Toxic metals in jewellery. Assessment protocols 69.pdf · 2011. 8. 29. · These substances were mainly distributed as homogeneous metallic materials (base alloy, brazing or coatings,

Toxic metals in

jewellery. Assessment

protocols

2010 Project Report

The Toxic Metals in Jewellery Project is part of a global action whose goal is the

assessment of the presence of toxic metals in jewelry and the creation of

classification criteria for the products that contain them.

The final objective is to provide the Jewelry Sector with a set of trustworthy

methodologies capable of proving their product’s compliance to current

legislation (REACH Regulation, CLP Regulation and GPSD Directive) in order to

guarantee the absence of health and safety risks.

The part of the project that corresponds to jewelry from Asia, Spain and the

rest of Europe was accomplished during 2010.

2010

G. Lloret

AIMME

01/12/2010

This project has been supported by IMPIVA and

FEDER

IAAO 69

Toxic metals in jewellery. Asses

[email protected]

AIMME

http://www.aimme.es

1. Introduction

In 2010 work was carried out on the Project “Toxic Metals in Jewellery. Assessment Protocols”

(IMIDIC/2010/48).

This work was undertaken a

(AIMME) and funded by I

co-funded by the European Regional Development Fund (ERDF) and makes up part of a global

action aimed at assessing the presence of toxic metals in jewellery and setting criteria for

classifying products containing these metal

This Project is the follow on from a series of actions that were initiated in 2008, which were all

funded by IMPIVA and the ERDF and have gone through the following stages:

---

These actions are having important repercussions in different areas of society: economic,

corporate, professional, technological, institutional,

are the multiple references to be found in the RPA Ltd. Report for the European Commission

(D.G. Enterprise and In

of the International A

We would like to remind everyone that the ultimate aim of the project is to provide the

jewellery sector with a set of reliable methodologies to prove conformity of their products

without putting

-

-

-

-


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AIMME - Instituto Tecnológico Metalmecánico

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Introduction


(IMIDIC/2010/48).


(AIMME) and funded by I

funded by the European Regional Development Fund (ERDF) and makes up part of a global





- 2008: Assessment of jewellery coming from Asia

- 2009: Assessment of jewellery com

- 2010: Assessment of jewellery coming from Asia + Europe + Spain




(D.G. Enterprise and In

of the International A



without putting people’s health and safety at risk, while making it possible to:

Know all instruments for prevention and control demanded by the market under any

circumstances

Set up a surveillance or warning framework that is useful to all members of the supply

chain and competent authorities

Assess the degree of conformity of items of jewellery using the provisions laid down in

the GPSD Directive and the

Limit or eradicate substances of great concern that can be released on contact with

the skin (sweat), mu

digestive juices (ingestion)

Toxic metals in jewellery. Assessment

Instituto Tecnológico Metalmecánico

http://www.aimme.es


Introduction


(IMIDIC/2010/48).


(AIMME) and funded by IMPIVA as part of its R&D Program






2008: Assessment of jewellery coming from Asia

2009: Assessment of jewellery com

2010: Assessment of jewellery coming from Asia + Europe + Spain




(D.G. Enterprise and Industry) or the presentation of

of the International Association of Assay Offices (IAAO, Zurich, 2010 April).



people’s health and safety at risk, while making it possible to:


circumstances


nd competent authorities


GPSD Directive and the


the skin (sweat), mucous membranes (saliva),


ment protocols



protocols


This work was undertaken and developed by the M

MPIVA as part of its R&D Program







2009: Assessment of jewellery com





dustry) or the presentation of

ssociation of Assay Offices (IAAO, Zurich, 2010 April).






nd competent authorities


GPSD Directive and the REACH and CLP Regulations


cous membranes (saliva),



protocols


nd developed by the M

MPIVA as part of its R&D Program



classifying products containing these metals.




2009: Assessment of jewellery coming from Asia + Europe (except Spain)



corporate, professional, technological, institutional, sociopolitical and citizens. Examples of this


dustry) or the presentation of








ACH and CLP Regulations


cous membranes (saliva),


protocols


nd developed by the Metal-Processing

MPIVA as part of its R&D Programme fo






ing from Asia + Europe (except Spain)



sociopolitical and citizens. Examples of this


dustry) or the presentation of results of the project in the








ACH and CLP Regulations.


cous membranes (saliva), dermis (intradermal fluids)

http://observatorio.aimme.es



Processing Technology Institute

me for Technology Institutes. It is










results of the project in the









dermis (intradermal fluids)


2 de

ment


Technology Institute

r Technology Institutes. It is








results of the project in the 5th Meeting








dermis (intradermal fluids) or with the


de 47


Technology Institute

r Technology Institutes. It is







5th Meeting







or with the


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AIMME

http://www.aimme.es

2. Results for 2010

During 2010 a total of 817 shipments were checked, both imported or of Spanish manufacture,

which account for 82% of

Distribution according to origin is:

-

-

Highly toxic metals (nickel, cobalt,

total of 337 shipments, equivalent to 41.2 % of those checked and distributed as follows:

----

These substances were mainly distributed as homogeneous metallic materials (base alloy,

brazing or coatings, as laid down in ANNEX

toxic metals in decorative areas of the jewellery (gems, stones, pearls,

Classification of toxic metal detected based on homogeneous material affected and

characteristics. The shipments were divided up according to the toxic metal:

Homogeneous material

White gold

Yellow gold

Coated gold

Silver

Gold-plated silver

Coated silver

Decorative parts

Total

Table 1. Distribution of shipments according to toxic metal and homogeneous material affected


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Results for 2010


which account for 82% of


- 510 import shipments (397 Asian, 109 European and 4 American)

- 307 shipments of manufactured goods, all of Spanish origin



- Asia

- USA :1 shipment (0.1 % of total

- Europe

- Spain







White gold

Yellow gold

Coated gold

plated silver

Coated silver

Decorative parts

1. Distribution of shipments according to toxic metal and homogeneous material affected



http://www.aimme.es

Results for 2010


which account for 82% of consignments of articles arriving at AIMME for hallmarking.


510 import shipments (397 Asian, 109 European and 4 American)

307 shipments of manufactured goods, all of Spanish origin



:172 shipments (21 % of total and 43 % of Asian share)

USA :1 shipment (0.1 % of total

:39 shipments (5 % of total and 46 % of European share)

:125 shipments (12 % of total and 46 % of Spanish share)






Shipments

194

4

3

18

3

139

4

365


ment protocols



consignments of articles arriving at AIMME for hallmarking.




Highly toxic metals (nickel, cobalt, cadmium, antimony, selenium or lead) were detected in a



USA :1 shipment (0.1 % of total








Nickel

194

1

3

3

---

25

---

226






cadmium, antimony, selenium or lead) were detected in a



USA :1 shipment (0.1 % of total and 25 % of American share)




brazing or coatings, as laid down in ANNEX I). Only 4 cases were detected with the presence of




Cadmium Selenium

---

3

---

9

3

---

---

15









and 25 % of American share)




). Only 4 cases were detected with the presence of




Selenium Antimony

---

---

---

6

---

---

---

6










and 25 % of American share)





toxic metals in decorative areas of the jewellery (gems, stones, pearls, crystals or enamel)



Antimony Cobalt

--- ---

--- ---

--- ---

--- ---

--- ---

80 34

--- ---

80 34



3 de







crystals or enamel)


Cobalt Lead

--- ---

--- ---

--- ---

--- ---

--- ---

34 ---

--- 4

34 4


de 47





crystals or enamel)


Chromium

---

---

---

---

---

---

---

0


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From the previous figures it may appear that the number of shipments in which

of a toxic metal was found should be greater than 337. The difference can be put down to the

fact that some of them contain up to two or three different toxic metals.

It is rather surprising to see the large increase produced when compared wit

2009 for import consignments, as well as the particularly high rate of Spanish manufacturing

using white gold. (See Table 2)

It is also surprising to see how certain problems that began to show up in previous years have

grown in strength in

shown itemized by the type of homogeneous material. This also includes a comparison of

absolute figures from previous years and a chart of the most representative origins.

3. Homogeneous mat

A distinction is made between alloys of white gold, alloys of yellow gold and alloys of

electroformed yellow gold (hollow jewellery). The final column shows the total number of

items involved in shipments from 2010 that were put on the

hallmarking in the AIMME laboratory

Au alloy and toxic

metal

White Au with Ni

White Au with Cd

Yellow Au with Ni

Yellow Au with Cd

Yellow Au with Cd

(electroformed.)

In 2010 a growth in shipments of 375 ‰ gold was detected which was triggered off by a

shortage of the metal. A halving of the gold content is accompanied by a proportional increase

in alloy content, except, generally speaking, for silver or palladium.

For this reason, high levels of nickel have been showing up in 375 white gold alloys (around

150 ‰) never detected in the past


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grown in strength in



Homogeneous mat





Au alloy and toxic

metal 2008

White Au with Ni 24

White Au with Cd ---

Yellow Au with Ni ---

Yellow Au with Cd ---

Yellow Au with Cd

(electroformed.)

1

Table 2. Comparison of distribution of gold shipments checked in 2010 + chart of origins.

Symbols: Au = gold, Ni = nickel, Cd = cadmium. Note* = the United States

n 2010 a growth in shipments of 375 ‰ gold was detected which was triggered off by a



this reason, high levels of nickel have been showing up in 375 white gold alloys (around




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grown in strength in the market. Detailed information of statistics from 2010 will now be



Homogeneous material: Gold alloys





2008 2009 2010

61 194

1 ---

--- 1

1 3

--- ---

Comparison of distribution of gold shipments checked in 2010 + chart of origins.







ment protocols









the market. Detailed information of statistics from 2010 will now be



erial: Gold alloys




hallmarking in the AIMME laboratory.

2010 China

194 38

--- ---

---

---

--- ---







0 ‰) never detected in the past.










erial: Gold alloys




Thailand India

7 2

--- ---

--- ---

--- ---

--- ---



















India Turkey

6

--- ---

--- ---

--- 1

--- ---



















items involved in shipments from 2010 that were put on the market after undergoing

Italy Spain

23 117

--- ---

1 ---

2 ---

--- ---








4 de

From the previous figures it may appear that the number of shipments in which the presence


It is rather surprising to see the large increase produced when compared with figures from








market after undergoing

Spain Others*

1

---

---

---

---





de 47

the presence


h figures from







market after undergoing

Items

36.414

---

39

463

---





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AIMME

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White gold alloys generally include coatings of rhodium to achieve whiteness and shine. They

may also include undercoatings of pal

If nickel is found at the same time in the base alloy and in the subsequent series of coatings, it

is very difficult to pick up on its content of both homogeneous materials or

contributions to releasing a toxic substance.

This does not happen if the base alloy only includes palladium it is possible, using electronic

microscopy (SEM), to sequence both materials and determine the quantity of nickel in

palladium

It is surprising the extent to which alloys of white gold containing nickel have consolidated

themselves in the market, in particular within Spanish jewellery. In the case of Spain it can be

concluded that the use of palladium has fallen int

The presence of nickel as a substitute for silver in yellow gold alloys can be taken as incidental.

The only case found in 2010 has no analogy with previous years. This is an emerging situation

that needs to be kept u

Finally, it is worth highlighting the drop in electroformed yellow gold (hollow jewellery)

shipments. The explanation is to be found in the present downturn in demand

manufacture of electroformed jewellery is only p

4. Homogeneous material: Silver alloys

Silver alloys always include an electrolytic coating of silver to enhance the shine. Additionally,

other coatings are included to achieve

This section only includes cases in which the toxic metal is evenly distributed within the base

alloy. The layers of coatings are considered separately, since they are viewed as

homogeneous materials

Ag alloy and

toxic metal

Ag with Ni

Ag with Cd


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palladium-nickel coating.






that needs to be kept u




Homogeneous material: Silver alloys






Ag alloy and

toxic metal 2008

Ag with Ni 2

Ag with Cd ---

Table 3. Comparison of distribution of silver shipments checked in 2010 + chart of origins.

Symbols: Ag = silver, Ni = nickel, Cd = cadmium



http://www.aimme.es








ckel coating.






that needs to be kept under surveillance in the future









homogeneous materials.

2008 2009 2010

1 3

7 7

Comparison of distribution of silver shipments checked in 2010 + chart of origins.


ment protocols



may also include undercoatings of palladium or palladium











nder surveillance in the future






other coatings are included to achieve coloured



2010 China

1

---




ladium or palladium








concluded that the use of palladium has fallen into disuse at the expense of nickel.



nder surveillance in the future



manufacture of electroformed jewellery is only profitable for large batches of articles.



coloured finishes



Thailand India

--- ---

1 6




ladium or palladium-nickel.







o disuse at the expense of nickel.



nder surveillance in the future.



rofitable for large batches of articles.


finishes, including



India Turkey

--- ---

---




.














, including gold-plating



Italy Spain

1 1

--- ---



5 de



is very difficult to pick up on its content of both homogeneous materials or their separate









shipments. The explanation is to be found in the present downturn in demand as the



plating.


alloy. The layers of coatings are considered separately, since they are viewed as different

Spain Others

---

---


de 47



their separate








as the



different

Items

1.353

11.088


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AIMME

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Nickel is not usual as an alloying

shown during

The situation is markedly different when dealing with electrolytic coatings on silver in order to

achieve coloured surfaces, or in the series of multilayer coatings, where nickel can be seen

more often as

The presence of cadmium in silver alloys has maintained the same rate of consolidation as in

2009, especially in imports of Asian origin (India).

5. Homogeneous material: Platinum alloys

Frequently used platinum alloys

can also include tungsten, cobalt or nickel

In this report, those that include nickel or cobalt are important due to the risks that they pose

for people’s health and safety and the limitations o

classified according to risk type

However, no case has been detected in AIMME’s laboratory over the last three years of

research

6. Homogeneous material: Brazing

In jewellery brazing is used and applied to particular areas of

In order to aid penetration through the gaps that are prepared, alloys with low melting points

are added, such as cadmium, lead, zinc,

Brazed

Mechanically prepared chains are an exception; here appreciable amounts of braz

found near fasteners

In 20

“Combinations between different homogeneous materials”)


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shown during progress of the project over the last three years



more often as part of an alloy



Homogeneous material: Platinum alloys





assified according to risk type


research.

Homogeneous material: Brazing




Brazed joints are located in very speci


found near fasteners

In 2010 silver chains were detected with cadmium in all of the links (see section 9




http://www.aimme.es


progress of the project over the last three years



part of an alloy








assified according to risk type






joints are located in very speci


found near fasteners.

silver chains were detected with cadmium in all of the links (see section 9


ment protocols


Nickel is not usual as an alloying-forming metal with silver and is only found occasionally, as




part of an alloy (see section 8)




Frequently used platinum alloys include copper (jewellery) or ruthenium (watchmaking). They




assified according to risk type.





are added, such as cadmium, lead, zinc, tin or indium

joints are located in very specific areas, which sometimes make




forming metal with silver and is only found occasionally, as




section 8)




include copper (jewellery) or ruthenium (watchmaking). They

can also include tungsten, cobalt or nickel.


for people’s health and safety and the limitations of content laid down in REACH Regulations,





tin or indium.

fic areas, which sometimes make





progress of the project over the last three years.







f content laid down in REACH Regulations,


In jewellery brazing is used and applied to particular areas of the article by capillary action


.

fic areas, which sometimes make













the article by capillary action


fic areas, which sometimes make it difficult to find them.




6 de









the article by capillary action


it difficult to find them.

Mechanically prepared chains are an exception; here appreciable amounts of brazing can be



de 47









the article by capillary action.


it difficult to find them.

ing can be



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7. Homogeneous material: Singular coatings

Electrolytic coatings and surface conversion finishes are much used in jewellery to provide the

articles with properties that are difficult to achieve only from base alloys, mainly a

shine

To achieve this, single

are evenly distributed in the layers containing them (external and/or underlying)

According to what has just been mentioned, and the definitions given in ANNEX

understood that each of the deposi

which, at the same time is perfectly distinguishable from other homogeneous materials such

as the base metal or the brazing

In this section, the presence of

regardless of whether we are considerin

The presence of toxic metals in coatings is without a doubt the most worrying case in the

study, more so the nearer they are found to the surface. Indeed, the t

spread throughout the article but rather concentrates in a zone measuring few

which comes into direct contact with the skin or very close to it.

Therefore, the local effect a coating has is formidable and stimulates the appearance of the

different pathologies

The standard practice followed by watchdogs and laboratories to assess conformity with

REACH or CLP

be considered a

the homogeneous

Obviously, if the toxic metal is distributed b

not present, its content is minimized in such a way that it is even possible to obtain lower

values than the threshold levels laid down

the values are normally

The content of toxic substance as % in weight is established with respect to the homogeneous

material it contains. This could constitute an important limitation since it makes it necessary to

have equipment and analytical techniques, which

laboratories


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Homogeneous material: Singular coatings



shine and colour.

To achieve this, single





he base metal or the brazing








different pathologies


REACH or CLP – through determination of the toxic metal content in terms of % weight

be considered a serious error

homogeneous




the values are normally




laboratories.



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.

To achieve this, single-layer or series of mu





he base metal or the brazing








different pathologies associated with the toxic metal


through determination of the toxic metal content in terms of % weight

serious error

homogeneous affected material




the values are normally well exceeded.




ment protocols





layer or series of mu



understood that each of the deposited layers constitutes a distinct homogeneous material,


he base metal or the brazing.

In this section, the presence of a single toxic metal within a single

regardless of whether we are considering a single or multilayer system






associated with the toxic metal



serious error if carried out by total weight of the piece and not by weight of

affected material.




well exceeded.







layer or series of multi-layer coatings are used, where the toxic metals



ted layers constitutes a distinct homogeneous material,


a single toxic metal within a single

g a single or multilayer system






associated with the toxic metal.



if carried out by total weight of the piece and not by weight of

Obviously, if the toxic metal is distributed between other homogeneous materials where it is


values than the threshold levels laid down under REACH or CLP



have equipment and analytical techniques, which are




layer coatings are used, where the toxic metals





a single toxic metal within a single

g a single or multilayer system






.




etween other homogeneous materials where it is


REACH or CLP



are often beyond the reach









a single toxic metal within a single coating

g a single or multilayer system.


study, more so the nearer they are found to the surface. Indeed, the toxic action is not evenly








criteria, even in cases where



often beyond the reach


7 de


articles with properties that are difficult to achieve only from base alloys, mainly a spec



According to what has just been mentioned, and the definitions given in ANNEX I, it is



coating is identified,


oxic action is not evenly

spread throughout the article but rather concentrates in a zone measuring few micrometers


The standard practice followed by watchdogs and laboratories to assess conformity with GPSD,

through determination of the toxic metal content in terms of % weight –




, even in cases where



often beyond the reach of many assay


de 47


specular


, it is



is identified,


oxic action is not evenly

micrometers


GPSD,

could




, even in cases where



of many assay


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Cases recorded in 2010 are shown in the following table:

Base alloy + coating

Toxic metal

White Au + Ni

(black colour)

Yellow Au + Au

(3N colour)

Ag plated with Au

Cd (yellow gold)

Ag + Ag

Ag + Ni

(White colour)

Ag + Co

Ag + Ni

Ag + Ni

Ag blackened

(selenides)

The analysis of reasons and trends provides the followin

All of

on silver, involve external coatings, which are consequently in permanent or prolonged contact

with the skin (sweat), mucous membranes (saliva) or intradermal

The risks associated with these substances allegedly show up immediately and are intense.

Generally, they remain present for a long time as, due to their notable thickness, their

resistance to wear and their durability last for practically

Dark or black ruthenium finishes on white gold and silver have grown in the last few years and

are highly valued for their beauty and colour contrast. These sensorial qualities are heightened

when underlying coatings of pallad

Parallel to this, the use of other black coatings of nickel

ruthenium substitutes

developed swiftly for silver finishes and


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Base alloy + coating

and

Toxic metal

White Au + Ni-Zn

(black colour)

Yellow Au + Au-Ni

(3N colour)

Ag plated with Au-Cu-

Cd (yellow gold)

Ag + Ag-Sb (White

colour)

Ag + Ni or Pd-Ni

(White colour)

Ag + Co-Sn (black

colour)

Ag + Ni-Zn (black

colour)

Ag + Ni-Sn (black

colour)

blackened with Se

(selenides)

Table 4. Comparison of distribution of gold and silver shipments with coatings containing a single toxic metal,

checked in 2010 + its chart of origins (* Germany / ** Indonesia)

Cu = copper, Co = cobalt, Sn = tin, Se = selenium


All of the cases in this section, with the exception of coatings of pure nickel or palladium










ruthenium substitutes




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2008 2009

--- ---

--- ---

1 ---

2 37

2 3

1 3

--- 2

--- ---

--- ---

Comparison of distribution of gold and silver shipments with coatings containing a single toxic metal,


Symbols: Au = gold, Ni = nickel, Zn = zinc, Ag = silver, Cd = cadmium, Sb = antimony, Pd = palladium,



the cases in this section, with the exception of coatings of pure nickel or palladium










ruthenium substitutes has spread, due to both its lower cost and ease of use. This trend has


ment protocols



2010 China

1 ---

2 ---

3 2

58 49

2 1

28 21

6 2

3 3

6 ---














when underlying coatings of palladium and y


has spread, due to both its lower cost and ease of use. This trend has

developed swiftly for silver finishes and mor


China Thailand

--- 1

--- ---

---

49 1

---

21 3

3

---

--- ---














ium and yellow gold are applied



more slowly in the case of gold


India Turkey

--- ---

--- ---

--- ---

--- ---

--- ---

1 3

1 ---

--- ---

--- 1




The analysis of reasons and trends provides the following singularities and conclusions






resistance to wear and their durability last for practically all their lifespan.



ellow gold are applied

Parallel to this, the use of other black coatings of nickel-zinc, nickel


e slowly in the case of gold


Turkey Italy Spain

---

1

1

4

1

---

---

---

1



g singularities and conclusions



fluids (piercings).



all their lifespan.



ellow gold are applied.

zinc, nickel-tin or cobalt


e slowly in the case of gold.


8 de

Spain Others

--- ---

1 ---

--- 1*

3 1**

--- ---

--- ---

--- ---

--- ---

4 ---



g singularities and conclusions:

the cases in this section, with the exception of coatings of pure nickel or palladium-


(piercings).





tin or cobalt-tin as



de 47

Items

9

443

829

113.28

6

41

30.183

48.975

2.620

1.805



-nickel






tin as



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Not all of the cases described in Table 4, for nickel

external coatings. Four cases were detected where the black finishes lies below a yellow gold

coating having very little

The aim of using multi

due to interference between black and yellow colours

obtained as it is not necessary to use coatings of alloys of greater thickness.

---

-

None of the cases involve gold plating but rather a very thin coating in order to favour

chromatic

against the release of nickel and cobalt is very tenuous.

White finishes aimed at enhancing the luster of silver are mostly of silver

occasionally, palladium

both coatings combined as a series of coatings prior to rhodium. In

whole piece is enhanced, whilst there is a reduction in the thickness of the rhodium of

approximately 0.1

2009 and 2010 have seen a consolidation in coatings of silver

is great

coating. These qualities explain the advance in the presenc

Lastly, it is worth pointing out the impact of black oxides on silver due to for

of silver sulphoselenide

a respectable position and incorp

toxic via saliva intake

Strictly speaking, we

compound formed by reaction with silver. It is consequently in a combined state and it is

unnecessary for an attack to take place

state. Simply by dissolving the compound it is able to penetrate the body and instantaneous

exert all its toxic capacity


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ng having very little

The aim of using multi



- A shipment of silver coming from China, with a series of Co

- coatings that make a total of 1,715 items

- Two shipments of silver coming from China, with a series of Ni

coatings that make a total of 9,258 items

- One shipment of silver coming from India, with a series of Ni

make a total of 169 items


chromatic interference (approx. 0.2 micrometers



occasionally, palladium



approximately 0.1


is greater than those of pure silver, and its appearance holds similarities with a rhodium



silver sulphoselenide


toxic via saliva intake

Strictly speaking, we



tate. Simply by dissolving the compound it is able to penetrate the body and instantaneous

exert all its toxic capacity



http://www.aimme.es



ng having very little thickness

The aim of using multi-coatings is to provide jewellery with an eye



A shipment of silver coming from China, with a series of Co


Two shipments of silver coming from China, with a series of Ni


One shipment of silver coming from India, with a series of Ni



interference (approx. 0.2 micrometers



occasionally, palladium-nickel. As explained in the next section, it is common to come across



approximately 0.1 – 0.3 micro


er than those of pure silver, and its appearance holds similarities with a rhodium



silver sulphoselenide. These finishes, which were unheard of until 2010, have slowly built up


toxic via saliva intake.

Strictly speaking, we are not dealing with a metallic coating but rather with a selenium




exert all its toxic capacity on contact with the saliva or via ingestion

ment protocols




thickness.

coatings is to provide jewellery with an eye










interference (approx. 0.2 micrometers



nickel. As explained in the next section, it is common to come across



0.3 micrometers.





. These finishes, which were unheard of until 2010, have slowly built up

a respectable position and incorporated a new metal to the study

are not dealing with a metallic coating but rather with a selenium


unnecessary for an attack to take place –


on contact with the saliva or via ingestion

Not all of the cases described in Table 4, for nickel-zinc, nickel











interference (approx. 0.2 micrometers). For this reason, their effect as a barrier











orated a new metal to the study



– through sweat or saliva



zinc, nickel-tin and cobalt



due to interference between black and yellow colours. At the same time, a reduction in costs is






). For this reason, their effect as a barrier






2009 and 2010 have seen a consolidation in coatings of silver-antimony on silver, whose shine


coating. These qualities explain the advance in the presence of antimony in plating silver



orated a new metal to the study



through sweat or saliva




tin and cobalt-tin, correspond to


coatings is to provide jewellery with an eye-catching chromatic tonality,

. At the same time, a reduction in costs is

obtained as it is not necessary to use coatings of alloys of greater thickness. This happened in

A shipment of silver coming from China, with a series of Co-Sn + Au-Cu,

Two shipments of silver coming from China, with a series of Ni-

One shipment of silver coming from India, with a series of Ni-Zn + Au coatings that



White finishes aimed at enhancing the luster of silver are mostly of silver-antimony and, just


both coatings combined as a series of coatings prior to rhodium. In this way, the shine of the


antimony on silver, whose shine


e of antimony in plating silver

Lastly, it is worth pointing out the impact of black oxides on silver due to formation of a patina


orated a new metal to the study (selenium)



through sweat or saliva – for it to change to its ionic


on contact with the saliva or via ingestion.


9 de

tin, correspond to


catching chromatic tonality,


This happened in

Cu,

-Zn o Ni-Sn + Au

Zn + Au coatings that



antimony and, just


this way, the shine of the




e of antimony in plating silver.

mation of a patina


(selenium) which is highly



for it to change to its ionic



de 47

tin, correspond to


catching chromatic tonality,


This happened in:

Sn + Au

Zn + Au coatings that



antimony and, just


this way, the shine of the




mation of a patina


highly



for it to change to its ionic

tate. Simply by dissolving the compound it is able to penetrate the body and instantaneously


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8. Homogeneous material: Combined coatings

This section identifies the multilayer systems

different multi

In accordance with the definitions set out in ANNEX

homogeneous material. A distinction must be made between those containing toxic metals in

order to separately assess their percentage content in weight, or to make the system for

determining the

When considering the casuistry of coatings, and the increase in inherent pathologies due to

their local effect, the case

In fact, the presence of two or more toxic materials that make up a series of overlapping layers

could produce a synergic effect whose equivalent risk is greater than what eac

pose separ

All the considerations described in the previous section can be applied here. This highlights

even more the need to apply protocols and strict test methods in order to properly assess the

degree of conformity or non

and CLP regulations

Table 5 shows cases identified in 2010. In the first column the multi

same order as they appear

--

Base alloy + coatings

and toxic metal

Ag + Ag

(white colour)*

Ag + Ag

Ni (white colour)**

Ag + Ag

Ni (black

Ag + Ag

(black colour)

Ag + Ag

(black colour)

Table 5


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Homogeneous material: Combined coatings


different multi-coatings



der to separately assess their percentage content in weight, or to make the system for

determining the rate of release a reliable one


their local effect, the case



pose separately.




and CLP regulations


same order as they appear

- Substrate + internal coatings, or

- Substrate + internal coatings + external

Base alloy + coatings

and toxic metal

Ag + Ag-Sb + Pd-Ni

ite colour)*

Ag + Ag-Sb + Ni + Pd-

hite colour)**

Ag + Ag-Sb + Ni + Pd-

black colour)**

Ag + Ag-Sb + Ni-Zn

(black colour)

Ag + Ag-Sb + Ni-Sn

(black colour)

Table 5. Comparison of distribution of shipments of silver having combined coatings containing several

toxic metals, checked in 2010 + the chart of origins.

Symbols: Ag = silver,



http://www.aimme.es



coatings.




rate of release a reliable one


their local effect, the case of combined coatings is an extremely worrying issue






and CLP regulations.


same order as they appear:

Substrate + internal coatings, or

Substrate + internal coatings + external

2008 2009

--- ---

--- ---

--- ---

--- ---

--- ---

Comparison of distribution of shipments of silver having combined coatings containing several


Symbols: Ag = silver, Sb = antimony, Pd = palladium,

ment protocols







rate of release a reliable one


of combined coatings is an extremely worrying issue





degree of conformity or non-conformity of affected articles


Substrate + internal coatings, or

Substrate + internal coatings + external

2010 China

7 6

1 1

6 6

--- ---

6 6



Sb = antimony, Pd = palladium,


This section identifies the multilayer systems by showing different toxic metals located in




rate of release a reliable one.







conformity of affected articles


Substrate + internal coatings + external coating (or finish)

China Thailand

---

---

---

--- ---

---



Sb = antimony, Pd = palladium, Ni = nickel, Zn = zinc, Co = cobalt, Sn = tin


by showing different toxic metals located in

In accordance with the definitions set out in ANNEX I, each layer is made up of a different









conformity of affected articles using


coating (or finish)

India Turkey

--- ---

--- ---

--- ---

--- ---

--- ---


Ni = nickel, Zn = zinc, Co = cobalt, Sn = tin



, each layer is made up of a different









using GPSD Directive and

Table 5 shows cases identified in 2010. In the first column the multi-coating is expressed i

coating (or finish)

Turkey Italy Spain

1

---

---

---

---


Ni = nickel, Zn = zinc, Co = cobalt, Sn = tin


10 de






of combined coatings is an extremely worrying issue.


could produce a synergic effect whose equivalent risk is greater than what each of them would



GPSD Directive and REACH

coating is expressed i

Spain Others

--- ---

--- ---

--- ---

--- ---

--- ---


de 47







h of them would



REACH

coating is expressed in the

Items

14.919

6.158

12.741

---

11.952


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The series marked as (*) or (**) all belong to white coloured internal sublayers

with an external coating of ruthenium (black colour) or rhodium (white colour). This has

enabled the identification of:

-

-

-

The speed with which these cases have appeared is

2009 and now they have reached a considerable degree of consolidation

The use of electronic microscopy (SEM) has enabled identification of the successive sublayers

in these series of combined coatings. The series mar

where the superimposition of three different coatings containing a toxic metal has been

detected.

This last case is an atypical event. In fact, it is common to find series where a first layer of

copper is applied to

surprising thing is that in place of it a pu

In this respect, there are doubts about the authenticity of the isolated case that was recorded

in 2008 for

whether we are dealing with a pure nickel coat

Given that the information obtained by XRF was not validated using SEM, there is still

uncert

9. Combination between different homogeneous metallic materials

This section shows situations in which toxic metals are located both in the base alloy or brazing

or in the series of coatings

As in the previous case, this is a

of synergies and the potentiating of ri

In 2010, there was only one case in which

combined with cadmium from


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- One shipment coming from Italy, with multi

total of 5,163 items

- Six shipments com

up a total of 9,756 items

- One shipment coming from China, with multi

making up a total of 6,158 items






detected.


copper is applied to



in 2008 for silver alloys containing nickel (see Section 4, Table 3). Actually, we do not know



ertainty about its authenticity

Combination between different homogeneous metallic materials


or in the series of coatings







http://www.aimme.es




One shipment coming from Italy, with multi

total of 5,163 items

Six shipments coming from China, with multi


One shipment coming from China, with multi








copper is applied to enhance adherence between the substrate and the multilayer system. The



silver alloys containing nickel (see Section 4, Table 3). Actually, we do not know



ainty about its authenticity



or in the series of coatings.





ment protocols






ing from China, with multi










enhance adherence between the substrate and the multilayer system. The

surprising thing is that in place of it a pure nickel coating has been used





ainty about its authenticity.



As in the previous case, this is a new scenario and is of extreme concern due to the appearance

of synergies and the potentiating of risks that are associated with it


combined with cadmium from the brazing, as shown in Table 6:




ing from China, with multi









re nickel coating has been used



whether we are dealing with a pure nickel coating electroplated on the silver




new scenario and is of extreme concern due to the appearance

sks that are associated with it

In 2010, there was only one case in which an internal series of

the brazing, as shown in Table 6:



One shipment coming from Italy, with multi-coating Ag-

ing from China, with multi-coating Ag

One shipment coming from China, with multi-coating Ag

The speed with which these cases have appeared is surprising. They were unheard of until



in these series of combined coatings. The series marked as (**) is particularly interesting,




re nickel coating has been used



ing electroplated on the silver





sks that are associated with it

an internal series of Ag

the brazing, as shown in Table 6:




-Sb + Pd-Ni + Ru, making up a

coating Ag-Sb + Pd-Ni + Rh (*), making

coating Ag-Sb+ Ni + Pd

surprising. They were unheard of until

2009 and now they have reached a considerable degree of consolidation.


ked as (**) is particularly interesting,




re nickel coating has been used.



ing electroplated on the silver.





sks that are associated with it.

Ag-Sb and Pd


11 de

The series marked as (*) or (**) all belong to white coloured internal sublayers finished off


Ni + Ru, making up a

Ni + Rh (*), making

Sb+ Ni + Pd-Ni + Rh (**)









.





Sb and Pd-Ni coatings have


de 47

finished off


Ni + Ru, making up a

Ni + Rh (*), making

Ni + Rh (**)












Ni coatings have


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Base alloy + brazing +

coatings and

toxic metal

Ag + Cd +Ag

Pd-Ni + Ru (black

colour)

Table 6.

This is an unheard of and emerging scenario, identified as

-

10. Homogeneous

As laid down in ANNEX I, the decorative parts of a jewel are made up of homogeneous

materials which are clearly differentiated from other metallic parts. Diverse materials are

grouped together under this name, such as: gems, ston

textiles, etc

Since both the skin and mucous membranes are exposed to these decorative parts, they have

also been ta

The cases explained refer solely to decorative parts regardless

contain other toxic metals.

Four cases were detected in 2010

--

-


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Base alloy + brazing +

coatings and

toxic metal

2008

Ag + Cd +Ag-Sb +

Ni + Ru (black

colour)

---

Table 6. Comparison of distribution of shipments of silver having braz

checked in 2010 + chart of origins.

Symbols: Ag = silver, Cd = cadmium,


- One shipment coming from Italy, containing Cd in the brazing and having the series

Ag-Sb + Pd

Homogeneous




textiles, etc.


also been taken into account for this study




- Presence of lead in mounted crystals in a shipment of silver jewellery

- Presence of lead in a mother

shipments

- Presence of lead in beads like “



http://www.aimme.es

2008 2009 2010

--- ---

Comparison of distribution of shipments of silver having braz


Symbols: Ag = silver, Cd = cadmium,


One shipment coming from Italy, containing Cd in the brazing and having the series

Sb + Pd-Ni + Ru, making up a total of 1,700 items

Homogeneous material: Decorative parts





ken into account for this study




Presence of lead in mounted crystals in a shipment of silver jewellery

Presence of lead in a mother

shipments of silver jewellery.

Presence of lead in beads like “

ment protocols


2010 China

1 ---

Comparison of distribution of shipments of silver having braz


Symbols: Ag = silver, Cd = cadmium, Sb = antimony, Pd = palladium,



Ni + Ru, making up a total of 1,700 items

material: Decorative parts





ken into account for this study




Presence of lead in a mother-

of silver jewellery.

Presence of lead in beads like “cat

Thailand India

---

Comparison of distribution of shipments of silver having brazing and series of coatings, with

Sb = antimony, Pd = palladium,









ken into account for this study.



-of-pearl coating of artificial pearls included in two

cat’s eye” in a shipment of silver jewellery

India Turkey

--- ---

ing and series of coatings, with

Sb = antimony, Pd = palladium, Ni = nickel, Ru =

This is an unheard of and emerging scenario, identified as:






grouped together under this name, such as: gems, stones, crystals, enamels,


The cases explained refer solely to decorative parts regardless of whether the metallic parts


pearl coating of artificial pearls included in two

’s eye” in a shipment of silver jewellery


Turkey Italy Spain

1 ---

ing and series of coatings, with different toxic metals,

Ni = nickel, Ru = ruthenium




es, crystals, enamels,


of whether the metallic parts





12 de

Spain Others

--- ---

different toxic metals,




es, crystals, enamels, rubber, leather,







de 47

Items

1.700

different toxic metals,




rubber, leather,





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Base alloy +

decorative part and

toxic metal

+ crystals

containing Pb

Ag + artificial pearls

containing Pb

Ag + beads like

“tiger’s eye”

containing Pb

Table 7.

Lead and lead compounds are very

certain types of brazing due to its low melting point. It is much more commonly used in alloys

of common m

After three years of Project work there has not been a s

component of alloys, brazing or coatings in jewellery. The four cases described for 2010

correspond to decorativ

--

-

In addition to lead, alloys of silver

antimony, which is highly carcino

Even though pearl articles come from the EU (Spain and Italy),

these artificial pearls actually come from China and that they are use

Europe

This new development has created an atmosphere of surprise and unrest for the companies

affected, who are aware of the extr

lead.

Such risks affect not only the person wearing the item of jewellery but also any children who

are present. The child’s eye may be drawn to the piece of jewellery and they may put it in their


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Base alloy +

decorative part and

toxic metal

2008

+ crystals

containing Pb ---

Ag + artificial pearls

containing Pb ---

Ag + beads like

“tiger’s eye”

containing Pb

---

Table 7. Comparison of distribution of

different toxic metals, checked in 2010 with its chart of origins.

Symbols: Ag = silver, Pb = lead



of common metals used in costume jewellery



correspond to decorativ

- Crystals with over 60% weight in lead

- Mother-

contents: 10 to 80% in weight. On a scale of grey, the

lowest lead content and the darkest to the highest.

- Cat’s eye” type of beads weighin

addition to lead, alloys of silver




Europe.







http://www.aimme.es

2008 2009 2010

--- ---

--- ---

--- ---

Comparison of distribution of shipments silver jewels including


Symbols: Ag = silver, Pb = lead



etals used in costume jewellery



correspond to decorative parts in which jewels are set

Crystals with over 60% weight in lead

-of-pearl from artificial pearls having variable and alternate lead and bismuth



’s eye” type of beads weighin

addition to lead, alloys of silver








ment protocols


2010 China

1 ---

2 ---

1 1

shipments silver jewels including


Lead and lead compounds are very toxic substances, though little used in jewellery except for


etals used in costume jewellery



e parts in which jewels are set


pearl from artificial pearls having variable and alternate lead and bismuth



’s eye” type of beads weighin

addition to lead, alloys of silver coming from Italy and China include a coating of silver

antimony, which is highly carcinogenic and corrosive to the skin




affected, who are aware of the extreme toxic risk posed by the prese



Thailand India

---

---

---

shipments silver jewels including decorative parts which

different toxic metals, checked in 2010 with its chart of origins. (* Origin of the

toxic substances, though little used in jewellery except for


etals used in costume jewellery.



e parts in which jewels are set





’s eye” type of beads weighing 95% of lead and 5% of cesium.

coming from Italy and China include a coating of silver

genic and corrosive to the skin




eme toxic risk posed by the prese



India Turkey

--- 1

--- ---

--- ---

decorative parts which

(* Origin of the pearls: China)



After three years of Project work there has not been a single documented case of lead as a


e parts in which jewels are set:




g 95% of lead and 5% of cesium.


genic and corrosive to the skin.

Even though pearl articles come from the EU (Spain and Italy), it has been demonstrated that



eme toxic risk posed by the prese




Turkey Italy Spain

---

1*

---

decorative parts which containing

pearls: China)



ingle documented case of lead as a



contents: 10 to 80% in weight. On a scale of grey, the whitest corresponds

g 95% of lead and 5% of cesium.


it has been demonstrated that

these artificial pearls actually come from China and that they are used extensively throughout


eme toxic risk posed by the presence of such high levels of




13 de

Spain Others

--- ---

1* ---

--- ---

containing






whitest corresponds with the



d extensively throughout


nce of such high levels of




de 47

Items

2.783

499

300






with the

coming from Italy and China include a coating of silver-


d extensively throughout


nce of such high levels of




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mouth. Due to its chloride content, the aggressive action of saliva ma

sweat

Certain countries, such as the USA or Canada consider this risk

In August 2008, the US Congress passed the “The Consume

(CEPSIA), setting out admissible limits of lead in products for use by children (children below

the age of 12) at 300ppm, in other words, 0.03 in weight.

-----

In turn, the U.S. Consumer Product Safety Commission (CPSC) warns that the intake of 175

micrograms of lead in short periods of time generates contents in blood above the threshold

of 10micrograms/decilitre

not ingest more

These regulations must be strictly kept to by companies whose products are destined, directly

or indirectly

In the case of the UE, France has recently subm

up restrictions for

11. Market situation. Imported products and products manufactured in

Spain

For imports that enter Spain legally (through customs) the situation is

reliable. There is a full correlation between the articles assessed by the hallmarking laboratory

and those on display i

According to figures described in Section 2, it can be seen that over a third of such articles

(41%) could be harmful to people’s health and safety as the proportions of toxic metals that

they conta

Nevertheless, it is not possible to know the magnitude of the problem in the case of illegal

imports


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sweat.





- Precious stones

- Semiprecious

- Natural and artificial pearls

- Precious metals: gold, silver, and PMGs (platinum group metals)

- Surgical steels and titanium



10micrograms/decilitre

not ingest more than 15 micrograms/day of lead


or indirectly, for the North American market


up restrictions for

Market situation. Imported products and products manufactured in

Spain



and those on display i


) could be harmful to people’s health and safety as the proportions of toxic metals that

they contain greatly exceed those allowed


imports. There are two reasons



http://www.aimme.es






Precious stones

Semiprecious stones and minerals

Natural and artificial pearls

Precious metals: gold, silver, and PMGs (platinum group metals)

Surgical steels and titanium



10micrograms/decilitre and also, in order to prevent any type of risk, a

than 15 micrograms/day of lead


, for the North American market


up restrictions for lead based on amounts released




and those on display in retail outlets



in greatly exceed those allowed


. There are two reasons

ment protocols







stones and minerals

Natural and artificial pearls


Surgical steels and titanium



and also, in order to prevent any type of risk, a

than 15 micrograms/day of lead


, for the North American market


lead based on amounts released




n retail outlets.



in greatly exceed those allowed


. There are two reasons why irregular situations occur






stones and minerals





than 15 micrograms/day of lead.


, for the North American market.

In the case of the UE, France has recently submitted a proposal for the Reach Regulation to set

lead based on amounts released.






in greatly exceed those allowed.


why irregular situations occur


Certain countries, such as the USA or Canada consider this risk of ingestion as highly worrying

In August 2008, the US Congress passed the “The Consumer Product Safety Improvement Act”


the age of 12) at 300ppm, in other words, 0.03 in weight. The types of products included are






itted a proposal for the Reach Regulation to set







why irregular situations occur:


mouth. Due to its chloride content, the aggressive action of saliva may be greater than that of

of ingestion as highly worrying

r Product Safety Improvement Act”


The types of products included are




and also, in order to prevent any type of risk, a young child should




For imports that enter Spain legally (through customs) the situation is representative and






14 de

y be greater than that of

of ingestion as highly worrying



The types of products included are



young child should




representative and






de 47

y be greater than that of

of ingestion as highly worrying.



The types of products included are:



young child should




representative and






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AIMME

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---

The absence of a subsequent compulsory surveillance of the market by the Competent

Authorities makes it impossible to

be wrong to assume that it far exceeds 41% of articles on sale in retail outl

For products manufactured in Spain it is necessary to understand that most items of gold and

silver arrive at th

polishing, coating and mounting

In consequence, the presence of toxic metals is mainly found in alloys and brazing and also, in

very isolated cases, in coatings or decorative parts.

indicate that another 41% of the manufactured articles include toxic metals and that this figure

will increase notably when

The detection of toxic metals in finished articles wou

collaboration between competent authorities (health, industry and consumerism) and assay

offices. In other words, this implies setting up effective surveillance action on how the market

reacts, i.e., monitoring retailing

Verification work at points of sale, which has been demanded for a long time by companies

with a sense of responsibility (Hallmark users) in the supply chain, has been extended due to

the recent demands of consumer associations and users, who are alarmed

the problem

There is a generalized state of concern shown by the different social partners in order to

correct the situation in which the Competent Authorities are neglecting their duties and to

strictly apply the established

-

-

-


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- Third countries: avoiding customs control

- EU countries with legislations that are

- EU countries with

onto a malicious reading of the free circulation of goods between EU countries.





silver arrive at th





will increase notably when




cts, i.e., monitoring retailing




the problem.




- Comply with guarantees laid down by law for a product that should be traded under

prior compulsory authorization (Hallmark)

- Guarantee compliance with existing health legislation and ensure the absence of any

article in retail

- Achieve the same degree of efficiency in the location and withdrawal of dangerous

products from the market as in other EU countries using the Community Exchange

System (RAPEX), in a

GPSD, as well as though work of rapid intervention and withdrawal from the market,

in accordance w



http://www.aimme.es

Third countries: avoiding customs control

EU countries with legislations that are

EU countries with different






silver arrive at the assay office in their raw state. Once marked, they are finished off by





will increase notably when they reach their finished state




cts, i.e., monitoring retailing







Comply with guarantees laid down by law for a product that should be traded under


Guarantee compliance with existing health legislation and ensure the absence of any

article in retail outlets that could pose indisputable risks for people’s health and safety

Achieve the same degree of efficiency in the location and withdrawal of dangerous


System (RAPEX), in a

, as well as though work of rapid intervention and withdrawal from the market,

in accordance with Regulation (EC) Nº 765/2008

ment protocols



EU countries with legislations that are

different legislation to Spain: evasion of their duties by clinging



Authorities makes it impossible to get hold of information on quantities, although it would not



e assay office in their raw state. Once marked, they are finished off by

polishing, coating and mounting.




they reach their finished state




cts, i.e., monitoring retailing.






control mechanisms in order to




outlets that could pose indisputable risks for people’s health and safety



System (RAPEX), in accordance with guidelines laid out in Directive 2001/95/EC or


ith Regulation (EC) Nº 765/2008


EU countries with legislations that are not equivalent

legislation to Spain: evasion of their duties by clinging



get hold of information on quantities, although it would not





very isolated cases, in coatings or decorative parts. In any case, the figures shown in Section 2


they reach their finished state









chanisms in order to







ccordance with guidelines laid out in Directive 2001/95/EC or



not equivalent with









In any case, the figures shown in Section 2


they reach their finished state.

The detection of toxic metals in finished articles would only be feasible by means of








chanisms in order to:










with Spain, and





be wrong to assume that it far exceeds 41% of articles on sale in retail outlets






ld only be feasible by means of





the recent demands of consumer associations and users, who are alarmed at the magnitude of











15 de

Spain, and





ets.











t the magnitude of











de 47














t the magnitude of











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12.

In 2010, a total of 13 characteristic cases were

manufacturing or import companies that go to AIMME’s laboratory in order to

jewellery hallmarked

A rigorous and representative study was carried out on the different casuistry of toxic metals

prese

The approach followed is according to the classification laid down for homogeneous materials

that can make up a jewel (see ANNEX


Base alloy

Combination of base alloys

Singular coatings

Combined coatings

Combination of different


Of the different casuistry submitted it is worth hi

1)


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Cases studied



jewellery hallmarked


present in the different homogeneous materials


can make up a jewel (see ANNEX


Base alloy

Combination of base alloys

Singular coatings

Combined coatings



Table 8.


1) Base alloy

We are dealing with articles in a raw state. It is understood that after hallmarking, they

will be reprocessed to give them the required finishes, which usually means

series of coatings

Unless overlapping non homogeneous zo

unquestionable sign of the presence of brazing

homogenous material with respect to its mass



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Cases studied



jewellery hallmarked.


different homogeneous materials


can make up a jewel (see ANNEX

� White gold with nickel

� Silver with cadmium

Combination of base alloys � White gold with nickel + yellow gold with cadmium

� Coating of cobalt

� Coating of nickel

� Conversion coating of silver sulphoselenide

� Coatings of silver

� Coatings of silver


homogeneous materials � Brazing with cadmium +

Table 8. List of cases studied in 2010 arranged by homogeneous material

and the metal or the toxic metals they contain


Base alloys



series of coatings.




ment protocols







can make up a jewel (see ANNEX I). The following were selected

White gold with nickel

Silver with cadmium

White gold with nickel + yellow gold with cadmium

Coating of cobalt-tin on silver

Coating of nickel-tin

Conversion coating of silver sulphoselenide

Coatings of silver-antimony + nickel on silver

Coatings of silver-antimony + nickel

Brazing with cadmium +

List of cases studied in 2010 arranged by homogeneous material

nd the metal or the toxic metals they contain







In 2010, a total of 13 characteristic cases were studied thanks to close collaboration with the



different homogeneous materials.


The following were selected

Case description

White gold with nickel

Silver with cadmium


tin on silver

tin on silver


antimony + nickel on silver

antimony + nickel-

Brazing with cadmium + Coatings of nickel + silver



Of the different casuistry submitted it is worth highlighting the following






studied thanks to close collaboration with the




The following were selected

Case description



antimony + nickel on silver

-tin on silver

Coatings of nickel + silver-antimony + palladium



ghlighting the following



Unless overlapping non homogeneous zones or points are detected

unquestionable sign of the presence of brazing – the article is considered to be a single

homogenous material with respect to its mass.






The following were selected:

antimony + palladium


ghlighting the following issues



nes or points are detected

the article is considered to be a single


16 de


manufacturing or import companies that go to AIMME’s laboratory in order to get their



Nº of cases

antimony + palladium-nickel

issues:


will be reprocessed to give them the required finishes, which usually means singular or

nes or points are detected



de 47


get their



Nº of cases

3

2

1

2

1

1

1

1

1


singular or

nes or points are detected – an



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2)

3)


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This is a common case in shipments of articles manufactured in Spain and, in p

for gold and platinum

Articles made from silver are usually found in a finished state, in other words with the

series of finished coatings, or at least having their

On the contrary, shipments of imports contain

include series of coating finishes. For this reason, apart from exceptions, they are not

included in this section.

As can be seen in Table 8, six cases were studied

� � �

2) Brazing

It is difficult to locate brazing because if their composition contains the same

components as the base alloy, it is h

Only the detection of zones or points where the alloying

with the rest of the components provides an indication of the presence of brazing.

These are overlapping components that break the

Of the thirteen cases studied in 2010 only one was found with irr

the presence of brazing. This case is described in the section on combinations between


3) Singular coatings

Except for platinum, all other alloys of precious metals tend to include galvanic or

surface transformation coatings to improve their decorative qu

colour.

Even yellow gold includes different electroplated coatings, or series of coatings, aimed

at providing the whole piece with different ranges of tonality (from pale yellow

pink).

If the atypical component is found in a single coating, it is not evenly spread in the

mass of the item and it is out of harmony with the piece as a whole, thereby breaking

the homogeneity.



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for gold and platinum







Three with white gold

Two with silver

One combina









Singular coatings


transformation coatings to improve their decorative qu





the homogeneity.

ment protocols



for gold and platinum.







Three with white gold

Two with silver

One combination of white gold and yellow gold





















hite gold and yellow gold


components as the base alloy, it is hard to distinguish between them















series of finished coatings, or at least having their binding

On the contrary, shipments of imports contain totally finished articles that generally


As can be seen in Table 8, six cases were studied:

hite gold and yellow gold


ard to distinguish between them



These are overlapping components that break the homogeneity of the whole piece












binding electrolytic silver coating

totally finished articles that generally



ard to distinguish between them.

Only the detection of zones or points where the alloying elements are out of harmony


homogeneity of the whole piece

Of the thirteen cases studied in 2010 only one was found with irrefutable evidence of



transformation coatings to improve their decorative qualities, mainly shine or






17 de

This is a common case in shipments of articles manufactured in Spain and, in particular


electrolytic silver coating




.

elements are out of harmony


homogeneity of the whole piece

efutable evidence of



alities, mainly shine or






de 47

articular


electrolytic silver coating.




elements are out of harmony


homogeneity of the whole piece.

efutable evidence of



alities, mainly shine or


at providing the whole piece with different ranges of tonality (from pale yellow to




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4)


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If in addition we are talking about a toxic substance

coating, its local action is very noticeable as it concentrates on the surface and is a few

microns thick. It will have a very intense toxic action, potentiating the appearance of

the different related pathologies

If they are not externally located but underneath in a series of multilayer coatings, in

order to estimate their toxic effect it is necessary to assess the effectiveness of the

shielding that may be exerted by the remaining overlapping coatings

In this section

� Two cases of cobalt

another underlying below a coating of gold

� One case of nickel

� One case of sur

(chemical conversion treatment), giving the piece a black finish

4) Combined coatings

Series of multilayer coatings may include the presence of two or more toxic metals

superimposed in different

This is a very complex case in which it is necessary to distinguish between layers to

identify the components separately and locate the position of

series.

Bearing in mind the shielding effect the overlap

the underlying toxic substa

� When and how immediate signs appear of their effects and physical harm to

people.

� Whether there will be a sequential timing in the appearance of the

harm for the whole lifespan of the piece of jewellery.

This turns out to be decisive in concluding whether the superimposed layers act as an

efficient block against the release of underlying toxic substances, or if on the contrary,

due to the

releasing other occluded species

Pending the conclusions that will be provided by assessing the shielding effect,

inferences can still be drawn about possible interactions and the

that would give rise to several toxic su



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s thick. It will have a very intense toxic action, potentiating the appearance of

e different related pathologies

ey are not externally located but underneath in a series of multilayer coatings, in



In this section, in 2010, four cases were studied in depth

Two cases of cobalt


One case of nickel

One case of sur


Combined coatings


superimposed in different




the underlying toxic substa

When and how immediate signs appear of their effects and physical harm to

people.

Whether there will be a sequential timing in the appearance of the




due to the effect of friction, wear or corrosion the surface will rapidly deteriorate

eleasing other occluded species




ment protocols





e different related pathologies.




, in 2010, four cases were studied in depth

Two cases of cobalt-tin (black) on silver, one as an outermost layer and


One case of nickel-tin on silver, giving the piece a black finish

One case of surface transformation on silver based on



superimposed in different layers or homogeneous materials




the underlying toxic substance, it is necessary to foresee






effect of friction, wear or corrosion the surface will rapidly deteriorate

eleasing other occluded species.







.




, in 2010, four cases were studied in depth

tin (black) on silver, one as an outermost layer and


tin on silver, giving the piece a black finish

face transformation on silver based on



or homogeneous materials




nce, it is necessary to foresee







.



that would give rise to several toxic substances being released jointly

If in addition we are talking about a toxic substance and it is included in the outermost






, in 2010, four cases were studied in depth:


another underlying below a coating of gold-copper (pink)





or homogeneous materials



Bearing in mind the shielding effect the overlapping layers can have on the release of

nce, it is necessary to foresee:









bstances being released jointly


and it is included in the outermost





shielding that may be exerted by the remaining overlapping coatings.


copper (pink)





or homogeneous materials.


identify the components separately and locate the position of each toxic metal in the

ping layers can have on the release of








inferences can still be drawn about possible interactions and the fierce synergic effect

bstances being released jointly.


18 de







face transformation on silver based on sulphoselenides




each toxic metal in the



Whether there will be a sequential timing in the appearance of the physical





fierce synergic effect

.


de 47







sulphoselenides



each toxic metal in the



physical





fierce synergic effect


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5)

6)

13.

The methodology used in this study has involved the following stages:

1)


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The following situations were assessed in this section:

� One series of silver

� One series of silver

5) Combination between different homogeneous materials

This is an extension of the previous section, where in addition to their presence in

different coatings, the toxic metals might be found as pa

All considerations

wear, simultaneous release and synergic effects, r

Only one case was studied while carrying out the project

� One series of nickel + silver

silver containing silver and cadmium brazing.

6) Decorative parts

As already stated (see Section 10 and Table 8), the presence of toxic components were

detected in decorative parts included in the jewellery (stones,

In all cases, the toxic metal identified was lead. Additionally, in some of them, there

was also the presence of other toxic metal

It was not possible to obtain samples in order to carry out a more

Hopefully, this shortcoming can be put right during the development stage of the

project in 2011

Methodology used


1) Identification of presence of toxic metals

Para For

identify the total of metals present in the different homogeneous materials.

This is an extremely valuable qualitative technique for the required aim. However,

since a differentia

the information offered does not make it possible to quantif



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One series of silver

One series of silver

Combination between different homogeneous materials



All considerations made in the previous section about the shielding effect, occlusions,



One series of nickel + silver


Decorative parts







project in 2011.

Methodology used


Identification of presence of toxic metals

For this purpose, x



since a differentiation was not obtained between the different homogeneous material,


ment protocols



One series of silver-antimony + nickel applied to silver

One series of silver-antimony + nickel




made in the previous section about the shielding effect, occlusions,



One series of nickel + silver








Methodology used



this purpose, x-ray fluorescence (XRF) was used, which makes it possible to



tion was not obtained between the different homogeneous material,



antimony + nickel applied to silver

antimony + nickel







One series of nickel + silver-antimony +





was also the presence of other toxic metals in coatings and/or base alloy





ray fluorescence (XRF) was used, which makes it possible to







antimony + nickel-tin on silver



different coatings, the toxic metals might be found as part of the base alloy or brazing


wear, simultaneous release and synergic effects, remain just as valid in this one

Only one case was studied while carrying out the project:

antimony + palladium





s in coatings and/or base alloy











silver


rt of the base alloy or brazing


emain just as valid in this one

:

palladium-nickel applied to an alloy of


detected in decorative parts included in the jewellery (stones, crystals, pearls, etc.)


s in coatings and/or base alloy








the information offered does not make it possible to quantify its composition


19 de


rt of the base alloy or brazing


emain just as valid in this one.

nickel applied to an alloy of


crystals, pearls, etc.)


s in coatings and/or base alloy.

It was not possible to obtain samples in order to carry out a more detailed study.






y its composition


de 47


rt of the base alloy or brazing.


nickel applied to an alloy of


crystals, pearls, etc.)


detailed study.






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2)

3)

4)


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2) Differentiation between homogeneous materials

For this purpose a scanning electron microscope (SEM) fitted

electronic microprobe was used

The preparation of micrographic samples and cross

enables the identification and quantification of all th

present.

All the toxic materials prese

segregating

In contrast, the microprobe provides a representative quantification of the percentage

composition in weight of each and every one of the metals present in ea

homogeneous material.

Laboratories that do not have the suitable means at their disposal miss this step out

and establish the results by the total weight of the article rather than the

homogeneous material. The consequences of such practice are

� Making serious mistakes when interpreting the regulations

� Issue of incorrect compliance certificates

� Appearance of compromising situations

3) Thickness determination of coatings

This information was obtained using SEM at the same time as the sequencing of the


It is of great use for drawing conclusions about the durability of the coatings and their

degree of permanence against wear

4) Simulation of

These tests are used to imitate the deterioration produced in articles of jewellery

during use, so that the results are comparable with perio

The aim is to remove obstacles preventing the release



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Differentiation between homogeneous materials


electronic microprobe was used



All the toxic materials prese

segregating them into homogeneous materials







Making serious mistakes when interpreting the regulations

Issue of incorrect compliance certificates

Appearance of compromising situations authorities

Thickness determination of coatings




gree of permanence against wear

Simulation of corrosion and surface wear




ment protocols




electronic microprobe was used.



All the toxic materials present are identified by scanning the sample, as well as

them into homogeneous materials









Appearance of compromising situations





gree of permanence against wear

corrosion and surface wear








nt are identified by scanning the sample, as well as

them into homogeneous materials








Appearance of compromising situations



different homogeneous materials.


gree of permanence against wear.

corrosion and surface wear






The preparation of micrographic samples and cross-sectional examination using SEM



them into homogeneous materials.








Appearance of compromising situations when dealing with the competent




during use, so that the results are comparable with periods of use of at least two years

The aim is to remove obstacles preventing the release of a


For this purpose a scanning electron microscope (SEM) fitted with a dispersive energy

sectional examination using SEM

enables the identification and quantification of all the homogeneous materials






homogeneous material. The consequences of such practice are evident:


when dealing with the competent




ds of use of at least two years

of a toxic metal such as


20 de

with a dispersive energy


e homogeneous materials






evident:





ds of use of at least two years

toxic metal such as:


de 47

with a dispersive energy


e homogeneous materials



composition in weight of each and every one of the metals present in each







ds of use of at least two years.


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5)


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� The shielding effect other overlapping coatings might exert

� The same effect produced by the patinas or surface

formed by the action of atmospheric agents (oxides)

Therefore, it is essential to

carrying out such tests

Experience shows that on occasions, if the toxic agent is located on the surface, the

tests may cause them to disappear making

Protocols al

for usage, mainly

� Release while article is worn as new or used occasionally

� Release due to deterioration after frequent or prolonged use.

5) Toxic metals release

The tests are

according to conditions laid down in the EN 1811 standard g

Regulation

Particularly in the case of nickel, the results make it possible to establish the degree of

compliance with the statutory criteria that authorize or restrict trading in jewellery.

For other toxic metals it is possible to assess

� Amount released

� Effectiveness of shielding effect in the case of the toxic metal bei

under a series of coatings

� Synergies that could arise if several toxic substances were released at the

same time.

This is determined using Inductive Couple

OES).



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The shielding effect other overlapping coatings might exert

The same effect produced by the patinas or surface


Therefore, it is essential to

carrying out such tests



Protocols allow for adjustments to subsequent release tests based on objec

for usage, mainly:

Release while article is worn as new or used occasionally

Release due to deterioration after frequent or prolonged use.

Toxic metals release

The tests are carried out by exposing the article to a solution of artificial sweat


Regulation.


mpliance with the statutory criteria that authorize or restrict trading in jewellery.


Amount released

Effectiveness of shielding effect in the case of the toxic metal bei


Synergies that could arise if several toxic substances were released at the

same time.


ment protocols





Therefore, it is essential to define the protocols that will decide the benefit or not of

carrying out such tests.



low for adjustments to subsequent release tests based on objec



carried out by exposing the article to a solution of artificial sweat





Amount released due to the action of sweat or saliva








define the protocols that will decide the benefit or not of


tests may cause them to disappear making it impossible to evaluate them








For other toxic metals it is possible to assess:

due to the action of sweat or saliva




This is determined using Inductive Coupled Plasma






it impossible to evaluate them











Plasma-Optical



The same effect produced by the patinas or surface passivation




it impossible to evaluate them





according to conditions laid down in the EN 1811 standard governed by the REACH






Optical Emission Spectroscopy (ICP


21 de

passivation layers that are



it impossible to evaluate them.

low for adjustments to subsequent release tests based on objective criteria



overned by the REACH



Effectiveness of shielding effect in the case of the toxic metal being occluded


Emission Spectroscopy (ICP


de 47

layers that are



tive criteria


overned by the REACH



ng occluded


Emission Spectroscopy (ICP-


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6)

7)


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6) Determination of surface development

Enables the amount of toxic metals released to be c

Without doubt, this is the most critical stage of assessment which, together with the

phase for differentiating between homogenous materials, gives

differences between assay laboratories

Using precise metrology instrumentation, it is only possible to evaluate regular

geometric surfaces to a minimum resolution of 50µm. However, this is not the most

common situation as articles

To digitalize the item is a very expensive method and does not always provide

acceptable results due to errors inherent to the technique

Only chemical methods for coatings (non electrolytic) make it possi

required precision and reduce uncertain

7) Functional characteristics

This is about the prevention of flaws produced during normal use of the articles, such

as peeling or loss of coatings, which could cause

This will happen when an article having

The situation is particularly worrying in the case of children, where erosion by the

teeth or corrosion due to saliva can give rise to the

substances exceeding the permitted levels, such as: nickel, cobalt, antimony, lead,

selenium, copper or zinc.

Tests that are recommended are all those that make it possible to assess the

adherence of coatings, as well as oth

durability against chemical agents in household or personal hygiene products.



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Determination of surface development




es between assay laboratories



common situation as articles





Functional characteristics











ment protocols


Determination of surface development




es between assay laboratories



common situation as articles of jewellery tend to have very com





Functional characteristics











Determination of surface development on the article of jewellery




es between assay laboratories.



of jewellery tend to have very com




required precision and reduce uncertainty in measurements in all cases



This will happen when an article having these flaws is put in the mouth





adherence of coatings, as well as other qualities such as their scratch resistance or


on the article of jewellery

Enables the amount of toxic metals released to be calculated as µg/cm





of jewellery tend to have very com




ty in measurements in all cases


as peeling or loss of coatings, which could cause problems for the health of consumers

these flaws is put in the mouth


teeth or corrosion due to saliva can give rise to the intake of quantities of certain



er qualities such as their scratch resistance or



on the article of jewellery

alculated as µg/cm


phase for differentiating between homogenous materials, gives rise to the majority of



of jewellery tend to have very complex geometries


acceptable results due to errors inherent to the technique.

Only chemical methods for coatings (non electrolytic) make it possible to increase the

ty in measurements in all cases


ems for the health of consumers

these flaws is put in the mouth


intake of quantities of certain






22 de

alculated as µg/cm2/week.


rise to the majority of



plex geometries.


ble to increase the

ty in measurements in all cases.


ems for the health of consumers

these flaws is put in the mouth.








de 47


rise to the majority of




ble to increase the


ems for the health of consumers.







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8)

9)


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8) Report

After assessing the results a report is drawn up to establish the degree of compliance

or non compliance with the

information and labeling in situations where there

This analysis is carried out based on existing jurisprudence in the following areas:

� Obligations of all members

� Personal health and safety prevention

� Public health and safety prevention

The Ruling accounts for all horizontal

� General Consumer and User Protection

November 16)

� Directive 2001/

1801/2003, December 26)

� Regulation

Evaluation,

� Regulations (EC) Nº 1272/2008 and Nº 790/2009 or CLP Classification,

Labelling

� Penalty System Law provided in REACH and CLP Regulations (Law 8/2010 of

March 31)

9) Recommendations

Lastly, a set of guidelines and recommendations are established for the manufacturer

or importer in order to adopt corrective measures that will mean only

enter the market

The recommendations differ depending on the EU manufacturer or import

jewellery, who may have some obligations toward their suppliers, or to the third

country importer, who is ultimately



http://www.aimme.es


or non compliance with the



Obligations of all members

Personal health and safety prevention

Public health and safety prevention


General Consumer and User Protection

November 16)

Directive 2001/

1801/2003, December 26)

Regulations

Evaluation, Authorization

Regulations (EC) Nº 1272/2008 and Nº 790/2009 or CLP Classification,

Labelling and Packaging of Dangerous Substances.

Penalty System Law provided in REACH and CLP Regulations (Law 8/2010 of

March 31))

Recommendations



enter the market.




ment protocols



or non compliance with the legislation in question, as well as stating derived duties:



Obligations of all members





November 16)

Directive 2001/95/CE or GPSD

1801/2003, December 26)

(EC) Nº 1907/2006

Authorization


and Packaging of Dangerous Substances.








legislation in question, as well as stating derived duties:



Obligations of all members of the supply chain



The Ruling accounts for all horizontal legislation affecting jewellery


95/CE or GPSD General Products Safety Regulation (R.D.

1801/2003, December 26) and related Decisions of the Commission

(EC) Nº 1907/2006 and Nº 552/2009

Authorization & Restriction of Chemicals.








country importer, who is ultimately responsible before the



information and labeling in situations where there is a potential risk to persons


of the supply chain


legislation affecting jewellery

General Consumer and User Protection Act or LGDCU

General Products Safety Regulation (R.D.

and related Decisions of the Commission

and Nº 552/2009

& Restriction of Chemicals.








responsible before the




is a potential risk to persons


legislation affecting jewellery:

Act or LGDCU (Legislative R.D. 1/2007,



and Nº 552/2009 or REACH Registration,

& Restriction of Chemicals.








responsible before the Authorities


23 de



is a potential risk to persons.


(Legislative R.D. 1/2007,



or REACH Registration,




or importer in order to adopt corrective measures that will mean only safe products



Authorities.


de 47



(Legislative R.D. 1/2007,


or REACH Registration,




safe products

The recommendations differ depending on the EU manufacturer or importer of



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14.

This section provides a summary of results obtained for each of the 13 cases

agreement with Table 8, five blocks of results are shown to cater for the ho

materials taking part


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Results summary



materials taking part



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Results summary



materials taking part:

ment protocols












24 de

This section provides a summary of results obtained for each of the 13 cases studied.

agreement with Table 8, five blocks of results are shown to cater for the homogeneous


de 47

studied. In

mogeneous


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Homogeneous Material

White gold alloy

∗ Shipment: 157 items of White Au

∗ State: Unprocessed

∗ Articles: Rings and earrings

► Release degree of Ni

► Content of CMR, PBT or vPv

► Compliance with

Part 3)

→ Non compliant

→

►Compliance with

→ Non compliant

(Absence of suitable information about

inherent risks

► REACH

Article 5

→ Very serious infracWons

→ Serious infracWons


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White gold alloy

Shipment: 157 items of White Au

State: Unprocessed

Articles: Rings and earrings

Release degree of Ni

- Corrosion and wear (EN 12472) : Yes

- Uncorrected value: 0.22 µg/cm

- Corrected value : 0.02 µg/cm

Content of CMR, PBT or vPv

- Ni: 4.9 % (exceeds 0.1 % in weight or 1000 mg/kg per

homogeneous material)

Compliance with

Part 3)

→ Non compliant

( Ni content exceeds 0.1 % in weight or

1000 mg/kg per homogeneous material)

→ Compulsory labelling

and 2 take priority

Compliance with

→ Non compliant


inherent risks during use of the jewellery)

REACH infractions

Article 5)





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State: Unprocessed (not finished)


Release degree of Ni

Corrosion and wear (EN 12472) : Yes

Uncorrected value: 0.22 µg/cm

Corrected value : 0.02 µg/cm2

Content of CMR, PBT or vPvB substances

Ni: 4.9 % (exceeds 0.1 % in weight or 1000 mg/kg per


Compliance with GPSD under

→ Non compliant �



labelling. Risk categories

and 2 take priority

Compliance with GPSD (Article 5)



during use of the jewellery)

infractions (in accordance

→ Very serious infracWons � �

→ Serious infracWons � �

ment protocols



(not finished)


Uncorrected value: 0.22 µg/cm2/week

2/week

B substances


under CLP criteria(Annex VI,



. Risk categories 1

(Article 5)


during use of the jewellery)

n accordance with Law 8/2010,

Case 1

Nickel alloyed with 750 ‰ gold

∗ Origin: Spanish manufactured

∗ Sample: Ring

► Components of the mix (alloy)

► Composition: ‰ in weight (XRF and SEM)

► Homogeneo


► Compliance with REACH

∗ According to EN 1811:1999

→ Compliance for all arWcles


→ Compliance for rings

→ No decision taken for earrings

Annex VI, ► Mandatory information for potential risks

a

CLP criteria (Annex VI, Part

►Compliance with LGDCU

→ Non compliant

(Absence of labelling for prevention

of alloy related risks)

8/2010, ►RECOMMENDATIONS

→ Purchase orders to suppliers requiring

total absence of nickel

→ Demand cerWficates of tests carried out

by accredited laboratories

→ Report repeated cases to the competent

Case 1


Origin: Spanish manufactured

Sample: Ring

Components of the mix (alloy)

- XRF identification: Au, Cu, Ni, Zn and Ag

Composition: ‰ in weight (XRF and SEM)

Au

758.2

Homogeneous materials : 1 (brazing not

Compliance with REACH

According to EN 1811:1999

→ Compliance for all arWcles


→ Compliance for rings

→ No decision taken for earrings

Mandatory information for potential risks

according to GPSD

CLP criteria (Annex VI, Part

▪ Causes cancer

▪ Mutagen

▪ Toxic to pregnant women

▪ Toxic for breastfeeding

▪Acute toxicity due to

▪ Cutaneous sensitizer

Compliance with LGDCU

→ Non compliant



RECOMMENDATIONS






authorities



Origin: Spanish manufactured


XRF identification: Au, Cu, Ni, Zn and Ag


Cu Ni

139.9 49.0

us materials : 1 (brazing not

Compliance with REACH (Annex XVII,


→ Compliance for all arWcles ☺


→ Compliance for rings ☺

→ No decision taken for earrings �


ccording to GPSD to provide to consumers under

CLP criteria (Annex VI, Part 3)

CONTAINS NICKEL

Causes cancer

Toxic to pregnant women

Toxic for breastfeeding

toxicity due to ingestion

Cutaneous sensitizer

Compliance with LGDCU(Article 18)




RECOMMENDATIONS







25 de

XRF identification: Au, Cu, Ni, Zn and Ag

Composition: ‰ in weight (XRF and SEM))

Zn Ag

32.1 20.9

us materials : 1 (brazing not detected)

(Annex XVII, Section 27)

☺

☺

�


to provide to consumers under

ONTAINS NICKEL

H 351

H 341

H 360

H 360

ingestion H 301

H 317

(Article 18)






de 47

20.9

detected)

Section 27)


351

341

H 360

360

H 301

H 317


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White gold alloy

∗ Shipment: 280 items of White gold

∗ State: Unprocessed (unfinished)

∗ Articles: Rings, earrings, pendants, etc.

► Release rate of Ni

-

-

-


-

► Compliance

Part 3)

→ Non compliant

(Ni content exceeds 0.1 % in weight or

1000 mg/kg per homogeneous material

→ Compulsory labelling. Risk categories 1

and 2 take priority

► Compliance with

→ Non compliant



► REACH

Article 5




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White gold alloy

Shipment: 280 items of White gold

State: Unprocessed (unfinished)

Articles: Rings, earrings, pendants, etc.

Release rate of Ni

Corrosion and wear (EN 12472) :

Uncorrected value

Corrected value : << 0.03 µg/cm


Ni: 4,93 % (exceeds 0.1 % in weight or 1000 mg/kg

per homogeneous material)

Compliance with GPSD

3)





and 2 take priority


→ Non compliant



REACH infractions (i

Article 5)





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Shipment: 280 items of White gold




Uncorrected value: << 0.3 µg/cm

Corrected value : << 0.03 µg/cm




GPSD under CLP criteria

�




GPSD (Article 5)




in accordance with



ment protocols




: << 0.3 µg/cm2/week

Corrected value : << 0.03 µg/cm2/week

B substances


criteria (Annex VI,






with Law 8/2010,

Case 2


∗ Origin: Manufactured in Spain

∗ Sample: Ring


-

► Composition: ‰ in weight (XRF and SEM

►Homogeneous materials: 1 (brazing not detected)




→ Compliant for all ArWcles



VI, ► Mandatory information for potential risks

according to GPSD


► Compliance with LGDCU

→ Non compliant



► RECOMMENDATIONS

→ Purchase





Case 2


Origin: Manufactured in Spain

Sample: Ring


XRF identification: Au, Cu, Ni and Zn

Composition: ‰ in weight (XRF and SEM

Au

763.4

Homogeneous materials: 1 (brazing not detected)







ccording to GPSD


CONTAINS NI

▪ Causes cance

▪ Mutagen

▪ Toxic to pregnant

▪Toxic for breastfeeding




→ Non compliant



RECOMMENDATIONS








Origin: Manufactured in Spain



Composition: ‰ in weight (XRF and SEM

Cu Ni

164.0 49.3


Compliance with REACH (Annex


→ Compliant for all ArWcles ☺






CONTAINS NICKEL

er



ute toxicity due to ingestion


Compliance with LGDCU (Article 18)




RECOMMENDATIONS

orders to suppliers requiring






26 de



Zn

49.3 23.3


XVII, Section 27)


provide to consumers under

CKEL

H 361

H 341

H 360

H 360

ingestion H 301

H 317

(Article 18)


orders to suppliers requiring


→ Report repeated cases to the competent authorities


de 47


Section 27)


authorities


[email protected]

AIMME

http://www.aimme.es

Homogeneous

White gold alloy

∗ Shipment: 181 items of white Au

∗ State: Unprocessed (unfinished)



-

- -


-

► Compliance with

Part 3)

→ Non compliant




► Compliance with

→ Non compliant



► REACH




[email protected]


http://www.aimme.es


White gold alloy

Shipment: 181 items of white Au



Release rate of Ni


Uncorrected value:

Corrected value : 0.20 µg/cm





Part 3)

→ Non compliant




and 2 take priority


→ Non compliant



REACH infractions





http://www.aimme.es

Material

Shipment: 181 items of white Au



Release rate of Ni







GPSD under CLP





and 2 take priority

GPSD (Article 5)




infractions (in accordance with



ment protocols



2.02 µg/cm2/week

Corrected value : 0.20 µg/cm2/week

B substances


CLP criteria (Annex




(Article 5)



n accordance with Law 8/2010

Case 3

Nickel in 375 ‰ gold alloy

∗

∗

►

►

►


►

nnex VI, ►

►

8/2010, Article 5) ►

Case 3


∗ Origin: manufactured in Spain

∗ Sample: Ring


- XRF Identification: Au, Cu, Ni, Zn and Ag

► Composition:

Au

376.7

►Homogeneous materials




earrings are on the borderline


→ Non compliant for all Articles

► Mandatory information for potential risks

according to GPSD


▪ Cause cancer

▪ Mutagen






→ Non compliant



► RECOMMENDATIONS








Origin: manufactured in Spain

Sample: Ring


Identification: Au, Cu, Ni, Zn and Ag


Cu Ni

361.5 136.1

Homogeneous materials : 1

Compliance with REACH (A





compliant for all Articles




CONTAINS NICKEL

cancer



cute toxicity due to ingestion






RECOMMENDATIONS

Purchase orders to suppliers requiring






27 de

Origin: manufactured in Spain



in weight (XRF and SEM)

Ni Zn

136.1 92.8

: 1 (no detection of brazing)

Annex XVII, Section 27)

☺ although the


compliant for all Articles �




CONTAINS NICKEL

H

H 341

H 360

H

ingestion H 301

H 317

(Article 18)


Purchase orders to suppliers requiring




de 47


Ag

42.9

detection of brazing)

Section 27)



H 351

H 341

H 360

H 360

H 301

H 317

authorities


[email protected]

AIMME

http://www.aimme.es


Silver alloy

∗ Shipment: 788 items of Ag

∗ State: Finished (including silver plating)

∗ Articles: Bracelets, pendants,

► Release rate of Cd

-

-


-

► Compliance with

Part 3)

→ Non compliant

(Cd content exceeds 0.01 % in weight or



and 2 take priority

► Compliance with

→ Non compliant



► REACH

Article 5


→ Serious

� Full respon


[email protected]


http://www.aimme.es


Silver alloy

Shipment: 788 items of Ag

State: Finished (including silver plating)

Articles: Bracelets, pendants,

Release rate of Cd (purely informative)




Cd: 10.2 % (exceeds 0.01 % in weight or 100 mg/kg per



3)

→ Non compliant




and 2 take priority


→ Non compliant




Article 5)


→ Serious infractions

Full responsibility for the product lies of



http://www.aimme.es




Articles: Bracelets, pendants, earrings

(purely informative)











GPSD (Article 5)




(in accordance with


infractions � �

sibility for the product lies of

ment protocols



earrings, etc.



/week

B substances


criteria (Annex VI,






n accordance with Law 8/2010,

sibility for the product lies of the importer

Case 4

Cadmium in silver alloy

∗ Origin: imported from Asia

∗ Country: India

∗ Sample: Pending


-

► Composition:

► Information obtained by SEM

▪System

(brazing not detected

-

-



∗ According to proposed amendment (comes into

force June, 2011)

→ Non compliant for all ArWcles

∗ Until amendment comes into force, Art.33 stands:

→ If CMR, PBT or vPv


according to GPSD



→ Non compliant

(Abse

the importer

► RECOMMENDATIONS

→ Purchase orders to suppliers requiring the total

absence of cadmium



→ Verify validity of cerWficates and origin against

Imported shipment

Case 4


Origin: imported from Asia

Country: India

Sample: Pending


XRF identification: Ag, Cu and Cd

Composition: ‰

Ag Cu

871.8 1

Information obtained by SEM

System made up of 2 homogeneous

(brazing not detected

Alloy base: Ag

- Coating: pure Ag (100%)


According to proposed amendment (comes into

force June, 2011)


Until amendment comes into force, Art.33 stands:


0.1 % in weight of homogeneous material:

Obligation to inform consignees and consumers


ccording to GPSD


CONTAINS CADMIUM

▪ Causes cancer

▪ Mutagen


▪Toxic for breastfeed



→ Non compliant


RECOMMENDATIONS

Purchase orders to suppliers requiring the total

absence of cadmium




Imported shipment



Origin: imported from Asia



in weight (XRF and SEM

Cu Zn

17.5 8.3


of 2 homogeneous

(brazing not detected)

Alloy base: Ag-Cu-Cd-Zn

Coating: pure Ag (100%)

Compliance with REACH (Annex XVII,


→ Non compliant for all ArWcles �


→ If CMR, PBT or vPvB substances exceed

% in weight of homogeneous material:





CONTAINS CADMIUM


Toxic for breastfeedin




nce of labelling for prevention

RECOMMENDATIONS


absence of cadmium




Imported shipment


28 de



Cd

102.0

of 2 homogeneous materials

XVII, Section 23)


�


B substances exceed

% in weight of homogeneous material:

Obligation to inform consignees and consumers.



CONTAINS CADMIUM

H 351

H 341

H 360

H 360

H 301

(Article 18)

nce of labelling for prevention of alloy related risks)





de 47




[email protected]

AIMME

http://www.aimme.es


Silver alloy


∗ State: Finished (including silver plating)

∗ Articles: Bracelets, r

► Release rate of Cd

-

-


-

► Compliance

Part 3)

→ Non compliant

→ Compulsory labelling. Risk categories 1 and 2 take

► Compliance with

→ Non compliant

(Absence of suitable information about inherent risks during

use of the jewellery)

► REACH

Article 5



�


[email protected]


http://www.aimme.es


Silver alloy



Articles: Bracelets, r

Release rate of Cd




Cd: 5.44 % (exceeds 0.01 % in weight or 100 mg/kg



Part 3)

→ Non compliant

(Cd content exceeds 0.01 % in weight or 100

homogeneous


priority


→ Non compliant



REACH infractions

Article 5)



Full responsibility for the product lies on the



http://www.aimme.es




Articles: Bracelets, rings, earrings , etc.







GPSD under CLP


xceeds 0.01 % in weight or 100

homogeneous material


GPSD (Article 5)







lity for the product lies on the

ment protocols



ings, earrings , etc.




B substances


CLP criteria (Annex

xceeds 0.01 % in weight or 100 mg/kg per


(Article 5)


accordance with Law 8/2010,

lity for the product lies on the importer

Case 5


∗ Origin: Imported from Asia

∗ Country: India

∗ Sample: Ring

► Components of the mix

► Composition:


▪


-

-

-



∗

∗

nnex VI,

mg/kg per





→ Non compliant

8/2010,

importer

► RECOMMENDATIONS

→



Case 5


Origin: Imported from Asia

Country: India

Sample: Ring

Components of the mix

- XRF identification: Ag, Cu and Cd

Composition: ‰

Ag

931.5


▪ System made up of


- Alloy base: Ag-Cu

- Coating: pure Ag (

- Decorative stones


∗ According to proposed amendment (comes into force

June, 2011)


∗ Until amendment comes into force,


weight of homogeneous material: Obligation to

inform consignees and consumers.


according to GPSD


CONTAINS CADMIUM

▪ Causes cancer

▪ Mutagen





→ Non compliant


RECOMMENDATIONS


absence of cadmium




Imported shipment






‰ in weight (XRF and SEM)

Cu Cd

14.1 54.4


System made up of 3 homogeneous materials


Cu-Cd

Ag (100%)

Decorative stones


According to proposed amendment (comes into force


Until amendment comes into force,







CONTAINS CADMIUM






nce of labelling for prevention

RECOMMENDATIONS


absence of cadmium




Imported shipment


29 de


(XRF and SEM)

Cd

54.4

3 homogeneous materials

nnex XVII, Section 23)




B substances exceed 0.1%






CONTAINS CADMIUM

H 351

H 341

H 360

H 360

H 301

(Article 18)

nce of labelling for prevention of alloy related risks)





de 47

Section 23)


Art.33 stands:

in



H 351

1

H 360

H 360

301




[email protected]

AIMME

http://www.aimme.es

Homogeneous materials

Combination of alloys: White and yellow gold

∗ Shipment: 157 items of White and yellow Au

∗ State: Finished (Rhodium

∗ Articles: Rings, pendants and bracelets

►Release rate of Ni

-

- -

►Release rate of Cd

- -


- -

* % in weight per homogeneous material

► Compliance

Part 3)

→ Non compliant

∗ Ni content exceeds 0.1% in weight or


∗ Cd content exceeds 0.01 % in weight or



and 2 take priority


[email protected]


http://www.aimme.es



Shipment: 157 items of White and yellow Au

State: Finished (Rhodium

Articles: Rings, pendants and bracelets

Release rate of Ni






Value: 0.70 µg/cm


Ni: 3.7 % >> 0.1 % in weight or 1000 mg/kg*

Cd: 1.4 % >> 0.01% in weight or 100 mg/kg*



Part 3)


Ni content exceeds 0.1% in weight or


Cd content exceeds 0.01 % in weight or



and 2 take priority



http://www.aimme.es




State: Finished (Rhodium-plated white gold)



Uncorrected value: 0.12 µg/cm2




µg/cm2/week






�






and 2 take priority

ment protocols




plated white gold)


Corrosion and wear (EN 12472) : yes

2/week

/week

(purely informative) Corrosion and wear (EN 12472) : Yes

B substances




under CLP criteria (Annex VI,






Case 6

Nickel and cadmium in 750% gold alloys


∗ Country: Turkey

∗ Sample: Bracelet

► Components of the mix - XRF identification: Au, Cu, Ni, Zn, Ag, Cd and Rh

► Alloy composition:

Material

White

Yellow

► Information obtained by SEM ▪ System made up of 4 homogeneous materials


- - - -


� For nickel

∗

∗

→

�� For cadmium

∗ According to proposed amendment (June, 2011)


∗ Until amendment comes into force,

Art.33 stands:



according to GPSD


▪ Causes cancer

▪ Mutagen

▪ Toxi


▪ A




Country: Turkey

Sample: Bracelet Components of the mixXRF identification: Au, Cu, Ni, Zn, Ag, Cd and Rh

Alloy composition:

Material Au

Au 751.3 162.2

Yellow Au 750.7 105.8

Information obtained by SEMSystem made up of 4 homogeneous materials


Base alloy : Au

Base alloy: Au

Coating (White

Decorative stones


For nickel (Annex XVII, Section.




→ Compliant for all Articles

For cadmium (Annex

According to proposed amendment (June, 2011)



Art.33 stands:


homogeneous material:

Obligation to inform consignees and


ccording to GPSD


CONTAINS NICKEL

Causes cancer

Mutagen



Acute toxicity due to





Components of the mix

XRF identification: Au, Cu, Ni, Zn, Ag, Cd and Rh

Alloy composition: ‰ in weight (XRF

Cu Ni

162.2 37.3 36.8

105.8 ---




Base alloy : Au-Cd (yellow gold)

Base alloy: Au-Ni (white gold)

Coating (White gold): Rh (100%)

Decorative stones


XVII, Section. 27)




Compliant for all Articles ☺

nnex XVII, Section. 23)




→ If CMR, PBT or vPvB substances


Obligation to inform consignees and




CONTAINS NICKEL

regnant women





30 de


XRF identification: Au, Cu, Ni, Zn, Ag, Cd and Rh


Zn Ag Cd

36.8 --- ---

--- 130 13.6


Cd (yellow gold)

gold): Rh (100%)

XVII, Section. 23)


�


B substances ≥ 0.1 % in weight of

Obligation to inform consignees and consumers.


consumers under

CONTAINS NICKEL

H 351

H 341

H 360

H 360

H 301

H 317


de 47

Cd Rh

--- 12.5

13.6

% in weight of

consumers.

consumers under


[email protected]

AIMME

http://www.aimme.es


according to GPSD


▪ Causes cancer

▪ Mutagen





→ Non compliant



► RECOMMENDATIONS

→Purchase

nickel and/or cadmium

→ Demand cerWficates of tests carried out by accredited

laboratories



[email protected]


http://www.aimme.es


ccording to GPSD


CONTAINS CADMIUM

Causes cancer

Mutagen


oxic for breastfeeding

cute toxicity due to


→ Non compliant



RECOMMENDATIONS

Purchase orders to suppliers requiring total absence of



laboratories




http://www.aimme.es




CONTAINS CADMIUM


oxic for breastfeeding






RECOMMENDATIONS

orders to suppliers requiring total absence of




ment protocols




CONTAINS CADMIUM

H 351

H 341

H 360

H 360

H 301

(Article 18)





► Compliance with

→ Non compliant



► REACH



�










Full responsibility for the product lies on the im


GPSD (Article 5)

�



(in accordance with Law



Full responsibility for the product lies on the im

�


31 de



n accordance with Law 8/2010, Article 5

Full responsibility for the product lies on the importer


de 47

8/2010, Article 5)

orter


[email protected]

AIMME

http://www.aimme.es


Singular coating: cobalt

∗ Shipment: 1.715 items of Ag

∗ State: Finished (coating series: Ag + Co

Au-Cu)

∗ Articles: Bracelets, r

►

Characteristics


* Chromatic interference between Au

(black) coatings




0.1% in weight of homogeneous

material: Must inform consignee or consumer


according to GPSD



[email protected]


http://www.aimme.es



Shipment: 1.715 items of Ag

State: Finished (coating series: Ag + Co

Cu)

Articles: Bracelets, r


Characteristics of homogenous material


Base alloy

Coating 1

Coating 2*

Coating 3*

Chromatic interference between Au

(black) coatings







ccording to GPSD


CONTAINS COBALT

▪ Causes cancer

▪ Mutagen



▪ Acute toxicity due to


▪ Respiratory sensitizer



http://www.aimme.es


Singular coating: cobalt-tin alloy



Articles: Bracelets, rings, earrings , etc.


of homogenous material

Homogeneous material Composition

(% in weight

Ag: 92.7

Cu: 7.3

Ag: 100.0

Co: 27.3

Sn: 72.7

Au: 77.0

Cu: 23.0

Chromatic interference between Au

Compliance with REACH (Article 33)








CONTAINS COBALT

Causes cancer





espiratory sensitizer

ment protocols


State: Finished (coating series: Ag + Co-Sn black +

ings, earrings , etc.


of homogenous materials

Composition

(% in weight)

Thickness

(µm)

92.7

Cu: 7.3 -----

Ag: 100.0 0.3

Co: 27.3

: 72.7 0.2

Au: 77.0

Cu: 23.0 0.3

Chromatic interference between Au-Cu (pink) and Co

(Article 33)


B substances exceed




CONTAINS COBALT

H 351

H 341

H 360

H 360

ingestion H 301

H 317

H 334

Case 7

Cobalt in coating on silver alloy

Sn black +


∗ Country: China

∗ Sample: Ring

► Components of Article

- XRF

► Information obtained by XRF

► Information obtained by SEM ▪ System made up of 5 homogenous materials


- - - - -

Thickness

(µm)

-----

0.3

0.2

0.3

Cu (pink) and Co-Sn

► Release rate of Co

- -


-

► Compliance with

Part 3)

→ Non compliant

(Co content exceeds 0.01 % in weight

or 100 mg/kg per homogeneous material)


and 2 take priority


► Compliance with

→ Non compliant




→ Non compliant

(Absence of labelling for prevention of alloy related risks)

Case 7



Country: China

Sample: Ring

Components of Article

XRF identification: Ag, Cu, Co, Sn, and Au

Information obtained by XRF

Ag Cu

713.3 92.3

Information obtained by SEMSystem made up of 5 homogenous materials


Alloy base: Ag

Coating 1: pure Ag

Coating 2: Alloy Co

Coating 3: Alloy Au

Decorative stones

Release rate of Co


Value : 0.69 µg/cm


Co: 27,3 % (exceeds 0.1 % in weight or 1000 mg/kg


Compliance with

Part 3)

→ Non compliant




and 2 take priority

Compliance with

→ Non compliant




→ Non compliant






identification: Ag, Cu, Co, Sn, and Au

Information obtained by XRF (‰ in weight)

Cu Co Sn

92.3 5.97 10.5


System made up of 5 homogenous materials


Alloy base: Ag-Cu

Coating 1: pure Ag

Coating 2: Alloy Co-Sn (black)

Coating 3: Alloy Au-Cu (pink)

Decorative stones

Release rate of Co (purely informative)


Value : 0.69 µg/cm2/week




Compliance with GPSD under CLP





and 2 take priority









32 de

identification: Ag, Cu, Co, Sn, and Au

(‰ in weight)

Sn Au

10.5 159.9



Corrosion and wear (EN 12472) : yes

B substances


CLP criteria (Annex




(Article 5)



(Article 18)



de 47


nnex VI,



[email protected]

AIMME

http://www.aimme.es

► REACH

Articles5



�


[email protected]


http://www.aimme.es

REACH infractions

Articles5)



� Ful responsibility for the product lies on the



http://www.aimme.es




responsibility for the product lies on the

importer

ment protocols


(in accordance with law 8/2010,


8/2010,


► RECOMMENDATIONS


absence of cobalt




Imported shipment

RECOMMENDATIONS


absence of cobalt




Imported shipment


RECOMMENDATIONS





Imported shipment


33 de





de 47


[email protected]

AIMME

http://www.aimme.es




∗ State: Finished (

∗ Articles: Bracelets


Characteristics of homogeneous materials




→ If the CMR, PBT or vPv

0.1% in weight of homogeneous material:

Must inform consignee or consumer


according to GPSD


▪ Causes cancer

▪ Mutagen



▪ Acute


▪ Respiratory


[email protected]


http://www.aimme.es





Articles: Bracelets




Base alloy

Coating 1

Coating 2



→ If the CMR, PBT or vPv




ccording to GPSD


CONTAINS

Causes cancer

Mutagen



Acute toxicity due


Respiratory sensitizer



http://www.aimme.es


Singular coating: cobalt-tin alloy


coating series: Ag + Co




(% in weight)

Ag: 92.6

Cu: 6.7

Zn: 0.7

Ag: 100.0

Co: 66.7

Sn: 33.3



→ If the CMR, PBT or vPvB substances exceed




ccording to GPSD to provide to consumers


CONTAINS COBALT



toxicity due ingestion


sensitizer

ment protocols


coating series: Ag + Co-Sn black)


Composition

eight)

Thickness

(µm)

Ag: 92.6

Cu: 6.7

Zn: 0.7

-----

Ag: 100.0 0.3

Co: 66.7

3.3 2.9 –

(Article 33)

�

B substances exceed





COBALT

H 351

H 341

H 360

H 360

H 301

H 317

H 334

Case 8

Cobalt in Coating on silver alloy

black)


∗ Country: China

∗ Sample: Bracelet

► Components of Article-



▪ System made up of 4 homogeneous materials


- - - -

Thickness

(µm)

-----

0.3

3.1

► Release rate of Co

- -


-

*Tests prior to corrosion and wear cause a loss in cobalt

release obtained is equivalent to that of a new article or one

that is in its first years of use.

► Compliance with

Part 3)

→ Non compliant




and 2 take priority

under

H 351

H 341

H 360

H 360

H 301

H 317

H 334

► Compliance with

→ Non compliant




→ Non compliant



Case 8



Country: China

Sample: Bracelet

Components of Article XRF identification: Ag, Cu, Co, Zn, and Sn


Ag Cu

926.5 20.8




Base alloy: Ag

Coating 1: Pure Ag

Coating 2: Co-

Decorative stones

Release rate of Co


Value : 0.69 µg/cm




prior to corrosion and wear cause a loss in cobalt



Compliance with

Part 3)

→ Non compliant




and 2 take priority

Compliance with

→ Non compliant




→ Non compliant






Components of Article XRF identification: Ag, Cu, Co, Zn, and Sn


Cu Co Zn

20.8 38.3 8.2




Base alloy: Ag-Cu-Zn

Coating 1: Pure Ag

-Sn (black) alloy

stones

Release rate of Co (purely informative)






prior to corrosion and wear cause a loss in cobalt








and 2 take priority

GPSD (Article 5)




Compliance with LGDCU(Article 18)





34 de

XRF identification: Ag, Cu, Co, Zn, and Sn

(‰ in weight)

Zn Sn

8.2 8.2



Corrosion and wear (EN 12472) : No*

B substances Co: 66,7 % (exceeds 0.1 % in weight or 1000 mg/kg

prior to corrosion and wear cause a loss in cobalt. The


CLP criteria (Annex




(Article 5)



(Article 18)



de 47


. The


nnex VI,


[email protected]

AIMME

http://www.aimme.es

► REACH

Article 5



�

► RECOMMENDATIONS


absence of cobalt




Imported shipment


[email protected]


http://www.aimme.es

REACH infractions

Article 5)



Full responsibility for th

RECOMMENDATIONS


absence of cobalt




Imported shipment



http://www.aimme.es

infractions (in accordance with law 8/2010,




importer

RECOMMENDATIONS





Imported shipment

ment protocols


n accordance with law 8/2010,

product lies on the




n accordance with law 8/2010,

product lies on the

► FUNCTIONAL CHARACTERISTICS

→ Lack of adherence

→ Peeling off and loss of coaWng through regular wear

→ Serious risk of ingesWng cobalt

- -

→ Extremely concerning risk for children

► ADDITIONAL RECOMMENDATIONS

→ Preventive action against product flaws

→Verify product

- - -

→ Set up provisos in purchase orders to cover these flaws

FUNCTIONAL CHARACTERISTICS

Lack of adherence



By erosion on contact with the mouth

By corrosion on contact with saliva


ADDITIONAL RECOMMENDATIONS

Preventive action against product flaws

→Verify product behaviour

Adherence and scratch resistance

Resistance to wear

Endurance to chemical household and personal

hygiene products




Lack of adherence of Co-Sn coating




corrosion on contact with saliva




behaviour through following tests:


Resistance to wear


hygiene products



35 de


Sn coating



corrosion on contact with saliva




through following tests:





de 47





[email protected]

AIMME

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Singular coating: nickel


∗ State: Finished (coating series: Ag + Ni

∗ Articles: Earrings, pendants and Rings



Homogeneous




the earrings

∗ According to



according to GPSD



[email protected]


http://www.aimme.es


Singular coating: nickel


State: Finished (coating series: Ag + Ni

Articles: Earrings, pendants and Rings



Homogeneous

material

Base alloy

Coating 1

Coating 2




the earrings


Non compliant for all Articles


ccording to GPSD


CONTAINS NICKEL

▪ Causes cancer

▪ Mutagen

▪ Toxic to preg

▪Toxic for brea





http://www.aimme.es


Singular coating: nickel-tin alloy


State: Finished (coating series: Ag + Ni




Composition

(% in weight)

Ag: 92.6

Cu: 6.7

Zn: 0.7

Ag: 100.0

Ni: 44.0

Sn: 56.



→ Compliant for all ArWcles ☺ including

EN 1811:2011

Non compliant for all Articles �




CONTAINS NICKEL

Causes cancer





ment protocols


State: Finished (coating series: Ag + Ni-Sn black)



Composition

(% in weight)

Thickness

(µm)

Ag: 92.6

Cu: 6.7

Zn: 0.7

------

Ag: 100.0 0.1-0.2

Ni: 44.0

6.0 0.5

XVII, Section 27)

including



CONTAINS NICKEL

H 351

H 341

H 360

H 360

ingestion H 301

H 317

Case 9

Nickel in coating on silver alloy


∗ Country: China

∗ Sample: Ring

► Components

- XRF identification: Ag, Cu, Ni, Zn, and Sn





----

Thickness

(µm)

------

0.2

0.5


---


-

* Tests prior to corrosion

release obtained is equivalent to that of a new article or

one

XVII, Section 27) ► Compliance

Part 3)

→Non compliant

(Nickel content exceeds 0.1 % in weight


→Compulsory labelling. Risk categories 1


► Compliance with

→ Non compliant




→ Non compliant



Case 9



Country: China

Sample: Ring


XRF identification: Ag, Cu, Ni, Zn, and Sn


Ag Cu

922.8 7.1




- Alloy base: Ag

- Coating 1: Pure Ag

- Coating 2: Ni

- Decorative parts

Release rate of Ni

- Corrosion and wear (EN 12472) : No*

- Uncorrected value: 0.97 µg/cm

- Corrected value: 0.1 µg/cm


- Ni: 44.0 % (exceeds 0.1 % in weight or 1000 mg/kg


Tests prior to corrosion


one that is in its first years of use.


Part 3)

Non compliant




and 2 take priority

Compliance with

→ Non compliant




→ Non compliant






of Article



Cu Ni

7.1 33.7




Alloy base: Ag-Cu-Zn

Coating 1: Pure Ag

Coating 2: Ni-Sn (black) alloy

Decorative parts

Release rate of Ni



Corrected value: 0.1 µg/cm2


Ni: 44.0 % (exceeds 0.1 % in weight or 1000 mg/kg


Tests prior to corrosion and wear cause a loss in nickel



with GPSD under CLP

Non compliant �




and 2 take priority










36 de


(‰ in weight)

Zn Sn

3.9 31.3


Sn (black) alloy



2/week

B substances



and wear cause a loss in nickel


CLP criteria (Annex




(Article 5)



(Article 18)



de 47

(‰ in weight)


and wear cause a loss in nickel The


nnex VI,


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► REACH infractions

Article 5)



�


[email protected]


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REACH infractions

Article 5)



Full responsibility for th



http://www.aimme.es

REACH infractions (In accordance with law 8/2010,




importer

ment protocols


(In accordance with law 8/2010,

product lies on the

(In accordance with law 8/2010,

product lies on the

► RECOMMENDATIONS


Absence of nickel




RECOMMENDATIONS


Absence of nickel




Imported shipment


RECOMMENDATIONS


Absence of nickel




Imported shipment


37 de





de 47


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AIMME

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Singular coating:


∗ State: Finished (with a black


∗ Articles: Earrings, pendants, Rings, etc.


Characteris

Homogeneous





Obligation to inform consignees or consumers


according to GPSD


▪ Specific toxic for respiratory tract

▪Acute toxicity due to inhalat


►REACH

Article 5



�


[email protected]


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Singular coating: sulphoselenides


State: Finished (with a black


Articles: Earrings, pendants, Rings, etc.


Characteristics of

Homogeneous

material

Base alloy

Coating 1

Coating 2







ccording to GPSD


CONTAINS SELENIUM

Specific toxic for respiratory tract

Acute toxicity due to inhalat

cute toxicity due to

REACH infractions

Article 5)



Full responsibility for the pr



http://www.aimme.es


sulphoselenides colouring


State: Finished (with a black conversio

silver sulphoselenide: Ag + Ag4SeS)



tics of homogeneous materials

Composition

(% in weight)

Ag: 92.9

Cu: 7.

Ag: 100.0

Ag: 97.0

S: 13.0

Se ≈ 0.05









CONTAINS SELENIUM

Specific toxic for respiratory tract

Acute toxicity due to inhalation


infractions (In accordance with



responsibility for the pr

importer

ment protocols


colouring

conversion of

: Ag + Ag4SeS)



Composition

(% in weight)

Thickness

(µm)

Ag: 92.9

7.1 -----

Ag: 100.0 Indiscernible

Ag: 97.0

S: 13.0

≈ 0.05

1

(Article 33)

�

B substances exceed





CONTAINS SELENIUM

H 373

H 331

H 301

(In accordance with Law 8/2010,


Case 10

Selenium in conversion coating on silver alloy


∗ Country: Turkey

∗ Sample: Ring

► Components of Article

- XRF identification: Ag, Cu, Zn, S and Se

► Information obtained by XRF (




- - -

Thickness

(µm)

-----

scernible

► Release rate of Se (purely informative)

�Corrosion and wear (EN 12472) :

-


-

*Tests prior to corrosion and wear cause a loss in selenium.

The release obtained is equivalent to that of a new

article or one that is in its first years of use.

► Compliance with

Part 3)

→ Non compliant

(Se content exceeds 0.1 % in weight




H 373

H 331

H 301

► Compliance with

→ Non compliant




→ Non compliant



8/2010,

oduct lies on the

► RECOMMENDATIONS


absence of selenium (modify system for

tarnishing silver)



→ Verify validity of cerWfi

Imported shipment

Case 10



Country: Turkey

Sample: Ring


XRF identification: Ag, Cu, Zn, S and Se

Information obtained by XRF (

Ag Cu

943.7 36.6




Base alloy: Ag

Coating 1: Pure Ag

Coating 2: Se conversion coating

Release rate of Se (purely informative)


Value < 0.05 µg/cm


Se: 0.34 % (As

weight or 1000 mg/kg per homogeneous material)

Tests prior to corrosion and wear cause a loss in selenium.



Compliance with

Part 3)

→ Non compliant




and 2 take priority

Compliance with

→ Non compliant




→ Non compliant



RECOMMENDATIONS



tarnishing silver)



→ Verify validity of cerWfi

Imported shipment






Information obtained by XRF (‰Cu Zn

36.6 0.5 18.6




Base alloy: Ag-Cu

Coating 1: Pure Ag



Corrosion and wear (EN 12472) : No

Value < 0.05 µg/cm2/week


Se: 0.34 % (As silver sulphoselenide










and 2 take priority

GPSD (Article 5)








RECOMMENDATIONS






Imported shipment


38 de



‰ in weight)

S Se

18.6 0.6




No*

B substances

silver sulphoselenide. Exceeds 0.1 % in





CLP criteria (Annex




(Article 5)



(Article 18)





cates and origin against


de 47

. Exceeds 0.1 % in



nnex VI,


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Combined coatings: Nickel + silver and antimony alloy


∗ State: Finished (Pd + Rh coatings)




Homogenous material

*In view of the results, the presence of a coating of an alloy


�� For nickel




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State: Finished (Pd + Rh coatings)




Homogenous material

Ba e alloy

Coating 1

Coating 2*

Coating 3*

Coating 4

In view of the results, the presence of a coating of an alloy

of Pd-Ni is ruled out


For nickel (Annex


� New articles (no corrosion or wear)

→ Borderline compliance for rings

→ Non compliant for the earrings

� Used articles (with corrosion and wear)



� New articles (no corrosion or wear)


� Used articles (with




http://www.aimme.es




State: Finished (Pd + Rh coatings)




Homogenous material Composition

(% in weight)

Ag: 92.7

Cu: 6.1

Zn: 1.2

Ag: 97.3

Sb: 2.7

Ni: 100.0

Pd: 100.0

Rh: 100.0


Ni is ruled out


XVII, Section. 27)


New articles (no corrosion or wear)

→ Borderline compliance for rings


Used articles (with corrosion and wear)




Non compliant for all Articles



ment protocols




Composition

(% in weight)

Thickness

(µm)

Ag: 92.7

Cu: 6.1

Zn: 1.2

-----

Ag: 97.3

Sb: 2.7 3.5

Ni: 100.0 0.4

Pd: 100.0 0.3

Rh: 100.0 0.3


XVII, Section. 27)


→ Borderline compliance for rings �

→ Non compliant for the earrings �



Non compliant for all Articles �

corrosion and wear)


Case 11

Antimony and nickel in coatings on silver alloy


∗ Country: China

∗ Samples: Two rings

► Components of Articles - XRF identification: Ag, Cu, Ni, Zn, Sb, Pd and Rh


951.2

► Information obtained by SEM ▪ System made up of 6 homogenous materials


- - - - - -

Thickness

(µm)




- -

�Corrosion and wear (EN 12472) : Yes

- -

►Release rate of Sb (purely

�Corrosion and wear (EN 12472) : No

- �Corrosion and wear (EN 12472) : Yes

- ► Content of CMR, PBT or vPv

- -



� For antimony





�� Shielding and synergic effects

�

�

�

Case 11



Country: China

Samples: Two rings

Components of ArticlesXRF identification: Ag, Cu, Ni, Zn, Sb, Pd and Rh


Ag Cu

951.2 19.4 12.1

Information obtained by SEMSystem made up of 6 homogenous materials


Base alloy: Ag-

Coating 1: Ag-

Coating 2: Pure Ni or Pd

Coating 3: Pure Pd or Pd

Coating 4: Pure R

Decorative stones

Release rate of Ni







Release rate of Sb (purely


Value << 0.1 µg/cm


Value: 5.9 µg/cm


Ni: 100 % >> 0.1 % in weight or 1000 mg/kg*

Sb: 2.7 % >> 0.1% in



For antimony (Article 33)





Shielding and synergic effects

� In new articles, coatings 2, 3 and 4 shield the

Sb with hardly any release. The shielding

is lower for Ni, which is released in greater quantity

� This situation is reversed with use (corrosion and wear)

� It can be concluded that with use, Ni and Sb are jointly

released. The synergic effect greatly increases the effect all

associated pathologies




Components of Articles

XRF identification: Ag, Cu, Ni, Zn, Sb, Pd and Rh


Ni Zn

12.1 8.1




-Cu-Zn

-Sb alloy

Coating 2: Pure Ni or Pd-Ni alloy

Coating 3: Pure Pd or Pd-Ni alloy

Coating 4: Pure R

Decorative stones







Release rate of Sb (purely informative)


Value << 0.1 µg/cm2/week


Value: 5.9 µg/cm2/week



Sb: 2.7 % >> 0.1% in weight or 1000 mg/kg*



(Article 33)


→ If CMR, PBT or vPvB substances exceed 0.1% in weight of



Shielding and synergic effects In new articles, coatings 2, 3 and 4 shield the

Sb with hardly any release. The shielding


This situation is reversed with use (corrosion and wear)

It can be concluded that with use, Ni and Sb are jointly


pathologies


39 de


XRF identification: Ag, Cu, Ni, Zn, Sb, Pd and Rh

in weight)

Sb Pd

6.5 1.7


alloy

Ni alloy





informative)

B substances


weight or 1000 mg/kg*


�

B substances exceed 0.1% in weight of


In new articles, coatings 2, 3 and 4 shield the

Sb with hardly any release. The shielding effect






de 47

Pd Rh

1.7 1.0

B substances exceed 0.1% in weight of






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► Compliance with

Part 3)

→ Non compliant

∗

∗


and 2 take priority


according to GPSD



→ Non compliant



► RECOMMENDATIONS


total absence of nickel and/or antimony




authorities


[email protected]


http://www.aimme.es


Part 3) → Non compliant

∗ Ni content exceeds 0.1 % in weight or


∗ Sb content exceeds 0.1 % in weight or



and 2 take priority


ccording to GPSD


CONTAINS ANTIMONY

▪ Causes cancer

▪ Corrosive to skin

▪ Respiratory tract irritant


→ Non compliant



RECOMMENDATIONS






authorities



http://www.aimme.es

GPSD under CLP


Ni content exceeds 0.1 % in weight or


Sb content exceeds 0.1 % in weight or



and 2 take priority




CONTAINS ANTIMONY

Causes cancer

Corrosive to skin

Respiratory tract irritant





RECOMMENDATIONS






ment protocols


CLP criteria (Annex








CONTAINS ANTIMONY

H 351

H 314

H 360

(Article 18)






nnex VI, ► Mandatory information for potential risks

according to GPSD



► Compliance with GSPD

→ Non compliant



► REACH



�


ccording to GPSD


CONTAINS NICKEL

▪ Causes cancer

▪ Mutagen





Compliance with GSPD

→ Non compliant



REACH infractions



Full responsibility





CONTAINS NICKEL

Causes cancer


or breastfeeding



Compliance with GSPD (Article 5)




infractions (in accordance with Law 8/2010, Article 5




importer

�


40 de



CONTAINS NICKEL

H 351

H 341

H 360

H 360

ingestion H 301

H 317

(Article 5)



with Law 8/2010, Article 5

or the product lies on the


de 47


with Law 8/2010, Article 5)

or the product lies on the


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Combined coatings: Alloy of silver

Alloy of nickel


∗ State: Finished (Series of coating finishes:

Pd + Rh + Ni

∗ Articles: Rings, earrings, Bracelets, etc.




*Persisting

Pd-Ni. Its proximity to the Ni

it difficult to distinguish between them


� For nickel (ANNEX XVII, Section. 27)




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Combined coatings: Alloy of silver

Alloy of nickel-tin


State: Finished (Series of coating finishes:

Pd + Rh + Ni-Sn black)

Articles: Rings, earrings, Bracelets, etc.




Base alloy

Coating 1

Coating 2*

Coating 3*

Coating 4

Persisting doubt whether Coating 2

Ni. Its proximity to the Ni



For nickel (ANNEX XVII, Section. 27)


▪ New articles (no corrosion or wear)


▪ Used articles (with corrosion and wear)



▪ New articles (no corrosion or wear)




→ No decision taken for rest of ArWcles



http://www.aimme.es


Combined coatings: Alloy of silver-antimony +



Sn black)





(% in weight)

Ag: 93.1

Cu: 4.6

Zn: 2.3

Ag: 96.9

Sb: 3.1

Pd: 100.0

Rh: 100.0

Ni: 42.3

Sn: 57.7

doubt whether Coating 2 is pure

Ni. Its proximity to the Ni-Sn alloy and low thickness make















ment protocols


antimony +




Composition

% in weight)

Thickness

(µm)

Ag: 93.1

Cu: 4.6

Zn: 2.3 -----

Ag: 96.9

Sb: 3.1 2.1

Pd: 100.0 0.1

Rh: 100.0 0.1

Ni: 42.3

Sn: 57.7 0.5

is pure Pd or an alloy of

Sn alloy and low thickness make








→ Non compliant for the earrings �

→ No decision taken for rest of ArWcles �

Case 12



∗ Country: China

∗ Sample: Two rings

► Components of Articles

- XRF identification: Ag, Cu, Ni,


945.5




- - - - - -

Thickness

(µm)

-----

2.1

0.1

0.1

0.5

Pd or an alloy of

Sn alloy and low thickness make



- -


- -

► Release rate of Sb


- �Corrosion and

-


- -

* % in weight


�� For antimony


→ If CMR, PBT o

�� Shielding and synergic effects

▪

▪

Case 12



Country: China

Sample: Two rings


XRF identification: Ag, Cu, Ni,


Ag Cu

945.5 8.2 27.8




Base alloy: Ag

Coating 1: Ag

Coating 2: Pure Pd or Pd

Coating 3: Pure Rh

Coating 4: Ni

Decorative stones

Release rate of Ni



Corrected value : 0.57




Release rate of Sb


Value : 0.24 µg/cm


Value: 0.53 µg/cm






For antimony (Article 33)






The series of Pd + Rh + Ni

thickness of 0,7

it does not act as an effective shield to the release of Sb

▪ It can be concluded that with use, Ni and Sb are jointly

released. The synergic effect greatly increases the effect

of all associated pathologies





XRF identification: Ag, Cu, Ni, Zn, Sb, Sn, Pd and Rh

Information obtained by XRF (‰

Ni Zn Sb

27.8 4.9 6.3




Ag-Cu-Zn

Coating 1: Ag-Sb alloy

Coating 2: Pure Pd or Pd-Ni alloy

Coating 3: Pure Rh

Coating 4: Ni-Sn (black) alloy

Decorative stones







Release rate of Sb (purely informative)



wear (EN 12472) : Yes

Value: 0.53 µg/cm2/week




per homogeneous material


(Article 33)


r vPvB substances exceed




The series of Pd + Rh + Ni-Sn coatings has a total

thickness of 0,7 µm. Due to its low resistance to wear




of all associated pathologies


41 de


Zn, Sb, Sn, Pd and Rh

‰ in weight)

Sb Sn Pd

6.3 5.2 1.6


Ni alloy

Sn (black) alloy


µg/cm2/week






wear (EN 12472) : Yes

B substances



per homogeneous material

�

B substances exceed



Sn coatings has a total

m. Due to its low resistance to wear





de 47

Rh

1.3



m. Due to its low resistance to wear





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► Compliance

Part 3)

→ Non compliant

∗

∗


and 2 take priority


according to GPSD



→ Non compliant



► FUNCTIONAL CHARACTERISITCS

→ Lack of adherence of Ni



- -


► ADDITIONAL RECOMMENDATIONS

→ PrevenWve acWon against product flaws

→Verify product behaviour through following tests:

- - -



[email protected]


http://www.aimme.es


Part 3)

→ Non compliant






and 2 take priority


ccording to GPSD


CONTAINS ANTIMONY

▪ Causes cancer

▪ Corrosive to the skin



→ Non compliant



FUNCTIONAL CHARACTERISITCS

→ Lack of adherence of Ni










Resistance to wear


hygiene products




http://www.aimme.es

GPSD under CLP







and 2 take priority




CONTAINS ANTIMONY

Causes cancer

Corrosive to the skin

espiratory tract irritant





FUNCTIONAL CHARACTERISITCS → Lack of adherence of Ni-Sn coating










Resistance to wear


hygiene products


ment protocols


CLP criteria(Annex








CONTAINS ANTIMONY

H 351

H 314

H 360

(Article 18)


Sn coating












according to GPSD



► Compliance with GSPD

→ Non compliant



► REACH

Article



�


► RECOMMENDATIONS


absence of nickel and antimony




Imported shipment




ccording to GPSD


CONTAINS NICKEL

▪ Causes cancer

▪ Mutagen





Compliance with GSPD

→ Non compliant



REACH infractions

Article 5)



Full responsibility for the

RECOMMENDATIONS






Imported shipment





CONTAINS NICKEL

Causes cancer





Compliance with GSPD (Article 5)




infractions (In accordance



responsibility for the

importer

RECOMMENDATIONS






Imported shipment

�


42 de



CONTAINS NICKEL

H 351

H 341

H 360

H 360

ingestion H 301

H 317

(Article 5)



with Law 8/2010,

product lies on the

importer





de 47


with Law 8/2010,

roduct lies on the


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AIMME

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Combination of different homogeneous materials:

Brazing

silver-antimony + Alloy of palladium


∗ State: Finished (Series of coating finishes: Au + Pd

+ Ru)

∗ Articles: Rings, earrings, chains, etc.




*Non homogeneous interpos

base alloy.

approximate value


� For nickel


▪

▪

∗ According to

▪




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Brazing with cadmium + coatings of (Nickel + Alloy of

antimony + Alloy of palladium


State: Finished (Series of coating finishes: Au + Pd

+ Ru)

Articles: Rings, earrings, chains, etc.




Base alloy

Brazing*

Coating 1

Coating 2

Coating 3

Coating 4

Coating 5

Coating 6

Non homogeneous interpos

base alloy. Likely alloy is

approximate value


For nickel (Annex XVII, Section. 27)














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with cadmium + coatings of (Nickel + Alloy of

antimony + Alloy of palladium







(% in weight)

Ag: 92.9

Cu: 6.2

Zn: 1.9

Cd: 0.5

Cu: 60.0

Sn: 40.0

Ni: 100.0

Ag: 97.0

Sb: 3.0

Au: 100.0

Pd: 83.0

Ni: 17.0

Ru: 100.0

Non homogeneous interposition between the brazing and

is Ag-Cu-Zn-Cd. Content of Cd is an


XVII, Section. 27)






EN 1811:2011


compliant for the earrings




ment protocols




antimony + Alloy of palladium-nickel)




Composition

(% in weight)

Thickness

(µm)

Ag: 92.9

Cu: 6.2

Zn: 1.9

-----

Cd: 0.5 -----

Cu: 60.0

Sn: 40.0 0.5

Ni: 100.0 0.2

Ag: 97.0

Sb: 3.0 1.0

Au: 100.0 0.5

Pd: 83.0

Ni: 17.0 0.2

Ru: 100.0 0.5

tion between the brazing and

Cd. Content of Cd is an




compliant for the earrings �

→ No decision taken for rest of ArWcles �





Case 13

Cadmium in brazing + Nickel and antimony in coatings on

silver alloy

State: Finished (Series of coating finishes: Au + Pd-Ni

∗ Origin: Imported from EU

∗ Country: Italy

∗ Sample: Two chains

► Components of Articles - XRF identification: Ag, Cu, Ni, Zn, Sb, Sn, Pd


Ag

754

► Information obtained by SEM ▪ System made up of 8 homogeneous materials

- - - - - - - -

Thickness

(µm)

tion between the brazing and

Cd. Content of Cd is an



- -


- -

► Release rate of Cd and Sb (purely informative)

�Corrosion and

-


-


- - - -



�� For antimony and cadmium



of homogeneous material (0.01%

Must inform consignees and consumers

� Shielding and synergic effects

�

�

Case 13


silver alloy

Origin: Imported from EU

Country: Italy

Sample: Two chains

Components of ArticlesXRF identification: Ag, Cu, Ni, Zn, Sb, Sn, Pd


Ag Cu Zn

754 97 14

Information obtained by SEMSystem made up of 8 homogeneous materials

Base alloy: Ag-

Brazing: Alloy of Ag

Coating 1: Alloy of Cu

Coating 2: Pure Ni

Coating 3: Ag-Sb alloy

Coating 4: Pure Au

Coating 5: Pd-Ni alloy

Coating 6: Pure Ru

Release rate of Ni







Release rate of Cd and Sb (purely informative)


Value < < 0.011 µg/cm


Value << 0.012 µg/cm




Sb: 3.0 % > 0.1 % in weight or 1000 mg/kg*

Cd: 0.5 % > 0.01 % in weight or 100 mg/ kg*



For antimony and cadmium


→ If CMR, PBT or vPvB substances exceed 0.1% in weight

of homogeneous material (0.01%



� In new articles, Ru acts as a shield against Pd

reduces the release of Ni. The effectiveness diminishes

with time due to wear and the release of Ni increases.

� Sb and Cd are totally shielded and are not released

through wear. Consequently, there are no synergic effects

between Ni, Sb and Cd



Origin: Imported from EU

Sample: Two chains


XRF identification: Ag, Cu, Ni, Zn, Sb, Sn, Pd


Sn Ni Cd

20 53 4



-Cu-Zn

Brazing: Alloy of Ag-Cu-Zn-Cd (probably)

Coating 1: Alloy of Cu-Sn-Zn (white bronze)

Coating 2: Pure Ni

Sb alloy

Coating 4: Pure Au

Ni alloy

Coating 6: Pure Ru








wear (EN 12472) : No

Value < < 0.011 µg/cm2/week


Value << 0.012 µg/cm2/week




3.0 % > 0.1 % in weight or 1000 mg/kg*




For antimony and cadmium (Article 33)


B substances exceed 0.1% in weight

of homogeneous material (0.01% for Cd).



In new articles, Ru acts as a shield against Pd



Sb and Cd are totally shielded and are not released


between Ni, Sb and Cd


43 de


XRF identification: Ag, Cu, Ni, Zn, Sb, Sn, Pd and Rh

in weight)

Cd Sb Pd Au

15 19


Cd (probably)

Zn (white bronze)

No



Corrosion and wear (EN 12472) : Yes Uncorrected value: 1.74 µg/cm

2/week



wear (EN 12472) : No


B substances



3.0 % > 0.1 % in weight or 1000 mg/kg*



(Article 33)


for Cd).


In new articles, Ru acts as a shield against Pd






de 47


Au Ru

4 20


In new articles, Ru acts as a shield against Pd-Ni and






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AIMME

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► Compliance with

Part 3)

→ Non compliant

∗

∗

∗



according to GPSD


► Compliance with

→ Non compliant

► REACH

Article 5



�


[email protected]


http://www.aimme.es


Part 3)

→ Non compliant

∗ Ni content exceeds 0.1 % in weight or




∗ Cd content exceeds 0.01 % in weight or



and 2 take priority


ccording to GPSD


CONTAINS CADMI

▪ Causes cancer

▪ Mutagen





→ Non compliant



REACH infractions

Article 5)






http://www.aimme.es

GPSD under CLP







mg/kg per homogeneous material)


and 2 take priority




CONTAINS CADMI

Causes cancer




GPSD (Article 5)




infractions (In accordance wit




importer

ment protocols


CLP criteria (Annex






mg/kg per homogeneous material)




CONTAINS CADMIUM

H 351

H 341

H 360

H 360

ingestion H 301

(Article 5)



(In accordance with Law 8/2010,



according to GPSD




according to GPSD



→ Non compliant


h Law 8/2010,


► RECOMMENDATIONS


absence of nickel, antimony and cadmium





according to GPSD


C

▪ Causes cancer

▪ Mutagen






ccording to GPSD


CONTAINS ANTIMONY

▪ Causes cancer

▪ Corrosive to the skin



→ Non compliant


RECOMMENDATIONS






Imported shipment



according to GPSD to provide to consumers under


CONTAINS NICKEL

Causes cancer








CONTAINS ANTIMONY

Causes cancer

Corrosive to the skin

Respiratory tract irritant




RECOMMENDATIONS






Imported shipment


44 de



ONTAINS NICKEL

H 351

H 341

H 360

H 360

H 301

H 317



CONTAINS ANTIMONY

H 351

H 314

H 360

(Article 18)







de 47





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ANNEX I

In order to define the different homogeneous materials a piece of jewellery is made up of, we

need to

and CLP Regulations; the RoHS Directive):

-

-

-

Therefore, an article of jewellery is basically made up of four homogeneous materials:

- - - -

If the coating is made up of a series of different multilayer coatings, each of them (individually)

is a homogeneous material. The same thing occurs for decorative parts: gems, stones, pearls,

enamels, rubber, leather, etc.

The previous


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ANNEX I: Definitions


need to take into account the definitions laid down in the related European legislation (REACH


Alloy: Metallic material, macroscopically homogeneous, composed of two or more

elements combined in such a way to make it diff

mechanically [(EC) Regulation Nº 1907/2006 (REACH); Art. 3.41] and [(EC) Nº

1272/2008 (CLP); Art. 2.27]

Homogeneous material: Uniformly composed material in all parts. Therefore, it cannot

be separated from other different

[Frequently Asked Questions (FAQ) on Directive 2002/95/EC (RoHS) and Directive

2002/96/EC (WEEE)]


Base alloy

Brazing

Coating

Decorative parts




The previous definitions are shown in the following diagram:

Figure 1. Breakdown of the different homogeneous materials a piece of jewellery is made up of



http://www.aimme.es

tions


take into account the definitions laid down in the related European legislation (REACH





1272/2008 (CLP); Art. 2.27]




2002/96/EC (WEEE)]


Base alloy

Decorative parts




definitions are shown in the following diagram:


ment protocols








1272/2008 (CLP); Art. 2.27]

















be separated from other different materials by mechanical methods










elements combined in such a way to make it difficult for them to be separated



materials by mechanical methods











icult for them to be separated



materials by mechanical methods







45 de













de 47











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ANNEX II

of content by weight according to CLP Regulation

A schematic summary now follows of the information found in Annex VI, Part 3 of (EC)

Regulation Nº 1272/2008 or “CLP” and the modifying (EC) Regulation Nº 790/2009, for all

dangerous s

Carcinogen (metal)

Carcinogen (chlorides, oxides and hydroxides)

Mutagen (chlorides and hydroxides)

Toxic to pregnant women and breastfeeding (chlorides and

hydroxides)

Acute toxicity due to consumption (saliva) and inhalation

(chlorides and hydroxides)

Specific toxicity to respiratory tract (chlorides and

hydroxides)

Cutaneous sensitizer (chlorides)

Cutaneous sensitizer (metal, oxides and hydroxides)

Carcinogen (metal, chlorides and oxides)

Mutagen (metal, chlorides and oxides)

Toxic to pregnant women and breastfeeding (metal

oxides

Toxic to pregnant women and

Acute toxicity (deadly) through inhalation (metal, chlorides

and oxides)

Acute toxicity due to consumption (saliva) (c

Specific toxicity to respiratory tract

oxides)

Carcinogen (oxide)

Cutaneous corrosion (chlorides)

Respiratory tract irritants (chlorides)


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ANNEX II: List of dangerous substances, associated risks, risk class




dangerous substances

Risks associated with nickel

Carcinogen (metal)




hydroxides)




hydroxides)



Table II.1 Risk classes and threshold values associated with metallic nickel and its derivatives

(chlorides, oxides and hydroxides)

Risks




oxides)



and oxides)



oxides)

Table II.2. Risk class and threshold value associated with metallic cadmium and its derivatives

(chlorides and oxides)

Risks associated with antimony

Carcinogen (oxide)



Table II.3. Risk classes and threshold values associated with antimony derivatives




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List of dangerous substances, associated risks, risk class




ubstances and mixtures (alloys)


Carcinogen (metal)











Risks associated with cadmium











Carcinogen (oxide)





ment protocols






and mixtures (alloys)











associated with cadmium




Toxic to pregnant women and breastfeeding (c



Specific toxicity to respiratory tract (metal, chlorides and












and mixtures (alloys) of interes








associated with cadmium

Toxic to pregnant women and breastfeeding (metal and

breastfeeding (chlorides


Acute toxicity due to consumption (saliva) (chlorides)

(metal, chlorides and







of interest that are used in jewellery.

Class




Class

and

hlorides)


)

(metal, chlorides and


Class



List of dangerous substances, associated risks, risk class and threshold values



that are used in jewellery.

Class Threshold value (%)

2

1

2

1B

3

1

1

1



1B

1B

2

1B

2

3

1



2

1B

3



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and threshold values



that are used in jewellery.

Threshold value (%)

C ≥ 0,1

C ≥ 0,1

C ≥ 0,1

C ≥ 0,3

C ≥ 0,1

0,1≤ C≤ 1

C ≥ 0,01

C ≥ 0,1

Threshold value (%)

C ≥ 0,01

C ≥ 0,1

C ≥ 0,3

C ≥ 0,3

C ≥ 0,3

C ≥ 0,1

0,1 ≤ C≤ 7

Threshold value (%)

C ≥ 0,1

C ≥ 0,1

C ≥ 5


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and threshold values



Threshold value (%)

Threshold value (%)

Threshold value (%)


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Carcinogen (chloride)

Mutagen (chloride)

Toxic for mother and foetus (chloride)

Acute toxicity due to consumption (saliva) (chlorides and

oxides)

Cutaneous sensitizer (metal, chlorides and oxides)

Respiratory sensitizer (metal, chlorides and oxides)

Toxic for

Acute toxicity due to inhalation (chlorides and oxides)


oxides)

Specific toxicity to respiratory tract (chlorides and oxides)

Carcinogen (all chromates except zinc chromate*)

Cutaneous sensitizer (all chromates)

Acute toxicity due to consumption (saliva) (only zinc

chromate*)


Acute toxicity due to consumption (saliva)


When faced by such a wide variety of associated risks the most limiting threshold value is the

one that would take preference


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Risks associated with cobalt


Mutagen (chloride)



oxides)



Table II.4. Risk class and threshold values associated with metallic cobalt and its derivatives


Toxic for mother and foetus (chlorides and oxides)



oxides)


Table II.5. Risk classes and threshold values associated with lead derivatives


Risks associated with chromium (Chromium VI)




chromate*)

Table II.6. Risk classes and threshold values associated with chromium derivatives (chromates)

*Zinc chromate may be present in silver alloys passivised using chromium plating. It is a class 1A

carcinogen

Risks associated with selenium




Table II.7. Risk classes and threshold values associated with selenium derivatives

*Possible presence of





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Mutagen (chloride)







Risks associated with lead

mother and foetus (chlorides and oxides)












carcinogen






*Possible presence of



ment protocols























Acute toxicity due to inhalation (sulphoselenides)


Specific toxicity to respiratory tract (sulphoselenides)


*Possible presence of the sulphoselenide


one that would take preference (blue-coloured


















(sulphoselenides)

Acute toxicity due to consumption (saliva) (sulphoselenides)

(sulphoselenides)


the sulphoselenide on blackened gold and silver


coloured box)

Class



Clas





Risks associated with chromium (Chromium VI) Class



Class

(sulphoselenides)


on blackened gold and silver



Class Threshold value

1B

2

1B

4

1

1


Class Threshold value

1A

4

4

2


1B

1

4




3

3

2

Table II.7. Risk classes and threshold values associated with selenium derivatives (sulphoselenides)

on blackened gold and silver



47 de

Threshold value

C ≥ 0,01

C ≥ 0,1

C ≥ 0,3

C ≥ 1

C ≥ 0,1

C ≥ 0,1

Threshold value

C ≥ 0,1

C ≥ 1

C ≥ 1

C ≥ 0,5

Threshold value (%)

C ≥ 0,1

C ≥ 0,1

C ≥ 1


Threshold value (%)

C ≥ 0,1

C ≥ 0,1

C ≥ 1

oselenides)



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Threshold value (%)

Threshold value (%)

Threshold value (%)


Threshold value (%)


Documents

Toxic metals in jewellery. Assessment protocols 69.pdf · 2011. 8. 29. · These substances were mainly distributed as homogeneous metallic materials (base alloy, brazing or coatings,