Slimes and Sludges, copper electrolytic

Additional physico-chemical information

Administrative data

Endpoint:

other: representative mineralogy

Type of information:

experimental study

Adequacy of study:

key study

Reliability:

2 (reliable with restrictions)

Rationale for reliability incl. deficiencies:

other: No GLP study but other quality assurance

Cross-reference

Reason / purpose for cross-reference:

reference to same study

Data source

Reference

Reference Type:

study report

Title:

Unnamed

Year:

2010

Materials and methods

Principles of method if other than guideline:

Chemistry /elemental analysis was determined using ICP (inductively Coupled Plasma spectroscopy). Metal speciation/metal mineralogy was assessed from Sequential extraction/metal analysis and mineralogical analysis (XRD and microscopes equipped with EDS (Energy Dispersive Spectrometry) and WDS (Wavelength Dispersive Spectrometry) analysers. The interpretation of the overall results was performed by expert (with profound knowledge of metal particularities).

GLP compliance:

no

Remarks:

but equivalent Quality Assurance

Test material

Test material information

Constituent 1

Reference substance name:

Slimes and Sludges, copper electrolytic

EC Number:

266-972-5

EC Name:

Slimes and Sludges, copper electrolytic

Cas Number:

67711-95-9

Molecular formula:

Not applicable

IUPAC Name:

slimes and sludges, copper electrolytic

Details on test material:

test material was dried before sending to test labs. Sampling of representative samples was made according to Sampling protocol of the REACH Copper Consortium (iuclid 1.4 attachment).
B6 anodic slime from primary smelter (site 1a, not decopperized) (representative, dried, homogenized) lab code: 09TT03746
B6 anodic slime from primary smelter (site 1b, decopperized) (representative, dried, homogenized) lab code: 09TT03745
B6 anodic slime, site 2A lab code: 09TT06661
B6 anodic slime, site 2B lab code: 09TT06662

Results and discussion

Results:

The tested materials were characterized (physico-chemical and mineralogical properties) in view of the upcoming REACH registrations of copper intermediates and copper slags by the Copper Consortium.
The studied four anode slime samples includes two types of anode slimes, first ones that consist mainly of anglesite –type lead sulphate, silver and antlerite –type copper sulphate. The other anode slimes consists mainly of naumannite, Ag2Se, anglesite, barite, Sb-As –oxides, copper chlorides and sulfates.
Chemically first anode slimes contains 21.5 and 27.5% silver, 10.3 and 11.6% copper, 1.9 and 2% arsenic, 18.5 and 24% lead and 6.5 and 10.7% sulphur. The chemically second anode slimes contain 13.1 and 21.9% silver, 0.5 and 8.1% copper, 3.6 and 5.3% arsenic, 1.14 and 10.7% lead and 6.4 and 7.8% sulphur.

Any other information on results incl. tables

The chemical analysis of studied sampled are given in Table 7 and Table 8 and their mineralogical composition in Table 9 and Table 10 with distribution of copper. The microscope images, XRD and TG/DSC –graphs and results of water solubility tests are given for sample09TT03745 in Appendix A, 09TT03746 in Appendix B, 09TT06661 in Appendix C and 09TT06662 in Appendix D.

 

Table 7: Chemical composition of studied sample, part 1

Lab code			09TT03745	09TT03746	09TT06661	09TT06662
Sample code			B6	B6	B6	B6
Cu	P1	%	11.20	4.10	0.19	2.56
	P2	%	0.03	5.84	0.03	0.09
	P3	%	0.09	0.15	0.27	5.24
	P4	%	0.02	0.05	0.05	0.04
	Sum		11.34	10.14	0.54	7.93
	TOT	%	11.60	10.30	0.53	8.09
As	P1	%	1.34	0.03	0.09	0.07
	P2	%	0.39	1.84	0.74	0.88
	P3	%	<0.005	<0.005	2.06	3.88
	P4	%	0.13	0.19	0.23	0.33
	Sum		1.86	2.06	3.12	5.15
	TOT	%	1.91	1.99	3.55	5.25
Fe	P1	%	0.02	0.03	0.01	0.17
	P2	%	<0.010	0.02	0.03	0.05
	P3	%	<0.005	<0.005	0.01	0.01
	P4	%	0.02	0.01	0.03	0.02
	Sum		0.04	0.05	0.08	0.26
	TOT	%	0.09	0.05	0.08	0.26
Ni	P1	%	0.63	0.11	<0.004	0.01
	P2	%	<0.010	0.02	<0.011	<0.016
	P3	%	<0.005	<0.005	<0.005	0.01
	P4	%	0.02	0.01	<0.002	0.00
	Sum		0.64	0.13	0.00	0.02
	TOT	%	0.68	0.15	<0.004	0.01
Pb	P1	%	0.06	0.02	0.09	0.03
	P2	%	0.12	0.13	0.10	0.13
	P3	%	0.87	1.10	0.05	0.06
	P4	%	16.70	21.70	9.63	1.05
	Sum		17.76	22.95	9.86	1.27
	TOT	%	18.50	24.00	10.70	1.14

P1= H₂O , P2= H₂SO₄, P3= KCN+Br-MeOH, P4= HNO₃–soluble, TOT= total -, BM= bromine-methanol dissolutions, KEM= ion exchange chromatography, LECO = S/C analyzer, satmagan = Fe₃O₄analyzer n.a. = Not analyzed

 

Table 8: Chemical composition of studied sample, part 2

Lab code			09TT03745	09TT03746	09TT06661	09TT06662
Sample code			B6	B6	B6	B6
Co	TOT	%	0.03	<0.004	<0.004	<0.004
Sb	TOT	%	0.69	1.05	8.16	9.80
Sn	TOT	%	0.04	0.13	0.05	0.02
Zn	TOT	%	0.02	0.01	0.00	0.00
Ag	TOT	%	21.50	27.50	21.90	13.10
Se	TOT	%	n.a.	n.a.	7.83	10.4
Te	TOT	%	n.a.	n.a.	1.30	1.06
SiO2	KEM	%	0.16	0.25	3.60	1.60
Al2O3	TOT	%	0.08	0.03	0.29	0.18
Cr2O3	TOT	%	<0.006	0.01	0.01	0.03
K2O	TOT	%	<0.072	<0.072	0.09	0.04
MgO	TOT	%	0.01	<0.007	0.04	0.01
MnO	TOT	%	<0.005	<0.005	<0.003	0.00
Na2O	TOT	%	0.06	0.05	0.10	0.05
CaO	TOT	%	0.11	0.05	0.13	0.08
Ba	TOT	%	n.a.	n.a.	7.16	15.30
S	Leco	%	10.70	6.46	6.38	7.82
SO42-	KEM	%	33.10	20.00	6.50	5.50
C	Leco	%	0.17	0.19	0.94	0.86
Satmagan		%	0.00	0.00	0.00	0.00
Surface area		m2/g	0.81	2.99	3.53	2.37
Density		g/cm3	4.13	4.94	4.94	4.56

P1= H₂O , P2= H₂SO₄, P3= KCN+Br-MeOH, P4= HNO₃–soluble, TOT= total -, BM= bromine-methanol dissolutions, KEM= ion exchange chromatography, LECO = S/C analyzer, satmagan = Fe₃O₄analyzer,n.a. = Not analyzed

 

 

Table 9: Mineral composition and distribution of copper, arsenic and silver

Sample		09TT03745				09TT03746
Type
Mineral composition		B6				B6
PbSO4	Anglesite	53.07		PbSO4	Anglesite	44.85
Ag	Silver	21.81		Ag	Silver	27.74
CuSOx	Antlerite	21.56		CuSOx	Antlerite	15.12
As2O3	Arsenolite	2.15		CuAsOx	Cornubite	7.68
SbAsO	Cervantite	1.12		SbSnO	Cervantite	4.35
SiO2	Quartz	0.16		SiO2	Quartz	0.25
CoNiSbSO4	Aplowite	0.13
Total		100.00		Total		100.00
Distribution of copper
CuSOx		100.00		CuSOx		66.33
				CuAsOx		33.67
Distribution of iron
CoNiSbSO4		100.00
Distribution of arsenic
As2O3		85.69		CuAsOx		94.90
SbAsO		10.18		CuSOx		2.64
CoNiSbSO4		0.05		PbSO4		2.46
Distribution of silver
Ag		94.79		Ag		91.78
PbSO4		2.18		PbSO4		5.40
SbAsO		0.25		CuSOx		2.64
				CuAsOx		0.18

 

 

Table 10: Mineral composition and distribution of copper, iron and arsenic

Sample		09TT06661				09TT06662
Type
Mineral composition		B6				B6
Ag2Se	Naumannite	31.14		Ag2Se	Naumannite	30.45
PbSO4	Anglesite	19.96		BaSO4	Barite	24.37
BaSO4	Barite	13.26		SbAs -oxide	SbAsOx	22.65
SbAs -oxide	SbAsOx	13.22		Cu2S	Chalcocite	7.05
AgCl	Chlorargyrite	12.04		Cu(SO4)*5(H2O)	Chalcanthite	5.75
SiO2	Quartz	3.60		PbSO4	Anglesite	5.17
SbTe -oxide	SbTeOx	3.28		SiO2	Quartz	1.60
CaSO4	Gypsum	1.67		CaSO4	Gypsum	1.49
Bi	Bismuth	0.86		CuFeS2	Chalcopyrite	0.85
Cu2S	Chalcocite	0.39		Au	Gold	0.62
Cu2Cl(OH)3	Atacamite	0.36
Au	Gold	0.22
Total		100.00		Total		100.00
Distribution of copper
Cu2S		50.57		Cu2S		64.77
Cu2Cl(OH)3		49.43		Cu(SO4)*5(H2O)		31.64
				CuFeS2		3.58
Distribution of iron
Cu2Cl(OH)3		100.00		CuFeS2		100.00
Distribution of arsenic
SbAs -oxide		100.00		SbAs -oxide		100.00

 

Applicant's summary and conclusion

Conclusions:

Good quality study that assessed full chemistry and mineralogy of several representative Copper slimes. Proposed RWC mineralogy (distribution pattern for each key element, i.e. % from Total into the various mineralogical forms/species present into the UVCB) can be used for classification of the UVCB substance (mixture toxicity rules)

Executive summary:

The studied four anode slime samples includes two types of anode slimes, first ones that consist mainly of anglesite –type lead sulphate, silver and antlerite –type copper sulphate. The another anode slimes consists mainly of naumannite, Ag2Se, anglesite, barite, Sb-As –oxides, copper chlorides and sulfates.Chemically first anode slimes contains 21.5 and 27.5% silver, 10.3 and 11.6% copper, 1.9 and 2% arsenic, 18.5 and 24% lead and 6.5 and 10.7% sulfur. The second Chemically first anode slimes contains 13.1 and 21.9% silver, 0.5 and 8.1% copper, 3.6 and 5.3% arsenic, 1.14 and 10.7% lead and 6.4 and 7.8% sulfur.

Based on these resulst the following RWC Distribution pattern is derived (relevant for classification):

Arsenic in oxyde As2O3/AsO3 (85.69% of total As) + in other oxide forms (10.18% of total As) + in metal (4.13% of total As)

Nickel in NiSO4 forms (100% of total Ni)

Cu in CuSO4 forms (100% of total Cu)

Cobalt in CoSO4 form (100% of total Co)

Lead in PbSO4/Pb compounds forms (100% of total Pb)

Sb in Sb sulphates/compounds forms (100% of total Sb)