Search

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.

The current study evaluates the effect of seawater physico-chemical characteristics on the relationship between the concentration of metals measured by Diffusive Gradients in Thin films (DGT) passive samplers (i.e., DGT-labile concentration) and the concentrations measured in discrete water samples. Accordingly, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to measure the total dissolved metal concentrations in the discrete water samples and the labile metal concentrations obtained by DGT samplers; additionally, lead and cadmium conditional labile fractions were determined by Anodic Stripping Voltammetry (ASV) and total dissolved nickel was measured by Cathodic Stripping Voltammetry (CSV). It can be concluded that, in general, the median ratios of DGT/ICP and DGT/ASV(CSV) were lower than 1, except for Ni (median ratio close to 1) and Zn (higher than 1). This indicates the importance of speciation and time-integrated concentrations measured using passive sampling techniques, which is in line with the WFD suggestions for improving the chemical assessment of waterbodies. It is the variability in metal content in waters rather than environmental conditions to which the variability of the ratios can be attributed. The ratios were not significantly affected by the temperature, salinity, pH, oxygen, DOC or SPM, giving a great confidence for all the techniques used. Within a regulatory context such as the EU Water Framework Directive this is a great advantage, since the simplicity of not needing to use corrections to minimize the effects of environmental variables could help in implementing DGTs within monitoring networks.

This good practice guide is focused on the DGT devices, which are the most widely used passive sampler for metals, covering the following aspects: ■ Principle ■ Handling passive sampling devices for metals ■ Estimation of appropriate field deployment time ■ A Good Practice Guide for the Use of DGTs ■ Passive sampling device preparation and assembly ■ Selection of sampling site and safety precautions ■ Passive sampling device deployment and retrieval ■ Extraction of analytes from passive sampling devices ■ Analysis ■ Calculations

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.

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 balance (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.

This study investigates the relationships among Ni, Cd and Pb's different chemical forms determined by different methodologies in coastal and transitional waters across a broad geographical scale. Concentrations were measured in spot samples and through passive sampling (DGT). High variability of metal concentrations was found among sampling sites and methodologies due to natural water fluctuations rather than to a given metal or method. Total dissolved metal concentrations in spot samples were lower than the EQS-WFD values. The labile fractions of Cd and Pb, measured in spot samples by Anodic Stripping Voltammetry and by DGT-ICPMS, were highly correlated. Similar labilities were found for Cd, while for Pb, the ASV labile fraction was ≈50% lower. These results reflect the pool of mobile and labile species available towards each technique kinetic window, and they seem not to be affected by discrete sampling flaws.

Terrestrially-derived dissolved organic carbon (DOC) and nitrogen (DON) transported by rivers have been recognised as contributors to aquatic nutrient burdens, and can be of importance in rivers and estuaries already impacted by anthropogenic inorganic nutrient discharges. The concentration of DOC and DON and the flux of both to the estuary and ultimately the coastal zone is dependent upon many factors including rainfall, catchment land use, and biological processes. DOC and DON concentrations together with nitrate plus nitrite and ammonium concentrations were measured in the anthropogenically-impacted estuary Christchurch Harbour (UK) and at sites in the lower reaches of its two source rivers, the Hampshire Avon and the Stour, at weekly intervals for a year during which time several extreme rainfall events occurred. A series of transects along the estuary were also performed after weekly sampling was completed. DOC concentrations were correlated between both rivers and the estuary and were positively related to increases in river flow, but DON concentrations revealed a more complicated picture. Peak instantaneous fluxes of DOC and DON exceeded 60,000 kg C d−1 and 7000 kg N d−1 respectively both in the Stour and the estuary during high flow periods. The sources of both and routes by which they enter the aquatic system may account for the differences in dynamics, with flushing of superficial soils being a key source of DOC and point sources such as sewage treatment works being proposed as sources of DON. Removal processes within the estuary were also of importance for DON concentrations whilst DOC behaved more conservatively with some evidence of local production within the estuary. Estimated annual loads of DON and DOC to the coastal zone from Christchurch Harbour were 118 kg N km−2 y−1 and 2296 kg C km−2 y−1.

Pesticides present at trace concentrations are a common cause of poor water quality. Their concentrations can change dynamically, due to the stochastic nature of pesticide pollution. Consequently, characterisation of pesticide residues that are intermittently present, poses significant monitoring and analytical challenges. Traditional approaches rely on quantitation of a limited number of pesticides present in a discrete water sample. Expanding the analytical suite and/or the frequency of sampling to meet these challenges is often impractical. Comprehensive methods are needed, with selectivity and sensitivity for the hundreds of pesticides potentially present, and temporal representativeness to ensure changing conditions are understood, in order to identify and prioritise risk. Recent analytical advances have enabled the targeted screening of hundreds of compounds in the same run, and automated work-flows can now reliably identify compounds through the comparison of retention time and accurate mass with spectral libraries. Screening generates large qualitative data sets, therefore, there is a need for improved monitoring methods and data interpretation strategies to reduce the need for repetition, and increase the quality of information for end-users. Passive sampling is an in situ time integrative technique, increasingly used for monitoring pesticides in water. Here, we describe a method using the Chemcatcher® passive sampler, coupled to targeted screening using liquid chromatography-quadrupole-time-of-flight mass spectrometry, and a commercially available library. Statistical analysis was performed using Agilent Mass Profiler Professional software. Water sampling took place over one year, at three riverine sites in the south of England, UK. Statistical interpretation of time integrative data from passive sampling could distinguish regular and episodic pesticide inputs, and detected compounds neglected by routine monitoring methods. One hundred and eleven pesticides were identified including legacy and current use compounds with diverse origins and uses. Spatial and temporal trends were identified enabling prioritisation of seasonal monitoring at each site. This approach maximises the utility of qualitative assessment and may help water quality managers to rationalise pesticide fate in future, providing significant additional insight without the need to increase the scope and cost of monitoring.

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. Electronic supplementary material The online version of this article (10.1007/s11356-020-09077-5) contains supplementary material, which is available to authorized users.

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. Electronic supplementary material The online version of this article (10.1007/s10661-020-8138-0) contains supplementary material, which is available to authorized users.

Metaldehyde is a molluscicide and the active ingredient in formulated slug pellets used for the protection of crops. Due to its mobility in the environment it is frequently found in river catchments, often at concentrations exceeding the EU Drinking Water Directive limit of 100 ng L-1 for a single pesticide. This presents a major problem for water companies in the UK where such waters are abstracted for production of potable drinking water supplies. Therefore, it is important to understand the sources, transport and fate of this emerging pollutant of concern in the aquatic environment. We monitored metaldehyde in two contrasting river catchments (River Dee (8 sites) and River Thames (6 sites)) over a twelve month period that coincided with the agricultural application period of the molluscicide. Spot samples of water were collected typically weekly or fortnightly. Chemcatcher® passive samplers were deployed consecutively every two weeks. At the River Dee, there was little variability in the concentrations of metaldehyde (-1) measured in the spot samples of water. The Chemcatcher® gave similar time-weighted average concentrations which were higher following increased rain fall events. At the River Thames, concentrations of metaldehyde varied more widely (-1) with several samples exceeding 100 ng L-1. Generally these concentrations were reflected in the time-weighted average concentrations obtained using the Chemcatcher®. Both monitoring techniques gave complementary data for identifying input sources, and in the development of catchment management plans and environmental remediation strategies.

Assessment of the effects of sediment metal contamination on biological assemblages and function remains a key question in marine management, especially in relation to disposal activities. However, the appropriate description of bioavailable metal concentrations within pore-waters has rarely been reported. Here, metal behaviour and availability at contaminated dredged material disposal sites within UK waters were investigated using Diffusive Gradient in Thin films (DGT). Three stations, representing contrasting history and presence of dredge disposal were studied. Depth profiles of five metals were derived using DGT probes as well as discrete analysis of total metal concentrations from sliced cores. The metals analysed were: iron and manganese, both relevant to sediment biogeochemistry; cadmium, nickel and lead, classified as priority pollutants. DGT time-integrated labile flux profiles of the metals display behaviour consistent with increasingly reduced conditions at depth and availability to DGT (iron and manganese), subsurface peaks and a potential sedimentary source to the water column related to the disposal activity (lead and nickel) and release to pore-water linked to decomposition of enriched phytodetritus (cadmium). DGT data has the potential to improve our current understanding of metal behaviour at impacted sites and is suitable as a monitoring tool. DGT data can provide information on metal availability and fluxes within the sediment at high depth-resolution (5 mm steps). Differences observed in the resulting profiles between DGT and conventional total metal analysis illustrates the significance of considering both total metals and a potentially labile fraction. The study outcomes can help to inform and improve future disposal site impact assessment, and could be complemented with techniques such as Sediment Profile Imagery for improved biologically relevance, spatial coverage and cost-effective monitoring and sampling of dredge material disposal sites. Additionally, the application of this technology could help improve correlative work on biological impacts under national and international auspices when linking biological effects to more biologically relevant metal concentrations.

Metaldehyde is the active ingredient in most slug pellets used to protect crops. This molluscicide is considered an emerging pollutant and is frequently detected in surface water bodies above the EU statutory drinking water limit of 0.1 μg L−1 for a pesticide. This presents a challenge for providers of drinking water. Understanding the sources, transport and environmental fate of this compound is therefore important. This critical review discusses these aspects including monitoring and analytical techniques used for the detection of metaldehyde in environmental matrices. Novel techniques used for the removal of metaldehyde from drinking water are presented together with potential catchment management strategies and initiatives useful for the mitigation of this molluscicide in the environment.

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.

International audience; Groundwater systems are being increasingly used to provide potable and other water supplies. Due to human activities, a range of organic pollutants is often detected in groundwater. One source of groundwater contamination is via stormwater infiltration basins, however, there is little information on the types of compounds present in these collection systems and their influence on the underlying groundwater. We developed an analytical strategy based on the use of passive sampling combined with liquid chromatography/high resolution quadrupole-time-of-flight mass spectrometry for screening for the presence of pesticide and pharmaceutical compounds in groundwater and stormwater runoff. Empore™ disk-based passive samplers (SDB-RPS and SDB-XC sorbents) were exposed, using for the first time a new specially designed deployment rig, for 10 days during a rainfall event in five different stormwater infiltration systems around Lyon, France. Stormwater runoff and groundwater (via a well, upstream and downstream of each basin) was sampled. Exposed Empore™ disks were solvent extracted (acetone and methanol) and the extracts analysed using a specific suspect compound screening workflow. High resolution mass spectrometry coupled with a suspect screening approach was found to be a useful tool as it allows a more comprehensive analysis than with targeted screening whilst being less time consuming than non-targeted screening. Using this analytical approach, 101 suspect compounds were tentatively identified, with 40 of this set being subsequently confirmed. The chemicals detected included fungicides, herbicides, insecticides, indicators of human activity, antibiotics, antiepileptics, antihypertensive and non-steroidal anti-inflammatory drugs as well as their metabolites. Polar pesticides were mainly detected in groundwater and pharmaceuticals were more frequently found in runoff. In terms of detection frequency of the pollutants, groundwater impacted by infiltration was found not to be significantly more contaminated than non-impacted groundwater.

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. Electronic supplementary material The online version of this article (10.1007/s10661-019-7515-z) contains supplementary material, which is available to authorized users.

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. Electronic supplementary material The online version of this article (10.1007/s10661-019-7221-x) contains supplementary material, which is available to authorized users.

The presence of polar pesticides in environmental waters is a growing problem. After application their migration into the aqueous phase is promoted by their high water solubility. Transport processes are usually complex and inputs are generally stochastic; this makes monitoring of this class of pesticides challenging using low volume spot samples of water. Recently there has been a trend to use passive samplers to monitor pesticides in river catchments as it is an in-situ time integrative sampling technique. The three main types of device used for this purpose are, Chemcatcher®, POCIS and o-DGT. This article reviews the fate and current state-of-the-art for monitoring polar pesticides in aqueous matrices. Principles and the theory of passive sampling and strategies for passive sampler design and operation are presented. Advances in the application of passive sampling devices for measuring polar pesticides are extensively critiqued; future trends in their use are also discussed.

Acidic herbicides are used to control broad-leaved weeds. They are stable, water-soluble, and with low binding to soil are found frequently in surface waters, often at concentrations above the EU Drinking Water Directive limit of 0.10 μg L−1. This presents a problem when such waters are abstracted for potable supplies. Understanding their sources, transport and fate in river catchments is important. We developed a new Chemcatcher® passive sampler, comprising a 3M Empore™ anion-exchange disk overlaid with a polyethersulphone membrane, for monitoring acidic herbicides (2,4-D, dicamba, dichlorprop, fluroxypyr, MCPA, MCPB, mecoprop, tricolpyr). Sampler uptake rates (R s = 0.044–0.113 L day−1) were measured in the laboratory. Two field trials using the Chemcatcher® were undertaken in the River Exe catchment, UK. Time-weighted average (TWA) concentrations of the herbicides obtained using the Chemcatcher® were compared with concentrations measured in spot samples of water. The two techniques gave complimentary monitoring data, with the samplers being able to measure stochastic inputs of MCPA and mecoprop occurring in field trial 1. Chemcatcher® detected a large input of MCPA not found by spot sampling during field trial 2. Devices also detected other pesticides and pharmaceuticals with acidic properties. Information obtained using the Chemcatcher® can be used to develop improved risk assessments and catchment management plans and to assess the effectiveness of any mitigation and remediation strategies.

Organotins present a toxicological risk to biota in the aquatic environment. Understanding the behaviour of these compounds in sediment is challenging, with sophisticated analytical techniques required for their measurement. We investigated the use of silica-bound sorbents for diffusive gradients in thin-films (DGT) adsorption gels to pre-concentrate five organotins (monobutlytin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPhT), triphenyltin (TPhT)) found frequently in coastal sediment. C8 sorbent showed optimum performance in uptake and recovery of organotins for pH and ionic strength ranges typical of coastal waters. Recoveries from adsorption gels deployed in filtered sea water were MBT = 123 ± 20%, DBT = 75 ± 12%, TBT = 81 ± 16%, DPhT = 72 ± 30%, TPhT = 58 ± 10% respectively. Devices were used to investigate DGT fluxes and pore water concentrations of organotins in coastal sediment collected from a contaminated site. DGT fluxes measured in sediment cores for the five organotins ranged between 4.3 × 10−8 – 1.6 ×10−5 ng cm2 s−1. The depletion of organotin species within pore waters at the interface with DGT devices was measured over a series of deployment times (2, 7, 14, 21 and 28 days) and provided estimates of the concentration of organotins in pore waters at Langstone Harbour, UK, prior to depletion by the DGT device and information on their spatial heterogeneity. The novel in situ DGT device developed can pre-concentrate organotins from pore waters in coastal sediment core samples and allows their detection at low environmental concentrations using conventional gas chromatographic/mass spectrometric instrumentation. Use of the DGT device overcomes many problems associated with the conventional pore water sampling of organotins. Our preliminary data suggests it has potential in the future to be a useful tool in investigating the environmental fate of these pollutants. The use of the C8 gel will also allow for the simultaneous sequestration of other semi- and non-polar analytes present in the pore water.

Metaldehyde is a potent molluscicide. It is the active ingredient in most slug pellets used for crop protection. This polar compound is considered an emerging pollutant. Due to its environmental mobility, metaldehyde is frequently detected at impacted riverine sites, often at concentrations above the EU Drinking Water Directive limit of 0.1 µg L−1 for an individual pesticide. This presents a problem when such waters are abstracted for use in the production of potable water supplies, as this chemical is difficult to remove using conventional treatment processes. Understanding the sources, transport and fate of this pollutant in river catchments is therefore important. We developed a new variant of the Chemcatcher® passive sampler for monitoring metaldehyde comprising a Horizon Atlantic™ HLB-L disk as the receiving phase overlaid with a polyethersulphone membrane. The sampler uptake rate (Rs) was measured in semi-static laboratory (Rs = 15.7 mL day−1) and in-field (Rs = 17.8 mL day−1) calibration experiments. Uptake of metaldehyde was linear over a two-week period, with no measurable lag phase. Field trials (five consecutive 14 day periods) using the Chemcatcher® were undertaken in eastern England at three riverine sites (4th September-12th November 2015) known to be impacted by the seasonal agricultural use of metaldehyde. Spot samples of water were collected regularly during the deployments, with concentrations of metaldehyde varying widely (~ 0.03–2.90 µg L−1) and often exceeding the regulatory limit. Time weighted average concentrations obtained using the Chemcatcher® increased over the duration of the trial corresponding to increasing stochastic inputs of metaldehyde into the catchment. Monitoring data obtained from these devices gives complementary information to that obtained by the use of infrequent spot sampling procedures. This information can be used to develop risk assessments and catchment management plans and to assess the effectiveness of any mitigation and remediation strategies.

Estimates of bed stability in coastal environments are essential to physical, biological, and chemical investigations of cohesive sediments. The Core Mini Flume (CMF), a 200 mm diameter annular flume has been designed to undertake sediment stability experiments on collected intact sediment box cores. Bed properties were assessed for replicate box cores at 3 contrasting sites in UK coastal waters (Tyne [in 2011 and 2012], Plymouth and Celtic Deep), each covering a maximum area of 80 m2. No significant horizontal spatial variations were found for grain size, bulk density, porosity, or oxygen penetration at the sites. Resuspension experiments performed on replicate cores yielded highly replicable results for each site, giving average erosion thresholds of 0.33 ± 0.02 (Tyne 2011), 0.215 ± 0.03 (Tyne 2012), 0.23 ± 0.01 (Plymouth), and 0.09 ± 0.006 (Celtic Deep) Pa and erosion depths of 10.7 ± 1.7, 6.63 ± 1.10, 3.65 ± 0.95, and 4.6 ± 0.5 mm. Using an already established methodology, the CMF allowed detailed replicate experiments to be performed on-board ship rapidly after sediment collection, while minimizing the time spent at each station. The use of intact box cores minimized the disturbance to the bed often associated with recovering material to a laboratory or remoulding a bed. We have demonstrated that the convenience of laboratory-based methodologies can be combined with the benefit of prompt investigations on undisturbed beds complete with overlying in situ water to produce robust measurements of sediment stability.

A phytoplankton bloom shown to be naturally iron (Fe) induced occurs north of the Crozet Islands (Southern Ocean) every year, providing an ideal opportunity to study dissolved trace metal distributions within an island system located in a high nutrient low chlorophyll (HNLC) region. We present water column profiles of dissolved nickel (Ni), zinc (Zn), cobalt (Co), cadmium (Cd), lead (Pb), aluminium (Al), and manganese (Mn) obtained as part of the NERC CROZEX program during austral summer (2004–2005). Two stations (M3 and M1) were sampled downstream (north) of Crozet in the bloom area and near the islands, along with a control station (M2) in the HNLC zone upstream (south) of the islands. The general range found was for Ni, 4.64–6.31 nM; Zn, 1.59–7.75 nM; Co, 24–49 pM; Cd, 135–673 pM; Pb, 6–22 pM; Al, 0.13–2.15 nM; and Mn, 0.07–0.64 nM. Vertical profiles indicate little island influence to the south with values in the range of other trace metal deprived regions of the Southern Ocean. Significant removal of Ni and Cd was observed in the bloom and Zn was moderately correlated with reactive silicate (Si) indicating diatom control over the internal cycling of this metal. Higher concentrations of Zn and Cd were observed near the islands. Pb, Al, and Mn distributions also suggest small but significant atmospheric dust supply particularly in the northern region.

Pore-fluid Fe isotopes may be a unique tracer of sediment respiration by dissimilatory Fe-reducing bacteria, but to date, pore-fluid Fe isotope measurements have been restricted to continental shelf settings. Here, we present δ56Fe values of pore fluids from two distinct sedimentary settings: (1) a riverine-dominated site on the northern California margin (Eel River shelf; 120 m water depth) and (2) biogenic opal-rich volcaniclastic deep-sea sediments from the Southern Ocean (north and south of the Crozet Plateau; 3000-4000 m water depth). The Fe isotope compositions of Crozet region pore fluids are significantly less fractionated (δ56Fe = +0.12‰ to -0.01‰) than the Eel River shelf (δ56Fe = -0.65‰ to -3.40‰) and previous studies of pore-fluid Fe isotopes, relative to average igneous rocks. Our data represent the first measurements of Fe isotope compositions in pore fluids from deep-sea sediments. A comparison of pore-fluid δ56Fe with the relative abundance of highly labile Fe in the reactive sedimentary Fe pool demonstrates that the composition of Fe isotopes in the pore fluids refl ects the different extent of sedimentary Fe redox recycling between these sites. © 2009 Geological Society of America.

Graphical abstract, Tributyltin (TBT) is a legacy pollutant in the aquatic environment, predominantly from its use in anti-foulant paints and is listed as a priority hazardous substance in the European Union’s Water Framework Directive (WFD). Measuring low concentrations of TBT and other organotins (e.g. monobutyltin (MBT), dibutyltin (DBT), diphenyltin (DPhT) and triphenyltin (TPhT)) at sub ng/L concentrations in coastal waters using standard laboratory instrumentation is very challenging. Conventional, low injection volume gas chromatography/mass spectrometry (GC/MS) combined with liquid-liquid extraction typically achieves limits of detection for TBT ∼10 ng L−1. We describe a simple, programmed temperature vaporisation-large injection volume (50 μL), GC/MS selected ion monitoring method for measuring DBT, TBT, DPhT and TPhT in coastal waters at lower concentrations. Quantification of MBT was not possible using these injection volumes but was achieved using a 10 μL injection volume together with a reduced injection speed. This new approach offers: • When using a 50 μL injection, limits of detection = 0.70 ng L−1 and limits of quantification = 2.1 ng L−1 for TBT were achieved in derivatised standards. • Recoveries of TBT and TPhT from coastal water >97%. • Time consuming, off-line sample pre-concentration methods are unnecessary.

Graphical abstract, The molluscicide metaldehyde (2,4,6,8-tetramethyl-1,3,5,7-tetraoxocanemetacetaldehyde) is an emerging pollutant. It is frequently detected in surface waters, often above the European Community Drinking Water Directive limit of 0.1 μg/L for a single pesticide. Gas chromatography mass spectrometry (GC–MS) can be used to determine metaldehyde in environmental waters, but this method requires time consuming extraction techniques prior to instrumental analysis. Use of liquid chromatography-tandem mass spectrometry (LC–MS/MS) can overcome this problem. We describe a novel LC–MS/MS method, using a methylamine mobile phase additive, coupled with on-line sample enrichment that allows for the rapid and sensitive measurement of metaldehyde in surface water. Only the methylamine adduct of metaldehyde was formed with other unwanted alkali metal adducts and dimers being suppressed. As considerably less collision energy is required to fragment the methylamine adduct, a five-fold improvement in method sensitivity, compared to a previous method using an ammonium acetate buffer mobile phase was achieved. This new approach offers: • A validated method that meets regulatory requirements for the determination of metaldehyde in surface water. • Improved reliability of quantification over existing LC–MS/MS methods by using stable precursor ions for multiple reaction monitoring. • Low limits of quantification for tap water (4 ng/L) and river water (20 ng/L) using only 800 μL of sample; recoveries > 97%.

Convergent plate volcanism typically occurs close to the oceans, hence a high proportion of fresh, highly reactive, volcanogenic material is rapidly deposited onto the seafloor. Previous studies (Haeckel et al., 2001) have shown that dissolved oxygen (O2) is extensively depleted in the pore waters of ash deposited in the South China Sea from the 1991 Pinatubo eruption. Here, we report the results of an extensive field, laboratory and modelling study of dissolved O2 concentrations and ancillary geochemical data (pore water NO2 + NO3 and solid phase FeII/FeIII and organic carbon) in the sediments surrounding the volcanic island of Montserrat, Lesser Antilles. Dissolved O2 is depleted to zero within 0.3 cm of the sediment–water interface in sites containing the thickest layers of volcanogenic material (35 cm), compared to a penetration depth of ?6 cm in sites with minimal ash loading of

Benthic-pelagic exchange processes are recognised as important nutrient sources in coastal areas, however, the relative impact of diffusion, resuspension and other processes such as bioturbation and bioirrigation are still relatively poorly understood. Experimental ship-based data are presented showing the effects of diffusion and resuspension on cohesive sediments at a temperate shelf location in the North Sea. Measurements of diffusive fluxes in both spring (1.76, 0.51, −0.91, 17.6 μmol/m2/h) and late summer (8.53, −0.03, −1.12, 35.0 μmol/m2/h) for nitrate, nitrite, phosphate and dissolved silicon respectively, provided comparisons for measured resuspension fluxes. Increases in diffusive fluxes of nitrate and dissolved silicon to the water column in late summer coincided with decreases in bottom water oxygen concentrations and increases in temperature. Resuspension experiments using a ship board annular flume and intact box core allowed simultaneous measurement of suspended particulate matter, water velocity and sampling of nutrients in the water column during a step wise increase in bed shear velocity. The resuspension of benthic fluff led to small but significant releases of phosphate and nitrate to the water column with chamber concentration increasing from 0.70–0.76 and 1.84–2.22 μmol/L respectively. Resuspension of the sediment bed increased water column concentrations of dissolved silicon by as much as 125% (7.10–15.9 μmol/L) and nitrate and phosphate concentrations by up to 67% (1.84–3.08 μmol/L) and 66% (0.70–1.15 μmol/L) respectively. Mass balance calculations indicate that processes such as microbial activity or adsorption/desorption other than simple release of pore water nutrients must occur during resuspension to account for the increase. This study shows that resuspension is potentially an important pathway for resupplying the water column with nutrients before and during phytoplankton blooms and should therefore be considered along with diffusive fluxes in future ecosystem models.

PurposeThis article aims to review the different devices that are available for the in situ monitoring of analytes found in the marine environment.Design/methodology/approachFollowing a short introduction to the topic, this paper discusses physical‐ and chemical‐based sensors, automatic analysers (flow injection, spectroscopic and spectrometric), electrochemical devices and biosensors.FindingsA wide range of in situ monitoring systems (and associated deployment apparatus) for measuring concentrations of various analytes (e.g. nutrients, organic chemicals and metallic elements) have been developed in recent decades. Many of these systems are still at the laboratory or prototype stage and are yet to be fully developed into commercially available products. The harsh conditions often found in the marine environment can further limit the utility and application of these sensors. Further development work is needed; however, the need now is for field deployments, validation and inter‐calibration between sensors and other analytical measurement techniques.Originality/valueThis paper provides up‐to‐date information on in situ technologies that are available, either at the laboratory and prototype stages or commercially, and are suitable for deployment in the marine environment. Applications of these sensing systems are discussed together with their associated advantages and disadvantages over other existing water monitoring methods.

Volcanogenic sediments are typically rich in Fe and Mn-bearing minerals that undergo substantial alteration during early marine diagenesis, however their impact on the global biogeochemical cycling of Fe and Mn has not been widely addressed. This study compares the near surface (0-20cm below sea floor [cmbsf]) aqueous (5cmbsf and largely controlled by the oxidation of organic matter. Dissolved Fe and Mn distributions in Montserrat pore waters were lowest in the surface oxic-layer (0.3μM Fe; 32μM Mn), with maxima (20μM Fe; 200μM Mn) in the upper 1-15cmbsf. Unlike Montserrat, Fe and Mn in Crozet pore waters were ubiquitously partitioned between 0.2μm and 0.02μm filtrations, indicating that the pore water distributions of Fe and Mn in the (traditionally termed) 'dissolved' size fraction are dominated by colloids, with respective mean abundances of 80% and 61%. Plausible mechanisms for the origin and composition of pore water colloids are discussed, and include prolonged exposure of Crozet surface sediments to early diagenesis compared to Montserrat, favouring nano-particulate goethite formation, and the elevated dissolved Si concentrations, which are shown to encourage fine-grained smectite formation. In addition, organic matter may stabilise authigenic Fe and Mn in the Crozet pore waters. We conclude that volcanogenic sediment diagenesis leads to a flux of colloidal material to the overlying bottom water, which may impact significantly on deep ocean biogeochemistry. Diffusive flux estimates from Montserrat suggest that diagenesis within tephra deposits of active island volcanism may also be an important source of dissolved Mn to the bottom waters, and therefore a source for the widespread hydrogenous MnO x deposits found in the Caribbean region. © 2011 Elsevier Ltd.

The in situ annular flume, Voyager II, was deployed at three sites in the North Sea in order to investigate resuspension events, to determine the physical characteristics of the seabed, to determine the threshold of resuspension of the bed and to quantify erosion rates and erosion depths. These are the first controlled, in situ flume experiments to study resuspension in the North Sea, and were combined with long-term measurements of waves and currents. Resuspension experiments were undertaken at two muddy, and one sandy site: north of the Dogger Bank (DG: water depths ∼80 m, very fine, poorly sorted, very fine-skewed sediment experiencing seasonal thermal stratification of the water column along with oxygen depletion); the Oyster Grounds (OG: ∼40 m, similar bed properties, year round water column thermal stratification, Atlantic forcing); and in the Sean Gas Field (SGF: ∼20 m, moderately sorted, very coarse-skewed sand, and well mixed water column). The erosion thresholds of the bed were found to be 0.66–1.04 Pa (DG) and 0.91–1.27 Pa (OG), with corresponding erosion depths of 0.1–0.15 mm and 0.02–0.06 mm throughout the experiments. Evaluation of a year of current velocities from 2007 indicated that at OG, resuspension of the consolidated bed was limited to on average ∼8% of the time as a result of tidal forcing alone for short ( Resuspension of bed material and erosion rates were closely related to applied bed shear stresses, and eroded depths were significantly correlated with the physical properties of the bed. Therefore, while complex variations in biogeophysical factors affected the critical threshold of erosion, once exceeded, erosion rates were related to the nature of the sediment.

Recently, it has been proposed that anthropogenic CO2 emissions may affect marine ecosystems by causing ocean acidification. In particular, it is suggested that within acidified waters, calcifying organisms would be subject to malformation and enhanced dissolution. Here, we present evidence suggesting that this process occurs naturally where explosive volcanism deposits ash directly into ocean surface waters. Sediment cores from around the island of Montserrat, Lesser Antilles volcanic arc, contain distinct horizons of planktic fauna associated with recently deposited volcanic ash layers from the Soufrière Hills volcano. Within these layers are abundant thecosome pteropod shells that display evidence of partial dissolution and etching of their aragonitic shells, and appear to have suffered mass mortality during large eruptions from the volcano. Laboratory studies show that the acids bound to ash surfaces from the 2003 volcanic dome collapse event of the Soufrière Hills volcano could have caused the upper 5 m of the water column to become undersaturated with respect to aragonite. When combined with the large fluxes of acidic aerosols (principally as SO2) from the volcano during eruptions, it is proposed that volcanogenic ocean acidification by marine ash falls is a significant contributing factor to these observed mass mortality events.

article Natural iron fertilization processes are occurring around the Crozet Islands (46°26'S-52°18'E), thus relieving the water masses from the normally encountered High Nutrients Low Chlorophyll (HNLC) conditions of the Southern Ocean. During austral summers 2004/2005 and 2005/2006, iron and aluminium concentrations were investigated in large particles (N53 µm) collected from just below the mixed layer at stations under the influence of island inputs, and also in adjacent HNLC waters. These large particles are anticipated to sink out of the mixed layer, and to reflect the net effects of input and cycling of these elements in the overlying mixed layer. Labile and refractory fractions were determined by a two-stage leaching technique. Data showed that water masses downstream of the islands were enriched in total iron and aluminium (0.25-2.68 nmol L �1 and 0.34-3.28 nmol L �1 respectively), relative to the southern HNLC control sites (0.15-0.29 nmol L �1 for Fe and 0.12-0.29 nmol L �1 for Al), with only a small fraction (typically b1%) being acid leachable in both environments. Particulate iron predominantly derived from the island system represents a significant fraction of the total water column iron inventory and may complement dissolved Fe inputs that help support the high summer productivity around the Crozet islands.

Summary Nectochaete larvae of the ecologically and economically important ragworm, Nereis virens, were exposed to cadmium, chromium, copper, lead and zinc dissolved in seawater to nominal concentrations ranging from 0 to 5000 μg l−1. Copper was the most toxic (mean LC50 of 76.5 μg l−1 ± 95% CI 73.8–79.2 after 96 h exposure) and so was used for subsequent experiments. Exposure of gametes to greater than 500 μg l−1 copper for 2 or 4 h at 10°C prior to fertilization, or a 10 min exposure during fertilization, significantly reduced embryo developmental success. The effect of copper on larval settlement was also assessed using sediment spiked to a range of concentrations (0, 50, 250, 500, 1000 mg kg!1 dry weight). Significantly fewer larvae were found in sediment of $250 mg kg!1 in comparison to the control or the 50 mg kg!1 treatment. Assessment of living larvae also confirmed a significant reduction in settlement, but in all treatments compared to the control, although the number of dead larvae also increase...

The annual phytoplankton bloom occurring north of the Crozet Plateau provides a rare opportunity to examine the hypothesis that natural iron fertilization can alleviate high-nutrient low-chlorophyll (HNLC) conditions normally associated with the Southern Ocean. Therefore, during CROZet natural iron bloom and EXport experiment (CROZEX), a large multidisciplinary study performed between November 2004 and January 2005, measurements of total dissolved iron (DFe⩽0.2 μm) were made on seawater from around the islands and atmospheric iron deposition estimated from rain and aerosol samples. DFe concentrations were determined by flow injection analysis with N,N-dimethyl-p-phenylenediamine dihydrochloride (DPD) catalytic spectrophotometric detection. DFe concentrations varied between 0.086 and 2.48 nM, with low values in surface waters. Enrichment of dissolved iron (>1 nM) at close proximity to the islands suggests that the plateau and the associated sediments are a source of iron. Waters farther north also appear to be affected by this input of coastal and shelf origin, although dissolved iron concentrations decrease as a function of distance to the north of the plateau with a gradient of ∼0.07 nM km−1 at the time of sampling. Using lateral and vertical diffusion coefficients derived from Ra isotope profiles and also estimates of atmospheric inputs, it was then possible to estimate a DFe concentration of ∼0.55 nM to the north of the islands prior to the bloom event, which is sufficient to initiate the bloom, the lateral island source being the largest component. A similar situation is observed for other Sub-Antarctic Islands such as Kerguelen, South Georgia, that supply dissolved iron to their surrounding waters, thus enhancing chlorophyll concentrations.

Elevated levels of productivity in the wake of Southern Ocean island systems are common despite the fact that they are encircled by high-nutrient low-chlorophyll (HNLC) waters. In the Crozet Plateau region, it has been hypothesized that iron from island runoff or sediments of the plateau could be fueling the austral summer phytoplankton bloom. Here, we use radium isotopes to quantify the rates of surface-ocean iron supply fueling the bloom in the Crozet Plateau region. A 1D eddy-diffusion-mixing model applied to a 228 Ra profile (t1/2 ¼ 5.75 years) at a station north of the islands suggests fast vertical mixing in the upper 300 m (Kz ¼ 11–100 cm 2 s � 1 ) with slower mixing between 300 and 1000 m (Kz ¼ 1.5 cm 2 s � 1 ). This estimate is discussed in the context of Kz derived from the CTD/LADCP data. In combination with the dissolved Fe profile at this location, we estimated a vertical flux of between 5.6 and 31 nmol Fe m � 2 d � 1 . The cross-plateau gradients in the short-lived radium isotopes, 224 Ra (t1/2 ¼ 3.66 d) and 223 Ra (t1/2 ¼ 11.4 d), yielded horizontal eddy diffusivities (Kh )o f 39 and 6.6 m 2 s � 1 , respectively. If we assume that the islands (surface runoff) alone were supplying dissolved Fe to the bloom region, then the flux estimates range from 2.3 to 14 nmol Fe m � 2 d � 1 . If the plateau sediments are considered a source of Fe, and conveyed to the bloom region through deep winter mixing combined with horizontal transport, then this flux may be as high as 64–390 nmol Fe m � 2 d � 1 . Combined, these Fe sources are sufficient to initiate and maintain the

Biotite dissolution rates were determined at 25°C, at pH 2-6, and as a function of mineral composition, grain size, and aqueous organic ligand concentration. Rates were measured using both open- and closed-system reactors in fluids of constant ionic strength. Element release was non-stoichiometric and followed the general trend of Fe, Mg>Al>Si. Biotite surface area normalised dissolution rates (ri) in the acidic range, generated from Si release, are consistent with the empirical rate law:ri=kH,iaH+xiwhere kH,i refers to an apparent rate constant, aH+ designates the activity of protons, and xi stands for a reaction order with respect to protons. Rate constants range from 2.15×10-10 to 30.6×10-10(molesbiotitem-2s-1) with reaction orders ranging from 0.31 to 0.58. At near-neutral pH in the closed-system experiments, the release of Al was stoichiometric compared to Si, but Fe was preferentially retained in the solid phase, possibly as a secondary phase. Biotite dissolution was highly spatially anisotropic with its edges being ~120times more reactive than its basal planes. Low organic ligand concentrations slightly enhanced biotite dissolution rates. These measured rates illuminate mineral-fluid-organism chemical interactions, which occur in the natural environment, and how organic exudates enhance nutrient mobilisation for microorganism acquisition., SCOPUS: ar.j, info:eu-repo/semantics/published

Vertical profiles of trace metals were measured at 1-mm intervals by deploying DGT probes in sediment cores collected from the deep Atlantic Ocean (Feni Drift) before and after the spring phytoplankton bloom. DGT (diffusive gradients in thin-films) accumulates metals on a chelating resin after their diffusive transport through a layer of hydrogel. The mean concentration of metal in the porewaters at the surface of the device during its deployment was derived from the measured mass of metal. Well-defined laboratory systems were used to establish the reproducibility and accuracy of the DGT technique for measuring metals at 1-mm intervals. The Fe and Mn profiles showed the expected redox sequence with depth, with additional fine-scale (2–5 mm) features. The close correspondence between the Mn and Co profiles, on both coarse and fine scales, showed that their chemistry is closely coupled in sediments as well as water columns. Changes in the background concentrations of Cd, Cu, Ni and Zn with depth were well correlated with Mn and Co, but the four metals also displayed mm-scale maxima that were largely independent of Mn, Co or Fe. Two-dimensional measurements at a 100-μm resolution on a DGT probe, deployed in situ with an autonomous lander, showed that the maxima were most likely associated with near-spherical, highly localised sources. The results were consistent with release of Cd, Cu, Ni and Zn from organic and planktonic skeletal material. Where there was associated release of Mn and/or Fe, through their oxides acting as electron acceptors in the decomposition of the organic matter, trace metals could also be supplied by release from the oxides. The microniches responsible for high local concentrations of metals in the porewaters were hypothesised to be due to downward mixing of material by burrowing organisms, known to be prevalent in these sediments. Much of this material appeared to be present as faecal pellets of various origins, with sizes in the range of 50um to 1 cm.

We report real-time, in situ determination of free copper ion at picomolar levels in seawater using a fluorescence-based fiber optic biosensor. The sensor transducer is a protein molecule, site-specifically labeled with a fluorophore that is attached to the distal end of an optical fiber, which binds free Cu(II) with high affinity and selectivity. The transducer reports the metal's concentration as a change in fluorescence intensity or lifetime, using a frequency domain approach. The transducer's response time is diffusion-limited, with a typical measurement requiring 30 s. The sensor demonstrates a detection limit of 0.1 pM free Cu(II) in a seawater model. Accuracy and precision of the sensor were at least comparable to cathodic ligand exchange/adsorptive cathodic stripping voltammetry. Measurements of tidal flushing of a copper-contaminated inlet are shown.

The effect of metal interactions on phytochelatin production by marine phytoplankton has received little attention but yet is critical to understanding the biochemical production of this potentially important metal-binding ligand in the field. Cd, Cu, and Zn additions were made singly and in combination to three species of laboratory cultures and to a natural algal assemblage from pristine coastal seawater. In the laboratory cultures intracellular phytochelatin varied with metal exposure and demonstrated metal- and concentration-dependent synergisms and antagonisms. Most notably, the addition of all three metals together greatly suppressed phytochelatin production in all cultures. Particulate phytochelatin was also measured at two field sites. In the field, phytochelatin production is related to ambient Cd, Cu, and Zn levels, and the deviations from the dose-response relationship are potentially explained by metal interactions similar to those observed in the laboratory cultures. Though particulate glutathione concentrations were very low in some field samples, it did not appear to limit phytochelatin production. Particulate phytochelatin concentrations in samples from both field sites were very similar to those measured in the laboratory cultures when exposed to all three metals together, and thus phytochelatin levels in the field may be regulated by the interaction of Cd, Cu, and Zn.

Commercially available Diphonix(®) resin (TrisKem International) was evaluated as a receiving phase for use with the diffusive gradients in thin-films (DGT) passive sampler for measuring uranium. This resin has a high partition coefficient for actinides and is used in the nuclear industry. Other resins used as receiving phases with DGT for measuring uranium have been prone to saturation and significant chemical interferences. The performance of the device was evaluated in the laboratory and in field trials. In laboratory experiments uptake of uranium (all 100% efficiency) by the resin was unaffected by varying pH (4-9), ionic strength (0.01-1.00 M, as NaNO3) and varying aqueous concentrations of Ca(2+) (100-500 mg L(-1)) and HCO3(-) (100-500 mg L(-1)). Due to the high partition coefficient of Diphonex(®), several elution techniques for uranium were evaluated. The optimal eluent mixture was 1M NaOH/1M H2O2, eluting 90% of the uranium from the resin. Uptake of uranium was linear (R(2)=0.99) over time (5 days) in laboratory experiments using artificial freshwater showing no saturation effects of the resin. In field deployments (River Lambourn, UK) the devices quantitatively accumulated uranium for up to 7 days. In both studies uptake of uranium matched that theoretically predicted for the DGT. Similar experiments in seawater did not follow the DGT theoretical uptake and the Diphonix(®) appeared to be capacity limited and also affected by matrix interferences. Isotopes of uranium (U(235)/U(238)) were measured in both environments with a precision and accuracy of 1.6-2.2% and 1.2-1.4%, respectively. This initial study shows the potential of using Diphonix(®)-DGT for monitoring of uranium in the aquatic environment.

The performance of the diffusive gradient in thin film technique (DGT) was evaluated as a tool for the long-term monitoring of water quality, using uranium as a case study. DGTs with a Metsorb™ (TiO2) sorbent were deployed consecutively at two alkaline freshwater sites, the River Enborne and the River Lambourn, UK for seven-day intervals over a five-month deployment period to obtain time weighted average concentrations. Weekly spot samples were taken to determine physical and chemical properties of the river water. Uranium was measured in these spot samples and after extraction from the DGT devices. The accuracy of the DGT device time weighted average concentrations to averaged spot water samples in both rivers was 86% (27 to 205%). The DGT diffusive boundary layer (DBL) (0.037-0.141 cm - River Enborne and 0.062-0.086 cm - River Lambourn) was affected by both water flow and biofouling of the diffusion surface. DBL thicknesses found at both sites were correlated with flow conditions with an R(2) value of 0.614. Correlations were also observed between the DBL thickness and dissolved organic carbon (R(2) = 0.637) in the River Lambourn, indicating the potential presence of a complex zone of chemical interactions at the surface of the DGT. The range of DBL thicknesses found at the River Lambourn site were also attributed to of the development of macro-flora on the active sampling surface, indicating that the DBL thickness cannot be assumed to be water flow dependant only. Up to a 57% under-estimate of uranium DGT concentration was observed compared to spot sample concentrations if the DBL was neglected. This study has shown that the use of DGT can provide valuable information in environmental monitoring schemes as part of a 'tool-box' approach when used alongside conventional spot sampling methods.

DET (Diffusive equilibration in thin films) and DGT (diffusive gradients in thin films) have been deployed in situ using an autonomous benthic lander to measure concentrations and induced fluxes of Fe and Mn (DET/DGT) and trace metals (DGT) in pore waters at millimeter spatial resolutions. The newly developed deployment system is described, and based on these first results, its strengths and weaknesses are discussed. Deployments were made in the Western Black Sea in shelf sediments overlain by well‐oxygenated water at a water depth of 77 m. Maxima of the redox‐sensitive metals at 4 and 8 cm deep within the sediment indicated that two zones of reduction dominated the geochemistry. Sharp, but systematic, features were superimposed on this general picture and were well replicated in the profiles of Mn, Co, and Cd, but the sharp features in the Fe profile were offset from those of the others elements by several millimeters. Detection of this functional discrimination between Fe and Mn as regulators of trace metals would not have been possible using more conventional sampling procedures.

A new, multi-purpose autonomous benthic lander is described, and preliminary experimental data are presented relating to deployments in the Atlantic Frontier (eastern north Atlantic) during the recent UK Thematic Programme ‘BENBO’. The autonomous lander was deployed at two contrasting sites — Site A (mouth of Rockall Trough; 3570 m) and Site B (Hatton-Rockall Bank; 1100 m) — before and following the spring-time surface ocean phytoplankton bloom (May & July, 1998, respectively). Diffusive oxygen uptake and nutrient flux data were obtained using two interchangeable modules — a profiling oxygen micro-electrode unit and a benthic chamber unit. Diffusive O 2 uptake across the sediment–water interface and the O 2 penetration depths within the sediment were determined from the oxygen micro-profiles. The shallower site, which had previously received phyto-detrital input, had a comparatively large diffusive oxygen uptake within the sediment (1.2 mmol m −2 d −1 ) and a maximum penetration depth of only 21 mm. The deeper site had greater oxygen penetration depths (∼80 mm) but a lower diffusive oxygen uptake of 0.6 mmol m −2 d −1 , indicative possibly of little or no phyto-detrital input. Visual observations of retrieved sediment cores support this conclusion, however Site A has also displays generally lower organic content and lower macrobenthic biomass which may contribute to this observation. Nutrient pore water profile data indicated fluxes of nitrate of 0.161 mmol m −2 d −1 and phosphate 0.0008 mmol m −2 d −1 into the overlying water. However, the benthic chamber studies showed virtually no change in nutrient concentrations, due probably to the relatively short deployment time used.