Performance optimization of a membrane assisted passive sampler for monitoring of ionizable organic compounds in water

A thin-walled silicone rubber hollow fibre membrane has been developed as a passive sampler. The inside of the tube is filled with an aqueous solution at an appropriate pH. The tube is sealed at both ends and then immersed in a water sample. In order for the ionizable permeating compounds to be trapped in the aqueous receiving phase, the pH is adjusted such that the compounds are ionized and trapped. The major advantages are its simplicity, low cost and high selectivity, since only ionizable organic compounds are trapped. Additionally, the sampler uses no organic solvent. By adjusting the pH of the acceptor phase, it is possible to control the extraction process and whether the sampler is used in the kinetic or equilibrium regime. Since it is very selective, no further clean-up of the extract is required. The membrane assisted passive sampler has been tested for extraction of chlorophenols under laboratory conditions. The extraction process was found to be linear over a 72 h sampling period. Selectivity of the passive sampler in river water was demonstrated and the extraction process was independent of sample concentration, even at lower concentration levels of analytes. However, the sample matrix in some river water samples led to incomplete trapping, thereby reducing the amount trapped in the acceptor phase. Detection limits (three times signal to noise ratio) were dependant on sample matrix and type of detection system and ranged from 0.05 microg L(-1) to about 1 microg L(-1) with a UV photodiode detector in water samples from one river and 1.0 microg L(-1) to 20 microg L(-1) in another but with an ordinary UV detector. The enrichment factors in river water were 28 for 2-chlorophenol and 44 for 2,4-dichlorophenol over a 72 h sampling period. 4-chlorophenol was poorly extracted and its enrichment factor was 3.     

南水北调中线工程输水干线水质监测管理信息系统研究

介绍了由数据采集与传输子系统、数据库子系统、水质预警预报子系统、数据输出子系统和人机交互界面组成的南水北调中线工程输水干线的水质监测管理信息系统,根据该系统的实际需求,阐述了开发该系统应该具备的关键技术。     

环境监测实验室样品智能物流管理系统的设计研究

环境监测实验室样品管理是质量管理的重要环节,样品管理的智能化、信息化将大幅提升实验室的管理水平。通过分析当前监测实验室样品管理现状和不足,借鉴相关行业样品智能物流管理系统应用经验,结合江苏省环境监测中心新建的监测实验大楼,开展环境监测样品智能物流管理系统设计研究。提出,考虑环境监测样品接收、任务分配、样品交接、样品留存各个环节,以样品属性为基准进行样品管理系统设计;同时,结合物联网集成管控、气动传输和机器人输送技术,构建包含分布式存储工作站和密集型土壤样品库的样品智能物流管理系统,实现高效、智能、规范的样品管理目标。     

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.     

Turbidimetric determination of chloride in different types of water using a single sequential injection analysis system

A sequential injection analysis system for the turbidimetric determination of chloride in different types of water is proposed. The determination is based on the reaction of chloride with silver ions and the subsequent measurement of the turbidity caused by silver chloride precipitation. In this method, the use of toxic reagents, such as mercury thiocyanate, commonly employed in most spectrophotometric techniques for chloride determination, is avoided. The main feature of the developed system is the use of a single configuration to carry out the determination over a wide concentration range (2-400 mg L(-1)) by changing only the aspirated sample volume. This characteristic allows the determination of chloride in ground, surface and wastewaters using the same manifold. In addition, a considerable saving of precipitating reagent is achieved due to non-continuous consumption. The results obtained with the developed system were statistically indistinguishable from those of the potentiometric titration reference method. Relative standard deviations for ten consecutive injections were lower than 3.7%, with a sampling frequency of between 55 and 57 determinations per hour.     

海洋水质在线监测系统中硝酸盐测量方法比较

硝酸盐是海洋水质监测的重要指标,目前在海洋水质在线监测系统中搭载的硝酸盐在线分析仪的种类较多,采用的测量原理也不尽相同.选取了 3种采用不同测量方法的代表性硝酸盐分析仪[氯化钒还原比色法硝酸盐分析仪、二乙烯三胺五乙酸还原比色法(DTPA)硝酸盐分析仪、紫外分光光度法硝酸盐分析仪],结合各自的测量原理、化学试剂特性等,就...     

Assessment of vehicular pollution in Kolkata, India, using CALINE 4 model

Michigan water quality standards for public bathing beaches require local health departments to collect and analyze a minimum of three water samples for Escherichia coli during each sampling event. The geometric mean number of E. coli colonies is then compared to the 300 colonies per 100 ml standard to determine compliance. This article compares the results of the currently mandated procedure to a composite sampling method, whereby the three samples are mixed in equal volumes and analyzed once. This effectively replaces the geometric mean of the individual sample results with an arithmetic mean. Although arithmetic means are more affected by outliers, this sensitivity to high concentrations is more health conservative than the geometric mean. During the 2007 sampling season, nine bathing beaches were monitored once each week. Three individual point samples and a composite sample were analyzed for each sampling event. No statistically significant differences in bacteria concentrations were found between composite sample analysis and the arithmetic mean of individual point sample analyses. No violations were detected in the 2007 sampling season, so using historical data, a retrospective analysis was performed on samples gathered at nine bathing beaches in Kalamazoo County, Michigan during the years 2001–2007. The arithmetic mean of the three samples taken at each site served as a surrogate composite sample. The benefits of compositing the three samples were investigated assuming a 2/3 reduction in analytical costs. In the traditional sampling method, three individual samples were obtained and analyzed once in every 3-week period during the summer season, whereas compositing was simulated by taking the arithmetic mean of each week’s results. The results of this retrospective cost analysis indicates that ten to 14 violations would have been missed using the less frequent traditional sampling and analysis methodology. Composite sampling is a cost-saving alternative to traditional sampling techniques that can be more protective of public health, particularly when the savings are applied to increased numbers of samples in time or space.     

挥发性有机物污染土壤样品采样方法比较

以苯系物污染土壤样品的采集为例,比较了4种不同采样方法导致样品检测结果的差异。其中,方法 1将样品装填至广口瓶内并压实密封,方法2采用非扰动采样器采集10 g样品后转移至加有10 mL甲醇保护剂的Vial瓶中密封,方法 3用非扰动采样器采集10 g样品后直接将其密封于采样器内,方法 4用Encore采样器采样后将其密封于采样器内。结果表明,方法 2采集样品的检出率最高,其余3种方法的差异不明显,方法 2采集样品的检出结果 71%以上都大于其余3种方法。而且,对于挥发性较强的苯与甲苯,以方法 2采集的样品91%以上都大于其余3种方法,最大及平均检出浓度高出2~3个数量级。5种不同土质样品检测结果表明,对于有机质含量较低的细砂,方法2的最高及平均检出浓度均高于其余3种方法 1~3个数量级,差异随土壤有机质含量的升高而降低。可见,对于苯系物及挥发性强于苯系物的其他挥发性有机物污染土壤样品的采集,方法 2效果最优,可指定为VOCs污染场地土壤样品的采样方法。     

Temporal moments analysis of preferential solute transport in soils

Temporal moments analysis of solute breakthrough curves is used to investigate the preferential leaching of chloride, nitrate and phosphate through an Australian soil. Recent studies have shown that current models and methods do not adequately describe the leaching of nutrients through soil, often underestimating the risk of groundwater contamination by surface-applied chemicals, and overestimating the concentration of resident solutes. This inaccuracy results primarily from ignoring soil structure and non-equilibrium between soil constituents, water and solutes. Therefore simple models are required to accurately characterise solute transport in natural and agricultural soils under non-equilibrium conditions. A multiple sample percolation system, consisting of 25 individual collection wells was constructed to study the effects of localised soil heterogeneities on the transport of nutrients (NO₃ ^–, Cl^–, PO₄ ^{3 –}) in the vadose zone of an agricultural soil predominantly dominated by clay. Using data collected from the multiple sample percolation experiments, this paper compares and contrasts the performance of temporal moments analysis with two mathematical models for predicting solute transport, the advective-dispersion model with a reaction term (ADR) and a two-region preferential flow model (TRM) suitable for modelling preferential transport. The values for solute transport parameters predicted by temporal moments analysis were in excellent agreement with experimental data and results from ADR and TRM. It is concluded that temporal moments analysis when applied with other physical models such as the ADR and TRM, provide an excellent means of obtaining values for important solute transport parameters and gaining insight of preferential flow. These results have significant ramifications for modelling solute transport and predicting nutrient loadings.     

环境空气中挥发性有机物监测技术细化研究

真空罐/气相色谱-质谱法是我国目前用于环境空气中挥发性有机物（VOCs）监测的主要方法。对该方法的采样前及采样环节的技术细节（包括流量控制器和过滤器的校准检查,采样罐的性能检查,样品的采集、运输及保存）,以及实验室分析环节的技术细节（包括色谱柱的选择,内标物的选择,湿度及气体稀释仪对分析结果的影响,标准曲线绘制方式和系统性能优劣的判断）进行讨论和分析。并针对以上技术细节提出解决方案和注意事项,以期为分析人员提供技术参考。     

Further studies using X-ray fluorescence to sample lead contaminated carpeted surfaces

The sampling of carpeted surfaces to test for lead contamination primarily focuses upon vacuum techniques. Vacuum sampling techniques, however, require time-consuming, expensive laboratory analysis of the dusts obtained and are unable to determine total lead load on the carpet. X-ray fluorescence (XRF) analysis is an on-site, inexpensive, non-destructive, quick technique for predicting metals levels in a variety of media, such as water, soil, filter paper and painted surfaces. A 1992 study of the feasibility of XRF to analyze for lead and soil loadings on carpeted surfaces indicated that XRF can detect lead at a low enough level to warrant further study. This paper expands this earlier study and developes lead and soil loading calibration curves for three different carpet types based upon XRF lead L-beta peak areas and XRF iron and barium K-alpha peak and background areas. Results indicate that variation in the data can be reduced through modifications of the XRF analysis technique, thus reducing the statistically determined detection level, and that carpet type does affect the calibration. Detection levels of approximately 70 mg/m² for lead and 5 g/m² for soil were obtained. Overall, good agreement was found between results of this study and the earlier one. XRF shows excellent potential for quantitative analysis of lead on carpeted surfaces.     

Application of portable gas chromatography-photo ionization detector combined with headspace sampling for field analysis of benzene, toluene, ethylbenzene, and xylene in soils

A method based on headspace (HS) sampling coupling with portable gas chromatography (GC) with photo ionization detector (PID) was developed for rapid determination of benzene, toluene, ethylbenzene, and xylenes (BTEX) in soils. Optimal conditions for HS gas sampling procedure were determined, and the influence of soil organic matter on the recovery of BTEX from soil was investigated using five representative Chinese soils. The results showed that the HS-portable-GC-PID method could be effectively operated at ambient temperature, and the addition of 15 ml of saturated NaCl solution in a 40-ml sampling vial and 60 s of shaking time for sample solution were optimum for the HS gas sampling procedure. The recoveries of each BTEX in soils ranged from 87.2 to 105.1 %, with relative standard deviations varying from 5.3 to 7.8 %. Good linearity was obtained for all BTEX compounds, and the detection limits were in the 0.1 to 0.8 μg kg^?1 range. Soil organic matter was identified as one of the principal elements that affect the HS gas sampling of BTEX in soils. The HS-portable-GC-PID method was successfully applied for field determination of benzene and toluene in soils of a former chemical plant in Jilin City, northeast China. Considering its satisfactory repeatability and reproducibility and particular suitability to be operated in ambient environment, HS sampling coupling with portable GC-PID is, therefore, recommended to be a suitable screening tool for rapid on-site determination of BTEX in soils.     

浮游动物DNA宏条形码多样性监测采样方法研究

浮游动物是水生生态系统的重要组成部分,对环境因子敏感,是水生生态健康状况的重要指示生物.基于传统形态学的浮游动物调查方法无法鉴定桡足类幼体,难以准确了解浮游动物群落组成.DNA宏条形码技术基于DNA序列差异识别物种,为浮游动物群落组成的准确解析提供了新方法.比较了不同浮游动物采样方法(直接过滤法和网富集法)对浮游动物D...     

Field cryofocussing hydride generation applied to the simultaneous multi-elemental determination of alkyl-metal(loid) species in natural waters using ICP-MS detection

Two hydride generation manifold systems, utilizing flow injection and cryotrapping techniques for alkyl-metal(loid) speciation analysis in natural waters, are described in this paper. They provide shipboard capacity for simultaneous derivatization of analytes with NaBH4 and cryotrapping of the generated products in a field packed column at -196 degrees C. The first system is a large-volume hydride generator, using a reagent-injection flow technique as a flow batch type, that has been fully optimized and applied to the simultaneous detection of alkylated species in estuarine waters. The technique permits the analysis of a large volume sample (0.5-11) at a sampling rate of 3 h-1. The second is an online continuous flow hydride generator. A sampling rate of 3-12 h-1 can be achieved with samples of 0.1-0.51. In addition, shipboard operation eliminates major problems related to sample pretreatment, transport and storage. Ultra-trace multi-element determination is finally performed in the laboratory by cryogenic GC hyphenated with ICP-MS. Routine detection limits of 0.5-10 pg (as metal) for 0.51 water samples were achieved for the selected alkyl-metal(loid) species of arsenic, germanium, mercury and tin. Concentrations of various species, obtained from water samples taken from the Rhine estuary, are also presented. These species include alkylated arsenic compounds, other than methyl derivatives, that have been tentatively identified and are reported here for the first time.     

Sampling The Soil In Long-Term Forest Plots: The Implications Of Spatial Variation

Long-term monitoring of forest soils as part of a pan-European network to detect environmental change depends on an accurate determination of the mean of the soil properties at each monitoring event. Forest soil is known to be very variable spatially, however. A study was undertaken to explore and quantify this variability at three forest monitoring plots in Britain. Detailed soil sampling was carried out, and the data from the chemical analyses were analysed by classical statistics and geostatistics. An analysis of variance showed that there were no consistent effects from the sample sites in relation to the position of the trees. The variogram analysis showed that there was spatial dependence at each site for several variables and some varied in an apparently periodic way. An optimal sampling analysis based on the multivariate variogram for each site suggested that a bulked sample from 36 cores would reduce error to an acceptable level. Future sampling should be designed so that it neither targets nor avoids trees and disturbed ground. This can be achieved best by using a stratified random sampling design.     

Assessing temporal representativeness of water quality monitoring data

The effectiveness of different monitoring methods in detecting temporal changes in water quality depends on the achievable sampling intervals, and how these relate to the extent of temporal variation. However, water quality sampling frequencies are rarely adjusted to the actual variation of the monitoring area. Manual sampling, for example, is often limited by the level of funding and not by the optimal timing to take samples. Restrictions in monitoring methods therefore often determine their ability to estimate the true mean and variance values for a certain time period or season. Consequently, we estimated how different sampling intervals determine the mean and standard deviation in a specific monitoring area by using high frequency data from in situ automated monitoring stations. Raw fluorescence measurements of chlorophyll a for three automated monitoring stations were calibrated by using phycocyanin fluorescence measurements and chlorophyll a analyzed from manual water samples in a laboratory. A moving block bootstrap simulation was then used to estimate the standard errors of the mean and standard deviations for different sample sizes. Our results showed that in a temperate, meso-eutrophic lake, relatively high errors in seasonal statistics can be expected from monthly sampling. Moreover, weekly sampling yielded relatively small accuracy benefits compared to a fortnightly sampling. The presented method for temporal representation analysis can be used as a tool in sampling design by adjusting the sampling interval to suit the actual temporal variation in the monitoring area, in addition to being used for estimating the usefulness of previously collected data.     

Development of an integrative passive sampler for the monitoring of organic water pollutants

The development of convenient and competitive devices and methods for monitoring of organic pollutants in the aquatic environment is of increasing interest. An integrative passive sampling system has been developed which consists of a solid poly(dimethylsiloxane) (PDMS) material (tube or rod), acting as hydrophobic organic receiving phase, enclosed in a water-filled or an air-filled low-density polyethylene (LDPE) membrane tubing. These samplers enable the direct analysis of the pollutants accumulated during exposure in the receiving phase by thermodesorption-GC/MS, avoiding expensive sample preparation and cleanups. The capabilities of these sampling devices were studied for the sampling of 20 persistent organic pollutants (chlorobenzenes, hexachlorocyclohexanes, p,p'-DDE, PAHs, and PCBs) in laboratory exposure experiments. For the three sampler designs investigated the uptake of all target analytes was integrative over exposure periods up to 9 days (except PCB 101). The determined sampling rates range from 4 to 1340 microl h(-1) for the water-filled samplers and from 20 to 6360 microl h(-1) for the air-filled ones, respectively. The sampling rate of the analytes is dependent on their molecular weight, partition between water and sampler media (PDMS, polyethylene, water, air) and also of the sampler design. The passive samplers enable the estimation of time-weighted average (TWA) concentration of water pollutants in the lower ng l(-1) to pg l(-1) range.     

Energy-dispersive X-ray fluorescence systems as analytical tool for assessment of contaminated soils

To determine the heavy metal content in soil samples at contaminated locations, a static and time consuming procedure is used in most cases. Soil samples are collected and analyzed in the laboratory at high quality and high analytical costs. The demand by government and consultants for a more dynamic approach and by customers requiring performances in which analyses are performed in the field with immediate feedback of the analytical results, is growing. Especially during the follow-up of remediation projects or during the determination of the sampling strategy, field analyses are advisable. For this purpose four types of ED-XRF systems, ranging from portable up to high performance laboratory systems, have been evaluated. The evaluation criteria are based on the performance characteristics for all the ED-XRF systems such as limit of detection, accuracy and the measurement uncertainty on one hand, and also the influence of the sample pretreatment on the obtained results on the other hand. The study proved that the field portable system and the bench top system, placed in a mobile van, can be applied as field techniques, resulting in semi-quantitative analytical results. A limited homogenization of the analyzed sample significantly increases the representativeness of the soil sample. The ED-XRF systems can be differentiated by their limits of detection which are a factor of 10 to 20 higher for the portable system. The accuracy of the results and the measurement uncertainty also improved using the bench top system. Therefore, the selection criteria for applicability of both field systems are based on the required detection level and also the required accuracy of the results.     

Verification of a depth-integrated sample arm as a means to reduce solids stratification bias in urban stormwater sampling

A new water sample collection system was developed to improve representation of solids entrained in urban stormwater by integrating water-quality samples from the entire water column, rather than a single, fixed point. The depth-integrated sample arm (DISA) was better able to characterize suspended-sediment concentration and particle size distribution compared to fixed-point methods when tested in a controlled laboratory environment. Median suspended-sediment concentrations overestimated the actual concentration by 49 and 7% when sampling the water column at 3- and 4-points spaced vertically throughout the water column, respectively. Comparatively, sampling only at the bottom of the pipe, the fixed-point overestimated the actual concentration by 96%. The fixed-point sampler also showed a coarser particle size distribution compared to the DISA which was better able to reproduce the average distribution of particles in the water column over a range of hydraulic conditions. These results emphasize the need for a water sample collection system that integrates the entire water column, rather than a single, fixed point to properly characterize the concentration and distribution of particles entrained in stormwater pipe flow.     

C OD在线分析仪比对中应注意的问题

分析了COD在线分析仪和实验室比对结果人为差异的原因是样品不均匀,在线分析仪取样装置滤过,取样层面和采样方式以及沉淀消除的方法不同造成的.提出应在相同的地点、层面和同一容器取样,用相同沉淀消除方法去除样品中氯离子干扰,保证两方法比对中使用水样的一致均匀,使测试结果正确可信.