Fate and transport of polychlorinated biphenyls (PCBs) in the River Thames catchment - Insights from a coupled multimedia fate and hydrobiogeochemical transport model.

The fate of persistent organic pollutants (POPs) in riverine environments is strongly influenced by hydrology (including flooding) and fluxes of sediments and organic carbon. Coupling multimedia fate models (MMFMs) and hydrobiogeochemical transport models offers unique opportunities for understanding the environmental behaviour of POPs. While MMFMs are widely used for simulating the fate and transport of legacy and emerging pollutants, they use greatly simplified representations of climate, hydrology and biogeochemical processes. Using additional information about weather, river flows and water chemistry in hydrobiogeochemical transport models can lead to new insights about POP behaviour in rivers. As most riverine POPs are associated with suspended sediments (SS) or dissolved organic carbon (DOC), coupled models simulating SS and DOC can provide additional insights about POPs behaviour. Coupled simulations of river flow, DOC, SS and POP dynamics offer the possibility of improved predictions of contaminant fate and fluxes by leveraging the additional information in routine water quality time series. Here, we present an application of a daily time step dynamic coupled multimedia fate and hydrobiogeochemical transport model (The Integrated Catchment (INCA) Contaminants model) to simulate the behaviour of selected PCB congeners in the River Thames (UK). This is a follow-up to an earlier study where a Level III fugacity model was used to simulate PCB behaviour in the Thames. While coupled models are more complex to apply, we show that they can lead to much better representation of POPs dynamics. The present study shows the importance of accurate sediment and organic carbon simulations to successfully predict riverine PCB transport. Furthermore, it demonstrates the important impact of short-term weather variation on PCB movement through the environment. Specifically, it shows the consequences of the severe flooding, which occurred in early 2014 on sediment PCB concentrations in the River Thames.

Determination of cyclophosphamide and ifosfamide in sewage effluent by stable isotope-dilution liquid chromatography-tandem mass spectrometry.

A reliable and specific method was developed for the determination of the cytotoxic drugs cyclophosphamide and ifosfamide in sewage effluent. The most successful combination was found to be Strata-X solid-phase extraction followed by Florisil® clean-up with analysis by liquid chromatography-tandem mass spectrometry. Quantification by internal standardisation was achieved using custom synthesised d4-cyclophophosphamide. The mass spectrometer was operated in highly selective reaction monitoring (HSRM) mode, which significantly reduced matrix noise and improved sensitivity. Although it suffered from some ionisation suppression, electrospray ionisation (ESI) was found to give an order of magnitude better sensitivity in terms of limit of detection than atmospheric pressure chemical ionisation (APCI). Using final effluent from two different sewage treatment plants, the method was validated following official European guidelines and shown to be a high performance tool for routine analysis at the sub-nanogram per litre level. Depending on the matrix, the limit of detection for cyclophosphamide was between 0.03 ng/L and 0.12 ng/L and for ifosfamide between 0.05 ng/L and 0.09 ng/L. For cyclophosphamide the accuracy and precision, tested at 1.7 ng/L, were 98-109% and ≤ 13%, CV respectively. For ifosfamide the accuracy and precision, tested at 1.1 ng/L, were 98-113% and ≤ 15% CV, respectively. Depending on the sample matrix the absolute recovery of the internal standard was between 57% and 70%. The method was tested by analysis of spot samples taken from the final effluent discharges of two sewage treatment plants; the first using a conventional trickling filter treatment process and second employing activated sludge followed by ultra violet treatment. Cyclophosphamide was detected at 0.19 ng/L at the first plant and at the second detected at 3.7 ng/L and 3.5 ng/L, before and after the UV treatment process; ifosfamide was not detectable at either plant.

Indices of stress in three-spined sticklebacks Gasterosteus aculeatus in relation to extreme weather events and exposure to wastewater effluent.

Whole-body concentrations of cortisol and glucose were measured in three-spined sticklebacks Gasterosteus aculeatus from two rivers (Rivers Ray and Ock) in southern England during a 30 month period in order to assess effects on the stress axis of (1) remediation of a wastewater treatment works (WWTW) effluent (River Ray) and (2) episodic changes in flow rate arising from periods of high rainfall (Rivers Ray and Ock). The postcapture concentrations of cortisol and glucose in fish from both rivers did not exhibit a seasonal periodicity but did show significant between-sample, between-site and between-river variation, superimposed upon a consistent downward trend for each analyte during the monitoring period. Corticosteroid and glucose concentrations following capture were inversely linked with a progressive increase in condition of the fish during this period. Site-dependent trends possibly related to exposure to the WWTW effluent were detected for both analytes in fish from the River Ray. For fish in the River Ray, a significant proportion of variation in both corticosteroid and glucose concentrations, additional to the downward trend with time, was accounted for by temporal proximity of the sample to exceptional flow events arising from episodes of high rainfall and high turbidity. This relationship was not statistically significant for fish from the River Ock. These data suggest that the responsiveness of the stress axis in free-living G. aculeatus may be altered by exposure to WWTW effluent and by exposure to physical changes in the aquatic environment such as those arising from extreme weather events. The magnitude of these effects may be increased by exposure to both stressors concurrently.