HG-ICP-MS法测定纯镍中痕量As、Sb、Bi、Se、Te、Sn

应用本实验室设计的雾室座作为接口，采用气动型流动注射氢化物发生(HG)装置与电感耦合等离子体质谱仪(ICP-MS)联机。考察了各种介质条件及镍基体对生成氢化物的影响并应用氢氧化镧共沉淀分离富集，HG与ICP-MS联机测定纯镍中易于生成氢化物的As、Sb、Bi、Se、Te、Sn 6个元素，加标回收率为96．5％-102．2％，RSD为2．4％-5．8％，方法检出限为7．1-30ng／L。     

Simultaneous Determination of Cd(II), Cu(II), Pb(II) and Zn(II) in Human Plasma by Potentiometric Stripping Analysis

In this paper, Potentiometric Stripping Analysis (PSA) was simultaneously used to determine the concentrations of trace metals (Zn, Cd, Pb and Cu) in human plasma. The metal ions were concentrated as their amalgams on the glassy carbon surface of a working electrode that was previously coated with a thin mercury film and then stripped by a suitable oxidant. The selection of the experimental conditions was made by using the experimental‐designed methodology. The optimum conditions of the method includes a 0.2 M HAc‐NaAc buffer mixture (pH 4.5) as supporting electrolyte, and an electrolysis potential of‐1220 mV. The limits of detection (LOD) were obtained 1 μg L^?1 for Zn(II) and Pb(II), 0.5 μg L^?1 for Cu(II) and 2 μg L^?1 for Cd(II) in the studied medium. The good recoveries were obtained for the analysis in human plasma. The method was applied to blood samples, using the method of standard additions and the results were compared with Inductively Coupled Plasma‐Atomic Emission Spectrometry (ICP‐AES) as reference method. Furthermore, a simple digestion protocol of samples is investigated compared to the conventional digestion method.     

A pilot study for the production of a certified reference material for trace elements in honey

In the context of the general mandate of the European Union Community Reference Laboratory (CRL) for residues in living animals and their products established at the Istituto Superiore di Sanità, a pilot study was undertaken to assess the possibility of producing a new certified reference material (CRM) for trace elements in a matrix of honey. The elements considered were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sn, V and Zn. Their determination was performed by inductively coupled plasma (ICP)-based techniques. Data obtained with different ICP techniques were generally in good agreement. In light of these results, the next step was the effective production of a candidate CRM in a honey matrix. In the preliminary phase, two different types of honey, i.e., Eucalyptus (solid and sticky) and Robinia (viscous and sticky), were pretreated at the Institute for Reference Materials and Measurements, Joint Research Centre, European Commission (EC-JRC-IRMM) in order to produce the materials candidate for the certification process. Approximately 600 ampoules were thus produced for the Robinia honey and 450 ampoules for the Eucalyptus honey, each ampoule containing 5 g of an aqueous solution of honey (with 20% and 30% high purity water, respectively) and sealed under inert gas (Ar). A ring test to determine the levels of the chemical elements and a long-term study to evaluate the stability of the samples is in progress. Tentative figures for the analytes of interest are (in ng g⁻¹): Robinia, As, 1.28±0.09; Cd, 0.59±0.08; Cr, 2.36±0.21; Cu, 57.6±3.2; Fe, 209±9; Mn, 90.8±3; Ni, 18.1±0.6; Pb, 23±1.5; Sn, 8.10±0.35; V, 1.19±0.37; and Zn, 178±4; Eucalyptus, As, 3.18±0.21; Cd, 0.70±0.08; Cr, 2.73±0.22; Cu, 141±6; Fe, 926±16; Mn, 1905±81; Ni, 7.77±0.4; Pb, 138±4; Sn, 7.97±0.16; V, 3.47±0.15; and Zn, 405±9.     

电感耦合等离子体质谱法测定钨矿石、钼矿石中铼的方法确认

本文在修订国家标准 GB/T 14352.18－2010《钨矿石、钼矿石化学分析方法第18部分：铼量测定》研究工作中,不再使用原先的有机试剂萃取-比色法测定的方法,建立了用氧化镁烧结分解-水提取,ICP-MS法测定钨矿石、钼矿石中铼的分析方法。测定范围为0.05 μg/g～300 μg/g,检出限为0.005μg/g。根据规范要求开展了8 个实验室协同参加的准确度试验,统计参数显示,大量测试结果的算术平均值与标准值之间有较好的一致性,测量方法对铼在限定水平的检测偏倚不显著,分析方法精密度满足《地质矿产实验室测试质量管理规范》的要求。     

碱消解-电感耦合等离子体发射光谱法(ICP-OES)测定土壤中六价铬的研究

采用碱消解—电感耦合等离子体发射光谱(ICP-OES)检测方法对土壤中六价铬含量进行分析。土壤样品以碳酸钠-氢氧化钠为消解液,加入氯化镁和磷酸氢二钾-磷酸二氢钾缓冲溶液,经90-95℃消解溶出六价铬,用电感耦合等离子体发射光谱仪测定消解液中六价铬含量。在选定的测定条件下,方法的检出限为0.24 mg/kg,测定下限为0.96 mg/kg,加标回收率在99.6 %～104.1%之间,相对标准偏差2.53%-7.48%。该方法简便快速,稳定性好,结果准确可靠,适用于土壤中六价铬含量的分析。     

Elimination of Interferences in the Determination of Arsenic and Determination of Arsenic in Percolate Waters from an Industrial Landfill by Inductively Coupled Plasma Mass Spectrometry

Abstract

The determination of arsenic in environmental samples suffers interference by chloride which gives rise to the polyatomic interference of ⁴⁰Ar³⁵Cl on ⁷⁵As. Mathematical correction methods based on the ratios ⁴⁰Ar³⁷ Cl/⁴⁰ Ar³⁵Cl, ³⁵Cl¹⁶O/⁴⁰ Ar³⁵Cl or ³⁷Cl¹⁶O/⁴⁰ Ar³⁵Cl, are discussed and compared with each other. The method is applied for the determination of arsenic in treated percolate water from a landfill where arsenic containing waste is landfilled. The results obtained when applying the different equations were in good agreement with each other. The results for the untreated percolate water, which could be diluted far enough to eliminate matrix effects and showed negligible interference from chloride, were in good agreement with results obtained with Capillary Zone Electrophoresis. Hydride generation made it possible to determine As(III) and by difference As(V) in both waters. 99.7% of the arsenic present in the percolate water was As(V), which means that during the landfilling, possibly by the infiltration of rainwater, the arsenic is oxidised because the original industrial waste contained 100% As(III).     

Monitoring trace elements in selected organs of Antarctic penguin (Pygoscelis adeliae) by plasma-based techniques

A study was undertaken to evaluate the content and distribution of eight key elements, namely, As, Cd, Co, Cu, Hg, Mn, Pb and Se in liver, kidney and muscle of chick individuals of Adélie penguin (Pygoscelis adeliae). Samples were collected during the 2002/2003 austral summer season campaign around Jubany Station (Argentine scientific station), Potter Cove, King George Island. Solutions of organs were prepared by acid-assisted microwave (MW) digestion by employing HNO₃ and H₂0₂. Instrumental techniques selected to analyze the different tissues were inductively coupled plasma optical emission spectroscopy (ICP OES) and inductively coupled plasma mass spectrometry (ICP-MS). A wide range of elements retention capacity among the different organs was observed and the ranges ascertained are as follows (in μg g^− 1): As, 0.5 (liver)-0.8 (muscle); Cd, < 0.07 (muscle)-3.4 (kidney); Co, 0.07 (liver)-0.7 (muscle); Cu, 0.6 (muscle)-18 (liver); Hg, 0.2 (kidney)-2.7 (liver); Mn, 1.5 (muscle)-10 (liver); Pb, 0.1 (muscle)-2.0 (liver); Se, 3.0 (muscle)-8.4 (liver). The observed trend in metal accumulation in the three organs of chick penguins was in the order Cu > Mn > Se ? As > Co > Pb ? Cd > Hg. Levels of metals and metalloids were, in general terms, higher in liver that is a specific target organ for metal accumulation. This study aimed at contributing to the establishment of base-line data on potential pollutants of ecotoxicological interest in the Antarctic ecosystem.     

Application of routine estimation of Pb isotopic ratios by inductively coupled plasma mass spectrometry for studying the Pb origin in hair of children living in polluted areas. A pilot study

The analysis of ²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb isotope ratios for environmental Pb markers (leaded gasoline, air-borne particulate matter, house window dust) and hair of children was undertaken by the routine quadrupole inductively coupled argon plasma mass spectrometry (Q-ICP-MS). Hair samples collected from 10-year-old children living in Krakow in 1995 and 35 randomly selected children, aged 11, both sexes were included in the current study. Air-borne particles were collected by PM-2.5 (an aerodynamic diameter dac <2.5 μm) and PM-10 (fraction with an dac <10 μm) samplers in the proximity of steel factories situated near Krakow. Imprecision of routine estimations was approximately 0.6–0.7% or less, and was the lowest for the ²⁰⁷Pb/²⁰⁸Pb ratio (approx. 0.2%). These conditions were sufficient to distinguish Pb from air-borne dust from that in gasoline or window dust. No differences were found between Pb in PM-2.5 and PM-10 particles. The associations of the Pb in the these environmental sources and that in hair of children were discussed. The relationships of the Pb isotope ratios and other parameters related to environmental pollution were also analyzed. The analysis of distribution of the ²⁰⁷Pb/²⁰⁸Pb ratio in the hair of children, provided some evidence of the fact that hair lead of approximately 20% of the investigated population could arise from gasoline, while the Pb from air-borne dust and remaining sources can be attributed to approximately 80% of the population.     

Determination of trace elements in olive oil by ICP-AES and ETA-AAS: A pilot study on the geographical characterization

The determination of trace elements in edible oils is important because of both the metabolic role of metals and possibilities for adulteration detection and oil characterization.The most commonly used techniques for the determination of metals in oil samples are inductively coupled plasma atomic emission spectrometry (ICP-AES) and atomic absorption spectrometry (AAS). For this study, a microwave assisted decomposition of the olive oil in closed vessels using a mixture of nitric acid and hydrogen peroxide was applied as sample preparation.The low achievable LODs enable the determination by ICP-AES of even very low concentrations of most elements of interest. The proposed ICP-AES method permits the determination of Ca, Fe, Mg, Na, and Zn in olive oils. Elements present in small amounts (Al, Co, Cu, K, Mn, Ni) were measured by ETA-AAS in the same sample digest. The concentrations of Al, Co, Cu, K, Mn, and Ni were in the range from 0.15 to 1.5 μg/g and differ according to the geographical origin of the oils. For the amounts of Fe, Mg, Na, and Zn in the samples, no significant differences according to the geographical origin of the oils could be observed, the mean concentrations being 15.31, 3.26, 33.10, and 3.39 μg/g, respectively. The Ca content varies in the range of 1.3 to 9.0 μg/g.The dependency of the trace elemental content of olive oils on their geographical origin can be used for their local characterization.     

100例鼻咽癌患者与健康人头发中微量元素含量的比较

用原子吸收和火焰光谱分析法检测鼻咽癌患者100例，并以本地区100例健康人及同期我院内科住院非肿瘤患者150例为对照组，进行头发锌、铜、铁，钙，镍等的含量进行测定，结果发现鼻咽癌患者头发中钙及镍的含量比对照组明显升高，而头发中锌、铜的含量明显降低。     

Extension and application of multivariate curve resolution-alternating least squares to four-way quadrilinear data-obtained in the investigation of pollution patterns on Yamuna River,India—A case study

This study focuses on the development and extension of Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) to the analysis of four-way datasets. The proposed extension of the MCR-ALS method with non-negativity and the newly developed quadrilinear constraints can be exploited to summarize and manage huge multidimensional datasets and resolve their four way component profiles. In this study, its application is demonstrated by analyzing a four-way data set obtained in a long term environmental monitoring study (15 sampling sites × 9 variables × 12 months × 7 years) belonging to the Yamuna River, one of the most polluted rivers of India and the largest tributary of the Ganges river. MCR-ALS resolved pollution profiles described appropriately the major observed changes on pH, organic pollution, bacteriological pollution and temperature, along with their spatial and temporal distribution patterns for the studied stretch of Yamuna River. Results obtained by MCR-ALS have also been compared with those obtained by another multi-way method, PARAFAC. The methodology used in this study is completely general and it can be applied to other multi-way datasets.     

冠心病（心肌纤维化）微量元素谱的多元分析

用ＩＣＰ－ＡＥＳ分析了冠心病中心肌纤维化男、女患者血液中的１９种元素含量，结果通过因子分析得到男女不同性能别的判别元素谱、应用非线性映射得以二维空间图、男性分辨率达９６．６％，女性达８７．３％。     

A systematic study on the extractability of arsenic species from algal certified reference material IAEA-140/TM (Fucus sp., Sea Plant Homogenate) using methanol/water extractant mixtures

Using methanol/water mixtures (from pure water to pure methanol), with different desorption and solubility parameters, and varying extractant volume to algal mass (V/m) ratios, the extractability of arsenic species from CRM IAEA-140/TM was investigated. A linear sorption isotherm-based model was developed to process the data obtained with variable volume extraction, allowing the unambiguous deduction of the maximal extractable species concentrations under the specific extraction conditions, even for more stable species.The maximal extractable arsenic fraction ranged from 41 to 68% of the total arsenic concentration in CRM IAEA-140/TM, depending on the extractant composition, with pure methanol giving the lowest extraction yield and pure water giving erratic extractability (probably due to bad wettability). The main arsenic species quantified in the methanol/water extracts were arsenosugars, with arsenosugars 1 (glycerol arsenosugar), 3 (sulfonate arsenosugar) and 4 (sulfate arsenosugar) making up ca. 90% of the maximal extractable arsenic. The rest accounts for DMA (dimethylarsinate), arsenosugar 2 (phosphate arsenosugar) and As(V). There is no clear extraction pattern emerging from the data although it may be seen that extraction of more polar species (e.g. arsenosugar 1) is favoured in pure methanol and less polar more ionic species (e.g. arsenosugar 2 and As(V)) in methanol extractants with a higher water percentage.The precise and highly accurate data may be used for quality control purposes under strictly followed extraction conditions since the extraction is operationally defined. Additionally, the variable volume extraction methodology presented may be applied to other elemental species in other matrices using other extractants. Although this approach does not maximise the absolute extractability but only that which is extractant-specific, experimentators are forewarned that in most cases only a fingerprint of the extractant-specific species is produced unless a quantitative extraction of all species is obtained.     

Speciation of aluminium fluoride complexes and Al in soils from the vicinity of an aluminium smelter plant by hyphenated High Performance Ion Chromatography Flame Atomic Absorption Spectrometry technique

The paper presents a new tool for the determination of inorganic speciation forms of aluminium: AlF_n^{(3 − n)+}, and Al³⁺ by means of the HPIC-FAAS. The proposed method has been successfully used for speciation analysis (qualitative and quantitative) of inorganic aluminium forms AlF_n^{(3 − n)+} in soil samples. In order to isolate the most environmentally available fraction, 5 g of the sample was collected and extracted in deionised water (water soluble fraction) for 1 h using a magnetic stirrer. The determinations in a hyphenated technique system were performed for a number of prepared water extracts. Concentration determinations of particular aluminium forms were performed based on model studies and real samples. The separation of Al species with nominal charge of + 1, + 2, and + 3 required a run time of less than 4 min during a single analysis. Based on the analysis of water extracts of soil, it was obtained that aluminium forms elute in the following order: 1PA (first signal) — AlF₂⁺ and/or AlF₄⁻; 2PA (second signal) — AlF²⁺ and/or AlF₃⁰; 3PA (third signal) — Al³⁺. In order to confirm the occurrence of these forms a simulation using the Mineql program was conducted. The details of speciation analysis of aluminium fluoride forms by means of an HPIC-FAAS instrument equipped are presented. Interpretation of the speciation analysis of the water soluble fraction of soil samples is proposed, based on the separation during chromatographic run and calculated data by Mineql.     

湖州表层土壤稀土元素含量及分布特征

为了研究湖州表层土壤样品中稀土元素的分布特征,利用ICP-MS测定了土壤中稀土元素的含量。结果表明湖州表层土壤中稀土元素含量的大小顺序为：Ce＞La＞Nd＞Pr＞Sm＞Gd＞Dy＞Yb＞Er＞Eu＞Ho＞Tb＞Tm＞Lu,遵循Oddo-Harkins法则。湖州表层土壤中稀土元素的分量均值和总量均值皆高于全国水平,稀土元素存在显著的分馏现象,轻稀土元素明显富集。表层土壤中Ce和Eu都有部分亏损。     

A kinetic and thermodynamic study on hydrolysis of sodium laurate in aqueous phase accompanied by transfer into oil phases containing different organic additives (I)

The kinetic and thermodynamic behavior at the interface between an aqueous solution of sodium laurate (NaLA) and various oil phases comprised primarily of benzene (Bz) and/or different organic compounds including amphiphiles has been investigated in regard to the hydrolysis of NaLA accelerated at the interface, transfer of lauric acid (LA) into oil phase and reverse transfer of Bz into aqueous phase in addition to interface tension. The contact of aqueous NaLA solution with the oil phase was found to accompany the mass transfer of LA and simultaneously promote the hydrolysis of NaLA in water phase. Analysis of the change of OH⁻ ion concentration ([OH⁻]) over time allowed us to treat the events as a first order reaction. From the rate constant data the activation parameters such as the activation enthalpy and entropy, both of which control the transfer of LA molecules, were determined. The parameters were found to depend greatly on varied situations of the oil phase, being clearly able to explain the physicochemical behavior of the interface. Comparing the cases where the oil phase is one of the respective single systems such as Bz, dodecane (C₁₂) and dodecylbenzene (C₁₂Bz), C₁₂Bz resulted in the lowest rate constant. The transfer (or hydrolysis) rate was measured for the amphiphile-added oil systems as a function of amphiphile concentration. When 0.206 M C₁₆OHBz came in contact with aqueous phase, emulsion formation at the interface layer was brought about with approximately zero activation enthalpy, leading to facile or spontaneous transfer of LA. In addition, UV absorbance representing the transfer of Bz from the oil phase to the aqueous phase also demonstrated the effects of added amphiphiles on the action of the interface.     

Metal content in mosses from the Metropolitan Area of the Toluca Valley: a comparative study between inductively coupled plasma optical emission spectrometry (ICP-OES) and total reflection X-ray fluorescence spectrometry (TXRF)

The comparison between inductively coupled plasma optical emission spectrometry (ICP-OES) and total reflection X-ray fluorescence spectrometry (TXRF) for simultaneous determination of metal content (Cr, Cu, Fe, Mn, Pb and Zn) in mosses from the Metropolitan Area of the Toluca Valley was performed. Epiphytic mosses (Fabriona ciliaris and Leskea angustata) were collected in two sampling campaigns and were digested with HNO₃, HCl and HF for ICP-OES method and HNO₃ and HCl for TXRF method. The certified reference material (IAEA-336, Lichen) and the Standard Reference Material (SRM-1573, tomato leaves) were used for the quality control and to evaluate trueness and precision. Linearity, detection and quantification limits were also determined. Results show an ICP-OES and TXRF trueness mean of 101 ± 5% and 97 ± 9%, respectively; the relative standard deviation (RSD percent) was less than 17% in both methods. The moss samples exhibit a satisfactory precision (RSD ≤ 20%), because the RSD percent for ICP-OES, from 2% to 15%, and that for TXRF, from 1% to 17%, were obtained. One factor experimental design and simple regression analysis (α = 0.05) were used to compare the ICP-OES and TXRF metal concentrations. The statistical results do not show significantly different values for Cu, Mn, Pb and Zn in both the sample campaigns. In addition, the average results for Cr in the first sample campaign (30.3 ± 11.4 mg/kg for ICP-OES and 18.6 ± 9.8 mg/kg for TXRF) and Fe values in the second sample campaign (10,810 ± 2980 mg/kg for ICP-OES and 8380 ± 2350 mg/kg for TXRF) were significantly different in both methods. These differences are attributed to an incomplete sample digestion in the TXRF sample preparation. The results of the simple regression analyses show p-value less than 0.05, which indicates an equivalent and significant relation between ICP-OES and TXRF.     

Formation pathways of DMSO from DMS-OH in the presence of O(2) and NO(x): A theoretical study

The relative importance of the reaction pathways and thus the product yields in the dimethyl sulfide (DMS) degradation scheme initiated by the hydroxyl (OH) radical has been said to be influenced by the content of nitrogen oxides (NO(x)) in chamber experiments. In this study, ab initio and density functional electronic structure calculations of all the possible reaction pathways corresponding to the reaction process initiated by DMS-OH + oxygen (O(2)), leading to the formation of the dimethyl sulfoxide (DMSO) product in the presence of NO(x) (NO and NO(2)), are carried out for the first time. The results for the different pathways are compared with the objective of inferring their kinetic relevance in the laboratory experiments that measure DMSO formation yields. Our theoretical results clearly show the existence of NO(x)-dependent pathways leading to the formation of DMSO in addition to O(2)-dependent channels. So then, NO(x)-containing conditions would have to modify the relative importance of the addition channel in the DMS oxidation process.     

Indoor measurements of microclimate variables and ozone in the church of San Vincenzo (Monastery of Bassano Romano — Italy): A pilot study

This experiment describes a way of operation in MMA-CH, Microclimate Multivariate Analysis for Cultural Heritage. It is realised by choosing appropriate meteorological and air composition parameters according to the environment to be investigated, measuring them by appropriate instruments and making acquisition of time series to find out all possible correlations. It is possible to understand how this branch of multivariate analysis could contribute to the “science of conservation” by applying an appropriate microclimatic and air composition monitoring and processing. Microclimate parameters such us air temperature, relative humidity, mixing ratio and air composition parameters such as tropospheric ozone content were monitored during a summer period to assess their impact on the cultural heritage of the Benedictine Monastery dedicated to San Vincenzo Martire (Diocletian's Christians persecution). This marvellous place is settled next to Bassano Romano village, in the Sabatini mountains rural area. The importance of the site is established by the presence of many art treasures, like 2 frescos of '700, 2 frescos of '600 (Caravaggio School) and by a marble statue of Jesus (“The Jesus cross carrying”) which is recently attributed to Michelangelo as the original one.     

Coupled TG-MS study on the intermediate for formation of PbO(t) from PbO(O) in synthesis of perovskite PMN-PT

Pb(OH)₂ was previously proposed as an intermediate in the synthesis of PMN [Pb(Mg_1/3Nb_2/3)O₃] and PMN-PT [0.9Pb(Mg_1/3Nb_2/3)O₃-0.1PbTiO₃] from a mixture of PbO, Nb₂O₅, Mg(NO₃)₂·6H₂O (w/w₀) TiO₂ by the modified mixed oxide method based on TG/DSC and XRD data. Coupled TG-MS of the precursor reveals that the intermediate is Pb₆O₅(NO₃)₂, not Pb(OH)₂ because the evolved gas was nitric oxide and oxygen, not water.