Measurement of environmental pollutants using passive sampling devices--a commentary on the current state of the art

Passive sampling devices have been used since the 1970s to measure time-weighted average (TWA) or equilibrium concentrations of pollutants in various environmental matrices (e.g. air, soils and sediments and water). In recent years the popularity of using such samplers has increased and the technology in now well established for the measurement of atmospheric pollutants. This sector has a long experience of using passive samplers in the short- and long-term assessment of air quality in the local environment and on a global scale (e.g. within the United Nations Stockholm Convention on the trans-boundary movement of persistent organic pollutants (POPs) where large networks of samplers on a continental scale have been established). In comparison, the use of passive samplers for monitoring the aquatic environment has been slower to take off. There has, however, been a recent research drive to develop devices for measuring the wide range of pollutants that can be found in environmental waters (e.g. ground, surface, and marine). It is now being recognised that passive samplers can play a valuable role in monitoring water quality within a legislative framework such as the European Union's Water Framework Directive (WFD). The data from these devices can be used alongside the results obtained from conventional spot or bottle sampling to improve risk assessments and to inform decisions on undertaking potentially expensive remedial actions. Such monitoring techniques may have uses within the European Registration, Evaluation, Authorisation & restriction of CHemicals (REACH) Directive and the forthcoming European Marine Strategy Directive. It is expected that the aquatic monitoring sector will follow a transition similar to that which occurred in air monitoring where data obtained from passive samplers can use used within a legal framework. There has also been increased interest in extending the role of passive samplers to both the measurement of equilibrium concentrations and investigating the movement and release of the dissolved fraction of various pollutants in the pore water of sediments and soils.     

Use of macroinvertebrate assemblages for assessing performance of stabilization ponds treating effluents from sugarcane and molasses processing

Wastewater discharge from sugarcane processing is a significant pollutant of tropical aquatic ecosystems. For most developing countries, monitoring of the level of pollutants is done mostly through chemical analysis, but this does not reflect potential impacts on aquatic assemblages. In addition, laboratory facilities for accurate concentration measurements are often not available for regular monitoring programs. In this study, we investigated the use of benthic macroinvertebrates for biological monitoring in western Kenya. Benthic macroinvertebrates were sampled in stabilization ponds treating wastewater from sugarcane- and molasses-based processing plants to assess their composition and abundance in relation to different concentrations of chemical variables. Optimum concentrations and tolerance values were identified for various taxa, and a biotic index was developed that combined tolerance values (ranked between 0 and 10) for the various macroinvertebrate taxa. A succession in composition and distribution of macroinvertebrate taxa was observed from the inlet to the outlet of the pond systems. Diptera dominated in the first ponds that had high concentrations of chemical oxygen demand (COD), biological oxygen demand (BOD₅), and nutrients, while intolerant Ephemeroptera, Plecoptera, and Trichoptera (EPT) appeared as the concentrations dropped in subsequent ponds. The effluent quality was classified as “good,” “fair,” and “poor,” corresponding with biotic index value ranges 0–3.50, 3.51–6.50, and 6.51–10, respectively. During validation, the index grouped sites with respect to levels of measured environmental variables. The study revealed that the developed biotic index would help in monitoring the quality of sugarcane processing and molasses effluents before release into recipient aquatic ecosystems, replacing the need for costly chemical analyses.     

Monitoring of trace metals and pharmaceuticals as anthropogenic and socio-economic indicators of urban and industrial impact on surface waters

The research focuses on the monitoring of trace metals and pharmaceuticals as potential anthropogenic indicators of industrial and urban influences on surface water. This study includes analysis of tracers use for the indication of water pollution events and discussion of the detection method of these chemicals. The following criteria were proposed for the evaluation of indicators: specificity (physical chemical properties), variability (spatial and temporal), and practicality (capacity of the sampling and analytical techniques). The combination of grab and passive water sampling (i.e., diffusive gradient in the thin film and polar organic chemical integrated samplers) procedure was applied for the determination of dissolved and labile trace metals (Ag, Cd, Cr, Cu, Ni, Pb, and Zn) and pharmaceuticals (carbamazepine, diazepam, paracetamol, caffeine, diclofenac, and ketoprofen). Samples were analyzed using inductively coupled plasma mass spectrometry (MS; trace metals) and liquid chromatography–tandem MS electrospray ionization+/? (pharmaceuticals). Our results demonstrate the distinctive spatial and temporal patterns of trace elements distribution along an urban watercourse. Accordingly, two general groups of trace metals have been discriminated: “stable” (Cd and Cr) and “time varying” (Cu, Zn, Ni, and Pb). The relationship Cd???Cu?>?Ag?>?Cr?≥?Zn was proposed as an anthropogenic signature of the industrial and urban activities pressuring the environment from point sources (municipal wastewaters) and the group Pb–Ni was discussed as a relevant fingerprint of the economic activity (industry and transport) mainly from non-point sources (runoff, atmospheric depositions, etc.). Pharmaceuticals with contrasting hydro-chemical properties of molecules (water solubility, bioaccumulation, persistence during wastewater treatment processes) were discriminated on conservative, labile, and with combined properties in order to provide information on wastewater treatment plant efficiency, punctual events (e.g., accidents on sewage works, runoff), and uncontrolled discharges. Applying mass balance modeling, medicaments were described as relevant socio-economic indicators, which can give a picture of main social aspects of the region.     

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.     

Baseline ambient gaseous ammonia concentrations in the Four Corners area and eastern Oklahoma, USA

Ambient ammonia monitoring using Ogawa passive samplers was conducted in the Four Corners area and eastern Oklahoma, USA during 2007. The resulting data will be useful in the multipollutant management of ozone, nitrogen oxides, and visibility (atmospheric regional haze) in the Four Corners area, an area with growing oil/gas production and increasing coal-based power plant construction. The passive monitoring data also add new ambient ammonia concentration information for the U.S. and will be useful to scientists involved in present and future visibility modeling exercises. Three week integrated passive ammonia samples were taken at five sites in the Four Corners area and two sites in eastern Oklahoma from December, 2006 through December, 2007 (January, 2008 for two sites). Results show significantly higher regional background ammonia concentrations in eastern Oklahoma (1.8 parts per billion (ppb) arithmetic mean) compared to the Four Corners area (0.2 ppb arithmetic mean). Annual mean ammonia concentrations for all Four Corners area sites for the 2007 study ranged from 0.2 ppb to 1.5 ppb. Peak ambient ammonia concentrations occurred in the spring and summer in both areas. The passive samplers deployed at the Stilwell, Oklahoma site compared favorably with other passive samplers and a continuous ammonia monitoring instrument.     

Field comparison of passive samplers versus UV-photometric analyser to measure surface ozone in a Mediterranean area

The aim of the present work is to compare the performance of the Radiello passive sampler versus UV-photometric ozone analyser to measure surface ozone in a Mediterranean Spanish coastal area. The comparison presented considers precision, bias, accuracy, selectivity, detection limit, cost and applicability. For assessing precision, co-located samplers were exposed in duplicate in two reference-sampling sites, beside UV-photometric ozone analyser. Bias was calculated comparing results of passive samplers exposed in three reference-sampling sites and two contrast-sampling sites with the measurements given by the reference analysers. Accuracy was calculated following the EN 482:1994 standard. The limit of detection was calculated as 3 times the standard deviation of the blanks in a batch of passive samplers. The compared Radiello passive samplers give a precision of 5.2%, a bias of 13.8%, an accuracy of 20.5% and a limit of detection of 12.6 microg m(-3). The selectivity and applicability of this methodology is in both aspects successful. Surface ozone levels measured with passive samplers were comparable with the averaged values measured with the reference analyser both in the reference-sampling sites and in the contrast-sampling sites.     

Nutrient baselines of Cerrado low-order streams: comparing natural and impacted sites in Central Brazil

The aquatic systems responsible for water supply in the Brazilian Federal District (FD) have been threatened by anthropogenic pressures, especially considering the expressive demographic increase in the region during the last decades. The purposes of this research were: (a) to assess the water quality in streams located in the FD by monitoring physical–chemical variables; (b) to define baselines for these variables among different ecological status categories. The 14 investigated streams were sampled between 2006 and 2009, in the dry (August–September, 2006, 2008, 2009) and rainy (March–April, 2008, 2009) seasons. All sampling sites were classified in four categories (“very impacted”, “impacted”, “in transition” and “natural”) using an adaptation of a rapid habitat assessment protocol. Differences in water quality among sites were generally well predicted in the four ecological status categories defined by the protocol, which showed a gradient in nutrient concentrations from reference sites classified as “natural” (medians: electrical conductivity?=?7.3 μS cm^?1; nitrate?=?0.040 mg L^?1; ammonium?=?0.039 mg L^?1; soluble reactive phosphorus (SRP)?=?<0.001 mg L^?1; total phosphorus (TP)?=?0.006 mg L^?1; ) to those classified as “very impacted” (medians: electrical conductivity?=?87.7 μS cm^?1; nitrate?=?0.247 mg L^?1; ammonium?=?0.219 mg L^?1; SRP?=?0.010 mg L^?1; TP?=?0.035 mg L^?1). Point sources inputs were the main factor for water quality deterioration. The nutrient baselines reported were relatively low when compared to data collected from reference areas in Brazil (e.g., São Paulo State) or temperate regions, especially for TP.     

Isotopic evidence of natural uranium and spent fuel uranium releases into the environment

Uranium and plutonium isotopes were measured in soils, sediments and waters in an area subject to the past and present discharges from the uranium conversion plant of Malvési (France). The isotopes (236)U and (239)Pu are well known activation products of uranium and they prove to be powerful tracers of spent fuel releases in soils and sediments. On the other hand (234)U and (238)U activities measured in waters can be used to distinguish between releases and background uranium sources. Such findings contribute to improve the monitoring of the actinides releases by nuclear fuel facilities (mining sites, conversion, enrichment and fuel plants, reprocessing plants).     

Evaluation of chromium contamination in water, sediment and vegetation caused by the tannery of Jijel (Algeria): a case study

In order to evaluate the chromium (Cr) contamination due to the discharge of waste waters from the tannery of Jijel in the Mouttas river (Algeria), samples of water, sediment and vegetation (Agropyrum repens) were collected during a 6 month period in four stations located upstream (control) and downstream of the tannery. The total chromium was measured by atomic absorption spectrophotometry. Metal inputs were clearly related to effluent discharges from the tannery into the river. Although only traces of chromium were found in water samples upstream of the tannery, very high concentrations (up to 860 times higher) were detected downstream. The contamination was not limited to water of Mouttas River because a same difference in chromium concentrations was also found in sediments and plants Agropyrum repens that were sampled upstream and downstream of the tannery. This work showed that the treatment process used in the wastewater treatment plant of the tannery of Jijel is not able to remove the chromium detected in their influents. The occurrence and chromium levels detected in the aquatic environment represent a major problem concerning drinking water resources and environmental protection of water bodies.     

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.     

工业园区水污染源精细化管控系统的应用

针对工业园区污水排放监管问题,以北京某园区为例,提出了水污染源精细化管控方案。按照多级防控的思路,在企业级、管网级、园区级建成在线监测系统和精细化管控平台,实现园区水环境监管的全覆盖,有效监控企业排污动态,实时掌握园区污水排放状况,为企业、园区管理部门和环保管理部门提供决策支持。     

The distribution of triclosan and methyl-triclosan in marine sediments of Barker Inlet, South Australia

In this work, we investigated the transport and burial of triclosan and its methylated derivative, in surface sediments near the mouth of Barker Inlet in South Australia. The most likely source of this commonly used bactericide to the area is a wastewater outfall discharging at the confluence of the inlet with marine waters. Triclosan was detected in all samples, at concentrations (5-27 μg kg(-1)) comparable to values found in other surface sediments under the influence of marine wastewater outfalls. Its dispersal was closely associated with fine and organic-rich fractions of the sediments. Methyl-triclosan was detected in approximately half of the samples at concentrations <11 μg kg(-1). The occurrence of this compound was linked to both wastewater discharges and biological methylation of the parent compound. Wastewater-borne methyl-triclosan had a smaller spatial footprint than triclosan and was mostly deposited in close proximity to the outfall. In situ methylation of triclosan likely occurs at deeper depositional sites, whereas the absence of methyl-triclosan from shallower sediments was potentially explained by photodegradation of the parent compound. Based on partition equilibrium, a concentration of triclosan in the order of 1 μg L(-1) was estimated in sediment porewaters, a value lower than the threshold reported for harmful effects to occur in the couple of species of marine phytoplankton investigated to date. Methyl-triclosan presents a greater potential for bioaccumulation than triclosan, but the implications of its occurrence to aquatic ecosystem health are difficult to predict given the lack of ecotoxicological data in the current literature.     

The use of multiple tracers for tracking wastewater discharges in freshwater systems

The assessment of potential impacts of wastewater effluent discharges in freshwater systems requires an understanding of the likely degrees of dilution and potential zones of influence. In this study, four tracers commonly present in wastewater effluents were monitored to compare their relative effectiveness in determining areas in freshwater systems that are likely to be impacted by effluent discharges. The four tracers selected were the human pharmaceutical carbamazepine, anthropogenic gadolinium, fluorescent-dissolved organic matter (fDOM), and electrical conductivity (EC). The four tracers were monitored longitudinally in two distinct freshwater systems receiving wastewater effluents, where one site had a high level of effluent dilution (effluent <1 % of total flow) and the other site had a low level of effluent dilution (effluent ～50 % of total flow). At both sites, the selected tracers exhibited a similar pattern of response intensity downstream of discharge points relative to undiluted wastewater effluent, although a number of anomalies were noted between the tracers. Both EC and fDOM are non-specific to human influences, and both had a high background response, relative to the highly sensitive carbamazepine and anthropogenic gadolinium responses, although the ease of measuring EC and fDOM would make them more adaptable in highly variable systems. However, the greater sensitivity and selectivity of carbamazepine and gadolinium would make their combination with EC and fDOM as tracers of wastewater effluent discharges highly desirable to overcome potential limitations of individual tracers.     

Concentrations of heavy metals and aquatic macrophytes of Govind Ballabh Pant Sagar an anthropogenic lake affected by coal mining effluent

Five heavy metals Cu, Cd, Mn, Pb and Hg were found in high concentration from three sampling sites located in Asia’s largest anthropogenic lake Govind Ballabh Pant GBP Sagar. Concentrations of these heavy metals were measured in Water, bottom sediment and in different parts of the aquatic macrophytes collected from the reservoir. Plants collected from the lake were Eichhornia crassipes, Azolla pinnata, Lemna minor, Spirodela polyrrhiza, Potamogeton pectinatus, Marsilea quadrifolia, Pistia stratiotes, Ipomea aquqtica, Potamogeton crispus, Hydrilla verticillata and Aponogeton natans. These plants have shown the high concentrations of Cu, Cd, Mn, Pb and Hg in their different parts due to bioaccumulation. In general plant roots exhibited higher concentrations of heavy metals than corresponding sediments. A comparison between different morphological tissues of the sampled plants reveled the metal concentration in following order roots > leaves. Analyses of bottom sediment indicated the higher concentrations of Cd, Mn, Cu and Pb. Strong positive correlations were obtained between the metals in water and in plants as well as between metal in sediment and in plants. Indicating the potential of these plants for pollution monitoring of these metals.     

Occurrence of PAHs and PCBs in the Alna River, Oslo (Norway)

Thirty two polychlorinated biphenyl congeners (PCBs), hexachlorobenzene (HCB) and pentachlorobenzene (PeCB) were analysed in passive sampler extracts from surface water-exposed semipermeable membrane devices (SPMDs) and in bed sediment samples from a small urban watercourse, the River Alna (Oslo, Norway). Performance reference compound-corrected data from the passive samplers deployed at three sites along the river were used to track PCB contamination in the overlying water. SPMDs were able to detect an increase in dissolved PCB concentrations at the site furthest downstream that was corroborated by bed sediment concentrations. In comparison, no major increase in concentration of HCB, PeCB or PAHs could be observed. Comparison of passive sampling-based overlying water concentrations with total concentrations measured in bed sediments supports the possibility of further PCB sources upstream of the study area. Diagnostic PAH ratios (from SPMDs) and PCB congener pattern (from sediments) were used in an attempt to identify possible contaminant sources to the Alna River. Selected PAH diagnostic ratios support a multiple emission source scenario and demonstrate the complexity of identifying specific sources of these compounds to surface waters. PCB congener patterns in sediments from all three sites tend to indicate a source of highly chlorinated PCBs (of the Archlor 1260 type) and either a source of lower chlorinated PCBs or the less-likely occurrence of dechlorination in sediment. Information collected during the present screening study also confirms the Alna River as a continuous source of PCBs to the Oslofjord.     

Evaluation of Potential Molecular Markers for Urban Stormwater Runoff

Source specificity and persistence of several sulfur-polycyclic aromatic hydrocarbons (S-PAHs), nitro-PAHs (N-PAHs), and triphenylene were examined via analyses of stormwater runoff and wastewater effluent samples and spiked samples upon exposure to sunlight. Samples were collected during the 1997/1998 wet weather season from two major storm channels and four major wastewater treatment plants in southern California. Among the target compounds examined, 2-(4-morpholinyl)benzothiazole, dibenzothiophene, and triphenylene/chrysene were detected in storm runoff only. However, 2-(4-morpholinyl)benzothiazole appeared to degrade rapidly in seawater and sediment after sunlight exposure, which might impede its use as a runoff indicator. Dibenzothiophene and triphenylene also degraded quickly in sunlight-exposed seawater samples, but remained fairly abundant in sediments after six months of exposure to sunlight. They are by far the most promising candidates of urban runoff markers based on the criteria of abundance, source specificity, and persistence, although more research efforts are needed to ensure that no other sources would also contribute significantly to their presence in the aquatic environment.     

Highway runoff quality in Ireland

Highway runoff has been identified as a significant source of contaminants that impact on the receiving aquatic environment. Several studies have been completed documenting the characteristics of highway runoff and its implication to the receiving water in the UK and elsewhere. However, very little information is available for Ireland. The objective of this study was to determine the quality of highway runoff from major Irish roads under the current road drainage design and maintenance practice. Four sites were selected from the M4 and the M7 motorways outside Dublin. Automatic samplers and continuous monitoring devices were deployed to sample and monitor the runoff quality and quantity. More than 42 storm events were sampled and analysed for the heavy metals Cd, Cu, Pb, and Zn, 16 US EPA specified PAHs, volatile organic compounds including MTBE, and a number of conventional pollutants. All samples were analysed based on the Standard Methods. Significant quantities of solids and heavy metals were detected at all sites. PAHs were not detected very often, but when detected the values were different from quantities observed in UK highways. The heavy metal concentrations were strongly related to the total suspended solids concentrations, which has a useful implication for runoff management strategies. No strong relationship was discovered between pollutant concentrations and event characteristics such as rainfall intensity, antecedent dry days (ADD), or rainfall depth (volume). This study has demonstrated that runoff from Irish motorways was not any cleaner than in the UK although the traffic volume at the monitored sites was relatively smaller. This calls for a site specific investigation of highway runoff quality before adopting a given management strategy.     

被动采样监测环境空气中SO 2和NO 2

用自主研制的采样管开展环境空气中SO2和NO2的被动采样监测.结果表明,被动采样监测结果与自动监测结果高度相关,经回归方程修正后,两者的结果没有显著性差异,被动采样的采样和分析产生的误差得以消除.     

Improving suspended sediment measurements by automatic samplers

Suspended solids either as total suspended solids (TSS) or suspended sediment concentration (SSC) is an integral particulate water quality parameter that is important in assessing particle-bound contaminants. At present, nearly all stormwater runoff quality monitoring is performed with automatic samplers in which the sampling intake is typically installed at the bottom of a storm sewer or channel. This method of sampling often results in a less accurate measurement of suspended sediment and associated pollutants due to the vertical variation in particle concentration caused by particle settling. In this study, the inaccuracies associated with sampling by conventional intakes for automatic samplers have been verified by testing with known suspended sediment concentrations and known particle sizes ranging from approximately 20 μm to 355 μm under various flow rates. Experimental results show that, for samples collected at a typical automatic sampler intake position, the ratio of sampled to feed suspended sediment concentration is up to 6600% without an intake strainer and up to 300% with a strainer. When the sampling intake is modified with multiple sampling tubes and fitted with a wing to provide lift (winged arm sampler intake), the accuracy of sampling improves substantially. With this modification, the differences between sampled and feed suspended sediment concentration were more consistent and the sampled to feed concentration ratio was accurate to within 10% for particle sizes up to 250 μm.     

EOX concentrations in sediment in the part of the Bothnian Bay affected by effluents from the pulp and paper mills at Kemi, Northern Finland

The Bothnian Bay, which is the northernmost part of the Gulf of Bothnia in Northern Finland, is affected by effluents discharged from point sources such as the pulp and paper mills of Stora Enso Oyj Veitsiluoto Mill and Oy Metsä-Botnia Ab Kemi Mill at Kemi, and the Kemi municipal sewage plant, as well as the River Kemijoki. In this paper we discuss, how modernisation of the wastewater treatment plant at the mills, and process investments in the Best Available Techniques (BAT) for effluent treatment, have decreased the effluent discharges of biological oxygen demand (BOD), chemical oxygen demand (COD), total phosphorus (Tot-P), total nitrogen (TOT-N), total suspended solids (TSS) and adsorbable organically bound halogens (AOX) from the mills since 1988. One specific aim of the study was to determine the EOX (Extractable Organically Bound Halogens) concentrations in bottom sediment of the Bothnian Bay in order to assess whether the EOX concentrations reflect the reduction in discharges of chlorinated compounds. According to the monitoring program carried out every third year between 1997–2006, the decreasing trend in EOX concentrations in the top 2 cm of the bottom sediment reflect the decrease in organochlorine discharges (AOX) from the mills. In 1997 the EOX concentrations in bottom sediment varied between 3–70 μg of Cl g^?1 (dry weight), and in 2006 between 3.3–32 μg of Cl g^?1 (dry weight).