European Union Risk Assessment Report

Voluntary Risk assessment of COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE

CAS No: 7440-50-8, 7758-98-7, 1317-3-1, 1317–38–0, 1332-65-6
EINECS No: 231–159–6, 231–847–6, 215-270-7, 215–269–1, 215-572-9

Responsible for this voluntary risk assessment : European Copper Institute (ECI)
Contact person: Dr. Katrien Delbeke, European Copper Institute, Brussels, Belgium
e-mail: kmd @eurocopper.org

Review country for this voluntary  risk assessment : Italy
Contact person: Dr. Roberto Binetti , Istituto Superiore di Sanità, Rome, Italy
e-mail: binetti@iss.it

CHAPTER 3 – EnvironmentalHazard classification

Appendix K5:   Refined information on the Transformation/dissolution of copper - Tests performed as a response to the comments from Sweden

Patricio H. Rodriguez, Centro de Investigacion Minera y Metalurgica (CIMM), e-mail : prodrigu@cimm.cl

Date of Last Literature Search :	2006	
Review of report by MS Technical Experts finalised:	April 2008	
Final report:	June 2008	

LEGAL NOTICE
Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which migh be made of the following information

A great deal of additional information on the European Union is available on the Internet.
It can be accessed through the Europa Server(http://europa.eu.int).

Foreword

In response to a request from the European Commission to “start preparing the initial assessments for substances on the EU working list as these were considered as Community priorities in the context of the industry voluntary initiatives for high production volume chemicals” the copper industry committed to undertake a Voluntary Risk Assessment (VRA) for copper and the copper compounds on the EU working list: Cu, CuO, Cu2O, CuSO4 and Cu2Cl(OH)3. This initiative was endorsed by the EU CAs in 2001. Yearly summaries on progress have been presented at the CA meeting.
This comprehensive VRA dossier has taken four years to complete, with the whole process managed by the European Copper Institute. It was compiled in co-operation with expert consultants from the University of Birmingham/ICON for human health toxicity, from BR. Stern and Associates for human health deficiency, and from Euras/Ecolas for the environment. It is based on the principles of Regulation 793/93, 1488/94 and the detailed methodology laid down in the revised Technical Guidance Document on Risk Assessment for New and Existing Substances. Methodological experiences gained through other metal Risk Assessments, e.g. the incorporation of bioavailability for zinc, were incorporated as appropriate. Additional up to date scientific information was integrated into the assessment where scientifically relevant (i.e. the use of bioavailability models for water, sediment and soil, plus information on copper as an essential nutrient). A broad cross section of the European copper industry has been fully involved in the process and has submitted a significant amount of proprietary data.

To ensure the transparency and quality of the dossier, the initial draft RA reports have been refined by incorporating inputs from the Review Country (Italy – Istituto Superiori di Sanità) and independent peer review panels.

For several of the substances under consideration, targeted risk assessments are required under the Biocidal Product Directive (98/8/EC) and the Plant Protection Products Directive (91/414). These dossiers, which have been/will be provided to the competent authorities (France) by the respective end user industry groups, contain confidential information not available to ECI. However, ECI has worked closely with both of these groups in incorporating relevant information to ensure consistency to the extent possible.
A single dossier covers the assessments for copper metal and the copper compounds, with substance specific aspects provided where relevant. For the base data compilation, extensive literature searches were performed for each substance. Data gaps were filled with analogous data, where relevant, or by additional testing where possible. Where the information was either unnecessary for the copper risk assessment, or impossible to obtain, waiving for testing and/or justification to support derogation is discussed. Some remaining data gaps were identified and will be tackled as a follow-up to this report.
Since the initial submission of the dossier on 15 May 2005, comments have been received from several Member States. The current version reflects comments made by the Member States in writing and during the TCNES meetings. To ensure the transparency and quality of the dossier, the current version and the responses to Member States comments have been refined in close co-oporation with the Review Country (Italy – Istituto Superiori di Sanità).

The human health and environmental sections of the report have been agreed by TCNES (see TCNES opinions) and sent to SCHER for final review.
This Draft Risk Assessment Report is the responsibility of the European Copper Insitute (ECI).  The member companies of the copper industry risk assessment consortium are the owners of the assessment.  These companies are listed below.
Industries/companies wishing to use all or part of the Risk Assessment Reports, and/or their appendices, for regulatory purposes such as for EU REACH registrations, EU Biocidal Products Directive Registrations, or EU Plant Protection Product Directive Registrations, are required to contact ECI to agree terms of access.

In order to avoid possible misinterpretations or misuse of the findings in this draft, anyone wishing to cite or quote any part of this report, or its related appendices, is advised to contact ECI beforehand.

Contact details of the responsible:
Dr. Katrien Delbeke, European Copper Insitute, Tervurenlaan 168, B-1150 Brussels, Belgium.  Tel: +32 2 777 7083, e-mail: kmd @eurocopper.org

Ownership
The industry companies that are part of the industry consortium are listed here:
	COPPER VOLUNTARY RISK ASSESSMENT - COMPANY MEMBERS IN INDUSTRY CONSORTIUM		
				
SITE	ADDRESS	CITY	COUNTRY	
ALCHEMA	East Ord Industrial Estate	Berwick Upon Tweed TD15 2XF	UK	
ANGLO AMERICAN BASE METALS	20 Carlton House Terrace	London SW1Y 5AN	UK	
ANTOFAGASTA MINERALS S.A.	Ahumada 11 - Piso 6	Santiago	CHILE	
Atlantic Copper - Cordoba	Barriada Electromecanica, s/n	E-14005 CORDOBA	SPAIN	
Atlantic Copper Barcelona	Ctra. Palaudaries, Km 0.4	E-08185 Llica de Vall	SPAIN	
ATLANTIC COPPER HOLDING S.A. -Huelva	Avda Francisco Montenegro, s/n	E-21001 HUELVA	SPAIN	
B. MASON & SONS LTD.	WHARF STREET, ASTON	BIRMINGHAM B6 5SA	UK	
BHP Billiton Plc	Avenida Americo Sur Nr. 100 - 8th Floor	Santiago	CHILE	
BOLIDEN AB.	Smaltverket	S-93281 Skelleftehamm	SWEDEN	
BOLIDEN CUIVRE ET ZINC	RUE DU FOURNEAU, 43	B-4030 GRIVEGNEE (LIEGE)	BELGIUM	
BOLIDEN LDM NEDERLAND B.V.	P.O. BOX 42 - LIPSSTRAAT 44	NL-5150 AA DRUNEN	NETHERLANDS	
BOLIDEN MINERAL AB	Klarabergsviadukten 90	SE - 101 20 Stockholm	SWEDEN	
BRAZE TEC GmbH	Rodenbacher Chaussee 4	D-63457 Hanau-Wolfgang	GERMANY	
BUNTMETALL AMSTETTEN GES.M.B.H.	FABRIKSTRASSE 4	A-3300 AMSTETTEN	AUSTRIA	
CODELCO-Chile	Huerfanos 1270, piso 11	650-0544 Santiago	CHILE	
Compañia Minera Doña Ines Collahuasi	Av. Andres Bello 2687 Piso 11	Las Condes, Santiago 6760276	CHILE	
Compañia Mineraria Zaldívar	1125 Seventeenth Street, Suite 2310	Denver, Colorado 80202	USA	
CUMERIO (was Umicore Copper)	Watertorenstraat 33	B-2250 OLEN	BELGIUM	
DEUTSCHE GIESSDRAHT GmbH	Kupferstraße 5	D-46446 EMMERICH	GERMANY	
ELMET S.L.	Barrio Arene 20	E-48640 BERANGO (Vizcaya)	SPAIN	
ENZESFELD-CARO METALLWERKE AG	Postfach 1, FABRIKSTRASSE 2	A-2551 ENZESFELD/TRIESTING	AUSTRIA	
Erachem Comilog SA	Rue du Bois	B-7334 Saint-Ghislain	BELGIUM	
EUROPA METALLI S.P.A Fornaci	Via della Repubblica, 257	I-55052 Fornaci di Barga (Lucca)	ITALY	
EUROPA METALLI S.P.A. Serravalle	Via Cassano 113	I-15069 Serravalle Scrivia (Alessaandria)	ITALY	
EUROPA METALLI SpA Campo Tizzoro	Viale L. Orlando 325	I-51023 Campo Tizzoro (Pistoia)	ITALY	
HALCOR METAL WORKS S.A. 	16 Himaras Str. 	Maroussi , GR 151 25	GREECE	
HALCOR METAL WORKS S.A. casting shapes	Foundry, Oinofyta (55th km)	GR	GREECE	
HALCOR METAL WORKS S.A. rolling mill	Rolling Mill, 252 PIRAEUS STREET	GR-17778 ATHENS	GREECE	
HALCOR METAL WORKS S.A. tube	Copper Tube Mill, Oinofyta (57th km)	GR	GREECE	
HÜTTENWERKE KAYSER AG.	Postfach 15 60, Kupferstraße 23	D-44505 LÜNEN	GERMANY	
IBP Group Services Limited	Whitehall Road 	Tipton, West Midland DY4 7JU	UK	
ISAGRO (ex Caffaro)	Via Caldera, 21	20153 Milano	ITALY	
KGHM Polska Miedz SA	ul. Sklodowsklej-Curie 48	59-301 Lubin	POLAND	
KM EUROPA METAL AG	POSTFACH 3320, Klosterstraße 29	D-49023 OSNABRUECK	GERMANY	
KME - Berlin	Miraustraße 10-14	D-13509 Berlin	GERMANY	
KME - Menden	Carl-Benz-Straße 13	D-58706 Menden	GERMANY	
KME Group	P.O. Box 33 20 Klosterstrasse	D-49074 Osnabruck	GERMANY	
LA FARGA LACAMBRA, SA	Ctra C-17, Km 73,5 COLONIA LACAMBRA	E-08509 LES MASIES DE VOLTREGA (BARCELONA)	SPAIN	
MANICA	Via all'Adige,4	38068 ROVERETO (Trento)	ITALY	
Méxicana de Cobre, S.A. de C.V.	Baja California No. 200 Sixth Floor	Mexico City 06760	MEXICO D.F.	
Minera Escondida Limitada	Avenida Americo Vespucio Sur Nr. 100 - 9th Floor	La Condes, Santiago	CHILE	
Mitsubishi Materials Corporation	20F OtemachiFirst Square West, 1-5-1, Ohtemachi, Chiyoda-KU	100-8117 Tokyo	JAPAN	
MKM MANSFELDER KUPFER UND MESSING GMBH	POSTFACH 1254, Lichtlöcherberg 40	D-06323 HETTSTEDT, D-0ß6333 Hettstedt	GERMANY	
MUELLER INDUSTRIES, Inc.	8285 Tournament Drive, Suite 150	Memphis, TN 38125	USA	
NEXANS	4-10, rue Mozart 	92587 Clichy Cedex	FRANCE	
NEXANS BOURG EN BRESSE	PO Box 101	F-01003 Bourg en Bresse	FRANCE	
Nexans IKO Sweden AB	 	S-514 81 Grimsas	SWEDEN	
NEXANS MEHUN SUR YEVRE	 	F-18500 Mehun Sur Yevre	FRANCE	
NEXANS WIRES CHAUNY	128, avenue Jean Jaures, BP30	F-02301 Chauny	FRANCE	
NEXANS WIRES MÂCON	Rue du Port	F-71000 Macon	FRANCE	
Nippon Mining & Metals Co., Ltd	Toranomon 2-chome, Minato, Ku	105-0001 Tokyo	JAPAN	
NORANDA Inc.	Avda Andrés Bello 2777 Oficina 801	Las Condes, Santiago 6760276	CHILE	
NORDDEUTSCHE AFFINERIE AG.	Postfach 10 48 40, Hovestraße 50	D-20033 HAMBURG, D-20539 Hamburg	GERMANY	
NORDIC BRASS AB	Box 524	S-721 09 Västeras	SWEDEN	
Nordox Industries AS	Ostensjovn. 13, PB 6639 Etterstad	N-0607 Oslo	NORWAY	
OK Tedi Mining Limited	P.O. Box 1, Dakon Road, Tabubil	Western Province, Papua	NEW GUINEA	
OMG Kokkola Chemicals Oy	PO Box 286
	67101 Kokkola	Finland	
OUTOKUMPU American Brass 	70 Sayre Street, P.O. Box 981	Buffalo, NY 14240	USA	
OUTOKUMPU COPPER Products AB	Box 510, Metallverksgatan 5	S-721 88 VAESTERAS, S-721 09 Västeras	SWEDEN	
OUTOKUMPU Copper Products Oyj	Riihitontuntie 7 A, P.O. Box 144	Espoo FIN-02201 	FINLAND	
OUTOKUMPU COPPER STRIP AB	Metallverksgatan 20-22	S-721 88 VAESTERAS, S-721 10 Västeras	SWEDEN	
Outokumpu Copper Strip AB- Finspang	 	S-612 81 Finspang	SWEDEN	
OUTOKUMPU COPPER TUBES S.A.	Bº ARKOTXA S/N	E-48480 ZARATAMO	SPAIN	
OUTOKUMPU HARJAVALTA METALS OY	P.O.Box 89	FIN-29200 Harjavalta	FINLAND	
OUTOKUMPU MKM LTD. (ex Boliden MKM)	MIDDLEMORE LANE - ALDRIDGE	WALSALL, West Midlands WS9 8DN	UK	
Outokumpu Nordic Brass AB (was BOLIDEN GUSUM AB)	Gräsdalens Industrial site	S-610 40 GUSUM	SWEDEN	
OUTOKUMPU PORICOPPER OY	P.O. Box 60	FIN-28101 Pori	FINLAND	
P.T. Freeport Indonesia Inc.	1615 Poydras Street P.O. Box 51777	New Orleans, Louisiana 70112	USA	
PALABORA Mining Company	P.O. Box 65 Phalaborwa, 1390	Limpopo Province	SOUTH AFRICA	
Phelps Dodge Corporation	One North Central Avenue	Phoenix, AZ 85004	USA	
PRYMETALL GMBH & CO. KG	Zweifaller Strasse 150	D-52224 Stolberg	GERMANY	
Revere Copper Products Inc.	One Revere Park	Rome, NY 13440-5561	USA	
RIO TINTO Plc	6 St. James' Square	London SW1Y 4LD	UK	
Sahna Kaimer GmbH/KG	Im Teelbruch 80	D-45219 Essen-Kettwig	GERMANY	
SCHWERMETALL HALBZEUGWERK GMBH	POSTFACH 6264, Breiniger Berg 165	D-52211 STOLBERG, D-52223 STOLBERG	GERMANY	
SOCIETE DE COULEE CONTINUE DE CUIVRE	42 RUE FERDINAND-BUISSON - B.P. 105	F-02301 CHAUNY CEDEX	FRANCE	
SOCIETE LENSOISE DU CUIVRE	Boulevard du Marais	F-62300 LENS CEDEX	FRANCE	
SPIESS URANIA	Heidenkampsweg 77	D-20097 Hamburg	GERMANY	
STOLBERGER METALLWERKE GMBH & CO. KG	POSTFACH 1929, Frankentalstraße 5	D-52206 STOLBERG, D-52222 Stolberg	GERMANY	
SUMITOMO Metal Mining Co., Ltd	1 1-3, Shimbasi 5-Chome, Minato-KU	105-871 6 Tokyo	JAPAN	
Thyssen Krupp VDM	Plettenberger Strsse 2	D-58791 Werdohl	GERMANY	
TREFILERIES ET LAMINOIRS DE LA MEDITERRANEE	35 RUE LE CHATELIER	F-13015 MARSEILLE CEDEX 15	FRANCE	
TREFIMETAUX - Givet Plant	Rue des Vieilles Forges	F-08600 Fromelennes	FRANCE	
TREFIMETAUX - Niederbruck	31, Rue Joseph Vogt	F-68290 Niederbruck	FRANCE	
TREFIMETAUX - Serifontaine	Rue M. Thorez, BP3	F-60590 Serifontaine	FRANCE	
TREFIMETAUX --usine de Boisthorel	 	F-61270 Rai	FRANCE	
UMICORE ITALIA SRL	nucleo industriale di Pianodardine (Avellino)	I-AVELLINO	ITALY	
WEDNESBURY TUBE & FITTINGS - MUELLER EUROPE	OXFORD STREET	GB- BILSTON WEST MIDLANDS WV14 7DS	UK	
WIELAND-WERKE AG Ulm Vöhringen	POSTFACH 42 40, Graf-Arco-Straße 36	D-89070 ULM, D-89079 ULM	GERMANY	
WIELAND-WERKE AG, WERK LANGENBERG	POSTFACH 110269,  Ziegeleiweg 20	D-42530 VELBERT, D-42555 VELBERT	GERMANY	
WIELAND-WERKE AG, WERK VILLINGEN	POSTFACH 1780, Lantwattenstr 11	D-78007 VILLINGEN, D-78050 VILLINGEN-SCHWENNINGEN	GERMANY	
WILLIAM BLYTHE LIMITED	Church, Accrington	Lancashire, BB5 4PD	UK	
WMC Copper uranium/WMC Resources Limited	IBM Tower 60 City Road	Southbank Vic 3006	AUSTRALIA	
Wolstenholme International	Springfield House, Lower Ecclesfield Road, Darwen	Lancashire BB3 0RP	UK	
XSTRATA Copper 	Level 9, Riverside Centre, 123 Eagle Street	Brisbane Q 4000	AUSTRALIA	
YORKSHIRE COPPER TUBE LTD. (KME)	East Lancashire Road, Kirby	LIVERPOOL L33 7TU	UK	
YORKSHIRE Fittings Ltd	P.O. Box 166	Leeds, LS10 1NA	UK	
				
European Copper Institute - May 12th 2005				

COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE

CAS No: 7440-50-8, 7758-98-7, 1317-3-1, 1317–38–0, 1332-65-6
EINECS No: 231–159–6, 231–847–6, 215-270-7, 215–269–1, 215-572-9

VOLUNTARY Risk Assessment

Appendix K5:   Refined information on the Transformation/dissolution of copper - Tests performed as a response to the comments from Sweden

P. Rodriguez, Centro de Investigacion Minera y Metalurgica (CIMM), e-mail : prodrigu@cimm.cl

Introduction
In the copper Risk Assessment Report ( RAR Submitted May 2005, Appendix K2),  T/D  data of copper wires indicated abrasion of the copper wire during the test.  Evaluation of the influence of the stirring rate on the abrasion, demonstrated that a reduction of the stirring rate from 100 rpm to 50 rpm allowed to limit the influence of abrasion.  
To further understand the importance of abrasion, samples of copper were submitted to a 7 days transformation/dissolution test, in accordance to the OECD protocol but using abrasion-fee devices (polypropylene wheels).   The test set-up used involved a 7 days transformation/dissolution of 100mg copper/L, at a  pH of 6.0  and using a stirring rate of 100 RPM. Transformation/dissolution with and without using the abrasion- free device were compared.

Figure 1 : Anti-abrasion device used for the T/D tests

Results
The  results of the measurements of pH, Temperature and Dissolved Oxygen in the test vials during the test are provided in table 1

Table 1 : pH, temperature and oxygen concentrations measured during the 7 days transformation/dissolution tests

pH	5.86	±	0.08	
				
Temperature, ºC	22.36	±	1.39	
				
O2, mg/L	7.80	±	0.20	

The results of the measurements of dissolved copper concentrations are provided in table 2 and figure 2
Figure 2 : Dissolved copper concentrations (µg/L) with without anti-abrasion device

Table 2 : Dissolved copper concentrations (µg/L) with without anti-abrasion device
		Copper		
Blanks	Time	Mean	SD	
	0	1.18	1.23	
	2	0.59	1.31	
	6	0.90	0.51	
	24	0.23	0.25	
	48	0.19	0.19	
	96	0.35	0.63	
	168	0.19	0.46	
With anti-abrasion	Time	Mean	SD	
	0	0.72	0.26	
	2	1.50	0.70	
	6	0.88	0.52	
	24	1.82	0.80	
	48	1.59	0.31	
	96	3.21	1.40	
	168	6.47	1.15	
Standard conditions	Time	Mean	SD	
	0	0.80	0.73	
	2	1.97	0.72	
	6	2.49	0.79	
	24	5.15	0.83	
	48	9.64	0.67	
	96	23.08	1.00	
	168	50.76	7.95	

The results confirm that at 100 rpm, abrasion of copper wire influences the data.  After 7 days of T/D, the amount of copper released during the classic T/D test was shown to be overestimated due to abrasion of the wire against the glass wall.   Comparing the surface area–specific release rate of copper massive at pH 6  using  the abrasion –fee device (0.15 µg Cu/mm2)  with the one form the classic test-set-up (1.1 Cu/mm2) respectively observed in this report  and used in the RAR emphasizes shows an overestimation of the copper release rate from copper massive in a classic test set-up due to abrasion at 100 rpm and even at 50 rpm by a factor of 6.9 times.   The new test set-up thus confirms the no classification proposal of copper massives.