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1.
Recent studies have demonstrated the utility of ultrasonic extraction (UE), followed by portable anodic stripping voltammetry (ASV), for the on-site determination of lead in environmental and industrial hygiene samples. The aim of this work was to conduct an interlaboratory evaluation of the UE-ASV procedure, with a goal of establishing estimates of method performance based on results from collaborative interlaboratory analysis. In this investigation, performance evaluation materials (PEMs) with characterized lead concentrations were used for interlaboratory testing of the UE-ASV procedure. The UE-ASV protocol examined has been promulgated in the form of two separate national voluntary consensus standards (one for UE and another for electroanalysis, which includes ASV). The PEMs consisted of characterized and homogenized paints, soils, and dusts (the last of which were spiked onto wipes meeting national voluntary consensus standard specifications), and air filter samples (mixed cellulose ester membrane) generated using characterized paints within an aerosol chamber. The lead concentrations within the PEMs were chosen so as to bracket pertinent action levels for lead in the various sample matrices. The interlaboratory evaluation was conducted so as to comply with an applicable national voluntary consensus standard that can be used to estimate the interlaboratory precision of a given analytical test method. Based on the analytical results reported by the participating laboratories, relative standard deviations (RSDs) for repeatability and reproducibility were computed for three different lead contents of the four PEMs. RSDs for repeatability were 0.019-0.100 for paints; 0.030-0.151 for soils; 0.085-0.134 for dust wipes; and 0.095-0.137 for air filters. RSDs for reproducibility were 0.127-0.213 for paints; 0.062-0.162 for soils; 0.085-0.134 for dust wipes; and 0.114-0.220 for air filters. With the exception of one of the air filter samples and one of the paint samples, the precision estimates were within the +/- 20% precision requirement specified in the US Environmental Protection Agency National Lead Laboratory Accreditation Program (NLLAP). The results of this investigation illustrate that the UE-ASV procedure is an effective method for the quantitative measurement of lead in the matrices evaluated in this study.  相似文献   

2.
Analytical methods for the determination of trace beryllium in soils are needed so that anthropogenic sources of this element can be distinguished from native (background) levels of beryllium. In this work, a collaborative interlaboratory evaluation of a new extraction and fluorescence-based procedure for determining beryllium in soil samples was carried out to fulfil method validation requirements for ASTM International voluntary consensus standard test methods. A Canadian reference material, CCRMP Till-1 soil, with a background beryllium concentration of 2.4 microg g(-1), was selected for study. This certified reference material (CRM) was spiked and homogenized with varying levels of beryllium oxide in order to give batches of material with beryllium concentrations of 4.36 +/- 0.69, 11.5 +/- 0.7, 124 +/- 7 and 246 +/- 16 microg g(-1) (+/- values are standard deviations). In the interlaboratory study (ILS), which was carried out in accordance with an applicable ASTM International standard practice (ASTM E691), samples of these spiked soils were subjected to extraction in dilute ammonium bifluoride at approximately 90 degrees C for 40 h. Fluorescence measurement of the extracted beryllium was carried out via detection using the high quantum yield fluorophore, hydroxybenzoquinoline sulfonate (HBQS). Interlaboratory precision estimates from six participating laboratories ranged from 0.048 to 0.103 (relative standard deviations) for the five different beryllium concentrations. Pooled bias estimates resulting from this ILS were between -0.049 and 0.177 for the various beryllium levels. These figures of merit support promulgation of the analytical procedure as an ASTM International standard test method.  相似文献   

3.
土壤重金属元素检测国际实验室比对研究   总被引:1,自引:0,他引:1  
IERM和CNAS合作组织开展了亚太实验室合作组织(APLAC)能力验证计划"APLAC T066土壤重金属元素检测",其目的是评价参加实验室定量分析土壤重金属元素总量的能力。研究所用的能力验证样品为IERM研制的土壤标准样品。结果表明,参加实验室检测土壤砷、铜、汞、镍、铅和锌的结果满意率分别为85.7%、95.8%、77.1%、83.3%、93.5%和91.7%。样品消解过程加入氢氟酸时,铅和锌的检测结果与标准值更加接近,说明检测土壤重金属元素总量时氢氟酸的加入非常关键。文章还对比对实验室结果评价的统计方法进行了探讨。  相似文献   

4.
Occupational sampling and analysis for multiple elements is generally approached using various approved methods from authoritative government sources such as the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency (EPA), as well as consensus standards bodies such as ASTM International. The constituents of a sample can exist as unidentified compounds requiring sample preparation to be chosen appropriately, as in the case of beryllium in the form of beryllium oxide (BeO). An interlaboratory study was performed to collect analytical data from volunteer laboratories to examine the effectiveness of methods currently in use for preparation and analysis of samples containing calcined BeO powder. NIST SRM(?) 1877 high-fired BeO powder (1100 to 1200 °C calcining temperature; count median primary particle diameter 0.12 μm) was used to spike air filter media as a representative form of beryllium particulate matter present in workplace sampling that is known to be resistant to dissolution. The BeO powder standard reference material was gravimetrically prepared in a suspension and deposited onto 37 mm mixed cellulose ester air filters at five different levels between 0.5 μg and 25 μg of Be (as BeO). Sample sets consisting of five BeO-spiked filters (in duplicate) and two blank filters, for a total of twelve unique air filter samples per set, were submitted as blind samples to each of 27 participating laboratories. Participants were instructed to follow their current process for sample preparation and utilize their normal analytical methods for processing samples containing substances of this nature. Laboratories using more than one sample preparation and analysis method were provided with more than one sample set. Results from 34 data sets ultimately received from the 27 volunteer laboratories were subjected to applicable statistical analyses. The observed performance data show that sample preparations using nitric acid alone, or combinations of nitric and hydrochloric acids, are not effective for complete extraction of Be from the SRM 1877 refractory BeO particulate matter spiked on air filters; but that effective recovery can be achieved by using sample preparation procedures utilizing either sulfuric or hydrofluoric acid, or by using methodologies involving ammonium bifluoride with heating. Laboratories responsible for quantitative determination of Be in workplace samples that may contain high-fired BeO should use quality assurance schemes that include BeO-spiked sampling media, rather than solely media spiked with soluble Be compounds, and should ensure that methods capable of quantitative digestion of Be from the actual material present are used.  相似文献   

5.
This paper provides additional data on a sewage sludge amended soil certified reference material, CRM 483, which was certified in 1997 for its EDTA and acetic acid extractable contents of some trace metals, following standardised extraction procedures. The additional work aimed to test the long-term stability of the material and the applicability of an improved version of the BCR three-step sequential extraction procedure on the sewage sludge amended soil (CRM 483). The paper demonstrates the CRM 483 long-term stability for EDTA and acetic acid extractable contents of Cd, Cr, Cu, Ni, Pb and Zn and gives the results (obtained in the framework of an interlaboratory study) for the extractable contents of the same elements in the CRM 483, following the BCR three-step sequential extraction scheme. The aqua regia extractable contents following the ISO 11466 Standard are also given. The data are given as indicative (not certified) values.  相似文献   

6.
Reliable results for the determination of trace elements in urban and industrial wastewaters are of paramount importance for both checking the performance of sewage treatment and for detecting possible urban or industrial contamination sources. The quality control of measurements should in principle rely on external tools such as certified reference materials (CRM), which should represent, as closely as possible, the matrix of samples currently analysed, e.g., in the frame of environmental monitoring. To date, however, no CRM representatives of wastewater composition are available, which limits the possibility for control laboratories to check their QC externally. To fill this gap, the European Commission's Standards, Measurements and Testing Programme (formerly BCR) has started a European collaborative project of which the aim is to test the feasibility of preparation of wastewater reference materials and the analytical state-of-the-art to enable the certification of trace elements in such matrices. This paper presents the results of the first phase of this project, namely the feasibility study and the results of an interlaboratory trial.  相似文献   

7.
Moss interspecies comparisons in trace element concentrations   总被引:5,自引:0,他引:5  
Within the framework of a European-scaled moss survey, various moss species were sampled throughout The Netherlands [NL], Germany [D], and Switserland [CH], and used in moss interspecies comparisons of elemental concentrations. Moss species considered were Pleurozium schreberi [NL,D,CH], Brachythecium rutabulum [NL], Hypnum cupressiforme [D,CH], Hylocomium splendens [D,CH], and Scleropodium purum [D]. Element analysis was carried out directly (The Netherlands, Instrumental Neutron Activation Analysis: As, Br, Ce, Cr, Cs, Fe, La, Mn, Na, Rb, Sc, Se, Sm, Th, Ti, V and Zn), or after sample digestion (The Netherlands, ICP-MS: Pb, Germany, AAS/ICP-AES: Cd, Cr, Cu, Fe, Ni, Pb, Ti, V, and Zn; Switzerland, ICP-AES/ICP-MS: Co, V, and Zn).Local variations (=within sampling sites) in element concentrations were estimated, based upon in-site multiple sampling and analysis of Pleurozium schreberi species in The Netherlands. Element concentrations in moss species were compared in linear correlations, both in unweighted and weighted fits, with weighing factors based on the local variation data. Weighted fits were shown to generally improve the calibration characteristics, as tracked by X 2 calculations.The calibration data suggest the presence of previously unnoticed outliers in element concentrations. The absence of further information, however, may prescribe the use of all data in comparison procedures. These results indicate that interlaboratory analysis of replicate samples and the use of dedicated certified reference materials may help solving problems in the analysis of the sample series.For several of the considered interspecies comparisons, weighted calibrations could be based on significant correlations (P=0.05). Actual use, however, will remain arbitrarily decided upon, and may be based on decisions as to what to accept with respect to the levels of uncertainty in the calibration parameters. Furthermore, the use of calibrations in extrapolation modes is greatly restricted by the necessary reservations in geographically larger-scaled applications.  相似文献   

8.
BGIA has organised round robins for the analysis of samples of inorganic acids in workplace air for a number of years. Test samples of the volatile acids HCl and HNO(3) are collected from a standard atmosphere and samples of the non-volatile acids H(3)PO(4) and H(2)SO(4) are prepared by spiking filters with acid solution. The last two round robins have also covered the sampling of volatile acids, with up to 15 "active" participants able to visit the test facility in Dresden and take samples themselves. For other "passive" participants, BGIA takes samples from the same atmosphere. The acid concentrations generated lie between 0,1 and 1 times the German limit values for HCl and HNO(3). The results for the last round robin showed no significant difference between the performance of the "active" and "passive" participants. The participant means were in good agreement with the theoretical concentrations and the quality control measurements. For "active" participants RSDs were between 7% and 14% and for all participants between 8% and 16%. The round robin for the non-volatile acids showed similar results. The participant means were again in excellent agreement with the quality control measurements and RSDs were between 12% and 15%. The BGIA round robins have demonstrated the proficiency of laboratories measuring exposure to inorganic acids in air. However, concerns remain about the performance of published methods. It has shown that the sampling efficiency of sorbent tubes falls off with increasing particle size and hence silica gel tube methods may give low results for acid mists. Another issue with silica gel tubes is that a substantial proportion of the sample can be collected on the glass wool plugs that retain the sorbent. This can be up to 50% for HCl and 100% for HNO(3). Hence, low results may be obtained if the glass wool plugs are discarded. Similarly, methods for volatile inorganic acids that use a pre-filter to remove particulates usually overlook the fact that the acids can react with co-particulate matter on the pre-filter. Low recoveries in the range 30%-50% have been found when sampling HCl through filters loaded with potential interferents. Finally, particulate salts interfere with filter sampling methods for non-volatile inorganic acids. A two-part International Standard is in preparation for inorganic acids by ion chromatography and the issues discussed above are being taken into consideration during its development.  相似文献   

9.
研究以单元素标准膜为基础,结合NIST SRM 2783颗粒物滤膜标准样品,建立了波长色散-X射线荧光光谱法测定PM2.5中23种无机元素的测定方法,优化了测试条件,测量一个样品耗时约15 min,计算了各元素的方法检出限。对NIST SRM 2783滤膜标准品在一周内重复测定10次来计算方法的准确度与精密度,测定结果显示大多数元素的测量值在给出的参考值范围内,且测量标准偏差一般在10%以内。对比了石英与聚四氟乙烯材质(Teflon)滤膜的空白值,石英滤膜中Si、Fe、Na、Mg、Al、K、Ca等元素的背景值较高,Teflon滤膜的背景值较低,推荐选用Teflon滤膜作为PM2.5组分分析采样滤膜。分别用波长色散-X射线荧光光谱法及酸消解-ICP-MS法测定了样品膜中的元素组分,得到的测定结果基本一致。  相似文献   

10.
Marine sediment toxicity tests are widely applied in monitoring programs, yet relatively little is known about the comparability of data from different laboratories. The need for comparability information is increased in cooperative monitoring programs, where multiple laboratories (often with variable skill levels) perform toxicity tests. An interlaboratory comparison exercise was conducted among seven laboratories in order to document the comparability of sediment toxicity measurements during the Bight'98 regional sediment survey in southern California. Sediments from four stations in Los Angeles and Long Beach Harbors were tested using a 10-day survival test of the amphipod Eohaustorius estuarius. All laboratories successfully performed the sediment test and associated reference toxicant test. Statistically significant differences were found in mean amphipod survival rates among some laboratories for the field-collected sediments, but there was little evidence of a consistent bias among laboratories. Although the reference toxicant test indicated a five-fold variation in test sensitivity among laboratories, these results were not accurate predictors of interlaboratory performance for the sediment tests. The laboratories demonstrated excellent concordance (Kendall's W = 0.91) in ranking the field-collected sediments by toxicity. Agreement on classifying the sediments into categories (nontoxic, moderately toxic, and highly toxic) based upon the percent of survival was best for highly toxic sediments. An analysis of test precision based upon the variance among replicates within a test indicated that the measured survival rate for a sample may vary by up to 12 percentage points from the actual response.  相似文献   

11.
Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).  相似文献   

12.
提出了沸水浴混合酸法消解,以异丙醇为增感剂,电感耦合等离子体质谱直接测定土壤和沉积物中硒的方法。实验表明2mol/L硝酸-4mol/L盐酸混酸能有效溶出土壤和沉积物中各种形态的硒。相对于1%硝酸基体,4%(V/V)异丙醇基体中硒的ICP-MS响应值提高了12.1倍;而且4%(V/V)异丙醇基体可有效抑制硒的质谱干扰。ICP发射功率和雾化气流速是影响异丙醇在ICP-MS测定过程增敏效应的主要因素。以78硒为测定同位素,方法检出限为0.005mg/kg,实际样品测定精密度均小于5%。用于测定土壤和沉积物国家标准样品并对其消解液进行加标回收实验,结果令人满意。  相似文献   

13.
A European standard for the determination of Cr(vi) in solid material has been elaborated in the framework of an international co-operation and finally validated in the course of an interlaboratory comparison. The procedure is based on the alkaline digestion prescribed by EPA method 3060A followed by ion chromatography and determines an operationally defined content of Cr(vi), including water-soluble and insoluble chromates. A preliminary robustness study was carried out in order to compare different extraction methodologies and to study the equivalency of different analytical methods for the determination of Cr(vi) in alkaline extracts of soil and waste materials. During an interlaboratory validation trial with 19 European laboratories a set of 4 samples (2 soil and 2 waste samples) was analysed to determine performance characteristics for different combinations of digestion and detection methods. With the procedures prescribed by the new European standard (EN 15192) acceptable results were obtained for both soil samples and one of the waste samples (sludge). However, for the second waste sample (fly ash) a large deviation in analytical results was observed. This indicates that particularly for waste materials a possible occurrence of strong matrix effects has to be considered and supplementary quality control data are needed in order to assess the validity of analytical results. The accuracy of the determination of Cr(vi) in solid matrices remains a challenging field in terms of maximum extraction efficiency and minimum species interconversion.  相似文献   

14.
Topsoil samples (n?=?40) were collected from a heavily industrialized region in Turkey. The region includes several scrap processing iron–steel plants with electric arc furnaces (EAFs), a petroleum refinery, a petrochemical complex, steel rolling mills, a natural gas-fired power plant, ship-breaking yards and very dense transportation activities. The region has undergone a rapid transition from an agricultural region to a heavily industrialized region in the last three decades. Collected soil samples were analyzed for 48 trace elements using inductively coupled plasma-mass spectrometry (ICP-MS). The elemental distribution pattern in the region indicated that Nemrut area with dense iron–steel production activities was a hotspot for elemental pollution. In addition to crustal elements, concentrations of anthropogenic trace elements (i.e., Fe, Zn, Pb, Mn, Cu, Cd, Cr and Mo) were very high in the area influencing many parts of the region. Elemental compositions of fugitive sources polluting the soil (i.e., paved and unpaved roads, slag piles, EAFs filter dust piles and coal piles) were also determined. The methods (enrichment factors [EFs] and the index of geoaccumulation [I geo]) used for determination of pollution status of soil showed that Cr, Ag, Zn, As and Pb were the strongly contaminating elements for the region. Principal component analysis (PCA) clearly indicated that anthropogenic sources (steel production, refinery and petrochemical processes and traffic) were important sources in this region.  相似文献   

15.
建立了微波消解一氢化物发生原子荧光光度法测定土壤中砷的方法。对微波消解条件进行了优化,用5mL硝酸和2mL过氧化氢的混合酸作消解溶剂,在设定的微波条件下砷提取完全。用5%的盐酸作为反应载流,12g/L硼氢化钾与0.5%氢氧化钠的混合液为还原剂,直接定容后应用HG.AFS测定,并通过测定国家标准参考物质和加标回收实验,对方法进行了验证。实际土壤加标同收率97%~103%。  相似文献   

16.
On-site measurement of lead in workplace air filter samples and paint chip samples by ultrasonic extraction and anodic stripping voltammetry (UE-ASV) was evaluated in the field during renovation and remodeling activities in residences having leaded paint. Aerosol and paint samples were collected using standard techniques, and the samples were analyzed on-site for lead content by portable UE-ASV. Lead in sample extracts was subsequently determined by atomic absorption (AA) spectrometry in a fixed-site laboratory. The remaining sample extracts plus undissolved material (air filters or paint particles) were then subjected to hot plate digestion in concentrated nitric acid-30% hydrogen peroxide prior to AA analysis for lead. Field UE-ASV lead data were thereby compared to UE-AA and hot plate digestion-AA results from fixed-site laboratory lead measurement. Determination of lead in air filter samples by UE-ASV (over the range of 5 microg to approximately 800 microg Pb per sample) was extremely well correlated with lead measurement by UE-AA and hot plate digestion-AA procedures. However, a significant negative bias associated with ASV measurement was observed, and this was attributed to a matrix effect. Lead measurement in paint chip samples by UE-ASV (over the range of approximately 10 to approximately 550 microg Pb g(-1)) was well correlated with lead measurement by UE-AA and hot plate digestion-AA procedures. However, correlation and precision were lower for lead measurement in paint samples as compared to aerosol samples, and a negative bias was also observed. Lead measurements by UE-AA were compared to lead determinations by hot plate digestion-AA; these data were highly correlated and demonstrated no significant bias. Thus it was concluded that the ultrasonic extraction procedure performed equivalently to hot plate digestion. It was reasoned that matrix effects due to the preparation and analysis of paint chip particles resulted in greater imprecision as well as negative bias by ASV measurement. Despite significant negative bias in this sample set, UE-ASV offers promise for on-site measurement of lead in samples of interest in occupational and environmental health.  相似文献   

17.
烟尘监测时采样滤筒的质量控制   总被引:7,自引:0,他引:7       下载免费PDF全文
介绍了合格滤筒的筛选方法和采样滤筒在实验室分析中的质量控制,分析了影响滤筒称量恒重的原因,指出空气湿度、冷却时间和烘干时间对滤筒称量恒重都有影响.  相似文献   

18.
介绍了国家重大科学仪器设备开发专项"基于质谱技术的全组分痕量重金属分析仪器开发和应用示范"项目在电感耦合等离子体质谱仪(ICP-MS)研发、低温等离子体样品引入ICP-MS联用系统、ICP-MS监测汞的采样与预处理等方面的研究进展,并对ICP-MS应用发展及产业化前景进行了展望。  相似文献   

19.
建立了一种电感耦合等离子体质谱测定土壤中微量稀土金属的方法.分析了土壤标准样品中的微量稀土元素,结果与标准值一致.土壤实际样品分析也得到可靠结果.该方法样品采用微波溶样,灵敏度高,是一种比较可靠的微量稀土元素分析新方法.  相似文献   

20.
Elutriate bioassays are among numerous methods that exist for assessing the potential toxicity of sediments in aquatic systems. In this study, interlaboratory results were compared from 96-h Ceriodaphnia dubia and Pimephales promelas static-renewal acute toxicity tests conducted independently by two laboratories using elutriate samples prepared from the same sediment. The goal of the study was to determine if the results from the elutriate tests were comparable between two U.S. Environmental Protection Agency (USEPA) laboratories when different elutriate preparation procedures were employed by each lab. Complete agreement in site characterization was attained in 22 of the 25 samples for both bioassays amongst each lab. Of the 25 samples analyzed, 10 were found to be toxic to at least one of the species tested by either laboratory. The C. dubia elutriate tests conducted by the National Exposure Research Laboratory (NERL) indicated that 7 of the 25 sediment samples were toxic, while 8 sediment samples were characterized as such in testing conducted by USEPA Region 6 (Region 6). The P. promelas elutriate tests conducted by NERL determined 8 samples as toxic, while Region 6 tests displayed toxicity in 5 of the samples. McNemar's test of symmetry for C. dubia (S?=?0.33, p?=?0.5637) and P. promelas (S?=?3.0, p?=?0.0833) tests indicated no significant differences in designating a site toxic between NERL and Region 6 laboratories. Likewise, Cohen's kappa test revealed significant agreement between NERL and Region 6 C. dubia (K?=?0.7148, p?<?0.01) and P. promelas (K?=?0.6939, p?<?0.01) elutriate tests. The authors conclude that differences in interlaboratory elutriate preparation procedures have no bearing on the ability of either the C. dubia or P. promelas bioassay testing methods to detect toxicity while yielding similar results.  相似文献   

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