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.     

Silver near municipal wastewater discharges into western Lake Ontario,Canada

Because of the widespread use of silver nanoparticles in commercial products, discharges of municipal wastewater may be a point source of silver in the aquatic environment. We monitored two sites in western Lake Ontario impacted by discharges from wastewater treatment plants serving the City of Toronto. Concentrations of silver were elevated in bottom sediments and suspended sediments collected at the two sites. We also deployed two types of passive samplers in the water column at the two sites, the newly developed Carbon Nanotube Integrative Samplers for monitoring “CNIS-labile” silver and Diffusive Gradient in Thin Film samplers for monitoring “DGT-labile” silver. Results from these passive samplers indicated that the concentrations of silver at the two sites were either below detection limits or were in the ng/L range. In laboratory experiments where the sediments were re-suspended in Milli-Q water, a small proportion of the silver (i.e., <?25%) was labile and partitioned as colloidal or dissolved silver into the liquid phase after agitation. Nanoparticles tentatively identified as silver nanoparticles were detected by single-particle ICP-MS in suspension after agitation of both suspended and bottom sediments. Therefore, there is a need to assess whether silver species, including silver nanoparticles are transported from wastewater treatment plants into sediments in the aquatic environment. This study is unique in focusing on the in situ distribution of silver in natural waters and in sediments that are potentially impacted by urban sources of nanoparticles.     

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.     

Evaluation of the Chemcatcher and DGT passive samplers for monitoring metals with highly fluctuating water concentrations

Passive sampling devices accumulate chemicals continuously from water and can provide time weighted average (TWA) concentrations of pollutants over the exposure period. Hence, they offer a number of advantages over other conventional monitoring techniques such as spot or grab sampling. The diffusive gradient in thin film (DGT) and the Chemcatcher passive samplers can be used to provide TWA concentrations of labile metals, but the approaches to their calibration differ. DGT uses diffusion coefficients of metals in the hydrogel layer, whereas Chemcatcher uses metal specific uptake rates, with both sets of values obtained under controlled laboratory conditions with constant aqueous metal concentrations. However, little is known of how such samplers respond to fluctuating concentrations. We evaluated the responsiveness of these two passive sampling devices to rapidly changing concentrations of Cd, Cu, Ni, Pb and Zn in natural freshwater, over a relatively short deployment time. Maximum metal concentrations in water were varied between 70 and 140 microg L(-1). Experiments were carried out in a tank with a rotating carousel system and filled with Meuse river water, allowing a degree of control over experimental conditions while using natural river water. Fluctuating concentrations were obtained by stepwise addition of standard solutions of the metals. The reliability and accuracy of the TWA concentrations measured by the samplers were assessed by comparison with concentrations of the metals in spot samples of water taken regularly over the deployment period. The spot samples of water were either unfiltered (total), filtered (0.45 microm) or ultrafiltered (5 kDa). Predictive speciation modelling using the visual MINTEQ programme was also undertaken. There was reasonable agreement between the TWA concentrations of Cd and Ni obtained with Chemcatcher and DGT and the total Cd and Ni concentrations measured in repeated unfiltered spot samples. For elements (i.e. Cu, Pb, Zn) that associate to a significant degree with suspended solids, colloids or dissolved organic carbon, or form complexes with large organic ligands, optimum agreement was with the filtered or ultrafiltered fractions and with the predicted inorganic and inorganic-fulvic acid associated fractions. While Chemcatcher-based TWA concentration ranges for Cu and Zn were in best agreement with the total filtered fraction, there was lack of agreement for Pb. The combined use of DGT devices with open pore (OP) and restricted pore (RP) gels allowed the labile fraction of metal associated with large organic ligands or DOC to be differentiated and quantified, since this is available to DGT OP but unable to diffuse into the DGT RP. This evaluation of the two sampling devices clearly demonstrated their ability to react reliably to transient peaks in concentration of metal pollutants in water and indicated where future efforts are needed to improve calibration data. Such samplers may prove valuable in responding to the monitoring requirements of the European Union's Water Framework Directive.     

Remote in situ voltammetric techniques to characterize the biogeochemical cycling of trace metals in aquatic systems

The contamination of aquatic ecosystems by natural and anthropogenic metals has lead to a need to better characterize their impact in the environment. To a large extent, the fate and the (eco)toxicity of these elements in aquatic systems are related to their chemical speciation, which may vary continuously in space and time. Detailed measurements of the fraction of specific metal species or groups of homologous metal species and their variation as a function of the bio-physicochemical conditions of the natural media are thus of prime importance. To determine these metal fractions as well as redox chemical species regulating their distribution (dissolved oxygen, sulfides, iron and manganese oxides), new analytical tools capable of performing in situ, real-time monitoring in both water columns and sediments with minimum perturbation of the media are required. This paper reviews the challenges associated with metal speciation studies, and the progress made with state of the art voltammetric techniques to measure the speciation of metals in situ. More specifically, it summarizes the specific conceptual, analytical, and technical criteria that must be considered and/or fulfilled to develop rugged, field deployable, non-perturbing sensors and probes. Strategies used to satisfy these criteria are presented by describing the up-to-date most advanced voltammetric sensors, mini-/micro-integrated analytical systems, and submersible equipments developed for in situ measurements of trace metals and main redox species in aquatic systems. The spatial and temporal resolutions achieved by these news tools represent a significant advantage over traditional laboratory techniques, while simultaneously remaining cost effective. The application of these tools to aquatic systems is illustrated by several examples of unattended and remote in situ monitoring and/or profiling in water columns and sediments.     

Atmospheric Volatile Organic Compound Monitoring. Ozone Induced Artefact Formation

Assessment of population exposure to VOC in ambient atmospheres is receiving heightened interest as the adverse health effects of chronic exposure to certain of these compounds are identified. Active (pumped) and passive samplers are the most commonly used devices for this type of monitoring. It has been shown, however, that these devices, along with all other preconcentration techniques, are susceptible to ozone interference. It is demonstrated that this interference occurs even at low ozone concentrations and that it may result in the under-estimation of population exposure. A convenient and effective ozone scrubbing method is identified and successfully applied and validated for both active and passive samplers for a range of VOC.     

Changes in valued “Capacities” of soils and sediments as indicators of nonlinear and time-delayed environmental effects

This paper discusses the buffering, oxygen-donating, and sorption capacities of soils and sediments as an inter-connected system for regulating the retention and release of chemical pollutants. In this context, the author discusses the chemical conditions under which sediments may serve as a source or a sink for toxic materials, and conditions under which soils may retain or release them. It is demonstrated that nonlinear, time-delayed ecological transformations in soils and sediments often can be understood in terms of the interlinked system. The author discusses some possible future long-term environmental problems that might beset Europe, and some implications for a monitoring strategy for foresseing such problems.Because the release of adsorbed toxic chemicals from heavily polluted sediments and soils can occur suddenly owing to changes in oxygen status (i.e., redox potential) or acidity, strategies for preventing the long-term release of such materials should not only consider current conditions of pH and redox potential, but also, how those conditions might change in the future.     

Simultaneous measurements of dissolved CH<Subscript>4</Subscript> and H<Subscript>2</Subscript> in wetland soils

Biogeochemical processes in wetland soils are complex and are driven by a microbiological community that competes for resources and affects the soil chemistry. Depending on the availability of various electron acceptors, the high carbon input to wetland soils can make them important sources of methane production and emissions. There are two significant pathways for methanogenesis: acetoclastic and hydrogenotrophic methanogenesis. The hydrogenotrophic pathway is dependent on the availability of dissolved hydrogen gas (H₂), and there is significant competition for available H₂. This study presents simultaneous measurements of dissolved methane and H₂ over a 2-year period at three tidal marshes in the New Jersey Meadowlands. Methane reservoirs show a significant correlation with dissolved organic carbon, temperature, and methane emissions, whereas the H₂ concentrations measured with dialysis samplers do not show significant relationships with these field variables. Data presented in this study show that increased dissolved H₂ reservoirs in wetland soils correlate with decreased methane reservoirs, which is consistent with studies that have shown that elevated levels of H₂ inhibit methane production by inhibiting propionate fermentation, resulting in less acetate production and hence decreasing the contribution of acetoclastic methanogenesis to the overall production of methane.     

A new attachment device for deployment of monitoring equipment in estuaries and other high-energy environments

Biomonitoring is an important component of estuarine research and monitoring programs because living organisms integrate biological, chemical, and physical conditions over time. The deployment of biomonitoring devices in ecosystems that are subject to changes in water level and flow can be very challenging. This paper describes a new device, which facilitates such applications such as the deployment of periphytometers. The device is designed to encircle posts, poles, or pilings, such as channel markers common in many waterways. This device has been evaluated and approved for use by the US Coast Guard, needed for attachment to navigational aids. It allows attachment of monitoring devices requiring in situ deployment at fixed water depths in systems with dynamic water levels or velocities while minimizing the potential for shading, damage, theft, or poor long-term performance.     

Passive sampling in combination with thermal desorption and gas chromatography as a tool for self-assessment of chemical exposure

Diffusive samplers for monitoring of air quality are user-friendly devices that can normally be operated by the user himself. Hence these samplers are suitable for self-assessment. Practical and work organisational aspects of self-assessment of chemical exposure were studied in different occupational settings. It was found that the diffusive sampler used in these studies, the Perkin-Elmer tube in combination with thermal desorption, worked well for the purpose and could be correctly handled by the individuals using it. The results from self-assessments agreed well with expert measurements carried out by an occupational hygienist. However, in order to obtain a sustainable system of self-assessment strong organizational support is needed.     

Lake Ontario sediments in monitoring pollution

An investigation was carried out to select locations for long-term monitoring of inputs of contaminants into Lake Ontario using fine-grained bottom sediments as an historical record of pollution. The sediment sampling program was designed to determine sediment heterogeneity in the western, central and eastern depositional basins of the lake. Surficial sediments and sediment cores were collected in each basin to obtain information on horizontal distribution and concentration profiles of major and trace elements in the sediments (Si, Al, Ca, Mg, Fe, Na, K, Ti, Mn, P, As, Co, Cu, Cr, Ni, Pb and Zn). The results of the investigation indicated that fine-grained sediments in three Lake Ontario depositional basins are homogeneous to a high degree, and that only a few sediment cores need to be collected within each basin for the long-term monitoring of inputs of contaminants to the lake.     

Development and use of a floristic quality index for coastal Louisiana marshes

The Floristic Quality Index (FQI) has been used as a tool for assessing the integrity of plant communities and for assessing restoration projects in many regions of the USA. Here, we develop a modified FQI (FQI_mod) for coastal Louisiana wetlands and verify it using 12 years of monitoring data from a coastal restoration project. Plant species that occur in coastal Louisiana were assigned a coefficient of conservatism (CC) score by a local group with expertise in Louisiana coastal vegetation. Species percent cover and both native and non-native species were included in the FQI_mod which was scaled from 0–100. The FQI_mod scores from the long-term monitoring project demonstrated the utility of this index for assessing wetland condition over time, including its sensitivity to a hurricane. Ultimately, the FQI developed for coastal Louisiana will be used in conjunction with other wetland indices (e.g., hydrology and soils) to assess wetland condition coastwide and these indices will aid managers in coastal restoration and management decisions.     

Thermodynamic influences on size fractionated measurements (PM 2.5, PM 10) of ambient aerosols

Mass concentrations of PM 10 and PM 2.5 are planned as new standards for the monitoring of ambient air quality in the European Union. Standard procedure is the removal of particles > 10 microns and > 2.5 microns aerodynamic diameter, respectively, by impaction in a preseparator. Different samplers work according to different principles of flow control. The influence of ambient temperature, pressure and relative humidity on different devices is calculated to estimate the comparability of various aerosol samplers. Therefore, the effects of these ambient factors on the volume flow as well as on the cut-off dp50 are investigated. In a second step, the influence of relative humidity on the flow control device is calculated. The results show that the cut-off shifts (up to 6.4%) for varying ambient conditions. Therefore, the influence on the impaction process should not be neglected and an 'ideal sampler' would measure temperature, pressure and relative humidity and adapt the volume flow to avoid a systematic error in the cut-off.     

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.     

Selecting the optimum plot size for a California design-based stream and wetland mapping program

Accurate estimates of the extent and distribution of wetlands and streams are the foundation of wetland monitoring, management, restoration, and regulatory programs. Traditionally, these estimates have relied on comprehensive mapping. However, this approach is prohibitively resource-intensive over large areas, making it both impractical and statistically unreliable. Probabilistic (design-based) approaches to evaluating status and trends provide a more cost-effective alternative because, compared with comprehensive mapping, overall extent is inferred from mapping a statistically representative, randomly selected subset of the target area. In this type of design, the size of sample plots has a significant impact on program costs and on statistical precision and accuracy; however, no consensus exists on the appropriate plot size for remote monitoring of stream and wetland extent. This study utilized simulated sampling to assess the performance of four plot sizes (1, 4, 9, and 16 km²) for three geographic regions of California. Simulation results showed smaller plot sizes (1 and 4 km²) were most efficient for achieving desired levels of statistical accuracy and precision. However, larger plot sizes were more likely to contain rare and spatially limited wetland subtypes. Balancing these considerations led to selection of 4 km² for the California status and trends program.     

Long-Term Relationship between Phosphorus Inputs and Wetland Phosphorus Concentrations in a Northern Everglades Marsh

Assessments of long-term relationships between changes innutrient inputs and wetland nutrient concentrations can becomplicated by fluctuations in other environmental factors aswell as by problems typical of long-term monitoring data.Consequently, statistical analysisof these types of data sets requirescareful consideration of environmental covariates, potentialbiases in the monitoring design, and irregularities caused bychanges in field sampling protocols. We evaluated therelationship between anthropogenic phosphorus (P) inputs andwater-column total P (TP) concentrations in a northernEverglades marsh by statistically analyzing available datacollected from several sampling programs over the past 20 years(1978–1997). Canal inputs of agricultural runoff contributemost of the P to the marsh and have produced a zone ofenrichment within the marsh during the past few decades.Regression analyses showed that both canal and marsh TPconcentrations increased during the 1980s and then decreased inthe 1990s. However, the statistical relationship between canal Pinputs and marsh TP, while significant, generally was weakexcept for marsh locations adjacent to the canal. Strongerrelationships existed between marsh TP and hydrologic parameterssuch as marsh water depth, which is controlled by changes inweather patterns and marsh management. In particular, dryconditions during the 1980s may have contributed to observedincreases in marsh P concentrations and the movement of a P`front' further into the marsh. Higher rainfall and water depthsand agricultural best management programs initiated during the1990s have been associated with reduced P concentrations incanal waters entering the marsh. While it is anticipated thatthis reduction eventually will result in lower marsh TPconcentrations, this effect is not yet evident, possibly due tointernal loading of P from enriched marsh soils. Our findingsillustrate some of the environmental factors that can complicateattempts to develop empirical relationships between P inputs andwetland P concentrations and to use such relationships to forecast changesin marsh concentrations based on past monitoring data alone.     

Long-term environmental monitoring for assessment of change: measurement inconsistencies over time and potential solutions

The importance of long-term environmental monitoring and research for detecting and understanding changes in ecosystems and human impacts on natural systems is widely acknowledged. Over the last decades, a number of critical components for successful long-term monitoring have been identified. One basic component is quality assurance/quality control protocols to ensure consistency and comparability of data. In Norway, the authorities require environmental monitoring of the impacts of the offshore petroleum industry on the Norwegian continental shelf, and in 1996, a large-scale regional environmental monitoring program was established. As a case study, we used a sub-set of data from this monitoring to explore concepts regarding best practices for long-term environmental monitoring. Specifically, we examined data from physical and chemical sediment samples and benthic macroinvertebrate assemblages from 11 stations from six sampling occasions during the period 1996–2011. Despite the established quality assessment and quality control protocols for this monitoring program, we identified several data challenges, such as missing values and outliers, discrepancies in variable and station names, changes in procedures without calibration, and different taxonomic resolution. Furthermore, we show that the use of different laboratories over time makes it difficult to draw conclusions with regard to some of the observed changes. We offer recommendations to facilitate comparison of data over time. We also present a new procedure to handle different taxonomic resolution, so valuable historical data is not discarded. These topics have a broader relevance and application than for our case study.     

Application of a three-tier framework to assess ecological condition of Gulf of Mexico coastal wetlands

A multi-level coastal wetland assessment strategy was applied to wetlands in the northern Gulf of Mexico (GOM) to evaluate the feasibility of this approach for a broad national scale wetland condition assessment (US Environmental Protection Agency’s National Wetlands Condition Assessment). Landscape-scale assessment indicators (tier 1) were developed and applied at the sub-watershed (12-digit hydrologic unit code (HUC)) level within the GOM coastal wetland sample frame with scores calculated using land-use maps and geographic information system. Rapid assessment protocols (tier 2), using a combination of data analysis and field work, evaluated metrics associated with landscape context, hydrology, physical structure, and biological structure. Intensive site monitoring (tier 3) included measures of soil chemistry and composition, water column and pore-water chemistry, and dominant macrophyte community composition and tissue chemistry. Relationships within and among assessment levels were evaluated using multivariate analyses with few significant correlations found. More detailed measures of hydrology, soils, and macrophyte species composition from sites across a known condition gradient, in conjunction with validation of standardized rapid assessment method, may be necessary to fully characterize coastal wetlands across the region.     

A novel high-frequency groundwater quality monitoring system

High-frequency, long-term monitoring of water quality has revolutionized the study of surface waters in recent years. However, application of these techniques to groundwater has been limited by the ability to remotely pump and analyze groundwater. This paper describes a novel autonomous groundwater quality monitoring system which samples multiple wells to evaluate temporal changes and identify trends in groundwater chemistry. The system, deployed near Fresno, California, USA, collects and transmits high-frequency data, including water temperature, specific conductance, pH, dissolved oxygen, and nitrate, from supply and monitoring wells, in real-time. The system consists of a water quality sonde and optical nitrate sensor, manifold, submersible three-phase pump, variable frequency drive, data collection platform, solar panels, and rechargeable battery bank. The manifold directs water from three wells to a single set of sensors, thereby reducing setup and operation costs associated with multi-sensor networks. Sampling multiple wells at high frequency for several years provided a means of monitoring the vertical distribution and transport of solutes in the aquifer. Initial results show short period variability of nitrate, specific conductivity, and dissolved oxygen in the shallow aquifer, while the deeper portion of the aquifer remains unchanged—observations that may be missed with traditional discrete sampling approaches. In this aquifer system, nitrate and specific conductance are increasing in the shallow aquifer, while invariant changes in deep groundwater chemistry likely reflect relatively slow groundwater flow. In contrast, systems with high groundwater velocity, such as karst aquifers, have been shown to exhibit higher-frequency groundwater chemistry changes. The stability of the deeper aquifer over the monitoring period was leveraged to develop estimates of measurement system uncertainty, which were typically lower than the manufacturer’s stated specifications, enabling the identification of subtle variability in water chemistry that may have otherwise been missed.     

Using a neural network approach and time series data from an international monitoring station in the Yellow Sea for modeling marine ecosystems

The international marine ecological safety monitoring demonstration station in the Yellow Sea was developed as a collaborative project between China and Russia. It is a nonprofit technical workstation designed as a facility for marine scientific research for public welfare. By undertaking long-term monitoring of the marine environment and automatic data collection, this station will provide valuable information for marine ecological protection and disaster prevention and reduction. The results of some initial research by scientists at the research station into predictive modeling of marine ecological environments and early warning are described in this paper. Marine ecological processes are influenced by many factors including hydrological and meteorological conditions, biological factors, and human activities. Consequently, it is very difficult to incorporate all these influences and their interactions in a deterministic or analysis model. A prediction model integrating a time series prediction approach with neural network nonlinear modeling is proposed for marine ecological parameters. The model explores the natural fluctuations in marine ecological parameters by learning from the latest observed data automatically, and then predicting future values of the parameter. The model is updated in a “rolling” fashion with new observed data from the monitoring station. Prediction experiments results showed that the neural network prediction model based on time series data is effective for marine ecological prediction and can be used for the development of early warning systems.