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Survey and health assessment of chemical substances in jewelleries

3 Survey and purchase

• 3.1 The market for jewelleries in Denmark
  • 3.1.1 Division of jewelleries into jewellery parts
  • 3.1.2 Categorization of jewellery parts
• 3.2 Purchase of metal jewelleries
  • 3.2.1 Price per weight unit
  • 3.2.2 Product types
  • 3.2.3 Product categories
  • 3.2.4 Purchase in relation to country of origin
  • 3.2.5 Where are the purchases made?
• 3.3 Purchase of textile necklaces
• 3.4 Results from the screening
  • 3.4.1 The uncertainty of the XRF screening
  • 3.4.2 Test for a content of Arsenic and Barium
  • 3.4.3 Content of heavy metal in the metal jewelleries
  • 3.4.4 Content of heavy metal in relation to price/gram
  • 3.4.5 Content of heavy metal in relation to the country of origin
  • 3.4.6 Content of heavy metal in the different product types
  • 3.4.7 Content of heavy metal in the different types of jewellery parts
  • 3.4.8 Content of heavy metal in the overall product categories gold, silver and non-precious metal
  • 3.4.9 Content of heavy metal in the specified product categories
  • 3.4.10 Content of heavy metal in relation to shop type

3.1 The market for jewelleries in Denmark

Jewelleries on the market in Denmark are in statistical respect divided into a number of groups as described in Appendix C. Largely, it is distinguished between jewelleries of precious metals (in this project also named precious metal jewelleries) and bijouterie. According to the legislation jewelleries of precious metals must contain at least 333 per thousand gold, 800 per thousand silver, 850 per thousand platinum and 500 per thousand palladium. Bijouterie covers on the whole all other types of jewelleries consisting of metals, precious metals, plastic, wood etc. In practice, it is an open question how the specific differentiation between the product groups within bijouterie is made.

An extract from Statistics Denmark (see Appendix D) shows that in 2005 the turnover was approx. 706 tonnes of bijouterie on the Danish market of which metal-bijouterie with and without precious metal represented approx. 358 and 312 tonnes respectively. Non-metallic bijouterie which includes plastics and textiles jewelleries represented approx. 36 tonnes. It was not possible to get data from Statistics Denmark which specifically deals with sale and production of the different types of non-metallic bijouterie.

Far the main part of the bijouterie is imported from Asia, primarily China, but other countries such as Hong Kong, South Korea and Taiwan also represent a relatively large part of the total import as stated in the table below (see Appendix D for more details).

Table 3-1: Import of jewelleries from abroad in percent.

The market for precious metal jewelleries is not that transparent as companies with below 10 employees (which is typical for goldsmith's and silversmith’s workshops) have no obligation to report the amount of produced products to Statistics Denmark.

In the project no complete survey of the market for jewelleries in Denmark was performed. The primary attempt was to cover the market by purchasing jewelleries from typical players in the retail trade as well as through the Internet. The main part of the jewelleries is bought in the retail trade, however, primarily in shop types like clothes shops, supermarkets, 10 kroner’s shops, jewellery shops etc. In the following sections there is a detailed description telling how the purchases of metal jewelleries as well as textile necklaces have been carried out and how the purchased jewelleries are classified.

3.1.1 Division of jewelleries into jewellery parts

The primary purpose of this project is to identify whether there is a problematic content of heavy metals in metal jewelleries (hereafter mentioned as jewelleries) in Denmark. However, jewelleries typically consist of several different metal parts (catch, chain, charm etc.) which each may have a different content of heavy metal. Therefore, in this project it is decided to analyse a maximum of 3 parts of each purchased piece of jewellery.

In the project, these different parts of the jewelleries are mentioned as “jewellery parts” as illustrated in the figure below. In the project a total of 170 pieces of jewelleries were purchased. These pieces of jewelleries were each scanned on a maximum of three different parts which has resulted in 318 jewellery parts.

Figure 3-1: Illustration of the definition of a jewellery part.

3.1.2 Categorization of jewellery parts

The categorization of the jewelleries is made on each jewellery part as jewelleries as mentioned often consist of several different metal parts, each with a unique appearance (gold, silver etc.) which makes an overall categorization of the jewellery as a whole impossible.

The jewellery parts in this project are categorized according to the following product categories:

Table 3-2: Description of product categories used to classify the jewellery parts.

Alloyed jewelleries consist of metal which is ”melted together” while the category ”coated jewelleries” includes jewelleries where precious metals lie as a separate metal layer on the surface. There are no jewelleries of the type “gold alloy” as on the whole genuine gold jewelleries always are alloyed jewelleries, i.e. the jewelleries which are defined as “genuine gold” here are in practice alloyed jewelleries.

Furthermore, the jewellery parts are generally divided into ”gold”, ”silver” and “clearly non-precious metal” since it for the consumer is possible visually to distinguish between these types of goods. In other words, with this division the consumer will have the possibility of deselecting a product if a possible relation between a problematic content of heavy metal and type of jewellery (gold, silver or non-precious metal) is proved.

According to content of precious metal, the categorization of precious metal has taken place on basis of analysis results from a XRF screening of the different jewellery parts by means of X-rays; however, it shall be mentioned that the results imply a relatively large uncertainty factor, as described in section 3.4.1.

The contents of precious metal in percentage which is the basis of the categorization of the jewellery parts in the groups “coated” and “alloyed” are solely based on experiences from the Danish assay office. Thus, this division cannot be regarded as an “official” categorization in terms of “alloyed” and “coated” jewelleries.

The reason that gold and silver jewellery parts are divided into “coated”, “alloyed” and “-like” respectively is due to the fact that a possible problematic content of heavy metals might be released differently, depending on whether the product is coated with precious metals, alloyed with precious metals or does not contain precious metals at all. The Danish assay office states that coatings of especially precious metals can to a certain degree prevent heavy metals from being released and thus reduce a potential health risk.

In a few cases, a small content of gold or silver (< 1%) is ignored during the categorization as the uncertainty of the XRF measurements are relatively large when the content appears to be below one percent. In other words, where the XRF result indicates a content of gold of for instance 0.08% a jewellery part can prove to contain no gold at all.

Finally, the categories ”genuine silver” and “genuine gold” are included even if these jewelleries are not in focus in this survey. The reason why is that a few of the purchased jewelleries turned out to contain jewellery parts which in fact had a content of precious metal which fulfils the legal requirement for precious metal jewelleries.

3.2 Purchase of metal jewelleries

In total, 170 metal jewelleries are purchased, divided into the product types rings, necklaces, bracelets, earrings, piercing jewelleries and ankle chains. These product types are selected as they all are products getting into contact with the skin.

The purchases were made in three phases with duration of 1-2 days during a total period of about 1.5 months. In the periods between the purchases the purchased jewelleries were screened for a content of heavy metals and then categorized. Based on this knowledge the strategy for the following purchases was made.

The primary elements which were assessed after each purchase/screening with regard to the next purchase were as follows:

• Proportionally equal distribution of price per gram.
• Proportionally equal distribution between the product types (rings, necklaces etc.).
• Proportionally equal distribution between the product categories (gold, silver etc.).
• A representative distribution in relation to country of origin.
• Reasonable distribution of purchases in the different types of shops.

3.2.1 Price per weight unit

During the purchases it was important to get a representative selection of products which were different with regard to price and quality. The basic measurements used to describe the relation between price and quality is price per weight unit (gram) as the type and price of the raw materials may be expected to be a substantial element in this situation. However, it shall be mentioned that it is difficult to define quality in relation to jewelleries as also a certain degree of subjective aesthetics is included in the term. For instance, a high degree of processing (e.g. in filigree jewelleries) can be a quality, which influences the price without the used raw materials necessarily being expensive.

The table below shows the purchase of jewelleries divided into the different relations regarding price/gram.

Table 3-3: The division of jewelleries in the different relations regarding price/gram.

3.2.2 Product types

As far as possible it was attempted to purchase an equal division of jewelleries in the different product types. However, it was judged that the use of products like piercing jewelleries and ankle chains are not as widespread as for instance necklaces, rings, bracelets and earrings. Thus, the purchase of piercing jewelleries and ankle chains was not in the same proportion as the remaining product types.

Table 3-4: The division of purchased jewelleries in the different product types

The product type ”Others” covers for instance toe rings etc.

3.2.3 Product categories

Furthermore, the purchase of the jewelleries was attempted to be equally divided on the different product categories (gold coated; silver-like etc.). However, in the purchase situation it was not possible to clarify whether the jewellery in fact contained precious metal, neither if it was alloyed or coated. Even if the purchases were made in several phases and the jewelleries were categorized continuously it was necessary with a more pragmatic approach to the purchase situation in the form of some overall product categories. This meant that focus was on purchasing a representative selection of jewelleries in the overall product categories “gold jewelleries”, “silver jewelleries” and “clearly non-precious jewelleries”. In other words, the overall product category “gold jewelleries” included jewelleries coated with gold as well as golden-like jewelleries. The categorization of the jewelleries has, as mentioned earlier, taken place on each part of the jewellery (with a maximum of three parts) as jewelleries as mentioned can consist of a silver part as well as a gold part. In the table below the distribution of the purchases in relation to the overall product category is shown.

Table 3-5: Division of purchases in relation to overall product category.

3.2.4 Purchase in relation to country of origin

As one of the purposes with the project was to clarify whether there is a relation between content/release of heavy metal and country of origin it was attempted, if possible, in the purchase situation to get information about the country of origin of the jewellery. However, it turned out to be difficult to get information regarding country of origin as most of the shop assistants had no possibility of replying to this. However, at a number of shops it was possible to get a telephone number to their supplier, head office etc. This contact information is registered in the database. Subsequently, it was tried to contact the supplier by phone to get information about importer/producer as well as country of origin. However, it was not possible to get this information in all cases and within the time frame of the project it was not possible to contact all shops. The table below represents the procured information.

Table 3-6: Division of purchased jewelleries in relation to country of origin

The definition ”The shop does not know” represents the shops which have not been contacted by phone and which in the purchase situation were not able to inform country of origin. The definition “Investigated but cannot be informed” represents situations where phone calls to the supplier have not resulted in an identification of the country of origin.

In total, information regarding country of origin was procured for 66 out of the 170 purchased jewelleries corresponding to 39%.

As it has not been possible in the main part of the purchase situation to get information about country of origin it has been difficult to purchase an equal distribution of jewelleries representing different countries. As the results immediately indicate the main part of the purchased jewelleries originates from Asia, especially China. However, this is not surprising as information from Statistics Denmark shows that the main part of bijouterie is imported from Asia, primarily China (see Table 3-1 and Appendix D).

However, it can be mentioned that the jewelleries are selected and purchased at random which means that with the large amount of purchased jewelleries there ought to be a representative distribution of the jewelleries as to their country of origin.

3.2.5 Where are the purchases made?

Purchase of the jewelleries is primarily made in retail trade (156 pcs.), however, supplemented by a small purchase via the Internet (14 pcs.). The purchases were made in the area of Copenhagen as it was assessed that jewelleries sold in this area cover a representative selection of the jewelleries being sold on national basis. Jewelleries were purchased in the following areas:

• Town centre Copenhagen: Strøget, Købmagergade incl. several side streets.
• Frederiksberg: Frederiksberg Center, Falkoner Allé, Godthåbsvej and Gl. Kongevej.
• Nørrebro: Nørrebrogade, Elmegade and Ravnsborggade.
• Vesterbro: Istedgade, Vesterbrogade and Fisketorvet.
• Lyngby: Lyngby Storcenter and Magasin.
• Kgs. Nytorv: Magasin.
• Strøget: Illum.
• Brønshøj/Husum: Frederikssundsvej.

The main part of the jewelleries was purchased in shops as it was assessed that only a small part of the population buys jewelleries via the Internet. Jewelleries were purchased in the following shop types:

• 10 kr’s shop types
• Other type of shops
• Shops with owners of different ethnic background
• Internet shops
• Jewellery shops
• Department stores
• Supermarkets
• Clothes shops

The category ”Other type of shops” covers among other shops booksellers, toyshops, children’s wear shops and different non-definable shops.

3.3 Purchase of textile necklaces

In total 62 textile necklaces were purchased. The main part of the textile necklaces were purchased at the same time as the metal jewelleries which means that the above-mentioned shop types also represent the shops where the textile necklaces were purchased. However, it was tried to purchase a little more of textile necklaces in children’s wear shops and toyshops as the notified textile necklace with a content of benzidine was targeted children.  Furthermore, during the purchase phase there was a focus on purchase of textile necklaces of different kind and colour.

3.4 Results from the screening

All 170 pieces of metal jewelleries were screened for a content of metals by means of a XRF device. In each case it was assessed how many different parts of the jewellery it was relevant to screen; however, a maximum of 3 different parts of the jewellery were screened. In total 318 screenings of jewellery parts were made.

3.4.1 The uncertainty of the XRF screening

Results reached through a XRF screening indicate first and foremost which elements being present as well as their approximately proportional distribution with regard to amount. Thus the result does not represent a reliable value for the exact content of the metal in percentages.

The content of for instance lead in the screening will be determined with a much greater reliability if for instance the content of lead is located on the outside of the jewellery than if the content of lead is placed in the middle of the jewellery. The reason being, that the XRF device uses X-rays to indicate a content of metal. These X-rays have more difficulties in penetrating into the middle of the jewellery and out from the jewellery (especially if it is coated with precious metals) which is the reason for the larger uncertainty of the result if the searched metal is in the middle of the jewellery (here the volume of the jewellery also has an influence). When using this type of measurements alone there is no possibility of immediately assessing where in the jewellery a possible content of heavy metals is located.

Another reason why it is not possible to describe the exact uncertainty of the completed XRF measurements is that the jewelleries vary a lot in shape and construction in relation to known reference samples. The XRF device shows in percentages a content of metal in the surface which the device immediately can “see”. Thus, to achieve a “perfect” screening the sample should consist of a perfect homogeneous surface which is not the case with the different jewellery parts.

At the semi-quantitative screening, which is the one being carried out in this project, a positive result implies that there is a content of the element in question; i.e. a positive quantitative determination. A strong signal implies that the jewellery contains relatively large amounts of the element in question.

It is judged that the results from the XRF screening are usable to form a reasonable impression of which jewelleries ought to be selected for further test for release of problematic heavy metals.

3.4.2 Test for a content of Arsenic and Barium

The used XRF device was not calibrated to test for a content of As and Ba and therefore a test for a content of these elements was made through a visual examination of the spectrum which came out for each XRF scanning.

The method consisted in defining the wavelength which As and Ba respectively represented and thereafter in interpreting visually whether there was a “top” on level with the respective “wavelength”. Despite the visual character of the method it can still indicate a possible content of these two metals with an acceptable certainty.

However, all the screenings showed no sign of a content of either As or Ba which was not expected anyway as normally these two metals are not used in  the production of jewelleries.

3.4.3 Content of heavy metal in the metal jewelleries

The 170 pieces of metal jewelleries were tested for a content of the following metals: Au, Ag, Cu, Sb, Pb, Se, Cr, Cd, Hg, Sn, Al, Mo, Nb, Zr, Bi, W, Zn, Ni, Co, Fe, Mn, V, Ti, In, Pt, Pd, As, Ba.

The following eight metals were judged to be the most interesting in terms of potential health risks related to migration to the skin as well as ingestion through the mouth: Pb, Hg, Cd, Se, Cr, Sb, As, Ba.

Appendix A shows the content of the above-mentioned 8 metals as well as gold, silver and copper in all the 318 screenings (corresponding to all the 170 pieces of jewelleries).

The screening revealed that approx. 58% of all examined jewelleries contained lead in a concentration above 100 ppm.

As regards the content of cadmium the screening showed that approx. 24% of all the examined jewelleries contained cadmium in a concentration above 75 ppm. However, based on the XRF screening it is not possible to conclude whether the content of cadmium is found in the form of a cadmium plating of the surface or whether it is found in the middle of the jewellery.

Regarding mercury, 4 pieces of jewelleries, corresponding to 2% of the examined jewelleries, exceeded the maximally allowed content of 75 ppm Hg.

Table 3-7: Content of Pb, Cd, Hg and Ni respectively in the examined jewelleries/jewellery parts.

The completed tables presenting the content of Ni, Cd, Pb, Hg, Sb and Cr respectively in all the jewellery parts (sorted in descending concentration) are enclosed in Appendix A. No content of Se was found in the jewelleries.

The maximum content of lead of 69.6% was found in a gold coated catch (jewellery part no. 95.3). Furthermore, 47 jewellery parts were found to contain above 10% of lead. Of these 47 jewellery parts, 16 (corresponding to 34%) were catches.

For cadmium, the maximum content in a jewellery part was 29.2% and in total 9 jewellery parts had content above 1% cadmium.

40 jewellery parts contained above 10% of nickel while two jewellery parts contained 93 and 95% of nickel respectively. Up to 25% of all examined jewelleries turned out to contain nickel in a volume percentage above 1. However, the legislation regarding nickel does not ban the use of nickel in jewelleries but there are requirements on the amount of nickel which maximally may migrate from the jewellery.

3.4.4 Content of heavy metal in relation to price/gram

The tables and figures below are included with the purpose of showing  whether there is a relation between the quality of the jewelleries (price per gram) and the content of heavy metals. The tables show the content of Pb and Cd respectively in relation to the quality of the jewellery (price per gram of jewellery – i.e. the price of the jewellery divided by the weight of the jewellery).

Table 3-8: Content of Pb in relation to kr/gram

Table 3-9: Content of Cd in relation to kr/gram

The figures below show the distribution in relation to kr/gram of the jewellery parts which were found to contain Cd and Pb respectively. Immediately, there seems to be a greater chance of a large content of Pb in the cheaper metal jewelleries (0 – approx. 10 kr. per gram) while for Cd there does not seem to be an immediate relation.

Figure 3-2: The distribution of jewellery parts containing Pb in relation to kr/gram

NB. A screening result for a single jewellery part with a kr/gram ratio of 66.64 (Pb content of 0.11%) is not included here. The reason for this is to create a more clearly visual presentation of the remaining data.

Figure 3-3: The distribution of jewellery parts containing Cd in relation to kr/gram

3.4.5 Content of heavy metal in relation to the country of origin

In the table below the content of Pb and Cd in jewelleries from the different countries is seen. Only data from the jewelleries where it has been possible to get information about the country of origin are included (i.e. 66 jewelleries out of the in total 170 purchased jewelleries).

Table 3-10 Content of Pb and Cd in relation to country of origin

Due to the limited amount of information regarding country of origin it is no possible to conclude anything about the probability of finding jewellery containing a certain amount of Pb and Cd in the respective countries. The reason for this is that there are not jewelleries enough from most of the countries to give a representative overview over the probability of a possible content of heavy metal. However, with a reasonable statistical certainty it can be said that for the 37 jewelleries being known to originate from China 30% has turned out to contain above 100 ppm of lead while 24% has turned out to contain above 75 ppm cadmium.

3.4.6 Content of heavy metal in the different product types

The XRF screening showed an even distribution of content of lead as well as cadmium among the different product types. Thus, it cannot be concluded that some of the product types have a larger probability of containing lead or cadmium than other product types. However, it is seen that none of the purchased ankle chains had a content of cadmium but the number of purchased ankle chains (6 pcs.) is not high enough to assume with certainty that in general ankle chains do not contain cadmium.

Table 3-11: Content of Pb and Cd in relation to product type

3.4.7 Content of heavy metal in the different types of jewellery parts

As shown in the tables below 70% of the examined charms (belonging to the product types earrings, necklaces and bracelets) has turned out to contain above 100 ppm of lead. Equally is that 78% of the examined charms (belonging to the product types earrings, necklaces and bracelets) has a content of cadmium above 75 ppm.

Furthermore, it has turned out that for the ”jewellery part type” catches belonging to the product types bracelets and necklaces 14% contained cadmium in a concentration above 75 ppm while 20% turned out to contain a minimum of 100 ppm lead.

From this it can be concluded that the tendency is that especially charms but also partly catches contain lead and cadmium. The jewellery part which turned out to contain the largest amount of lead (approx. 70%) was a catch. Furthermore, 15 other catches turned out to contain above 15% of lead (see Appendix A).

Table 3-12: Distribution of the content of heavy metal in relation to type jewellery part belonging to earrings

Table 3-13: Distribution of the content of heavy metal in relation to type jewellery part belonging to bracelet

Table 3-14: Distribution of the content of heavy metal in relation to type jewellery part belonging to necklaces

3.4.8 Content of heavy metal in the overall product categories gold, silver and non-precious metal

The results of the XRF screening showed that there does not seem to be a direct relation between the content of heavy metal and the overall product category (gold, silver or non-precious metal) (see Table 3-15). Thus it cannot be assumed that jewelleries of for instance gold have a greater possibility of containing lead or cadmium than jewelleries of silver or non-precious metal. Here it shall be mentioned that the overall product category “gold” covers jewelleries which contain gold as well as jewelleries looking like gold. Correspondingly for the overall product category “silver”.

Table 3-15: Content of Pb and Cd in relation to overall product category

3.4.9 Content of heavy metal in the specified product categories

As it is seen from the tables below there does not seem to be a significant difference of the content of lead in the specified product categories, i.e. it cannot directly be concluded that for instance precious metal-coated jewelleries contain less lead than precious metal-alike jewelleries. The same applies to cadmium.

Table 3-16: Number of jewellery parts with a content of Pb in the different product categories.

Table 3-17: Number of jewellery parts with a content of Cd in the different product categories.

3.4.10 Content of heavy metal in relation to shop type

The result from the screening did not show a clear relation between shop type and content of heavy metal. In other words, it cannot be directly concluded that there is a larger possibility of buying jewelleries with a content of lead and cadmium above 100 ppm and 75 ppm respectively in certain shop types.

It is calculated for each shop type how large a part of the purchased jewelleries that contained above 100 ppm lead and 75 ppm cadmium respectively (se the table below). However, it shall be mentioned here that the average does not take into account the uncertainty related to the fact, that in some of the shop types only a very few pieces of jewelleries were purchased.

Table 3-18: Percentage of jewelleries with above 100 ppm lead and 75 ppm cadmium respectively, seen in relation to shop type

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Version 1.0 October 2008, © Danish Environmental Protection Agency