ELSEVIER

Applied Clay Science 11 (1996) 237-249

'Ecological bricks' made with clays and steel dust pollutants

Eduardo A. Domlnguez a,., Rosa Ullmann b,l
a

Departamento de Geologfa, Universidad Nacional del Sur, San Juan 670, 8000 Bahfa Blanca, Argentina b Losa/Techint, Casilla de Correos 50, 7400 Olavarrfa, Argentina

Received 2 April 1996; revised 3 September 1996; accepted 3 September 1996

Abstract
More than 27,000 tons of steel dust containing Zn, Pb, Cd, Ni and Cr are generated each year by two steel mills in Argentina. The waste can be classified as low-zinc carbon dust and its treatment is governed by environmental rather than economical considerations. The aim of this work was to test the use of clays in the formulation of a ceramic body that could incorporate steel dust and met environmental regulations. Once the raw materials were characterised, a ceramic body was prepared in the laboratory and subjected to the EP-TOXIC leaching test. The ceramic body passed this test. Based on these promising results a prototype of commercial brick incorporating 20% steel dust was produced. The brick meets standard commercial regulations being inert to the EP-TOXIC and full TCLP leaching tests and the ceramic process has low emission of dangerous gases. The addition of steel dust, reduces the firing temperature of the ceramic process meeting the recycling EPA requirements for the disposal of hazardous waste.
Keywords: steel dust; pollutants; clay; ceramics

1. Introduction
As a result o f the m e l t i n g process in electric arc furnaces (EAF), m o r e than 27,000 tons o f steel dust waste are generated e a c h y e a r in two steel mills in Argentina. A c c o r d i n g to the regulations o f the E n v i r o n m e n t a l Protection A g e n c y (EPA), this waste, designated as K 061, is c o n s i d e r e d hazardous. T h e waste generated in the m e l t i n g process is about 2% o f the product mass o f fine dusts containing a w i d e variety o f

* Corresponding author. Fax: +54-91-556756/883933; e-mail: ghcraver@criba.edu.ar i Fax: +54-284-93041. 0169-1317/96/$15.00 Copyright 1996 Elsevier Science B.V. All rights reserved. PII SO 169- 1 3 17(96)00020-8

238

E.A. Domlnguez, R. Ullmann / Applied Clay Science 11 (1996)237 249

elements, including Zn, Pb, Cd, Ni and Cr among others. Consequently the disposal of this material in dumps and landfills would produce water contamination. The main purpose of this work was to test the use of clays in the formation of a ceramic body that could incorporate steel dust and meet the Argentinean environmental laws based on the US-EPA regulations. Although many solutions have been proposed for the technical treatment of the steel dusts (Barcza and Nelson, 1990), in this case the use of ceramic and vitrification processes seems to be useful for making the dust environmentally friendly hence meeting the recycling EPA requirements, According to these authors, the Argentinean waste can be classified as low-zinc ( < 15%) carbon steel dust. Because of the low metal content it is not worth recycling it for metal recovery, therefore, its treatment is governed by environmental rather than economic considerations. The first step in this work was the determination of the physical and chemical characteristics of the steel dust. Taking into account physical and chemical testing results, ceramic test bars are made mixing the dust with different types of clay. Ceramic and leaching tests are performed on these bodies. If the results will be as expected, a brick could be produced on a pilot scale. Previous work (Ek et al., 1992) concluded that vitrification of steel dust (K 061) is a process that could recycle this hazardous waste into an usable commodity. Using dust from Oregon Steel Mills Ek et al. (1992) made an inert product, as defined by the USA EPA toxic characteristics leaching procedures protocols (TCLP). Licis and Bermark (1995) evaluated the vitrification recycling process in the Jorgensen Steel facility Seattle, WA, and concluded that the glasses are relatively non leacheable, giving values lower than those allowed by EPA regulations for TCLP. They did not investigate air emissions and suggested that research had to be conducted to evaluate the possibility of air contamination. In Brazil, Bernfirdez et al. (1993) made a ceramic floor tile incorporating steel dust. The addition of dust produced a lowering in both the firing temperature and porosity, with a good final colour. It also increased the mechanical strength and the body density. The ceramic body was inert to leaching tests. In Spain the work of Rinc6n et al. indicated that the ceramic process is a good way for recycling industrial wastes (Rinc6n et al., 1994a,b).

2. Materials and methods Because of their high plasticity, APM-112 and Chenque II kaolin clays, LA-AM illitic clay and Greda loam were selected for mixing with steel dust. These samples were taken from the stock piles of the LOSA ceramic factory. Several samples of steel dust (1 kg each) were taken from the mill dumps of SIDERCA and SIDERAR. In the SIDERCA factory, two types of samples were analysed, one of normal steel dust (SIDENO) and the other of the dust recycled in the electric arc furnace (SIDERE). The geographical localization of the steel factories, ceramic factory and the clay pits are shown in Fig. 1. The mineralogy of the clays and the steel dust was studied by XRD methods, using a Rigaku Denki Geiger Flex Max II-C with Cu and Fe radiation, Ni and Mn filters and 2/rain, at 35 kV and 15 mA. The semi-quantitative clay mineralogy was determined

E.A. Domlnguez, R. Ullmann /Applied Clay Science 11 (1996) 237-249

239

70
r

6;>

54

'~
)

/~ I

r'

SIDERAR ~-"" GREDA

;
3sP r
~--L

', I
]___~ . . . .
t

/',"~SIDERCA
t

'

i "7

e-----~ CERAMIC PLANT -~LA-AM

44I"

'

ARGENTINA Fig. ]. Location of the clay pits, steel mi]|s and the ceramic factory.

using the Chung (1974) method. Atterberg limits were used to determine the plasticity of both the clays and the steel dust. For the steel dust, bulk chemical analyses were taken from internal reports; qualitative XRF elemental analyses were performed on natural and fired samples using a Phillips PW 1400 apparatus with Rh anode, crystal Fli 200, PET, TLAP, under vacuum/air. Moisture content at 105C and loss on ignition at 1000C were determinated as well. The steel dust density was measured with the picnometer method and soluble salts were studied using the IRAM 12528/59 extraction procedure with millipore filtration. On the filtrate, the salt species, after evaporation, were determined by XRD. The grain size of the steel dust was analysed by mechanical sieving and SEM. Ceramic analysis was performed following the ASTM specifications on extruded laboratory bodies that contained 20% steel dust, 60% clay and 20% fine sand. The losses on firing were calculated through the chemical balance assuming that the amount of A1203 has remained constant (Kemp, 1949). With this method, gas emissions are reported as percentage as the samples underwent volumetrical changes. To estimate the air emissions during firing, major and trace elements were determined on the bodies before and after firing. On each sample, 42 elements were determined by ICP at ActLabs, Canada. Leaching tests were performed on both the dust and ceramic bodies. The test used was the extraction procedure toxicity test (EP Tox, US EPA, 1986). The leaching was performed by CRIBABB and the leachates were analysed in three different laboratories, Plapiqui, Argentina, A.A.A., Cerzos, Argentina and Actlab, Canada, by ICP. After these tests, a prototype brick was industrially produced using 20% steel dust and 80% Greda loam. On this brick, both leaching tests EP Toxic and full TCLP were performed. The first

240

E.A. Domlnguez, R. Ullmann / Applied Clay Science 11 (1996) 237 249

one was performed by ActLabs, Canada and the second one by Accredited Laboratories, NJ. In this last case, the sample was crushed and sieved to obtain the < 9.5 mm particles. The crushed brick was extracted with #1 fluid according to the TCLP protocol. The extraction was made at a liquid/solid ratio of 2 0 / 1 with 4.93 + 0.05 pH acetate buffered solution (#1), during a period of 18 h.

3. Results

3.1. Clay characterization

Clay characteristics are summarised in Table 1. LA-AM is a yellow illitic clay. The iron oxide mineral is a yellow ochre pigment with a strong 2.69 A XRD reflection, corresponding to hematite a n d / o r goethite. The clay pit is located in Barker, Buenos Aires Province in a small hilly area. The 4 - 6 m thick clay bed is interfingered with quartzite layers. The clay was deposited in a Precambrian coastal marine environment (Leveratto and Marchese, 1983). Chenque II is a greyish white kaolinite clay. The clay pit is located in Chubut Province, in a river valley developed on the kaolinised rhyolitic tufts of Bahia Laura Group (Middle Jurassic). The clay bed, with several sandy lenses intercalations, has an average thickness of 9 m. The clay bed, formed in a fluvial environment, was covered by Palaeocene limestones and coquina sandstones (Aliotta et al., 1977). APM-112 is a massive grey kaolinite clay. Although it is not reported in Table 1, the clay presents traces of I / S formed by illite degradation (Cravero et al., pers. commun.). The clay mine is located in the Neuqurn Province and the clay beds occur in a gently dipping Middle Jurassic fluvial sequence. A 20 m thick bed with several levels is mined, with A P M - t l 2 being one of the main levels. The clay comes from a weathered area developed during Lower to Middle Jurassic (Cravero et al., 1994). Greda is a brownish loam composed of 42% clays: low crystallinity illite, poorly crystalline smectite and allophane type material, reported as illite in Table 1 (Domfnguez et al., 1995). The 40 cm thick loam is found in a soil under the black A organic horizon, belonging to the B horizon developed on the Pampeano (Pleistocene) loess in the Campana area, Buenos Aires Province. Typical X-ray diffractograms of each sample are shown in Fig. 2.

Table 1 Clay characterization Type of clay Mineralogy (%) Illite LA-AM Chenque II APM-112 Greda 65 8 45 a Kaolinite 12 20 64 Quartz 9 63 36 45 Feldspar Goethite 14 ~ Atterberg plasticity L.L. 47 40 39 59 P.L. 26 20 21 24 P.I. 21 20 18 35

13

a See text for further information.

E.A. Domfnguez, R. Ullmann/ Applied Clay Science 11 (1996) 237-249

1K p$ Q~

241

! 1OlJ

I 2oll

I 3oll

20 Fig. 2. X-ray diffractograms of clay tested as raw materials.

3.2. Steel dust characterization (K 061)

I n o r d e r to d e s i g n t h e a p p r o p r i a t e c e r a m i c a p p l i c a t i o n s , it is e s s e n t i a l to c h a r a c t e r i s e the waste before and after the ceramic process.

Table 2 Steel dust chemical analysis (%) SIDENO

1 2 3 4 5

SIDERAR
1

Fe203 SiO 2 AL203 MnO PbO MGO ZnO Na20 CaO K20 C S Cr Ni Cd P F Cu ppc

42.00 3.10 0.90 2.30 1.60 4.60 12.10 10.70 1.50 0.31 0.10 0.03

51.20

1.80 5.50 13.80 12.60 2.10 0.46 0.30

43.80 11.7 1.50 4.80 0.89 7.00 3.61 11.80

1.06 4.36

1.19 0.86 1.38 7.47

45.50 7.03 1.19 0.86 2.67 0.07 14.80 0.14 0.10

0.01 0.05 0.01

0.004 0.003 0.12 0.001

0.005 0.004 0.014 0.13 0.002

0.09

1, 2, 3, 4 and 5 denote various samples.

242

E.A. Domlnguez, R. Ullmann / Applied Clay Science 11 (1996) 237-249

The c h e m i c a l c o m p o s i t i o n o f the dust varies according to the different casts and to the type o f steel produced. In the steel factories, S I D E R C A and S I D E R A R , the average steel dust p r o d u c e d varies b e t w e e n 15 to 20 kg per ton of steel. The c h e m i c a l data 50
3
-1

SIDER
,,

.,,.
o ,1
~

m%~ ~'
,~-

xl0
o

I~

(2,

20.0

30.0

40.0

50 0

600

50
s,BE.o

xl0

O ~

o
~

20.0

300

40.0

50.0

60.0

5O

SIDERAR
x103
4

~
0 rq O

8,,,
"~0 ~

6
c~ 0 ~ 0
cq ~

~
~ c q c,1

,,

2(1 0

30 0

4lJO

50'.0

66.0

t!
Ce

8.0 xl02

FIRED BRICK
cq 0

t
~
0 o~

O'

el

100

20.0

300 2O

40.0

50.0

60.0

Fig. 3. X-ray diffractograms of steel dust samples and the fired brick.

E.A. Domlnguez, R. Ullmann / Applied Clay Science 11 (1996) 237-249

243

shown in Table 2 were taken from internal reports. The moisture content is highly variable (SIDENO 1.8-9.9% and SIDERAR 8.1-18.1%) depending on the storage time. XRF analysis show that after firing at 1000C some changes occur in several elements such as Zn, Pb, Cu, C1 (SIDENO) plus Ca and P (SIDERAR). Neither F nor Hg were confirmed. The loss on ignition varies between 4.4-6.6 in SIDENO and 5.0-14.9 in SIDERAR. The steel dust is composed of either magnesium ferrite with minor amounts of zincite (samples SIDERE and SIDENO) or, magnesium ferrite, calcium carbonate, iron oxide and graphite (sample SIDERAR). In the case of SIDERAR hematite and quartz have also been detected. (Fig. 3) The data obtained from the grain size analysis varied that much, depending on the dispersion method and the moisture content, that they were not taken into consideration. SEM pictures (Fig. 4a and b microphotographs) clearly indicate that the dust is very fine grained, normally < 30 /zm, with a tendency to form agglomerates. The Atterberg plasticity index is nil.

Fig. 4. SEM microphotographs of the steel dust (sample SIDENO) showing: (a) agglomerates of small particles and (b) larger grains ( > 10 /xm).

244

E.A. Domlnguez, R. Ullmann/ Applied Clay Science 11 (1996) 237-249

Table 3 EP toxicity test SIDERCA steel dust Contaminant BA Cd Cr Pb Ag Co Cu Ni Zn SIDERE (mg/I) 323.00 4.50 <1 50.00 < 0.5 <l I. 10 < 0.5 1450.00 SIDENO (mg/1) 340.00 3.10 <t 29.00 < 0.5 <1 1.60 0.50 790.00 Regulatory level (mg/l) 100.00 0.50 5.00 1.00 5.00 100.00 1.34 500.00

A 6.91% salt content was found in the SIDENO dust. Potassium and calcium chlorides and sodium and calcium sulphates were the main salt species identified. The leaching tests on samples SIDENO and SIDERE show that the values of Ba, Cd, Pb, Cu and Zn are above the regulatory levels (Table 3).

4. Ceramic body formulations

The initial ceramic tests were done under laboratory conditions on 4 bodies composed of 60% of each plastic clay, 20% fine quartz sand and 20% steel dust. The raw material was milled in a ball mill and the blend has a grain size smaller than the 35 ASTM mesh. The laboratory extruded test bars have a size of 140 30 34 30 mm. The usual firing temperature of 900C used for these clays in laboratory had to be reduced to 830C because the addition of the dust promoted excessive fusion. The Greda loam developed good firing colour (light-brownish grey, HUE10YR 6 / 2 ) . However, because of difficulties in drying it was not used for the first tests. Chenque II and APM-1 12 were discarded, because of their non-commercial firing colour (reddish brown H U E 5 Y R 5 / 3 , H U E 7 5 Y R 5 / 2 , respectively). The ceramic characteristics of the body made with the LA-AM are shown in Table 4 and the leaching tests performed on pieces lower and larger than 9.5 mm are shown in Table 5.
4.1. Industrial applications

The steel dust leachates, Ba, Cd, Pb and Zn are above the regulatory levels. The ceramic process stabilises them even in the worst conditions represented by the crushed test bars (lower than 9.5 ram) (Table 5). Since the brick itself has a structural integrity, the test should be done only on the larger pieces ( > 9.5 mm) in a similar way to that made on monolithic wastes (structural integrity procedures). Based on these results an industrial prototype brick was made using 80% Greda loam and 20% steel dust (Fig. 5a and b). The Greda loam was used after a careful study of its

E.A. Domfnguez, R. Ullmann / Applied Clay Science 11 (1996) 237-249

Table 4 Summary of ceramic properties of test bars made with steel dust and LA-AM clay Ceramic property Firing temperature (C) LOI (%) Drying shrinkage (%) Firing shrinkage (%) Final shrinkage (%) Drying flection strength ( k g / c m 2) Firing flection strength ( k g / c m 2 ) Firing compression strength ( k g / c m 2) Water absorption (%) Arrow (mm) SIDENO 830.00 8.52 6.90 0.69 7.59 41.20 81.70 234.80 18.50 0.45 SIDERAR 830.00 8.68 7.00 0.32 7.32 66.60 i 15.70 248.80 16.40 0.20

245

Table 5 Test bars EP toxicity test Contaminants (mg/1) SIDENO < 9.5 mm 1 Ba Cd Cr Pb Ag Co Cu Ni Zn Fe 11.0 < 0.2 < 1 <1 < 0.5 < 1 < 0.5 < 0.5 1.9 < 0.5 2 32.0 < 0.2 1.0 <1 < 0.5 < 0.5 < 0.5 < 0.5 3.4 < 0.5 Fragments 1 8.0 < 0.2 < 1 <1 < 0.5 < 0.5 < 0.5 < 0.5 0.6 < 0.5 2 4.0 < 0.2 < 1 <1 < 0.5 < 0.5 < 0.5 < 0.5 0.2 < 0.5 SIDERAR < 9.5 mm 1 30.0 < 0.2 < 1 <1 < 0.5 < 0.5 < 0.5 < 0.5 0.6 < 0.5 Fragments 1 4.2 < 0.2 < 1 <1 < 0.5 < 0.5 < 0.5 < 0.5 0.3 < 0.5 2 4.5 < 0.2 < 1 <1 < 0.5 < 0.5 < 0.5 < 0.5 0.2 < 0.5 100.00 0.50 5.00 1.00 5.00 100.00 1.34 500.00 Regulatory level ( m g / l )

1 = sample, 2 = duplicate.

Fig. 5. Prototype of the 'ecological brick'. (a) Production line and (b) drying section.

246

E.A. Dominguez, R. Ullmann / Applied Clay Science 11 (1996) 237-249

VV

@~

gZ-

~$~--

b~

d5

dd

~ 0

VV

VV

dd

dd

< M

gg~
~

gg~
do dd

8X
m

N~

~~

E.A. Domlnguez, R. Ullmann / Applied Clay Science 11 (1996) 237-249

247

extrusion possibilities and drying conditions. The most important factor that made the Greda loam attractive for this application is the proximity of its pits from the steel mills. The brick prototype was made at the factory, using the regular procedures for an industrial roof tile. The ceramic body was shaped by extrusion at 20% moisture content. The 48 h drying cycle was performed in chamber dryers with an initial humid environment and 100C m a x i m u m temperature. A 100 m long gas fuelled tunnel kiln was utilized for the 24 h firing cycle. A m a x i m u m temperature of 890C under oxidizing conditions were used because these are the firing conditions applied in the factory for roof tile products. The bricks were placed in the upper tray of the kiln cars where the temperature is 30 lower, therefore the actual firing temperature was about 860C. A ten chamber brick of 31 17 17 cm was produced. The brick weight was 7600 g with 2.10 g / c m 3 ceramic frame fired density. The lineal drying shrinkage was 6.7% and the firing shrinkage was 2%. The flexion strength was 8.9 k g / c m 2 and the compression strength was 27.3 k g / c m 2 with a water absorption of 13.6% and weak efflorescences (bassanite). This brick meets commercial international standards. Quartz, feldspars and hematite were the only crystalline phases remaining in the fired brick (Fig. 3). The chemical balance on the bodies made with steel dust and L A - A M and Greda loam reveals that the losses during the firing are H 2 0 , CO 2, C1, Br, Pb, Zn and Hg (Table 6). The major emissions are H 2 0 (7%), CO e ( 1 - 3 % ) , C1 (0.13%) with minor quantities of Pb (58 ppm), Zn (205 ppm), Hg (23 ppb) and Br (27 ppb). The leaching tests on the brick are presented in Tables 7 and 8. As it is shown the brick generates leachates with values lower than the regulatory levels. U S - E P A uses the TCLP as the basis for the promulgation of best demonstrated available technologies ( B D A T ) treatment standards under the land disposal restrictions program. The EP-Tox is similar in design to the TCLP and generally yields similar or little lower leachates concentration of metals (Newcomer et al., 1986). The steel dust has been used for improving the ceramic framework lowering the

Table 7 EP toxicity test ecological brick Contaminant (mg/l) Hg As Cr Ni Se Ag Cd Pb Cu Zn Ba Ecological brick < 9.5 mm 0.00010 0.03040 0.11200 0.00061 0.00050 0.00001 0.00016 0.00029 0.00167 0.03346 0.01726 Fragments 0.00010 0.00580 0.09340 0.00066 0.00020 nd 0.00009 0.00021 0.00041 0.01958 0.01032 H 2 Target 0.00040 0.00020 nd 0.00017 0.00010 nd 0.00003 nd 0.00062 0.00097 0.00122 Regulatory level (rag/l) 0.10 1.00 5.00 1.34 1.00 5.00 0.50 1.00 100.00 500.00 100.00

H20 target = water used in the extraction procedures.

248

E.A. Domlnguez, R. Ullmann / Applied Clay Science 11 (1996) 237-249

Table 8 TCLP analyses ecological brick Contaminant Benzene 2-Butanone Carbon tetrachloride Chlorobenzene Chloroform 1.1-Dichloroethene 1.2-Dichloroethene Tetrachloroethene Trichloroethene Vinylchloride 2.41-D Silvex Arsenic Barium Cadmium Chromium Lead Mercury Selenium Silver Sample (mg/l) nd nd nd nd nd nd nd nd nd nd nd nd nd /).340 nd 0.086 nd nd nd nd Regulatory level ( m g / l ) 0.50 200.00 0.50 100.00 6.00 0.70 0.50 0.70 0.50 0.20 10.00 1.00 5.00 100.00 1.00 5.00 5.00 0.20 1.00 5.00

nd = not determined. Accredited Laboratories, New Jersey. Sample 9510198.

firing temperature of the body. The ceramic process meets the requirements for recycling a hazardous waste.

5. Conclusions The ceramic process using either Greda loam or L A - A M clay is suitable for the disposal of hazardous steel dusts generated in Argentina. The 'ecological bricks' incorporating 20% of steel dusts meet the most stringent EPA leaching regulations. The low emission of dangerous gases and the firing temperature of 830C instead of 890C are results concluded from laboratory tests. It is assumed that the dangerous constituents such as Zn are fixed in the sintered/vitreous phase since no new Zn mineral phase was found in the fired brick. These hollow bricks would be used for structural purposes covered with cements, paints or other agents, therefore they are not exposed to weathering in that sense, bassanite efflorescences are not expected to be a problem. Alternative ceramic bodies using other types of clay must be tested. The clays must have high plasticity, be capable of incorporating steel dusts of high densities and yield a good fired colour. Based on this work an environmentally inert brick, with good commercial characteristics, was made incorporating 20% SIDERCA steel dust in a ceramic body made with Greda loam. The Greda loam was selected because of the closeness of its pits to the steel

E.A. Domfnguez, R. Ullmann/ Applied Clay Science 11 (1996) 237-249

249

factories. In this c a s e t h e c e r a m i c p r o c e s s m e e t s t h e R e c y c l i n g E P A r e q u i r e m e n t s for the disposal of hazardous waste.

Acknowledgements
T h e a u t h o r s are g r a t e f u l to L O S A - T E C H I N T d i r e c t o r s for s u p p o r t i n g this i n v e s t i g a t i o n a n d a l l o w i n g t h e p u b l i c a t i o n o f this r e s u l t s a n d to S I D E R C A h e a l t h a n d safety t e a m . W e w i s h to t h a n k H. F r e e m a n ( U S - E P A , C i n c i n a t t i ) , M. M a c L a r e n - R u t g e r s ( N e w J e r s e y ) , H. T h i e s s e n - B r o w n a n d C a l d w e l l a n d H.H. M u r r a y ( I n d i a n a U n i v e r s i t y ) for the e n l i g h t e n i n g d i s c u s s i o n s . W e are also i n d e b t e d to J. E l z e a f o r r e v i e w i n g the m a n u s c r i p t a n d to G. A l i o t t a a n d F. C r a v e r o f o r a s s i s t i n g in its p r e p a r a t i o n . T h e m a n u s c r i p t w a s m u c h i m p r o v e d t h r o u g h t h e c o m m e n t s o f A.B. P o o l e a n d J. Y v o n ( A p p l i e d Clay Science r e v i e w e r s ) .

References
Aliotta, G., Dom~nguez, E. and Whewll, R., 1977. Sedimentologla de las psamitas del Terciario inferior entre dique Ameghino y Boca Toma, Provincia de Chubut, Argentina. RAGA, 32(2): 81-98. Barcza, N.A. and Nelson, LI.R., 1990. Technology for the treatment of steel plant dust. World Steel Rev., I(1), 21 pp. Bemfirdez, J.L., Abreu, O.M. and Araujo, J.A., 1993. Utilicazao do po' de aciaria electrica (PAE) na fabricazao de pisos ceramicos. DEDINI S.A., Siderfirgica, Brasil Cravero, F., Gonzfilez, I., Galfin, E. and Domlnguez, E. (1994). El caolln de Misud (Argentina). Geologla, mineralogla y aplicaciones. Bol. Soc. Esp. Mineral. V, 17(1): 27. Chung, F.H., 1974. Quantitative interpretation of X-ray diffraction patterns of mixtures. I. Matrix flushing method for qualitative multicomponent analysis. J. Appl. Cystallogr., 7:519-525 Domlnguez, E., Cravero, F., All6, W. and Ullmann, R., 1995. Origen de la plasticidad en Gredas del centro de la Provincia de Buenos Aires. VI Reuni6n Argentina de Sedimentologla-I Simposio de Arcillas, Bahia Blanca, May 1996, submmitted. Ek, R.B., Bray, K.J. and Richartz, III, J.O., 1992. Glassification of electric arc furnace dusts al Oregon Steel Mills Inc., USA. Oregon steel, Tech. Rep. Kemp, J.F., 1949. A Handbook of Rocks. F.F. Grout (Editor). Van Nostrand, New York, NY, 300 pp. Leveratto, M.A. and Marchese, H., 1983. Geologla y estratigrafla de la Formaci6n La Tinta (y hom61ogas) en el 5.tea clave de Sierra de La Tinta-Barker-Villa Cacique-Arroyo Calaveras, Provincia de Buenos Aires. RAGA 38(2): 235-247. Licis, I.V. and Bermark, R.C., 1995. On site recycling of electric arc furnace dust: The Jorgensen Steel Facility. EPA 21 Ann. RREL Res. Symp. Abstr. Proc. EPA/600/R95/012. Cincinnati, OH. Newcomer, L., Blackburn, W.B and Kimmell, T.A., 1986. Perfomance of the Toxicity Characterisitic Leaching Procedure. In: Stabilization/solidification of CERCLA and RCRA wastes 1989. US-EPA 625/6-89/022. US-EPA, Cincinatti, OH. Rinc6n, J.M., Romero, M. and Zayas, M.E., 1994a. Reciclado de residuos industriales como ecoproductos vitro cer~imicos. Posibilidades de aplicaci6n de esta tecnologla en Castell6n, Espafia. Parte I. Trc. Cerfim., 222:220-229 Rinc6n, J.M., Romero, M. and Zayas, M.E., 1994b. Reciclado de residuos industriales como ecoproductos vitro cerfirnicos. Posibilidades de aplicaci6n de esta tecnologla en Castell6n, Espafia. Parte II. Trc. Cerfim., 223: 315-331. US EPA, 1986. Extraction Procedure Toxicity Test (EP Tox). In: Stabilization/solidification of CERCLA and RCRA wastes 1989. US-EPA 625/6-89/022. US-EPA, Cincinatti, OH.