Comparison of three sampling and analytical methods for the determination of airborne hexavalent chromium

A field study was conducted with the goal of comparing the performance of three recently developed or modified sampling and analytical methods for the determination of airborne hexavalent chromium (Cr(VI)). The study was carried out in a hard chrome electroplating facility and in a jet engine manufacturing facility where airborne Cr(VI) was expected to be present. The analytical methods evaluated included two laboratory-based procedures (OSHA Method ID-215 and NIOSH Method 7605) and a field-portable method (NIOSH Method 7703). These three methods employ an identical sampling methodology: collection of Cr(VI)-containing aerosol on a polyvinyl chloride (PVC) filter housed in a sampling cassette, which is connected to a personal sampling pump calibrated at an appropriate flow rate. The basis of the analytical methods for all three methods involves extraction of the PVC filter in alkaline buffer solution, chemical isolation of the Cr(VI) ion, complexation of the Cr(VI) ion with 1,5-diphenylcarbazide, and spectrometric measurement of the violet chromium diphenylcarbazone complex at 540 nm. However, there are notable specific differences within the sample preparation procedures used in three methods. To assess the comparability of the three measurement protocols, a total of 20 side-by-side air samples were collected, equally divided between a chromic acid electroplating operation and a spray paint operation where water soluble forms of Cr(VI) were used. A range of Cr(VI) concentrations from 0.6 to 960 microg m(-3), with Cr(VI) mass loadings ranging from 0.4 to 32 microg, was measured at the two operations. The equivalence of the means of the log-transformed Cr(VI) concentrations obtained from the different analytical methods was compared. Based on analysis of variance (ANOVA) results, no statistically significant differences were observed between mean values measured using each of the three methods. Small but statistically significant differences were observed between results obtained from performance evaluation samples for the NIOSH field method and the OSHA laboratory method.     

Preconcentration technique for the determination of trace elements in natural water samples by ICP-AES

A procedure was developed for the determination of Cd, Cu, Zn, Co, Ni, Mn, Pb and Mo in water samples by inductively coupled plasma atomic emission spectrometry (ICP-AES) after preconcentration on a morpholine dithiocarbamate (mor-DTC) supported by bagasse (Saccharam aphisinaram). The sorbed elements were subsequently eluted with 4,M HNO₃ and the acid eluates were analysed by ICP–AES. The influence of various parameters such as pH, flow rate of sample, eluent concentration, volume of the sample and volume of eluent were investigated to enhance the sensitivity of the present method. A 20,mL disposable syringe served as preconcentration column. Under the optimal conditions Cd, Cu, Zn, Co, Ni, Mn, Pb and Mo in aqueous sample was concentrated about 100-fold. The sorption recoveries of elements were higher than 99.6%. The method is also applied for the analysis of natural and spiked water samples.     

Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

分光光度法测定水中微量草酸盐

研究了在酸性介质中 ,锌与草酸的还原反应 ,生成的乙醛酸与盐酸苯肼反应生成乙醛酸苯腙 ,而苯肼转化为重氮盐后与乙醛酸苯腙反应生成粉红色偶氮化合物。据此建立了分光光度法测定微量草酸盐的分析方法。     

Techniques and methods for the determination of haloacetic acids in potable water

Haloethanoic (haloacetic) acids (HAAs) are formed as disinfection byproducts (DBPs) during the chlorination of natural water to make it fit for consumption. Sundry analytical techniques have been applied in order to determine the concentrations of the HAAs in potable water supplies: gas chromatography (GC-MS, GC-ECD); capillary electrophoresis (CE); liquid chromatography (LC), including ion chromatography (IC); and electrospray ionization mass spectrometry (ESI-MS). Detection limits required to analyze potable water samples can be regularly achieved only by GC-ECD and ESI-MS. Without improvements in preconcentration or detector sensitivity, CE and LC will not find application to potable water supplies. The predominant GC-ECD methods use either diazomethane or acidified methanol to esterify (methylate) the carboxylic acid moiety. For HAA5 analytes, regulated under the EPA's Stage 1 DBP Rule, diazomethane is satisfactory. For HAA9 data gathered under the Information Collection Rule, acidified methanol outperforms diazomethane, which suffers from photo-promoted side reactions, especially for the brominated trihaloacetic acids. Although ESI-MS can meet sensitivity and selectivity requirements, limited instrumentation availability means this technique will not be widely used for the time being. However, ESI-MS can provide valuable confirmatory information when coupled with GC-ECD in a research setting.     

Comparison of analytical results for chloride, sulfate and nitrate obtained from adjacent ice core samples by two ion chromatographic methods

The anions chloride, sulfate and nitrate in nearly 500 pairs of ice core samples from the same depth were determined in a 121 m long ice core from Svalbard. The analyses were performed separately using an ion chromatograph with Dionex AS9 and AS15 columns with Na(2)CO(3) and NaOH eluents. Results showed a small (5-6 microg l(-1)) but statistically significant difference in mean concentrations for chloride and sulfate but not for nitrate. 2% of the data indicate real differences in concentrations across the ice core. Despite these differences ion information in ice core layers are comparable for ice core paleoclimate and environmental studies even though analyses are made using two different procedures.     

An online preconcentration system for the determination of uranium in water and effluent samples

Amberlite XAD-4 resin functionalized with β-nitroso-α-naphthol was applied to an online system for the preconcentration and determination of uranium. U (VI) ions were retained on the minicolumn at an appropriate pH and then desorbed with acid solution. The amount of uranium in the eluate was measured spectrophotometrically at 650 nm using Arsenazo III as a colorimetric reagent. The limit of detection and the preconcentration factor were 1.8 μg L^???1 and 10, respectively. The chemical and flow variables affecting the preconcentration were studied. The influence of several ions on the system was also investigated. The method was successfully applied for the evaluation of uranium in water and in effluent samples.     

Application of natural zeolites for preconcentration of arsenic species in water samples

Zeolites of the clinoptilolite type produced in Mexico and Hungary were investigated with respect to their sorption efficiency for various redox species of arsenic. Long-term experiments showed that arsenate remains stable for a long period in spiked deionised water and drinking water, as well as in the surface water of the Biela valley in Saxony, Germany. Both clinoptilolites are able to decrease the initial arsenic concentration of 200 microg l(-1) by more than 75% in deionised, drinking, ground and surface waters. In the case of the Mexican zeolite, both the arsenite and the arsenate concentrations (200 microg l(-1)) can be lowered from 200 microg l(-1) to 10 microg l(-1), which is the World Health Organisation's (WHO's) recommended maximum level. It was found that the presence of cations and anions in the natural waters of Biela, Germany, and Zimapán, Mexico, did not reduce the efficiency of the selected zeolites. The Hungarian zeolite removed 75% of the arsenate in the Zimapán water and only 50% when the sample was first acidified. This zeolite totally desorbed the fixed arsenic into a water volume that was half the volume in the adsorption experiment.     

Spectrophotometric method for the determination of chromium (VI) in water samples

A simple and sensitive spectrophotometric method for the determination of chromium has been developed. The method is based on the diazotization of Dapsone in hydroxylamine hydrochloride medium and coupling with N-(1-Napthyl) Ethylene Diamine Dihydrochloride by electrophilic substitution to produce an intense pink azo-dye, which has absorption maximum at 540 nm. The Beer's law is obeyed from 0.02-1.0 microg mL(-1) and the molar absorptivity is 3.4854 L mol(-1) cm(-1). The Limits of quantification and Limit of detection of the proposed method are 0.0012 microg mL(-1) and 0.0039 microg mL(-1) respectively. The method has been successfully applied for the determination of chromium in water samples and the results were statistically evaluated with that of the reference method.     

Reliable test methods for the determination of a natural production of chloroform in soils

Chloroform is one of the most frequently found anthropogenic groundwater contaminants. Recent investigations, however, suggested that chloroform in groundwater may also originate from a natural production in soils. As societies response to the occurrence of chloroform in groundwater may depend upon its origin as anthropogenic or naturally produced, test methods are needed to measure the potential of natural soil chloroform production. Field measurements of ambient air and soil air, and field and laboratory incubation studies were evaluated for measurement of relative soil chloroform production at a site with four different vegetation types (spruce forest, beech forest, grassland, and grain field) on comparable geological soil. All test methods showed varying soil production of chloroform with spruce forest soil being most productive and grain field soil being least productive. Field measurements of the ratio of soil air to ambient air chloroform concentrations exhibited the smallest difference between high production and low production areas, whereas laboratory incubation studies showed the largest difference. Thus, laboratory incubation studies are suggested as most efficient for estimating relative chloroform production in soil. The study indicated that soil samples should be tested not more than 14 days after sampling. Furthermore, it was found that potentially limiting compounds, such as chloride or nitrate, are not needed to be added in spike experiments to obtain reliable production results. However, it should be recognized that the processes of soil chloroform production are not known yet in all details. Other factors than those studied here may affect the test methods for soil chloroform production too.     

Interlaboratory trial to determine the analytical state-of-the-art of bromate determination in drinking water

The new European Directive for water intended for human consumption has established a regulatory level for bromate at 10 microg L(-1). This Maximum Admissible Concentration requires analytical methods with detection limits of a least 2.5 microg L(-1). A project funded by the Standards, Measurements and Testing Programme of the European Commission has enabled the improvement and/or development of methods for the determination of bromate at such concentration levels. This collaborative work was concluded by the organisation of an interlaboratory trial involving 26 European laboratories, which enabled the testing of both a draft ISO Standard method and alternative methods. This paper presents the results of this interlaboratory trial, along with results of a bromate stability study. The progress made with respect to the analytical state-of-the-art for bromate will greatly benefit the quality of measurements carried out in water quality monitoring.     

银离子电极法现场快速测定水中氰化物

利用银离子电极及银氰络合物的平衡指示作用,探讨了在事故现场快速测定水中氰化物的方法.试验表明方法灵敏,操作简单、快速.银离子电极对氰化物浓度从0.04～20mg/L呈线性响应.     

A nanosilver-based spectrophotometric method for determination of malachite green in surface water samples

A new spectrophotometric method is reported for the determination of nanomolar level of malachite green in surface water samples. The method is based on the catalytic effect of silver nanoparticles on the oxidation of malachite green by hexacyanoferrate (III) in acetate–acetic acid medium. The absorbance is measured at 610 nm with the fixed-time method. Under the optimum conditions, the linear range was 8.0?×?10^?9–2.0?×?10^?7?mol?L^?1 malachite green with a correlation coefficient of 0.996. The limit of detection (S/N?=?3) was 2.0?×?10^?9?mol?L^?1. Relative standard deviation for ten replicate determinations of 1.0?×?10^?8?mol?L^?1 malachite green was 1.86 %. The method is featured with good accuracy and reproducibility for malachite green determination in surface water samples without any pre-concentration and separation step.     

Speciation of iron in river water using a specific catalytic determination and size fractionation

A comprehensive speciation scheme was proposed for the speciation of iron in river water (0.45 microm filtrate). The speciation was based on the catalytic determination of reactive iron as Fe3+ and Fe(III)Li/(3 -in)+, where i = 1 or 2 for a unidentate and i = 1 for a bidentate ligand, Ln-. The scheme incudes size fractionation and acid decomposition of the sample and determination of the coexisting species. The proposed scheme was applied to natural and artificial samples and acidified preparations of these. Resulting fractionation patterns of reactive and unreactive iron and of coexisting humic acid were useful for the characterization of iron species in the natural samples. The reactive iron in the molecular weight (Mr) > or = 10(4) fraction was associated with humic iron aggregates and estimated as iron complexed with them. The unreactive iron in this fraction dissociated in 0.1 M HCI and was estimated as iron in the aggregates of iron(III) hydroxide (s) and humic iron. From the fractionation results of the artificial sample, the reactive and unreactive iron in the Mr < 10(3) fraction may be formed by complexing simple anions like F- and C2O4(2-) at their naturally-occurring concentration levels. The fractionation results also suggested that humic acid and Si contributed to the formation of reactive and unreactive iron in the Mr > or = 10(4) fraction.     

Comparison of USEPA digestion methods to heavy metals in soil samples

The use of appropriate analytical methods is of paramount importance for risk assessment and monitoring of potentially toxic metals in soils. In this sense, the objective of this study was to compare the effectiveness of two sample digestion methods, recommended by the Brazilian legislation for the management of contaminated areas (CONAMA 2009), aiming at the determination of environmentally available metal concentrations (USEPA 3050B, USEPA 3051A), as well as a total digestion method (USEPA 3052). Samples from 10 classes of soils were analyzed for Cu, Zn, Cd, Pb, Ni, and Hg. The results showed that the USEPA method 3051A is more efficient than the USEPA method 3050B in the extraction of levels considered environmentally available of Zn, Cu, Cd, Pb, and Ni. Besides providing a higher recovery of these elements, the method requires shorter digestion time, lower consumption of acids, and reduced risk of contamination. The USEPA method 3051A showed greater efficiency in Hg extraction in soils with higher clay content. Therefore, it is suitable for situations where a wide range of soils with different mineralogical characteristics are analyzed or in order to decrease the losses due to volatilization of the element in open systems.     

The determination and distribution of Zn in surface water samples collected in the northeast Atlantic Ocean

Dissolved Zn concentrations were determined in surface water samples collected on-line along transects in the eastern North Atlantic in spring (March 1998). Two frontal zones could be identified in the research area by a change in salinity, temperature and nutrient concentrations. One zone was identified at 42 degrees N, separating the North Atlantic central water (NACW) and the Atlantic surface water (ASW) from each other, and another one crossing the continental slope at 12 degrees and 8 degrees E, respectively. Variability in Zn concentrations was observed near these zones, not only as a result of a change of water mass, but also due to external Zn sources. Surface Zn concentrations were 0.5-1 nM and 2 nM in the NACW and ASW, respectively, increasing to 4 nM over the continental shelf and finally 5-6 nM in the English Channel. Contributions of Zn derived from shelf sediments appear to be the major source for the enriched surface values in the continental zone.     

环境水体中吡唑硫磷残留量的测定及光降解规律研究

通过气相色谱—质谱联用仪(GC-MS)建立环境水体中吡唑硫磷残留量的测试方法,模拟光照的条件初步探讨不同浓度吡唑硫磷的光降解效率,优化不同固相萃取小柱对水样中的吡唑硫磷进行富集,使用GC-MS对浓缩后的样品进行定性与定量分析,通过对检测方法的特性指标进行确认,添加3种浓度的吡唑硫磷(0.2、1.0、2.0μg/L)在实...     

连续流动分析快速测定环境水样中的硫化物

用新型的连续流动分析对环境水样中的硫化物进行分析测定。与传统的分析方法相比,该方法具有快速、灵敏度高、检出限低的特点。该方法的分析频率可达60次/小时,检测下限为0.006mg/L,大大提高了实验室自动化程度。     

Iodide-assisted total lead measurement and determination of different lead fractions in drinking water samples

Lead and its compounds are toxic and can harm human health, especially the intelligence development in children. Accurate measurement of total lead present in drinking water is crucial in determining the extent of lead contamination and human exposure due to drinking water consumption. The USEPA method for total lead measurement (no. 200.8) is often used to analyze lead levels in drinking water. However, in the presence of high concentration of the tetravalent lead corrosion product PbO(2), the USEPA method was not able to fully recover particulate lead due to incomplete dissolution of PbO(2) particles during strong acid digestion. In this study, a new procedure that integrates membrane separation, iodometric PbO(2) measurement, strong acid digestion and ICP-MS measurement was proposed and evaluated for accurate total lead measurement and quantification of different lead fractions including soluble Pb(2+), particulate Pb(II) carbonate and PbO(2) in drinking water samples. The proposed procedure was evaluated using drinking water reconstituted with spiked Pb(2+), spiked particulate Pb(II) carbonate and in situ formed or spiked PbO(2). Recovery tests showed that the proposed procedure and the USEPA method can achieve 93-112% and 86-103% recoveries respectively for samples containing low PbO(2) concentrations (0.018-0.076 mg Pb per L). For samples containing higher concentrations of PbO(2) (0.089-1.316 mg Pb per L), the USEPA method failed to meet the recovery requirement for total lead (85-115%) while the proposed method can achieve satisfactory recoveries (91-111%) and differentiate the soluble Pb(2+), particulate Pb(II) carbonate and PbO(2).