IMEP-24 analysis of eight trace elements in toys

The International Measurement Evaluation Program (IMEP) organized the IMEP-24 interlaboratory comparison after reports in the media about high levels of lead in toys. The aim of this comparison was to verify the laboratories’ capacity to evaluate trace-element levels in a possible toy-like material according to the European Standard EN 71-3:1994. As test material, it used a former certified reference material containing levels of antimony, arsenic, barium, cadmium, chromium, mercury, lead and selenium around the limits set in the standard.Four expert laboratories confirmed the reference values (Xref) for all elements but Hg, and established a reference value for Hg. The scatter of the results reported by the participants was large, as expected, but showed a close to normal distribution around the reference values for five of the eight trace elements. The spread of results was mainly attributed to sampling and sample preparation.One major issue observed in this exercise was the lack of legislative rules about how to report the result, or, more specifically, the use of the analytical correction, which was introduced in EN 71-3:1994 to achieve consistent interpretation of results and which is to be applied when values are equal to or above the maximum limits set in the standard. Its application by the participants was very inconsistent and led to problems in their evaluation. There is clearly a need for clarification and for more formal regulations with regard to result reporting in order to minimize the risk of confusion.Participants were also asked to give their opinion with regard to the acceptability of the test material for the market. The majority correctly considered the material as non-compliant. However, almost one-third incorrectly assessed the material as compliant.     

The certification of a new paint reference material

The use of paint as a coating for toys intended for sale on the European market is controlled by a European Standard (EN 71-3: 1994-European Standard for the Safety of Toys, Part 3—Migration of Elements). This work is the result of a preliminary study organised by the European Commission to produce a new paint reference material which can be used to validate the test methods given in the European Standard. The migration of elements from painted panels and comminuted paint produced by the Laboratory of the Government Chemist, (U.K.) was studied. Several methods were used in this certification exercise and this work reports the recults of neutron activation analysis and inductively coupled plasma mass spectrometry to determine the migration of As, Ba, Cd, Cr, Hg, Pb, Se and Sb into a simulated stomach environment. Replicate extracts obtained from paint samples gave a precision of within 10% for most elements by both analytical techniques for the paint panels and for the comminuted paint sample. This preliminary study has shown that the standard method can provide reproducible results for each of the paint materials studied and indicates that the study should be continued to produce a fully certified paint reference material.     

Multi-element determination of dissolved heavy metal traces in sea water by total-reflection x-ray fluorescence spectrometry

Dissolved heavy metal traces in sea water are determined by a procedure based on total-reflection x-ray fluorescence spectrometry (t.x.r.f.). The trace elements are separated from the salt matrix by chelation with sodium dibenzyldithiocarbamate, selective chromatographic adsorption of the metal complexes onto a lipophilized silica-gel carrier, and subsequent elution of the metal chelates by a chloroform/methanol mixture. Aliquots of the eluate are then dispensed onto highly polished quartz sample carriers and evaporated to thin films for the t.x.r.f. measurements. The following elements can be determined: V, Mn, Fe, Co, Ni, Cu, Zn, Se, Mo, Cd, (Hg), Pb, and U. For 200-ml samples and a measuring time of 1000 s, detection limits of 5–20 ng kg^?1 are achieved for most of these elements. The limits are slightly higher for iron, zinc and mercury because of fluctuations in the blank values. Systematic investigations of the yield in the separation and enrichment step are described, and the procedure is characterized with regard to blanks, detection limits, precision and accuracy. The accuracy was checked with the aid of the sea-water reference material NASS-1. Some applications to Baltic sea water and open ocean waters are reported and discussed in terms of their information content.     

Determination of metals in marine species by microwave digestion and inductively coupled plasma mass spectrometry analysis

A microwave digestion method suitable for determination of multiple elements in marine species was developed, with the use of cold vapor atomic spectrometry for the detection of Hg, and inductively coupled plasma mass spectrometry for all of the other elements. An optimized reagent mixture composed of 2 ml of HNO₃, 2 ml of H₂O₂ and 0.3 ml of HF used in microwave digestion of about 0.15 g (dry weight) of sample was found to give the best overall recoveries of metals in two standard reference materials. In the oyster tissue standard reference material (SRM 1566b), recoveries of Na, Al, K, V, Co, Zn, Se, Sr, Ag, Cd, Ni, and Pb were between 90% and 110%; Mg, Mn, Fe, Cu, As, and Ba recoveries were between 85% and 90%; Hg recovery was 81%; and Ca recovery was 64%. In a dogfish certified reference material (DORM-2), the recoveries of Al, Cr, Mn, Se, and Hg were between 90% and 110%; Ni, Cu, Zn, and As recoveries were about 85%; and Fe recovery was 112%. Method detection limits of the elements were established. Metal concentrations in flounder, scup, and blue crab samples collected from coastal locations around Long Island and in the Hudson River estuary were determined.     

Development and certification of the new SRM 695 trace elements in multi-nutrient fertilizer

During the past seven years, several states within the US have enacted regulations that limit the amounts of selected non-nutritive elements in fertilizers. Internationally, several countries, including Japan, China, and Australia, and the European Union also limit the amount of selected elements in fertilizers. The elements of interest include As, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, and Zn. Fertilizer manufacturers and state regulatory authorities, faced with meeting and verifying these limits, need to develop analytical methods for determination of the elements of concern and to validate results obtained using these methods. Until now, there were no certified reference materials available with certified mass fraction values for all elements of interest in a blended, multi-nutrient fertilizer matrix. A new standard reference material (SRM) 695 trace elements in multi-nutrient fertilizer, has been developed to help meet these needs. SRM 695 has recently been issued with certified mass fraction values for seventeen elements, reference values for an additional five elements, and information values for two elements. The certificate of analysis includes an addendum listing percentage recovery for eight of these elements, determined using an acid-extraction inductively-coupled plasma optical-emission spectrometry (ICP–OES) method recently developed and tested by members of the Association of American Plant Food Control Officials.     

On the role of neutron activation analysis in the certification of a new reference material for trace-element studies,mixed human diet,H-9

A new biological reference material, which is representative of diets consumed in Finland, has been characterized by means of an intercomparison exercise conducted by the IAEA in the second half of 1985 and in 1986. Results for 35 elements received from 79 participants in 33 countries have been evaluated. A certificate of analysis has been issued with provisional certified values for 22 elements and information values for 2 elements. Neutron activation analysis (NAA) provided approximately one third of all the results reported. Instrumental NAA was used approximately 5 times as frequently as radiochemical NAA. Overall, NAA played an important role in providing useful data for the following 20 elements: Al, As, Br, Cl, Co, Cr, Cs, F, Fe, Hg, I, K, Mn, Mo, Na, Rb, Sb, Sc, Se and Zn. In comparison with the main competing non-nuclear method (usually atomic absorption spectrometry), NAA showed a larger dispersion of results for Cd, Cu, K, and Mg, and a smaller degree of dispersion for Co, Cr, Hg, and Se.     

Toxic and essential metals determination in commercial seafood: Paracentrotus lividus by ICP-MS

Toxic and essential metals content was determined by inductively coupled plasma mass spectrometry in commercial sea urchins samples from the Mediterranean Sea and Pacific Ocean. Results show that Chilean samples have the highest values of Cd, As, Ni, Cr and V; Spanish samples have the maximum Hg content while Sicilian samples have the lowest content of toxic metals. The toxic metal traces were compared with the limits of European Community (EC) No. 1881/2006 for bivalve molluscs. All samples exceed Pb and Cd limit levels; regarding Hg levels, only Sicilian and Sardinian samples have Hg content below the EC limits. The dietary intake of toxic and essential elements was evaluated for an adult. Furthermore, our study highlights a correlation between the toxic elements content and the marine environmental conditions of the places of origin even though only the generic FAO fishing area is specified.     

Interlaboratory study of trace and other elements in the iaea powdered human hair reference material,HH-1

A powdered intercomparison material for trace element studies was prepared from human scalp hair and distributed to more than 100 laboratories of which 66 reported results for altogether more than 40 elements. By statistical evaluation of these data certified concentration values were derived for 20 elements, namely As, Au, Br, Ca, Cd, Cl, Co, Cr, Cu, Fe, Hg, Mg, Mn, Na, Pb, S, Sb, Se, Sr and Zn. The data also made it possible to compare different methods of analysis and to judge the value of different levels of experience on the part of the analyst concerned; these comparisons are presented here with special reference to the elements As, Cd, Hg, Pb and Sb.     

Determination of cadmium,mercury and lead in coal fly ash by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

Ultrasonic slurry sampling electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry (USS-ETV-ID-ICP-MS) has been applied to the determination of Cd, Hg and Pb in coal fly ash samples. Thioacetamide (TAC) was used as the modifier. Since the sensitivities of the elements studied in coal fly ash slurry and aqueous solution were quite different, isotope dilution method was used for the determination of Cd, Hg and Pb in these coal fly ash samples. The isotope ratios of each element were calculated from the peak areas of each injection peak. This method has been applied to the determination of Cd, Hg and Pb in NIST SRM 1633a coal fly ash reference material and a coal fly ash sample collected from Kaohsiung area. Analysis results of reference sample NIST SRM 1633a coal fly ash agreed satisfactorily with the certified values. The other sample determined by isotope dilution and method of standard additions was agreed satisfactorily. Precision was better than 6% for most of the determinations and accuracy was better than 4% with the USS-ETV-ID-ICP-MS method. Detection limits estimated from standard addition curves were in the range of 24–58, 6–28 and 108–110 ng g⁻¹ for Cd, Hg and Pb, respectively.     

Evaluation of a proficiency test on cadmium and lead in herbal material using assigned reference values

This paper presents an international proficiency testing program (APLAC T065) on two trace elements, cadmium and lead, in an herbal sample, Herba Desmodii Styracifolii. The program was registered with a total of 109 laboratories from 42 countries. The assigned reference values of the analytes for performance assessment were provided by the organizers using an accurate gravimetric isotope dilution inductively coupled plasma-mass spectrometry technique. z-Score was used as the numerical indicator to interpret participants' competence. The between-laboratory variations for cadmium and lead were respectively 18.7% and 19.8% and the consensus values were found to be consistent with the assigned reference values. Twenty-two participants gave at least one unsatisfactory z-score, but the performance of the majority of participants on the analysis of cadmium and lead in herbal matrix was generally good when compared with the assigned reference values.     

Certification of trace and major elements and methylmercury concentrations in a macroalgae (Fucus sp.) reference material, IAEA-140

A marine reference material, IAEA-140, prepared with a macroalgae (Fucus sp.) was recently produced by the International Atomic Energy Agency and certified for trace and major elements and for methylmercury (MeHg). Certification of this material was achieved as an outcome of an international analytical intercomparison study which resulted in 116 independent sets of results reported by participants from 54 countries. The statistical evaluation of the collected data and the criteria used for assignment of the mean and uncertainty values are described. The analysis of data allowed to certify concentration values for 24 elements and MeHg, and to provide information values for another 10 elements. Regarding the elements which could be given certified values, between two and eight different instrumental methods were used to measure metal concentrations, and four independent analytical procedures were used to measure MeHg concentrations. In order to assess the results of the certification procedure, a comparison was made between the certified values obtained from the world-wide intercomparison results and the values obtained from a small subgroup of well-qualified laboratories. The means and 95% confidence intervals for reference values obtained by the two methods are similar for most elements showing that the usual method of certification used by the IAEA, based on large groups of participants, is indeed pertinent.     

微波消解样品-电感耦合等离子体原子发射光谱法测定铅精矿中铅、砷、镉、汞

采用微波消解样品-电感耦合等离子体原子发射光谱法同时测定铅精矿中主体元素铅及有毒有害元素砷、镉、汞的含量。0.20g试样置于消解罐中,先后加入硝酸9mL、盐酸3mL、氟硼酸2mL及过氧化氢2.5mL,密闭罐盖按设定的微波消解程序进行消解。试验选择铅、砷、镉和汞的分析线分别为220.351,189.042,228.802,184.950nm以消除基体干扰。铅、砷、镉、汞的检出限分别为16.0,2.2,0.4,0.8μg.g-1。方法用于铅精矿标准样品(GBW 07617)和铅精矿实际样品分析,此方法的测定值与认定值及原子吸收光谱法或原子荧光光谱法的测定值相一致。方法的相对标准偏差(n=10)在0.15%～3.9%之间。     

含Hg等元素的铝基光谱标准样品的制备和定值

阐述含Hg等元素的铝基光谱标准样品的制备工艺及定值结果.在制备过程中,创建了"间接加入法",采用铝箔包裹氯化汞(固态)的方式加入汞,解决了加入的汞元素分布不均匀的难题.采用StndMtrl软件系统进行数据处理和均匀性检验,并通过多家实验室协作分析给出标准值,制备出了含Hg等元素的铝基光谱标准样品.该标准样品满足食品行业...     

Certification of trace and major elements and methylmercury concentrations in a macroalgae (Fucus sp.) reference material, IAEA-140

A marine reference material, IAEA-140, prepared with a macroalgae (Fucus sp.) was recently produced by the International Atomic Energy Agency and certified for trace and major elements and for methylmercury (MeHg). Certification of this material was achieved as an outcome of an international analytical intercomparison study which resulted in 116 independent sets of results reported by participants from 54 countries. The statistical evaluation of the collected data and the criteria used for assignment of the mean and uncertainty values are described. The analysis of data allowed to certify concentration values for 24 elements and MeHg, and to provide information values for another 10 elements. Regarding the elements which could be given certified values, between two and eight different instrumental methods were used to measure metal concentrations, and four independent analytical procedures were used to measure MeHg concentrations. In order to assess the results of the certification procedure, a comparison was made between the certified values obtained from the world-wide intercomparison results and the values obtained from a small subgroup of well-qualified laboratories. The means and 95% confidence intervals for reference values obtained by the two methods are similar for most elements showing that the usual method of certification used by the IAEA, based on large groups of participants, is indeed pertinent.     

Analysis of FDA in-house food reference materials with anticoincidence INAA

In-house reference material (IRM) cocoa powder (CCP) has been in use at US Food and Drug Administration laboratories for about 15 years. A single lot of commercial material was originally characterized for 32 elements by several laboratories and five techniques. A unique approach for basis weight determination based upon ambient relative humidity was developed for CCP, eliminating the need for dry weight determinations. The CCP Reference Sheet is updated by incorporating new results approximately every 5 years. The last update occurred in 2006. As part of an effort to revalidate and update values for CCP, anticoincidence instrumental neutron activation analysis (INAA) was used to determine mass fractions for 16 of the originally characterized elements, as well as to provide information on 16 other elements. Results were in very good agreement with 2006 Reference Sheet values. A new candidate IRM, fresh-frozen swordfish (FFSF) powder, was produced by adding inorganic As, Cd, Cr, Hg, Pb, Sb, and Se to liquid nitrogen-frozen commercial swordfish filets which were then homogenized. Portions of FFSF were analyzed by INAA to provide mass fraction and homogeneity information for As, Cd, Cr, Hg, Sb, and Se as well as for eight other elements occurring naturally in the material. Non-homogeneities were ≤2.5 % for As, Br, Cd, and Cs, and ≤1.8 % for Cr, Hg, Rb, Sb, and Se. Certified reference materials DORM-3 Fish Protein powder and fresh-frozen SRM 1947 Lake Michigan Fish Tissue were analyzed as controls.     

Determination of cadmium,mercury and lead in seawater by electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry

Electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry (ETV-ID-ICP-MS) has been applied to the determination of Cd, Hg and Pb in seawater samples. The isotope ratios of the elements studied in each analytical run were calculated from the peak areas of each isotope. Various modifiers were tested for the best signal of these elements. After preliminary studies, 0.15% m/v TAC and 4% v/v HCl were added to the sample solution to work as the modifier. The ETV-ID-ICP-MS method has been applied to the determination of Cd, Hg and Pb in NASS-4 and CASS-3 reference seawater samples and seawater samples collected from Kaohsiung area. The results for reference sample NASS-4 and CASS-3 agreed satisfactorily with the reference values. Results for other samples determined by isotope dilution and method of standard additions agreed satisfactorily. Detection limits were approximately 0.002, 0.005 and 0.001 ng ml⁻¹ for Cd, Hg and Pb in seawater, respectively, with the ETV-ICP-MS method. Precision between sample replicates was better than 20% for most of the determinations.     

AFS-230E双道原子荧光光度计测定蔬菜中的砷和汞

采用湿法消解蔬菜样品,用AFS-230E型双道原子荧光光度计测定蔬菜中的As、Hg重金属含量。在最佳实验条件下,As、Hg元素的工作曲线相关系数(r)分别为0.9992、0.9996,检出限分别为0.0119ug/L、0.0139ug/L,回收率分别为：91.6%~101.50%,89.8%~97.3%,相对标准偏差（RSD%,n=7）分别为1.39%、0.52%,该法可供各地测定该类蔬菜中As、Hg等重金属元素含量的参考。     

Collaborative study for the quality control of trace element determinations in paint coatings Part 1. Interlaboratory study

Since the adoption of the European Standard EN71: Part 3 on toy safety, there has been dissatisfaction with the poor reproducibility obtained between laboratories using the test method for the determination of the migration of certain elements from paints to toys. This lack of quality control could result in toys being judged unacceptable with regard to the requirements of the EC Directive 88/378/EEC, which creates a potential barrier to trade. In order to improve the methods of measurements and testing, the Standards, Measurements and Testing Programme (SM&T) is currently supporting a project of which the final aim is to produce paint reference materials. The first step of this collaborative project is aimed to assess and possibly improve the state-of-the-art of trace element determinations in paint coatings through an interlaboratory study, the results of which are presented in this paper.