An intercomparison exercise for trace metal monitoring in oxygen-rich and anoxic Baltic waters

Seawater samples for a laboratory intercomparison of trace metal concentrations (Mn, Fe, Ni, Cu, Cd, Pb) in the dissolved (<0.4 μm filtered) and particle-bound phases as well as total and reactive Hg were collected in the Gotland Basin, a region in the Baltic Sea with trace metal gradients in the halocline and the redox boundary. Two laboratories took part in this exercise, each laboratory analysing samples from two vertical profiles collected using ”clean” sampling techniques. The hydrographic and hydrochemical situation was determined to characterise the water column and help interpret the results. An estimation of the conformity of the two laboratories was performed by comparing the results with international intercalibration exercises and certified reference materials. For all metals the characteristic vertical distribution and the concentration range of the data were comparable to other results published for the region. The concentration differences in the amount contents of Mn, Fe, Ni, Cu, Cd, Pb and Hg determined between both laboratories were better than the confidence intervals given by an ICES (International Council for the Exploration of the Sea) international comparison exercise for Baltic waters. Differences for Ni in the anoxic water body are attributed to the sulphidic matrix and their influence on the different methods used by the laboratories. For Pb and Hg the concentrations were near the detection limit of our methods, low level contamination was possibly responsible for the concentration differences. Small differences for dissolved Mn were attributed to different sampling techniques. We conclude that sampling and sample handling are still weak links in the trace metal analysis of anoxic seawater and that the analytical methods we used for this exercise are satisfactory for the accurate determination of Cd, Cu, Pb, Mn, Fe, and also for studying biogeochemical cycling of these trace metals in oxygen-rich and anoxic water bodies. Received: 8 February 2001 Accepted: 8 August 2001     

Certification of a new selenized yeast reference material (SELM-1) for methionine, selenomethinone and total selenium content and its use in an intercomparison exercise for quantifying these analytes

A new selenized yeast reference material (SELM-1) produced by the Institute for National Measurement Standards, National Research Council of Canada (INMS, NRC) certified for total selenium (2,059±64 mg kg⁻¹), methionine (Met, 5,758±277 mg kg⁻¹) and selenomethionine (SeMet, 3,431±157 mg kg⁻¹) content is described. The ±value represents an expanded uncertainty with a coverage factor of 2. SeMet and Met amount contents were established following a methanesulfonic acid digestion of the yeast using GC-MS and LC-MS quantitation. Isotope dilution (ID) calibration was used for both compounds, using ¹³C-labelled SeMet and Met. Total Se was determined after complete microwave acid digestion based on ID ICP-MS using a ⁸²Se spike or ICP-OES spectrometry using external calibration. An international intercomparison exercise was piloted by NRC to assess the state-of-the-art of measurement of selenomethione in SELM-1. Determination of total Se and methionine was also attempted. Seven laboratories submitted results (2 National Metrology Institutes (NMIs) and 5 university/government laboratories). For SeMet, ten independent mean values were generated. Various acid digestion and enzymatic procedures followed by LC ICP-MS, LC AFS or GC-MS quantitation were used. Four values were based on species-specific ID calibration, one on non-species-specific ID with the remainder using standard addition (SA) or external calibration (EC). For total selenium, laboratories employed various acid digestion procedures followed by ICP-MS, AFS or GC-MS quantitation. Four laboratories employed ID calibration, the remaining used SA or EC. A total of seven independent results were submitted. Results for methionine were reported by only three laboratories, all of which used various acid digestion protocols combined with determination by GC-MS and LC UV. The majority of participants submitted values within the certified range for SeMet and total Se, whereas the intercomparison was judged unsuccessful for Met because only two external laboratories provided values, both of which were outside the certified range.     

An international intercalibration for methylmercury in biological tissue

An intercalibration exercise between 13 laboratories from seven countries was conducted for comparing the methylmercury measurement techniques for marine biological tissues. Analyses have been conducted on two sets of samples: a fish muscle and a mussel soft tissue. Most of the participating laboratories performed six replicate analyses, allowing statistical comparisons. Various analytical techniques have been used, including cold vapour atomic absorption spectrophotometry (CVAA), electron capture gas liquid chromatography (GCEC), neutron activation (NAA), and inductively coupled plasma–isotopic dilution mass spectrometry (ICPIDMS). All of these methods offer similar results. They allow us to define consensus values which seem good estimates of the real concentrations. In addition the results show, for most of the participating laboratories, good accuracy and precision in the determination.     

Evaluation of CP Sil 8 CB film thickness for the capillary GC determination of methyl mercury

Different commercially available CP-Sil 8 CB capillary columns have been tested with a mixed standard containing methyl mercury chloride, ethyl mercury chloride and a stable nonpolar chlorinated hydrocarbon. The aim of the study was to see whether the columns tested could be used without special pretreatments and precautions for the determination of organo-mercury compounds. The GC conditions in these determinations where similar to those conditions used for the determination of chlorinated pesticides. The best peak shapes where found using a normal packed column injector, modified with a commercially available insert for on-column injections on wide bore columns, and a 5.35 m thick stationary phase. It was concluded that this CP Sil 8 CB column gave good results although minor interactions between the organomercury compounds and the column could be seen.     

An international intercomparison exercise for the determination of purified microcystin-LR and microcystins in cyanobacterial field material

The comparability of current microcystin analysis methods has been evaluated in an international intercomparison exercise. The focus was on the analysis of microcystins by high-performance liquid chromatography coupled with ultraviolet or photodiode-array detection (HPLC-PDA/UV), currently the most widespread method for microcystin analysis, but the exercise was open for other methods such as enzyme-linked immunosorbent assay (ELISA), protein phosphatase inhibition assay (PPA) and high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS).Thirty-one laboratories from 13 countries participated in the study. For a microcystin-LR (MC-LR) standard solution (S1) of undisclosed quantity, and for a field sample (S3) from a natural cyanobacterial bloom, repeatabilities between 4 and 15% and reproducibilities between 24 and 49% were obtained. No significant differences between single methods were found for S1 and S3, except for a significantly higher repeatability value of ELISA for S1. However, the analysis of microcystins in the field sample (S3) by HPLC-PDA/UV was significantly more variable than for the standard solution (S1). Both the extraction and the analysis of the microcystins appeared to contribute to this variability.It is concluded that standard MC-LR (S1) can be measured with adequate precision by all participating laboratories independently of the method used. With respect to the different methods used the results for the field sample can also be regarded as satisfactory, but clearly showed the need for improvement by standardisation between laboratories. Furthermore, quantification with in-house standards compared to quantification using the supplied MC-LR standard indicated that routine microcystin analysis in laboratories may be also influenced by the variability of available standards, emphasising the need for the production of certified reference materials (CRM).     

Titrimetric analysis of total mercury ions including mercury(I) ions

A systematic analytical method is proposed and applied to directly determine the total concentration of Hg(II) and Hg(I) ions in water. Experimental results demonstrate that this method provides a low detection limit of 0.05 mM and small relative error within 1.5% in an ion concentration range of 0.2–50 mM. The technique is especially applicable for sample solutions that the traditional titration method like Volhard and EDTA complexation titrimetry could not analyze directly. This method could be employed to analyze solutions in any ratio of Hg(II) and Hg(I) ions including pure Hg(II) or pure Hg(I) ions, exhibiting several advantages, such as simple operation, good reproducibility, and low cost. Correspondence: Xin-Gui Li, Key Laboratory of Advanced Civil Engineering Materials, Institute of Materials Chemistry, College of Materials Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, China.     

The determination of organochlorine compounds and petroleum hydrocarbons in a seaweed sample: results of a world-wide intercomparison exercise

A seaweed sample (Fucus sp.) was prepared, homogenised and distributed to laboratories worldwide as the IAEA-140 intercomparison material for the analysis of organochlorine compounds and petroleum hydrocarbons. A total of 80 laboratories from 51 countries reported results for this sample. The data sets reported by laboratories were evaluated statistically and the mean concentration values could be computed with 95% confidence limits for a large number of analytes. The accuracy of the analytical performance of each laboratory has been introduced by using Z-scores. The spread of results reported generally indicates that the accurate determination of many persistent organic pollutants, such as hexachlorobenzene, lindane, Aroclors or fluoranthene, is still difficult for many laboratories. The final results of this intercomparison exercise enable individual participants to assess their performance and, where necessary, to introduce appropriate modifications in their analytical procedures. Furthermore, as a series of statistical criteria was fulfilled for a number of compounds, the sample IAEA-140 can now be used as a reference material for quality control in the determination of chlorinated compounds and petroleum hydrocarbons in environmental samples.     

Flow system device for the on-line determination of total mercury in seawater

The instrumental set-up for the on-line sampling, digestion and quantification of total mercury in seawater is described. Based on a flow system and cold vapour atomic absorption spectrometry (CVAAS) detection limit was improved by a gold amalgam preconcentration to 0.5 ng l(-1). The manifold design was optimized by the variation of the gas flow, length of reaction coils, shape and material of the gas-liquid separator and flow rate of the reductant. A calibration following the equations p=0.039c+0.0813 (p, peak area; c, concentration) and a correlation coefficient of r=0.9996 was obtained. The relative standard deviation of three measurements of 0.5 ng l(-1) Hg(2+) was 3.8%. The long-time (12 h) reproducibility was 6.2% RSD (n=25) of 0.5 ng l(-1) Hg(2+). With a recovery rate >90% mercury can be determined after on-line UV digestion. For a complete analysis, 6 min is required. The technique is fast, simple to handle and robust. The apparatus is designed for the use on research vessels under sea conditions.     

Standardization of methods for the determination of traces of mercury : Part I. Determination of total inorganic mercury in inorganic samples

A method is described for the routine determination of mercury in the process and product streams of chlor alkali electrolysis plants (with the exception of chlorine) and also in the plant waste waters. The procedure is based on flameless atomic absorption spectrophotometry. Results for interlaboratory trials involving up to 37 participating laboratories are presented. Both synthetic and technical samples were analysed with mercury contents varying between 20 μg kg^-1 and 20 mg kg^-1. Statistical evaluation of the results gave a value of from 4 to 8% for the repeatability and from 6 to 22% for the reproducibility.     

固体进样直接测定法测定铜精矿中汞

建立了固体进样直接测定法测定铜精矿中汞含量的方法。铜精矿样品在测汞仪的分解炉中经300℃干燥和750℃高温热分解后,汞被催化分解为汞原子,于850℃齐化成金汞齐。汞蒸气被氧气流带入单波长光学吸收池,在波长253.7 nm处测量汞的吸光度,采用标准曲线法计算汞量。方法的线性范围分别为0~1.00,0~100μg/mL,线性相关系数为0.9999,检出限分别为0.10,0.04 ng/g。5个汞含量不同的铜精矿样品测定结果的相对标准偏差为2.14%~4.35%(n=11),样品加标回收率为92.00%~104.02%。采用该方法分别对2个铜精矿样品和铜精矿国际标准物质进行测定,测定结果与标准分析方法测定值和标准物质标示值基本一致。该方法简便、快速、准确,可以作为标准方法推广使用。     

大体积进样-原子荧光光谱法 测定海水中痕量汞

海洋中的汞在生物体内会转化为毒性高的甲基汞,影响海洋生物体的健康,进而威胁到人类的健康。同时,由于汞元素的记忆效应,使其会残留在光谱仪器设备中,影响仪器空白值和参数设置,以及测量结果的准确性和可靠性。海水中的汞含量处于超痕量水平,其分析检测是目前的难点之一。本文研究了一种大体积进样-原子荧光光谱法测定海水中痕量汞的方法,考察了不同前处理方式、酸的种类、还原剂浓度和原子化方式对检测的影响,并针对性利用烷基汞验证了不同条件下的检测结果,对方法进行了改进和验证,并对不同海域的海水进行了检测。实验结果表明：采用大体积进样,用盐酸代替硫酸,检测低浓度样品结果更准确;用甲基汞、乙基汞加标和低浓度还原剂对比验证过硫酸钾消解前处理时室温消化24h和加热煮沸1min两种消解方式,两种方式的加标回收率均接近100%;测量不同海域海水样品平行性好,结果准确,该方法对不同海域海水具有普遍适用性。     

Trace metals (Cu, Pb, Zn, Cd, Al, Li, Fe, Mn, Ni, Co) in marine suspended particulate matter: an international ICES intercomparison exercise

 The aim of this intercomparison exercise was to assess the comparability of trace metal analyses of blank filters and of marine suspended particulate matter (SPM) on filters performed by laboratories in ICES member countries. Fifteen experts from the United Kingdom, Canada, France, Germany, the Netherlands, Norway, Poland, Russia, and the United States were invited to participate in this exercise for trace metal analyses of Cu, Pb, Zn, Cd, Al, Li, Fe, Mn, Ni and Co (tentative) in SPM. Each filter analysed in this project was an individual sample, the absolute loadings on the filters varying from 0.8 to 2 mg of SPM. The inter-laboratory means and the relative standard deviations (RSD) from the grand mean for the metals determined were: Al 67.5 mg/g, 8.3%, Fe 51.7 mg/g, 10.9%, Cd 1.5 μg/g, 22.7%, Cu 39 μg/g, 13.3%, Pb 38 μg/g, 34.7%, Mn 1060 μg/g, 13%, Ni 49.2 μg/g, 29%, Zn 182 μg/g, 32.5%, Li 52.8 μg/g, 26.1%, Co 15.4 μg/g, 23.6%. In general, the exercise demonstrated that it is possible for the various participants to collect very small amounts of SPM and analyse it by the different determination techniques. Compared to earlier exercises, comparability between laboratories was still difficult to achieve and limited. Received: 27 June 1996 Accepted: 15 August 1996     

Development of a novel and robust microprecipitation approach using cetyltrimethyl ammonium bromide (CTAB) for preconcentration and speciation of mercury in waters prior to CVAAS determination

A novel and simple microprecipitation method was developed for the preconcentration of ultra-trace quantities of inorganic and methyl mercury species (iHg and MeHg) prior to their determination by cold vapour atomic absorption spectrometry (CVAAS). This method is based on the formation of anionic complexes of Hg²⁺ with KI followed by ion-associate complex with cetyltrimethyl ammonium bromide (CTAB) that forms a fluffy precipitate in perchloric acid medium. As a result, a fluffy coagulated mass separates and collects at the top of the liquid surface with clear phase separation without need of cooling or heating or centrifugation. The ion-association complex of iHg was then extracted into surfactant-rich phase (top layer) of CTAB-perchlorate precipitate while the uncomplexed MeHg remained in the aqueous phase (bottom layer). This condition also facilitates the removal of aqueous phase by simply draining out. The fluffy mass formed was dissolved in a mixture of HNO₃ and HCl which was subsequently treated with chloroform to separate the surfactant from the mixture. Then the aqueous phase containing the preconcentrated iHg was analysed for mercury by CVAAS. Key factors such as sample pH, concentration of KI and CTAB that affect the performance of the proposed microprecipitation method were thoroughly investigated. For the determination of total mercury, another fresh aliquot of water was initially adjusted to pH ~ 3.5 with perchloric acid and subjected to oxidation by using modified UV-irradiation set-up and then taken through the microprecipitation procedure. This method allows speciation of mercury with a preconcentration factor of 200 and the limits of detection (LOD) of mercury obtained for CVAAS in conjunction with the present preconcentration method was found to be 2.4 ng L^?1. Average recoveries obtained with the proposed approach were found to be in the range of 96–104% with RSD values < 5%. The interfering effects of various cations and anions were also investigated. The method was successfully applied for the determination of ultra-trace quantities of mercury species in real samples such as bottled water, tap water, lake water and ground waters.     

Assessing bias in total mercury results after removing a subsample from the bottle

U.S. EPA Method 1631 for total mercury (THg) analysis in water recommends that bromine monochloride (BrCl) be added to the original bottle in which the sample was collected, to draw into solution any Hg that may have adsorbed to the bottle walls. The method also allows for the removal of a subsample of water from the sample bottle for methylmercury (MeHg) analysis prior to adding BrCl. We have demonstrated that the removal of a subsample from the sample bottle prior to THg analysis can result in a positive concentration bias. The proposed mechanism for the bias is that ‘excess’ inorganic Hg, derived from the subsample that was removed from the bottle, adsorbs to the bottle walls and is then drawn into solution when BrCl is added. To test for this bias, we conducted an interlaboratory comparison study in which nine laboratories analysed water samples in fluorinated polyethylene (FLPE) bottles for THg after removing a subsample from the sample bottle, and analysed a replicate sample bottle from which no subsample was removed. We received seven complete data sets, or 63 unique sample pairs. The positive concentration bias between the bottles was significant when comparing all samples in aggregate (1.76 ± 0.53 ng/L after subsample removal, 1.57 ± 0.58 ng/L with no subsample removal, P < 0.05), however when comparing each of the three samples individually, the only significant bias was in the saline sample (Site UJ; 1.51 ± 0.31 ng/L after subsample removal, 1.32 ± 0.47 ng/L with no subsample removal, P < 0.05). Based on the findings presented here, we conclude that water chemistry, volume of water poured off, and the sample storage temperature explain some but not all of the observed bias, and we recommend collecting THg and MeHg samples in separate bottles whenever possible.     

The measurement of99Tc in seaweed: Results from an international intercomparison exercise

Five samples of brown seaweed, collected from a variety of sites around northern Europe, were distributed to 14 laboratories for analysis of⁹⁹Tc. Consistency in results between laboratories was found to be strongly correlated with concentration levels, with results diverging markedly at⁹⁹Tc concentrations below 100 Bq·kg⁻¹. No systematic differences were apparent between radiometric and mass based techniques but the results do suggest that the use of Re as a tracer may lead to an underestimation of⁹⁹Tc levels.     

Measurement techniques for mercury species in ambient air

This review critically evaluates the measurement methodologies most commonly employed for the analysis of the various forms of mercury (Hg) in air. Emphasis is given to the three most common forms of mercury in air [i.e. gaseous elemental mercury (GEM, Hg⁰), reactive gaseous mercury (RGM), and particle-bound mercury (Hg_p)]. Moreover, we also briefly describe methods dealing with gas-phase analysis of organic mercury species (e.g., mostly methyl mercury), as they are also reported to be present in air on rare occasions. To begin with, we describe the approaches to sampling airborne mercury species and associated sample-treatment strategies. We evaluate both conventional and emerging alternative detection techniques for different mercury forms with respect to their applicability in airborne mercury analysis. We also discuss the artifacts and the biases associated with analysis of different mercury species. Finally, the review summarizes current methodological developments for the determination of mercury in air and highlights future prospects for improvements.     

ET-AAS in the Analysis of high-purity mercury

ET-AAS is investigated for the analysis of high purity mercury. Two possibilities are proposed: ET-AAS determination of trace analytes in the presence of high mercury concentrations or after matrix separation by reduction. The ET-AAS analysis of high-purity mercury under optimal instrumental parameters permits fast and reproducible determination of 0.03 gg^–1 Al, Cd and Mn; 0.05 gg^–1 Cu, Co, Cr, Fe, Ni and Pb and 0.2 gg^–1 V. Preliminary mercury matrix reductive separation with ascorbic acid allows determination of 0.005 gg^–1 Cd, 0.02 gg^–1 Cu, Cr and Mn, 0.03 g g^–1 Co, Ni and Pb, 0.05 g g^–1 Al and Fe and 0.1 gg^–1 V, but the reproducibility is lower. The main advantage of the second procedure is that it avoids laboratory and instrument pollution with toxic mercury.     

Pretreatment of water samples using UV irradiation-peroxodisulfate for the determination of total mercury

Potassium peroxodisulfate (14 g l⁻¹, 25 ml) has been observed to readily oxidize water under UV irradiation (30 W mercury arc tube), even at room temperature. The reaction is complete in 20 min, producing oxygen in stoichiometric amounts. The reaction was applied to pretreatment for the determination of total mercury by cold vapor atomic absorption spectrometry (AAS).The response of mercury(II) chloride by the UV irradiation method was higher than that by the standard permanganate method (95 °C, 2 h). The conversion efficiency of mercury by the UV irradiation method, the standard method and by non-treatment was found to be 100, 93.6 and 85.0%, respectively. The study is also applied to methylmercury, ethylmercury and phenylmercury chlorides.     

Cofactors in Biota: results of a German interlaboratory exercise on the determination of total lipids in fish tissue

 The content of total lipids is a common cofactor necessary for a normalisation of organic contaminant concentrations in biological materials. Lipids are routinely determined gravimetrically after extraction of the material with chlorinated solvents. A new method substituting chlorinated solvents for a cyclohexane/isopropanol mixture was to be evaluated by an intercomparison exercise. The participating laboratories were requested to determine total lipid content in three different samples of fish tissue following their own procedures as well as the new method described in a standard protocol. No significant differences in the overall means of total lipid content were found for the investigated samples regardless of the determination method. Using the harmonised protocol of the new method, between laboratory reproducibilities below 10% were obtained in the exercise. The results indicate the applicability of the harmonised method for the determination of total lipids as a cofactor in the analyses of contaminant concentrations in marine biota samples. Received: 27 June 2000 / Accepted: 20 September 2000     

An intercomparison exercise on the determination of neptunium-237 in an environmental material

An intercomparison exercise has been carried out on the measurement of²³⁷Np in a sample of sea-born sediment taken from the estuary of the River Esk in Cumbria, United Kingdom. The sediment had been contaminated by radioactive liquid discharges from the nuclear fuels reprocessing plant at Sellafield. The measure of agreement between the submitted values was such that one would accept with confidence²³⁷Np analyses reported by the participating laboratories. The exercise was arranged by the Analysts' Informal Working Group (AIWG). The AIWG is a small group of chemists from several Government laboratories in the United Kingdom having an interest in radionuclides in the environment. From time-to-time the Group arranges intercomparison exercises; these exercises are in addition to the members' normal quality assurance schemes, and in addition to intercomparison exercises arranged by other organizations. So far as the authors are aware, there has been no report of such an exercise involving²³⁷Np, and there appear to be no natural matrix reference materials available for environmental²³⁷Np.