Bromate analysis in groundwater and wastewater samples

Bromate (BrO(3)(-)) is a disinfection by-product formed during ozonation of potable water supplies containing bromide (Br(-)). Bromate has been classed by the World Health Organisation as a 'possible human carcinogen', leading to implementation of 10-25 microg L(-1)(as BrO(3)(-)) drinking water limits in legislative areas including the United States and European Union. Techniques have been developed for bromate analysis at and below regulatory limits, with Ion Chromatography (IC) coupled with conductivity detection (IC-CD), post-column reaction and ultra-violet (UV) detection (IC-PCR), or inductively coupled plasma-mass spectrometry detection (IC-ICPMS) in widespread use. The recent discovery of bromate groundwater contamination in a UK aquifer has led to a requirement for analysis of bromate in a groundwater matrix, for environmental monitoring and development of remediation strategies. The possibility of bromate-contaminated water discharge into sewage treatment processes, whether accidental or as a pump-and-treat strategy, also required bromate analysis of wastewater sources. This paper summarises techniques currently available for trace bromate analysis in potable water systems and details studies to identify a methodology for routine analysis of groundwater and wastewater samples. Strategies compared were high performance liquid chromatography (HPLC) with direct UV or PCR/UV detection, IC-CD, IC-PCR, and a simple spectrophotometric technique. IC-CD was the most cost-effective solution for simultaneous analysis of bromate and bromide within groundwater samples, having a 5 microg L(-1) detection limit of both anions with limited interference from closely-eluting species. Wastewater samples were successfully analysed for bromate only using HPLC with PCR/UV detection, with detection limits below 20 microg L(-1)(as BrO(3)(-)) and low interference. HPLC with direct UV detection was unsuitable for bromate analysis within the concentration range 50-5000 microg L(-1) which was required for this project, but column choice was shown to be a major factor in determining limits of detection. Spectrophotometry could not reproducibly determine bromate concentration, although the technique showed promise as a quick field method for high-level groundwater bromate analysis.     

红外法测定石油类的一些技巧及改进

针对红外分光光度法分析过程耗时、耗力、试剂用量大等问题,在保证分析质量的前提下对操作技术进行了一些改进。通过这些改进,对解决石油类测定过程中出现的一些问题,具有很好的应用价值。     

石油类测试中不同品牌四氯乙烯试剂的稳定性

多年来四氯乙烯试剂的稳定性一直是业内关注的难题,其稳定性显著影响《水质 石油类和动植物油类的测定 红外分光光度法》(HJ 637—2018)的实施。针对市场上8个品牌四氯乙烯试剂开瓶后的吸光度开展测试,研究四氯乙烯试剂稳定性。结果显示:科密欧化学试剂有限公司、国药集团化学试剂有限公司、南京化学试剂股份有限公司、天津基准化学试剂有限公司、天津傲然精细化工研究所和吉林市吉联油脂化工有限公司6家厂商生产的"环保级"等相关级别四氯乙烯试剂稳定性较好,在开瓶7周时间内可以满足《水质 石油类和动植物油类的测定 红外分光光度法》(HJ 637—2018)标准中针对四氯乙烯试剂的要求。Sigma Aldrich和Alfa Aesar品牌四氯乙烯试剂虽然稳定性较好,但吸光度不满足上述标准中针对该试剂的要求,不可用于该方法检测。通过采取相关工艺(如提高纯度、调整溶剂的酸碱度、添加稳定剂等),可提升四氯乙烯试剂稳定性。该研究成果可为《水质 石油类和动植物油类的测定 红外分光光度法》(HJ 637—2018)标准中四氯乙烯试剂的保存时间及使用等提供一定参考。     

Determination of rotenoids and piperonyl butoxide in water, sediments and piscicide formulations

Rotenone is a naturally occurring insecticide and piscicide (fish poison) found in many leguminous plants. This paper describes high-performance liquid chromatography (HPLC) methods for the quantitative analysis of rotenone's principal biologically active components (rotenone, tephrosin, rotenolone, deguelin) and the synergist piperonyl butoxide (PBO) in various media. Compounds were separated on a C18 reversed phase column with an acetonitrile-0.025 M phosphoric acid mobile phase and detected by UV absorbance or fluorescence (PBO only). Solid phase extraction (SPE) was used in either coupled (on-line) mode with a C18 concentrator column or automated off-line mode using Empore C18 disks. The on-line extraction efficiency was improved significantly by adding small amounts of methanol to water. Method detection limits (MDLs) for rotenoids and PBO in reagent water were 0.3 and 2 micrograms L-1, respectively, with optimal recoveries ranging from 90% to 99%. Aquatic sediments were extracted with methanol and the extracts were diluted in water prior to analysis by coupled SPE-HPLC. In wet sediments, detection limits were approximately 20-100 micrograms kg-1 with recoveries of 71% to 87%. Sonication in dimethyl sulfoxide (DMSO) followed by dilution in acetonitrile and filtration allowed determination of the active ingredients in powdered rotenone formulations. Details of sample preparation, cartridge column cleanup and analyte confirmation are provided.     

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.     

自制固相微萃取涂层用于自来水中五氯酚的测定

采用石英毛细管作为模具,甲基丙烯酸和乙二醇二甲基丙烯酸酯在石英纤维表面原位聚合得到聚(甲基丙烯酸-乙二醇二甲基丙烯酸酯)作为固相微萃取涂层,并以五氯酚为研究对象,采用顶空SPME-GC-ECD法对该涂层的萃取性能进行评价。使用正交试验优化萃取温度、萃取时间、盐浓度、pH和搅拌速度。在最优条件下,建立了水样中五氯酚的分析方法,方法检出限为1ng/L,线性范围为2～5000ng/L,线性相关系数为0.9999,相对标准偏差(RSD,n=5)为8.9%,加标回收率为110.8%。     

Simultaneous determination of p-arsanilic acid and roxarsone in feed by liquid chromatography-hydride generation online coupled with atomic fluorescence spectrometry

A novel, simple and sensitive liquid chromatography-hydride generation online coupled with atomic fluorescence spectrometry (LC-HG-AFS) method was developed for simultaneous determination of p-arsanilic acid (p-ASA) and roxarsone in feed. 20% Methanol aqueous was used as extraction reagent, after preprocessing samples by ultrasonic oscillation, then injected into the chromatography Waters symmetry shield RP18 analytical column (150mm x 4.6mm, 5 microm), finally detected by an atomic fluorescence spectrometer. The calibration curves of analyses were linear over a range of concentrations (0.2-4mg L-1 and the correlation coefficients were higher than 0.9990. The limits of detection were 0.2 mg L-1. The method has been validated by linearity, precision and recovery. p-ASA and roxarsone in feed can be successfully and simultaneously determined using the developed method without a tedious pretreatment procedure.     

Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.     

Determination of technical grade isocyanates used in the production of polyurethane plastics

A method for determination of technical grade isocyanates used in the production of polyurethane (PUR) is presented. The isocyanates in technical grade products were characterised as di-n-butylamine (DBA) derivatives using LC-MS and LC-chemiluminescent nitrogen detection (CLND) and the total isocyanate content was compared to a titration assay. For collection of isocyanates in air, an impinger-filter sampling technique with DBA as derivatisation reagent was used. Characterised DBA and nonadeuterium labelled DBA derivatives of isocyanates in technical products were used as calibration standards and internal standards, respectively, in the analysis of air samples. Three workplaces were studied where PUR products were produced either by spraying or by moulding. In both technical products and in air samples, a number of monomeric, oligomeric and prepolymeric isocyanates of e.g. methylenebisphenyl diisocyanate (MDI) and hexamethylene diisocyanate (HDI) were characterised. Several of these have not previously been described in workplace atmospheres. In the technical isocyanate products, between 69 and 102% of the NCO content determined by titration was accounted for by LC-CLND. Quantifications of a wide range of isocyanates in air samples were performed with correlation coefficients in the range 0.988-0.999 (n= 8) and the instrumental detection limits were 0.7-25 pg. At the two workplaces where MDI- and HDI isocyanurate-based products were sprayed, the isocyanate composition in the air reflected the composition in the technical product. At the workplace where a MDI-based product was used in a moulding process, only the monomeric isocyanates were found in the air. The advantage of using characterised technical grade isocyanates as analytical standards was clearly demonstrated and the possibility of using index compounds when monitoring isocyanate exposure is discussed.     

Methodologies for determination of antimony in terrestrial environmental samples

Methodologies for the environmental analysis of total antimony and aqueous chemical speciation are critically reviewed, including preparation techniques for aqueous and solid matrices and the determination of solid state partitioning and recommendations are given for future research directions. Concentrations of total antimony commonly present in aqueous and solid environmental samples are readily determined using present day analytical techniques. This has resulted primarily from technological advances in microwave digestion for solid matrices and the development of plasma based analyte detection systems. ICP-AES and ICP-MS techniques are both utilised for the environmental analysis of total antimony concentrations. However, ICP-MS is increasingly favoured as a result of reduced spectral interferences and the potential for analyte detection in the pg mL(-1) range. Determination of aqueous antimony speciation presents a number of complex analytical challenges and highly selective separation and identification techniques are required prior to detection. The majority of published techniques including common applications of hydride generation are insufficiently selective for the determination of intrinsic chemical speciation and often only oxidation state data are obtained. The recent in-line applications of HPLC-ICP-MS offer the potential for highly selective separations of aqueous antimony species and determination of detailed chemical speciation data. However, considerable development work is required to optimise chromatographic separations and identify uncharacterised species resident in environmental systems. Analytical techniques to aid the determination of antimony's associations with solid environmental matrices include the application of chemical extraction procedures and leaching experiments. To date, this area of analytical research has received little attention and further studies are required to elucidate this aspect of antimony's environmental chemistry.     

Validation of a diffusive sampler for NO2

A diffusive sampler for NO2, Willems badge, was validated in laboratory experiments and field tests. The collecting reagent for NO2 in the sampler is triethanolamine, and the analysis is based on a modified colorimetric method, the Saltzman method. The analysis was performed by a flow injection analysis (FIA) technique. The sampling rate for the sampler was determined to be 40.0 ml min-1. There was no effect of NO2 concentration or relative humidity on sampling rate, and the influence of sampling time was found to be small. The detection limit was 4 micrograms m-3 for a 24 h sample. The capacity is high enough to allow sampling of 150 micrograms m-3 for 7 days, which is twice the recommended Swedish short-term (24 h) guideline value as a 98-percentile over 6 months. In field tests, the sampler performed well, even at wind speeds higher than 2 m s-1, and at low temperatures. The overall uncertainty of the method was 24%. The sensitivity and capacity of the method also make it suitable for personal sampling for 2-8 h in working environments.     

Role of halogen(I) cation-transfer mechanisms in water chlorination in the presence of bromide ion

Bromide ion is rapidly converted to HOBr via BrCl by reaction with HOCl. The subsequent slow reactions of (HOCl, OCl-)/(HOBr, OBr-) mixtures are monitored directly by multiwavelength UV-vis absorbance methods and simultaneously by ion chromatographic measurement of ClO2-, ClO3-, and BrO3- (p[H+] 5.6-7.6). A first-order loss of HOCl is observed which is catalyzed by trace concentrations of Br- and BrCl. Chlorite ion forms first and is subsequently oxidized to ClO3-. The loss of HOBr is slower and is second-order in HOBr, so that BrO3- formation takes longer than ClO3- formation. Under the conditions of this work, the relative yield of BrO3- increases with increase in pH. The decomposition of HOCI by bromide proceeds primarily by a series of halogen(I) cation-transfer reactions with subsequent halide release. The presence of HOCI increases the BrO3- yield three-fold from HOBr decay alone.     

Determination of acrylic acid in air by using diffusion denuder tubes combined with HPLC technique

A procedure for the determination of atmospheric acrylic acid in air at the microgram m-3 to mg m-3 level is described. Diffusion-based sampling, designed to discriminate gaseous analytes from their particulate counterparts, has been used. Acrylic acid is collected with an efficiency of > 98% in tubular denuders coated with sodium hydroxide-barium hydroxide-hydroquinone monomethyl ether, and analyzed by high performance liquid chromatography with UV absorbance detection. The detection limit is 2.9 micrograms m-3 at a flow rate of 0.5 L min-1 and 30 min sampling time. A precision (p = 0.95, n = 10) of 7.5% of the overall procedure was achieved at the 100 micrograms m-3 level. Results of laboratory studies concerning the effect of the coating reagent and the relative humidity on the sampling efficiency as well as possible interferences, in particular by ozone, and the elimination of these interferences are discussed. This method was developed to monitor workplace atmospheres as well as ambient air in industrial environments.     

Effects of humidity and filter material on diffusive sampling of isocyanates using reagent-coated filters

Diffusive sampling of methyl isocyanate (MIC) on 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ)-coated glass fibre (GF) filters is strongly affected by high relative humidity (RH) conditions. It is shown that the humidity interference is a physical phenomenon, based on displacement of reagent from the filter surface. In this paper, this drawback has been overcome by changing the filter material to the less polar polystyrene divinyl benzene (SDB). A series of experiments was performed to compare the analyte uptake on the two filter materials for different sampling periods and analyte concentrations at both low and high RH conditions. Additionally, the materials were investigated as well for passive sampling of ethyl (EIC) and phenyl isocyanate (PhIC) with NBDPZ and 1-(2-methoxyphenyl) piperazine (2-MP) as an alternative derivatising agent. Using 2-MP, the mean GF/SDB response ratios were determined to be 1.02 for MIC (RSD: 6.1%) and 1.03 for EIC (RSD: 6.8%), whereas PhIC could only be determined on SDB filters. Using NBDPZ as reagent, the negative influence of high humidity disappeared when SDB filters were used instead of GF filters. Even at low RH conditions, sampling with SDB material generally resulted in a higher analyte uptake than with GF filters. The GF/SDB response ratios were independent of sampling time or analyte concentration and were determined to be 0.70 (RSD: 4.7%) for MIC, 0.84 (RSD: 4.5%) for EIC and 0.95 (RSD 5.4%) for PhIC, meaning that the NBDPZ diffusive sampler based on SDB can be used at all humidity conditions without any restrictions.     

On-line solid phase extraction with polyurethane foam: trace level spectrophotometric determination of iron in natural waters and biological materials

This paper reports the development of a simple and accurate on-line procedure for preconcentration and determination of dissolved iron in waters and biological materials using unloaded polyether-type polyurethane foam as solid extractor. In the developed flow injection system, the analyte was preconcentrated from acidic aqueous medium as iron-thiocyanate complex with post-elution with ascorbic acid solution and spectrophotometric measurement with 1,10-phenanthroline as colorimetric reagent. In order to improve the performance of the system several chemical and flow variables were investigated as well as the effect caused by the presence of possible interferents. The method was validated by the analysis of two certified reference materials. Application of the methodology was carried out by the determination of dissolved iron content in eight natural water samples with different characteristics. The results were compared with those obtained by electrothermal atomic absorption spectrometry (ETAAS) and no statistical difference was observed. The detection limit was 0.75 microgram l-1 and the RSD was 1.2% for 2 min preconcentration time. At this condition, a productivity of 20 samples h-1 was achieved. Increasing the preconcentration time up to 3 min, a detection limit of 0.45 microgram l-1, an RSD of 1.5% and an analytical throughput of 15 h-1 were verified.     

恒压氮气隔断连续流动分析法测定水中化学需氧量

为建立恒压氮气隔断连续流动分析法测定水样化学需氧量的分析方法,将连续流动分析法恒流空气隔断改为恒压氮气隔断,优化试剂配方和反应模块,结果表明：恒压氮气隔断法注入氮气的压力是0.06 MPa,仪器稳定时间是20～35 min,持续分析样品时间大于4 h,指标均优于恒流空气隔断法;标准曲线在2.5～40.0 mg/L范围内,相关系数大于0.999,方法检出限为0.44 mg/L,相对标准偏差为0.2%～2.6%,加标回收率在93.8%～103.8%之间,检出限优于恒流空气隔断法,精密度和正确度满足质量控制要求;实样和标样方法比对测定结果相对标准偏差小于5%,结果精密度优于标准的手工法。恒压氮气隔断连续流动分析法适用于大批量低浓度水样化学需氧量的快速检测,对于密度大、黏度大液流恒压氮气隔断具有更好的稳定性、灵敏度和正确度。     

Determination of organophosphorus pesticides and related compounds in water samples by membrane extraction and gas chromatography

A membrane extraction-gas chromatography method was developed fordetermination of organophosphorus pesticides and related compounds including methamidophos, DDVP, dimethoate, methyl parathion, parathion, thiophosphoric acid trimethyl ester, and thiophosphoramidic acid dimethyl ester in water samples. In thismethod, surface-modified acetic cellulose membranes were used to extract the target analytes in water samples, the extracted analytes were back-extracted into a small amount of methanol, andgas chromatography with pulsed flame photometric detector (GC-PFPD) was used to determine the concentrations of targetanalytes in the extracts. The recoveries obtained for thetarget analytes spiked into the water samples ranged from 66to 94%. The method detection limit for each target analyte was 0.05 g L^-1. The method developed in this study had shown the advantages of being cheap, simple, fast, and reliable. It had been used successfully to determine the concentrations of target analytes in river water samples.     

离子色谱法测定地表水和饮用水中亚氯酸盐、溴酸盐和氯酸盐

采用KOH梯度淋洗离子色谱法测定地表水和饮用水中ClO2-、BrO3-和ClO3-,在试验确定的条件下,3种离子与F-、Cl-、NO2-、NO3-、SO2-4、Br-、I-等7种离子分离度良好。 ClO2-、BrO3-、ClO3-在50．0μg/L～1000μg/L范围内线性良好,检出限分别为5．2μg/L、8．9μg/L、7．6μg/L,环境水样加标平行测定的RSD分别为2．1％～5．4％、4．1％～5．4％、2．5％～4．8％,两个质量浓度水平加标的平均回收率分别为93．7％～96．5％、90．3％～94．8％、98．7％～111％。     

Uranium bioassay and radioactive dust measurements at some uranium processing sites in Egypt--health effects

The safety of radiation workers in the uranium mining industry requires close and continuous monitoring of their working conditions. In this study, external radiation surveillance, radioactive dust monitoring and the bioassay of uranium were carried out in some processing sites. As dust represents one of the most important sources of radiation exposure in mills and mines, dust monitoring and bioassays were performed for a sample of workers on the production lines. The concentration of uranium in air ranged from 22.6 x 10(-7) to 11.1 x 10(-5) Bq cm-3, and the exposure levels ranged from 1 to 80 microSv h-1. Laser fluorimetric determination of uranium in urine samples showed concentrations in the range 8.4-29.2 micrograms L-1. Renal function parameters, such as serum creatinine and urea, and hematological parameters were determined in an attempt to correlate them with radiation exposure and the health status of the workers. Urine specimens collected from workers at the ore crushing and separation site showed elevated concentrations of uranium (up to 29.2 micrograms L-1) and a strong correlation between these concentrations and the registered serum creatinine. The mean uranium excretion in the investigated group was more than 20 times the occupational exposure decision level for urine uranium of 0.8 microgram L-1.     

微波消解—石墨炉原子吸收法测定农产品中痕量铅空白值的降低方法探讨

对于铅含量痕量级的水果、蔬菜等农产品,微波消解-石墨炉原子吸收法分析时称样量受到限制,其样品消解液中待测元素的总量很小,常出现空白值大于样品值的情况.本文就造成空白值高的原因及处理方法逐一进行了分析研究.