Speciation of organotins in polyvinyl chloride pipe via X-ray absorption spectroscopy and in leachates using GC-PFPD after derivatisation

Three different polyvinyl chloride (PVC) pipe types were subjected to de-ionized water exposures over the course of at least 180 days. Water exposed to the pipe was analyzed for organotin speciation and concentration. Organotin concentrations were the highest during the first 1-5 days. The species and concentrations of organotins leached varied by pipe type. Data were normalized by surface area in order to compare laboratory results with results from a residential pipe system. For one pipe type, the lowest non-zero concentrations from the laboratory tests overestimated organotin concentrations in solution when compared with water samples from the same pipe type in a residence. For organotin exposure estimates, a range of 0.1 ng m(-2) to 10 ng m(-2) could be used for mature pipes (e.g. in use for 1 year). These estimates should be refined with more field study, however, due to the high variation in organotin species and concentrations leached as a function of pipe type, accuracy within an order of magnitude may be optimal as, in many instances, the type of pipe installed or buried may be unknown. X-ray absorption spectroscopy (XAS) was used to identify organic and inorganic tin species in reference materials and the PVC samples. Monobutyl tin was identified as the primary organotin species in the pipes. Results from the XAS analyses also indicate that the technique shows promise for distinguishing between inorganic tin and organotins. Furthermore, organotins may be distinguished between mono-, di-, and tri-ligand species using XAS.     

Speciation of arsenic using solid phase extraction cartridges

Various solid phase extraction (SPE) cartridges were investigated for speciation of arsenite [As(III)], arsenate [As(v)], monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). Cartridges containing different types of sorbent materials were tested for arsenic retention and elution characteristics. Alumina cartridges were found to completely retain all the four target arsenic species, and are suitable for removal and preconcentration purposes. For speciation analysis, different arsenic species were separated on the basis of their selective retention on and elution from specific cartridges. DMA was retained on a resin-based strong cation exchange cartridge and eluted with 1.0 M HCl. MMA and As(v) were both retained on a silica-based strong anion exchange cartridge and sequentially eluted with 60 mM acetic acid (for MMA) and 1.0 M HCl [for As(v)]. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently quantified by using flow injection with hydride generation atomic fluorescence spectrometry (FI-HGAFS) and hydride generation atomic absorption spectrometry (FI-HGAAS). A detection limit of 0.05 microg L(-1) arsenic in water sample was achieved using HGAFS. An application of the method was demonstrated at a drinking water treatment facility. As(III) and As(v) species were determined in water at various stages of treatment. The method is suitable for routine determination of trace levels of arsenic in drinking water to comply with more stringent environmental regulations.     

上海城市污泥成分特性及分析方法研究

采用扫描电镜、X射线衍射仪、能量色散X荧光分析仪、原子吸收光谱等现代分析技术对上海市某污水处理厂的污泥中复杂的化合物的形貌及其中无机化合物的物种进行了综合分析,并对其中痕量重金属的分子存在状态进行分析和评价。     

Organotin compounds in surface sediments from seaports on the Gulf of Gda??sk (southern Baltic coast)

Sediment samples were collected in two Polish ports of international significance--the Port of Gdańsk and the Port of Gdynia (Gulf of Gdańsk, Baltic Sea)--in order to assess their butyltin and phenyltin contamination; this was done in 2008, just after the total ban on using harmful organotins in antifouling paints on ships came into force. Altogether, 21 sampling stations were chosen to present a diversity of port sites: from port canals and shipyards to anchorages and dumping sites. The organic carbon content and grain size of all the sediment samples were determined, and some environmental parameters (oxygen content, salinity) were measured as well. Total concentrations of butyltin compounds in sediment samples were very different and ranged between 1 and 18,520 ng Sn g(-1) d.w. Phenyltin contents were distinctly lower and ranged from below the limit of detection (most samples) to 660 ng Sn g(-1) d.w. The highest concentrations of organotins were found in the shipyards, the maximum total organotin content (19,180 ng Sn g(-1) d.w.) being found in the Gdańsk Ship Repair Yard 'Remontowa'. Butyltin degradation indices indicate a recent tributyltin input into the port sediments. The results obtained from this work prove that the international ban on using organotins may not be enough to protect the marine environment. It is necessary to monitor organotin contamination in ports and establish concentration limits of these compounds for the disposal of dredged material at sea.     

Determination of traces of copper and zinc in honeys by the solid phase extraction pre-concentration followed by the flame atomic absorption spectrometry detection

A simple and fast solid phase extraction procedure was developed to pre-concentrate traces of Cu and Zn prior to their determination in honey samples by flame atomic absorption spectrometry. The sample preparation included dissolution of honey samples and the passage (at 20 ml/min) of resulting 10 % m/v solutions (100 ml) through Dowex 50W?×?8-400 resin beds in order to quantitatively retain Cu and Zn and separate them from the glucose and fructose matrix. Enriched Cu and Zn traces were recovered with 5.0 ml of a 3.0 mol/l HCl solution and quantified by flame atomic absorption spectrometry. The procedure proposed was used to analyze sixty nine commercially available and freshly ripened honey samples coming from the Lower Silesia region (Poland). It enabled to measure Cu and Zn within the range of 0.01–1.42 and 0.03–15.38 μg/g, respectively, with precision better than 4 %. Accuracy, assessed on the basis of the recovery test and the comparison of results with those obtained using wet digestion and inductively coupled plasma optical emission spectrometry, was ranged from ?4 % to +6 %. Detection limits of Cu and Zn achieved with this method were 5 and 7 ng/g, respectively.     

微波消解-石墨炉原子吸收法测定小麦中钴

利用微波消解-石墨炉原子吸收法检测小麦样品中的低含量钴，方法简单、操作便捷，测定结果精确度和准确度好。钴的线性回归方程为A=0．003303c＋0．004218，测定结果的相对标准偏差为4．1％（标准样品ESP-1）和1．1％（6#小麦样品），检出限为0．005mdkg。     

石墨炉原子吸收光谱法测定空气中四乙基铅

采用一氯化碘的盐酸溶液吸收光谱法和三氯甲烷萃取-石墨炉原子吸收光谱法测定空气中四乙基铅,优化了试验条件。此方法对测定空气中四乙基铅的灵敏度、准确度都有很大的提高,方法的最低检出浓度为0.70μg/L,当采样体积为60 L,四乙基铅最低检出浓度为0.000 1 mg/m3。对实际样品进行分析,四乙基铅的加标回收率为89.1%~105.9%。     

Chromium fractionation and speciation in natural waters

It is common for leather industries to dump chromium-contaminated effluent into rivers and other bodies of water. Thus, it is crucial to know the impacts caused by this practice to the environment. A study on chromium partitioning and speciation, with determination at trace levels, was carried out in a potentially contaminated creek. Chromium fractionation and speciation was performed using a flow-injection preconcentration system and detection by flame atomic absorption spectrometry. High levels of this element were found in the particulate material (449-9320 mg kg(-1)), which indicates its compatibility with this fraction. The concentration of Cr(iii) in the water samples collected ranged from 5.2-105.2 μg L(-1). Cr(vi) was always below of the DL (0.3 μg L(-1)). Chromium accumulation observed in the sediment (873-1691 mg kg(-1)) may confirm contamination due to the long term release of contaminated effluents in the creek.     

两种原子吸收法测定环境水样中镍的比较

用加热浓缩-火焰原子吸收光谱法和石墨炉-原子吸收光谱法对环境水样中的镍进行了比较测定,结果表明,两种方法测定镍的各项指标均在要求范围,两种方法测定结果的相对误差均＜7.1%,表明两种方法可以视为等效方法,作用可以相互替补使用.     

固体进样-电热蒸发-原子吸收法测定土壤中的镉

采用固体进样原子吸收法直接测定土壤中的镉,可以避免传统酸消解预处理过程耗时长、试剂消耗大、操作步骤繁琐等缺点,提升镉的检测效率。通过优化测镉仪的仪器参数,确定了固体进样-电热蒸发-原子吸收法的优化仪器条件。采用优化条件测定了不同浓度的土壤样品,研究了该方法的检出限、正确度、精密度。研究结果表明:镉质量范围为0~200 ng时与峰面积的线性相关系数优于0.999 5,空气流下优化的灰化温度和热解温度均为800 ℃,优化的热解气体氢气流量为300 mL/min,当样品进样量为0.1 g时,检出限为0.009 mg/kg,7次连续测定相对标准偏差为1.4%~5.0%,加标回收率为96.2%~102.1%,分析时间小于4 min。该方法操作简便,用时短,无需高压气源,可以用于土壤中镉的高效检测。     

热分解齐化原子吸收光度法测定废水中的总汞

建立用热分解齐化原子吸收光度法测定废水中总汞的方法。将样品加热至650℃,使所有汞转化成蒸气,利用催化管将蒸气中的二价汞转化成零价汞,再利用金管捕集零价汞,加热金管释放零价汞并使其进入分析单元,在253.7 nm处以冷原子光谱法测定汞含量。方法检出限(t S)为0.045μg/L,测定下限为0.180μg/L。相对标准偏差RSD为2.3%~4.6%,加标回收率P为86.2%~94.8%。用热分解齐化原子吸收光度法直接测定废水中总汞,操作简单,污染小,毒性低,可替代《水质总汞的测定冷原子吸收分光光度法》(HJ 597-2011)。     

石墨炉原子吸收光谱法测定水中四乙基铅

采用三氯甲烷萃取-石墨炉原子吸收光谱法测定水中四乙基铅,优化了试验条件。方法在2.00μg/L～50.0μg/L范围内线性良好,检出限为1.3×10^-5mg/L,标准溶液测定的RSD≤8.6%,实际水样加标回收率为90.4%～108%。     

改性沸石分离富集-火焰原子吸收光谱法测定长江水中镉

采用改性沸石分离富集-火焰原子吸收光谱法测定长江水中微量镉,优化了富集和洗脱条件,讨论了干扰离子的影响。方法在0μg~4.00μg范围内线性良好,检出限为0.214μg/L,长江水平行测定的RSD为1.8%,加标回收率为99.0%~104%。     

Determination of three alkylphenol isomers in various water samples using a new HPLC method based on a duet stationary phase

The level of three alkylphenols (APs) 4-nonylphenol, 4-octylphenol and 4-tert-octylphenol was monitored in various water samples using a new developed and validated HPLC method. The HPLC method employed a column with a mixed-mode stationary phase (C18/SCX) using a mobile phase of water to methanol?=?15:85 (v/v) delivered at a flow rate of 1 mL/min at room temperature. Both diode array, DAD and fluorescence, FLD detectors were employed. The method is linear when APs concentration ranged from 0.025 to 0.5 μg/mL with a DAD detection at 279 nm and between 0.0008 and 0.1 μg/mL when the detection was made by FLD (excitation at 220 nm, emission at 315 nm). The limit of detection and limit of quantitation for alkylphenols were found to be 5 and 15 ng/mL, respectively (detection by DAD). The method was employed with good results for the determination of APs in the presence of polycyclic aromatic hydrocarbons in various water samples.     

原子吸收法测定水中锌质量控制指标研究

根据地域和监测技术代表性的筛选,在11个省份中选择了70家实验室参加测试工作,通过大量的监测数据,研究了原子吸收分光光度法测定水中锌的质量控制指标。研究表明:在0.3～1.5mg/L范围内,标准样品RSD≤3.0%,RSD’≤10.0%;浓度小于等于0.5mg/L时RE在±10.0%范围内,浓度为0.5～1.5mg/L时RE在±5.0%范围内。实际样品浓度小于等于0.05mg/L时,RD≤20.0%;浓度0.05～3.5mg/L时,RD≤5.0%。加标回收率控制范围为85%～110%。     

氯化铵-火焰原子吸收光谱法测定地表水中的总铬

应用原子吸收法测定水样中的总铬，在不同条件下对空白样品、标准样品和实际样品进行试验分析，进一步验证了方法的准确度和精密度，加标回收率在96.8%-103%之间，相对标准偏差为2.1%。试验表明，该方法准确可靠，实际操作具有可行性，适用于工业废水和受污染地表水中总铬的测定。     

Development of an efficient and sensitive analytical method for the determination of copper at trace levels by slotted quartz tube atomic absorption spectrometry after vortex-assisted dispersive liquid-liquid microextraction in biota and water samples using a novel ligand

This study describes the determination of trace levels of copper by slotted quartz tube atomic absorption spectrometry after dispersive liquid-liquid microextraction. A ligand synthesized from the reaction of salicylaldehyde and 1-naphthylamine was used to form coordinate copper complex prior to extraction. All parameters that influence the output of complex formation, extraction, and instrumental measurement were optimized to enhance the absorbance signal of copper. Under the optimum conditions, about 104-fold enhancement in sensitivity was recorded over the conventional flame atomic absorption spectrometer, corresponding to a 0.51 ng/mL detection limit. The percent relative standard deviation calculated for the lowest concentration (4.8%) indicated high precision for the experimental procedure. Accuracy and applicability of the optimum method were determined by performing spiked recovery tests on urine, lake water, and mineral water samples. Satisfactory recovery results were obtained between 82.2 and 106.3% at four different concentrations. Matrix matching method was also performed to increase the accuracy of quantification, and the percent recovery calculated for 175 ng/mL was 105.14%.     

Total and inorganic arsenic in dietary supplement supplies in northern Mexico

The aim of this study was to evaluate the presence of total and inorganic arsenic in dietary supplements composed of herbal plants and seaweed, and to determine the potential toxicological risk. Total arsenic was determined by dry ashing and hydride generation atomic absorption spectrometry, and inorganic arsenic was determined by acid digestion, solvent extraction, and hydride generation atomic absorption spectrometry. Total and inorganic arsenic in the supplements ranged from 0.07 to 8.31 mg?kg^?1 dry weight and from 0.14 to 0.28 mg?kg^?1 dry weight, respectively. Daily intake of total arsenic ranged from 0.05 to 12.46 μg?day^?1. Inorganic arsenic intake ranged from 0.21 to 0.83 μg?day^?1, values that are below the Benchmark Dose Lower Confidence Limit recommended by the Word Health Organization. Therefore, there appears to be a low risk of adverse effects resulting from excess inorganic arsenic intake from these supplements. This is the first study conducted in Mexico that investigates total and inorganic arsenic in dietary supplements. Although the results do not suggest toxicological risk, it is nonetheless important considering the toxicity of inorganic arsenic and the increasing number consumer preferences for dietary supplements. Moreover, it is important to improve and ensure the safety of dietary supplements containing inorganic arsenic.     

The application of ICP-SMS, GF-AAS and HG-AFS to the analysis of water and sediment samples from a temperate stratified estuary

Three atomic spectrometry techniques, namely sector field inductively coupled plasma mass spectroscopy, graphite furnace atomic absorption spectrometry and hydride generation atomic fluorescence spectroscopy (ICP-SMS, GF-AAS and HG-AFS, respectively), housed at separate independent laboratories, were used to analyse water and sediment samples collected from the Huon River Estuary, SE Tasmania (Australia) in the Austral spring 1998. A dithiocarbamate-chelation/back-extraction technique was used to separate and preconcentrate Co, Ni, Cu, Zn, Cd and Pb from eight collected water samples prior to analysis by ICP-SMS and GF-AAS. A number of other elements in the waters were analysed directly (Mn, Fe and Zn by GF-AAS; As by HG-AFS), or following sample dilution (1 + 19: V, Mn, Fe, As, Mo, Ba and U by ICP-SMS). Where possible, previously corroborated GF-AAS and HG-AFS techniques were used to verify obtained ICP-SMS results. From the analysis of four reference waters (SLEW-1 and -2, SLRS-3 and NASS-5), good agreement, to within +/- 10-20%, was typically found between certified (or information only values) and measured results (irrespective of analytical technique). Exceptions included Zn (and sometimes Fe) that could not be quantified by ICP-SMS due to elevated blank signals, and As which was found to lie below ICP-SMS detection limits. For Huon Estuary water samples, inter-method agreement was within +/- 10-20% (for those elements amenable to analysis by more than one technique). Nitric acid extracts of two certified reference materials (Buffalo River Sediment and BCSS-1) and six Huon Estuary sediments were analysed by ICP-SMS (for Al, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Cd and Pb) and HG-AFS (for As). Results from the certified reference materials indicated extraction efficiencies of 60 70% (for most elements). A close correlation between ICP-SMS and HG-AFS was obtained for leachable As in the sediments. In terms of potential inorganic contaminants, the Huon Estuary was found to be a relatively 'clean' water system. The elemental concentrations measured in water and sediment samples from this region were found to lie within current Australian guidelines for estuaries. In general, no one analytical technique was able to accurately determine all elements in all samples from this relatively pristine estuarine environment. A combination of all three analytical techniques was necessary for the successful analysis of the elements considered in this study.     

高通量固定污染源废气颗粒物中总汞的测定

用玻璃纤维滤筒采集固定污染源废气颗粒物,借助硝酸和氢氟酸的作用,使滤筒和废气颗粒物在160℃下消解,再用原子荧光法测定消解液中总汞。用50%热硝酸溶液处理玻璃纤维滤筒,消除滤筒本底值不一对测定结果的干扰,并优化消解过程,使该方法在0.050μg/L~1.00μg/L范围内线性良好。当采样体积为10 L时,方法检出限为4.5×10~(-5)mg/m~3,空白加标样6次测定结果的RSD为7.2%,加标回收率为87.0%~113%。将该方法用于测定某固定污染源废气颗粒物中总汞,测定值在标准排放限值内。