Using high-frequency phosphorus monitoring for water quality management: a case study of the upper River Itchen, UK.

Increased concentrations of phosphorus (P) in riverine systems lead to eutrophication and can contribute to other environmental effects. Chalk rivers are known to be particularly sensitive to elevated P levels. We used high-frequency (daily) automatic water sampling at five distinct locations in the upper River Itchen (Hampshire, UK) between May 2016 and June 2017 to identify the main P species (including filterable reactive phosphorus, total filterable phosphorus, total phosphorus and total particulate phosphorus) present and how these varied temporally. Our filterable reactive phosphorus (considered the biologically available fraction) data were compared with the available Environment Agency total reactive phosphorus (TRP) values over the same sampling period. Over the trial, the profiles of the P fractions were complex; the major fraction was total particulate phosphorus with the mean percentage value ranging between 69 and 82% of the total P present. Sources were likely to be attributable to wash off from agricultural activities. At all sites, the FRP and Environment Agency TRP mean concentrations over the study were comparable. However, there were a number of extended time periods (1 to 2 weeks) where the mean FRP concentration (e.g. 0.62 mg L-1) exceeded the existing regulatory values (giving a poor ecological status) for this type of river. Often, these exceedances were missed by the limited regulatory monitoring procedures undertaken by the Environment Agency. There is evidence that these spikes of elevated concentrations of P may have a biological impact on benthic invertebrate (e.g. blue-winged olive mayfly) communities that exist in these ecologically sensitive chalk streams. Further research is required to assess the ecological impact of P and how this might have implications for the development of future environmental regulations.

Use of the Chemcatcher® passive sampler and time-of-flight mass spectrometry to screen for emerging pollutants in rivers in Gauteng Province of South Africa.

Many rivers in urbanised catchments in South Africa are polluted by raw sewage and effluent to an extent that their ecological function has been severely impaired. The Hennops and Jukskei Rivers lying in the Hartbeespoort Dam catchment are two of the worst impacted rivers in South Africa and are in need of rehabilitation. Passive sampling (Chemcatcher® with a HLB receiving phase) together with high-resolution tandem mass spectrometry-targeted screening was used to provide high sensitivity and selectivity for the identification of a wide range of emerging pollutants in these urban waters. Over 200 compounds, including pesticides, pharmaceuticals and personal care products, drugs of abuse and their metabolites were identified. Many substances (~ 180) being detected for the first time in surface water in South Africa. General medicines and psychotropic drugs were the two most frequently detected groups in the catchment. These accounted for 49% of the emerging pollutants found. Of the general medicines, antihypertensive agents, beta-blocking and cardiac drugs were the most abundant (28%) classes detected. The Hennops site, downstream of a dysfunctional wastewater treatment plant, was the most polluted with 123 substances detected. From the compounds detected, peak intensity-based prioritisation was used to identify the five most abundant pollutants, being in the order caffeine > lopinavir > sulfamethoxazole > cotinine > trimethoprim. This work provides the largest available high-quality dataset of emerging pollutants detected in South African urban waters. The data generated in this study provides a solid foundation for subsequent work to further characterise (suspect screening) and quantify (target analysis) these substances.

Comparison of different monitoring methods for the measurement of metaldehyde in surface waters.

Metaldehyde is recognised as an emerging contaminant. It is a powerful molluscicide and is the active compound in many types of slug pellets used for the protection of crops. The application of pellets to land generally takes place between August and December when slugs thrive. Due to its high use and physico-chemical properties, metaldehyde can be present in the aquatic environment at concentrations above the EU Drinking Water Directive limit of 100 ng L-1 for a single pesticide. Such high concentrations are problematic when these waters are used in the production of drinking water. Being able to effectively monitor this pollutant of concern is important. We compared four different monitoring techniques (spot and automated bottle sampling, on-line gas chromatography/mass spectrometry (GC/MS) and passive sampling) to estimate the concentration of metaldehyde. Trials were undertaken in the Mimmshall Brook catchment (Hertfordshire, UK) and in a feed in a drinking water treatment plant for differing periods between 17th October and 31st December 2017. This period coincided with the agricultural application of metaldehyde. Overall, there was a good agreement between the concentrations measured by the four techniques, each providing complementary information. The highest resolution data was obtained using the on-line GC/MS. During the study, there was a large exceedance (500 ng L-1) of metaldehyde that entered the treatment plant; but this was not related to rainfall in the area. Each monitoring method had its own advantages and disadvantages for monitoring investigations, particularly in terms of cost and turn-a-round time of data.

The acetaminophen metabolite N-acetyl-p-benzoquinone imine (NAPQI) inhibits glutathione synthetase in vitro; a clue to the mechanism of 5-oxoprolinuric acidosis?

1. Metabolic acidosis due to accumulation of l-5-oxoproline is a rare, poorly understood, disorder associated with acetaminophen treatment in malnourished patients with chronic morbidity. l-5-Oxoprolinuria signals abnormal functioning of the γ-glutamyl cycle, which recycles and synthesises glutathione. Inhibition of glutathione synthetase (GS) by N-acetyl-p-benzoquinone imine (NAPQI) could contribute to 5-oxoprolinuric acidosis in such patients. We investigated the interaction of NAPQI with GS in vitro. 2. Peptide mapping of co-incubated NAPQI and GS using mass spectrometry demonstrated binding of NAPQI with cysteine-422 of GS, which is known to be essential for GS activity. Computational docking shows that NAPQI is properly positioned for covalent bonding with cysteine-422 via Michael addition and hence supports adduct formation. 3. Co-incubation of 0.77 µM of GS with NAPQI (25-400 µM) decreased enzyme activity by 16-89%. Inhibition correlated strongly with the concentration of NAPQI and was irreversible. 4. NAPQI binds covalently to GS causing irreversible enzyme inhibition in vitro. This is an important novel biochemical observation. It is the first indication that NAPQI may inhibit glutathione synthesis, which is pivotal in NAPQI detoxification. Further studies are required to investigate its biological significance and its role in 5-oxoprolinuric acidosis.

In Situ Calibration of a New Chemcatcher Configuration for the Determination of Polar Organic Micropollutants in Wastewater Effluent.

Passive sampling is proposed as an alternative to traditional grab- and composite-sampling modes. Investigated here is a novel passive sampler configuration, the Chemcatcher containing an Atlantic HLB disk covered by a 0.2 µm poly(ether sulfone) membrane, for monitoring polar organic micropollutants (personal care products, pharmaceuticals, and illicit drugs) in wastewater effluent. In situ calibration showed linear uptake for the majority of detected micropollutants over 9 days of deployment. Sampling rates (RS) were determined for 59 compounds and were generally in the range of 0.01-0.10 L day(-1). The Chemcatcher was also suitable for collecting chiral micropollutants and maintaining their enantiomeric distribution during deployment. This is essential for their future use in developing more accurate environmental risk assessments at the enantiomeric level. Application of calibration data in a subsequent monitoring study showed that the concentration estimated for 92% of micropollutants was within a factor of 2 of the known concentration. However, their application in a legislative context will require further understanding of the properties and mechanisms controlling micropollutant uptake to improve the accuracy of reported concentrations.

2-Pentanone production from hexanoic acid by Penicillium roqueforti from blue cheese: is this the pathway used in humans?

Production of 2-pentanone, a methylketone, is increased in fasting ketotic humans. Its origin is unknown. We hypothesised that it is formed via ß -oxidation of hexanoic acid by the peroxisomal pathway proposed for methylketone-producing fungi and yeasts. We used Penicillium roqueforti cultured on fat (margarine) to investigate 2-pentanone production. Headspace gas of incubates of the mould with a range of substrates was analysed using solid-phase microextraction with gas chromatography-mass spectrometry. Consistent with the proposed pathway, 2-pentanone was formed from hexanoic acid, hexanoyl-CoA, hexanoylcarnitine, and ethyl-3-oxohexanoic acid but not from ethylhexanoic, 2-ethylhexanoic, octanoic, or myristic acids, octanoylcarnitine, or pentane. However, the products from deuterated (D) hexanoic-D11 acid and hexanoic-2, 2-D2 acid were 9D- and 2D-2-pentanone, respectively, and not 8D- and 1D-2-pentanone as predicted. When incubated under (18)O2/(14)N2, there was only a very small enrichment of [(16)O2]- with [(18)O2]-containing 2-pentanone. These are new observations. They could be explained if hydrogen ions removed from hexanoyl-CoA by acyl-CoA oxidase at the commencement of ß -oxidation were cycled through hydrogen peroxide and reentered the pathway through hydration of hexenoyl-CoA. This would protect other proteins from oxidative damage. Formation of 2-pentanone through a ß -oxidation cycle similar to Penicillium roqueforti would be consistent with observations in humans.

Assessment of occupational exposure to polycyclic aromatic hydrocarbons via involuntary ingestion of soil from contaminated soils in Lagos, Nigeria.

Soils from 12 sites in Lagos area, Nigeria impacted by anthropogenic activities were extracted by ultrasonication and analysed for the concentration of 16 priority polycyclic aromatic hydrocarbons (PAHs) by gas chromatograph-mass spectrometer (GC-MS). The concentration of the sum of PAHs ranged from 0.2 to 254 µg/g at these sites. The sum benzo[a]pyrene-equivalent dose (BaPeq) at the sites ranged from 0.0 (K, forest soil) to 16.7 µg/g (C, the lubricating oil depot soil). Mean daily intake (MDI) for the composite soils samples when compared that of food revealed that some of the individual PAH in samples from sites A (Dump site), C (Depot and loading point for used for black oil), F (Dump site), G(petroleum depot), H (Roadside) and L (Car park) exceeded the recommended the recommended MDI threshold for food, indicating some risk associated with activities on these sites based on this ingestion estimate exceeded value. 8.2 × 10(-6), 7.1 × 10(-7), 1.2 × 10(-4), 4.9 × 10(-7), 7.3 × 10(-7), 1.4 × 10(-5), 7.9 × 10(-5), 4.6 × 10(-6), 3.4 × 10(-7), 2.4 × 10(-7), 2.2 × 10(-7) and 1.1 × 10(-4) estimated theoretical cancer risk (ER) for an adult with a body weight of 70 kg working on sites were composite soil samples A, B, C, D, E, F, G, H, I, J, K and L respectively were sampled. The ER from occupational exposure to surface soil based on oral ingestion were all higher than the target risk of 1 × 10(-6) for normal exposure but were all within the 1 × 10(-4) for extreme exposure for most of the sites except for site C and L. The differences in concentration and risk were related to the different activities (e.g., handling of petroleum products, open burning, bush burning) undertaken at these locations. However, it should be noted here that the resultant risk could be overestimated, since these calculations were based on an exhaustive extraction technique which may be different from uptake by the human guts (bioavailability study).

Quantification and risk assessment of polar organic contaminants in two chalk streams in Hampshire, UK using the Chemcatcher passive sampler.

Freshwater systems are facing a number of pressures due to the inputs of polar organic contaminants from a range of sources including agriculture, domestic and industry. The River Itchen and River Test are two sensitive chalk streams in Southern England that are experiencing a decline in invertebrate communities. We used Chemcatcher passive samplers to measure time-weighted average concentrations (14 days) of polar pollutants at nine sites on the River Itchen and eight sites on the River Test over a 12-month period. Sampler extracts were analysed using a targeted LC/MS method. In total, 121 plant protection products and pharmaceutical and personal care products were quantified (range of log Kow from - 1.5 to 7). Concentrations (sub ng L-1 to >500 ng L-1) in both rivers showed spatial and temporal variations. A greater number of compounds and higher concentrations were found in the River Test. The chemical profile was dominated by inputs from wastewater treatment plants and legacy plant protection products. On the River Itchen, high concentrations (∼100 ng L-1) of caffeine were observed directly downstream of a fish farm. Using the NORMAN database, the predicted no effect concentration (PNEC) freshwater values were exceeded by only five contaminants (2-hydroxy-terbuthylazine, alprazolam, azithromycin, diclofenac and imidacloprid). In addition, venlafaxine was detected above its EU Watch List concentration. These exceedances were mainly downstream of direct inputs from treatment plants. These compounds are known to have ecotoxicological effects on a range of aquatic biota including macroinvertebrates. Of concern is the ubiquitous presence of the ectoparasiticide imidacloprid, highlighting the need to control its use. The impact of the cocktail of pollutants found in this study on the long-term effects on chalk stream ecosystems remains unknown and needs further investigation.

Robotic beyond total mesorectal excision (TME) for locally advanced or recurrent rectal cancer: a systematic review protocol.

INTRODUCTION: The surgical treatment for locally advanced or recurrent rectal cancer requires oncological clearance with a pelvic exenteration or a beyond total mesorectal excision (TME). The aim of this systematic review is to explore the safety and feasibility of robotic surgery in locally advanced and recurrent rectal cancer by evaluating perioperative outcomes, oncological clearance rates, and survival and recurrence rates postrobotic beyond TME surgery. METHODS: The systematic review will include studies published until the end of December 2023. The MEDLINE, EMBASE and Scopus databases will be searched. The screening process, study selection, data extraction, quality assessment and analysis will be performed by two independent reviewers. Discrepancies will be resolved by consensus with a third independent reviewer. The risk of bias will be assessed with validated scores. The primary outcomes will be oncological clearance, overall and disease-free survival, and local and systemic recurrence rates post robotic or robot-assisted beyond TME surgery for locally advanced or recurrent rectal cancer. Secondary outcomes will include perioperative outcomes. ETHICS AND DISSEMINATION: No ethical approval is required for this systematic review as no individual patient cases are studied requiring access to individual medical records. The results of the systematic review will be disseminated with conference presentations and peer-reviewed paper publications. PROSPERO REGISTRATION OF THE STUDY: CRD42023408098.

Monitoring of polar organic compounds in fresh waters using the Chemcatcher passive sampler.

The monitoring of polar organic pollutants in surface water is now undertaken to fulfil a number of legislative requirements. Passive sampling is being frequently used for this purpose and includes the commercially available Chemcatcher device. This protocol is based on knowledge that has been acquired over the past ten years in the use of the Chemcatcher for monitoring a wide range of polar organic compounds in freshwater. It provides detailed procedures and guidelines of how to prepare the sampler in the laboratory, deploy and retrieve the device in the field (including water and sampling site measurements) and subsequent sample processing in the laboratory up to instrumental analysis. By end users adopting this standardized, systematic protocol it will help to ensure the reproducibility of their monitoring data.•Robust and detailed procedure for the sampling of polar pollutants in surface waters using the Chemcatcher passive sampler•A low cost, novel and versatile apparatus for deploying the Chemcatcher at riverine sites•Practical tips based on extensive experience of using the Chemcatcher are provided for end-users.

Occurrence of organic pollutants in the River Itchen and River Test-two chalk streams in Southern England, UK.

The River Itchen and River Test, two chalk streams in Southern England, are sites of special scientific interest. These ecosystems face a number of environmental pressures from anthropogenic inputs of organic pollutants. Hence, we investigated the occurrence of these chemicals within the two catchments. Spot water samples (1 L) were collected at nineteen sites along the catchment on two occasions (March and June 2019). Samples were extracted (HLB-L sorbent disks) and analysed using high-resolution liquid chromatography-quadrupole-time-of-flight mass spectrometry and gas chromatography-mass spectrometry. Compounds were identified against commercially available databases. Using this approach, we found 115 pharmaceutical and personal care products, 81 plant protection products and 35 industrial chemicals. This complex mixture of pollutants covered a range of physico-chemical properties and included priority substances in the EU Water Framework Directive or currently on the third Watch List. Both rivers had similar chemical profiles for both months. Herbicides and fungicides were dominant in the spring, whereas insecticides occurred more frequently in the summer. Point discharges from wastewater treatment plants were the main source of pharmaceutical and personal care products. Agricultural activities were the main contributor to the presence of plant protection products. The impact of these organic chemicals on the ecology, particularly on macroinvertebrate biodiversity, is unknown and warrants further investigation. Our suspect screening approach could guide future toxicological investigations to assess the environmental impacts of these diverse chemicals.

Pesticide fate during drinking water treatment determined through passive sampling combined with suspect screening and multivariate statistical analysis.

Emerging contaminants such as polar pesticides pose a potential risk to human health due to their presence in drinking water. However, their occurrence and fate in drinking water treatment plants is poorly understood. In this study we use passive sampling coupled to suspect screening and multivariate analysis to describe pesticide fate throughout the treatment stream of an operational drinking water treatment plant. ChemcatcherÒ passive sampling devices were deployed at sites (n = 6) positioned at all stages of the treatment stream during consecutive deployments (n = 20) over a twelve-month period. Sample extracts (n = 120) were analysed using high-resolution liquid chromatography-quadrupole-time-of-flight mass spectrometry and compounds identified against a commercially available database. A total of 58 pesticides and transformation products from different classes were detected. Statistical analysis of the qualitative screening data was performed to identify clusters of pesticides with similar fate during ozonation, granular activated carbon (GAC) filtration, and chlorination. The performance of each treatment process was investigated. Adsorption to GAC media was found to account for the greatest proportion of pesticide attenuation (average removal of 70% based on detection frequency), however, operational performance varied for certain pesticides during periods of episodic and sustained pollution. GAC breakthrough occurred for 21 compounds detected in the GAC filtrate. Eleven pesticides were found to occur in potable water following treatment. We developed a management plan containing controls, triggers, and responses, for five pesticides and a metabolite (atrazine, atrazine desethyl, DEET, dichlorobenzamide, metazachlor, and propyzamide) prioritised based on their current and future risk to treated water quality.

A miniaturized passive sampling-based workflow for monitoring chemicals of emerging concern in water.

The miniaturization of a full workflow for identification and monitoring of contaminants of emerging concern (CECs) is presented. Firstly, successful development of a low-cost small 3D-printed passive sampler device (3D-PSD), based on a two-piece methacrylate housing that held up to five separate 9 mm disk sorbents, is discussed. Secondly, a highly sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method reduced the need for large scale in-laboratory apparatus, solvent, reagents and reference material quantities for in-laboratory passive sampler device (PSD) calibration and extraction. Using hydrophilic-lipophilic balanced sorbents, sampling rates (Rs) were determined after a low 50 ng L-1 exposure over seven days for 39 pesticides, pharmaceuticals, drug metabolites and illicit drugs over the range 0.3 to 12.3 mL day-1. The high sensitivity LC-MS/MS method enabled rapid analysis of river water using only 10 µL of directly injected sample filtrate to measure occurrence of 164 CECs and sources along 19 sites on the River Wandle, (London, UK). The new 3D-PSD was then field-tested over seven days at the site with the highest number and concentration of CECs, which was down-river from a wastewater treatment plant. Almost double the number of CECs were identified in 3D-PSD extracts across sites in comparison to water samples (80 versus 42 CECs, respectively). Time-weighted average CEC concentrations ranged from 8.2 to 845 ng L-1, which were generally comparable to measured concentrations in grab samples. Lastly, high resolution mass spectrometry-based suspect screening of 3D-PSD extracts enabled 113 additional compounds to be tentatively identified via library matching, many of which are currently or are under consideration for the EU Watch List. This miniaturized workflow represents a new, cost-effective, and more practically efficient means to perform passive sampling chemical monitoring at a large scale. SYNOPSIS: Miniaturized, low cost, multi-disk passive samplers enabled more efficient multi-residue chemical contaminant characterization, potentially for large-scale monitoring programs.

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.

Applications for Passive Sampling of Hydrophobic Organic Contaminants in Water-A Review.

We comprehensively review the current state-of-the-art of environmental monitoring for hydrophobic organic contaminants in aqueous matrices using passive sampling devices. Principles of the theory of passive sampling are presented. Strategies for passive sampler design and operation, limitations in performance and data quality-assurance and quality-control are reviewed. Advances in applications of available passive sampling devices are extensively critiqued. Future trends and current challenges facing practitioners and barriers to further adoption of the devices are discussed.

Passive sampling with suspect screening of polar pesticides and multivariate analysis in river catchments: Informing environmental risk assessments and designing future monitoring programmes.

Pollution of surface water by polar pesticides is a major environmental risk, particularly in river catchments where potable water supplies are abstracted. In these cases, there is a need to understand pesticide sources, occurrence and fate. Hence, we developed a novel strategy to improve water quality management at the catchment scale using passive sampling coupled to suspect screening and multivariate analysis. Chemcatcher® passive sampling devices were deployed (14 days) over a 12 month period at eight sites (including a water supply works abstraction site) in the Western Rother, a river catchment in South East England. Sample extracts (n = 197) were analysed using high-resolution liquid chromatography-quadrupole-time-of-flight mass spectrometry and compounds identified against a commercially available database. A total of 128 pesticides from different classes were found. Statistical analysis of the qualitative screening data was used to identify clusters of pesticides with similar spatiotemporal pollution patterns. This enabled pesticide sources and fate to be identified. At the water supply works abstraction site, spot sampling and passive sampling were found to be complementary, however, the passive sampling method in conjunction with suspect screening detected 50 pesticides missed by spot sampling combined with targeted analysis. Geospatial data describing pesticide application rates was found to be poorly correlated to their detection frequency using the Chemcatcher®. Our analysis prioritised 61 pesticides for inclusion in a future water quality risk assessment at the abstraction site. It was also possible to design a seasonal monitoring programme to effectively characterise the spatiotemporal pesticide profiles within the catchment. A work flow of how to incorporate passive sampling coupled to suspect screening into existing regulatory monitoring is proposed. Our novel approach will enable water quality managers to target the mitigation (non-engineered actions) of pesticide pollution within the catchment and hence, to better inform drinking water treatment processes and save on operational costs.

Rapid direct analysis of river water and machine learning assisted suspect screening of emerging contaminants in passive sampler extracts.

A novel and rapid approach to characterise the occurrence of contaminants of emerging concern (CECs) in river water is presented using multi-residue targeted analysis and machine learning-assisted in silico suspect screening of passive sampler extracts. Passive samplers (Chemcatcher®) configured with hydrophilic-lipophilic balanced (HLB) sorbents were deployed in the Central London region of the tidal River Thames (UK) catchment in winter and summer campaigns in 2018 and 2019. Extracts were analysed by; (a) a rapid 5.5 min direct injection targeted liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for 164 CECs and (b) a full-scan LC coupled to quadrupole time of flight mass spectrometry (QTOF-MS) method using data-independent acquisition over 15 min. From targeted analysis of grab water samples, a total of 33 pharmaceuticals, illicit drugs, drug metabolites, personal care products and pesticides (including several EU Watch-List chemicals) were identified, and mean concentrations determined at 40 ± 37 ng L-1. For targeted analysis of passive sampler extracts, 65 unique compounds were detected with differences observed between summer and winter campaigns. For suspect screening, 59 additional compounds were shortlisted based on mass spectral database matching, followed by machine learning-assisted retention time prediction. Many of these included additional pharmaceuticals and pesticides, but also new metabolites and industrial chemicals. The novelty in this approach lies in the convenience of using passive samplers together with machine learning-assisted chemical analysis methods for rapid, time-integrated catchment monitoring of CECs.

Short-term exposure testing of six different passive samplers for the monitoring of hydrophobic contaminants in water.

Passive sampling devices are increasingly relied upon for monitoring non-polar organic contaminants in water. While many types of devices are available they have seldom been evaluated alongside each other. We tested six passive sampling devices namely: Chemcatcher, two modified versions of the membrane enclosed sorptive coating (MESCO I (m) and MESCO II), silicone rod and strip and semipermeable membrane device (SPMD). Samplers spiked with a range of performance reference compounds (PRCs) were exposed (5 days) in a continuous flow-through tank using Meuse river water fortified with fluctuating concentrations (20-700 ng L(-1)) of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, hexachlorobenzene and p,p'-DDE. Dissipation rates of PRCs appeared to provide reliable information on exchange kinetics even under these short-term exposure conditions. They accounted for differences between masses of contaminants accumulated by replicate samplers, indicating that the variability between replicates was in part due to differences in water turbulences and hence boundary layer thickness. In this system, resistances in the membrane and boundary layers are likely to be in the same order of magnitude for PRCs. Sampler performance was evaluated by comparing masses accumulated in the devices only for analytes for which uptake was linear (integrative) and limited by transport across the boundary layer. Consistent data were obtained across the range of samplers despite their different configurations, and the analysis being conducted in three separate laboratories. The pattern in analyte masses accumulated by Chemcatcher and MESCO II data could be explained by the extraction and analysis being conducted only on the receiving phase of the samplers and a significant impact of the lag-phase prior to obtaining a steady flux of contaminants across the polyethylene membranes.

Field performance of the Chemcatcher passive sampler for monitoring hydrophobic organic pollutants in surface water.

Six field trials were carried out to assess the performance of the Chemcatcher passive sampler alongside spot sampling for monitoring priority hydrophobic organic pollutants (polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides) in a wide range of conditions in surface water. The trials were performed in three European rivers: Elbe (Czech Republic), Alna (Norway) and Meuse (Netherlands), in two seasons (April-June 2004, and September-October 2004). Samplers spiked with performance reference compounds (PRCs) were deployed for either 14 or 28 days. Ten spot samples of water were collected over the course of the trial and filtered through a 0.7 microm glass fibre filter. Concentrations of pollutants measured using the Chemcatcher were compared with the average concentrations found in spot samples. This study describes the operational performance of Chemcatcher for measuring hydrophobic (log K(OW) 3.7-6.8) chemicals in surface water. Site specific Chemcatcher sampling rates up to 0.5 L d(-1) were found using the PRC approach that reduced the uncertainty in estimates of sampling kinetics where temperature, local flow conditions and biofouling potential varied between sites and seasons, and with time during sampler exposure. The limits of quantification of sampled analytes ranged from one to tens ng L(-1). Highest sensitivity was achieved for compounds with a favourable combination of low instrument quantification limits and high sampling rates including dieldrin, hexachlorobenzene, lindane, pentachlorobenzene, and PAHs with less than five aromatic rings. The direct comparison of time weighted average (TWA) concentrations (mostly close to method limits of detection) obtained using passive and spot sampling was possible for lindane, hexachlorobenzene, and PAHs < 4 rings. Implications of using the Chemcatcher in regulatory monitoring programmes such as the European Union Water Framework Directive are discussed.

Detection of pharmaceuticals in wastewater effluents-a comparison of the performance of Chemcatcher® and polar organic compound integrative sampler.

Chemcatcher® and POCIS passive sampling devices are widely used for monitoring polar organic pollutants in water. Chemcatcher® uses a bound Horizon Atlantic™ HLB-L sorbent disk as receiving phase, whilst the POCIS uses the same material in the form of loose powder. Both devices (n = 3) were deployed for 21 days in the final effluent at three wastewater treatment plants in South Wales, UK. Following deployment, sampler extracts were analysed using liquid chromatography time-of-flight mass spectrometry. Compounds were identified using an in-house database of pharmaceuticals using a metabolomics workflow. Sixty-eight compounds were identified in all samplers. For the POCIS, substantial losses of sorbent (11-51%) were found during deployment and subsequent laboratory analysis, necessitating the use of a recovery factor. Percentage relative standard deviations varied (with 10 compounds exceeding 30% in both samplers) between individual compounds and between samplers deployed at the three sites. The relative performance of the two devices was evaluated using the mass of analyte sequestered, measured as an integrated peak area. The ratio of the uptake of the pharmaceuticals for the POCIS versus Chemcatcher® was lower (1.84x) than would be expected on the basis of the ratio of active sampling areas (3.01x) of the two devices. The lower than predicted uptake may be attributable to the loose sorbent material moving inside the POCIS when deployed in the field in the vertical plane. In order to overcome this, it is recommended to deploy the POCIS horizontally inside the deployment cage.