Determination of 226Ra at ultratrace level in mineral water samples by sector field inductively coupled plasma mass spectrometry

An analytical procedure has been proposed for the determination of (226)Ra at the low femtogram per ml concentration level in mineral water samples using double focusing sector field ICP-MS (ICP-SFMS). For the pre-concentration and separation of radium from the matrix elements in water a tandem of a laboratory-prepared filter, based on MnO(2), and Eichrom "Sr-specific" resin was used. The recovery of the method was determined to be 70.5%. The limit of detection for (226)Ra determination was 0.02 fg ml(-1), including a pre-concentration factor of 10. In addition, uranium concentration and uranium isotope ratios were measured by ICP-SFMS. In several mineral water samples with a relatively high uranium content, (226)Ra concentrations were found between 0.7-15 fg ml(-1). The effective dose of the contribution was calculated using the radionuclide concentration and dose conversion factors from the World Health Organization, WHO (1993). Assuming a mineral water consumption of 2 l d(-1), a slightly higher calculated dose than the suggested limit for drinking water (0.1 mSv y(-1)) was found in some samples.     

Interlaboratory evaluation of trace element determination in workplace air filter samples by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) is becoming more widely used for trace elemental analysis in the occupational hygiene field, and consequently new ICP-MS international standard procedures have been promulgated by ASTM International and ISO. However, there is a dearth of interlaboratory performance data for this analytical methodology. In an effort to fill this data void, an interlaboratory evaluation of ICP-MS for determining trace elements in workplace air samples was conducted, towards fulfillment of method validation requirements for international voluntary consensus standard test methods. The study was performed in accordance with applicable statistical procedures for investigating interlaboratory precision. The evaluation was carried out using certified 37-mm diameter mixed-cellulose ester (MCE) filters that were fortified with 21 elements of concern in occupational hygiene. Elements were spiked at levels ranging from 0.025 to 10 μg filter(-1), with three different filter loadings denoted "Low", "Medium" and "High". Participating laboratories were recruited from a pool of over fifty invitees; ultimately twenty laboratories from Europe, North America and Asia submitted results. Triplicates of each certified filter with elemental contents at three different levels, plus media blanks spiked with reagent, were conveyed to each volunteer laboratory. Each participant was also provided a copy of the test method which each participant was asked to follow; spiking levels were unknown to the participants. The laboratories were requested to prepare the filters by one of three sample preparation procedures, i.e., hotplate digestion, microwave digestion or hot block extraction, which were described in the test method. Participants were then asked to analyze aliquots of the prepared samples by ICP-MS, and to report their data in units of μg filter(-1). Most interlaboratory precision estimates were acceptable for medium- and high-level spikes (RSD <25%), but generally yielded greater uncertainties than were anticipated at the outset of the study.     

Chemical speciation studies on DU contaminated soils using flow field flow fractionation linked to inductively coupled plasma mass spectrometry (FlFFF-ICP-MS)

Flow field flow fractionation (FlFFF) in combination with inductively coupled plasma mass spectrometry (ICP-MS) was used to study the chemical speciation of U and trace metals in depleted uranium (DU) contaminated soils. A chemical extraction procedure using sodium pyrophosphate, followed by isolation of humic and fulvic substances was applied to two dissimilar DU contaminated sample types (a sandy soil and a clay-rich soil), in addition to a control soil. The sodium pyrophosphate fractions of the firing range soils (Eskmeals and Kirkcudbright) were found to contain over 50% of the total U (measured after aqua regia digestion), compared to approximately 10% for the control soil. This implies that the soils from the contaminated sites contained a large proportion of the U within more easily mobile soil fractions. Humic and fulvic acid fractions each gave characteristic peak maxima for analytes of interest (Mn, Fe, Cu, Zn, Pb and U), with the fulvic acid fraction eluting at a smaller diameter (approximately 2.1 nm on average) than the humic fraction (approximately 2.4 nm on average). DU in the fulvic acid fraction gave a bimodal peak, not apparent for other trace elements investigated, including natural U. This implies that DU interacts with the fulvic acid fraction in a different way to all other elements studied.     

Determination of toxic inorganic elements pollution in ground waters of Kahuta Industrial Triangle Islamabad, Pakistan using inductively coupled plasma mass spectrometry

The present study deals with the ground water quality assessment in Kahuta Industrial Triangle Islamabad, Pakistan. The objective of the study was to assess ground water quality against the drinking water standards for various toxic inorganic elements. Representative groundwater samples were collected and analyzed in the Water Quality Laboratory of Pakistan Council of Research in Water Resources (PCRWR) at Islamabad, Pakistan. The samples were run on ICP-MS (Inductively coupled plasma mass spectrometry), which has the capability to separate and quantify 70 elements at a time. One of the finding of study is that ICP-MS is a very good tool to analyze broad range of toxic inorganic elements to the level of parts per billion (ppb). World Health Organization drinking water standards shows that these toxic inorganic elements such as heavy metals even at this concentration level (ppb) are injurious to human health. This analysis indicated pollution of various toxic elements including Selenium. Vertical leachate through industrial waste septic tanks is identified as major cause of groundwater pollution in the Industrial Triangle. Monitoring of the septic tanks and groundwater quality in study area is suggested along with remedial measures.     

Determination of antimony in human blood with inductively coupled plasma-mass spectrometry

A method is presented for the determination of antimony in whole human blood samples with an ICP-MS instrument using a quadrupole mass analyzer. A nitric acid/hydrogen peroxide open digestion procedure was employed for the blood sample treatment and preparation for analysis. The precision and accuracy of the method were evaluated by analyzing several Seronorm trace elements whole blood reference materials. The precision of the method at various antimony levels was better than 4% RSD and the recovery was greater than 92% at all levels. The detection limit, calculated as three times the standard deviation of the blank (3sigma, n= 12), was 0.03 microg L(-1). The method was successfully applied for the determination of antimony in blood samples from school children in rural areas of Kwazulu/Natal, South Africa and adults from Dearborn, Michigan. Blood antimony levels ranged from <0.03 to 3.82 microg L(-1) in children and 1.40 to 4.35 microg L(-1) for adults.     

Determination of toxic metals in leather by wavelength dispersive X-ray fluorescence (WDXRF) and inductively coupled plasma optical emission spectrometry (ICP OES) with emphasis on chromium

The tanning industry is one of the largest environmental polluters due to high generation waste in all production processes, but the tanning is particularly worrisome due to the use of significant amounts of chromium. Cr is an element potentially toxic to both health and the environment, depending on the concentration and the oxidation state. Cr(VI) can come in contact with human skin when using leather goods, which can cause allergies and dermatitis, besides being carcinogenic. Considering that approximately 90% of the world production of leather is performed with Cr salts, the determination of this element in leather is necessary to avoid exposure to the risks that the element can provide. The main goal of this study was the development of an alternative analytical method for the determination of Cr in leathers (ovine and bovine leather tanned with Cr and vegetable tannin) using wavelength dispersive X-ray fluorescence (WDXRF) for direct solid analysis. Besides performing analysis of the chemical composition and determination of Al, As, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Ni, Pb, Sb, Sr, Ti, and Zn in leather by inductively coupled plasma optical emission spectrometry (ICP OES). Principal component analysis (PCA) was also used in the evaluation of the WDXRF and ICP OES data sets. WDXRF calibration models for Cr presented satisfactory figures of merit and the analysis of the leathers revealed an alarming concentration of total Cr in the samples reaching 21,353 mg kg^?1.     

Determination of arsenic species in fish, crustacean and sediment samples from Thailand using high performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS)

Suitable techniques have been developed for the extraction of arsenic species in a variety of biological and environmental samples from the Pak Pa-Nang Estuary and catchment, located in Southern Thailand, and for their determination using HPLC directly coupled with ICP-MS. The estuary catchment comprises a tin mining area and inhabitants of the region can suffer from various stages of arsenic poisoning. The important arsenic species, AsB, DMA, MMA, and inorganic arsenic (As III and V) have been determined in fish and crustacean samples to provide toxicological information on those fauna which contribute to the local diet. A Hamilton PRP-X100 anion-exchange HPLC system employing a step elution has been used successfully to achieve separation of the arsenic species. A nitric acid microwave digestion procedure, followed by carrier gas nitrogen addition- (N2)-ICP-MS analysis was used to measure total arsenic in sample digests and extracts. The arsenic speciation of the biological samples was preserved using a Trypsin enzymatic extraction procedure. Extraction efficiencies were high, with values of 82-102%(As) for fish and crustacean samples. Validation for these procedures was carried out using certified reference materials. Fish and crustacean samples from the Pak Pa-Nang Estuary showed a range for total arsenic concentration, up to 17 microg g(-1) dry mass. The major species of arsenic in all fauna samples taken was AsB, together with smaller quantities of DMA and, more importantly, inorganic As. For sediment samples, arsenic species were determined following phosphoric acid (1 M H3PO4) extraction in an open focused microwave system. A phosphate-based eluant, pH 6-7.5, with anion exchange HPLC coupled with ICP-MS was used for separation and detection of AsIII, AsV, MMA and DMA. The optimum conditions, identified using an estuarine sediment reference material (LGC), were achieved using 45 W power and a 20 minute heating period for extraction of 0.5 g sediment. The stability and recovery of arsenic species under the extraction conditions were also determined by a spiking procedure which included the estuarine sediment reference material. The results show good stability for all species after extraction with a variability of less than 10%. Total concentrations of arsenic in the sediments from the Pak Pa-Nang river catchment and the estuary covered the ranges 7-269 microg g(-1)and 4-20 [micro sign]g g(-1)(dry weight), respectively. AsV was the major species found in all the sediment samples with smaller quantities of AsIII. The presence of the more toxic inorganic forms of arsenic in both sediments and biota samples has implications for human health, particularly as they are readily 'available'.     

Arsenic compounds in the haemolymph of the Dungeness crab, Cancer magister, as determined by using HPLC on-line with inductively coupled plasma mass spectrometry

Arsenobetaine, two arsenosugars, dimethylarsinate and several unidentified arsenic species were detected in extracts of the haemolymph of the Dungeness crab, Cancer magister, by using HPLC-ICP-MS. This is the first report of the presence of arsenosugars in the haemolymph/blood of marine animals. Total, extractable and residual arsenic concentrations were determined by ICP-MS. The concentration of total arsenic was in the range of 1.4-3.8 [micro sign]g ml(-1). Nearly all (98%) the arsenic was found to be extractable, and accounted for primarily by arsenobetaine, two arsenosugars and dimethylarsinate. The results demonstrate that arsenic compounds present in the diet of crabs are not fully metabolized in the gut. They are, at least partly, taken up into the haemolymph. The concurrence of arsenobetaine and arsenosugars suggests that the use of repeated haemolymph sampling in crustaceans could facilitate investigations into the kinetics of the biotransformation pathways of arsenic compounds. Finally, the present study clearly demonstrates the unique capabilities of HPLC-ICP-MS for the detection and identification of minor arsenic components amongst the predominant arsenobetaine.     

Optimization of digestion parameters for analysing the total sulphur of mine tailings by inductively coupled plasma optical emission spectrometry

The oxidation of sulphidic mine tailings and consequent acid generation poses challenges for the environment. Accurate and precise analysis of sulphur content is necessary for impact assessment and management of mine tailings. Here, the authors aim at developing a rapid and easy digestion procedure, which may analyse and measure the total amount of sulphur in mine tailings by using inductively coupled plasma. For evaluating effects of several variables, the researchers used a univariate (analysis of variance (ANOVA)) strategy and considered factors such as composition of the acid mixture, heating time, and refluxing device to optimize the performance. To do the experiment, the researchers have used two certified reference materials (KZK-1 and RTS-2) and samples of tailings from Musselwhite mine. ANOVA result shows that heating time is the most influencing factor on acid digestion of the reference materials whereas in case of a digestion of tailings sample, hydrochloric acid proved to be the most significant parameter. Satisfactory results between the measured and referenced values are found for all experiments. It is found that the aqua regia (1 ml HNO₃ + 3 ml HCl) digestion of 0.1 g of samples after only 40 min of heating at 95°C produced fast, safe, and accurate analytical results with a recovery of 97% for the selected reference materials.     

Determination of Ni(CO)4, Fe(CO)5, Mo(CO)6, and W(CO)6 in sewage gas by using cryotrapping gas chromatography inductively coupled plasma mass spectrometry

Evidence for the occurrence of Ni(CO)4 in addition to Mo(CO)6 and W(CO)6 in fermentation gases from a municipal sewage treatment plant is presented for the first time. The gases were sampled at the top of the sewage sludge digester using Tedlar bags, and were analysed using cryotrapping followed by gas chromatography coupled with inductively coupled mass spectrometry (GC-ICP-MS). The use of an ICP-MS as an element-specific detector gives sufficiently low detection limits for metals and was coupled to a packed column gas chromatograph. This method provides information about the speciation of volatile transition metals in contrast to previously used methods for the determination of Ni(CO)4 in gas samples. The element-specific detection of three different isotopes (m/z 58, 60, 62) and the correspondence of the samples' retention times with those of the standard provided convincing evidence that Ni(CO)4 is present in the fermentation gas. The concentrations found were in the sub-ppb level, which is at least one order of magnitude lower than the threshold level of 1 ppb (v/v). In addition, Mo(CO)6 and W(CO)6 were also measured in the sub-ppb range in contrast to the absence of Fe(CO)5. The stabilities of Ni(CO)4, Fe(CO)5, and Mo(CO)6 were tested in a carbon monoxide atmosphere. In the presence of distilled water, the following order of stability was found after 11 weeks: Fe(CO)5 < Ni(CO)4 < Mo(CO)6. In the presence of an aqueous solution containing nickel, molybdenum, tungsten and iron, however, only Fe(CO)5 was significantly decomposed (< 0.3% recovery); Ni(CO)4 and Mo(CO)6 were stable after 11 weeks. No W(CO)6 was formed. The low stability of Fe(CO)5 in the presence of water could be the reason why no volatile iron compound was found in sewage gas. This study showed that GC-ICP-MS can be employed to identify species-specific traces of metal carbonyls in process gases such as sewage gas.     

Monitoring and assessment of heavy metal/metalloid concentration by inductively coupled plasma mass spectroscopy (ICP-MS) method in Gonyeli Lake,Cyprus

The presence of heavy metals/metalloids in the ecosystem has been an increasing ecological and global public health concern due to their potential to cause adverse health effects. For this reason, the accumulation of some heavy metals such as Cr, Mn, Ni, Cu, As, Cd, Pb was assessed by way of ICP-MS in water, sediment and fish (Cyprinus carpio) sampled from Gonyeli Lake, North Cyprus. The results showed that these metals/metalloids are found widespread throughout the study area. In water, most concentrated element was manganese with 92.1 ppb and least concentrated was lead with 0.914 ppb. In sediment, copper had the highest concentration with 613 ppm, and cadmium the lowest with 1.57 ppm. In fish tissues (muscle and gills), the most concentrated element was manganese with 12.5 ppm and the least concentrated cadmium with 0.017 ppm. These results indicate that future remediation efforts are indispensable for the rehabilitation of the lake.     

环境空气中痕量挥发性有机硫监测分析方法研究

采用预浓缩系统与GC MS联用,建立了环境空气中痕量挥发性有机硫的分析方法,该法用苏玛罐或Tedlar袋采集空气样品在预浓缩系统中经液氮于-160℃冷冻浓缩后,进入GC MS进行分析。甲硫醇、乙硫醇、甲硫醚、乙硫醚、二甲二硫的最低检出限分别为2 0、1 0、1 0、1 0、0 5μg m3。经6次的重复测定,其相对标准偏差小于9 0%。该方法已用于环境空气的测定,取得了令人满意的结果。     

Natural concentrations and reference values of heavy metals in sedimentary soils in the Brazilian Amazon

The soils of the Brazilian Amazon exhibit large geochemical diversity reflecting the different soil formation processes in an area covering 49% of the Brazilian territory. Soil contamination by heavy metals is one of the threats to the sustainability of this Biome but establishing quality reference values (QRVs) for the region is a challenging owing to the immense territorial area of the Amazon. This study aimed to determine the natural background of heavy metals in soils from the southwestern Brazilian Amazon in order to propose QRVs for Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, and Zn for alluvial sedimentary soils. One hundred and twenty-eight soil samples were collected at a depth of 0.0–0.2 m in sites with minimal anthropogenic interference. Soil sample digestion was based on the EPA 3051A method and metal concentrations were determined by ICP-OES. QRVs calculated for the southwestern Brazilian Amazon are among the lowest recorded in Brazil (mg kg^?1): Ba (16.5), Cd (0.1), Cr (6.9), Cu (2.8), Fe (15.4), Mn (13.4), Ni (1.7), Pb (4.4), Sb (0.9), and Zn (5.7). The low metal concentration is likely a result of the sedimentary origin of the soils. The results of this study can serve as a basis for defining public policies to investigate the environmental impacts resulting from changes in land use in areas of the Brazilian Amazon.     

空气中挥发性有机物(VOCs) 的监测方法研究

建立了热脱附仪和气相色谱-质谱联用测定室内空气和环境空气中35种挥发性有机污染物的分析方法,方法的最低检出限为0.1～0.9μg/m3, 20μg/m3挥发性有机物标准经6次的重复测定,其相对标准偏差小于8.4%.该方法已用于室内空气和环境空气的测定,取得令人满意的结果.     

吹扫捕集与气相色谱-质谱联用测定饮用水和地表水中挥发性有机污染物

报道了Trap I(VOCARB 4000)柱捕集水中挥发性有机污染物的性能和条件,建立了吹扫捕集和气相色谱-质谱联用测定饮用水和地表水样中25种挥发性有机污染物的分析方法.水样的加标回收率在90%～110%之间,最低检测限在0.04～0.85μg/L之间,20μg/L的挥发性有机物标准溶液经重复6次测定,其相对标准偏差基本小于5.0%.该方法已成功地运用于饮用水和地表水中挥发性有机污染物的测定,结果令人满意.     

Determination of total and partially extractable solid-bound element concentrations using collision/reaction cell inductively coupled plasma-mass spectrometry and their significance in environmental studies

Determination of solid-bound element concentrations is an important initial step in environmental studies especially for assessment of contamination level, and of origin, relative mobility, and fate of contaminants. This study revealed that a relatively new collision/reaction cell inductively coupled plasma-mass spectrometry is a potent tool for determining total and partially extractable solid-bound element (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, and Pb) concentrations in a complex matrix solution containing HF and/or HCl. Six different extraction methods commonly used for environmental monitoring studies were tested for their bias and variability using estuarine and marine standard reference materials. Microwave-assisted methods based on concentrated [HNO₃] or [HNO₃?+?HF (4:1)] and [HNO₃?+?HF?+?HCl (10:3:2)] were applied for determining pseudo-total and total element concentrations, respectively. Dilute-acids (1 M HNO₃, 1 M HCl, and 0.5 M HCl) were utilized in single-step partial extraction protocols. Except the 0.5 M HCl cold-extraction method which was performed at room temperature, other partial extraction protocols used microwave-digestion. This study demonstrated that the use of microwave-assisted methods in studies aimed at determining the non-residual, non-specific extractable fractions of elements in solid environmental samples may result in overestimation, and thus needs to be re-examined. We believe that the cold extraction method will play a significant role in future environmental monitoring studies. Nevertheless, results of the cold extraction method not accompanied with total element concentrations have limited value, as the amount of extraction may vary significantly with the nature (origin) of the elements, and with the types of the samples. Therefore, we suggest combining microwave-assisted total digestion and 0.5 M HCl cold-extraction methods as a relatively cost- and time-effective, environmentally sound screening procedure for routine environmental monitoring programs involving a large number of samples from diverse geological and anthropogenic settings.     

Determination of synthetic musk compounds in sewage biosolids by gas chromatography/mass spectrometry

A review of sewage sludge regulations and land application practices by the United States National Research Council (2002) recommended development of improved analytical techniques to adequately identify and quantify new chemical contaminants, such as synthetic musk compounds in Class A sewage sludge (i.e., biosolids). This prompted the development of a rugged analytical method using gas chromatography coupled to mass spectrometry to detect this group of organic pollutants in biosolids. In this paper, the term "biosolids" is used interchangeably with "sewage sludge", which is defined in the regulations and used in the statue (Clean Water Act). Samples of Class A biosolids obtained from sewage treatment plants in Los Angeles, California, the City of Las Vegas, Nevada, and also in the form of a commercial fertilizer, were extracted using pressurized liquid extraction technique, subjected to gel permeation chromatography clean-up, and analyzed by GC/MS using the selected ion monitoring mode. The method developed has the potential to detect synthetic musk compounds in complex matrices, may provide accurate data useful in human health and environmental risk assessment, and may be useful in determining the efficacy of municipal sewage treatment plants for removing synthetic musk compounds.     

Dissipation and residues determination of propamocarb in ginseng and soil by high-performance liquid chromatography coupled with tandem mass spectrometry

Two-year field trials were performed at two experimental sites to investigate dissipation and terminal residues of propamocarb in ginseng root, stem, leaf, and soil by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). Mean recoveries ranged from 80.5 to 95.6 % with relative standard deviations (RSDs) of 5.5–9.1 % at fortified levels of 0.01, 0.02, 0.05 and 0.20 mg kg^?1. The half-lives of propamocarb were 5.00–11.36 days in root, 5.07–11.46 days in stem, 6.83–11.31 days in leaf and 6.44–8.43 days in soil. The terminal residues of propamocarb were below the maximum residue limits (MRLs) of EU (0.20 mg kg^?1) and South Korea (0.50 mg kg^?1 in fresh ginseng and 1.0 mg kg^?1 in dried ginseng) over 28 days after last spraying at recommended dosage. The results provide a quantitative basis for establishing the MRL and give a suggestion of safe and reasonable use of propamocarb in ginseng.     

Impaction collection and slurry sampling for the determination of arsenic, cadmium, and lead in sidestream cigarette smoke by inductively coupled plasma-mass spectrometry

The slurry sampling technique has been applied for the determination of arsenic, cadmium and lead in sidestream cigarette smoke condensate (SS CSC) by inductively coupled plasma mass spectrometry (ICP-MS). The smoke collection system consists of a "fishtail" chimney in conjunction with an impaction trap and a mixed cellulose ester (MCE) backup filter for the SS CSC collection. The smoke condensates, collected at three different regions of the system (i.e. the inner wall of the chimney, the impaction trap and the MCE filter), were individually prepared and analyzed and showed that about 70 and 20% of Cd and Pb, respectively, were trapped by the impaction trap and the MCE filter with less than 5% trapped by the chimney. In contrast, about 60% of As was trapped by the impactor and a relatively high percentage of As, about 30%, was deposited onto the inner wall of the chimney. The uneven distribution of trace metals at each collection stage strongly suggested that the composition of smoke aerosol and the associated physical form of the analytes may be different. The yields of As, Cd and Pb for the sidestream cigarette smoke of the 1R4F reference cigarette were 29.5 +/- 2.4, 421 +/- 6.6 and 46.4 +/- 0.9 ng cigarette(-1)(n= 3) respectively, when the cigarette was smoked according to the smoking regime: 45 mL puff volume of 2-s puff duration at an interval of 30 s with 50% ventilation holes covered. The analytical results for the slurry sampling technique were also compared with other sample preparation techniques and show good agreement.