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Article history: Degraded land that is historically contaminated from different sources of industrial waste provides an
Received 21 February 2009 opportunity for conversion to bioenergy fuel production and also to increase sequestration of carbon in
Received in revised form soil through organic amendments. In pot experiments, As mobility was investigated in three different
23 April 2009
brownfield soils amended with green waste compost (GWC, 30% v/v) or biochar (BC, 20% v/v), planted
Accepted 3 May 2009
with Miscanthus. Using GWC improved crop yield but had little effect on foliar As uptake, although the
proportion of As transferred from roots to foliage differed considerably between the three soils. It also
Keywords:
increased dissolved carbon concentrations in soil pore water that influenced Fe and As mobility. Effects of
Green waste compost
Biochar BC were less pronounced, but the impacts of both amendments on SOC, Fe, P and pH are likely to be
Bioenergy crop critical in the context of As leaching to ground water. Growing Miscanthus had no measurable effect on As
Water-soluble organic carbon mobility.
Iron Ó 2009 Elsevier Ltd. All rights reserved.
Arsenic transfer
0269-7491/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2009.05.011
W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662 2655
growth and As uptake in Miscanthus x giganteus grown in three Biochar was obtained from Bodfari Charcoal, Denbigh, UK (www.bodfari-charcoal.
diverse As-polluted soils and (ii) to determine if water-soluble co.uk); it is manufactured from hardwoods including Common Ash (Fraxinus
excelsior), Oak (Quercus spp.) and Cherry (Prunus spp.). The wood is heated to 400 C
organic carbon (WSOC) derived from these amendments affected in the absence of oxygen in ring kilns and upon reaching this temperature, volatile
As mobility, assessed by changing concentrations in soil pore water. gases from the wood continue the charring process. Green waste compost (PAS 100
quality) was sourced from Whitemoss Horticultural Supplies, Kirby, UK. Untreated
2. Materials and methods soils were used as controls. A proprietary peat-based potting compost from
Whitemoss Horticultural Supplies was used as a positive control.
2.1. Study sites and sources of arsenic
2.3. Pore water sampling
Three soils, with different sources of As contamination were collected for
a glasshouse-based pot investigation. Site 1, Rixton clay pits (hereafter referred to as
Once filled with soil, a hole was drilled in the side of each pot 10 cm below the lip
Rixton) near Warrington, Cheshire (53 240 34.8000 N 2 280 38.8000 W), is an area adja-
and a ‘Rhizon’ soil pore water sampler inserted at a 45 angle. These consist of
cent to brickworks, where coal fly ash (CFA) and other industrial wastes have been
a porous polymer tube (10 cm) at one end that is inserted into the soil. This is
disposed of. CFA is alkaline and the main environmental problems are due to
connected to a PVC tube (10 cm) and a Luer-Lock connector, from which pore water
leaching of metal(loids) from the coal ash settling ponds, causing phytotoxicity
is obtained using a syringe and vacuum tube (Clemente et al., 2008). Pore water
(Prasad et al., 1996). Clay from the pits was used for brick making until the mid 1960s
samples were analysed for pH, WSOC, As, P (phosphorus) and Fe (iron) for all
(Warrington MBC Ranger Service, pers. comm.).
treatments and controls with the exception of the positive control.
Site 2 is located between two canals at Kidsgrove near Stoke-on-Trent (hereafter
referred to as Kidsgrove) (53 050 28.4600 N 2 15019.0300 W). Dredged sediment from
one canal has been deposited on the embankment that separates the two water- 2.4. Analytical methods
ways. This is contaminated with As and heavy metals, including Cu and Zn; the latter
may have originated from a pigment factory located further down the canal. The Soil pH, was determined using a 20 g dry sample mixed to a slurry with
origins of As in the sediment are not known. deionised water (50 ml). The supernatant was tested using a PHM85 precision pH
Site 3 is a former landfill site at Merton Bank, St. Helens, Merseyside (hereafter meter. Organic matter content was determined by loss-on-ignition (LOI) (450 C).
referred to as Merton Bank) (53 270 33.2100 N 2 420 50.1600 W). An alkali works oper- Available soil phosphate (PO4 3 ) in untreated soils was measured by the Olsen
ated on the site from 1873 within an industrial landscape, and subsequently the area method (Olsen et al., 1954). Pore water-soluble phosphorus (P) concentrations were
developed into a disused industrial waste site with shallow soils contaminated with determined by Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-
Le Blanc process waste (10–30 cm). Following remediation in the 1980s this 6.6 ha OES; Thermo Scientific, MA, USA). Soil samples for determination of pseudo-total As,
site is now intensively mown open grassland (mainly perennial Ryegrass (Lolium Cu, Zn, Cd and Ni (mg l1) concentrations were air-dried (25 C), sieved (<4 mm
perenne) and Yorkshire Fog (Holcus lanatus)) used for public recreation, within diameter) and aliquots (0.2 g) digested with Analar grade 15.55 M HNO3 (10 ml)
a residential and industrial area. using a CEM Mars Xpress microwave (Programme; 1600w 100% power 10 min; hold
at 160 C 20 min). Solutions were analysed by Inductively Coupled Plasma-Mass
2.2. Collection and preparation of soil samples Spectrometry (XSERIES 2 ICP-MS; Thermo Scientific, MA, USA). Accuracy was
checked regularly by reference to international certified standard water (NWRI-
Soil samples were collected following guidelines according to ISO 10381-1 and TMDA-62) and to digests of a standard reference soil (CMI7004). Dissolved organic
-2. Sampling was conducted using a non-systematic pattern (W formation) across carbon and nitrogen were determined using a TOC-VE Shimadzu water analyzer
the sites. Bulk (50 kg) surface soil samples (0–10 cm) were obtained from each site. (Shimadzu, Tokyo, Japan). Inorganic carbon and total carbon in solid samples were
Table 1 provides the main characteristics of the untreated soils. The samples were determined using a TOC-VE/SSM-5000A (900 C).
homogenised in the laboratory using a cement mixer. For each site, a sub-sample A sequential extraction specifically designed for As was carried out on the
was taken from the homogenised soil. These soil samples were air-dried for one equilibrated amended soils. All reagents used in the extraction procedures were
week. Dried soils were crushed and sieved to a particle size of <4 mm diameter, then analytical grade. Soil samples (1.00 g) were weighed into Nalgene polypropylene
pH, organic matter content, available P and pseudo-total metal concentrations were centrifuge tubes and all stages of the extraction procedure were carried out in the
determined for each soil prior to experimental use. Amendments were applied to tubes to minimise soil loss. The following five-step procedure, modified by Shio-
the homogenised soils at a rate of 30% v/v for GWC, and 20% v/v for BC. CL:AIRE watana et al. (2001) was used to evaluate the distribution of As in the treated soils:
(Contaminated Land: Applications in the Real Environment) recently conducted
a study using GWC at application rates of 25% and 50% (v/v) (CL:AIRE, SUB 10, 2008), (1) H2O (water soluble);
whilst at present there is no ideal application rate for BC. Amended soils were (2) 0.5 M NaHCO3 (surface-adsorbed);
homogenised thoroughly by hand, then moistened to 70% of the soil water holding (3) 0.1 M NaOH (Fe and Al-associated);
capacity (WHC) with distilled water and allowed to equilibrate in plastic bags at (4) 1 M HCl (carbonate bound);
room temperature for 14 days prior to being transferred to plastic pots (5 kg). (5) HNO3 (residual (pseudo-total); the original method used HNO3–HF).
Table 1
Origin and physico-chemical characteristics of soils used in test study. Trace elements are pseudo-total concentrations (mg kg1 dry wt.) (n ¼ 3, with S.E.). Values followed by
the same letter are not significantly different (p < 0.05).
Table 2 particulate matter adhering to their surfaces. The material was then re-washed
Physico-chemical characteristics of the organic amendments (trace element (deionised water) and treated in the same way as the foliage.
concentrations are pseudo-total HNO3 digests unless otherwise stated) (n ¼ 3, with
S.E.). 2.7. Microwave digestion of plant material
Table 4
Total yield (n ¼ 3, with S.E.), As concentration (n ¼ 3, with S.E.) and As uptake in Miscanthus foliage grown in the three test soils.
Yield (g/pot) Arsenic concentration Plant Yield (g/pot) Arsenic concentration Plant Yield (g/pot) Arsenic concentration Plant
in foliage (mg kg1 uptake in foliage (mg kg1 uptake in foliage (mg kg1 uptake
dry wt.) (mg/pot) dry wt.) (mg/pot) dry wt.) (mg/pot)
Treatment
Untreated 53.5 6.79 0.6 0.11 0.03 134.5 8.61 0.06 0.02 0.008 29.7 11.19 0.67 0.22 0.02
GWC 133.77* 15.76 0.54 0.38 0.07 203.62* 2.14 0.12 0.05 0.02 132.86* 2.59 0.39 0.19 0.05
BC 55.63 2.32 0.54 0.12 0.03 142.52 8.78 0.07 0.11 0.01 27.35 3.7 0.62 0.16 0.02
Peat-based 380 11.75 nd nd 380 11.75 nd nd 380 11.75 nd nd
compost
*p < 0.001.
nd ¼ not determined.
W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662 2657
a 10 Root
1600 Residual
Carbonate-bound
Rhizome
1400 Fe & Al- associated
8 Foliage
surface-adsorbed
1200 water soluble
As (mg kg-1)
6
1000
As (mg kg-1)
4
800
2 600
a
400
0
b 10 200
0
8
140
As (mg kg-1)
6
120
4 a
100
a
2
As (mg kg-1)
80
0
60
c 10
40
8
20
As (mg kg-1)
6
0
4 100
a
2 80
a
0
As (mg kg-1)
60
Untreated GWC BC
Treatment
Fig. 1. Arsenic uptake in Miscanthus roots, rhizomes and foliage as affected by green 40
waste compost (GWC) and biochar (BC) when grown in (a) Merton Bank (b) Kidsgrove
and (c) Rixton soils (n ¼ 3, S.E.) (a ¼ p < 0.001).
20
Merton Bank soil and approximately 10% of the As pool was
transferred to foliage (as in Kidsgrove soil). Higher As transfer to
foliage in Rixton soil, despite low uptake to roots, confounded this
0
pattern.
Untreated GWC BC
Treatment
3.3. As mobility in soil Fig. 2. Arsenic fractionation (Shiowatana extraction) from Merton Bank (a), Kidsgrove
(b) and Rixton (c) soils and treated with green waste compost (GWC) and biochar (BC)
Incorporation of GWC increased As lability, with higher (mean values, n ¼ 3). Order of sequential fractions: I ¼ water soluble, II ¼ surface-
concentrations recorded in water soluble and surface-adsorbed adsorbed, III ¼ Fe- and Al-associated, IV ¼ carbonate bound, and V ¼ residual.
2658 W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662
3
0.2
0.2 Untreated
GWC
Fe (mg l-1)
As (mg l-1)
As (mg l-1)
0.1
0.1
1
0 0 0
0.2 3
0.2 Untreated
Biochar
Fe (mg l-1)
2
As (mg l-1)
As (mg l-1)
0.1 0.1
0 0 0
0 50 100 0 1 2 3 0 50 100
WSOC (mg l-1) Fe (mg l-1) WSOC (mg l-1)
Fig. 3. Relationship between concentrations of untreated (B) and GWC treated (:) pore water As (p 0.001), Fe (p 0.001) and water-soluble organic carbon (WSOC) and BC-
treated (-) pore water As (p ¼ 0.226), Fe (p ¼ 0.142) and water-soluble organic carbon (WSOC) in Merton Bank soil collected over the time period of the investigation (n ¼ 48).
fractions (Fig. 2). Biochar had little significant effects on As in foliage were 5.25, 21.7 and 2.94 mg kg1 respectively. The same
mobility. Concentrations of phytotoxic trace elements in Mis- fractionation procedure showed that these potentially phytotoxic
canthus foliage were within the normal range in uncontaminated trace elements (Cu, Zn and Ni) were largely (>40%) bound to
plant materials. Highest concentrations of Cu, Zn and Ni recorded carbonate in all the soils [data not shown]; limited mobility
0.016 0.016 2
Untreated
1.6 GWC
0.012 0.012
As (mg l-1)
As (mg l-1)
Fe (mg l-1)
1.2
0.008 0.008
0.8
0.004 0.004
0.4
0 0 0
2
0.016 0.016 Untreated
Biochar
1.6
0.012 0.012
As (mg l-1)
Fe (mg l-1)
As (mg l-1)
1.2
0.008 0.008
0.8
0.004 0.004
0.4
0 0 0
0 50 100 150 0 1 2 0 50 100 150
WSOC (mg l-1) Fe (mg l-1) WSOC (mg l-1)
Fig. 4. Relationship between concentrations of untreated (B) GWC treated (:) pore water As (p 0.001), Fe (p 0.001) and water-soluble organic carbon (WSOC) and BC-treated
(-) pore water As (p 0.001), Fe (p ¼ 0.207) and water-soluble organic carbon (WSOC) in Kidsgrove soil collected over the time period of the investigation (n ¼ 48).
W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662 2659
0.6 Untreated
0.6 1.5
GWC
0.4
As (mg l-1)
As (mg l-1)
0.4 1
Fe (mg l-1)
0.2 0.2 0.5
0 0 0
0.6
1.5 Untreated
0.6
Biochar
0.4
As (mg l-1)
Fe (mg l-1)
As (mg l-1) 0.4
0 0 0
0 100 200 300 0 0.5 1 1.5 0 100 200 300
WSOC (mg l-1) Fe (mgl-1) WSOC (mg l-1)
Fig. 5. Relationship between concentrations of untreated (B) and GWC treated (:) pore water As (p 0.001), Fe (p ¼ 0.005) and water-soluble organic carbon (WSOC) and BC-
treated (-) pore water As (p 0.001), Fe (p ¼ 0.436) and water-soluble organic carbon (WSOC) in Rixton soil collected over the time period of the investigation (n ¼ 48).
would have mitigated further against detrimental effects on increased availability of P limiting As uptake; the chemical simi-
growth and uptake. larity and behaviour of phosphate (PO3 4 ) and As means they may
Pore water WSOC significantly increased (p 0.001) following compete with each other for uptake sites (Adriano, 2001). When
incorporation of GWC to the test soils as did water-soluble Fe phosphate is limited, As is taken up into plants at higher rates due
concentrations (p 0.001) (Figs. 3–5). Pore water As increased in all to the stimulation of the phosphate uptake system under low
test soils following GWC-amendment, but most significantly in phosphate status (Thompson et al., 1990). Low P conditions that
Kidsgrove soil; the labile As pool increased threefold compared to would enhance uptake did not exist in the present study even in
untreated soils (Fig. 4). In comparison to untreated soils, P untreated soils. Higher rates of As uptake into roots at Merton Bank,
concentrations significantly increased (p 0.001) in Kidsgrove and where soil P was highest, require a different explanation. One
Rixton soils following GWC-amendment (Fig. 6). Biochar amend- possibility may be due to differences in soluble metal(loid)–organic
ment had a strong effect on increasing As mobility in Rixton soil complexes that are known to enter the root free space, but are not
(Fig. 5) but not otherwise; there was no relationship between necessarily translocated to the foliage. Therefore, As may be
WSOC, As and Fe with BC-amendment. Iron concentrations in all mobilised in pore water in GWC phosphorus-enriched soils (Qafoku
BC-treated soils were reduced compared to untreated soils. Mis- et al., 1999; Hartley et al., 2009) largely due to competitive anion
canthus had no measurable effect on As mobility when compared to exchange (Peryea, 1991), but without increasing uptake by plants.
soils without Miscanthus growing in them [data not shown]. Water-soluble organic carbon is the most mobile fraction of
organic ligands that exist in soils and may assist in the transfer of
4. Discussion metal(loids) through soil as organic complexes (Cao et al., 2003).
Whilst organic matter is generally beneficial to degraded soils,
In spite of similar As concentrations in the three test soils, there is some concern that contaminant solubility may also be
inherent differences existed between them in terms of As mobility increased through the formation of soluble organic complexes due
and bioavailability. This was probably a product of the different to incorporation of carbon-rich composts (Zhou and Wong, 2001;
sources of contamination, and particularly differences in P, pH, Fe, Mench et al., 2003). In the present study, soil pore water As was
OM and WSOC concentrations that existed between them before significantly increased in all test soils treated with GWC. Besides
and after amendment additions (Tables 1 and 3). Both BC and GWC the role of P enrichment, as discussed above, there is probably
represent the introduction of large pools of organic carbon that may a significant additional influence of soluble Fe and complex organic
have substantial further impact. As far as the authors are aware, BC acids on As lability.
has not previously been applied to As-polluted soils to evaluate its In a recent laboratory investigation, Wang and Mulligan (2009)
effect on retention and mobility of the metalloid. It is already well observed that mobilization of As was closely related to mobilization
established that DOC may reduce or increase metal adsorption onto of Fe in mine tailings treated with humic acid. They found that
soil surfaces by either (i) being preferentially surface-adsorbed presence of humic acid promoted formation of aqueous Fe–humate
rather than the metal(loid) it is competing with or (ii) by forming complexes preventing iron hydroxides forming and thereby
soluble organo-metallic complexes with the metal(loid) and hence reducing As retention in the tailings. Addition of GWC to the
increasing its mobility (Guisquiani et al., 1998). polluted soils in the present study resulted in significantly higher
In the present study, neither GWC nor BC substantially altered concentrations of Fe in pore waters compared to untreated soils
As uptake into Miscanthus foliage. One explanation may be (Figs. 3–5). Solubilisation of Fe in pore water may have affected the
2660 W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662
a 1 0.12
P
a 9 Untreated
Fe Biochar
As GWC
0.1 8.5
0.8
P (mgl-1) Fe (mg l-1)
0.08 8
pH
As (mg l-1)
0.6 a
7.5
0.06
0.4
7
0.04
0.2 6.5
0.02
b 9
0 0
8.5
b 1
a
0.01
a 8
pH
0.8 0.008
P (mgl-1) Fe (mg l-1)
7.5
As (mg l-1)
0.6 a 0.006
a 7
a
0.4 0.004
6.5
0.2 0.002 c 9
0 0 8.5
c 2.5 b 0.3 8
pH
a 7.5
2
P (mgl-1) Fe (mg l-1)
0.2 7
As (mg l-1)
1.5
6.5
1 1 2 3 4 5 6 7
0.1 Monthly sampling
Fig. 7. Change in pore water pH over the time period of the investigation as affected by
0.5 organic treatments in (a) Merton Bank, (b) Kidsgrove and (c) Rixton soils.
a
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