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.     

Changes in the nature of dissolved organics during pulp and paper mill wastewater treatment: a multivariate statistical study combining data from three analytical techniques

The paper-making process can produce large amounts of wastewater (WW) with high particulate and dissolved organic loads. Generally, in developed countries, stringent international regulations for environmental protection require pulp and paper mill WW to be treated to reduce the organic load prior to discharge into the receiving environment. This can be achieved by primary and secondary treatments involving both chemical and biological processes. These processes result in complex changes in the nature of the organic material, as some components are mineralised and others are transformed. In this study, changes in the nature of organics through different stages of secondary treatment of pulp and paper mill WW were followed using three advanced characterisation techniques: solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy, pyrolysis-gas chromatography mass spectrometry (py-GCMS) and high-performance size-exclusion chromatography (HPSEC). Each technique provided a different perspective on the changes that occurred. To compare the different chemical perspectives in terms of the degree of similarity/difference between samples, we employed non-metric multidimensional scaling. Results indicate that NMR and HPSEC provided strongly correlated perspectives, with 86 % of the discrimination between the organic samples common to both techniques. Conversely, py-GCMS was found to provide a unique, and thus complementary, perspective.     

Calibration of the Chemcatcher passive sampler for the monitoring of priority organic pollutants in water

An integrative passive sampler consisting of a C18 Empore disk receiving phase saturated with n-octanol and fitted with low-density polyethylene diffusion membrane was calibrated for the measurement of time-weighted average concentrations of hydrophobic micropollutants, including polyaromatic hydrocarbons and organochlorine pesticides, in water. The effect of temperature and water turbulence on kinetic and thermodynamic parameters characterising the exchange of analytes between the sampler and water was studied in a flow-through system under controlled conditions. It was found that the absorption of test analytes from water to the sampler is related to their desorption to water. This allows for the in situ calibration of the uptake of pollutants using offload kinetics of performance reference compounds. The sampling kinetics are dependent on temperature, and for most of the tested analytes also on the flow velocity. Sampler-water partition coefficients did not significantly change with temperature.     

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.     

Antimony impurity in lead arsenate insecticide enhances the antimony content of old orchard soils

Lead arsenate was a commonly used insecticide during the first half of the 20th century, particularly in deciduous tree fruit orchards. Antimony is cotransported with As during the ore refining process and could occur as an impurity in commercial lead arsenate products. The total concentrations of As and Sb in eight soil samples collected from eight orchards located throughout central Washington State were analyzed by neutron activation analysis. Total soil Sb concentrations ranged between 0.4 and 1.5 mg kg(-1), while total soil As concentration ranged from 1 to 170 mg kg(-1). Total soil Sb and As concentrations were positively related. Total Pb and As concentrations in four of the soils were substantially higher than natural background, while the Sb to As concentration ratios in these soils were consistent with values measured in three lead arsenate insecticide products. These results confirm that Sb impurity is present in lead arsenate insecticide and has contributed to Sb enrichment of soils on which lead arsenate-treated plants were grown. Although higher than in uncontaminated soils from the same region, the Sb concentrations in the affected soils fall within the normal range observed worldwide and are substantially lower than values associated with impaired human or environmental health.     

Modelling and field application of the Chemcatcher passive sampler calibration data for the monitoring of hydrophobic organic pollutants in water

Passive sampling of dissolved pollutants in water has been gaining acceptance for environmental monitoring. Previously, an integrative passive sampler consisting of a C18 Empore disk receiving phase saturated with n-octanol and fitted with low density polyethylene membrane, was developed and calibrated for the measurement of time weighted average (TWA) concentrations of hydrophobic pollutants in water. In this study, the exchange kinetics were modelled to obtain a better understanding of the mechanism of the accumulation process and to enable the measurement of TWA concentrations of hydrophobic pollutants in the field. An empirical relationship that enables the calculation of in situ sampling rates of chemicals using performance reference compounds was derived and its application was demonstrated in a field study in which TWA aqueous concentrations estimated from sampler data for target analytes were compared with TWA concentrations obtained from spot samples of water collected regularly during the sampler deployment period.