Performance optimisation of a passive sampler for monitoring hydrophobic organic pollutants in water

The performance of an integrative passive sampler that consists of a C18 Empore disk sorbent receiving phase fitted with low density polyethylene membrane was optimised for the measurement of time-weighted average concentrations of hydrophobic micropollutants in water. A substantial improvement of sampling characteristics including the rate of sampling and the sampling precision was achieved by decreasing the internal sampler resistance to mass transfer of hydrophobic organic chemicals. This was achieved by adding a small volume of n-octanol, a solvent with high permeability (solubility [times] diffusivity) for target analytes, to the interstial space between the receiving sorbent phase and the polyethylene diffusion-limiting membrane.     

Novel integrative passive samplers for the long-term monitoring of semivolatile organic air pollutants

Two types of passive sampler were developed for the long-term monitoring of semivolatile organic compounds (SOCs) in air. They consist of poly(dimethylsiloxane) (PDMS)-coated stir bars (type A) or silicone tubing (type B), acting as a solid receiving medium, enclosed in a heat-sealed low-density polyethylene (LDPE) membrane. These samplers combine the advantages of integrative passive sampling with those of analysing accumulated analytes by thermodesorption-GC-MS, whilst avoiding the use of solvents and expensive sample preparation and cleanup steps. The performance of these samplers was investigated for the integrative sampling of SOCs, including alpha- and gamma-hexachlorocyclohexanes, hexachlorobenzene, 2,4,4'-trichlorobiphenyl, 2,2',5,5'-tetrachlorobiphenyl and fluoranthene, in laboratory exposure experiments under controlled conditions. For both types of sampler, the uptake of all the analytes investigated was linear over an exposure period of 15 days. The sampling rates calculated ranged from 70 to 320 ml h(-1) (sampler A) and 630 to 4300 ml h(-1) (sampler B). The passive samplers are able to detect low time-weighted average air concentrations in the pg m(-3) range. The small, robust and inexpensive sampling devices were tested successfully for the long-term air monitoring of semivolatile organic pollutants in a polluted area over an exposure period of up to 28 days.     

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.     

Polar organic chemical integrative sampler (POCIS): application for monitoring organic micropollutants in wastewater effluent and surface water

In this paper, we discuss the advantages and drawbacks of POCIS (Polar Organic Chemical Integrative Sampler) for the evaluation of river water quality downstream of wastewater treatment plants. POCIS proved well adapted to sampling alkylphenols and several pharmaceuticals. Concentration factors and the decrease in limits of quantification, compared to grab water sample analyses, were significant except for hormones, β-blockers and bronchodilators. Promising preliminary results obtained in situ on deuterated atenolol used as a performance reference compound need to be confirmed in-lab. This work confirms that POCIS is a valuable tool for monitoring hydrophilic organic molecules in river and wastewaters.     

被动式个体采样器在环境监测中的应用

本文报道了用被动式个体采样器监测空气小常见污染物ＮＯ２,ＳＯ２．提出了样品测定之前对每种污染物的具体实验要求。对济南市有关场所空气进行了监测。总结了个体采样器的优点。     

A novel passive water sampler for in situ sampling of antibiotics

Passive water sampling has several advantages over active methods; it provides time-integrated data, can save on time and cost compared to active methods, and yield high spatial resolution data through co-deployment of simple, cheap units. However, one problem with many sampler designs in current use is that their uptake rates for trace substances of interest are flow-rate dependent, thereby requiring calibration data and other information to enable water concentrations to be derived from the mass per sampler. However, the 'family' of samplers employing the principle of diffusive gradients in thin films (DGT) provides an in situ means of quantitatively measuring labile species in aquatic systems without field calibration. So far, this technique has only been tested and applied in inorganic substances: metals, radionuclides, nutrients, etc. Design and applications of DGT to trace organic contaminants ('o-DGT') would be of widespread interest. This study describes the laboratory testing and performance characteristics of o-DGT, with the antibiotic sulfamethoxazole (SMX) as a model compound and XAD18 as the novel binding agent. o-DGT uptake of SMX increased with time and decreased with diffusion layer thickness, confirming the principle for SMX. XAD18 showed sufficiently high capacity for SMX for routine field applications. o-DGT measurement of SMX was independent of pH (6-9) and ionic strength (0.001-0.1 M) and not affected by flow rate once above static conditions. The diffusion coefficient of SMX in the sampler was measured using an independent diffusion cell and information is presented to allow temperature correction and derivation of aqueous concentrations from deployed samplers. The potential use of o-DGT for in situ measurement of pharmaceutical antibiotics is confirmed by this study and applications are briefly discussed.     

Uptake of some selected aquatic pollutants in semipermeable membrane devices (SPMDs) and the polar organic chemical integrative sampler (POCIS)

The uptake characteristics of semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs) were examined for mono, di and tributyltin, triphenyltin, pyrene, benzo[a]pyrene, 4-tert-butylphenol, 4-n-nonylphenol, PCBs 77 and 153, PBDE 47, lindane, triclosan and DDT. Exposure in a flow through system continued for 28 days with samplers removed every 7 days in order to study the relevant uptake kinetics. Uptake remained linear for POCISs with sampling rates (Rs) of up to 0.2 L d(-1). For SPMDs uptake varied from linear to approaching equilibrium with Rs values of up to 14 L d(-1). 7 out of 9 results for SPMDs could be explained by an empirical model (nonylphenol and lindane were exceptions). None of the four organo-tin compounds studied were detected in POCISs and only tributyltin was accumulated significantly by SPMDs. The establishment of these sampling rates allows the calculation of time weighted water concentrations for several important contaminants. Using presented methods, sampling rates and exposure conditions, theoretical detection limits for selected compounds by SPMDs were between 11-68 pg L(-1), which is well below the environment quality standard proposed for those compounds that are included in the European Water Framework Directive.     

A passive sampler for hydrogen sulfide

The silver nitrate/fluorescein mercuric acetate fluorimetric method for the measurement of atmospheric hydrogen sulfide has been adapted to passive sampling. Standard samplers have been tested and used in both indoor and outdoor environments. Sampler performance was not dependent on construction materials or sunlight intensity and gave similar results to active sampling. Two case studies were carried out, one in the Horniman Museum and its associated storage and study building, London, UK, and the other in the vicinity of a pulp and paper mill and geothermal area North Island, New Zealand. The detection limit of the samplers (50 ppt average for a one-week exposure) provides the opportunity to make measurements in a variety of locations provided exposure times are sufficiently long, i.e., up to one month in areas of low hydrogen sulfide concentration.     

Calibration of two passive air sampler configurations for monitoring concentrations of hexabromocyclododecanes in indoor air

While polyurethane foam (PUF) disk passive air samplers are employed increasingly to monitor persistent organic pollutants in indoor air, they essentially sample only the vapour phase. As a previous investigation of the vapour : particle phase partitioning of hexabromocyclododecanes HBCDs in (outdoor) air reported them to be present largely in the particulate phase, we monitored three offices using active air samplers. In each, approximately 65% of HBCDs were present in the vapour phase, suggesting PUF disk passive samplers are suitable for monitoring HBCDs in indoor air. Concentrations in the three offices (239-359 pg Sigma HBCD m(-3)) exceed substantially those reported in outdoor air from the United States (2.1-11 pg Sigma HBCD m(-3)), but are in line with outdoor air from Stockholm. The relative abundance of the three principal diastereomers in office air was closer to that found in technical HBCD formulations (i.e. predominantly gamma-HBCD) than in most US outdoor air samples. Time integrated air concentrations of alpha-, beta-, and gamma-HBCD were obtained for an office using a low volume sampler operated over a 50 d period alongside PUF disk samplers. This calibration exercise yielded the following passive air sampling rates for both a fully- and part-sheltered PUF disk sampler design: for alpha-, beta-, and gamma-HBCD, 0.87, 0.89, and 0.91 m3 d(-1) respectively (fully-sheltered) and 1.38, 1.54, and 1.55 m3 d(-1) respectively (part-sheltered). Deployment of the part-sheltered configuration yielded concentrations approximately 35% lower than those obtained using a high volume sampler, consistent with PUF disk samplers measuring primarily the vapour phase.     

Development of a novel passive sampling system for the time-averaged measurement of a range of organic pollutants in aquatic environments

A new sampling system has been developed for the measurement of time-averaged concentrations of organic micropollutants in aquatic environments. The system is based on the diffusion of targeted organic compounds through a rate-limiting membrane and the subsequent accumulation of these species in a bound, hydrophobic, solid-phase material. It provides a novel and robust solution to the problem of monitoring in situations where large temporal fluctuations in pollutant levels may occur. Accumulation rates are regulated by choice of diffusion-limiting membrane and bound solid-phase material and have been found to be dependent on the physico-chemical properties of individual target analytes. Two separate prototype systems are described: one suitable for the sampling of non-polar organic species with log octanol/water partition coefficient (log P) values greater than 4, the other for more polar species with log P values between 2 and 4. Both systems use the same solid-phase material (47 mm C18 Empore disk) as a receiving phase but are fitted with different rate-limiting membrane materials (polysulfone for the polar and polyethylene for the non-polar analytes). The two systems complement each other and together can be used for sampling a wider range of organic analytes than generally possible using current passive sampling techniques. Calibration data are presented for both devices. In each case, linear uptake kinetics were sustained, under constant conditions, for deployment periods of between 1 and 9 days. The effects of water temperature and turbulence on sampling rates have been quantitatively assessed. The performance of the system was further investigated by means of field exposures for one and two weeks in marine environments where calibrated samplers were used to determine the time-averaged concentrations of the polar biocides diuron and irgarol 1051. The quantitative results obtained using the passive sampler were compared with those obtained using spot sampling.     

水体有机污染物分析的研究进展

评述了水体有机污染物分析中GC、GC-MS、LC、GC-FTIR等方法的特性和适用范围,介绍了应用各种分析方法分析水体有机污染物的研究现状,提出了水体有机污染物分析的发展方向。     

A low-tech, low-cost passive sampler for the long-term monitoring of phosphate loads in rivers and streams

The concentration of dissolved reactive phosphorus (DRP) in rivers can change intermittently within minutes depending on the weather and water discharge (Q), or activities in the watershed. Accordingly, accurate estimation of the annual DRP load requires frequent sampling or even continuous monitoring, which is laborious and cost-intensive. We present the design and laboratory evaluation of a new, robust, low-cost, low-tech device based on passive samplers (P-traps). The traps use Fe-(oxy)hydroxide coated quartz sand as an adsorbent enclosed in a vertical grid of individual cells separated from the river water by filter membranes. They are inexpensive, easy to handle, resistant to repeated desiccation and immersion and exposable for several months. They permit estimation of discharge dependent time weighted average DRP concentrations (C-Q relationships) and annual P loads of rivers characterized by highly variable DRP concentrations with a relative accuracy of +/- 3%.     

Compact semi-automatic incident sampler for personal monitoring of volatile organic compounds in occupational air

Suddenly occurring and time limited chemical exposures caused by unintended incidents might pose a threat to many workers at various work sites. Monitoring of exposure during such occasional incidents is challenging. In this study a compact, low-weight and personal semi-automatic pumped unit for sampling of organic vapor phase compounds from occupational air during sporadic and suddenly occurring incidents has been developed, providing simple activation by the worker potentially subjected to the sudden occurring exposures when a trained occupational hygienist is not available. The sampler encompasses a tube (glass or stainless steel) containing an adsorbent material in combination with a small membrane pump, where the adsorbent is capped at both ends by gas tight solenoid valves. The sampler is operated by a conventional 9 V battery which tolerates long storage time (at least one year), and is activated by pulling a pin followed by automatic operation and subsequent closing of valves, prior to shipping to a laboratory. The adjustable sampling air flow rate and the sampling time are pre-programmed with a standard setting of 200 mL min(-1) and 30 min, respectively. The average airflow in the time interval 25-30 min compared to average airflow in the interval 2-7 min was 92-95% (n = 6), while the flow rate between-assay precisions (RSD) for six different samplers on three days each were in the range 0.5-3.7%. Incident sampler recoveries of VOCs from a generated VOC atmosphere relative to a validated standard method were between 95 and 102% (+/-4-5%). The valves that seal the sampler adsorbent during storage have been shown to prevent an external VOC atmosphere (500 mg m(-3)) to enter the adsorbent tube, in addition to that the sampler adsorbent is storable for at least one month due to absence of ingress of contaminants from internal parts. The sampler was also suitable for trapping of semi-volatile organophosphates.     

Investigation of polar organic chemical integrative sampler (POCIS) flow rate dependence for munition constituents in underwater environments

Munition constituents (MC) are present in aquatic environments throughout the world. Potential for fluctuating release with low residence times may cause concentrations of MC to vary widely over time at contaminated sites. Recently, polar organic chemical integrative samplers (POCIS) have been demonstrated to be valuable tools for the environmental exposure assessment of MC in water. Flow rate is known to influence sampling by POCIS. Because POCIS sampling rates (R_s) for MC have only been determined under quasi-static conditions, the present study evaluated the uptake of 2,4,6-trinitrotoluene (TNT), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and 2,4- and 2,6-dinitrotoluenes (DNT), by POCIS in a controlled water flume at 7, 15, and 30 cm/s in 10-day experiments using samplers both within and without a protective cage. Sampling rate increased with flow rate for all MC investigated, but flow rate had the strongest impact on TNT and the weakest impact on RDX. For uncaged POCIS, mean R_s for 30 cm/s was significantly higher than that for 7 cm by 2.7, 1.9, 1.9, and 1.3 folds for TNT, 2,4-DNT, 2,6-DNT, and RDX, respectively. For all MC except RDX, mean R_s for caged POCIS at 7 cm/s were significantly lower than for uncaged samplers and similar to those measured at quasi-static condition, but except for 2,6-DNT, no caging effect was measured at the highest flow rate, indicating that the impact of caging on R_s is flow rate-dependent. When flow rates are known, flow rate-specific R_s should be used for generating POCIS-derived time-averaged concentrations of MC at contaminated sites.     

海水中有机污染物的气相色谱－质谱法鉴定

本文采用一种简便的连续萃取装置．对海水中痕量有机物进行富集,大量的海水被萃取后,萃取物经干燥浓缩在毛细管气相色谱上进行了分离,并用质谱－计算机自动检索装置进行了定性鉴定,共确定出３６种组分。本方法的检测限为辛烷１０ｐｐｔ。     

焦化、染料废水和洹河水体的有机污染研究

采用GC/MS联用仪对焦化、染料废水和地表水中有机物进行定性、定量分析,探讨了污染源与受纳区的地表水中有机物种类和含量间的关系。     

Design and validation of a passive deposition sampler

A new, passive particle deposition air sampler, called the Einstein-Lioy Deposition Sampler (ELDS), has been developed to fill a gap in passive sampling for near-field particle emissions. The sampler can be configured in several ways: with a protective hood for outdoor sampling, without a protective hood, and as a dust plate. In addition, there is an XRF-ready option that allows for direct sampling onto a filter-mounted XRF cartridge which can be used in conjunction with all configurations. A wind tunnel was designed and constructed to test the performance of different sampler configurations using a test dust with a known particle size distribution. The sampler configurations were also tested versus each other to evaluate whether or not the protective hood would affect the collected particle size distribution. A field study was conducted to test the sampler under actual environmental conditions and to evaluate its ability to collect samples for chemical analysis. Individual experiments for each configuration demonstrated precision of the sampler. The field experiment demonstrated the ability of the sampler to both collect mass and allow for the measurement of an environmental contaminant i.e. Cr(6+). The ELDS was demonstrated to be statistically not different for Hooded and Non-Hooded models, compared to each other and the test dust; thus, it can be used indoors and outdoors in a variety of configurations to suit the user's needs.     

Validation of a passive atmospheric deposition sampler for polybrominated diphenyl ethers

An atmospheric deposition sampler was validated with respect to polybrominated diphenyl ethers (PBDEs), a compound group that is widely used as flame retardants in many types of consumer products. The deposition sampler consists of an adsorption cartridge that is connected to a glass funnel. Extraction tests with spiked cartridges using soxhlet extraction with acetone revealed recoveries of >80% for all of the investigated PBDEs. Once adsorbed, PBDEs are stable, as proven by extractions of spiked cartridges that were stored outdoors and collected after different periods of time, up to 84 days. High recoveries indicate that degradation of adsorbed PBDEs does not play a role under realistic field conditions. Bulk deposition rates of PBDEs were determined in a field test with 3 replicates, and a possible breakthrough of target compounds was assessed in the field using a second adsorption cartridge in series. No breakthrough of target compounds could be observed within a sampling period of 61 days, and a bulk deposition rate of approximately 1 ng m(-2) day(-1) for the sum of all analysed PBDEs was measured. The highest deposition rates were measured for octa-brominated congeners, followed by BDEs 99, 183, 153, and 47. Overall, the sampler was successfully validated regarding the atmospheric deposition of PBDEs.     

Reference materials for the monitoring of the aquatic environment--a review with special emphasis on organic priority pollutants

During recent years, the awareness of quality assurance and quality control in environmental analyses has constantly increased, especially due to the implementation of new guidelines and regulations at both the national and international level. Achieving comparable results by using certified reference materials is one of the primary concerns of the scientific community. As a result, there is a growing demand for certified reference materials to cover different matrices and pollutants. Moreover, these CRMs should be in close relationship to the determinants and target concentrations required by environmental bodies and European Directives as well. Supplementary information to this paper presents an inventory of reference materials available on the market from different suppliers against the priority pollutants listed in the Water Framework Directive. These CRMs cover matrices such as water, sediment and biota. The use of CRMs in relationship to appropriate analytical methods and relevant determinants is discussed and the need for matrix-CRMs, particularly for organic pollutants is emphasised. The use of proficiency testing schemes as an alternative for the lack of appropriate CRMs and future trends in the production of CRMs within the BCR framework are also discussed.     

Bacterial biosensors for rapid and effective monitoring of biodegradation of organic pollutants in wastewater effluents

Significant amounts of toxic substances which are hazardous to animals, plants, microorganisms, and other living organisms including humans are released annually into aquatic and terrestrial environments, mostly from improper wastewater discharges. Early detection of such pollutants in wastewater effluents and proper monitoring before their final release into the environment is therefore necessary. In this study, two whole-cell bacterial biosensors were constructed by transforming competent cells of Shigella flexneri and Shigella sonnei with pLUX plasmids and evaluated for their potential to monitor wastewater samples undergoing degradation by measuring bioluminescence response using a microplate luminometer. Both bacterial biosensors were found to be extremely sensitive to the wastewater samples, with different patterns, concomitant with those of the COD removals demonstrated at the different days of the degradation. Generally higher bioluminescence values were obtained at the later days of the degradation period compared to the initial values, with up to 571.76% increase in bioluminescence value obtained at day 5 for 0.1% (v/v) effluent concentration. Also, a steady decrease in bioluminescence was observed for the bacterial biosensors with increasing time of exposure to the wastewater effluent for all the sampling days. These biosensor constructs could therefore be applicable to indicate the bioavailability of pollutants in a way that chemical analysis cannot, and for in situ monitoring of biodegradation. This has great potential to offer a risk assessment strategy in predicting the level of bioremediation required during municipal wastewater treatment before their final discharge into the aquatic milieu.