2001);
Norton et al. (2001)
pH (59.5)
silica, sulfate, NOM
Silica
NOM
Robins et al. (2001); Jain et al. (1999);

Raven (1998); Gulledge and OConnor
(1973);Waychunas et al. (1993, 1995);
Nishimura and Umetsu (2000); Wong et al.
(1995); Chen et al. (2005);
Thirunavukkarasu et al. (2001)
Product formed from

crystalization of ferrihydrite
Belzile and Tessier (1990); Matis (1999);

Matis et al. (1997); Xiaohua and Harvey
(1998); Manning et al. (1998); OReilly et al.
(2001)
pH 7 max ads.
temp. reduces ads.
Singh et al. (1988)

Chang et al. (2004); Lombi et al. (1999);
Thirunavukkarasu et al. (2001); Khaodhiar
et al. (2000)
(Continued)
Table 2.1 (Continued)
Adsorbents tested
9
Amorphous iron hydroxide

Pyrite of 95% purity
Water quality
parameter
studied
Parameter limiting
level
References
Higher pH reduces
adsorption
Pierce and Moore (1982)
pH
pH < 4 required
Zouboulis et al. (1993); Han and Fyfe

(2000)
Twice as effective in
removing As(V) than
As(III)
Lackovic et al. (2000)

sulfate
Lackovic et al. (2000);

Krishna et al. (2001)
10
Iron-sulfide minerals
11
Zero-valent iron (ZVI)

(Column experiment data only)
(Cost: $250400/ton)
12
Ferruginous manganese ore (FMO)
Major mineral phases:

pyrolusite and geothite
pH 28
Divalent Cation (Ni2+,
Co2+, Mg2+) presence
enhances adsorption
Chakravarty et al. (2002)
13
Manganese greensand (MGS)
A zeolite-type glauconite
mineral
Fe/As molar ratio (20

optimal)
Initial As, Fe(II) and
Mn (IV) conc.
Subramanian et al. (1997);

Viraraghavan et al. (1999);
Thirunavukkarasu et al. (2001)
14
Manganese dioxide
15
Manganese dioxide coated sand (MDCS)
Formed by oxidation of Mn(II)

with permanganate in the
presence of sand
16
Manganese oxyhydroxide coated sand

(MOCS)
pHZPC of 2.87
17
Iron-modified AA
pH
Addition of
Mg2+,Pb2+, Ni2+, Ag
and Ca2+ significantly
increases As
adsorption
Tartrate, phosphate,
carbonate reduce
adsorption, as well as
Zn2+
Chen et al. (1999)
pH
For As (V),
pH < 7.5
Thomson et al. (1998)

(Continued)
Adsorbents tested
18
Activated Alumina (AA)
Water quality
parameter
studied
Salinity
pH 4-7 effective for
removal of As(V);
Effect of init. Conc.:
As (V) not-sig., As
(III) sig.
Parameter limiting
level
References
pH > 7, ads. decreases
Gupta and Chen (1978); Chang et al.

(2004); Norton et al. (2001)
Gupta and Chen (1978)
Activated carbon (AC)
Salinity
pH 35 effective
removal of As(V)
20
Coconut husk carbon (CHC)
Prepared by treating CH with

sulf. acid; pHpzc 7.5; surf area
206 m2/g ; AEC 1.23 meq/g
pH 212
Contact time 16 h
temp. 3060C
ads with temp.
pH 12 max uptake
Manju et al. (1998)
21
Quaternized rice husk (QRH)
150 g ground rice treated with

2L of 1% w/v Na2CO3
pH
NO3 no effect
SO42, CrO42
(concs. 10500 mg/L)
reduce adsorption
pH > 10 ads. decr.

sorbent dosage
(0.02 to 0.5 g in
uptake from 18 to
86%)
temp. 2580C
Lee et al. (1999)
22
Fly ash
By product from coal power

stations
pH
pH > 4 ads. Decr
Diamadopoulos et al. (1993)
23
Red mud
Waste from alumina

production
pH
As(III) ads effective at

pH 9.5
As(V) ads decr. at pH
>3.2
Altundogan et al. (2000)
24
Aluminiumloaded coral limestone

(AL-CL)
19
pH
H2PO4 significant
effect
Cl, NO3, SO42 none
Ohki et al. (1996)
(Continued)
25
Aluminium loaded shirasu-zeolites
Shirasuvolcanic pile present

in Kyushu area, Japan
26
Natural zeolites, volcanic stone and

cactaceous powder
27
California soils
28
Clay minerals (halloysite, kaolinite, illite,

chlorite montmorillonite
29
Zirconium oxide (Zr-resin)
Adsorbents tested
Zr (IV) loaded phosphoric acid chelating

resin
Water quality
parameter
studied
Parameter limiting
level
References
Xu et al. (1998)
Elizalde-Gonzales (2001)
Arid-zone soils from

California; fine-loamy and
coarse- loamy
pH 4-11
As(V) ads decreases at

pH >7; As(III) ads at
pH >7
Manning (1997)
Lin and Puls (1999); Manning and

Goldberg (1997)
Amberlite XAD-7 based on
cross-linked polyacrylate
copolymer
Phosphoric acid resin (RGP) in
the hydrogen form;
sp.surf area 29.2 m2/g;
acid cap. 7 meq/g;
P content 3.75 mmol/g
H2PO4 , fluoride
significant effect
River water versus salt
water
pH
presence of
electrolytes enhances
adsorption
pH >10
Suzuki et al. (2001)
Zhu and Jyo (2001)
Table 2.2
Batch isotherm studies: reported adsorption capacities and protocols used
Adsorption capacities achieved
Adsorbents tested
As(III)
As(V)
Initial As
(III) conc.
range
Initial As(V)
conc. range
Dose
added
Effect of water quality parameters

(or water quality parameters interferences)
pH
Phosphate
Silica
Fluoride
Sulfate
Magnetically impregnated
ion-exchange resins
(MIEX)
3.78 g/mg
0, 25, 50,
250, 1000,
2000 g/L
2 ml/L
Yes
For pH
5.5/7.5
Yes/No
For pH
9.5
Yes
For pH
5.5/7.5
No/No
For pH 5.5
Yes
Hydrous iron oxide

particles (HIOPs)
1.0 g/mg
02000 g/L
8 ml/L
None
No
Yes
No
No
Sulfur-modified iron
(SMI)
0.32 g/mg
02000 g/L
2,500
mg/L
Slightly
No
No
No
No
Granular ferric hydroxide

(GFH)
Chang et al. (2004)
2.51 g/mg
02000 g/L
500 mg/L
None
pH (59)
Yes
Yes
No
No
Driehaus et al. (1998)
ads. density
1 mmol/g Fe
residual
conc.
1040 g/L
10
Yes
No
Ferrihydrite (FH)
Raven (1998)
0.60 molAs/
molFe (at pH
4.6 and 9.2)
at pH 4.6: 0.25
molAs/molFe
at pH 9.2: 0.16
molAs/molFe
Chen et al. (2005)

Thirunavukkarasu et al.
(2001)
0.267
26.7 mmol/L
0.267
26.7 mmol/L
40 ml of
2.5 g/L FH
in 0.1 M
NaCl
As(V)
ads
higher at
pH 4.6
62.71 g/L
285 g/g
325 g/L
050 mg
SiO2/L
0.02
0.09 g FH
in 100 mL
pH 7.4
(Continued)

Adsorbents tested
6
As(III)
As(V)
Initial As(V)
conc. range
Dose
added

pH
Phosphate
Silica
Fluoride
Sulfate
Geothite (-FeOOH)
2.1 mol/m2
OReilly et al. (2001)

Manning et al. (1998)
Haematite
Iron oxide coated sands

(IOCS) or iron oxide
coated microsands
(IOC-M)
11
03 mM
133
266 mM
0.20 g/mg
Thirunavukkarasu et al.
(2001)
9
Initial As
(III) conc.
range
pH 6
20 ml of
2.5 g/L FH
110 mg/L
18.3 g/g
325 g/L
50 mm/g
0.667
667 mol/L
pH 2.85
none
0.5
1.2 g IOCS
in 100 mL
pH 7.4
Amorphous iron
hydroxide
Pierce and Moore (1982)
10
11
Zero-valent iron (ZVI)

Lackovic et al. (2000)
(Column experiment data
only)
50 mm/g
298 gAs/gFe0 669 gAs/gFe0 13.3 mol

after 1850 pore after 1850 pore
volumes
volumes
0.667
667 mol/L
13.3 mol
pH 410
Empty bed
vol. 14 mL
After As
ads
No
After As ads
No
No
(Continued)

Adsorbents tested
12
Ferruginous manganese
ore (FMO)
14
Manganese dioxide
As(III)
As(V)
At 0.040.18ppm
100% efficient
0.18ppm
100% efficient
Initial As
(III) conc.
range
0.040.18
ppm
Initial As(V)
conc. range
50 mg
MnO2 in
50 mL
16
Fluoride
Sulfate
pH 110
Yes
0.5 mg/L
10 g/L
Manganese oxyhydroxide
coated sand (MOCS)
at pH 7.5
1.6 g/mg
0.5 mg/L
pH 69
Iron-modified AA
(column exp.)
18
Silica
Manganese dioxide
coated sand (MDCS)
Thomson et al. (1998)

17
Phosphate
44.04 mg/g
0.5 mg/L
12
15
pH
0.040.18
ppm
Mean sorption
energy
15.5 kJ/mol
Chen et al. (1999)
Dose
added

3141 g/L
pH 8.7
9.2
Yes
Yes
Activated Alumina (AA)

4.10 mg/g
12.4 M
53.4 M
1 mg/L
1 mg/L
2 g/L of
AA in
100 mL
Yes, at
conc
>10 mg/L
Yes, at
conc
>2 mg/L
(Continued)

Adsorbents tested
19
As(III)
Initial As(V)
conc. range
Dose
added

pH
Phosphate
Silica
Fluoride
Sulfate
Activated carbon (AC)

20
As(V)
Initial As
(III) conc.
range
0.34 mg/g
Coconut husk carbon

(CHC)
13
copper-impregnated
coconut husk carbon
(CICHC)
146 g/g
3 g/L of
AC in
100 mL
50600
mg/L
0.1 g of
CHC in
50 mL
pH 212
2 g/L
21
Quaternized rice husk

(QRH)
19 mg/g
22
Fly ash
27.8 mg/g
23
Red mud
24
Aluminium loaded coral

limestone (AL-CL)
25
Aluminium loaded
shirasu-zeolites
26
Natural zeolites, volcanic

stone and cactaceous
powder
4.31 mol/L at
pH 9.5
26.4 M
100600
mg/L
Yes
pH 4, 7,
10
80%
reduction
at pH 4
5.07 mol/L at
pH 3.2
2.530 mg/L
20 g/L
Yes
150 g/g
2.550 mg/L
1 g of ALCL in 20
mL
pH 211
No
400 mg/L
0.05-2 g in
20 mL
Yes
No
(Continued)

Adsorbents tested
14
27
California soils
28
Clay minerals (halloysite,

kaolinite, illite, chlorite
montmorillonite
29
Zirconium oxide
(Zr-resin)
Zr (IV) loaded phosphoric
acid chelating resin
(column exp.)
As(III)
37279
mol/kg
1.06 mol/g
pH 8.5
As(V)
Initial As
(III) conc.
range
Initial As(V)
conc. range
Dose
added

pH
235300
mol/kg
0.2713.3
mol As
0.2713.3
mol As
1:10 (2 g
soil in 20
mL)
pH 411
As(V)
Yes
As(III)
Yes
Halloy site:
71.6 g/g
chlorite:
60.9 g/g
30 mol
35 mol
1 g in
30 mL,
24 h
5.57.5
0.72 mol/g
pH 4.5
0.613 mol/g
pH 1.14
0.453 mol/g
pH 8.55
0.5 g in
50 mL
Phosphate
Silica
Fluoride
Yes
Yes
Sulfate
Yes
Yes
CHAPTER 3
VENDOR AND MANUFACTURER SURVEY
Additional vendors and manufacturers, beyond those preliminarily identified in the original proposal submitted to the Awwa Research Foundation, were contacted. For media originally
identified, we made inquiries to manufacturers about their availability in different physical forms
(i.e., granular versus powdered) for use in different treatment configurations (i.e., packed beds
versus slurry and/or membrane reactors); moreover, we inquired about the availability of new
generations of existing products (e.g., sulfur modified iron (SMI)). The results of the vendor
survey were compiled in an access database (not included). Table 3.1 represents a synthesis of the
literature and vendor surveys; a longer version of this table appears in the appendix (Appendix B).
The references cited in Table 3.1 are summarized in the References chapter.
Through a critical examination based on the literature (i.e., Tables 2.1 and 2.2) and vendor
surveys (i.e., Table 3.1) as well as input from the Project Advisory Committee (PAC) during a
PAC meeting and through PAC comments in response to progress reports, a series of twelve
candidate adsorbents were identified (their identities are revealed in Chapter 6) for testing. These
included mostly commercially available media, both well developed and emerging, but also a
couple of experimental media corresponding to pure minerals.
15
Table 3.1
Adsorbents tested for arsenic removal: synthesis of literature review and vendor/manufacturer survey
Technology
Removal Arsenic capacity
Modified zeolite (Z-33)
<0.6 mg/g
Ferric salt prior to ceramic media

(Macrolite)
Market readiness
Pass TCLP?
Pass WET? Effective pH
Available
Yes
Yes
Available
Yes
Interfering parameters
Activated alumina (AA-300)
4.10 mg/g (15)
Available
<7 (1)
Sulfate (1)
Ion exchange (MIEX)
3.78 mg/g (7)
Available
Adversely
affected by high
pH (2)
Sulfate, silica, phophate, selenate (2)
Activated carbon
0.34 mg/g (15)
Available
35 studied
16
Granular ferric hydroxide (GFH)
<1 g/L
2.51 mg/g (7)
Available
Yes
Iron-coated diatomite (ADI-G2)
<2 g/L
2.4 mg/g
Available
Yes
Ferric hydroxide granules

(SP33/SORB 33)
<5 g/L
8-12 mg/g
Available
Modified activated alumina

(ActiGuard AAF550)
<5 g/L
Modified activated alumina

(Aqua-Bind)
44 mg/g
Manganese greensand with

continuous regeneration
No
<77.5
< 88.5
Available
Yes
Available
Yes
Silica, phosphate (2)
Silica, phosphate (2)
Available
Iron-impregnated GAC (Pica)
0.025 mg/g
Iron-modified activated alumina
Under development
69
Under development
Sulfur modified iron (SMI)
1 g/L
Alumina ore waste (Bauxsol)
1 g/L
Iron-based adsorption (ADA)
< 8 - 8.5
0.32 g/mg (7)
Silica, fluoride (14)
Under development Yes
Yes
Adversely
affected by high
pH (2)
Oxidants
Under development Yes
Likely
2.59.5 studied
Perhaps some metals
Under development
(Continued)

Technology
Hydrous iron oxide particles
(HIOPs)
Removal Arsenic capacity

1 mg/g
Iron oxide coated micro sand

Ferrihydrite
Market readiness
Pass WET? Effective pH
Experimental
Interfering parameters
Silica, selenate (2)
Experimental
0.285 mg/g (6)
Geothite
Experimental
Silica, natural organic matter (3)
Experimental
Haematite
0.2 mg/g (4)
Experimental
Zero-valent iron
0.298 mg/g (5)
Experimental
17
Experimental
Amorphous iron hydroxide
Experimental
Ferruginous manganese ore
Experimental
Manganese dioxide
Pass TCLP?
44.04 mg/g (11)
Manganese dioxide coated sand
High temperature (4)
<4 (8)
Experimental
Experimental
Manganese oxyhydroxide coated

sand
1.6 mg/g (13)
Experimental
Copper impregnated coconut

husk carbon
146 mg/g
Experimental
Quaternized rice husk
19 mg/g (16)
Experimental
Fly ash
27.8 mg/g (17)
Experimental
Aluminum-loaded coral
limestone
0.150 mg/g (19)
Experimental
California soils
37279 mol/kg
(20)
Experimental
411 studied
(20)
Zirconium oxide
0.071.6 mg/g (21)
Unknown
<10 (21)
Zr (IV) loaded phosphoric acid

chelating resin
0.613 mol/g (22)
Unknown
Sulfate, chromate (16)

<4 (17)
Phosphate (19)
Fluoride, phosphate (21)
CHAPTER 4
ARSENIC OCCURRENCE AND CO-OCCURRENCE ANALYSIS
The project literature review determined that limited data existed regarding the combined
presence of arsenic and its co-occurring parameters in drinking water sources. A key factor in evaluating the performance of adsorptive arsenic treatment media is to have some idea of the water
quality environment in which the media will be required to operate. Clearly, it is important to
understand at what levels arsenic is present in drinking water. Perhaps more importantly for this
project, an understanding of at what levels potentially interfering constituents tend to co-occur was
needed to assist in the evaluation of treatment media. The goal of this analysis was to determine
national arsenic occurrence and evaluate the composition of the water quality matrix in which
arsenic occurs.
OBJECTIVES OF THE ARSENIC CO-OCCURRENCE ANALYSIS
The objective of the analysis was to develop a first order estimate of arsenic occurrence and
determine at what level other constituents of concern occur in its presence. In a narrow sense, it
was felt that this analysis would be useful in developing test waters against which to perform bench
level evaluations. In a broader sense, an understanding of arsenic occurrence and co-occurrence
will assist in determining key parameters that may influence potential treatments, evaluating if
there are opportunities for process synergy through co-removal of other contaminants, and determine if multiple treatment processes may be required to treat arsenic contaminated water.
SOURCE DATA
A basic premise of this work was for the analysis to be performed retrospectively, that is
by using existing data. Several existing occurrence databases were investigated with respect to
their suitability for the project. It was determined that the National Water Information System
(NWIS) database created and maintained by the United States Geological Survey (USGS) would
provide the most comprehensive source of water quality data from which to perform the analysis.
NWIS is a compilation of water quality data for approximately 1.5 million sites across the United
States. While access to the NWIS data base is available online, the available online tools were not
suitable for the complex queries and large scale aggregation of data envisioned for this task. For
this reason a copy of the NWIS data was obtained through a third party reseller, EarthInfo Inc.
EarthInfo supplied the data in an eight CD-ROM set which included the complete NWIS data set
for surface and groundwaters up to 1998. Once the data was obtained from EarthInfo, it was transferred into a database residing on a MySQL 4.0.1 database server. In this form it could be
addressed as an ODBC data source using both Statistica and Microsoft Access software packages.
Although the NWIS data set was deemed to be the most suitable for the analysis, there are
some basic limitations inherent in the use of this data set. First it should be noted that the data
residing in NWIS is a compilation of hundreds, if not thousands, of surveys performed over the
past fifty plus years. It is unknown how many, if any, of these surveys were specifically focused on
determining arsenic occurrence. It is safe to assume that in practically all cases that arsenic was
not the focus of the sampling program. Arsenic was most likely one of a suite of parameters
measured during sampling program. Second, the data contained in NWIS is taken from a wide
19
Figure 4.1 Database development flow chart
variety of surface and groundwater sources, many of which are not suitable as drinking sources.
As will be discussed later, specific criteria were developed to ensure that the co-occurrence analysis was limited to waters whose overall quality would be suitable as a source of potable water.
Third, several analytical methods were employed to measure arsenic with varying detection
levels. Hence the co-occurrence analysis had to ensure the results were not unduly influenced by
detection levels or out of date analytical techniques. Fourth, while the NWIS data provided
geographically and geologically diverse sampling locations, the locations are not uniformly
distributed throughout the nation. Typically sample locations are grouped by political boundaries
(states) with some states over-represented and other under-represented for no other reason than
one State has collected a large amount of groundwater quality data and another did not. Ultimately this analysis has the drawback of any retrospective analysis, it is limited to the analysis of
existing data which was generally collected for a different purpose.
CREATION OF THE GROUNDWATER ARSENIC CO-OCCURRENCE DATABASE
Since a large amount of water quality data is contained in NWIS, a process had to be developed which extracted the specific data which would be of use to the project. A four step process was
developed to extract data from NWIS and create the Groundwater Arsenic Co-Occurrence Database.
The process is illustrated in Figure 4.1. The first step of the process involved querying the NWIS
database and extracting all the groundwater stations for which arsenic data existed along with the
stations arsenic concentration. Once the stations were identified, the values for co-occurring parameters of interest were also extracted for each station. Second, the mean values of these parameters
were tested against the criteria in listed in Table 4.1. If they failed to fall within pre-established the
criteria, it was assumed the water would not be suitable drinking water source and the site was not
included in the arsenic database. Third, detection levels for each parameter were considered. The
detection level for each parameter was tested against the criteria in Table 4.1. If the detection level
exceeded the acceptable detection level criteria (Table 4.1), the data point was dropped. Lastly, the
remaining data was placed into a MS Access database from which values could be extracted for
statistical analysis.
20
Table 4.1
Database parameters and data acceptance criteria
Acceptable data range
Parameter
Unit
Minimum
Maximum
Acceptable detection limit
Alkalinity
mg/L
1000
Arsenic
g/L
0.5
150
10
Calcium
mg/L
0.5
500
Chloride
mg/L
0.5
500
10
Fluoride
mg/L
0.1
10
0.1
Iron (dissolved)
g/L
8000
10
Iron (total)
g/L
8000
10
Potassium
mg/L
0.5
50
Magnesium
mg/L
0.1
100
0.1
Manganese (dissolved)
g/L
1500
10
Manganese (total)
g/L
1500
10
Sodium
mg/L
0.3
500
10
Nitrate
mg/L
0.1
50
pH
14
Phosphate (total)
g/L
0.1
500
0.1
Selenium
g/L
0.5
200
10
Silica
mg/L
0.1
150
0.1
Sulfate
mg/L
500
10
TDS
mg/L
10
1500
Temperature
50
Total Hardness
mg/L
10
1000
Well Depth
feet
N/A
N/A
Chromium (total)
g/L
500
10
Chromium (hexavalent)
g/L
0.2
500
10
21
Non-detects were handled as follows: If the value for a sample was recorded as zero (0)
and no detection level was indicated, the sample was not used for the statistical analysis of the
data. If the sample was listed as non-detect or 0 and a detection level within the accepted limit was
available, the value of the non-detect was estimated as 0.5 times the detection level when
performing statistical analysis.
The handling of arsenic data deserves special discussion. As indicated in Table 4.1, sites
with reported arsenic concentration of greater than 150 g/L were not included in the database
under the assumption that these sources would be unsuitable for drinking water consumption.
Sites with reported arsenic concentrations of less than 0.5 g/L were also excluded from the database, this time under the assumption that this value represents the lower bound of reliable arsenic
detection. Hence values which are reported to be less than this threshold value were deemed unreliable. Lastly, non-detects were handled as described above. Sites in which arsenic was not
detected and no detection level was indicated or sites with detection levels greater than 10 g/L
were excluded from the database.
Using the methods described above, the National Groundwater Arsenic Database was
developed. The database contained data for 9867 groundwater sites collected in 44 of the 50
states. The distribution of groundwater sites included in the database by state is illustrated in
Figure 4.2. As can be seen in the figure, the number sites are not uniformly distributed by State or
region. Three states are disproportionably represented in the database. These are Florida, Illinois
and South Dakota. This does not mean that these states have a higher occurrence of arsenic than
other states, but merely that NWIS contains a large number of sites in these states for which
arsenic data exists and whose water quality meets the criteria established in Table 4.1. This is an
unavoidable consequence of performing a retrospective analysis.
While water quality data is typically associated with political boundaries (e.g., states),
occurrence is likely to be physically related to geologic or physiographic features and not political
boundaries. Building upon an approach proposed by Welsh et al. (2000), arsenic occurrence can
be evaluated for the six physiographic zones of the conterminous United States. These zones,
along with two additional zones based upon political boundaries for Alaska (Zone 7) and Hawaii
(Zone 8) are presented in Figure 4.3.
CHARACTERISTICS OF ARSENIC OCCURRENCE
Based upon the data extracted from NWIS per the methods described above, the mean
groundwater (total) arsenic concentration of the 9867 sites whose water quality characteristics are
suitable for potable consumption and distributed throughout the United States was 4.5 g/L.
However, the median arsenic concentration for all sites in the database was 1 g/L, indicating that
arsenic occurrence does not follow a normal distribution.
The impact of a revised arsenic MCL on the industry can be estimated by developing a
cumulative probability distribution of arsenic occurrence. Assuming the probability of arsenic
occurrence is a continuous function, it can be represented by the cumulative probability function:
U
F(X) =
(4.1)
f ( x ) d( x )
L
where L and U represent the smallest and highest value measured arsenic values.
22
Figure 4.2 Distribution of groundwater arsenic sites by state
Rocky Mountain System

Appalachian Highlands
Interior Plains
Pacific Mountain
System
Intermontane Plateau
Atlantic Plain
Figure 4.3 Physiographic zones of the United States

23
Figure 4.4 National cumulative probability distribution for arsenic occurrence for 9867
stations extracted from NWIS
The national cumulative probability distribution for (total) arsenic is plotted in Figure 4.4.
Calculations based upon the distribution in Figure 4.4 indicate that 979 of the 9867 (9.9%) of the
groundwater sites in the database would require arsenic treatment to meet the MCL of 10 g/L.
Some states (e.g., New Jersey) are considering setting their MCL at 5 g/L. Based on this value,
2179 (22%) of the sites would exceed a 5 g/L MCL.
The occurrence of arsenic by physiographic zones is summarized in Table 4.2 and the
cumulative probability distributions, by physiographic zone, are plotted in Figure 4.5. Reviewing
this data it can be seen that there is significant variation in (total) arsenic occurrence between
physiographic zones. Overall the general trend of arsenic occurrence by physiographic zone is as
follows:
Intermontane Plateau >> Rocky Mountain System Appalachian Highlands
Pacific Mountain System > Interior Plains Atlantic Plain
The greatest occurrence of elevated arsenic levels are in the Intermontane Plains, with
49% of the sites in the database exceeding mean arsenic concentration of 10 g/L. These results
are consistent with the observation that many utilities in New Mexico and Arizona are currently in
the process of dealing with arsenic treatment issues. The lowest arsenic occurrence is in the
Atlantic Plain. Arsenic occurrence in the State of Alaska appears to be similar but less than the
Intermontane Zone. Arsenic occurrence in Hawaiian groundwater appears to be very low with no
sites exceeding 5 g/L. However it should be noted that the Hawaii dataset is limited to 46 sites.
None the less, referring to Table 4.2, it can be seen that the arsenic concentrations in excess
of 10 g/L occur in all physiographic zones of the United States (the political zone of Hawaii
excepted). Hence arsenic occurrence is not associated with any specific physiographic zones. While
there is significant variation of arsenic occurrence between physiographic zones, all physiographic
zones are impacted and the issue of arsenic occurrence is national and not regional in scope.
24
Table 4.2
Summary of arsenic occurrence by physiographic region
Percent of sites with arsenic
Zone
Physiographic region
Number of
sites
ND or
5 g/L
>5 g/L
10 g/L
20 g/L
Appalachian Highlands
701
84
16
11
Atlantic Plain
2155
90
10
Interior Plains
5505
90
10
Rocky Mountain System
108
83
17
13
Intermontane Plains
591
46
54
49
31
Pacific Mountain System
343
79
21
10
Alaska*
418
63
37
26
15
Hawaii*
46
100
9867
85
15
10
Total
* Political boundary
Figure 4.5 Cumulative probability distribution for arsenic occurrence by physiographic

zone. Physiographic zones are illustrated in Figure 4.3.
25
CHARACTERISTICS OF ARSENIC SPECIATION

The performance of arsenic treatment methods is strongly influenced by speciation.
Unfortunately, the NWIS database does not include arsenic speciation data, so an analysis of
speciation could not be performed. The use of other non-NWIS databases or arsenic surveys
containing speciation data was considered. Unfortunately no national, large scale and comprehensive data source which contained reliable speciation data was found to exist. So conclusions
regarding arsenic speciation are tentative at best.
Perhaps the most comprehensive speciation study performed to date was the Water
Industry Technical Action Fund (WITAF) National Arsenic Occurrence Survey (Frey and
Edwards, 1997). In this study, 47 arsenic bearing groundwaters located throughout the nation
were speciated with respect to As(III) and As(V) using a method described by Edwards et al.
(1998). This survey found As(V) to be the predominant arsenic species in 35 of the 47 (75%) the
groundwaters tested. Anecdotal evidence also seems to support that the occurrence of As(V) is
prevalent over As(III) in waters of the western Unites States. For example, speciation data
collected by the State of Colorado under the COSTAR program for nine small systems requiring
treatment to meet the revised arsenic rule found only one system in which As(III) was the predominant species. Until a sufficient speciation data is collected, the occurrence of individual arsenic
species in U.S. groundwaters will remain unknown. However, in other locations such as Bangladesh, As(III) dominates in anoxic groundwaters.
CHARACTERISTICS OF ARSENIC CO-OCCURRENCE
The water quality matrix in which arsenic occurs is of prime importance to the evaluation,
selection and ultimate performance of any arsenic treatment method. Experience gained in
treating for arsenic indicates that treatment methods can be very sensitive to the presence of other
contaminants. For example, the presence of sulfate, phosphate, silica, or the pH at which treatment occurs can influence the effectiveness of arsenic treatment.
In order to gain a better understanding of the water quality matrix in which arsenic occurs
a co-occurrence analysis was performed. The co-occurrence analysis attempted to answer basic
three questions. The first basic question was, What are the general water quality characteristics
of groundwaters containing various levels of arsenic? This is a general question that tries to
understand the basic water quality characteristics of groundwaters which may require arsenic
treatment. The second basic question asks, Are the water quality characteristics of groundwaters
containing elevated levels of arsenic fundamentally different from those which do not? Clearly
arsenic bearing water is different from non-arsenic bearing water; after all by definition it contains
elevated levels of arsenic. This leads to additional sub-questions such as, does the water differ
from non-arsenic bearing waters in other ways? More importantly, does arsenic bearing groundwater also typically contain elevated levels of co-occurring parameters, like silica for example,
which may detrimentally impact treatment performance? If so, arsenic treatment by adsorptive
media may be less effective than generally anticipated. A basic final question asks, Does the
presence of arsenic correlate with other water quality parameters? If the presence of arsenic does
correlate with other parameters, the concentration of that parameter could be inferred from the
concentration of arsenic in the sample.
For the purpose of subsequent co-occurrence analysis, arsenic occurrence was divided into
three categories, low arsenic sites, moderate arsenic sites and high arsenic sites. The criteria
26
defining these categories are admittedly somewhat arbitrary. They are defined as follows. A low
arsenic site contains 5 g/L arsenic or less. Practically speaking, it was assumed no utility would
conclude arsenic treatment is necessary for sites in this category. Sites containing between 5 g/L
and 20 g/L arsenic were classified as moderate arsenic sites. It was assumed that at a threshold of
5 g/L would be the lowest level at which a utility would consider arsenic treatment. Yet so long
as the mean arsenic concentration was less than 20 g/L, treatments such as blending would be
preferred and feasible. The bulk of utilities which will be required to treat for arsenic fall into this
category. Lastly sites containing mean concentrations of 20 g/L arsenic or greater were considered high arsenic sites. Sites in this category were assumed to only be able to meet the MCL
through the use of a treatment technology, such as adsorptive media. It should also be noted that
the low arsenic category includes all the sites for which the arsenic concentration was estimated
from the detection limit per the method described earlier (arsenic concentration = detection
level/2). As a corollary, the medium and high arsenic categories only use arsenic data derived
from the direct measurement of arsenic concentration.
General Water Quality Characteristics
The general water quality characteristics of groundwaters containing low, moderate, and
high levels of arsenic is summarized in Table 4.3. This table lists the 10th, 25th, 50th, 75th and
90th percentile concentration of twenty-two co-occurring parameters binned by the low, moderate
and high arsenic categories described above. In reviewing this table, it can be seen that arsenic can
be present in a wide range of water quality conditions. The clear implication is that adsorptive
arsenic treatment will be challenged by a broad range of co-occurring conditions and that, as
experience has shown, the general effectiveness of arsenic treatment can not be extrapolated from
the performance in simple model waters.
Using Table 4.3 the likely concentration of various co-occurring parameters can be estimated. For example, the median (50th percentile) co-occurrence concentration for each parameter
can be used to define a typical level of co-occurrence. Using this method a typical water
containing moderate levels of arsenic possesses an alkalinity of 246 mg/L as CaCO3, a pH of 7.7,
a TDS of 389 mg/L, sulfate of 27 mg/L and (total) silica of 14 mg/L as SiO2. In contrast a water
representing a 75th percentile level of co-occurring parameters contains an alkalinity of 344 mg/L
as CaCO3, a pH of 8.1, a TDS of 572 mg/L, sulfate of 79 mg/L and silica of 21 mg/L as SiO2.
Are Waters That Contain Arsenic Different From Those That Do Not?
Table 4.3 illustrates that the composition of groundwaters containing arsenic varies
greatly. But is an arsenic bearing water different from a water which contains little or no detectable levels of arsenic? In order to investigate this question, the cumulative probability distribution for each co-occurring parameters was developed and plotted using the three arsenic bins.
Clear differences in the distribution of several parameters known to impact the performance of
adsorptive treatment media were observed. Parameters for which there was an obvious difference in the cumulative probability distribution of occurrence binned by increasing arsenic
concentration included pH, silica, fluoride, alkalinity and phosphate. These plots are presented
in Figures 4.6, 4.7, 4.8, 4.9 and 4.10 respectively. As evidenced by the shift in probability distributions to higher concentrations, these parameters consistently occurred at higher concentrations in moderate and high arsenic waters than in low arsenic waters. From an arsenic treatment
27
Table 4.3
Summary of occurrence of co-occurring parameters in national groundwater arsenic database
10th percentile
Parameter
Unit
Alkalinity
25th percentile
50th percentile
28
Low As
Mod As
Hi As
Low As
Mod As
Hi As
Low As
Mod As
Hi As
mg/L CaCO3
18
82
104
130
157
166
262
246
286
Calcium
mg/L
15
26
17
53
55
43
Chloride
mg/L
11
11
20
31
33
Chromium TOT
g/L
0.6
1.0
2.0
2.5
2.5
3.0
5.0
5.3
8.0
Chromium VI
g/L
0.5
0.5
0.5
0.5
1.0
5.0
0.5
2.5
5.0
Fluoride
mg/L
0.1
0.1
0.1
0.1
0.2
0.2
0.2
0.3
0.5
Hardness
mg/L CaCO3
17
24
30
46
96
84
140
204
197
Iron DIS
g/L
20
20
50
30
80
385
120
Iron TOT
g/L
12
50
15
196
251
99
1656
2016
Magnesium
mg/L
13
12
18
Manganese DIS
g/L
20
30
30
Manganese TOT
g/L
12
15
23
17
44
45
Nitrate
mg/L N
0.1
0.2
0.5
0.3
3.7
1.0
5.7
6.7
6.8
6.2
7.2
7.3
7.3
7.7
7.8
pH
Phosphate
mg/L PO4
0.04
0.05
0.05
0.05
0.08
0.18
0.05
0.13
0.34
Potassium
mg/L
0.5
0.7
1.2
1.0
1.2
2.0
2.0
2.5
4.0
Selenium
g/L
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1.0
Silica
mg/L SiO2
10
12
10
14
18
Sodium
mg/L
14
23
30
43
87
Sulfate
mg/L
22
27
31
TDS
mg/L
67
203
186
186
302
312
374
389
436
Temperature
9.6
8.5
7.0
11.5
11.9
11.5
13.5
14.0
14.0
(Continued)

75th Percentile
Parameter
Unit
Alkalinity
90th Percentile
Valid N
29
Low As
Mod As
Hi As
Low As
Mod As
Hi As
Low As
Mod As
Hi As
mg/L CaCO3
360
344
438
504
466
627
6345
638
272
Calcium
mg/L
120
106
81
238
174
150
5152
579
227
Chloride
mg/L
63
84
99
206
273
225
2103
413
215
Chromium TOT
g/L
10.0
10.0
11.9
25.0
20.0
30.0
605
85
36
Chromium VI
g/L
4.0
5.0
15.0
16.0
18.0
127.9
67
26
21
Fluoride
mg/L
0.4
0.7
1.1
0.8
1.6
2.5
3464
528
222
Hardness
mg/L CaCO3
287
337
396
476
519
710
3301
539
236
Iron DIS
g/L
440
1960
763
2000
6700
2652
2350
400
170
Iron TOT
g/L
701
4750
4662
2500
7000
7800
7508
733
311
Magnesium
mg/L
39
26
34
86
50
69
4674
557
218
Manganese DIS
g/L
75
120
101
240
650
392
1841
295
150
Manganese TOT
g/L
81
216
215
373
800
1360
7272
636
258
Nitrate
mg/L N
18.8
5.3
40.8
14.8
739
119
7.8
8.1
8.2
8.1
8.5
8.4
1783
236
111
pH
Phosphate
mg/L PO4
0.08
0.28
0.55
0.60
0.55
0.60
451
38
17
Potassium
mg/L
4.0
5.6
10.0
8.4
15.2
22.0
3843
517
194
Selenium
g/L
1.0
1.9
2.5
3.0
5.0
7.0
711
91
48
Silica
mg/L SiO2
14
21
29
21
32
52
6462
667
275
Sodium
mg/L
130
120
203
333
330
474
3971
519
209
Sulfate
mg/L
68
79
118
231
260
517
2817
479
261
TDS
mg/L
560
572
582
909
1090
928
4096
489
210
Temperature
17.0
21.2
19.0
23.6
25.5
24.5
6873
767
355
Note: Number of low arsenic sites = 8414, moderate arsenic sites = 963, high arsenic sites = 490
Figure 4.6 Comparison of cumulative probability distributions of pH for waters containing

low, moderate, and high concentrations of arsenic
Figure 4.7 Comparison of cumulative probability distributions of silica for waters containing
low, moderate, and high concentrations of arsenic
perspective this important. Arsenic bearing groundwaters appear to naturally contain higher
levels of the very parameters which interfere with performance of adsorptive arsenic treatment
media. It also appears that the higher the arsenic concentration, the more likely it is that these
interfering parameters will be present.
Two other parameters deserve attention, namely iron and sulfate. It is widely accepted that
the fate of arsenic in the environment is tied to the presence of iron. The cumulative probability of
iron occurrence by binned by arsenic concentration appears to confirm this observation. As seen
in Figure 4.11, waters in which arsenic is detected contain much more iron than those that do not.
Unlike the parameters such as silica discussed above, it is unclear if the presence of iron is detrimental to disposable adsorptive arsenic treatment processes. However, elevated levels of iron can
be beneficial for some technologies such as greensand treatment.
30
Figure 4.8 Comparison of cumulative probability distributions of fluoride for waters

containing low, moderate, and high concentrations of arsenic
Figure 4.9 Comparison of cumulative probability distributions of alkalinity for waters

While having little impact on disposable adsorptive arsenic treatment media performance,
the performance of ion exchange is very sensitive to sulfate levels. Interestingly enough, as seen
in Figure 4.12, the cumulative probability distribution of sulfate occurrence was not different
between waters containing little or no arsenic and those which contain arsenic.
In summary, there appears to be basic differences in groundwaters containing arsenic
compared to those which do not. Based upon the analysis of the 9867 groundwaters in the database, waters which contain detectable levels of arsenic tend to be higher in pH, silica, fluoride
alkalinity phosphate and iron than those which do not.
31
Figure 4.10 Comparison of cumulative probability distributions of phosphate for waters

Figure 4.11 Comparison of cumulative probability distributions of iron for waters

Direct Correlation Between Arsenic and Other Parameters

The strength association between two variables and the direction of the association, if any,
can be estimated by performing a correlation analysis. Assuming the underlying distribution is
normally distributed, the correlation can be estimated by the Pearson Correlation Coefficient. The
Pearson Correlation Coefficient, r, is defined as:
S XY
r = -----------S X SY
(4.2)
32
Figure 4.12 Comparison of cumulative probability distributions of sulfate for waters

where SXY is the sample covariance and SX and SY are the standard deviation of the variables. The
Pearson Correlation Coefficient can take on values ranging from 1 to +1 with 1 or +1 indicating
the greatest relationship and + or indicating the direction of the relationship.
A total of four different co-occurrence correlation matrixes were created relating arsenic
concentration to the concentration of co-occurring parameters. The four matrixes are as follows:
Total arsenic at all sites

Arsenic at sites 5 g/L
Arsenic at sites between 5 g/L and 20 g/L
Arsenic at sites 20 g/L
The r values for the four correlation matrixes are summarized in Table 4.4. As can be seen
by reviewing the table, at a 95% confidence level, no statistically significant correlations were
found between arsenic and the various co-occurring parameters. Hence the presence of arsenic
cannot be directly correlated to the presence of any other parameter, including iron.
At first this may seem surprising given the strong trends observed in several of the cumulative distribution plots presented above. Yet it should be remembered that r values are in essence
a measure of the scatter of the data about a regression line. It is likely that the correlations are poor
because of the high variability within the datasets. Therefore the presence of arsenic cannot be
used to predict the presence or concentration of other co-occurring parameters.
ALTERNATIVE WATER QUALITY TESTING MATRICES
When evaluating the performance of arsenic treatment media a standard challenge water is
needed to provide a common basis for the evaluation. For this reason the NSF challenge water
was developed. It provides a common model water against which treatment media can be evaluated. Information extracted from the database can compared to the NSF challenge water to see
how well the NSF challenge water composition compares to the co-occurrence information
33
Table 4.4
Pearson correlation coefficients at 95% confidence level measuring the
degree of correlation between arsenic and co-occurring parameters
Sites with arsenic
Parameter
All
5 g/L
5 g/L As
20 g/L
20 g/L
Alkalinity
0.14
0.01
0.04
0.06
Calcium
0.00
0.10
0.02
0.05
Chloride
0.07
0.01
0.01
0.12
Total Chromium
0.02
0.02
0.06
0.42
Hexavalent Chromium
0.02
0.07
0.25
0.00
Fluoride
0.15
0.03
0.08
0.13
Dissolved Iron
0.00
0.15
0.05
0.21
Total Iron
0.13
0.07
0.06
0.26
Potassium
0.15
0.06
0.02
0.16
Magnesium
0.06
0.06
0.03
0.06
Dissolved Manganese
0.03
0.08
0.04
0.02
Total Manganese
0.06
0.06
0.03
0.04
Sodium
0.11
0.05
0.04
0.05
Nitrate
0.11
0.19
0.03
0.18
pH
0.15
0.10
0.06
0.03
Phosphate
0.07
0.06
0.01
0.44
Selenium
0.03
0.02
0.12
0.06
Silica as SiO2
0.25
0.04
0.20
0.21
Sulfate
0.05
0.02
0.01
0.18
Total Dissolved Solids
0.05
0.12
0.07
0.14
Temperature
0.01
0.03
0.04
0.08
Total Organic Carbon
0.07
0.18
0.05
0.16
Total Hardness
0.06
0.03
0.04
0.03
34
Table 4.5
Alternate water quality testing matrixes for waters containing
moderate or high levels of arsenic
Moderate arsenic
High arsenic
Parameter
Unit
NSF
water
Sodium
mg/L
74
43
120
330
87
203
474
Calcium
mg/L
40
55
106
174
43
81
150
Magnesium
mg/L
13
12
26
50
18
34
69
Alkalinity
mg/L CaCO3
150
246
344
466
286
438
627
Chloride
mg/L
71
31
84
273
33
99
225
Fluoride
mg/L
0.3
0.7
1.6
0.5
1.1
2.5
Sulfate
mg/L
48
27
79
260
31
118
517
Nitrate
mg/L N
5.3
14.8
Phosphate
mg/L P
0.12
0.13
0.28
0.55
0.34
0.55
0.6
Silica
mg/L SiO2
20
14
21
32
18
29
52
TDS
mg/L
307
374
572
1090
436
582
928
50th
75th
90th
50th
75th
90th
extracted from the database. As discussed above, a typical or 50th percentile water quality for
waters containing arsenic can be estimated from the median co-occurrence values. Table 4.5 illustrates different water quality matrixes for waters that contain moderate and high levels of arsenic.
Comparing the NSF water to the 50th percentile water it can be seen that the NSF challenge water and 50th percentile water are roughly similar in composition. The NSF water has
similar levels of phosphate, lower levels of alkalinity and higher levels of sulfate, fluoride and
silica than the 50th percentile water. So, as a challenge water, it roughly matches the 50th
percentile water. Yet the NSF water is much less aggressive than the 75th percentile water. Media
tested against the 75th percentile water is likely to perform poorer than against the 50th percentile
water. The NSF water appears to be an adequate challenge water for evaluating arsenic treatment
performance in a moderate arsenic water with typical levels of co-occurrence. However testing
with the NSF water does not provide an adequate measure of performance against waters with
co-occurrence exceeding the 50th percentile. Based upon these results it seems advisable that
adsorptive arsenic treatment be tested against both the NSF challenge water, and against a more
aggressive matrix, like the 75th percentile water, in order to complete a rigorous evaluation of the
treatment media.
SUMMARY
The occurrence of arsenic in groundwaters was estimated by a retrospective analysis using
water quality data extracted from USGSs NWIS. The co-occurrence of other key water quality
35
parameters was also estimated. Data extracted from NWIS was tested against a conservative set of
criteria selected to assure data quality and the suitability of the groundwater for potable consumption. The extracted data was then used to create a national groundwater arsenic occurrence database.
Using information from the database, the mean arsenic concentration for 9867 stations
in the conterminous United States, Alaska and Hawaii, whose water quality characteristics are
suitable for potable consumption was 4.5 g/L. When arsenic occurrence was compared
between the physiographic zones of the United States, arsenic occurrence was found to follow
the following trend:
Intermontane Plateau >> Rocky Mountain System Appalachian Highlands
Pacific Mountain System > Interior Plains Atlantic Plain
Even though this trend was noted, there is large variability of arsenic occurrence in the
United States. All zones (Hawaii excepted) had sites with arsenic in excess of 20 g/L.
The water quality characteristics of groundwaters containing little or no arsenic were
compared to groundwaters containing elevated levels arsenic. In general, sites with detectable
levels of arsenic (> 5 g/L) also had higher levels of alkalinity, fluoride, total iron, pH, silica, and
phosphate. It appears that the co-occurring contaminant composition of arsenic bearing water is
different than water which contains low or non detectable levels of arsenic. Yet correlation
matrixes failed to produce statistically significant correlations between the presence of arsenic and
specific co-contaminants. The failure to obtain statistically significant correlations was attributed
to the large variability in the data set.
The database was used to develop model waters based upon various levels of co-occurrence.
These waters were compared to the NSF challenge water. It was concluded that the NSF challenge
water roughly represents a 50th percentile co-occurrence. It was recommended that more aggressive
water matrixes, similar to the 75th percentile water, should be used to provide a robust test of arsenic
treatment media.
36
CHAPTER 5
EXPERIMENTAL PROTOCOLS AND ANALYTICAL METHODS
INTRODUCTION
This chapter summarizes the experimental methods and procedures used in the benchscale testing program discussed in Chapter 6. Both experimental protocols and analytical methods
are addressed. The experimental protocols include both bench-scale simulations in the form of
batch and column tests. The primary objective of the batch tests was to develop equilibrium
adsorption isotherms, with preliminary experiments done to assess adsorption reaction kinetics as
a basis for defining a time frame for establishing equilibrium conditions. A set of preliminary
batch experiments was performed to screen a larger number of candidate adsorbents down to a
smaller number of select adsorbents for more intensive batch testing. The primary goal of the
column tests was to develop breakthrough curves (BTCs) for several adsorbents under dynamic,
continuous-flow conditions. A final activity was to subject spent residuals to TCLP/WET testing
to assess their leaching potentials. Analytical methods included total arsenic, arsenic species
(As(V) versus As(III)), interferant species (phosphate, silica (silicate), vanadium (vanadate), and
fluoride), and miscellaneous parameters measured by standard methods (e.g., pH).
BATCH TESTING PROTOCOLS
Preliminary Screening Tests
Evaluation of pH Buffers
An important initial task was to identify an appropriate buffer for establishing prerequisite
pH conditions. The principal attribute of a buffer was that it be non-adsorbing and hence noninterfering. A control experiment was run with one representative adsorbent, granular ferric
hydroxide (GFH), with As(V) at pH 7.0 in the absence of interferants. Carbonate and borate
buffers were compared against a 2 mM BES (N,N-Bis(2-hydroxyethyl)-2-aminoethanesulfonic
Acid) buffer, with the knowledge that carbonate is a known interferant and that borate has a
limited buffer capacity at lower pH levels.
Kinetic and Equilibrium Isotherm Tests
From the various adsorbents revealed by the literature survey and the vendors survey,
twelve adsorbents, including ten commercially available media and two experimental (pure)
media, were screened for As(V) removal. The rationale for selecting these specific media is
discussed in Chapter 6. The candidate media included:
AA-400G (activated alumina (AA))

AA-FS50 (iron impregnated AA)
MIEX (amagnetized ion exchange resin)
Bayoxide E33 (granular ferric oxide (GFO))
Granular Ferric Hydroxide (GFH)
37
Metsorb (titanium dioxide)

Z33-Revision B (iron modified zeolyte)
ARM 100 (alumina based, with proprietary promoters)
Sulfur Modified Iron Version III (SMI)
ViroClear Bauxsol F3 (Bauxite Clay)
Geothite (-FeOOH)
Pyrolusite (-MnO2)
The preliminary experiments evaluated the adsorption of As(V), at an initial concentration

of 100 g/L), with three adsorbent doses (25, 100, and 500 mg/L), each at several contact times
ranging from 10 minutes to 24 hours (1440 minutes). Arsenate (or arsenite) was added as a
sodium salt, and pH was maintained at 7.0 using the BES buffer. These preliminary data were
intended to serve two purposes: (i) an evaluation of the contact time required to establish equilibrium conditions and (ii) representation of each adsorbent in terms of a three-point isotherm, used
a basis for selecting a sub-set of adsorbents for more intensive isotherm testing. In the preliminary
experiments, As(III) at 100 g/L was evaluated at only one intermediate adsorbent dose
(100 mg/L) and at only the longest contact time (24 hours), yielding a simple one-point isotherm
for comparison of adsorbents.
The preliminary experiments were performed by taking a series of 500 mL HDPE plastic
screw-top bottles and filling each with a given test water and an appropriate dose of adsorbent.
The bottles were placed on a rotating tumbler for 24 hours, and then sampled over time. Each
time-series sample was taken from each bottle via syringe and filtered through a 0.45 m syringe
filter. The bottles were returned to the tumbler and then sampled again over time. Unlike other
adsorbents added as a mass, MIEX was added as slurry; a dry weight conversion of 0.8 g/mL was
used for MIEX.
Intensive Testing of Select Adsorbents
Based on the results of the preliminary experiments, six adsorbents, all commercially
available, were selected for more intensive isotherm testing. The select adsorbents, for which the
rationale for their selection is further discussed in Chapter 6, included:

Characterization of Physical/Chemical Properties of Adsorbents

In order to more mechanistically understand the adsorption behavior of the select adsorbents, each was characterized according to important physical/chemical properties including:
pH of zero-point-charge (pHZPC)
Specific surface area
38
Minerology
Bulk density
Grain size
The pHZPC was determined by measuring zeta potential (ZP) as a function of pH. A
ZetaMeter+ was used to measure ZP as a constant ionic strength of 3 mM (established by
NaNO3); interpolation of the ZP versus pH results provided an estimate of pHZPC, corresponding
to the pH where the ZP is zero. Specific surface area were measured by BET-N2 adsorption by the
Plant Science Laboratory at the University of Georgia; results were expressed in terms of m2/g
and reflect both external, and in the case of porous adsorbents, internal (intraparticle) surface area.
Minerology was delineated by XRD (X-ray diffraction, Scintag PAD5); XRD reveals the dominant mineral form(s) and is more sensitive for recognition of more crystalline (e.g., geothite)
versus more amorphous (e.g., Fe(OH)3) structures. The bulk densities and grain sizes were those
reported by the manufacturer.
Equilibrium Isotherm Tests Performed With Synthetic Waters
The equilibrium isotherm tests were performed with an initial arsenic species, As(V) or
As(III), concentration of 100 g/L. While this level is considerably higher that the arsenic levels
found in most natural waters, it was used to provide a more robust isotherm over a wider range of
final equilibrium arsenic concentrations. All individual interferants studied; phosphate, silica (silicate), vanadium (vanadate), and fluoride; were spiked by using sodium salts. Target pH conditions
of 6.0, 7.0, or 8.0 were established with the BES buffer. Based on the results of the kinetic experiments, a contact time of 24 hours was employed; the adequacy of this time frame for establishing
equilibrium conditions is discussed in Chapter 6.
Depending on the adsorbent, a range of adsorbent doses were applied, ranging from as
low as 10 mg/L and to as high as 1,000 mg/L; the actual range for each adsorbent was based on
the results of the preliminary experiments. Thus, these experiments assessed a range of adsorbent to adsorbate ratios while maintaining a constant initial adsorbate concentration. For each
unique isotherm experiment, six adsorbent doses were employed. It is important to note that, in a
single adsorbate system, the resultant isotherm is independent of the initial adsorbate concentration. However, in a multi-adsorbate system, the result isotherm is dependent on the initial
concentrations of all adsorbates because such systems are truly competitive adsorbate systems.
In our work, we emphasized binary systems involving one arsenic species, As(V) or As(III), in
the presence of one interferant species (e.g., phosphate). While there are isotherm models to
describe multi-adsorbate (e.g., binary) competitive systems, they require measurement of the
equilibrium concentrations of all adsorbates. However, in our work, only the equilibrium
concentrations of the arsenic species were measured, not the interferants. Thus, the results are
expressed in terms of single adsorbate (Freundlich and Langmuir) adsorption models as
discussed in Chapter 6. For each adsorbent dose, a solid phase concentration (Q, g/mg) was
calculated from the initial (C0) and equilibrium (Ceq) concentrations (g/L) of arsenic resulting
from the given adsorbent dose (m, mg/L): Q = (C0 Ceq)/m. The data for each experiment were
plotted in the form of a classic isotherm: Q (g/mg) versus Ceq (g/L).
The isotherm experiments were performed by taking a series of 500 mL HDPE plastic
screw-top bottles and filling each with a given test water and an appropriate dose of adsorbent.
39
The bottles were placed on a rotating tumbler for 24 hours and then sampled via syringe and
filtered through a 0.45 m syringe filter.
Equilibrium Isotherm Tests Performed With Utility-Supplied Natural Waters
In some experiments, the simultaneous presence of multiple interferants was evaluated
with a NSF challenge water or utility-supplied natural waters; their water qualities are described
in Chapter 6. The NSF challenge water contained known interferants: phosphate, silica, fluoride,
and sulfate. For the utility-supplied natural waters, relevant parameters that were measured
included As (both As(V) and As(III)), conductivity, DOC, pH, alkalinity, phosphate, sulfate,
silica, and vanadium. ICP-MS was used to measure As, Si (converted to mg/L as SiO2) and V. Ion
Chromatography (IC) was used to measure SO42- and PO43-. Standard methods were used to
measure conductivity, alkalinity, and pH. A Sievers TOC analyzer was used to measure DOC after
0.45 m filtration.
COLUMN TESTING PROTOCOLS
Several of the adsorbents were tested in dynamic column tests employing the NSF challenge water spiked with higher As(V) at concentrations up to 1,000 g/L. High initial concentrations were employed to facilitate breakthrough within a reasonable experimental time frame. A
single empty bed contact time (EBCT) of 5 minutes was employed in all tests, considered to be
representative of an industry standard. Limitations in available laboratory equipment necessitated
the use of different columns ranging in column (media) depth (D) and column (media) crosssectional area (A); D varied from 10 to 40 cm and A varied from 1.3 to 5.1 cm2. Arsenate concentrations were monitored over time, with the resultant data expressed in terms of breakthrough
curves (BTC) showing normalized fractional concentration (C/C0) versus number of bed volumes
(BVs).
TCLP/WET TESTING PROTOCOLS
Spent media for several adsorbents was generated in batch mode with high initial As(V)
concentrations. The specific conditions employed were: (i) initial As(V) = 2,000,000 g/L; (ii)
adsorbent concentration = 400,000 mg/L; and (iii) contact time = 72 hours. The NSF challenge
water was used in these tests (see Chapter 6 for water quality summary).
Four samples were tested according to standard EPA TCLP and State of California WET
protocols. Leachate samples were analyzed for arsenic using an Agilent 7500c Inductively
Coupled Plasma-Mass Spectrometer (ICP-MS) with an octopole reaction system, following EPA
Method 200.8. The octopole system utilizes helium gas at 6 mL/min as a collision gas to eliminate
the 40Ar35Cl mass interference with arsenic (75As). Germanium (72Ge) was used as the internal
standard. The method detection limit (MDL) established according to the guidelines in 40 CFR
136 Appendix B was 0.1 ppb.
40
ANALYTICAL METHODS
Total Arsenic and Interferant Measurements
All measurements for total arsenic were done at the Geosciences Laboratory at the University of Colorado by ICP-mass spectrometry (ICP-MS) using a Varian UltraMass-700. All samples
were first filtered through a 0.45 m syringe filter and pre-acidified with concentrated nitric acid
prior to delivery. The lower level of quantitation (minimum reporting level) was 1 g/L and, in
synthetic water experiments performed with either spiked As(V) or As(III), the measured total
arsenic by ICP-MS was inferred to be the As(V) or As(III) concentration. ICP-AES (ARL 3410+)
was also used to measure certain interferants: silicon (Si), converted to silica (SiO2), and vanadium (V). Other interferents such as phosphate, fluoride, and sulfate were analyzed by the
Geosciences Laboratory by ion chromatography (IC) with a Dionex IC 4500I with conductivity
detection. DOC was measured using a Sievers 800 TOC analyzer. pH and alkalinity by titration
were measured according to Standard Methods (APHA et al. 1998).
Arsenic Speciation
Soluble arsenic occurs in natural waters as arsenite [As(III)] and arsenate [As(V)]. Over
the pH range typically encountered in water treatment, arsenite exists as the uncharged species
H3AsO3, while arsenate is distributed between the anionic species H2AsO4-, HAsO4-2 or AsO4-3
(Ferguson and Gavis, 1972). The total arsenic, measured by ICP-MS, was further differentiated
into arsenate and arsenite using an ion exchange resin (McNeill and Edwards, 1995). The basis for
the resin separation of arsenate from arsenite is anion exchange as described by Ficklin, (1983).
Similar methodology has been applied by Clifford et al., (1983). In a sample acidified with H2SO4
to pH 3, arsenate is anionic whereas arsenite is non-ionic. Passage through the anion exchange
column removes the arsenate quantitatively, but does not remove arsenite. ICP-MS analysis for
arsenic in the resin-treated water gives arsenite concentrations, and ICP-MS analysis for arsenic
in the filtered and acidified sample that was not passed through the resin gives the total soluble
arsenic in the sample.
QA/QC FOR ARSENIC ANALYSIS
Table 5.1 summarizes the Quality Assurance and Quality Control procedures and results.
Table 5.1
Summary of quality assurance and quality control procedures for arsenic analysis
Detection
method
Minimum
detection
level*
(g/L)
Minimum
reporting
level
(g/L)
Range of
known As
addition
(g/L)
Recovery of
known As
addition
(%)
Level of
duplication
(%)
Mean coefficient of
variation for all
duplicate samples
(%)
ICP-MS
0.1
1.0
5, 10
96 to 113
1.67
* Calculated as blank + 3 standard deviation of blank for 10 consecutive blank samples.

Spiked with As(III) and/or As(V).
41
CHAPTER 6
BENCH TESTING
The bench-testing program consisted of both batch-mode and column-mode tests. The
batch tests included an initial set of preliminary experiments followed by a subsequent set of
intensive experiments. The intent of the preliminary experiments was two-fold: (i) to screen
candidate adsorbents under standard water quality conditions from a larger to a smaller number
for more intensive testing and (ii) to determine an appropriate kinetic time frame(s) for establishing equilibrium conditions for developing isotherms within the subsequent intensive testing
program. The purpose of the intensive experiments was to elucidate a range of water quality
effects on adsorbent capacities, as delineated by equilibrium isotherms. Based on the isotherm
results and associated estimates of capacities, a still smaller number of adsorbents were carried
forward for dynamic column testing and TCLP/WET evaluation.
BATCH TESTING
Preliminary Screening Experiments
As indicated above, the purposes of the preliminary experiments were screening of a
larger set of candidate adsorbents and associated selection of smaller set of targeted adsorbents for
intensive testing, and kinetic evaluation of candidate adsorbents as a basis for determination of
required contact time(s) for establishing equilibrium isotherms. The intent was to acquire about a
dozen adsorbents from those revealed in the literature and vendor surveys, and to collapse this
number to about a half-dozen for subsequent, more intensive testing. The candidate adsorbents
were identified based on a combination of their past performance indicated in the literature and
their availability (in terms of manufacturer willingness to provide them or the ease of producing
pure materials in the laboratory). The candidate adsorbents included ten commercial and two
experimental media that were screened for As(V) removal:
AA-400G (activated alumina (AA)

MIEX (a magnetized ion exchange resin)
ARM 100 (alumina based, with proprietary promoters)
ViroClear Bauxsol F3 (Bauxite Clay)
Geothite (-FeOOH)
Pyrolusite (-MnO2)
The preliminary experiments were run with a synthetic water containing 100 g/L of
As(V) at pH 7.0 (established by a non-adsorbing 2 mM BES buffer [see Chapter 5]. For each
adsorbent, an experimental matrix was run consisting of three adsorbent doses (25, 100, and
43
500 mg/L) and four reaction times (10, 30, 60, and 1440 minutes (1440 minutes = 24 hours)). A
second synthetic water was also tested with 100 g/L of As(III) at pH 7.0 for a single adsorbent
dose (100 mg/L) and a single time (24 hours). Details of the experimental protocol (agitation,
filtration, etc.) appear in Chapter 5.
A control experiment, employing GFH and an initial As(V) of 100 g/L, was first run to
ensure that the BES buffer was indeed a non-adsorbing and non-interfering buffer. The results are
shown in Figure 6.1, which portrays the capacity of the BES buffer against alternative buffers that
comprise potential interferants (e.g., carbonate). The results demonstrate the merits of the BES
buffer in this application: no discernable arsenic adsorption and constant pH maintenance. pH
drift observed in the absence of a buffer confirmed the need for a buffer.
Kinetic data were then analyzed to determine an appropriate reaction time for establishing
equilibrium conditions in the development of isotherms. Adsorption kinetics are elucidated in
Figure 6.2 in terms of percent removals as a function of time for 10 of the candidate adsorbents
(excluding the SMI and ViroClear). Rapid kinetics were generally observed for Bayoxide E33,
ARM 100, Metsorb, MIEX, and pyrulosite: slower kinetics were generally observed for AA400G, AA-FS50, GFH, Z33, geothite. In all cases, there was either a clear attainment of equilibrium within 24 hours, or an asymptotic leveling off that indicated an approach to equilibrium,
corresponding to a pseudo equilibrium condition. Although surface areas and internal porosities
were not determined in this phase, the differences in kinetic may be due to pore/surface diffusion
limiting the rate of mass transfer for some of the larger, more porous media.
Based on a 24 hour contact time, equilibrium isotherms were elucidated for each of the
candidate adsorbents for As(V) at a pH of 7.0. The results of the screening experiments are
presented in Figure 6.3 as arithmetic isotherm plots, portraying adsorbent loadings (g As/mg
adsorbent) in equilibrium with solution-phase concentrations (g/L). In order to not bias the
results, the data are shown as discrete points without any curve fitting. Given the experimental
conditions employed (i.e., 3 media doses ranging from 25 to 500 mg/L and one initial As(V)
concentration of 100 g/L), it would be theoretically possible to derive three-point isotherms for
each of the adsorbents. However, in some cases, a zero (< MDL = 1 g/L) was determined,
making such data problematic for use in isotherm development; in the case of the Bayoxide E33,
all three final equilibrium concentrations were zero (< MDL). While a three-point isotherm is
prone to error, there purpose here is only semi-quantitative as a screening tool. In these cases, the
corresponding adsorbent-phase loading was plotted against a solution-phase concentration of
zero. The data were also graphed in an alternative format in Figure 6.4, portraying % As(V)
removal at each of the 3 media doses. In some cases, removals of 100% are shown, indicating
adsorbate (i.e., As) limiting conditions versus adsorbent limiting conditions. A similar graph for
As(III) was developed, as shown in Figure 6.5.
On a mass basis, the MIEX and the Pyrolusite appear to be the least effective in removing
As(V) although exchange capacity (exchange sites per unit mass) would be a more appropriate
way of describing the capacity of an ion exchange resin (i.e., MIEX). Of intermediate effectiveness for As(V) were Geothite, Z33, and Viroclear. The limited results for As(III) showed less
effectiveness for AA-400G, AA-FS50, ARM, Viroclear, and, as expected, MIEX. A decision was
made to eliminate Geothite because its capacity was less than or equal to that of the commercially
available iron oxide adsorbents. The AA-400G was dropped because the iron-impregnated AA
(AA-FS50) showed a higher capacity for As(V) removal. The Viroclear F3 was dropped because it
was ineffective for either As(V) or As(III). The ARM was eliminated because of its low As(III)
capacity.
44
Figure 6.1 (a) pH fluctuation and (b) arsenic removal in the absence or presence of a pH
buffer: initial pH of 7.0 with GFH and As(V) = 100 g/L
45
Figure 6.2 As(V) removal (100 g/L) at pH 7 as a function of time by (a) AA-400G, (b) AAFS50, (c) ARM 100, (d) Bayoxide E33, (e) GFH, (f) MetSorb, (g) MIEX, (h) Z33 Rev. B, (i)
Geothite, and (j) pyrolusite
46
Figure 6.2 (Continued)
47
48
49
50
Figure 6.3 Isotherms for candidate adsorbents: As(V) at a pH of 7.0 and 24 hours
Figure 6.4 Percent removal of As(V) by candidate adsorbents: As(V) = 100 g/L; pH = 7.0,
24 hours. (Data ordered from left to right within each media dose group according to
adsorbents listed in legend.)
51
Figure 6.5 Percent removal of As(III) by candidate adsorbents: media dose = 100 mg/L;
As(III) = 100 g/L; pH = 7.0, 24 hours. (Data ordered from left to right according to
adsorbents listed in legend.)
Thus, based on the results of the preliminary experiments, five of the candidate adsorbents
AA-FS50, Bayoxide E33, GFH, Metsorb, and Z33 were selected for subsequent intensive testing.
Among the criteria for selection were the As(V) and As(III) capacities. The Metsorb materials
tested in the preliminary experiments were both a powdered version (Metsorb) and a granular
version (Metsorb G); a decision was made to use Metsorb G in the intensive testing. SMI-Version
III (sulfur modified iron) was also selected for further intensive testing but experimentally difficulties in working with this material (discussed later) limited its extent of intensive testing. Thus,
the SMI results are reported within a separate section as a special study. Given the complexities of
silica chemistry in understanding silica as in interferant, an additional special study was
performed to address this issue.
Intensive Testing of Selected Adsorbents
Based on the more favorable results of the preliminary screening experiments, six adsorbents were selected and carried forward to be subjected to intensive batch-mode isotherm testing:
Bayoxide E-33
GFH
MetSorb G
AA-FS50
Z33 (Revision b)
SMI (Version III)
52
Table 6.1
Physical/chemical properties of adsorbents
Property
Adsorbent
Grain size
(mm or mesh)*
Bulk density
(g/mL)
pHZPC
Surface area
(m2/g)
(BET)
AA-FS50
2848 mesh
0.75 (dry)
7.28
246
Aluminum oxide
Hydrate (Boehmite)
E33
0.52.0 mm
( 1035 mesh)
1.19 (wet)
8.28
119
Iron oxide hydrate

(Geothite)
GFH
0.322.0 mm
1.19 (wet)
7.57
242
Iron oxide
(Akaganeite)
Metsorb G
1650 mesh
0.78 (dry)
0.88 (wet)
4.68
166
Titanium oxide
(Anatase)
Z33
100140 mesh
0.88
4.79
36.9
Calcium aluminum
silicate hydrate
(Heulandite)
SMI
n/a
2.15
n/a
4.46
n/a
Mineral identity
(by XRD)
* 10 mesh = 0.1 inches = 0.254 cm = 2.54 mm

Magnetite also identified in contrast to previous studies
Moreover, a decision was made to employ a standard contact time of 24 hours in developing isotherms, a contact time that was adequate to establish equilibrium for some of the adsorbents or at least pseudo equilibrium for others. Given the preliminary kinetic experiment results,
the assumption of pseudo equilibrium was strongest for Bayoxide E33 and Metsorb, and possibly
Z33, but probably more questionable for AA-FS50 and GFH.
These adsorbents were first characterized according to important physical/chemical properties that could help explain different trends of arsenic adsorption. The adsorbents were then
tested under a range of water quality conditions to develop a robust series of equilibrium
isotherms. Of the above, all but SMI were studied with a full matrix of water quality conditions
while a more limited set of experiments was performed with SMI. Only one of the selected adsorbents, Metsorb G, is not NSF approved.
Physical/Chemical Properties of Adsorbents
Important physical/chemical properties of the six adsorbents are summarized in Table 6.1.
Based on surface area measurements, all of the six adsorbents can be inferred to be porous with
the exception of SMI. This property is important because the kinetics of adsorption onto porous
adsorbents is controlled by intraparticle diffusion. The iron (and aluminum) oxides were found to
behave as basic minerals with their pHZPC > 7.0, while the Metsorb G and Z33 behave as acidic
minerals with their pHZPC < 7.0. The pHZPC is important because, given the anionic character of
arsenate, surface charge can play a role in terms of electrostatic interactions between the
53
Figure 6.6 Zeta potential versus pH for adsorbents
adsorbate and the adsorbent. The surface chemistry of the adsorbents is further elucidated through
a plot of zeta potential versus pH shown in Figure 6.6, in some cases, the limited range of experimental conditions tested did not capture the classical shape of an amphoteric particle (i.e., positive
and flatter at lower pH, steeper in approaching zero charge, and negative and flatter at higher pH).
The mineralogy is of particular importance for iron oxides, given that more amorphous forms
exhibit higher adsorption capacities than more amorphous crystalline forms. In addition to akaganeite, as documented previously, the presence of some magnetite was observed in the GFH media.
The property of media size plays a role in terms of head loss through fixed-bed adsorbers and, for
porous adsorbents, in diffusion-controlled adsorption kinetics.
Equilibrium Isotherm Tests
Synthetic Waters. The six adsorbents were tested in synthetic waters at three pH levels
(6.0, 7.0, 8.0) containing As(V) in the presence or absence of interferants; As(III) was tested at
only one pH (7.0) in the absence of interferants. A pH range of 6.0 to 8.0 covers a range encompassing most natural waters (see co-occurrence survey) as well as possible depressed pH conditions (e.g., 6.0) for improving adsorbent performance. Based on the interferant percentile levels
indicated in Table 6.2 (as delineated by the co-occurrence survey), tests were performed with
As(V) in the absence and presence of phosphate (at one of two occurrence levels), silica (at one of
two occurrence levels), vanadium (at higher occurrence level only), and fluoride (at higher occurrence level only). Like arsenic, the major source of these interferants is natural geochemical
sources. Silica was added as silicic acid while vanadium was added as vanadate, given its weak
acid similarities to arsenate. The Bayoxide E-33, GFH, and Metsorb G were subjected to the
complete testing matrix except for the presence of fluoride, known to be a significant interferant
with activated alumina. The AA-FS50 was not tested in the presence of silica or vanadium, while
54
Table 6.2
Concentrations of interferents based on the co-occurrence survey
Component
50th percentile concentration
75th percentile concentration
Units
Phosphate
125
250
g/L as PO43
Silicic acid
13.5
22
mg/L as SiO2
Vanadate
18
30
g/L as V
Fluoride
300
700
g/L
Table 6.3
Ionic composition of NSF challenge water (pH = 7.5)
Component
Concentration
Component
2
Concentration
Na+
73.7 mg/L
SO4
Ca2+
40.1 mg/L
NO3-N
2.00 mg/L
Mg2+
12.6 mg/L
1.00 mg/L
HCO3
183 mg/L
PO43-P
0.040 mg/L
Cl
71.0 mg/L
SiO2
20.0 mg/L
50.0 mg/L
the Z33 was not subjected to testing with silica, vanadium, or fluoride. The Bayoxide E33, GFH,
Metsorb G, AA-FS50, and Z33 were tested within a specific synthetic water matrix represented by
the NSF challenge water. More limited testing was done with the SMI because of experimental
difficulties, the major one being that it proved difficult to weigh out precise masses of the adsorbent based on the large grain size and high density of the SMI media. Thus, in the synthetic water
experiments discussed in this section, only SMI results derived from a triplicate series with As(V)
at one pH (7.0) in the absence of interferants are reported herein; other single- replicate series
results for SMI are reported in a separate section because of QA/QC concerns. The various adsorbents were added over a range of doses ranging from as low as 10 mg/L to as high as 1,000 mg/L
in the presence of a constant initial arsenic concentration of 100 g/L.
Besides the matrix of synthetic water experiments based on the co-occurrence survey,
additional tests were performed with a standard NSF challenge water described in Table 6.3 at a
single pH (7.5). This challenge water has informally become an industry standard in testing
various adsorbents for arsenic; NSF (National Sanitation Foundation) is a testing organization that
is known for certifying equipment and materials. In addition to synthetic water tests, natural water
tests were performed with waters provided by participating utilities, including Tucson AZ,
LADWP CA, El Paso TX, and Alamosa CO; their relevant water qualities are summarized in
Table 6.4. In some cases, the utility-supplied waters contained some As(III).
The resultant isotherms have been modeled according to the Freundlich equation:
55
Table 6.4
Water quality summary of utility-supplied waters
Water
Parameter
Tucson, AZ
LADWP, CA
El Paso, TX
Alamosa, CO
V (g/L)
66
125
SiO2 (mg/L)
28
28
28
93
PO43 (g/L)
18
78
35
26
SO42 (mg/L)
64
21
96
8.1
Alkalinity (mg/L as CaCO3)
100
122
64
92
Conductivity (S/cm)
484
352
503
214
pH
7.9
7.7
8.5
8.3
DOC (mg/L)
0.27
1.65
0.48
0.28
(g/L)*
12.6
25.6
22.9
40.9
As(V) (g/L)*
12.6
25.6
12.4
29.6
As(III) (g/L)*
10.5
11.4
Astotal
* Ambient levels
1
---
n
X
Q = ----- = K F [ As ]
M
where Q is the adsorption capacity of an adsorbent (g As/mg adsorbent); X is the mass of arsenic
adsorbed (g As), determined by difference between the initial concentration and the concentration
at 24 hr and the volume tested; M is the adsorbent mass (mg); KF and 1/n are empirical fitting
parameters or model constants; and [As] is the equilibrium concentration of arsenic remaining in
the solution after 24 hr (g/L). The model constants, KF and 1/n, are based on Q and [As] expressed
in terms of g/mg and g/L, respectively. The magnitude of each of the Freundlich constants
reveals different things about capacity. For a constant value of 1/n, KF serves as a direct capacity
factor, with increasing values indicative of high capacity. The 1/n constant is an indicator of adsorption favorability, with values of <1, 1, and >1 indicating favorable, linear, and non-favorable
adsorption, respectively. The resultant Freundlich isotherms have been used to estimate Q10 and
Q50 values, corresponding to predicted capacities in equilibrium with 10 and 50 g/L As, respectively. The former parameter, Q10, has relevance for describing batch-mode performance in the
concentration range of the new MCL, while the latter parameter, Q50, has relevance in elucidating
column-mode performance in a higher concentration range where the equilibrium [As] corresponds
to the initial [As]0 in equilibrium with Q0 in the zone of the column containing exhausted media
(adsorbent). The estimated values are not unique adsorbate-adsorbent specific numbers but rather
are operationally defined based on the specific test conditions (e.g., initial concentration of arsenic
species and interferant).
56
The Langmuir equation has also been used to model the data:
K L [ As ]
X
Q = ----- = Q max ------------------------------1 + K L [ As ]
M
where Qmax = maximum adsorption capacity based on monolayer coverage which, in our content,
correspond to a maximum capacity based on adsorption site saturation; and KL is a fitting parameter. Within this context, Qmax is greater than Q50 based on Freundlich model predictions, and is
indicative of the maximum adsorbate-specific adsorption sites under a given set of water quality
conditions. Within this context, Qmax has the same units as Q (g/mg) and values of KL are based
on Q and [As] expressed in terms of g/mg and g/L, respectively. Generally, the Langmuir
model is considered to be more accurate at higher and lower ranges of data while the Freundlich
model is considered to be more accurate over an intermediate range.
The Freundlich and Langmuir equations can be used, with appropriate values of constants,
to predict the final equilibrium concentration of arsenic (g/L) resulting from a given adsorbent
dose (mg/L), or the dose of adsorbent required to achieve a target final equilibrium concentration.
However, it must be recognized that any test done with an interferant represents a competitive
adsorption test with two adsorbates, and thus the resultant model constants are unique to the
conditions of the test in terms of initial adsorbate concentrations (both arsenic and interferant) as
well as pH. While there are competitive adsorption models, they require measurement of the
uptake of all adsorbates; in our experiments, the final equilibrium concentration of interferants
was not measured.
Besides the triplicate series for the SMI (see previous discussion), another experiment
using Metsorb G with As(V) at one pH (7.0) in the absence of interferants was also triplicated for
QA/QC purposes to establish experimental error. No other batch experiment replication was
performed, corresponding to a degree of replication of 4%. These replicated isotherms are shown
in Figures 6.7 and 6.8 for Metsorb G and SMI, respectively. For Freundlich constants, the average
values of KF and 1/n are 0.480 and 0.342 for Metsorb G, and 1.74 and 0.799 for SMI; for Langmuir constants, the average values of KL and Qmax are 0.131 and 2.14 for Metsorb G, and 0.015
and 92.8 for SMI. The two replicate series were used to calculate coefficients of variation
(CV (%) = standard deviation mean 100) for Freundlich and Langmuir constants (including
Qmax) as well as Freundlich predictions of Q10 and Q50. These results are summarized in
Table 6.5, and are helpful in elucidating statistically significant differences. The most noteworthy
values are those corresponding to Q10, Q50, and Qmax for Metsorb G: most of these CV values
cluster around 20% and thus one can use this percentage value as an approximate criterion for
gleaning statistically significant differences for the capacity estimates (Q10, Q50, and Qmax)
summarized in subsequent graphs and tables. For example, the C.V. values indicated for Q10 and
Q50 predictions with Metsorb G are about 5 percent (see Table 6.5) and one can conclude that
capacity parameter differences greater than this value can form an approximate basis for
discerning statistically significant differences. However, it is important to recognize that these
capacity estimates are based on curve-fitting trends of experimental data. The SMI results show
considerably more variability, confirming the aforementioned experimental difficulties in working
with this material (discussed futher in later section on special study with SMI).
The intensive-testing results based on various synthetic waters and the NSF challenge
water are summarized in Table 6.6, highlighting results in terms of the Freundlich model, and
57
Figure 6.7 Isotherm replicate (triplicate) series for Metsorb G with As(V) at a pH of 7.0 and
24 hours
Figure 6.8 Isotherm replicate (triplicate) series for SMI-III with As(V) at a pH of 7.0 and
24 hours
58
Table 6.5
CV values (%) for isotherm constants and Freundlich predictions
Freundlich constants
Langmuir constants
Adsorbent
KF
(g/mg)/(g/L)1/n
1/n
Qmax (g/mg)
KL
Metsorb G
23
22
21
55
SMI
62
18
47
61
Freundlich predictions
Q10 (g/mg)
Q50 (g/mg)
Metsorb G
5.2
5.5
SMI
22
6.7
Table 6.7, featuring Langmuir modeling results; of particular note here are the capacity parameters Q10, Q50, and Qmax. These results are also shown in Figures 6.9, 6.10, and 6.11, showing
single-solute isotherms in the absence of interferants at pH levels of 6.0, 7.0, and 8.0, respectively.
Figure 6.12 summarizes results in the presence of interferants in terms of an interference factor,
representing the ratio of As(V) capacity to that at pH 6.0 (based on improved capacity under lower
pH conditions) in the absence of interferents (the most favorable condition). Figure 6.12 encompasses the global trends among all of the select adsorbents under all ranges of water quality conditions studied. More adsorbent-specific and water quality-specific graphs follow to help glean
more focused effects.
Figure 6.13 shows As(V) capacities of the adsorbents in terms of Q10 for varying pH
conditions in the absence of interferants, based on synthetic waters. Figures 6.14 through 6.18
portray Q10 values for As(V) in the presence of various interferants (phosphate, silica, and vanadium). The results in Figure 6.13 (absence of interferants) can be compared against the results in
Figures 6.14 through 6.18 (presence of interferants) to discern the effects of individual interferants. Based on five adsorbents (AA-FS50, Bayoxide E33, GFH, and Metsorb G, and Z33 in
Figures 6.14 and 6.15), phosphate exerted an inhibitory effect on all of the adsorbents; The effects
on AA-FS50 and the Metsorb G were generally smaller than those on the iron oxides (Bayoxide
E33 and GFH) and the iron-modified zeolyte (Z33). Based on three adsorbents (Bayoxide E33,
GFH, and Metsorb G in Figures 6.16 and 6.17), silica exerted an influence on all of the adsorbents, with a much stronger inhibition effect at pH levels of 7.0 and 8.0 compared to 6.0, consistent with a greater degree of deprotonation of silicic acid at higher pH. Based on three adsorbents
(Bayoxide E33, GFH, and Metsorb G in Figure 6.18), vanadium exerted its strongest effect on
GFH and its least effect on Metsorb G.
As(III) results based on synthetic waters are shown in Figure 6.19, portraying isotherms for
three adsorbents (Bayoxide E33, GFH, and Metsorb G), and in Figure 6.20, portraying Q10 results in
the absence of interferants at a pH of 7.0. While all three of the adsorbents demonstrated a significant potential for As(III) removal, the order of performance is Bayoxide E33 > Metsorb G > GFH.
Based on the various figures showing individual interferant effects as well as the summaries in Tables 6.6 and 6.7 and Figure 6.12, a number of trends can be discerned from the work with
59
Table 6.6
Values of Freundlich isotherm fitting parameters (KF and 1/n) for adsorption of arsenic onto tested media
and predicted adsorption capacity when As(V) concentration in solution is 10 mg/L or 50 mg/L
Media
AA-FS50
60
Bayoxide E33
GFH
MetSorb G
SMI-III
Z33 Rev. B
As(V)
(g/L)
As(III)
(g/L)
PO4
(g/L)
SiO2
(mg/L)
V
(g/L)
F
(g/L)
NSF
challenge
water
KF
1/n
Q10
Q50
KF
1/n
Q10
Q50
KF
1/n
Q10
Q50
100
0.300
0.548
1.06
2.56
0.472
0.426
1.26
2.50
0.273
0.446
0.763
1.56
100
125
00392
0.432
1.06
2.13
0.451
0.352
1.01
1.79
0.334
0.304
0.673
1.10
100
250
0.424
0.346
0.940
1.64
0.424
0.315
0.876
1.45
0.304
0.282
0.582
0.916
100
700
0.192
0.592
0.753
1.95
100
0.707
0.285
1.36
2.15
0.620
0.261
1.13
1.72
0.606
0.219
1.00
1.43
100
125
0.585
0.236
1.01
1.47
0.454
0.218
0.750
1.07
0.277
0.333
0.595
1.02
100
250
0.441
0.253
0.790
1.19
0.210
0.411
0.542
1.05
0.162
0.443
0.449
0.916
100
13.5
0.615
0.250
1.09
1.64
0.510
0.205
0.819
1.14
0.136
0.493
0.424
0.938
100
22
0.531
0.298
1.05
1.70
0.023
1.006
0.235
1.19
0.053
0.737
0.291
0.952
100
30
0.190
0.252
0.340
0.509
100
yes
0.131
0.591
0.513
1.33
100
0.330
0.421
0.872
1.72
100
yes
0.001
1.36
0.027
0.237
100
0.671
0.340
1.47
2.54
0.514
0.283
0.986
1.55
0.385
0.172
0.573
0.756
pH 6
pH 7 or 7.5 (NSF challenge water)
pH 8
100
125
0.663
0.249
1.18
1.75
0.513
0.227
0.866
1.25
0.487
0.056
0.554
0.606
100
250
0.602
0.188
0.928
1.26
0.418
0.144
0.582
0.734
0.177
0.312
0.364
0.601
100
13.5
0.570
0.186
0.875
1.18
0.276
0.343
0.607
1.05
0.409
0.020
0.427
0.441
100
22
0.522
0.244
0.916
1.36
0.263
0.325
0.556
0.937
0.112
0.309
0.227
0.374
100
30
0.023
0.709
0.116
0.364
100
yes
0.164
0.365
0.381
0.686
100
0.152
0.502
0.482
1.083
100
yes
0.029
0.714
0.152
0.480
100
0.661
0.301
1.32
2.15
0.589
0.276
1.11
1.73
0.584
0.220
0.968
1.38
1.09
100
125
0.653
0.245
1.15
1.71
0.689
0.171
1.02
1.35
0.313
0.318
0.651
100
250
0.615
0.305
1.24
2.03
0.379
0.366
0.879
1.59
0.252
0.390
0.620
1.16
100
13.5
0.554
0.339
1.21
2.08
0.091
0.669
0.426
1.25
0.218
0.318
0.453
0.756
100
22
0.365
0.431
0.984
1.97
0.115
0.579
0.436
1.11
0.091
0.501
0.290
0.649
100
30
0.277
0.210
0.449
0.630
100
yes
0.234
0.478
0.703
1.52
100
0.233
0.444
0.648
1.33
100
yes
0.052
0.565
0.191
0.474
100
1.74
0.799
11.0
39.7
100
0.352
0.241
0.614
0.906
0.251
0.235
0.431
0.629
0.103
0.389
0.253
0.473
100
125
0.239
0.245
0.420
0.622
0.226
0.182
0.345
0.462
0.221
0.098
0.277
0.324
100
250
0.314
0.123
0.417
0.509
0.209
0.155
0.298
0.383
0.068
0.345
0.150
0.262
Table 6.7
Values of Langmuir isotherm fitting parameters (KL and Qmax) for adsorption of arsenic onto tested media
Media
AA-FS50
Bayoxide E33
61
GFH
MetSorb G
SMI-III
Z33 Rev. B
pH 7 or 7.5
(NSF challenge water)
As(V)
(g/L)
As(III)
(g/L)
PO4
(g/L)
SiO2
(mg/L)
V
(g/L)
F
(g/L)
NSF
challenge
water
Qmax
KL
Qmax
KL
Qmax
KL
100
3.996
0.038
2.210
0.203
0.664
1.826
100
125
2.084
0.145
1.777
0.198
1.003
0.436
100
250
1.597
0.223
1.469
0.229
0.868
0.424
100
700
2.355
0.051
100
2.120
0.339
1.878
0.204
1.570
0.225
100
125
1.586
0.182
1.274
0.109
1.435
0.051
100
250
1.374
0.112
1.637
0.036
1.744
0.023
100
13.5
1.596
0.316
1.255
0.192
1.517
0.032
100
22
1.730
0.186
19.803
0.001
4.080
0.006
100
30
0.697
0.055
100
yes
2.252
0.027
100
2.106
0.076
100
yes
0.843
-0.004
100
2.048
0.438
1.515
0.484
0.812
0.228
100
125
1.582
0.578
1.096
0.943
0.639
0.437
100
250
1.257
0.539
0.740
0.750
0.717
0.089
100
13.5
1.219
0.512
1.078
0.194
0.453
0.806
100
22
1.187
0.769
1.040
0.147
0.558
0.042
100
30
1.304
0.008
100
yes
0.951
0.056
100
5.521
0.015
100
yes
1.184
0.013
100
2.005
0.361
1.852
0.200
1.497
0.236
100
125
1.788
0.239
1.386
0.291
1.394
0.073
100
250
2.121
0.182
1.988
0.073
1.498
0.062
100
13.5
2.304
0.128
3.064
0.014
1.139
0.041
100
22
2.480
0.067
2.068
0.023
1.259
0.022
100
30
0.789
0.082
100
yes
2.321
0.038
100
3.600
0.026
100
yes
1.193
0.013
100
92.8
0.015
100
1.072
0.111
0.822
0.071
0.757
0.034
100
125
0.792
0.075
0.550
0.111
0.356
0.204
100
250
0.576
0.155
0.463
0.099
0.434
0.031
pH 6
pH 8
Figure 6.9 Single-solute isotherms for As(V) at pH 6.0: in the absence of interferents
62
Figure 6.12 Summary of interference factors: ratio of As(V) capacity to that at pH 6.0 in the
absence of interferents
63
Figure 6.13 Adsorption capacity, Q10, for As(V) as a function of pH: absence of interferants
Figure 6.14 Adsorption capacity, Q10, for As(V) as a function of pH: presence of phosphate
at 50% occurrence level
64
Figure 6.15 Adsorption capacity, Q10, for As(V) as a function of pH: presence of phosphate
Figure 6.16 Adsorption capacity, Q10, for As(V) as a function of pH: presence of silica at
50% occurrence level
65
Figure 6.17 Adsorption capacity, Q10, for As(V) as a function of pH: presence of silica at
75% occurrence level
Figure 6.18 Adsorption capacity, Q10, for As(V) as a function of pH: presence of vanadium
66
Figure 6.19 Isotherms for As(III) at a pH of 7.0: absence of interferants
Figure 6.20 Adsorption capacity, Q10, for As(III) as a pH of 7.0: absence of interferants
67
synthetic waters. First, in addressing the performance of each adsorbent independently, the
following observations can be made. The AA-FS50 showed a moderate deterioration in performance as pH increased, and phosphate exerted only a small effect. An experiment with AA-FS50
in the presence of fluoride (Tables 6.6 and 6.7) showed a significant decrease in Q10 and Q50 but
curiously little effect on Qmax. This result may perhaps be attributable to a mathematical anomaly
in least-squares estimation of the two Langmuir constants. The Bayoxide E33 media showed only
a slight pH effect but exhibited significant impacts by phosphate and vanadium with some silica
effects. GFH showed a decrease in performance as pH increased, with phosphate, silica, and vanadium exhibiting adverse effects. MetSorb G showed a decrease in performance as pH increases,
with phosphate, silica, and vanadium exhibiting effects, although the interferent effects were less
at lower pH. Z33 performance decreased as pH increased and phosphate had a significant effect.
Differences in physical/chemical properties of the adsorbents can help explain some of the differences. The order of pHZPC (high to low) was Bayoxide E33 > GFH > AA-FS50 > Z33 ~ Metsorb
G. The higher pHZPC of the Bayoxide E33 versus GFH helps explain the better performance of the
former iron oxide at higher pH conditions. The order of surface area (high to low) was AA-FS50 ~
GFH > Metsorb G > Bayoxide E33 > Z33. The very low surface area of the Z33 is manifested in a
lower number of adsorption sites per unit mass. The material composition differ significantly;
aluminum and iron content for AA-FS50, titanium dioxide for Metsorb G, clay content for Z33,
and iron oxides for GFH and Bayoxide E33. The high capacity exhibited by the Metsorb E33 may
involve a more complicated mechanism than simply surface complexation or ligand exchange.
Second, in addressing adsorbent comparisons, the following observations can be made.
The two iron oxide media (Bayoxide E33 and GFH) and Metsorb G generally showed comparable
weight-based capacities although GFH performance dropped sharply at the highest pH; interferant effects were lowest for Metsorb G. The iron-modified activated alumina (AA-FS50)
showed a higher capacity than the two iron oxide media and Metsorb G at lower pH, but a lower
capacity at higher pH, indicating more of a pH dependency. The iron-modified zeolite (Z33)
generally exhibited the lowest capacities.
Based on the one triplicated experiment with a specific synthetic water (As(V) at pH 7.0 in
the absence of interferants), the sulfur-modified iron (SMI) clearly exhibited the highest capacity
for As(V) compared to the other five adsorbents in terms of Q10, Q50, and Qmax. As indicated
earlier, the SMI was particularly problematical to evaluate because it was not possible to administer small amounts (doses) in batch tests because of its high density and large size (difficult to
reduce with a simple mortar and pestle). At a pH of 7.0 in the absence of interferants, the Q10,
Q50, and Qmax values for SMI were found to be 11.0, 39.6, and 92.8 g/mg, respectively. While a
significant experimental error occurred (Table 6.5), these parameter values nevertheless indicate a
higher capacity for SMI compared to the other five adsorbents in the absence of interferants and
at a pH of 7.0.
The capacities discussed above are based on a dry weight basis. Given that the GFH was
tested in its wet state containing 50% water by weight, its reported capacities would double if
expressed on a dry weight basis. Moreover, the capacities reported herein are based on mass.
These capacities could also be expressed in an alternative format based on surface area determinations (i.e., g/cm2). For example, the wet weight based capacity for GFH at pH 7.0 in the absence
of interferants was 1.55 g/mg, based on Q50. On a dry weight basis, this corresponds to
3.1 g/mg and, on a surface area basis, this corresponds to 0.063 g/cm2 (wet) or 0.126 g/cm2
(dry). One can also express capacities based on unit cost; this is indirectly addressed in Chapter 7.
68
For the vast majority of results, the Freundlich parameter exhibited values of 1/n < 1, indicating favorable adsorption. However, given the mathematical (i.e., curve fitting) linkage between
1/n and KF, the presence of an interferant did not result in clear increases in 1/n that would indicate a reduction in favorability. Hence, the capacity factors, Q10, Q50, and Qmax, are considered to
be more insightful into interferant effects. Another point to be made is that, in the graphical representations of Freundlich relationships, the graphs are shown forced through the zero-zero intercept. While such an approach is consistent with theory (i.e., no (zero) adsorption in the presence
of no (zero) driving force), this represents an extrapolation of experimental data.
The results based on the NSF challenge water are shown in Tables 6.6 and 6.7 and are
highlighted in Figures 6.21 through 6.24. The isotherm constants were determined by regression
analysis of the linear forms of the Freundlich and Langmuir equation. In the vast majority of
cases, the coefficient of determination (r2) was greater than 0.8, corresponding to a correlation
coefficient (r) of about 0.9.
The As(V) results are shown in Figure 6.21, portraying isotherms for three adsorbents
(Bayoxide E33, GFH, and Metsorb G), and Figure 6.22, portraying Q10 values for these same
three adsorbents. The order of capacities is Metsorb G > Bayoxide E33 > GFH. The higher pH of
the NSF challenge water (pH 7.5) was likely the most influential factor on the GFH. The As(III)
results are shown in Figure 6.23, portraying isotherms for three adsorbents (Bayoxide E33, GFH,
and Metsorb G), and Figure 6.24, portraying Q10 values for these same three adsorbents. The
order of capacities is Metsorb G >GFH > Bayoxide E33. The Bayoxide E33 was clearly less
effective than the other two adsorbents whose performance was generally comparable. Compared
to the single interferant tests previously discussed, the As(V) capacities with the NSF challenge
water, based on Q10, Q50, and Qmax, were in some cases lower and in some cases higher; this can
be attributed to the higher levels used for certain individual interferants (e.g., phosphate). On the
other hand, the As(III) capacities with the NSF challenge water were uniformly lower that that
observed for As(III) at pH 7.0 in the absence of interferants.
Utility-Supplied Waters. Three adsorbents (Bayoxide E33, GFH, and Metsorb G) were
tested in four different water quality matrices corresponding to the four natural waters provided
by utilities. All of the waters contained ambient levels of arsenic and were spiked up to a total of
100 g/L. The Tucson AZ and LADWP CA waters contained only As(V) and thus were spiked up
to a total of 100 g/L of As(V). The El Paso TX and Alamosa CO waters contained both As(V)
and As(III) and thus were spiked with both As(V) and As(III), based on their ratios of
As(V):As(III) (~1:1 for El Paso TX and ~ 2.6:1 for Alamosa CO), up to a total of 100 g/L of total
arsenic. The measurements of As(V) and As(III) shown in Table 6.4 were made immediately
before experiments and it was assumed that these levels did not change over the 24-hour time
frame of the experiments.
The results are shown as isotherms in Figures 6.25, 6.26, 6.27, and 6.28 for the Tucson
AZ, LADWP CA, El Paso TX, and Alamosa CO waters, respectively. For the Tucson AZ and the
LADWP CA waters, the capacities followed the order: Metsorb G > Bayoxide E33 > GFH. For
the El Paso TX water, Metsorb G and Bayoxide E33 provided significantly higher capacities than
the GFH. Very low capacities were observed for all of the adsorbents with the Alamosa CO water.
This latter water is characterized by very high levels of silica and vanadium. The observed capacities for the El Paso TX and Alamosa CO waters reflects their As(III) content. Some of the
isotherms for utility-supplied waters show unfavorable adsorption, with corresponding 1/n values
of greater than 1.0. In some cases, the isotherms shown encompass a significant extrapolation of
data toward the zero-zero intercept.
69
Figure 6.21 Isotherms for As(V) in NSF challenge water
Figure 6.22 Adsorption capacity, Q10, for As(V) in NSF challenge water
70
Figure 6.23 Isotherm for As(III) in NSF challenge water
Figure 6.24 Adsorption capacity, Q10, for As(III) in NSF challenge water
71
Figure 6.25 Isotherms for utility-supplied water: Tucson, AZ groundwater
Figure 6.26 Isotherms for utility-supplied water: LADWP, CA surface water
72
Figure 6.27 Isotherms for utility-supplied water: El Paso, TX groundwater
Figure 6.28 Isotherms for utility-supplied water: Alamosa, CO groundwater
73
Special Study on Sulfur Modified Iron (SMI)

While sulfur modified iron (SMI) performed well in the preliminary screening tests in
terms of a high As(V) adsorption capacity, it was not formally included in the detailed intensive
testing program because of concerns about experimental error and reproducibility (see previous
section). Given its large grain size and its high density, accurate testing would have required a
major revision to the general batch-testing protocol used for all of the other adsorbents such as
using larger sample volumes and/or higher constituent concentrations. Nevertheless, a decision
was made to perform additional experiments using the standard protocol to provide some semiquantitative insight into the effects of water quality on its adsorption capacity. These results are
summarized in Table 6.8 in terms of Freundlich and Langmuir isotherm constants and isothermbased predictions of capacity (Q10, Q50, and Qmax). The isotherm constants were determined by
regression analysis of the linear forms of the Freundlich and Langmuir equation. In a significant
number of cases, the coefficient of determination (r2) was less than 0.8, corresponding to a correlation coefficient (r) of about 0.9.
Table 6.8 reveals some trends but also some inconsistencies in the data. A clear result is
that SMI exhibits a very high As(V) capacity at lower pH levels (6.0 and 7.0) in the absence of
interferants. Moreover, the presence of interferants lowers its As(V) capacity, and the As(III)
capacity is much lower than the As(V) capacity. However, other than these general trends, elucidation of other trends are convoluted by several inconsistencies. Data inconsistencies include: (i)
the results of the QA/QC triplicate series do not compare well with the results of the corresponding single replicate performed in the special study; (ii) some values of Q50 are greater than
corresponding values of Qmax which, in theory, is not possible; (iii) values of Q10 are greater than
corresponding values of Q50 in a few cases which is not possible; (iv) Q values at a lower interferant are less than corresponding Q values at a higher interferant level in a few cases; and (v)
capacities observed in the NSF challenge water (phosphate = 40 g/L, silica = 20 mg/L, pH = 7.5)
are not completely consistent with individual interferant levels.
While SMI clearly exhibits a very high As(V) under lower pH levels in the absence of
interferants, there have been concerns raised about operational problems in using SMI including:
(i) a release of soluble iron, Fe(II); (ii) a release of reduced sulfur in the form of hydrogen sulfide,
H2S; and (iii) column clogging as a consequence of redox reactions (e.g., release of soluble iron
(Fe(II) and subsequent oxidation to insoluble iron (Fe(III)). The manufacturer has tried to address
these problems by product improvements through various versions of SMI (SMI Version III was
tested in this study) and through changes in operation of the media. In addition to operating the
media in an upflow configuration, the manufacturer now recommends the addition of post treatment filtration to prevent iron carryover.
While a precise mineral identity is not available, it is believed that the iron present in SMI
is zero valent iron, Fe(0), that is oxidized to iron(III)(hydr)oxides with a high adsorption capacity
through an initial corrosion or rust reaction followed by subsequent oxidation. However, the
corrosion or rust reaction is influenced by redox (dissolved oxygen) and pH conditions, further
contributing to reproducibility problems. This overall reaction pathway is quite complex and the
corrosion rate will vary in different water qualities. The pathway for the corrosion or rust reaction
74
Table 6.8
Summary of SMI results
As(V)
(g/L)
As(III)
(g/L)
pH
Interferant
Interferant
level
7.0
None
Freundlich
constants*
KF
1/n
Isotherm
predictions
(g/mg)
Langmuir
constants*
KL
Qmax
Q10
Q50
Qmax
92.8
11.0
39.7
92.8
Triplicate Series
100
Single Replicates
75
100
6.0
None
18.1
0.352
0.224
83.0
40.6
71.6
83.0
100
7.0
None
7.04
0.474
0.241
28.5
21.0
44.9
28.5
100
8.0
None
0.663
0.223
0.033
2.57
1.11
1.59
2.57
100
6.0
Phosphate
125 g/L
9.89
0.350
0.991
19.4
22.1
38.9
19.4
100
6.0
Phosphate
250 g/L
12.7
0.168
1.40
5.73
8.62
6.58
5.73
100
7.0
Phosphate
125 g/L
6.82
0.198
0.194
15.7
10.8
14-8
15.7
100
7.0
Phosphate
250 g/L
251
0.726
0.021
3.39
47.2
14.7
3.39
100
8.0
Phosphate
125 g/L
0.105
0.483
0.008
2.35
0.32
0.70
2.35
100
8.0
Phosphate
250 g/L
0.024
0.723
0.003
3.25
0.13
0.41
3.25
100
6.0
Silica
13.5 mg/L
13.7
0.061
0.152
19.6
15.8
17.4
19.6
100
6.0
Silica
22 mg/L
1.07
0.217
0.079
3.82
1.76
2.50
3.82
100
7.0
Silica
13.5 mg/L
0.863
0.169
0.034
2.47
1.27
1.67
2.47
100
7.0
Silica
22 mg/L
0.418
0.335
0.022
3.28
0.91
1.55
3.28
100
8.0
Silica
13.5 mg/L
0.012
0.726
0.002
1.97
0.06
0.21
1.97
100
8.0
Silica
22 mg/L
0.120
0.243
0.019
0.57
0.21
0.31
0.57
100
7.0
Vanadium
30 g/L
0.103
0.538
0.006
3.49
0.35
0.84
3.49
100
7.5
NSF
challenge water
2.73
0.543
0.677
7.05
9.54
22.9
7.05
100
None
0.235
0.662
0.060
1.14
1.08
3.13
1.14
100
NSF
challenge water
0.504
0.376
0.045
3.16
1.20
2.20
3.16
*Based on Q and C expressed as g/mg and g/L, respectively.
followed by subsequent oxidation is shown below, with the resultant am-Fe(OH)3(s) having a high
capacity for As(V) adsorption:
2 Fe(0) + O2 + 2 H2O 2 Fe2+ + 4 OH
4 Fe2+ + O2 + 2 H+ 4 Fe3+ + 2 OH
Fe3+ + 3 OH am-Fe(OH)3(s)
Another hypothetical reaction that might occur would be the reduction of As(V) to As(III)
by zero valent iron, Fe(0):
Fe(0) + As(V) Fe2+ + As(III)
However, the resultant As(III) would be adsorbed to a lesser degree than As(V) by the
am-Fe(OH)3(s) so, if this reaction occurs, it does appear to be dominant. The role of the sulfur
present in SMI is less clear. If it is present as a sulfide, oxidation should release sulfate; if it is
present as elemental S, reduction would yield sulfide.
Even with the indicated QA/QC concerns, a decision was made to include SMI as part of
the decision/cost framework presented in Chapter 7 with a warning given to the user about the
degree of accuracy of the SMI algorithms. Given the potential merits of SMI, one of the recommendations for future research is that a separate focused study should be performed on SMI (see
Chapter 8).
Special Study on Silica Effects
Based on results demonstrating that silica can be a significant interferant, a targeted set of
experiments was performed with one adsorbent, GFH. The chemistry of silica can be complex
with monomeric silica (silicic acid/silicate) dominating at lower concentrations and higher pH
levels, while polymeric silica dominates at higher concentrations and lower pH. Monomeric silica
can play a role as an interferant at higher pH levels above its pKa1 (9.5). Polymeric silica can foul
adsorbents and potential block access to the pores of porous adsorbents by adsorbate molecules.
First, a matrix of experiments was performed in which various solutions of silica were
prepared at varying concentrations and pH conditions, with resultant measurements of monomeric
and polymeric silica after equilibration (see Chapter 5). These results are shown in Table 6.9,
demonstrating the expected trends of polymeric silica formation, calculated by the difference
between total silica and monomeric silica.
Next, a series of isotherms were performed with As(V) at 100 g/L at each of two pH
conditions (6.5 and 7.5) in the presence of each of three silica concentration ranges (19.321.8,
32.533.4, and 687830 mg/L). The results are shown in Figure 6.29. These results indicate an
inhibition of As(V) adsorption at both pH conditions but only at the highest silica concentration
range (687 mg/L). However, interpolation between the intermediate silica concentration range
and the highest concentration range, between 33.4 and 687 mg/L suggests that significant silica
effects can be anticipated in natural waters such as the Alamosa CO water. While the results of
this special study were based on GFH, similar fouling effects can be anticipated for other porous
adsorbents (i.e., all of the other select adsorbents except for SMI).
76
Table 6.9
Monomeric versus polymeric silica concentrations
Silica dose (mg/L)
pH
Total Si (mg/L)
Monomeric Si (mg/L)
Polymeric Si (mg/L)
30
4.5
34.0
29.4
4.6
80
4.5
89.7
79.2
10.5
200
4.5
227
189
38.0
500
4.5
514
448
66.0
30
6.5
34.0
29.5
4.5
80
6.5
91.4
78.8
12.6
200
6.5
214
189
25.0
500
6.5
496
188
308
30
10
38.7
29.9
8.8
80
10
99.7
77.8
21.9
200
10
207
185
21.7
500
10
494
430
64.3
30
13
35.1
<0.2
35.0
80
13
94.2
75.1
19.1
200
13
202
192
9.6
500
13
482
436
45.5
Column Experiments
dynamic column tests employing the NSF challenge water spiked with As(V) at concentrations up
to 1,000 g/L to facilitate breakthrough. The empty bed contact time (EBCT) employed in all
tests was 5 minutes, considered to be representative of an industry standard. A summary of the
experimental conditions appears in Table 6.10 in terms of hydraulic loading rate (HLR), column
(media) depth (D), column (media) cross-sectional area (A), media mass, and bed volumes per
hour (BV/hour). As indicated in Chapter 5, different column dimensions were employed because
of the availability of only a limited number of laboratory-scale columns.
The results are shown in Figure 6.30 in terms of breakthrough curves (BTCs). These BTCs
were based on an initial As(V) of 1,000 g/L except for Metsorb G (250 g/L); the greater number
of BVs for Metsorb G is consistent with this lower initial concentration. The AA-FS50 and GFH
showed similar results with 50% breakthrough (i.e., C/C0 = 0.5) at about 4,000 to 5,000 bed
volumes (BVs). The experiments for these two adsorbents were terminated after about 6,000 BVs.
Upon termination, the average column-mode capacities were determined to be 3.46 and
3.51 g/mg for the AA-FS50 and GFH, respectively, based on graphical integration of the respective BTCs. The Metsorb G and Bayoxide E33 were run for longer periods of about 8,000 and
77
Figure 6.29 Isotherms for GFH with As(V) at varying pH levels and silica concentrations
Table 6.10
Experimental conditions employed in column tests
Adsorbent
Bayoxide E33
AA-FS50
GFH
Metsorb G
HLR (cm/min)
8.2
4.1
2.0
2.0
D (cm)
40
20
10
10
A (cm2)
1.3
5.1
5.1
1.3
Media mass (g)
20
110
59
9.3
BV/hour
12
12
12
12
As(V)0 (g/L)
250
1,000
1,000
1,000
EBCT (min)
12,000 BVs, respectively, before terminating the experiments. The Metsorb G experiment was
terminated before a clear breakthrough trend was observed. Upon termination of the experiments,
the corresponding normalized breakthrough concentrations (C/C0) were 0.07 and 0.3, respectively, with estimated column-mode capacities of 9.44 and 6.55 g/mg.
The column-mode capacities were compared with estimates of Q100, the adsorbent-phase
loading (capacity) predicted to be in equilibrium with an As(V) water-phase concentration of
100 g/L, based on the Freundlich equation. Values of Q100 for Metsorb G, Bayoxide E33, and
78
Figure 6.30 Breakthrough curves for column tests with NSF challenge water
GFH were estimated to be 2.11, 1.99, and 0.873 g/mg, respectively; a value for AA-FS50 could
not be determined since a corresponding isotherm was not developed. The higher column-based
loadings can potentially be attributed to several possible factors: (i) the 24-hour psuedo-equilibrium contact time employed in the batch tests was not adequate in establishing true equilibrium
for porous adsorbents; (ii) there may be another mechanism of As(V) removal other than adsorption such as, for example, surface precipitation.
The second explanation is noteworthy because of the departure of arsenic BTCs from ideal
BTC behavior (i.e., symmetrical S-shaped curve); most arsenic BTCs conform to ideal behavior at
lower fractional (C/C0) breakthrough concentrations of less than 0.5 but thereafter exhibit significant tailing, often without ever reaching a C/C0 value of 1.0. While iron oxides such as geothite
and akaganeite exhibit very low solubilities, arsenate (H2AsO4/HAsO42) may first act as a
ligand promoting release of Fe3+ as a complex, and second as a precipitant promoting formation
of FeAsO4(s) (log KSP = 21.7). Such a mechanism would lead to observed capacities being
greater than capacities predicted by isotherms (adsorption only).
Given that the column tests were based on solids-free synthetic waters, no backwashing
was necessary. In full-scale applications, periodic backwashing may be necessary, resulting in a
residual (backwash) wastestream.
TCLP/WET Tests
Spent media was generated in batch mode with high initial As(V) concentrations. The
specific conditions employed were: (i) initial As(V) = 2,000,000 g/L; (ii) adsorbent concentration = 400,000 mg/L; and (iii) contact time = 72 hours. The NSF challenge water quality was
79
Table 6.11
TCLP and WET results for spent arsenic sorptive media
TCLP As (g/L)
WET As (g/L)
Avg
Std dev
Avg
Std dev
Bayoxide E33
0.3
0.0
88
1.4
GFH
0.1
0.2
1,023
32
AA-FS 50
12.8
1.1
1,337
37
Metsorb
1.6
0.1
129
13
employed in these tests. While the final equilibrium concentration of As(V) was not determined,
the resultant solid phase loadings were approximated by use of the Freundlich isotherm equation
and constants for each of the four adsorbents with the NSF challenge water. The resultant solidphase loadings, Q, were estimated to be 6.55, 3.51, 9.44, 3.46 g/mg for Bayoxide E33, GFH,
Metsorb G, and AA-FS50, respectively.
All samples were found to be non-hazardous, as the arsenic concentration in the leachate
was less than 5 mg/L (Table 6.11). There was significantly more arsenic released by the WET
leaching procedure than by the TCLP.
80
CHAPTER 7
ARSENIC ADSORBENT DESIGN AND COSTING TOOL
INTRODUCTION
This section describes the Arsenic Adsorbent Design and Costing Tool and the algorithms
that were used in developing the tool. A copy of the tool is made available on the attached CDROM. The Arsenic Adsorbent Design and Costing Tool is an interactive tool which contains input
and output forms. The user can enter information in the input form, the tool will calculate design
and cost parameters and display the results in an output form. The type of input parameters that
the user is required to enter include system parameters (e.g., well capacity, average flow), water
quality (e.g., influent arsenic, phosphate, and silica concentrations), target water quality (e.g.,
treated-water arsenic), operational preferences (e.g., pH adjustment, pre-chlorination) and cost
parameters (e.g., interest, payback period, cost indices). The user has the option instructing the
use of either Freundlich or Langmuir models. The tool generates outputs that include the calculated Freundlich or Langmuir coefficients, adsorption capacities, capital costs, operations and
maintenance (O&M) costs, plant footprint, residuals quantities and water quality interference
warnings. The outputs are calculated based on the water quality and system information that the
user enters in the input form.
The tool generates results for seven promising adsorbents and displays them in the output
form. The seven adsorbents included in the tool are AA-400G (conventional, granular activated
alumina), AA-FS50 (iron-enhanced activated alumina), Bayoxide E-33 (granular ferric oxide),
GFH (granular ferric hydroxide), Metsorb G (granular titanium dioxide), Z-33 Rev B (ironenhanced zeolite), and SMI (sulfur modified iron). Detailed information on the adsorbents is
shown in Table 7.1. Table 7.1 exhibits information such as critical design parameters (e.g., manufacturer recommended empty bed contact time (EBCT), hydraulic loading rate (HLR), minimum
bed depth), suggested backwash protocols (e.g., backwash rate, backwash time, backwashing
interval), water quality interferents, suggested residuals handling and disposal practices, and unit
media costs. In addition to the seven adsorbents, the user has the option to enter a User-Defined
Adsorbent.
Further elaboration is needed to explain number of vessels per train in Table 7.1. Each
treatment process train was assumed to consist of two vessels in series with a third standby vessel,
which is used for substituting for the exhausted vessel as necessary. The first vessel in the series is
referred to as the roughing vessel, the second vessel is the polishing vessel. The roughing vessel
will reach exhaustion initially, after which the polishing vessel becomes the roughing vessel and
the standby vessel becomes the polishing vessel. The spent media in the initial roughing vessel is
replaced with virgin media. This approach of vessel operation is referred to as the merry-goround approach. Operating the vessels in the merry-go-round approach allows one to exhaust the
media completely before replacement. In this approach, media from the standby vessel can be
replaced without interrupting the treatment plant operation.
The tool was programmed as a series of Microsoft Excel spreadsheets interconnected with
Microsoft Visual Basic Programming to prompt the user for inputs, conduct calculations and
display outputs. After reviewing the results, the user can change parameters or adsorption models
and compare results for many different treatment scenarios. The outputs generated by the tool
should be verified with bench and/or pilot-scale testing prior to full-scale implementation.
81
Table 7.1
Design and operating criteria used in sizing and costing of arsenic adsorption systems
Parameter
AA-400G
AA-FS50
Bayoxide E-33
GFH
Metsorb G
Z-33 Rev B
SMI
Adsorbent Media General Properties
82
Media Type
Activated alumina
Iron modified
activated alumina
Ferric oxide
Ferric hydroxide
Titanium dioxide
Iron modified
zeolite
Sulfur modified
iron
Media Form
Granular, Dry
Granular, Dry
Granular, Dry
Granular, Wet
GFH is delivered in
wet form with 50%
water by weight
Granular, Dry
Granular, Dry
Granular
Manufacturer
Alcan Chemicals
Alcan Chemicals
Bayer-Severn
Trent
GEH
Wasserchemie-US
Filter
Hydroglobe
WRT
SMI, Inc.
Bulk Density
(lbs/ft3)
41
47 (wet)
75 (wet)
75 (wet)
49 (dry)
55 (wet)
55 (dry)
135 (dry)
NSF 61
Certification
Certified
Certified
Certified
Certified
In Process
Certified
Not Certified
Critical Design Parameters

Suggested
EBCT/vessel for
2 Vessels in
Series (minutes)
2.5
1.5
5
(Parallel Mode,
3 Vessels/System)
Suggested
Hydraulic
Loading Rate
(gpm/ft2)
68
68
68
68
68
68, Upward Flow
57, Upward Flow
Suggested
Minimum bed
depth (ft)
Suggested
Maximum bed
depth (ft)
(Continued)

AA-400G
AA-FS50
Bayoxide E-33
GFH
Metsorb G
Z-33 Rev B
SMI
Number of Vessels
per Train
2 Active and
1 Redundant
2 Active and
1 Redundant
2 Active and
1 Redundant
2 Active and
1 Redundant
2 Active and
1 Redundant
2 Active and
1 Redundant
2 Active and
1 Redundant per
System, Redundant
Vessel is for
Periodic Fluffing of
Media
Vessel Diameters
Considered (ft)
112
112
112
112
112
1-12
112
Pressure Vessels
Material
<500 gallons
Reinforced
Fiberglass
<500 gallons
Reinforced
Fiberglass
<500 gallons
Reinforced
Fiberglass
<500 gallons
Reinforced
Fiberglass
<500 gallons
Reinforced
Fiberglass
<500 gallons
Reinforced
Fiberglass
<500 gallons
Reinforced
Fiberglass
>500 gallons
Carbon Steel
>500 gallons
Carbon Steel
>500 gallons
Carbon Steel
>500 gallons
Carbon Steel
>500 gallons
Carbon Steel
>500 gallons
Carbon Steel
>500 gallons
Carbon Steel
Suggested
Backwash Rate
(gpm/ft2)
68
79
1012
1012
79
Does not require

backwashing since
it is operated in
upflow mode
3040. Media tends

to gather particles
and aggregate,
therefore requires
backwashing.
Suggested
Backwash Time
(min)
15
15
15
15
15
Does not require

backwashing
34
Backwashing
Interval
Every 34 weeks
(depends on raw
water quality)
Every 34 weeks
(depends on raw
water quality)
Every 34 weeks
(depends on raw
water quality)
Every 34 weeks
(depends on raw
water quality)
Every 34 weeks
(depends on raw
water quality)
Does not require

backwashing
Every 4872 hours

(fluffing interval)
83
Parameter
Backwash Practice
(Continued)

Parameter
AA-400G
Special Operational
Considerations
Can be regenerated
onsite
AA-FS50
Bayoxide E-33
GFH
Metsorb G
Z-33 Rev B
SMI
Water Quality
84
Cannot tolerate any

oxidants like
chlorine in feed
water.
Leaches iron in the
product water.
Recommended to
have an iron
removal system
after this adsorption
process.
pH
Silica
Fluoride
Phosphate
Vanadium?
pH
Phosphate
Silica?
Vanadium?
Fluoride?
pH > 8.5
pH > 8.5
pH > 8.5
pH > 8.5
pH
Phosphate
Silica
Vanadium
pH Adjustment
Recommended For
Raw Water
pH > 7.5
pH > 8.5
pH > 8.5
Suggested Optimal
pH
pH
Phosphate
Silica
Vanadium
pH
Phosphate
Silica?
Vanadium?
pH
Silica
Phosphate
pH
Silica
Phosphate
Significant Water
Quality Parameters
(in the Order of
Significance)
Residuals Handling and Disposal

Spent Media
Disposal
Landfill
Landfill
Landfill
Landfill
Landfill
Landfill
Landfill
Spent Backwash
Disposal
Sewer/Storm
Drain/Wash or
Recycled after
Filtration
Sewer/Storm
Drain/Wash or
Recycled after
Filtration
Sewer/Storm
Drain/Wash or
Recycled after
Filtration
Sewer/Storm
Drain/Wash or
Recycled after
Filtration
Sewer/Storm
Drain/Wash or
Recycled after
Filtration
Sewer/Storm
Drain/Wash or
Recycled after
Filtration
Not Applicable
(Continued)

Parameter
AA-400G
AA-FS50
Bayoxide E-33
GFH
Metsorb G
Z-33 Rev B
SMI
Unit Media Cost

($/lb or $/ft3)
For <2,000 lbs,

$1.00/lb
For >2,000 lbs,
$0.50/lb
For <2,000 lbs,

$1.30/lb or $61/ft3
For >2,000 lbs,
$0.82/lb or
$38.50/ft3
$5.50/lb-dry or
$159.50/ft3
For <15,000 lbs,

$3.00/lb or $225/ft3
For >15,000 lbs,
$2.50/lb or
$187.50/ft3
$6/lb-dry or
$294/ft3
$0.25/lb-dry
$4/lb-dry
Capital Cost
Includes
Pressure Vessels
Influent Strainer
Media Transfer System
Concrete, Valves, Pipes, Electrical and Instrumentation
Site Work
Permitting, Piloting, Operator Training
pH Adjust System (where used)
O & M Cost
Includes
Purchase of New Media for Replacement

Spent Media Transportation and Disposal
Chemical (if pH is adjusted)
Labor (to Operate and Maintain)
Process Monitoring Analytics
Energy
Cost Assumptions
85
The Arsenic Adsorbent Design and Costing Tool is presented solely for informational
purposes for utilities and individuals to research initial design and cost options for the adsorption
treatment of arsenic using various adsorbents. By using the tool with project specific flow rates
and water quality parameters, utilities can assess basic design options and costs associated with
the various adsorption media available in the marketplace.
SINGLE PARAMETER AND MULTIPLE REGRESSION MODELS
The water quality effects on the adsorptive capacities for arsenic by the various adsorbents
were modeled using single parameter and multiple regression models. These models were developed
using the data from bench-scale testing generated during the bench testing summarized in Chapter 6.
Single Parameter Model
The single parameter model is used when the user enters only arsenic and pH information,
and no other water quality information. In the single parameter model, the Freundlich and Langmuir coefficients were modeled based on raw water pH. The equations for the various adsorbents
for the single parameter model are shown in Table 7.2. The R2 value indicates the correlation
between measured and predicted adsorption capacities, with a higher R2 value indicating a better
correlation.
For example, the single parameter model equations for GFH are:
Freundlich Model
KF = 0.853 0.084 (pH)
1/n = 1.5243 0.143 (pH)
Langmuir Model
KL = 1.1183 0.105 (pH)
Qmax = 5.783 0.618 (pH)
(7.1)
(7.2)
(7.3)
(7.4)
Among the various water quality parameters, pH has the most significant effect on adsorbents performance. Therefore, pH was chosen as the modeling parameter for single parameter
models. Table 7.2 identifies the pH limits (i.e., boundary conditions) over which the single parameter models are applicable. The pH boundary conditions shown on the table corresponds to the
range of pH levels that were tested in bench-scale tests.
Multiple Regression Model
Multiple regression models were developed using Statistica (StatSoft, Tulsa, OK), a
statistical software package. Multiple regression models account for interferences from water
quality parameters such phosphate, silica, vanadium and fluoride, in addition to the effect of pH.
As discussed in earlier sections, performance of arsenic adsorbents is greatly influenced by cooccurring ions such as phosphate and silica. The effect of the co-occurring ions was modeled
using linear multiple regression modeling.
In linear multiple regression modeling, the independent variables (Xi; e.g., pH, phosphate,
silica, vanadium, fluoride) are placed into equations to predict their partial correlation coefficients
86
Table 7.2
Single parameter and multiple regression models
Sorbent
Models
87
Equations
KF = 0.853 0.084(pH)
1/n = 1.5243 0.143(pH)
Single Parameter
KL = 1.1183 0.105(pH)
Qmax = 5.7843 0.618(pH)
GFH
KF = 0.6791 0.1289(pH6.0) 0.00029(PO4) 0.010975(SiO2) 0.017583(V )
1/n = 0.2943 0.0575(pH6.0) 0.00042(PO4) + 0.000747(SiO2) + 0.15756(V)
Multiple Regression KL = 0.5346 0.072339(pH6.0) + 0.00839(PO4) 0.00387(SiO2) 0.015145(V)
Qmax = 1.8584 0.449943(pH6.0) 0.00251(PO4) 0.02582(SiO2)
0.003492(V)
KF = 0.9978 0.0505(pH)
1/n = 0.486 0.033(pH)
Single Parameter
KL = 0.655 0.057(pH)
Qmax = 3.781 0.275(pH)
KF = 0.813 0.16442(pH6.0) 0.001544(PO4) 0.01936(SiO2) 0.015276(V )
Bayoxide
1/n = 0.1066 + 0.090358(pH6.0) + 0.000654(PO4) + 0.018384(SiO2)
+ 0.001825(V)
Multiple Regression KL = 0.3269 0.079642(pH6.0) 0.000821(PO4) 0.00619(SiO2)
0.006403(V)
Qmax = 1.3742 + 0.1940255(pH6.0) 0.000165(PO4) + 0.035823(SiO2)
0.029029(V)
KF = 0.732 + 0.172(pH)
KF = 1.865 0.199(pH)
1/n = 0.8303 0.051(pH)
Single Parameter
KL = 0.952 + 0.165(pH)
KL = 11.158 + 1.623(pH)
FS50
Qmax = 13.952 1.666(pH)
KF = 0.3913 0.0341(pH6.0) + 0.00014(PO4)
1/n = 0.5122 0.0491(pH6.0) 0.00064(PO4)
Multiple Regression
KL = 0.232 + 0.379999(pH6.0) 0.00159(PO4)
Qmax = 3.0874 0.8571(pH6.0) 0.00391(PO4)
R2 * Water quality limits

0.46 6.0 pH 8.0
0.62 6.0 pH 8.0
0.93 If pH > 8.0 and 125 g/L PO4 250 g/L,
Set PO4 = 125 g/L
0.89 If pH > 8.0 and 125 g/L PO4 250 g/L,
Set PO4 = 125 g/L
0.44 6.0 pH 8.0
0.00 6.0 pH 8.0
0.52 If 7.5 pH 8.5, adjust pH = 6.0
If 100 g/L PO4 250 g/L, Set PO4 = 100 g/L
0.38 If 10 mg/L SiO2 22 mg/L, Set SiO2 = 10 mg/L
If 5 mg/L V 30 mg/L, Set V = 5 mg/L
0.52 pH 7.0
pH > 7.0
6.0 pH 8.0
0.67 pH 7.0
pH > 7.0
6.0 pH 8.0
0.79 6.0 pH 8.0, PO4 250 g/L
0.73 6.0 pH 8.0, PO4 250 g/L
(Continued)

Sorbent
88
Metsorb
Z33
Models
Equations
KF = 0.8808 0.0385(pH)
1/n = 0.58492 0.0405(pH)
KL = 1.327 0.161(pH)
Single Parameter
KL = 0.052 + 0.036(pH)
Qmax = 3.5627 0.254(pH)
KF = 0.7481 0.138961(pH6.0) 0.000712(PO4) 0.02034(SiO2)
0.011076(V )
1/n = 0.2395 + 0.012615(pH6.0) + 0.000314(PO4) + 0.01216(SiO2)
0.001398(V)
Multiple Regression
KL = 0.3108 0.054318(pH6.0) 0.00057(PO4) 0.01121(SiO2)
0.005805(V)
Qmax = 2.1453 0.391103(pH6.0) 0.000003(PO4) + 0.014399(SiO2)
0.032191(V)
KF 1.1068 0.1245(pH)
1/n = 0.277 0.006(pH)
1/n = 0.843 + 0.154(pH)
Single Parameter
KL = 0.3415 0.0385(pH)
Qmax = 1.9862 0.1575(pH)
KF = 0.3251 0.085545(pH6.0) 0.000154(PO4)
1/n = 0.227 + 0.037154(pH6.0) 0.000323(PO4)
KL = 0.0997 0.0122(pH6.0) + 0.000091(PO4)
Multiple Regression
Qmax = 0.9923 0.148767(pH6.0) 0.001573(PO4)
KL = 0.0997 0.0122(pH6.0) + 0.000091(PO4)
Qmax = 0.9923 0.148767(pH6.0) 0.001573(PO4)

0.60 6.0 pH 8.0
0.31 pH 7.0
pH > 7.0
6.0 pH 8.0
0.84 If pH > 8, adjust pH = 6.0
0.58 If 15 SiO2 22 mg/L, set SiO2 = 15 mg/L

If 5 V 30 mg/L, Set V = 5 mg/L
0.92 6.0 pH 8.0

pH 7.0
pH > 7.0
0.85 6.0 pH 8.0
0.95 6.0 pH 8.0, PO4 250 g/L
0.95 6.0 pH 8.0, PO4 250 g/L
0.86 6.0 pH 8.0, PO4 250 g/L
(Continued)

Sorbent
89
SMI-III
AA400G
Models
Equations
KF = 69.631 8.7185(pH)
1/n = 0.38 + 0.122(pH)
1/n = 2.231 0.251(pH)
Single Parameter
KL = 0.122 + 0.017(pH)
KL = 1.697 0.208(pH)
Qmax = 319.66 40.233(pH)
KF = 16.52 6.9093(pH6.0) 0.03769(PO4) 0.5238(SiO2) 0.31694(V )
1/n = 0.3339 + 0.049108(pH6.0) 0.000674(PO4) 0.00765(SiO2)
0.005107(V)
Multiple Regression
KL = 0.3447 0.238751(pH6.0) 0.002934(PO4) 0.00844(SiO2)
0.003345(V)
Qmax = 62.055 18.9939(pH6.0) 0.28(PO4) 2.4591(SiO2) 1.3192(V)
Q (g/mg)= 1.860271 + 0.001318(As) 0.237217(pH) 0.288581(PO4)
Multiple Regression 0.097215(F)
* Based on Qmeasured versus Qpredicted. Higher value indicates better correlations

Input Units: PO4 in g/L; SiO2 in mg/L, V in mg/L, F in mg/L
Units for Freundlich constants: KF in g-As/mg-media; 1/n no unit; Q = g-As/mg-media
Units for Langmuir constants: Qmax in g-As/mg-media; KL g/L; Q = g-As/mg-media

0.51 6.0 pH 8.0
pH 7.0
pH > 7.0
0.41 pH 7.0
pH > 7.0
6.0 pH 8.0
0.95 If 7.0 pH 8.5, adjust pH = 6.0
0.78 If 10 mg/L SiO2 22 mg/L, Set SiO2 = 10 mg/L
If 5 V 30 mg/L, Set V = 5 mg/L
0.67 If 7.0 pH 8.5, adjust pH = 6.0
If 4 F 10 mg/L, Set F = 4 mg/L
with the dependent variables (Yj; e.g., Freundlich and Langmuir coefficients). The general form of
linear multiple regression modeling is:
Yj = Co + C1X1 + C2X2 + + CnXn
(7.5)
where Yj is the predicted variable, Co is a constant, and Ci are coefficients for the various independent variables (Xi).
The predictability of the model was evaluated through various statistical parameters
including regression coefficient (R2), F statistics and p values (probability of null hypothesis). The
models were tested by performing internal validation based on the data used in development of
the models. Some of the models were also evaluated with natural water conditions based on
limited pilot-scale data that were available.
The multiple regression model equations for the seven adsorbents are shown in Table 7.2.
The water quality limits over which the models are applicable and the R2 values are also shown in
this table.
Discussed below is an example of linear multiple regression model for GFH. In this
example, the model predicts Freundlich constants, KF and 1/n, based on independent variables.
These constants are used to predict (column mode) adsorptive capacity, Q (i.e., Equation 7.3)
based on water quality and raw water arsenic (within this context, when Ce (equilibrium arsenic
concentration) = C0 (initial raw concentration), the predicted Q = Q0 (column capacity)).
KF = 0.6791 0.1289(pH 6.0) 0.00029(PO4) 0.010975(SiO2) 0.017583(V)
(7.6)
1/n = 0.2943 0.0575(pH 6.0) 0.00042(PO4) + 0.000747(SiO2) + 0.15756(V)
(7.7)
Q = KF Ce1/n (R2 = 0.93)
(7.8)
Equations 7.6 and 7.7 predicts the Freundlich constants, KF and 1/n, based on water
quality inputs for pH, phosphate, silica and vanadium. Increasing pH (above pH of 6) will
decrease the adsorption capacity and this effect is shown by the negative term in Equation 7.6:
0.1289(pH-6.0). The pH of 6.0 was assumed to be the baseline pH. Increasing concentrations of
phosphate, silica and vanadium will decrease KF, 1/n and Q (Equation 7.8). The limits for the
application of these equations are shown in Table 7.2.
DESCRIPTION OF TOOL ALGORITHMS AND CALCULATIONS
Various algorithms for the Arsenic Adsorbent Design and Costing Tool are shown in
Figures 7.1 to 7.4. These algorithms include the decision logics for costing, media replacement,
backwash calculations, and plant footprint calculations. The following is a brief description of the
step-by-step calculations that are carried out within the tool:
If split-stream treatment is selected, the tool calculates the split-stream flows for
design and operation; otherwise the inputted flows are used.
Capital costs are calculated based on pre-determined cost equations that account for
vessel size, number of vessels, influent Y-strainers, media transfer system, concrete,
90
Figure 7.1 Cost flowchart
91
Figure 7.2 Media replacement flowchart
Figure 7.3 Backwash calculation flowchart
92
Figure 7.4 Plant footprint calculation flowchart
valves, pipes, electrical and instrumentation, media staging area, media for first fill,
media transportation, vessel transportation, housing, piloting, permitting, land,
operator training, and pH adjustment (if selected or required). The cost equations were
developed for each media over the flow range of 103500 gpm. The capital costs are
then adjusted based on the current Engineering News Record (ENR) Construction
Cost Index.
The O&M costs are calculated within the tool based on:
Pre-determined media-specific equations for housing energy, process energy,
increased well pumping, and analytical costs.
The other O&M costs (such as media replacement) are calculated based on
associated project research that helps in identifying the Freundlich/Langmuir
parameters for the user-entered water quality. Adsorption parameters are estimated
for each media based on pH and concentrations of interfering ions (phosphate,
silica, vanadium and fluoride). The estimated adsorption parameters were used to
calculate the arsenic adsorption capacity for each media. Using the adsorption
capacities, the annual media replacement costs are calculated. Finally, the costs for
pH adjustment chemicals are calculated based on whether pH control has been
selected, the raw water pH and alkalinity. The O&M costs are then adjusted based
on the current ENR Skilled Labor Index.
The total of capital and O&M costs are then presented in several formats including
total present worth, total annual cost, and cost per 1000 gallons treated for comparison
of the various adsorption alternatives.
93
Figure 7.2 illustrates an example algorithm using the Freundlich model that the tool would
use to calculate the media replacement quantities. Depending on the water quality parameters
inputted, the tool selects either a single parameter model or a multiple regression model. The
multiple regression model will be used when the user enters water quality parameters other than
pH and arsenic. The media run lengths are estimated using the calculated adsorption capacities.
Figure 7.3 embodies the algorithm for calculating the volume of backwash water required
per backwash cycle. The tool uses design parameters of suggested backwash rate, suggested
loading rate, and suggested backwash time for each media to determine the overall volume of
backwash water that will most likely need to be contained for one backwash cycle.
Figure 7.4 embodies the flowchart that illustrates the calculations for treatment plant footprint. The tool calculates the required space for all adsorption vessels, backwash tanks, spent
media storage, and pH adjustment system tanks (if pH adjustment is selected or required). A 30
percent (%) contingency is then added to the total footprint for items such as safety gear, maintenance systems, pumps, and work space.
INSTRUCTIONS FOR USING THE TOOL
To begin using the arsenic tool, the user must enter project specific parameters on the input
form, choosing either the Freundlich or Langmuir adsorption models. It is recommended that the
Freundlich model be used for initial model determinations, followed by the Langmuir model for
comparison.
By clicking on the input parameters button for either model, a page of input parameters
will open for entering the key project specific parameters required for the model calculations. To
assist with some of the parameters which may not be known, click the default values button to
populate the input parameters page with a set of default parameters. Then, modify the input
parameters with any data that is available for the specific project, such as flow rates and water
quality parameters.
Selecting yes for split stream treatment can lead to more cost effective treatment
because only a portion of the total flow will be treated and then blended with the by-passed water
to meet the treated water arsenic goal.
Also, calculations for pH adjustment chemicals are considered when the pH adjustment
box is checked. Generally, the optimum pH for arsenic adsorption is pH 6. For pH 6 to 8, pH
adjustment may not be necessary, although it may still be economical because of higher adsorption capacity at adjusted pH conditions. If pH is between 6 and 8, results with/without pH adjustment should be compared for the most economical treatment. For pH values greater than 8, pH
adjustment is recommended. For pH values greater than 8.5, the tool automatically assumes pH
adjustment will be required.
On the input page, there is also a button to enter optional water quality parameters. These
parameters can affect the adsorption of arsenic onto specific media types and the model accounts
for these water quality parameters during calculations. It is only necessary to enter values for
those optional water quality parameters that are known for the specific project water. The model
will use default values for any parameters that are not entered.
In addition to the seven arsenic adsorbents built into the model, the ability to enter a user
defined adsorbent has been built into the model to account for newer adsorbents. A user defined
adsorbent may be entered by clicking on the corresponding button on the input form and entering
the required data for the adsorbent.
94
Once the input form is completed, press the Submit button and the tool will calculate all
of the output data and bring the user back to the main tool menu. Clicking on the output button
will bring the user to the output page. Tool output consists of treatment costs, media replacement,
backwash water requirements, and plant footprint estimates. The output page can be printed for
comparison of several runs. The outputs can be saved by clicking on the Save Output button.
From the output page, clicking on the Return to Main Menu will bring back the main menu
from which new information can be entered to test other scenarios.
In using the software to assess sulfur modified iron (SMI), the user is issued a warning
message, advising of the lesser reliability of the SMI algorithms compared to the other adsorbents. The issue of SMI data reliability was discussed in Chapter 6. Through a critical evaluation
of SMI data (see Table 6.8), only 9 of the 16 data sets were used in algorithm development. Thus,
the tool can be used to assess SMI but the results can be considered only semi-quantitative. Nevertheless, they have some value in screening the merits and demerits of SMI compared to the
various adsorbents.
BASIS OF COST OPINIONS
All cost data generated by the Arsenic Adsorbent Design and Cost Tool represent conceptual-level opinions of probable capital and operating and maintenance (O&M) costs for the
specific facilities selected by the user. Capital cost opinions are expressed in February 2004
dollars, corresponding with an Engineering News Record (ENR) 20-Cities Average Construction
Cost Index (CCI) of 6861.1. O&M cost opinions are expressed in February 2004 dollars, corresponding with an Engineering News Record (ENR) 20-Cities Average Skilled Labor Index (SLI)
of 6659.7. The user can adjust capital and O&M cost opinions to another time period by entering
different input values for the ENR CCI and SLI.
The conceptual cost opinions generated by the Arsenic Adsorbent Design and Cost Tool
are considered to fall within the range of Class 5 to Class 4 estimates as defined by the Association for the Advancement of Cost Engineering (AACE) International. These levels of engineering
cost estimating are generally conducted on the basis of limited preliminary information and
without detailed information such as process and instrumentation diagrams, engineering layouts,
and equipment schedules. This level of cost estimating is appropriate for strategic planning
purposes, assessment of initial viability, evaluation of alternative plans, project feasibility
screening, and long range capital planning. Typical accuracy ranges recognized for Class 5 to
Class 4 estimates are 30% to +50%.
95
CHAPTER 8
CONCLUSIONS
Extensive literature and vendor surveys revealed that there are a large number of adsorbents, commercially available and experimental, available for arsenic removal. Some of the
commercially available materials are mature products (e.g., activated alumina) that have been
widely tested, revealing both their attributes and limitations, while others are more recent products that have not been as rigorously tested (e.g., various iron oxides). Based on their predominant
adsorption mechanism as well as material composition, these adsorbents fall into several categories: (i) ion exchange media (e.g., MIEX); (ii) metal oxides (e.g., activated alumina and iron
oxides); and (iii) redox-reactive media (e.g., MnO2). In this study, we have chosen to highlight the
second category in the forms of both pure minerals and amended/impregnated materials. The
literature review also revealed that adsorption capacities were influenced by arsenic speciation,
arsenate (As(V)) versus arsenite (As(III)), and water quality in terms of pH conditions and the
presence on interfering species competing with arsenic for adsorption sites. Influential interferants
were revealed to include silica, phosphate, fluoride, sulfate, carbonate, and others. Based on the
literature and vendor surveys, a total of 12 adsorbents, 10 commercially available and 2 experimental, were identified for experimental evaluation. Besides pH as an important water quality
condition, phosphate and silica were identified for intensive interferant testing, later supplemented
by vanadium and fluoride for less intensive assessment.
An arsenic occurrence and co-occurrence survey was conducted to indicate national
(USA) occurrence levels of total arsenic, arsenic species domination, and co-occurrence trends
between arsenic and interferants. Based on statistical analysis of an integrated national database
for groundwater, the mean total arsenic concentration was determined to be 4.5 g/L, with a
90 percentile value of about 10 g/L. Geographically, the highest national levels were found in the
Intermontane region encompassing states west of the continental divide (e.g., Arizona and New
Mexico) except for Washington, western Oregon, and northern California; lowest levels were
found in the Atlantic Plain region. Binning of data showed that about 5% of all groundwater sites
contained 20 g/L, about 5% contained between 10 to 20 g/L, and about 5% between 5 to
10 g/L. While a rigorous study of arsenic speciation in groundwater was not found, several
limited studies suggested that As(V) is the predominant species in U.S. groundwaters although, in
other global settings such as Bangladesh, As(III) is known to dominate in more anoxic groundwaters. There were semi-quantitative trends to indicate that groundwaters with arsenic 5 g/L
tended to be higher in pH, silica, fluoride, alkalinity, and phosphate than those with <5 g/L;
however, at a 95% confidence level, no statistically significant correlations were found between
arsenic and the various co-occurring parameters according to the binning classifications. A decision was made to define a typical water and a difficult to treat water in terms of 50 and 75 percentile levels of interferants. For pH, levels of 6.0, 7.0, and 8.0 were specified for testing,
corresponding to roughly 10, 25, and 75 percentile levels; a lower pH (e.g., 6.0) than typical (i.e.,
50 percentile) is of interest because of observations on enhanced performance of many adsorbents
at lower pH conditions, suggesting the possibility of pH depression as a pre-treatment step.
Preliminary batch experiments were performed to screen twelve candidate adsorbents:
AA-400G (activated alumina (AA)); AA-FS50 (iron impregnated AA); MIEX (amagnetized ion
exchange resin); Bayoxide E33 (granular ferric oxide (GFO)); Granular Ferric Hydroxide (GFH);
Metsorb (titanium dioxide); Z33-Revision B (iron modified zeolyte); ARM 100 (alumina based,
97
with proprietary promoters); Sulfur Modified Iron Version III (SMI); ViroClear Bauxsol F3
(Bauxite Clay); Geothite (-FeOOH); and Pyrolusite (-MnO2). An initial set of preliminary
experiments indicated that pseudo equilibrium conditions could be established within a 24 hour
time frame, a basis for isotherm development. Additional preliminary experiments were
performed to approximate As(V) and As(III) adsorption capacities as a basis to reduce the number
of adsorbents to five select adsorbents for intensive batch testing of water quality effects: AAFS50, Bayoxide E33, GFH, Metsorb G, and Z33. Four of these adsorbents (AA-FS50, Bayoxide
E33, GFH, and Metsorb G) were further evaluated in continuous-flow column tests. Another of
the candidate adsorbents, SMI, was the focus of a special study because of interest in its high
As(V) capacity but with significant concerns about experimental reproducibility.
Based on batch testing results with synthetic waters at each of the three pH conditions and
the presence or absence of an individual interferant, a number of trends were discerned. First, in
addressing the performance of each adsorbent independently, the following observations were
made. The AA-FS50 showed a moderate deterioration in performance as pH increased, a significant decrease in capacity in the presence of fluoride, and only a small effect exerted by phosphate.
The Bayoxide E33 media showed only a slight pH effect but exhibited significant impacts by
phosphate and vanadium with some silica effects. GFH showed a decrease in performance as pH
increased, with phosphate, silica, and vanadium exhibiting adverse effects. MetSorb G showed a
decrease in performance as pH increased, with phosphate, silica, and vanadium exhibiting effects,
although the interferent effects were less at lower pH. Z33 performance decreased as pH increased
and phosphate had a significant effect.
Second, in addressing adsorbent comparisons, the following observations were made. The
two iron oxide media (Bayoxide E33 and GFH) and Metsorb G generally showed comparable
weight-based capacities although GFH performance dropped sharply at the highest pH; interferant effects were lowest for Metsorb G. The iron-modified activated alumina (AA-FS50)
showed a higher capacity than the two iron oxide media and Metsorb G at lower pH, but a lower
capacity at higher pH, indicating more of a pH dependency. The iron-modified zeolite (Z33)
generally exhibited the lowest capacities.
Differences in physical/chemical properties of the adsorbents helped to explain some of
the differences. The order of pHZPC (high to low) was Bayoxide E33 > GFH > AA-FS50 > Z33 ~
Metsorb G. The higher pHZPC of the Bayoxide E33 versus GFH helped explain the better performance of the former iron oxide at higher pH conditions. The order of surface area (high to low)
was AA-FS50 ~ GFH > Metsorb G > Bayoxide E33 > Z33. The very low surface area of the Z33
was manifested in a lower number of adsorption sites per unit mass. The material composition
differed significantly: aluminum and iron content for AA-FS50, titanium dioxide for Metsorb G,
clay content for Z33, and iron oxides for GFH and Bayoxide E33. The high capacity exhibited by
the Metsorb E33 may involve a more complicated mechanism than simply surface complexation
or ligand exchange.
Three of the adsorbents; Bayoxide E33, Metsorb G, and GFH; were tested for arsenite
removal; while all three adsorbents demonstrated a significant potential for As(III) removal, their
As(III) capacities were significantly less than their As(V) capacities; the order of performance
was Bayoxide E33 > Metsorb G > GFH.
Three adsorbents (Bayoxide E33, Metsorb G, and GFH) were tested in a NSF challenge
water containing As(V) or As(III) with multiple interferants at a constant pH (7.5) as well as
several utility-supplied natural waters containing multiple interferants and variable pH. The order
of capacities for As(V) in the NSF challenge water was Metsorb G > Bayoxide E33 > GFH, while
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the order of capacities for As(III) was Metsorb G >GFH > Bayoxide E33. The general order of
capacities for the natural waters was Metsorb G > Bayoxide E33 > GFH.
Results from a special batch study on SMI revealed a higher As(V) capacity than that of
the other adsorbents; however, its performance was substantially reduced at higher pH conditions
and/or in the presence of interferants. Moreover, its As(III) capacity was much lower than its
As(V) capacity.
Another special batch study was performed to more closely study the effects different
forms of silica, monomeric versus polymeric. It was found that at higher silica concentrations,
polymeric silica can form and potentially foul porous adsorbents, thus reducing their capacity.
dynamic column tests employing the NSF challenge water spiked with As(V) at concentrations of
250 g/L (for Metsorb G) to 1,000 g/L (for the other three adsorbents); the purpose of the high
initial concentration was to facilitate breakthrough. Based on an empty bed contact time (EBCT)
of 5 minutes, the AA-FS50 and GFH showed similar results with breakthrough at about 4,000 to
5,000 bed volumes (BVs). The Metsorb G and Bayoxide E33 were run for longer periods of about
8,000 and 12,000 BVs, respectively. The Metsorb G experiment was terminated before a clear
breakthrough trend was observed, however, this result is consistent with the lower initial As(V)
concentration employed in this test.
Based on the bench-testing results and synthesis of information from other sources, it was
possible to develop an arsenic adsorbent design and costing tool based on seven adsorbents:
AA-FS50, Bayoxide E-33, GFH, Metsorb G, Z-33, SMI, and AA-400G (conventional, granular
activated alumina). Based on user-provided input; system parameters (e.g., average flow), water
quality (e.g., influent arsenic, phosphate, and silica concentrations), target water quality
(e.g., treated-water arsenic), operational preferences (e.g., pH adjustment), and cost parameters
(e.g., interest); the software tool provides outputs that include: adsorption capacities, capital costs,
operations and maintenance (O&M) costs, plant footprint, residuals quantities, and water quality
interference warnings.
The study revealed several areas that warrant additional research. These include: (i) the
need for a more focused study on SMI, a promising adsorbent in terms of its high As(V) capacity,
but potentially problematic in terms of reproducibility in performance; (ii) a need for additional
study on whether silica is truly a competitive interferant or an adsorbent foulant; and (iii) an investigation to resolve discrepancies between isotherm- versus column-based adsorption capacities.
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APPENDIX A
LITERATURE SURVEY
101
BACKGROUND
Various treatment methods have been tested for their potential to remove arsenic from
drinking water under both laboratory and field conditions: coagulation-precipitation using iron
and aluminium salts; adsorption onto activated alumina/activated carbon/activated bauxite;
reverse osmosis; ion exchange; and oxidation followed by filtration (Viraraghavan et al., 1994;
Amy et al., 2000). The applicability of conventional adsorbents, including activated alumina (AA)
and ion exchange (IX) for the removal of arsenic, the associated water quality constraints (e.g.,
SO42 for IX) and their regeneration requirements have been previously reported (Amy et al.,
2000). Conventional treatment technologies including coagulation, Fe/Mn removal and softening;
sorption processes onto AA, IX and iron-oxide-coated sand (IOCs); membrane processes (nanofiltration (NF), ultrafiltration (UF) and microfiltration (MF)); and preoxidation of arsenite to
arsenate were discussed and summarized earlier (Edwards, 1994; Cheng et al., 1994; Jekel, 1994;
Scott and Morgan 1995; Hering and Elimelech, 1996; Amy et al., 2000; Brandhuber and Amy,
2001; Korngold et al., 2002). Amy et al. (2000) made a comparative assessment of existing
arsenic removal technologies. They discussed the selection of arsenic treatment options based on
costs, water quality, and a number of other considerations (e.g., residuals). In addition, they developed a decision tree to be used as a guide in selecting arsenic treatment options at a given utility
based on estimated costs (Amy et al., 2000). The overall conclusion of their assessment was that
the selection of a most appropriate treatment technology depends on water quality, initial arsenic
concentration and form, treatment (MCL) objectives, treatment system capacity, and residuals
handling costs. In addition, they stated that the decision tree was produced to define overall trends
in the selection process and therefore, site-specific work should be carried out for each particular
case (Amy et al., 2000).
LIMITATIONS ASSOCIATED WITH THE APPLICATION
OF CONVENTIONAL TECHNOLOGIES
One of the main disadvantages in the application of conventional technologies is that they
produce large quantities of sludge containing arsenic (hazardous in nature) that pose serious problems for safe disposal (Simeonova, 2000; Thirunavukkarasu et al., 2001). Another distinctive
disadvantage is in the fact that an oxidation step (transformation of arsenite to arsenate) is a prerequisite to achieve the highest efficiency. The research to date has demonstrated that activated
alum, for example, exhibits selectivity for arsenate species, and therefore only partial recovery
and regeneration of adsorbed arsenic are attainable. In addition, the adsorption onto As on alum
floc is very sensitive to pH. Another example is the application of ferric salts, which require the
oxidation of As (III) for effective removal (Subramanian et al., 1997). Ion exchange, reverse
osmosis and electrodialysis use anionic resins or specific membranes, but have limitations in
terms of market availability, residuals (brines), and high costs. Regeneration creates residuals
problems, and final pH readjustment and residuals management are often required (Simeonova,
2000).
Therefore, conventional treatment technologies require increased maintenance and costs
(due to the complexity, investment costs of the plants etc.), cost of chemical reagents (not always
available in developing countries), reagents quantity and volume of the toxic residues produced in
operation (transport, treatment, etc). (Saha et al., 2001; Amy et al., 2000; Simeonova, 2000;
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Thirunavukkarasu et al., 2001). In addition, they do not always ensure the established MCL for
drinking water.
International concern has also focused on the problem of arsenic pollution of groundwater
in Bagladesh and Bengal, India (Jiang, 2001; Thirunavukkarasu et al., 2001). Over the past 20
years, a significant amount of research has been conducted to develop an inovative technology to
achieve low levels of As in drinking water (Gupta and Chen, 1978; Huxstep and Sorg, 1988;
Edwards, 1994; Jekel, 1994; Hering and Elimelech, 1996, Amy et al, 2000; Robins et al, 2001).
ADSORBENTS TESTED
Arsenic can be removed by adsorption onto many adsorbent materials whose potential and
suitability of application depend on a number of factors, such as removal efficiency, longevity,
sensitivity to water quality parameters, costs, etc. This paper will review general characteristics
and performance of the materials that have been tested world-wide. In addition, suggestions for
selection criteria employed for screening of the materials will be provided. Two summary tables
have been prepared and are cited from the text in Chapter 2: Table 2.1. Adsorbents tested: description, water quality parameters and references; and Table 2.2. Batch Isotherm Studies: reported
adsorption capacities and protocols used.
Amy et al (2000; 2002) presented a brief overview of adsorbents applicable to arsenic
removal, classifying them to three categories: i) conventional (e.g., activated alumina, AA, activated carbon); ii) novel and commercially available (e.g granular ferric hydroxide, GFH); and iii)
novel but not commercially available (e.g., sulphur modified iron, SMI). Chang et al. (2004)
investigated the adsorption potential of six newly developed innovative adsorbents: magnetically
impregnated ion-exchange resins (MIEX); hydrous iron oxide particles (HIOPs); sulfur-modified
iron (SMI), iron oxide coated microsands (IOC-M); activated alumina (AA) and granular ferric
hydroxide (GFH). A detailed description and physico-chemical properties of those adsorbents are
discussed by (Chang et al., 2004). The performance of the adsorbents was compared with an innovative coagulation technique (ballasted flocculation) and immersed membrane technologies
coupled with innovative adsorbents in both synthetic (Milli-Q: carbon and ion free) and natural
waters (Chang et al., 2004).
The adsorption isotherm studies with MQ water were carried out at two different pH
values (pH 5.5 and 7.5). The results revealed that while MIEX and AA were more effective at
lower pH (5.5), HIOPs, GFH and SMI were efficient over a wider pH. When adsorptive capacities
were compared on the weight basis (w/w) MIEX, GFH and HIOPs had superior adsorptive
capacity to SMI and AA, with MIEX having the highest value of 3.78 g/mg for a As(V) equilibrium concentration of 10 g/L. On the other hand, when compared on a surface area basis (w/m2),
the order changed to MIEX > SMI > GFH >AA >HIOPs (Chang et al., 2004).
The adsorption isotherm studies with natural waters showed that there was no significant
difference in the efficiency of the adsorbents, when compared on weight basis (mg/L). The
conventional coagulants (both Al+3 and Fe+3) were equally effective in removing arsenic as innovative adsorbents (Chang et al., 2004). Among innovative adsorbents, HIOPs was more effective
then MIEX, AA and IOC-M, which was in discrepancy with a previous finding of adsorptive
capacities carried out in MQ water. The authors concluded that adsorptive capacities of both
MIEX and AA were adversely affected by the presence of various anions in natural waters. In
addition, they stated that although ferric chloride addition was more effective in arsenic removal
then any of investigated adsorbents, the later one have a distinguished advantage in arsenic
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removal applications due to the fact that they can be easily separated and regenerated (Chang
et al., 2004).
Driehaus et al. (1998) investigated the potential of the granular ferric hydroxide (GFH) for
arsenic removal from natural waters in Germany. They conducted batch studies at five different
pH values (between 5 and 9), with shaking provided for 96 h. The adsorption density was calculated from the arsenic residual concentrations (10 and 40 g/g versus 0.13 and 0.5 mol/L) and
the known initial concentrations of As (V) and GFH. As (V) adsorption was tested both in model
systems (synthetic water with no competing anions) and natural waters.
For the adsorption tests in natural waters, the initial As(V) concentration was 1.3 mol/L
(10 g /L) resulting in a molar ratio of phosphate to arsenate of nearly 5. The adsorption density
in natural water represented only 1020% of that in model systems. In addition, fixed bed
adsorber tests, consisting of two in-line columns were performed with natural waters. The height
of the columns was 0.12 m and the filtration rate 610 m/h. The GFH was screened to a grain
size of 0.20.4 mm and tap water was spiked with arsenate to a concentration of 100180 g/L.
The average amount of As (V) sorbed to GFH was 8.4 g/kg (which was in accordance with the
batch tests), after 34000 bed volumes were treated (Driehaus et al., 1998). The authors
concluded that GFH is an effective adsorbent for arsenate removal. The adsorption density in
model systems without competing water constituents was in the range of 1mmol As/g Fe at an
As(V) equilibrium concentration of 10 g/L and a pH of 7. However, the adsorption density
decreased with increasing pH and phosphate content. The adsorption density in natural waters
was only 0.10.2 mmol As/g Fe, depending on the pH and the amount of phosphate present in the
water. The specific capacity of fixed bed reactors with GFH depended on pH, phosphate content,
and on the raw water concentration of arsenate. It has been demonstrated that more then 50 000
bed volumes could be treated at filtration rates up to 15 m/h, which corresponds to lifetimes of
GFH of at least several months. Pal (2001) showed that the arsenate adsorption density on GFH is
very close to that of freshly prepared ferric hydroxide. He concluded that GFH can be applied
successfully over the pH range between 5.5 to 9. The author also stated that several As removal
plants using GFH in fixed bed reactors are being successfully operated in Germany and the UK. In
addition, the research results revealed that GFH is capable of removing As from an initial concentration of 5 mg/L to a level much below the permissible limit of 0.01 mg/L (Pal, 2001).
Selvin et al. (2001) presented further developments of granular ferric hydroxide media by
Severn Trent Company (UK). The adsorptive and hydraulic properties of a number of new variants of GFH were referred to as Ap, Bg and Cg (characteristics not presented). An experimental
feed As concentration of 20 g/L was supplied to 1 L of media at an empty bed contact time
(EBCT) of 45 seconds. The average As outlet concentration was 10 g/L, demonstrating As
removal of 50% (for 100,000 bed volumes). Of the four investigated materials, Cg demonstrated
the strongest potential for As removal (As outlet concentrations 05 g/L, for 120,000 bed
volumes, rising to 10 g/L between 120 and 150 000 bed volumes). In the hydraulic properties
tests, Cg showed again a superior performance when compared to other variants of GFH (Selvin
et al., 2001).
The potential of ferrihydrite (FH) for arsenic removal has been recognised for three
decades (Thirunavukkarasu et al., 2001; Robins et al., 2001, Jain et al., 1999; Raven 1998;
Gulledge and OConnor, 1973). Studies carried out by Waychunas et al. (1993; 1995) showed that
at pH > 7, As (V) was adsorbed to ferrihydrite as a strongly bonded inner-sphere complex with
either monodentate or bidentate attachment. Robins et al. (2001) reported that monodentate
attachment predominates at pH values of 45. This result is in discrepancy with the findings by
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Jain et al. (1999) who investigated surface charge reduction and net OH- release stoichiometry in
As (III and V) adsorption on ferrihydrite. They compared the experimentally observed surface
charge reduction and net optimal OH- release stoichiometry with the theoretical stoichiometry and
provided evidence that a monodentate bonding mechanism might play an increasing role during
As (V) adsorption on FH with increasing pH (at pH > 8). Adsorption of As (III) was reported to
occur at pH 89 (Nishimura and Umetsu, 2000).
Raven (1998) tested FH for As (III) and As (V) removal from synthetic waters, at two
different pH values (4.6 and 9.2). The initial As (arsenite or arsenate) solution concentrations
used in their experiments ranged from 0.26726.7 mmol/L (202000 mg/L), corresponding to
013.3 molAs/kg ferrihydrite. The results revealed that at high concentrations, the amount of
arsenite adsorbed on ferrihydrite was generally higher than the amount of arsenite. At lower pH
(4.6) the amounts of adsorbed arsenate and arsenite were equal only at low initial As concentration (less then 1 molAs/ kg ferrihydrite). At high pH (9.2), more arsenite was adsorbed even at
the lowest initial As concentrations. The adsorption maxima for arsenate on ferrihydrite corresponded to approximately 0.25 and 0.16 molAs/molFe at pH 4.6 and pH 9.2, respectively (Raven
1998). In contrast to arsenate, the maximum adsorption capacity of ferrihydrite for arsenite was
not reached even for initial As concentrations as high as 13.3 molAs/ kgF and the highest
observed adsorption density was approximately 0.60 molAs/ kgFe, regardless of the pH value.
Maximum adsorption densities for arsenate reported in this study (0.25 and 0.11 molAs/molFe)
are in accordance with the values reported by other researchers (Fuller et al., 1993; Ferguson
and Anderson, 1974). However, in their study of As (III) and As (V) adsorption onto amorphous
iron hydroxide, Pierce and Moore (1982) obtained significantly different values, with adsorption maxima as high as 5.0 molAs/ molFe for both arsenite and arsenate, which was attributed to
the extremely high molar ratio of As to Fe in the solution (0.014-0.29) as opposed to 0.028 and
0.083 molAs/ molFe, employed by Raven (1998). Wong et al. (1995) also showed that at molar
ratios of arsenic to iron greater then 3, a greater As (V) removal is achieved. The effect of
Fe/As molar ratio in solution on arsenic removal was reported by several researchers (Krause
and Ettel, 1988; Papassiopi et al., 1996).
Thirunavukkarasu et al. (2001) conducted a batch study using various amounts of FH
adsorbent and mixing it with raw water of high As concentration (325 g/L) for 5 h at 125 rpm.
The adsorption capacity of FH from their experiment was estimated at 285 g/g.In their review of
adsorption of arsenic on FH, Robins et al. (2001) pointed out that while extensive research has
been conducted over the years to investigate the potential of this material for As removal, very
little attention was given to the possibility of modifying the FH structure to improve its adsorptive
capacity. Therefore, they investigated the coprecipitation of both Al (III) and Mn(III) with Fe (III)
to form an aluminic ferrihydrite and a manganic ferrihydrite, respectively. They reported that both
materials showed considerably better capacity for arsenic adsorption.
The adsorption of As on geothite (-FeOOH), a product formed from the crystallization of
ferryhidrite, was investigated by Belzile and Tessier (1990), Matis (1999), Matis et al. (1997),
Xiaohua and Harvey (1996; 1998), Manning et al. (1998) and OReilly et al. (2001). Belzile and
Tessier (1990) compared the data (over the pH range 48) of Pierce and Moore (1980) for adsorption on ferrihydrite with existing data for adsorption on geothite and concluded that the adsorption
on ferrihydrite was superior to adsorption by geothite. Xiaohua and Harvey (1996) investigated
As (V) and As (III) bonding structures using Transmission-Fourier Transform Infrared (T-FTIR)
and Attenuated Total Reflectance FTIR (ATR-FTIR) spectroscopy. They showed that most of
the arsenate and arsenite oxyanions replaced two singly coordinated surface OH groups (A-type)
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to form binuclear bridging complexes: Fe-O-AsO, (OH)-O-Fe, and Fe-O-As(OH)-O-Fe. In addition, the authors used a sequential extraction method to evaluate different bonding strengths. They
concluded that a strong chemical extraction was necessary to remove 75-80% of adsorbed arsenite
or arsenate from geothite (Xiaohua and Harvey 1996). Xiaohua and Harvey (1998) conducted
another study, where both indirect (FTIR) and direct (X-ray Absorption Near Edge Structure
(XANES) spectroscopic techniques were applied to examine adsorption and oxidation of As(III)
on geothite. They showed that after 20 days of experimentation, more then 20% of adsorbed As
(III) was oxidized to As (V). Surface structures and stability of As (III) on geothite was also investigated by Manning et al. (1998), using a combination of standard batch techniques and X-ray
absorption spectroscopy (XAS). For adsorption isotherm studies, 20 mL volumes of a 2.5 g L-1
-FeOOH suspension containing 133 mM or 266 mM As (III) were equilibrated for 16 h. The
suspension pH was adjusted from 3-11 using not more then 0.25 mL of 0.1 M NaOH or HCl.
Experimental As (III) and As (V) adsorption envelopes on -FeOOH were compared with the
surface complexation model using the FITEQL computer program. The As (V) species displayed
a distinct behavior from As (III), with the adsorption maximum at low pH (3), decreasing rapidly
with an increase in pH. The authors postulated that this difference might have occurred due to
differences in the structure of the As (III) and As (V) surface complexes, as it has been reported
earlier that while As (III) forms a single bidentate binuclear surface structure, As (V) forms at
least two complexes (Waychunas et al., 1993; Fendorf et al., 1997).
Matis (1999) investigated sorption of As (V) by geothite particles and their flocculation.
The main parameters affecting the sorption process were studied, such are the ratios of geothite
and As (V), pH, contact time, temperature and ionic strength variations. The adsorption parameters were also determined (Table 2.2). OReilly et al. (2001) tested the effects of residence time on
arsenate adsorption/desorption mechanisms on geothite. A batch sorption experiment was
conducted employing an initial As concentration ranging from 0-3 mM (as sodium arsenate) for
24 h at 298 K on a reciprocating shaker. All solutions were pre-equilibrated at pH 6 and the pH
was also measured at the end of experiment. The experimental conditions and shape of the
isotherm obtained were similar to those found for arsenate on hydrous iron oxide and ferrihydrite,
reported by Hsia et al. (1994) and Raven (1998). an adsorption capacity of 2.1 mol/m2 was
achieved. Desorption studies were conducted for times ranging from 45 min to 7 months. Data
from the sorption kinetics study showed that initial arsenate sorption at pH 6 was very rapid, with
over 93% being sorbed within a 24-h period, followed by the long period of a plateau phase.
In India, Singh et al. (1988) studied the effect of different concentrations, pH and temperature on As (III) removal from aqueous solutions by haematite. Five different As (III) concentrations were used, ranging from 13.34133.49 mol/L (110 mg/L). The maximum adsorption
capacity (2.63 mol/g) (0.20 gl/mg), calculated from the Langmuir equation, was achieved at
20C, for pH 7.0. A two fold increase in temperature (from 20 to 40C resulted in 1.2 fold
decrease in adsorption capacity (Singh et al., 1988). pH had no significant effect on the amount of
As (III) adsorbed by haematite over a lower pH range (2.85.0). However, the adsorption capacity
started to increase abruptly at pH = 5, reaching a maximum at pH 7.0. Further increase in pH
resulted in a sharp decrease of adsorption up to pH 11.
The efficiency of iron oxide coated sand (IOCS) for As removal from drinking water was
investigated by Thirunavukkarasu et al. (2001), Khaodhiar et al. (2000), Lombi et al. (1999), and
Chang et al. (2004).
Lombi et al. (1999) studied the kinetics and reversibility of As sorption on IOCS and soils
with different chemical and physical characteristics. Soils and IOCS were equilibrated for five
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different periods of time, with solutions containing As (III) and/or As (V). Samples of materials
were sequentially extracted after 1, 10 and 30 days to access the effect of aging on the binding
forms of As. Khaodhiar et al. (2000) found that arsenate species were strongly adsorbed on IOCS,
forming inner-sphere surface complexes. They also studied the effect of the presence of copper
and/or chromate in the solution on As removal and reported neither had an effect on the extent of
adsorption. However, the presence of As (V) significantly decreased chromate adsorption, which
was attributed to the competition for adsorption sites and electrostatic effects.
Thirunavukkarasu et al. (2002) tested iron oxide coated sand (IOCS) and FH for arsenic
removal from a natural water in Canada. Batch tests were conducted using various amounts of the
adsorbents and mixing them with raw water of high As concentration (325 g/L) for 5 h at
125 rpm. The adsorption capacities of IOCS and FH were estimated at 18.3 g/g and 285 g/g,
respectively, with FH having a significantly higher affinity (a 15.6 fold higher As adsorption
capacity then IOCS). This difference was attributed to the differences in the specific areas of those
two adsorbents (5.1 and 141 m2/g, respectively). Speciation studies were also conducted with
natural water containing arsenic, and particulate and soluble As concentrations were determined.
The results revealed that particulate and soluble As contributed to 11.4 and 88.6% of total As
present in the natural water, respectively. In the case of soluble arsenic, As (III) and As (V) were
47.3 and 52.7%, respectively.
Several other iron based adsorbents were tested for their capacity to remove As (III) and
As (V). Pierce and Moore (1982) studied amorphous iron hydroxide; Zouboulis et al. (1993) and
Han and Fyfe (2000) studied iron-sulfide minerals, pyrite and pyrhotite. Lackovic et al. (2000),
Krishna et al. (2001) and Ramaswami et al. (2001) investigated the use of zero-valent iron. The
adsorbing capacities of these materials and experimental conditions employed are presented in
Tables 2.1 and 2.2, respectively.
Zeng (2001) developed a method for preparation of a granulated iron (III) based binary
oxide adsorbent, which consisted mainly of amorphous hydrous ferric oxide (FeOOH) with silica
as a binding agent. The key step in the method was the simultaneous generation of hydrous ferric
oxide (FeOOH) and silica in one reactor and resulted in the formation of Fe-Si complexes. The
author concluded that the addition of silica enhanced the granulated adsorbent strength but
reduced the As adsorption capacity. A Si/Fe molar ratio of approximately 0.33 was found optimal
for the balance of adsorbent strength and its adsorption capacity.
Krishna et al. (2001) developed an approach based on the preoxidation of As (III) using
hydrogen peroxide and the subsequent removal of total As using ferric (oxy) hydroxide coprecipitation. All experiments were performed at the natural pH of the water (6.8 7.1). It was
found that the addition of Fe (II) salt and H2O2 was capable of removing As to 20 g/L levels.
Given that the levels of residual peroxide have to be acceptable for drinking water purposes, the
authors carried out a set of optimisation experiments using lower amounts of reagents (ferrous
ammonium sulfate + H2O2), which also resulted in high residual peroxide levels. In order to
improve the efficiency of the treatment, the authors developed a two stage approach, where addition of Fentons reagent was used as a preliminary step, followed by passing the water through zero
valent iron. This treatment, employing Fe(II) ammonium sulphate + H2O2 per litre for 10 min
followed by passing the sample through iron scrap (at a relatively high flow rate of 150 ml/min)
and filtering through sand, consistently yielded waters with arsenic concentrations of less then
10 ppb from a starting initial concentration of 2.5 mg/L of As (III). The scaling up of this procedure is currently being investigated by the authors.
107
Lackovic et al. (2000) investigated the As removal efficiency by zero-valent iron in laboratory and field column studies. The results from the laboratory experiments showed that zerovalent iron was twice as effective in removing arsenate (669 g As/Fe) than arsenite (298 g
As/Fe) after 1850 pore volumes. Arsenic removal efficiencies of greater then 95% were observed
in both laboratory and columns studies. The high removal efficiency was related to the surface
area of the type of iron used. Spectroscopic analyses (SEM/EDX and XPS) provided evidence
that surface precipitation was a predominant removal mechanism. The overall conclusion was that
the use of iron fillings has a great potential for arsenic removal. Apart from the high efficiency, the
material is also cost-effective ($250-400 per ton) and versatile (both in situ, large-scale units, and
home-unit applications).
Ramaswami et al. (2001) developed a batch-mixed treatment to test the appropriateness of
zero-valent iron as a point-of use technology for arsenic removal in Bangladesh. A very high As
removal efficiency (>93%) was achieved even for an initial As concentration as high as
2000 g/L. These results are in accordance with those reported by Lackovic et al. (2000). The
authors also provided evidence for the regenerative capacity of the iron filings.
Chakravarty et al. (2002) studied a low cost ferruginous managanese ore (FMO) for As
removal from groundwater. The results demonstrated that FMO could remove both As (III) and As
(V) without any pre-treatment, the adsorption on As (III) being higher then for As (V). The
optimal pH for As removal was 2-8 and once adsorbed, As did not desorb even when pH conditions were varied. The presence of bivalent cations (Ni2+, Co2+ and Mg2+) enhanced the adsorption capacity of FMO. As was removed from six groundwater samples with As concentrations
ranging from 0.04-0.18 pm, with 100% efficiency.
The efficiency of manganese greensand (MGS) for Arsenic removal from drinking water
was tested by Subramanian et al. (1997), Viraraghavan et al., (1999) and Thirunavukkarasu et al.
(2001). Subramanian et al. (1997) conducted laboratory scale batch and column studies to assess
the effectiveness of KMnO4 oxidation followed by manganese greensand filtration for As removal
below 25 g/L. The physico-chemical characteristics of greensand, a zeolite-type glauconite
mineral, were described previously (Subramanian et al., 1997). The capacity of MGS for As
adsorption was tested by adding various masses of material (ranging from 2.5 to 30 g) to 250 mL
beakers containing 100 mL of tap water supplemented with 200 g/L As (III). The samples were
shaken at 30 rpm for 24 h, decanted and analysed for residual As (III), As (V), As (total) and Mn.
The results showed that adsorption capacity of MGS reached a plateau after 15 g of the adsorbent
was added. The highest efficiency was only 62%, producing an effluent As concentration of
75 g/L, which was 3 times higher then the value stated in objectives.
Column studies consisted of two columns (diameter 10 cm; height 180 cm), fed with the
tap water containing 200 g/L As (III) at a filtration rate of 1-1.5 L/min/m2, resulting in an
average residence time (empty bed contact time, EBCT) of 5.64 min.. The effect of Fe/As ratio
was tested in a separate experiment by adding Fe(II) in the form of FeSO46H2O to the influent to
produce Fe/As molar ratios of 10 [200 g/L As (III) and 2 mg/L Fe(II)], 20 [100 g/L As (III) and
2 mg/L Fe(II)] and 7 [50 g/L As (III) and 0.35 mg/L Fe(II)]. The results from column studies
showed that an As limiting concentration of 25 g/L was reached after only 3 h of operation,
corresponding to a throughput volume of 144 L. Testing was continued for another 21 h, before
MGS filter was backwashed (1,003 L). As removal efficiency was found to be 41.3%.
The investigation of the effect of Fe/As molar ratio showed, that at a Fe/As molar ratio of
10, and a KMnO4 dosage of 2.5 mg/L (as Mn) (for oxidation As (III) to As (II) and Fe(II) to Fe
(III)), an As removal efficiency of 89% was achieved. After operating a column for additional 30 h
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(volume passed during this time was approximately 1,440 L), the overall As removal efficiency
was still high (83%). A Fe/As ratio of 10 contributed to a two-fold increase in As removal efficiency. As (III) concentration in the filtrate was low (313.4 g/L, indicating almost quantitative
oxidation to As (V) by KMnO4 and by the hydrated MnO2coating of MGS. Similar studies were
conducted at Fe/As = 20 and Fe/As = 7. Overall, the highest As removal efficiency (81.8%) was
achieved at the highest Fe/As ratio, producing an effluent consistently below 10 g/L.
The authors concluded that the addition of Fe at the molar ratio of 20 had the greatest
performance in As (III) removal. This finding was in agreement with the work reported by other
authors (Lauf, 1996; Magyar, 1992), who showed that MGS following KMnO4 oxidation was
capable of removing As (III) from groundwater supplies, at >90% efficiency. Oxidation, adsorption and ion exchange represented the major removal mechanisms. Mn (IV) oxides coated on the
greensand surface provide a redox active surface and serve as effective oxidants for As (III). The
finding of this study, combined with the work reported by Scott and Morgan (1995) suggest that
mechanisms of As removal involve four major steps: i) formation of an inner sphere complex
where As (III) displaces the surface bound OH- and H2O species from the hydrated manganese
oxide via ligand substitution and then binds directly to the oxide surface; ii) transfer of two electrons from As (III) to Mn (IV) of the oxide [i.e., surface oxidation of As (III) to As (V), and
reduction of Mn (IV) to Mn (II)]; iii) adsorption of As (V) on the surface, and iv) release of the
reduced Mn.
Following this study, Viraraghavan et al. (1999) tested the effect of continuous vs. intermittent loading on the filter regeneration, reproducing the same experimental conditions described
in the previous study Subramanian et al. (1997). The results showed that continuous regeneration
gave better performance (Viraraghavan et al. 1999). A comparison of the MGS performance with
IOCS and ion exchange resins activated with ferric ions (IX) was also made. The results revealed
that, for the same initial As (III) concentration (200 g/L), MGS with Fe addition at the ratio 20:1
achieved the highest As removal performance (83.3%) followed by IOCS (49.7%) and IX
(37.6%).
Adsorption studies were conducted to test manganese dioxide for As removal. Physicochemical characteristics of the material are presented in Table 2.2. The effect of various anions
(nitrate, suphate, acetate, oxalate, sulphite, citrate, tartrate, phosphate and carbonate) and cations
(Mg2=, Pb2+, Ni2+, Ag=, Ca2+, Ba2+, Sr2+, Li+, Al3=, Zn2+ on the adsorption of As on MnO2 was
investigated. The anions were added in the form of their sodium salts, and the cations as their
nitrate salts at concentrations of ~102 mol/L. The results revealed that in general, the presence of
other anions in the solution had no significant effect on the distribution coefficient (Kd) of As on
MnO2. The only significant change in Kd value occurred in the presence of tartrate, phosphate and
carbonate ions which reduced adsorption by 90.5, 47.7 and 28.3%, respectively. In a case of
cationic species, the addition of Mg2+, Pb2+, Ni2+, Ag+, Ca2+ led to a significant increase in As
adsorption, while it was decreased in the presence of Zn2+ .
Kinetics of As adsorption on MnO2 was investigated using the equations established by
Weber and Morris (1963) as well as Langmuir and Freundlich equations (Barrow, 1973). The
sorption capacity was estimated at 1.02 mmol/g, with a binding energy of 15.5 kJ/mol.
Some researchers have studied removal of As from groundwater using MnO2.coated sand
(MDCS), which prepared by forming manganese dioxide ( -MnO2) by the oxidation of manganese ion with permanganate in the presence of sand. Both batch and column tests were carried
out. Batch arsenic removal kinetics tests were conducted by mixing ground water spiked with
1.0 mg/L As (0.5 mg As (III); 0.5 mg of As (V)) with MDCS (10 g/L). Column tests were
109
operated in a downflow direction, using 182 g (125 mL) of the MDCS in a 200 mm ID glass
column (bed depth 400 mm; porosity 0.36) and a flow rate of 1.7 mL/min (empty bed contact time,
EBCT = 74 min). The initial As concentration was the same as in the batch tests. The column was
run until the effluent As concentration exceeded 0.01 mg As/L. The MDCS was then regenerated in
situ by backwashing with 2 L of a 0.2 N sodium hydroxide solution. In addition, a home arsenic
removal unit was installed and its performance in removing As evaluated. The unit was comprised
of two chambers, with the top one (200 mm ID 380 mm) containing 6 kg of the MDCS medium
up to the height of 125 mm and serving as a raw water reservoir. The bottom chamber (200 ID
280 mm) served as storage for the treated water. The overall conclusion was that manganese
dioxide-coated send (MDCS) has promise as a medium for use in small systems or home-treatment
units. Thomson et al. (1998) investigated the use of manganese oxyhydroxide coated sand (MOCS)
as a filter media for As removal, both in the presence and absence of a strong oxidizing agent
(NaOCl). The results showed that surface charge of the MnOx coated sand and the charge of
dissolved species were the major parameters influencing the extent of As (and other investigated
contaminants, uranium and copper) removal. The authors concluded that as MnOx coating is negatively charged in the presence of OCl, with a pHpzc of 2.87, anionic As(V) species are not attracted
to the media at pH above that value. Overall, the results showed that while MnOx coated sand was
efficient in removing cationic species (copper), but exhibited poor performance in removing As. In
the absence of HOCl, only 0.0016 mg As/mg MnOx was removed. The flow rate, pH and the presence of an oxidant had the greatest effect on the results, while soluble Mn concentration did not
eafect the removal. It was concluded that MOCS was not efficient for As removal.
The performance of activated alumina, bauxite, and carbon for As removal are well documented in the literature; these materials belong to the group of convential adsorbents commonly
used in the past. However, the study carried out by Gupta and Chen (1978) is noteworthy as it
tested the effect of a number of water quality parameters (pH, salinity, silica) and type of adsorbent on As (III) and As (V) adsorption. The experiments were carried out using freshwater,
seawater, seawater diluted 10 times and a 0.67 M NaCl solution, 2g/L of activated alumina and
3g/L of activated carbon were mixed in 100 ml of solution. Among the investigated adsorbents,
activated alumina was most efficient in removing As (V). Within the first 10 minutes in fresh
water, 50% and 40% of 53.4 M As (V) was removed by activated alumina (2 g/L) and activated
bauxite (2g/L), respectively, while activated carbon (3 g/L) removed only 23% of 26.4 M As (V).
Rates of As (III) adsorption on activated alumina and bauxite were much slower than those of As
(V). Within the first 10 minutes, only 6% of 12.4 M As (III) and 2% 12.6 M As (III) were
removed, respectively.
An increase in salinity had a negative effect on the rate of adsorption and arsenic removal.
The adsorption capacity for As (V) on activated alumina decreased 5-fold (from 4.11 (freshwater)
to 0.81 (seawater) mg As(V)/g of adsorbent) with an increase in salinity.
pH had the most prominent effect on arsenic adsorption. As (V) was effectively adsorbed
by activated alumina and bauxite over the pH range 47, and then started to decrease with a
further increase in pH values above 7. Activated carbon adsorbed As (V) most efficiently in the pH
range of 35. For As(III) there was no significant difference in adsorption rate over the pH range
49; however further increase in pH values resulted in a sharp decrease of the adsorption capacity.
The effect of the initial As (III) and As (V) concentrations was significant in a case of As
(III), while As (V) removal was only slightly affected.
As removal by aluminium and ferric hydroxides through coagulation, sedimentation and
filtration also belongs to the group of conventional technologies, which is very well documented in
110
the general As literature. A study carried out by Gulledge and OConnor (1973) is presented as an
example of the technology efficiency. The results from this study showed that arsenic removal was
influenced by pH and coagulant dose. Adsorption on ferric hydroxides was more efficient then on
aluminium hydroxides. However, in both cases, increasing the coagulant dose resulted in an increase
of As(V) adsorption. At lower pH values (57.5), there was no significant difference in the amount
of As(V) adsorbed by any of the adsorbents. However, further increase in pH (8 and above) resulted
in a sharp decrease of As(V) on both aluminium and ferric hydroxides. The authors postulated that a
decrease in As(V) removal occurred either due to the change in the ionic form of As(V) (from
H2AsO4 to HAsO42) or the competition between hydroxyl ion and the exchange sites on the ferric
and aluminium hydroxide precipitates (Gulledge and OConnor, 1973).
Twidwell et al. (1999) reviewed the use of aluminium hydroxide/alum for arsenic removal.
They reported that arsenic adsorption was 3040 fold greater on amorphous aluminium hydroxide
(112 g/kg) than on the more crystalline gibbsite (2.6 g/kg) for the pH range 410. A number of
researchers demonstrated the efficiency of activated alumina in removing arsenic from drinking
water. The overall conclusion from these studies was that activated alumina is competitive in its efficiency for arsenate removal and relatively cheap when compared to other adsorbents. It has been
shown that activated alum was very efficient in removing arsenic for point-of-use water treatment. (a
pilot study showed arsenic [0.15 mg/L] and fluoride removal and estimated treatment effective cost
at $0.19 cents/1,000 gal (3,785 L). Arsenate adsorption by aluminium hydroxide or by activated
alum is a function of solution pH (optimal removal is achieved at pH 47).
Norton et al. (2001) investigated throw-away iron and aluminum sorbents (as emergent
adsorbing media) versus conventional activated alumina. The selection of emergent adsorbents
was based on several criteria: i) the media should exhibit high adsorption capacity at neutral pH;
ii) the media should be easily disposable without the requirement for an on-site regeneration;
iii) once saturated, the media should be non-hazardous and suitable for disposal in a municipal
landfill; iv) the media should be NSF 61 certified for drinking water applications. The media
selected for investigation were: conventional activated alumina, iron-modified activated alumina,
high porosity AA and granular ferric hydroxide (GFH). The objective of their study was to evaluate the feasibility of using the selected adsorbents to treat groundwater at two sites (Tuscon and
Scottsdale) in the USA, to meet an arsenic MCL of 10 ppb. Four columns containing 25 gallons
(95 L) were fed with 5 gallons per minute (19 L/min) of raw water each, with the exception of
GFH media, which was fed at 2 gpm (7.6 L/min) and an EBCT of 12.5 minutes (due to problems
experienced with head loss). The raw water pH (after chlorination) was between 8.7 and 9.2.
The results showed that initial As breakthrough for all of the investigated media occurred
at 1,000 bed volumes. The effluent As concentrations were 0.0150.06 mg/L compared with the
influent concentrations (0.0310.041 mg/L). Poor As removal by AA was expected since the
optimum water pH for this media is 5.5. However, the emerging aluminium based media showed
promising removal of As at pH as high as 8 to 8.5.
The GFH media was able to remove As with no pH adjustment. For the first 2,500 bed
volumes, there were no detectable As levels with a raw water pH of 9. However, from 2,000
4,000 bed volumes treated, the effluent As concentrations increased at or below 0.01 mg/L. At a
raw water pH of 6.6, the As levels were again non-detectable.
The effects of Si and fluoride concentrations were also studied. It was found that while
all media were successful in removing Si, the breakthrough of fluoride occurred sooner than it
was observed for Si. All four columns reached complete breakthrough of fluoride after 2000
volumes treated.
111
The authors concluded that at ambient pH conditions (8.79.3) GFH was the only media
that demonstrated high As removal efficiency. High Si concentrations could decrease its removal
capability, but when raw water pH is lowered to 6.5, the Si interference may be diminished. The
relatively poor performance of the alumina based media was attributed to the ambient pH condition and high Si concentration of the raw water.
A number of additional alternative adsorbing materials have been tested in different
parts of the world: Manju et al. (1998) tested the efficiency of coconut husk carbon (CHC) and
amine modified coconut coir (AMCC),while Lee et al. (1999) studied quaternized rice husk
(QRH) as a substitute for activated carbon (AC) which is not readily available and therefore not
suitable for use in developing countries; Diamadopoulos et al. (1993) tested the efficiency of fly
ash, Altundogan et al. (2000) studied adsorption on red mud, Ohki et al. (1996) and Xu et al.
(1998) investigated removal by aluminiumloaded coral limestone and aluminium loaded
shirasu-zeolites, Elizalde-Gonzalez et al. (2001) studied natural zeolites, volcanic stone and
cactaceous powder, Manning (1997) tested adsorbing potential of three California soils.
Dikshit et al. (2000) investigated As adsorption on kimberlite tailings, the mineral waste from
diamond mining. The summary of the performance of these materials and experimental conditions are presented in Tables 2.1 and 2.2, respectively.
Saha et al. (2001) performed a comprehensive study of arsenic removal efficiency of
different adsorbent materials to select the most appropriate adsorbent. They conducted batch
experiments on 18 different materials (kimberlite tailing, water hyacinth, wood characoal,
banana pith, coal fly ash, spent tea leaf, mushroom, saw dust, rice husk ash, sand, activated
carbon, bauxite, hematite, laterite, iron oxide coated sand (IOCS), actrivated alumina (AA),
CalSiCo, and hydrous granular ferric oxide (GFO). As (III) removal efficiency was <50% for
majority of tested materials (15). Rice husk ash had the worst performance (removing only 5%),
followed by banana pith, sand, wood charcoal and kimberlite tailing (1225%). The poor performance by kimberlite tailing reported in this study is in discrepancy with the earlier results
reported by the same authors (Dikshit et al., 2000). In the later study, they reported an adsorption
capacity of 0.27 mg/g adsorbent and removal efficiency as high as 9094%.
Similarly, overal As (V) removal was also poor, and only half of the investigated materials
achieved an efficiency higher then 50%. Overall, hydrous granular ferric oxide (GFH) had the
highest As (III) and As(V) removal efficiency (92 and 99%, respectively), followed by CalSiCo
(90 and 98%), activated alumina (90 and 96%), iron oxide coated sand (72 and 90%). Laterite and
bauxite also had relatively high removal efficiency for As (V) removal (70 and 80%, respectively)
but were less efficient in removing As (III). An interesting observation was the efficiency of water
hyacinth (widely available in Bangladesh and India): 70% for As (V), but 45% for As (III).
Based on the preliminary results from batch adsorption isotherms, four materials (IOCS,
CalSiCo, GFH and AA) were selected for furter studies. Apart from kinetic and isotherm studies,
the effect of different parameters were studied: pH, adsorbent dose, presence of chloride, sulfate,
nitrate, chromate, calcium, magnesium and iron as well as the effect of anionic species: fluoride
and phosphate. Column studies were also conducted (glass columns, 15 mm diameter, 220 mm
bed depth, geometric mean size of the adsorbents 0.2 mm) with tap water spiked with 1 mg/L of
arsenite and 1mg/L of arsenate, separately. The flow rate was maintained at 10 ml/min. Finally,
desorption and regeneration studies were also carried out to investigate the potential of reuse of
spent adsorbent.
It was found that all of the four materials were very effective in removing As (V): 90, 96,
98 and 99% for IOCS, AA, CalSiCo and GFH, respectively, at an initial As (V) concentration of
112
1 mg/L and aprroximately 85% for As (III) for an initial concentration of 1 mg/L at neutral pH.
AA, CalSiCo and GFH could be used for the selective removal of As over other ions, such as: Cl,
SO42, PO43, NO3, F, CrO42, Ca2+, Mg2+ and Fe2+. As removal was pH dependent; the highest
removal efficiency for As (V) was achieved at pH 7.2, and for As (III) above 9 for CalSiCo. For
other materials, pH 7.17.5 gave the best performance. The removal of As (V) was more effective
than As (III). Removal efficiency decreased in the presence of phosphate (more then 10 mg/L),
fluoride (more then 2 mg/L), and EDTA (more then 0.01 mol/L) but the presence of nitrate,
sulphate, chloride, chromate, calcium, magnesium and iron had no significant effect on As
removal.
Spent adsorbent could be regenerated with 15% H2O2 in 0.2 M HNO3 for CalSiCo and 1N
NaOH for IOCS, AA and GFH (Saha et al., 2001).
Lin and Puls (1999) discussed adsorption, desorption and oxidation of As affected by clay
minerals and aging process. Three types of clay minerals were studied: the 1:1 layer
clays [halloysite (IN), sedimentary M-kaolinite, and whethered EPK-kaolinite]; the 2:1 layer clays
[illite (MT) and illite/montmorillonite (MT)]; the 2:1:1 layer clay [chlorite (CA)]. The results
showed that halloysite (IN) and the chlorite (CA) had superior As (V) adsorption (at pH 5.5 and
initial As concentration of 35 M, 71.6 and 60.9 g/g As (V) was adsorbed, respectively) while
M-kaolinite, EPK kaolinite, ilite (MT) and ilite/ montmorillonite (MT) had moderate As (V)
adsorption of only 2 g/g, While an increase in pH from 5.5 to 7.5 had no effect on the adsorption
by halloysite (IN) and the chlorite (CA), its effect became apparent in M-kaolinite, EPK kaolinite,
ilite (MT) and ilite/ montmorillonite (MT), all of which experienced a decrease in As (V) adsorption. In general, the adsorption of As (III) by clay minerals was much lower then for As (V). Additional similarity observed was that the adsorption of As (III) increased at pH 7.5. The long-term
contact time of clay minerals with As (aging process) had a significant effect on desorption.
Manning and Goldberg (1997) investigated adsorption and stability of As (III) at the clay
mineral-water interface. In order to access differences in reactivity and stability of As (III) and As
(V), As (III) adsorption on kaolinite, illite, montmorillonite and amorphous aluminium hydroxide
(am-Al(OH)2) was firstly studied as a function of pH and ionic strength and then was compared to
As (V) adsorption. In addition, surface complexation modelling was applied to describe the mechanisms involved in adsorption. Batch tests were conducted by shaking clay suspensions in 40 mL
polycarbonate centrifuge tubes containing 500 mg of clay in 20 mL of 0.4 M As (III) or As (V)
for 16 h. Experiments with am- Al(OH)2 suspensions contained 50 mg of solid in 20 ml of 0.4 M
As (III). Ionic strength was maintained using 0.005, 0.05 or 0.1 M NaCl background electrolyte.
Differences between As (III) adsorption on the materials due to variations in ionic strength
were typically less then 10% between pH 4 and pH 9, except for montmorillonite. General similarities between the materials include low As (III) adsorption at low pH and maximum As (III)
adsorption between pH 7.5 and pH 9.5. Illite and Al(OH)2 removed the highest proportion of As
(III) from solution (80%) followed by kaolinite (60%).
Desorption studies revealed that As (III) oxidation resulted in measurable surface bound
As (V). The magnitude of As (V) was dependent on the original suspension pH and the mineral.
The authors hypothezed that As (III) was stable in the solution between pH 4 and pH 9, but that
homogeneous oxidation of As (III) to As (V) occurs in solutions at or above pH 9.2. The As (III)
oxidation process results in stronger adsorption of As (V), which could cause a decrease in the
mobility of As in the environment.
Suzuki et al. (2001) investigated adsorption characteristics of arsenic on porous polymers
loaded with monoclinic hydrous zirconium oxide (Zr-resin), while Zhu and Jyo (2001) studied
113
removal of As (V) by zirconium (IV) loaded phosphoric acid chelating resin. Suzuki et al. (2001)
used 0.5 g of Zr-resin in a buffer solution (acetate to adjust the solution of As (V) at pH 4.5 and
ammonia-ammonium chloride to adjust the solution of As (III) at pH 8). The 50-mL glass bottles
were placed on the shaker for 6 days at room temperature of 25C. The adsorption of both As (III)
and As (V) was effective over a wide pH range (39). The effects of coexisting ions (Cl, NO3,
CH3CO2 and SO42, H2PO4, etc) were also investigated and the results showed that only the
presence of H2PO4 and fluoride had a significant effect on the adsorption of As (V). Zr-resin
adsorption capacities for As (III) and As (V) were estimated using a Langmuir equation giving
values of 1.06 and 0.72 mmol/g, respectively. Column studies were also carried out, passing a
buffered As (III) and As (V) solution through the columns packed with 5 g (11.8 mL, i.d. 1.1
12 cm) of the Zr-resin, at a rate of 1 ml/min. Both As (III) and As (V) were well retained on the
column at pH 5 and 9, respectively. Leaking of zirconium was negligible for the whole duration of
the experiment.
Additional experiment was carried out to investigate As (V) removal from tap water,
spiked with 1 ppm As (V). The water was continuously passed through the column at flow rate
2.5 mL/min. The leaking of As (V) was below the Japanese standard allowance of drinking water
(>0.01 ppm) for three weeks. The authors concluded that Zr-resin shows promise for the removal
of low As (V) concentrations from actual tap water.
Zr (IV)-loaded phosphoric acid chelating resin (RGP) described by Zhu and Jyo (2001)
was effective in the removal of As (V) from natural water (including sea water), with a higher
affinity for As (III) than As (V). The performance of this adsorbent was tested in column experiments, at an initial As (V) concentration of 2.5 mmol/L, pH 2 and flow rate of 10 mL/h, for
120 bed volumes. The effect of pH was also studied over a range of pH values (1.14; 2.03; 3,05;
4.03; 7.53 and 8.55). Breakthrough capacities of As (V) were 0.132 mmol/mL of wet resin at
pH 1.14, decreasing to 0.077 mmol/L at pH 8.55 (0.250.44 mmol/g) per unit weight of dry resin.
SELECTION CRITERIA FOR ADSORBING MATERIALS
The general criteria include the cost of the material, the ease of operation and handling,
the cost of transport (if the material is not locally available), the potential of regeneration and
reuse and longevity (estimated life-time of the system) (Amy et al., 2000; Saha et al., 2001; Drizo
et al., 1999).
Drizo et al. (1999; 2000) and Forget (2001) conducted a significant amount of research to
establish selection criteria for adsorptive materials to be used for phosphorus removal from wastewater. The same criteria are applicable for fixed bed adsorbent treatment of arsenic, or any other
pollutant, and therefore will be stated here.
The first criteria in selecting the materials are their physico-chemical properties such are:
elemental composition, specific surface area, porosity, particle size distribution, hydraulic
conductivity, because they all affect the rate of pollutant adsorption and/or pollutant adsorption
capacity (Drizo et al., 1999). The adsorption capacity of candidate materials is then measured in
the laboratory employing pseudo-equlibrium batch experiments, a technique established as a
method of measuring P (phosphorus) retention characteristics of soils and sediments for several
decades (Olsen and Watanabe, 1957; Barrow, 1978; Nair et al., 1984). The adsorption capacity of
materials is estimated by fitting the Langmuir or Freundlich isotherm equations to experimental
data (e.g., Drizo et al., 1999 and all of the references reported in this review). However, it has been
shown recently that using the Langmuir equation with such experimental data can lead to biased
114
and unrealistic estimates of the adsorption parameters and should be used with caution for adsorption studies for fixed bed adsorption applications (Kinniburg, 1986; Drizo et al., 2000; Forget et
al., 2001). Langmuir and Freundlisch equations have been and still are repeatedly used in the estimation of both P and As adsorption capacity of potential media often neglecting very important
facts such as: i) the linear form of the Langmuir equation which enables the calculation of
P adsorption maxima and binding energy only describes adsorption over a limited range of
concentration; ii) the maximum adsorption capacity calculated from the observations at low
concentrations is exceeded at higher concentrations; iii) equations for which the affinity for
adsorption is constant, such as the Langmuir equation, are not consistent with the theoretical
scientific knowledge of the adsorption process; iv) fitting the data to the linear form of the Langmuir equation where concentration/adsorption is plotted as a function of concentration produces
variability and a low correlation coefficient; and v) if the Langmuir equation is used for data
which does not approach the maximum adsorption plateau, the calculated adsorption maximum
could be in error by 50% or more (Veith and Sposito, 1977; Harter, 1984; Kinniburg, 1986; Drizo
et al., 2000).
The problems associated with the lack of uniform methodology for estimation of materials
adsorptive capacities was also confirmed in this review. Even though the performance of 30
different materials have been presented, it was not possible to make a real comparison of the most
efficienct material. The adsorption capacity of any material used for water purification purposes
will depend on the experimental procedure employed. The extent and rate of As adsorption in
batch experiments is affected by a number of parameters: the range of initial As concentrations,
material to solution ratio (in a case of ferryhydrite, the Fe/As molar ratio), the rotational speed of
the shaker, time for equilibration, pH, ionic strength of the solution (Kinniburg et al., 1986; Drizo
et al., 2000). In addition, the presence of other aqueous species (e.g., phosphate, silicate, fluoride,
sulfate and organics) block the adsorption active sites and cause rapid saturation of the medium,
reducing arsenic removal efficiency (Twidwell et al., 1999; Simeonova, 2000; Amy et al., 2000)
A need for establishing a new procedure for P batch experiments which would provide a
more realistic comparison of the materials has been recognised and several criteria for this
purpose were suggested (Drizo et al., 2000; Forget et al., 2001). In addition, it is recommended
that batch experiments should be coupled with a longer-term investigation of materials performance in columns for the estimation of removal efficiencies and retention capacities by different
materials.
115
APPENDIX B
ADSORBENTS TESTED FOR ARSENIC REMOVAL:
SYNTHESIS OF LITERATURE AND
VENDOR/MANUFACTURER SURVEYS
117
118
119
120
121
122
123
124
125
126
127
128
129
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136
ABBREVIATIONS
AA
As
As(III)
As(V)
activated alumina
arsenic
arsenite
arsenate
BTC
BV
breakthrough curve
bed volume
EBCT
empty bed contact time
GFH
GFO
granular ferric hydroxide

granular ferric oxide
HLR
hydraulic loading rate
IX
ion exchange
KF
KL
a Freundlich constant: capacity parameter

a Langmuir constant
MDL
MIEX
minimum detection limit

magnetically impregnated ion exchange (resin)
pHZPC
zero-point charge pH
Q
Q10
Q50
Qmax
adsorption capacity
Q in equilibrium with 10 g/L As
Q in equilibrium with 50 g/L As
a Langmuir constant: maximum monolayer adsorption capacity
Si
SiO2
SMI
silicon
silica
sulfur modified iron
TCLP
toxicity characteristic leaching procedure
vanadium
WET
waste extraction test
XRD
x-ray diffraction
1/n
a Freundlich constant: index of favorability

137
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AWWA Adsorbent Treatment Technologies For Arsenic Removal

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Arsenic

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2005 AwwaRF. All rights reserved.

LIST OF FIGURES ..................................................................................................................

FOREWORD ............................................................................................................................ xiii

EXECUTIVE SUMMARY ...................................................................................................... xvii

CHAPTER 2: LITERATURE SURVEY SUMMARY...........................................................

CHAPTER 3: VENDOR AND MANUFACTURER SURVEY.............................................

CHAPTER 4: ARSENIC OCCURRENCE AND CO-OCCURRENCE ANALYSIS ............

CHAPTER 5: EXPERIMENTAL PROTOCOLS AND ANALYTICAL METHODS ..........

CHAPTER 6: BENCH TESTING ...........................................................................................

CHAPTER 7: ARSENIC ADSORBENT DESIGN AND COSTING TOOL.........................

CHAPTER 8: CONCLUSIONS ..............................................................................................

APPENDIX A: LITERATURE SURVEY ............................................................................... 101

4.1 Database parameters and data acceptance criteria .....................................................

4.2 Summary of arsenic occurrence by physiographic region .........................................

4.3 Summary of occurrence of co-occurring parameters in national groundwater

4.4 Pearson correlation coefficients at 95% confidence level measuring the

6.1 Physical/chemical properties of adsorbents ...............................................................

6.2 Concentrations of interferents based on the co-occurrence survey............................

6.3 Ionic composition of NSF challenge water (pH = 7.5)..............................................

6.4 Water quality summary of utility-supplied waters.....................................................

6.8 Summary of SMI results ............................................................................................

6.9 Monomeric versus polymeric silica concentrations...................................................

6.10 Experimental conditions employed in column tests ..................................................

7.2 Single parameter and multiple regression models .....................................................

4.1 Database development flow chart ..............................................................................

4.2 Distribution of groundwater arsenic sites by state .....................................................

4.3 Physiographic zones of the United States..................................................................

4.4 National cumulative probability distribution for arsenic occurrence for

4.5 Cumulative probability distribution for arsenic occurrence by physiographic

4.6 Comparison of cumulative probability distributions of pH for waters

4.7 Comparison of cumulative probability distributions of silica for waters

4.8 Comparison of cumulative probability distributions of fluoride for waters

4.9 Comparison of cumulative probability distributions of alkalinity for waters

4.10 Comparison of cumulative probability distributions of phosphate for waters

4.11 Comparison of cumulative probability distributions of iron for waters

4.12 Comparison of cumulative probability distributions of sulfate for waters

6.2 As(V) removal (100 g/L) at pH 7 as a function of time by (a) AA-400G,

6.4 Percent removal of As(V) by candidate adsorbents: As(V) = 100 g/L;

6.6 Zeta potential versus pH for adsorbents.....................................................................

6.7 Isotherm replicate (triplicate) series for Metsorb G with As(V) at a pH of

6.8 Isotherm replicate (triplicate) series for SMI-III with As(V) at a pH of

6.12 Summary of interference factors: ratio of As(V) capacity to that at pH 6.0

6.14 Adsorption capacity, Q10, for As(V) as a function of pH: presence of

6.15 Adsorption capacity, Q10, for As(V) as a function of pH: presence of

6.16 Adsorption capacity, Q10, for As(V) as a function of pH: presence of

6.17 Adsorption capacity, Q10, for As(V) as a function of pH: presence of

6.18 Adsorption capacity, Q10, for As(V) as a function of pH: presence of

6.19 Isotherms for As(III) at a pH of 7.0: absence of interferants .....................................

6.21 Isotherms for As(V) in NSF challenge water.............................................................

Isotherm for As(III) in NSF challenge water ............................................................

6.25 Isotherms for utility-supplied water: Tucson, AZ groundwater.................................

6.26 Isotherms for utility-supplied water: LADWP, CA surface water .............................

6.27 Isotherms for utility-supplied water: El Paso, TX groundwater ................................

6.28 Isotherms for utility-supplied water: Alamosa, CO groundwater ..............................

7.1 Cost flowchart ............................................................................................................

7.2 Media replacement flowchart.....................................................................................

7.3 Backwash calculation flowchart.................................................................................

7.4 Plant footprint calculation flowchart..........................................................................