ICP-MS/MS直接测定海水中12种痕量金属元素

建立一种采用电感耦合等离子体串联质谱 (ICP-MS/MS) 直接测定海水中12种元素的分析方法。采用标准加入法及配置超高基体进样系统实现基体匹配,应用ICP-MS/MS的多种分析模式测定海水中钒（V）、铬（Cr）、锰（Mn）、钴（Co）、镍（Ni）、铜（Cu）、锌（Zn）、砷（As）、钼（Mo）、镉（Cd）、铊（Tl）、铅（Pb）12种痕量元素。用该方法测定海水标准参考物质,结果准确。测定实际海水样品,加标回收率为85.0%~108%,相对标准偏差为1.5%~5.4%。12种元素的方法检出限为0.003~0.085 μg/L,定量下限为0.012~0.340 μg/L。该方法运行成本低,操作便捷,可作为实验室海水元素分析的常规检测方法。     

原子荧光度法测定城市污泥总砷的不确定度评定

根据《测量不确定度评定与表示》（JJF1059—1999），建立了原子荧光度法测定污泥泥质中砷不确定度的数学模型，分析了测试过程中不确定度的来源，并对各不确定度分量进行评定及合成，并计算得出合成不确定度和扩展不确定度。本次测量的合成相对不确定度值为0．023，其中由消化样浓度引起的相对合成不确定度为0．021；最大的不确定度分量是样品消化重复测定的不确定度，分量值为O．0152。本次测定结果为19．97±0．92mg／kg，k=2（置信水平约为95％）。     

氢化物发生原子荧光光度法测定水中锑的不确定度评定

介绍了原子荧光光度法测定水中锑的不确定度评定方法,分析和识别在测定过程中的不确定度来源,较为全面地评定了测量不确定度,最后计算出测定结果的合成标准不确定度和扩展不确定度.结果表明,标准溶液配制过程和标准曲线拟合引起的不确定度是原子荧光光度法测定水中锑含量不确定度的主要来源.     

硝酸银标准滴定溶液的不确定度评定

在掌握JJF1059-1999的基础上，对硝酸银标准滴定溶液浓度的不确定度进行评定，主要从方法概述、确定测量中不确定度的来源、建立数学模型、计算相对标准不确定度分量、合成相对标准不确定度、扩展不确定度等入手，详细介绍了硝酸银标准滴定溶液的不确定度评定过程。     

水中挥发酚的测量不确定度评定

建立了分光光度法测定水中挥发酚的合成标准不确定度的数学模式,它由质量的标准测量不确定度和体积的标准测量不确定度组成。应用一个实例对这两部分标准不确定度的分量作了详尽的分析和计算,得出测量扩展不确定度结果。     

测定水中挥发酚的测量不确定度评定

分析了采用预蒸馏的4-氨基安替比林萃取光度法，测定水中挥发酚过程中产生测量不确定度的主要来源．通过实例介绍了配制标准溶液、标准曲线拟合、重复性测量、分光光度计仪器等引入的各不确定度分量的量化计算方法．经合成计算出测定水中挥发酚的扩展不确定度为0．001mg／L．测量结果表示为（0．011±0．001）mg／L（=2）．     

电感耦合等离子体质谱法同时测定地下水中钴和钼

建立了一种用电感耦合等离子体质谱法同时测定水源地地下水中微量元素钴和钼的方法。与常规的元素测试方法相比,该方法可以同时快速有效地完成钴和钼测试,测试方法简单,结果准确可靠。     

纳氏试剂光度法测定水中氨氮含量不确定度评定

建立了分光光度法测定水中氨氮含量的合成不确定度的数学模式。按照分析方法操作步骤的先后顺序,分别对标准溶液的配制、稀释和取样、标准曲线的绘制及样品的测定的不确定度分量进行了详细的分析和计算,得出测量扩展不确定度结果。     

紫外分光光度法测定水中总氮的不确定度评定

运用测量不确度评定的基本方法和程序,分析影响紫外分光光度法测定总氮的不确定度的各种因素,建立数学模型,合成计算总氮的不确定度。     

用分光光度法测定工业废水色度的探讨

一、实验方法 1.试剂 铂钴色度标准、铬钴色度标准:按常规方法配制。 2.分光光度法 (1)按常规方法,配制0—200度的标准系列,并用分光光度计以420 nm波长、5cm比色皿测定吸光度,绘制标准曲线。 (2)澄清水样可直接测定,由标准曲线查得色度。若水样色度过高,应用蒸馏水稀释。     

Soil Contribution to the Elemental Composition of Epiphytic Lichens (Tuscany, Central Italy)

Total concentrations of Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Sr, Ti, V and Zn in the epiphytic lichen Parmelia sulcata and superficial soils from 60 remote sampling sites in Tuscany (central Italy) were determined to evaluate the contribution of soil to the elemental composition of the lichen. The results showed that in the Mediterranean environment, the trace element content of unwashed lichen samples is greatly affected by soil contamination. However, despite the strong correlations between the concentrations of lithogene elements such as Al, Fe and Ti in P. sulcata, lichen levels of these elements were not at all linearly correlated with their concentrations in the soil, suggesting that dust contamination is highly variable and probably dependent on local site characteristics. All methods evaluated to minimize soil contamination indicated Cu, Pb and Zn as elements of atmospheric origin. However, while levels of Pb were similar to those reported for background areas, moderate pollution by Cu and Zn, probably from fertilizers used in agriculture, was revealed. For elements such as Cd and Mo, identified as atmophile, some uncertainty exists due to the fact that they are essential for lichen metabolism and accumulate intracellularly in lichens; they may therefore occur in soluble form in the lichen thallus.     

滤膜在颗粒物无机元素监测中的适用性研究

筛选国内外12个制造商的玻璃纤维、石英、特氟龙、聚丙烯、乙酸纤维、硝酸纤维和混合纤维等7类材质34种滤膜,测定滤膜中的铍、铬、锰、钴、镍、铜、锌、砷、钼、镉、锡、锑、铊和铅等14种元素含量,探讨不同材质滤膜中各元素的质量分数分布,采用大气固定源污染物排放标准中项目限值和分析方法标准中质量控制要求,对铜、锌之外的12种元素进行适用性评价。结果表明:玻璃纤维滤膜比其他材质滤膜中无机元素的质量分数高1～5个数量级,进口玻璃纤维滤膜中铬、镍、砷、镉等4种元素质量分数高于多数国产玻璃纤维滤膜,国产A、H玻璃纤维滤膜中14种元素质量分数相对较低;仅混合纤维滤膜中镉、铅的测定值浓度低于最严标准限值的10%,玻璃纤维滤膜之外的其他材质滤膜均能满足监测其余10种元素的本底需求。     

Assessment of Atmospheric Deposition of Heavy Metals and Other Elements in Belgrade Using the Moss Biomonitoring Technique and Neutron Activation Analysis

This study aimed at assessing atmospheric deposition of heavy metals and other elements using the moss genera Brachythecium sp. (B. rutabulum and B. salebrosum) and Eurhynchium sp. (E. hians and E. striatum) collected in autumn 2004 in the urban area of Belgrade. The concentrations of 36 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Mo, Sb, I, Cs, Ba, La, Ce, Sm, Tb, Dy, Hf, Ta, W, Hg, Th, U) were determined in moss and local topsoil samples by instrumental neutron activation analysis. The concentration of elements in moss positively correlated to those obtained for topsoil. High enrichment factors for As, Zn, Mo, Br, Sb, Se, Hg and Cl, calculated to continental crust composition, gave an evidence for anthropogenic impact on urban area, mainly due to intensive vehicular traffic and fossil fuel combustion. The concentration of elements in moss, characteristic for fossil fuel combustion, obtained in this study were substantially lower than in the previous investigation (2000) conducted in the area of Belgrade. The level of concentrations for V, Cr, Ni, and As in moss from this study correlated to those measured for neighboring countries, and were several times higher than the base-level data from low polluted areas. The level of accumulated elements in both investigated moss genera were similar and all studied species could be combined for biomonitoring purposes in urban areas.     

北京灰霾天气PM10中微量元素的分布特征

采用电感耦合等离子体质谱法(ICP-MS)对北京市2008年4月和5月不同采样点采集的灰霾天PM₁₀样品中的15种微量元素进行了分析,得出了Ti、Fe、Zn、Sn、Pb为全样样品中相对含量较高元素;Ti、Mn、Ni、Cu、Zn、Pb是水溶样样品中相对含量较高元素。与晴天相比,灰霾天样品中微量元素可溶性增强,对人体危害更严重。与2002年分析数据进行对比,因2002年缺少Cr、Cd元素的测试值,全样样品中除了Co、Ni、Cu、Mo元素外,其余测试元素的浓度均有不同程度的升高,Fe和Sn元素的增幅最大。水溶样品中,参与对比元素的含量均下降。文中对含量相对较高的Cr、Mn、Fe、Cu、Zn、Cd、Sn和Pb元素进行了源解析,分析得出采样点附近的交通源及地面扬尘是这些元素的主要来源。     

Reduced Metals Concentrations of Water, Sediment and Hyalella Azteca from Lakes in the Vicinity of the Sudbury Metal Smelters, Ontario, Canada

Hyalella azteca (Crustacea: Amphipoda), water and sediments from 12 circum-neutral lakes between Sudbury and North Bay in Ontario, Canada were sampled in August 1998 and analyzed for 10 metals including Cu, Zn, Cd, Ni, Pb, Co, Mo, V, Ba and Ti. Statistical analyses showed that concentrations of the metals in H. azteca, water and sediment differed significantly (ANOVA, P<0.05) among lakes (except for Zn and Pb in H. azteca and Mo in water). There was a trend of declining metal concentration, especially for Cu, Ni and Co (in water, Hyalella and sediment), with distance from the smelters indicating the reduced impact of atmospheric pollution. Metal concentrations of lakes (water) in the Sudbury area were found to be lower compared to data from the 1970s and 1980s indicating an improvement in water quality. Metal concentrations in field-collected amphipods compared favorably with those measured in the laboratory in animals exposed to deep-water sediments, provided metal concentrations were not extremely low (e.g., Pb) and that water chemistry differences (e.g., pH) were taken into account for some metals (especially Cd). In general bioaccumulation of metals in H. azteca was predicted better from surface water than from sediment total metal.     

Assessing Spatial, Temporal, and Analytical Variation of Groundwater Chemistry in a Large Nuclear Complex, USA

Statistical analyses were applied at the Hanford Site, USA, to assess groundwater contamination problems that included (1) determining local backgrounds to ascertain whether a facility is affecting the groundwater quality and (2) determining a ‘pre-Hanford' groundwater background to allow formulation of background-based cleanup standards. The primary purpose of this paper is to extend the random effects models for (1) assessing the spatial, temporal, and analytical variability of groundwater background measurements; (2) demonstrating that the usual variance estimate s ², which ignores the variance components, is a biased estimator; (3) providing formulas for calculating the amount of bias; and (4) recommending monitoring strategies to reduce the uncertainty in estimating the average background concentrations. A case study is provided. Results indicate that (1) without considering spatial and temporal variability, there is a high probability of false positives, resulting in unnecessary remediation and/or monitoring expenses; (2) the most effective way to reduce the uncertainty in estimating the average background, and enhance the power of the statistical tests in general, is to increase the number of background wells; and (3) background for a specific constituent should be considered as a statistical distribution, not as a single value or threshold. The methods and the related analysis of variance tables discussed in this paper can be used as diagnostic tools in documenting the extent of inherent spatial and/or temporal variation and to help select an appropriate statistical method for testing purposes.     

Spatial and temporal variation of metal concentrations in adult honeybees (Apis mellifera L.)

Honeybees (Apis mellifera L.) have great potential for detecting and monitoring environmental pollution, given their wide-ranging foraging behaviour. Previous studies have demonstrated that concentrations of metals in adult honeybees were significantly higher at polluted than at control locations. These studies focused at a limited range of heavy metals and highly contrasting locations, and sampling was rarely repeated over a prolonged period. In our study, the potential of honeybees to detect and monitor metal pollution was further explored by measuring the concentration in adult honeybees of a wide range of trace metals, nine of which were not studied before, at three locations in the Netherlands over a 3-month period. The specific objective of the study was to assess the spatial and temporal variation in concentration in adult honeybees of Al, As, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, Ti, V and Zn. In the period of July-September 2006, replicated samples were taken at 2-week intervals from commercial-type bee hives. The metal concentration in micrograms per gram honeybee was determined by inductive coupled plasma-atomic emission spectrometry. Significant differences in concentration between sampling dates per location were found for Al, Cd, Co, Cr, Cu, Mn Sr, Ti and V, and significant differences in average concentration between locations were found for Co, Sr and V. The results indicate that honeybees can serve to detect temporal and spatial patterns in environmental metal concentrations, even at relatively low levels of pollution.     

土壤重金属分析方法间检测结果一致性判断方法——数据对t值检验法的改进与完善

不同分析方法测定结果间的比较,或者说如何判断两种分析方法测定结果的一致性,是检测实验室经常遇到的实际问题。其应用场景包括方法标准验证实验、新方法与经典方法间的比对,特别是在缺少标准样品、测试数据不满足t值检验的条件下,选用合适的判据尤其重要。以采用单波长激发型能量色散X射线荧光光谱法、电感耦合等离子体质谱法、波长色散X射线荧光光谱法测定土壤和水系沉积物样品中Cd、As、Pb、Cu、Zn、Ni、Cr、Co、V、Mn、Mo、Sb等重金属含量所得数据为例,探讨了《环境监测分析方法标准制订技术导则》(HJ 168—2020)附录B中规定的"数据对t值检验法"的不足及改进办法,即用数据对相对偏差和再现性限合格率作为判据,判断分析方法测定结果的一致性。对一组验证样品分别用两种分析方法进行了测定,在数据对t值检验的基础上,取各元素测定结果的相对偏差与相关限值进行比较,或者取两者的差值与基准分析方法标准规定的再现性限进行比较,利用合格率大小协助判断了两分析方法测定结果的一致性。研究结果表明,此方法符合日常质控技术规范中关于精密度的规定,实用性强,是一条将数理统计原理与专业知识相结合的合理技术路线。     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

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).     

Major and trace element contents in apples from a cultivated area of central Greece

Forty-two soil and apple samples from central Greece were collected and analyzed with regards to the content in major (Ca, Fe, K, Mg, Na, P, and S) and trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Sc, Se, Sr, Ti, and Zn). Soil samples were analyzed by inductively coupled plasma atomic emission spectrometry, while for the apples inductively coupled plasma mass spectrometry was implemented. Several elements such as As, B, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Se, Ti, and Zn, represent high concentrations in apples from the study area. These relatively high concentrations may be a consequence of the local geology, along with the excessive application of agricultural products such as fertilizers and agrochemicals.