Lead in children's jewelry: the impact of regulation.

BACKGROUND: In 2016 we identified a regulatory gap in Israel reflecting a lack of restrictions on lead in children's jewelry. We conducted surveys that found high levels of lead in children's jewelry. Following the findings, a new standard restricting lead content was introduced in 2018. OBJECTIVE: The goal of this study is to assess whether the new standard had an impact on lead concentrations in children's jewelry on the market 4 months after entry into force, and to examine factors that influenced the standard's effectiveness. METHODS: Thirty-five items of children's jewelry were sampled from stores in Israel in 2018. Lead content of 130 subsamples of these items was tested with X-ray Fluorescence Spectrometry (XRF). We compared these findings to those before the introduction of the standard. We also conducted five structured interviews with professionals from government ministries, industry and expert bodies to examine factors influencing the standard's enactment and implementation. RESULTS: 17% of jewelry samples exceeded the ASTM lead standard in 2018 compared with 50% in 2016. The mean of the jewelry subsamples analyzed in 2018 was 936 (±1700) compared to 1420 (±5740) ppm in 2016. Scientific and regulatory consensus among those setting the new standard led to its swift enactment. However, enforcement challenges may reduce the standard's impact. SIGNIFICANCE: A new standard on lead in children's jewelry was followed by a decline in lead concentrations, but some products with lead exceedances remained available on the market. Public health campaigns, standards and compliance monitoring, and higher penalties will all help to reach the goal of protecting public health.

Chromium and cobalt release from metallic earrings from the Danish market.

BACKGROUND: Chromium and cobalt are important skin sensitizers. It has, however, been difficult to identify causative exposures. Studies on nickel allergy have demonstrated piercing as critical for both sensitization and elicitation. It may be speculated that the same applies for chromium and cobalt. OBJECTIVE: To examine the content and release of chromium and cobalt from earrings randomly purchased in Denmark. METHODS: Three hundred four earrings were examined with x-ray fluorescence (XRF) spectrometry. Earrings with measured content of chromium or cobalt were spot tested with diphenylcarbazide spot test (n = 166) or Nitroso-R spot-test (n = 99), respectively. Chromium and cobalt release were quantified in a selected subsample (n = 100) with the artificial sweat test (EN 1811). RESULTS: Chromium was present in 54.6% (166/304) of earrings and cobalt was present in 72.0% (219/304),- measured by XRF. All chromium spot tests for chromium VI were negative. The cobalt spot test was positive for one component. Chromium release was found from 59/100 (median concentration = -0.06 µg/cm2 /week) and cobalt release from 29/100 (median concentration = -0.06 µg/cm2 /week) of earrings in tested subsample. CONCLUSION: Earrings for piercing release chromium and cobalt and may on a case basis be a source of chromium and cobalt allergy.

DNA fingerprinting: an effective tool for taxonomic identification of precious corals in jewelry.

Precious coral species have been used to produce jewelry and ornaments since antiquity. Due to the high value and demand for corals, some coral beds have been heavily fished over past centuries. Fishing and international trade regulations were put in place to regulate fishing practices in recent decades. To this date, the control of precious coral exploitation and enforcement of trade rules have been somewhat impaired by the fact that different species of worked coral samples can be extremely difficult to distinguish, even for trained experts. Here, we developed methods to use DNA recovered from precious coral samples worked for jewelry to identify their species. We evaluated purity and quantity of DNA extracted using five different techniques. Then, a minimally invasive sampling protocol was tested, which allowed genetic analysis without compromising the value of the worked coral objects.The best performing DNA extraction technique applies decalcification of the skeletal material with EDTA in the presence of laurylsarcosyl and proteinase, and purification of the DNA with a commercial silica membrane. This method yielded pure DNA in all cases using 100 mg coral material and in over half of the cases when using "quasi non-destructive" sampling with sampled material amounts as low as 2.3 mg. Sequence data of the recovered DNA gave an indication that the range of precious coral species present in the trade is broader than previously anticipated.

A Comprehensive Artificial Sweat Study for Quantitation of Nickel and Other Inorganic Elements Released from Imitation Earrings Purchased in Istanbul Market.

Element sensitization is frequent cause of allergic contact dermatitis, and Ni is the main reason for this condition owing to daily use of different Ni-containing items. European Union established a limit of 0.2 µg/cm2/week Ni release for the items by the Ni Directive in 2004. The aim of this study was to determine the amount of element release of imitation earrings sold in different points of Istanbul with different prices and consider the element release levels including 29 trace and toxic elements. After calculation of released nickel amounts, 31.80% of earrings (71 of 223) were observed over the limit of European Commission Directive's migration limit. Minimum and maximum nickel release amounts were found as 0.21 and 30.11 µg/cm2/week, respectively, and mean level was found 3.24 µg/cm2/week among 71 positive earrings. Results showed that essential part of imitation earrings used especially by women release nickel particles over the European Commission Directive's migration limit. In addition, other elements such as Cu, Cr, and Co were found to be in the structure of the imitation earrings, as well as high amounts of toxic element Pb.

Nickel dermatitis from earrings 15 years after EU directive implementation: a clinical-epidemiological study and a market survey in Rome, Italy.

BACKGROUND: Nickel (Ni) dermatitis remains a highly prevalent allergic condition in Italy. There is a continuous need for clinical and epidemiological surveillance to evaluate whether or not European Ni Directive has been effective in contact allergy prevention. OBJECTIVES: To assess the prevalence of Ni dermatitis among patch-tested patients and self-interviewed school students and to analyse Ni release from earlobe jewellery. METHODS: Results of patch tests performed in 2006-2007, 2015-2016 and 2017-2018 were retrieved. A questionnaire was compiled by 315 secondary school students. Ni release from earring parts was analysed with the EN1811:2015 method. RESULTS: A significant time trend of decreasing Ni positivity from 2006-2007 to 2017-2018 was observed both in the overall population (44.1% in 2006-2007, 33.0% in 2015-2016, 31.6% in 2017-2018, P < 0.0001) and in female patients (P < 0.0001). Conversely, change was not significant in males (P = 0.16). Decrease was significant for all age groups, except for those aged >60 years (P = 0.51). Among 242 students who reported earring use, 130 (54%) reported symptoms at earlobes, mostly associated with jewellery of materials other than gold and silver (59% of those with earlobe symptoms). Ni release exceeded the migration limit in 4/21 (20%) earring parts. CONCLUSIONS: A high prevalence of Ni dermatitis and earlobe symptoms were found in Rome. A decreasing time trend was noted, with a significant decline in Ni sensitivity compared to the situation observed right after Ni Directive implementation. This most likely represents the consequence of reduced Ni content in earring parts, although a major care in the use of Ni-containing objects could contribute to explain these findings.

Amber in prehistoric Iberia: New data and a review.

Provenancing exotic raw materials and reconstructing the nature and routes of exchange is a major concern of prehistoric archaeology. Amber has long been recognised as a key commodity of prehistoric exchange networks in Europe. However, most science-based studies so far have been localised and based on few samples, hence making it difficult to observe broad geographic and chronological trends. This paper concentrates on the nature, distribution and circulation of amber in prehistoric Iberia. We present new standardised FTIR analyses of 22 archaeological and geological samples from a large number of contexts across Iberia, as well as a wide scale review of all the legacy data available. On the basis of a considerable body of data, we can confirm the use of local amber resources in the Northern area of the Iberian Peninsula from the Palaeolithic to the Bronze Age; we push back the arrival of Sicilian amber to at least the 4th Millennium BC, and we trace the appearance of Baltic amber since the last quarter of the 2nd Millennium BC, progressively replacing Sicilian simetite. Integrating these data with other bodies of archaeological information, we suggest that the arrival of Baltic amber was part of broader Mediterranean exchange networks, and not necessarily the result of direct trade with the North. From a methodological perspective, thanks to the analyses carried out on both the vitreous core and the weathered surfaces of objects made of Sicilian simetite, we define the characteristic FTIR bands that allow the identification of Sicilian amber even in highly deteriorated archaeological samples.

Electrochemical Screening Spot Test Method for Detection of Nickel and Cobalt Ion Release From Metal Surfaces.

BACKGROUND: Present screening methods to rapidly detect release of nickel and cobalt ions from metallic surfaces involve colorimetric dimethylglyoxime (DMG)- and disodium-1-nitroso-2-naphthol-3,6-disulfonate-based spot tests with a cotton bud. There is a risk of false-negative test reactions because test outcomes are dependent on the pressure, area, and duration of surface wiping. OBJECTIVE: The aim of the study was to develop a miniaturized electrochemical device that uses a voltage to accelerate nickel and cobalt release from the tested item and perform an initial validation. METHODS AND RESULTS: A device was built in plastic, and its performance was investigated using 0.5 mL of test solutions of, respectively, DMG and disodium-1-nitroso-2-naphthol-3,6-disulfonate. Cotton buds that had been wetted in test solution were pressed against different metal surfaces at various voltages (0-9 V) and a range of test durations (0-120 seconds). Duplicate testing for nickel and cobalt release was also performed on a sample of 163 jewelry items. CONCLUSIONS: This novel electrochemical device makes it possible to perform nickel and cobalt ion release testing without rubbing, thereby reducing interindividual differences in testing technique. The nickel testing with the device seemed to be superior to conventional DMG spot testing.

Concentrations of trace metals, phthalates, bisphenol A and flame-retardants in toys and other children's products in Israel.

Trace metals and synthetic chemicals including phthalates, bisphenol A and flame retardants, are widely used in toys and childcare products, and may pose acute or chronic adverse health effects in children. In Israel, certain chemicals are regulated in childcare products, but there are still regulatory gaps. We tested regulated and unregulated contaminants in 174 item parts from 70 childcare items with potentially high oral or dermal exposure, including 22 children's jewelry items, 14 toys, 7 diaper-changing mats, 6 baby mattresses, 7 baby textiles and 14 feeding and bathing items. In children's jewelry, an unregulated product in Israel, 23% of samples exceeded the US standard for lead. In toys, a regulated product, we did not detect trace metals above the Israeli standard. In textiles, baby mattresses and diaper-changing mats, phthalates exceeded the European Union standard in 14-45% of tests with a mean of 6.74% by mass for diisononyl phthalate, and 1.32% by mass for di(2-ethylhexyl) phthalate. BPA migration exceeded the EU standard in 14-45% of tests with a mean of 1.03 ppm. The flame retardants polybrominated biphenyls, pentabromodiphenyl, octabromodiphenyl ether, tris(2,3-dibromopropyl) phosphate and tris-(aziridinyl)-phosphine oxide were not detected. For products regulated in Israel, our findings suggest general compliance with mandatory standards. However, a lack of comprehensive chemical regulation means that there are regulatory gaps, and products not regulated in Israel may contain high levels of chemical contamination, exceeding US or EU regulations. The results of this study have prompted the development of an Israeli safety standard for children's jewelry.

Nickel and cobalt release from earrings and piercing jewellery - analytical results of a German survey in 2014.

BACKGROUND: Nickel and cobalt are important metal allergens, and more knowledge on the levels of exposure to these from everyday contacts is needed. OBJECTIVES: To report the results of a repeat routine surveillance scheme in the Federal Republic of Germany on the release of nickel and cobalt. METHODS: Fifteen laboratories assessed earrings and piercing jewellery items from 12 of the states in 2014, complying with EN 1811:2011 + AC:2012 and using atomic absorption spectrometry, inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry for quantification. Kaplan-Meier analysis for left-censored data was employed to account for measurements below the limit of quantification. RESULTS: Nickel release exceeded 0.35 µg/cm2 per week in 26 of 160 piercing posts (16.2%), and 0.88 µg/cm2 per week in 2.0-5.9% of other parts, that is, the current respective 'pass' thresholds, with no change from the previous 2008 survey. The level of cobalt release was lower than that of nickel release, and also significantly lower than in the previous survey. CONCLUSIONS: The finding of the highest level of nickel release from piercing posts, with their deliberately lower threshold of acceptability, is worrying, as is the largely unchanged overall level of nickel release. A regulation on cobalt release is currently lacking; risk assessment and management based on dose-elicitation data are needed.

Analysis and evaluation for consumer goods containing NORM in Korea.

We analyzed the consumer goods containing NORM by ICP-MS and evaluated the external dose. To evaluate the external dose, we assumed the small room model as irradiation scenario and calculated the specific effective dose rate using MCNPX code. The external doses for twenty goods are less than 1 mSv considering the specific effective dose rates and usage quantities. However, some of them have relatively high dose and the activity concentration limits are necessary as a screening tool.

Residual radioactivity of treated green diamonds.

Treated green diamonds can show residual radioactivity, generally due to immersion in radium salts. We report various activity measurements on two radioactive diamonds. The activity was characterized by alpha and gamma ray spectrometry, and the radon emanation was measured by alpha counting of a frozen source. Even when no residual radium contamination can be identified, measurable alpha and high-energy beta emissions could be detected. The potential health impact of radioactive diamonds and their status with regard to the regulatory policy for radioactive products are discussed.

Spectrophotometric determination of gold(III) in forensic and pharmaceutical samples and results complemented with ICP AES and EDXRF analysis.

Spectrophotometric method with three systems were developed here for the determination of gold(III) using o-dianisidine, aniline sulphate and catechol. Gold(III),in the system 1 it oxidizes o-dianisidine, in the system 2 it oxidizes catechol followed by its coupling with o-dianisidine, in the system 3 it oxidizes catechol followed by its coupling with aniline sulphate forming dye products with respective λmax 446nm, 540nm, and 505nm. All the three systems were optimized and analytical parameters were calculated. The molar absorptivity values were 9.27×104, 1.97×104 and 1.62×104 respectively for the systems 1, 2 and 3 with the corresponding Sandell sensitivity values (µgcm-2), 0.0021, 0.0096 and 0.011. The optimized systems were used for the determination of gold present in some forensic jewellery and pharmaceutical samples and the results obtained were compared with the results of all samples determined by Inductively Coupled Plasma - Atomic Emission Spectrometric method and a few of them were also complemented by Energy Dispersive X-Ray Fluorescent spectral analysis.

Jewellery: alloy composition and release of nickel, cobalt and lead assessed with the EU synthetic sweat method.

BACKGROUND: Several studies have shown nickel and cobalt release from jewellery by using spot tests, but the metal composition of jewellery is largely unknown. OBJECTIVES: To evaluate the metal composition of a large worldwide sample of mainly inexpensive jewellery items, and investigate the release of nickel, cobalt and lead from a subsample by using EN 1811:1998-required methods. METHODS: A total of 956 metallic jewellery components were examined with X-ray fluorescence spectroscopy. A subsample of 96 jewellery items purchased in the United States were investigated for nickel, cobalt and lead release by the use of artificial sweat immersion and plasma optical emission spectroscopy. RESULTS: Eighteen elements were detected. The 10 most frequently occurring were, in order of frequency, copper, iron, zinc, nickel, silver, chromium, tin, manganese, lead, and cobalt. Release of nickel was noted from 79 of the 96 US samples (0.01-98 µg/cm(2) /week), release of cobalt from 35 samples (0.02-0.5 µg/cm(2) /week), and release of lead from 37 samples (0.03-2718 µg/cm(2) /week). CONCLUSIONS: We present here a comprehensive list of the most frequently encountered metals in jewellery and fashion accessories. Different allergenic and non-allergenic metals are utilized. We also report the frequent release of nickel, cobalt and lead from these objects, despite legislative restrictions.

Assessment of nickel and cobalt release from jewelry from a non-nickel directive country.

BACKGROUND: A directive restricting nickel release from jewelry and other skin-contact products has not been initiated in Thailand or in the United States. The prevalence of nickel and cobalt allergies is increasing, and the main cause of sensitization seems to be jewelry. OBJECTIVES: We aimed to investigate nickel and cobalt release from jewelry available in Thai marketplaces and to study the factors associated with nickel and cobalt release. METHODS: Used costume jewelry items were collected from volunteers. They were tested with the dimethylglyoxime and cobalt tests. RESULTS: Five hundred fifty-one items, including belt buckles, bracelets, earrings, necklaces, rings, and watches, were tested; 216 (39.2%) gave positive dimethylglyoxime tests, and 206 (37.4%) gave positive cobalt tests. The factors that determined nickel or cobalt release were shopping location and jewelry price. Cobalt-containing jewelry could be identified by its dark color. CONCLUSIONS: A large proportion of the jewelry sold in Thai markets release nickel or cobalt.

Removal of copper and iron by polyurethane foam column in FIA system for the determination of nickel in pierced ring.

Polyurethane foam (PUF) mini-column was used to eliminate copper and iron for the determination of nickel in pierced rings. The PUF mini-column was connected to FIA system for on-line sorption of copper and iron in complexes form of CuSCN(+) and FeSCN(2+). For this season, the acid solution containing a mixture of Ni(II), Fe(III), Cu(II) and SCN(-) ions was firstly flew into the PUF column. Then, the percolated solution which Fe(III) and Cu(II) ions is separated from analysis was injected into FIA system to react with 4-(2-pyridylazo) resorcinol (PAR) reagent in basic condition which this method is called pH gradient technique. The Ni-PAR complexes obtained were measured theirs absorbance at 500 nm by UV visible spectrophotometer. In this study, it was found that Cu(II) and Fe(III) were completely to form complexes with 400 mmol/L KSCN and entirely to eliminate in acidic condition at pH 3.0. In the optimum condition of these experiments, the method provided the linear relationship between absorbance and the concentration of Ni(II) in the range from 5.00 to 30.00 mg/L. Linear equation is y=0.0134x+0.0033 (R(2)=0.9948). Precision, assessed in the term of the relative standard deviation, RSD, and accuracy for multiple determinations obtained in values of 0.77-1.73% and 97.4%, respectively. The level of an average amount of Ni(II) in six piercing rings was evaluated to be 14.78 mg/g.

Estimating children's exposure to toxic elements in contaminated toys and children's jewelry via saliva mobilization.

Children's potential for exposure to potentially toxic elements in contaminated jewelry and toys via mouth contact has not yet been fully evaluated. Various toys and jewelry (metallic toys and jewelry [MJ], plastic toys, toys with paint or coating, and brittle/pliable toys; n = 32) were tested using the saliva extraction (mouthing) compartment of the DIN and RIVM bioaccessibility protocols to assess As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Sb, and Se mobilization via saliva. Total concentrations of As, Cd, Cu, Ni, Pb, and Sb were found elevated in analyzed samples. Four metals were mobilized to saliva from 16 MJ in significant quantities (>1 µg for highly toxic Cd and Pb, >10 µg for Cu and Ni). Bioaccessible concentrations and hazard index values for Cd exceeded limit values, for young children between 6 mo- and 3 yr-old and according to both protocols. Total and bioaccessible metal concentrations were different and not always correlated, encouraging the use of bioaccessibility for more accurate hazard assessments. Bioaccessibility increased with increasing extraction time. Overall, the risk from exposure to toxic elements via mouthing was high only for Cd and for MJ. Further research on children's exposure to toxic elements following ingestion of toy or jewelry material is recommended.

Cobalt release from earrings and piercing jewellery - analytical results of a German survey.

BACKGROUND: Contact sensitization to cobalt is common. Some industrial exposures have been identified, but cobalt allergy is also often diagnosed in 'non-occupational' patients. Exposure of consumers is largely unexplained. OBJECTIVE: To present the analytical results on cobalt release from earrings and piercing jewellery sampled in a German Federal surveillance scheme. METHODS: Two German state laboratories analysed cobalt release, after immersion in artificial sweat according to EN 1811, along with nickel release in 87 pieces of jewellery, which were mostly taken apart for separate examination of piercing posts (n = 139), clasps (n = 51), and/or decorative items (n = 52). The distribution of cobalt release was described by the use of Kaplan-Meier analysis, taking into account that the majority of measurements were left-censored, that is, below the limit of quantification. RESULTS: Thirty-eight of 87 earrings and piercing jewellery items had at least one part releasing cobalt. The median cobalt release was estimated as 0.013 µg/cm(2) /week, and 75% of parts released up to 0.085 µg/cm(2) /week. Release varied somewhat between the three parts, with, for example, 22.1% of posts releasing ≥ 0.2 µg/cm(2) /week. CONCLUSIONS: Cobalt release from earrings and piercing jewellery, in particular from piercing posts, is considerable. Scientifically based exposure limits should be set, as in the case of nickel.

Nickel and cobalt release from jewellery and metal clothing items in Korea.

BACKGROUND: In Korea, the prevalence of nickel allergy has shown a sharply increasing trend. Cobalt contact allergy is often associated with concomitant reactions to nickel, and is more common in Korea than in western countries. OBJECTIVE: The aim of the present study was to investigate the prevalence of items that release nickel and cobalt on the Korean market. MATERIALS AND METHODS: A total of 471 items that included 193 branded jewellery, 202 non-branded jewellery and 76 metal clothing items were sampled and studied with a dimethylglyoxime (DMG) test and a cobalt spot test to detect nickel and cobalt release, respectively. RESULTS: Nickel release was detected in 47.8% of the tested items. The positive rates in the DMG test were 12.4% for the branded jewellery, 70.8% for the non-branded jewellery, and 76.3% for the metal clothing items. Cobalt release was found in 6.2% of items. Among the types of jewellery, belts and hair pins showed higher positive rates in both the DMG test and the cobalt spot test. CONCLUSION: Our study shows that the prevalence of items that release nickel or cobalt among jewellery and metal clothing items is high in Korea.