Automated, high frequency, on-line dimethyl sulfide measurements in natural waters using a novel "microslug" gas-liquid segmented flow method with chemiluminescence detection.

Dimethyl sulfide (DMS) is the major biogenic volatile sulfur compound in surface seawater. Good quality DMS data with high temporal and spatial resolution are desirable for understanding reduced sulfur biogeochemistry. Here we present a fully automated and novel "microslug" gas-liquid segmented flow-chemiluminescence (MSSF-CL) based method for the continuous in-situ measurement of DMS in natural waters. Samples were collected into a flow tank and DMS transferred from the aqueous phase to the gas phase using a vario-directional coiled flow, in which microvolume liquid and gas slugs were interspersed. The separated DMS was reacted with ozone in a reaction cell for CL detection. The analytical process was automated, with a sample throughput of 6.6 h-1. Using MSSF for DMS separation was more effective and easily integrated with CL detection compared with the commonly used bubbling approach. Key parameters of the proposed method were investigated. The linear range for the method was 0.05-500 nM (R2 = 0.9984) and the limit of detection (3 x S/N) was 0.015 nM, which is comparable to the commonly used gas chromatography (GC) method and sensitive enough for direct DMS measurement in typical aquatic environments. Reproducibility and recovery were assessed by spiking natural water samples (river, lake, reservoir and pond) with different concentrations of DMS (10, 20 and 50 nM), giving relative standard deviations (RSDs) ≤1.75% (n = 5) and recoveries of 94.4-107.8%. This fully automated system is reagent free, easy to assemble, simple to use, portable (weight ~5.1 kg) and can be left in the field for several hours of unattended operation. The instrumentation can provide high quality DMS data for natural waters with an environmentally relevant temporal resolution of ~9 min.

Uncertainty associated with the leaching of aerosol filters for the determination of metals in aerosol particulate matter using collision/reaction cell ICP-MS detection.

High quality observational data with a firm uncertainty assessment are essential for the proper validation of biogeochemical models for trace metals such as iron. Typically, concentrations of these metals are very low in oceanic waters (nM and sub nM) and ICP-MS is therefore a favoured technique for quantitative analysis. Uncertainties in the measurement step are generally well constrained, even at sub-nM concentrations. However, the measurement step is only part of the overall procedure. For the determination of trace metal solubilities from aerosols in the surface ocean, aerosol collection on a filter paper followed by a leaching procedure is likely to make a significant contribution to the overall uncertainty. This paper quantifies the uncertainties for key trace metals (cobalt, iron, lead and vanadium), together with aluminium as a reference element, for a controlled, flow through laboratory leaching procedure using filters collected from three different sampling sites (Tudor Hill (Bermuda), Heraklion (Crete) and Tel-Shikmona (Israel)) and water, glucuronic acid and desferrioxamine B as leachants. Relative expanded uncertainties were in the range of 12-29% for cobalt, 12-62% for iron, 13-45% for lead and 5-11% for vanadium. Fractional solubilities for iron ranged from 0.2 ±â€¯0.1% to 16.9 ±â€¯3.5%.

The role of alkalinity in setting water quality metrics: phosphorus standards in United Kingdom rivers.

UK implementation of the European Union Water Framework Directive (for the 2015-2021 cycle) Ecological Status (ES) classification for river phosphorus is based on the calculation of reference conditions for reactive phosphorus (RP) using river alkalinity measurements. Underpinning this approach is that the alkalinity is primarily from rock weathering and is free of anthropogenic influences. However, the potential contribution of anthropogenic alkalinity needs to be considered and, if possible, quantified. In the rural South West River Basin District of England, 38 river sites were examined with respect to river alkalinity loads in order to test this consideration. At river base flow when RP can cause enhanced algal growth, 9 sites (24%) had effluent alkalinity contributions amounting to 25-49% of the total riverine alkalinity load, while 11 (29%) of the sites received ≥50% of their alkalinity load from effluent. When flows increased above base flow to Q95 flow at these 11 sites, catchment diffuse run-off became the largest load of alkalinity at 9 of the sites, and that at the Q95 flows, combined effluent and diffuse alkalinity loads contributed 68-100% of the total alkalinity load. Anthropogenic alkalinity is likely to be present in diffuse run-off, but it is difficult to apportion alkalinity loads between natural and contaminant sources. It is likely that diffuse loads of alkalinity will dominate on the annual timescales used to assess WFD compliance, even at sites where ground water alkalinity dominates at base river flows. In principle, inclusion of anthropogenic alkalinity in the calculation of ES boundary concentrations for RP may lead to a relaxation of the standards. In practice this may not follow. It is likely that at the river sites used initially to develop the algorithms now used for P standard setting, anthropogenic alkalinity was present, to varying and unknown degrees, and that this alkalinity would have influenced the measured and reference RP and biological metrics on which the P standards are based. Apart from RP, alkalinity is also used to underpin water quality metrics for additional chemical and biological parameters, and for this reason, understanding the complex factors determining river alkalinity loads should be an important task for water quality regulators.

Changes to polychlorinated biphenyl (PCB) signatures and enantiomer fractions across different tissue types in Guillemots.

Two Guillemot carcases were dissected, each providing 12 discrete tissue samples and 3 samples of partially digested food. One hundred and five PCBs from the 209 PCBs determined by GCxGC-ToFMS were detected. The relative proportions of individual PCBs did not vary greatly within tissue types, although the PCB profile from undigested food could be distinguished. Enantiomer fractions (EFs) were determined for CB-95, CB-136 and CB-149 by GC-HRqToFMS. EFs in the partially digested food were near racemic, with high levels of enrichment for E1 CB-95 in the kidneys and liver (EF of 0.80 and 0.84 respectively). This provides some of the clearest evidence to date that fractionation takes place in the organs where metabolic biotransformation and elimination of PCBs occurs. Our findings also confirm the ability of non-lethal sampling techniques, such as collection of small (<1 g) blood samples, to provide PCB signatures that are representative of an individual organism.

Mixtures of tritiated water, zinc and dissolved organic carbon: Assessing interactive bioaccumulation and genotoxic effects in marine mussels, Mytilus galloprovincialis.

Release of tritium (3H) in the marine environment is of concern with respect to its potential bioaccumulation and detrimental impact on the biota. Previous studies have investigated the uptake and toxicity of this radionuclide in marine mussels, and the interaction of 3H with dissolved organic ligands and elevated temperature. However, despite the well-established view that toxicity is partly governed by chemical speciation, and that toxic effects of mixture of contaminants are not always additive, there have been no studies linking the prevailing chemistry of exposure waters with observed biological effects and tissue specific accumulation of 3H in combination with other constituents commonly found in natural waters. This study exposed the marine mussel Mytilus galloprovincialis for 14 days to mixtures of 3H (as tritiated water, HTO) and zinc (Zn) at 5 Mbq L-1, and 383, 1913 and 3825 nM Zn, respectively, to investigate (a) 3H and Zn partitioning in soft tissues of mussels, and (b) DNA damage in haemocytes, determined using the single cell gel electrophoresis or the comet assay. Additionally, the extent of association of 3H with dissolved organic carbon (DOC, added as humic acid) over the exposure period was investigated in order to aid the interpretation of biological uptake and effects. Results concluded a clear antagonistic effect of Zn on 3H-induced DNA damage at all Zn concentrations used, likely explained by the importance of Zn in DNA repair enzymes. The interaction of DOC with 3H was variable, with strong 3H-DOC associations observed in the first 3 d of the experiment. The secretion of 3H-binding ligands by the mussels is suggested as a possible mechanism for early biological control of 3H toxicity. The results suggest risk assessments for radionuclides in the environment require consideration of potential mixture effects.

Flow analysis with chemiluminescence detection: Recent advances and applications.

This article highlights the most important developments in flow analysis with chemiluminescence (CL) detection, describing different flow systems that are compatible with CL detection, detector designs, commonly applied CL reactions and approaches to sample treatment. Recent applications of flow analysis with CL detection (focusing on outputs published since 2010) are also presented. Applications are classified by sample matrix, covering foods and beverages, environmental matrices, pharmaceuticals and biological fluids. Comprehensive tables are provided for each area, listing the specific sample matrix, CL reaction used, linear range, limit of detection and sample treatment for each analyte. Finally, recent and emerging trends in the field are also discussed.

Predicting Copper Speciation in Estuarine Waters-Is Dissolved Organic Carbon a Good Proxy for the Presence of Organic Ligands?

A new generation of speciation-based aquatic environmental quality standards (EQS) for metals have been developed using models to predict the free metal ion concentration, the most ecologically relevant form, to set site-specific values. Some countries such as the U.K. have moved toward this approach by setting a new estuarine and marine water EQS for copper, based on an empirical relationship between copper toxicity to mussels (Mytilus sp.) and ambient dissolved organic carbon (DOC) concentrations. This assumes an inverse relationship between DOC and free copper ion concentration owing to complexation by predominantly organic ligands. At low DOC concentrations, the new EQS is more stringent, but above 162 µM DOC it is higher than the previous value. However, the relationship between DOC and copper speciation is poorly defined in estuarine waters. This research discusses the influence of DOC from different sources on copper speciation in estuaries and concludes that DOC is not necessarily an accurate predictor of copper speciation. Nevertheless, the determination of ligand strength and concentrations by Competitive Ligand Exchange Adsorptive Cathodic Stripping Voltammetry enabled the prediction of the free metal ion concentration within an order of magnitude for estuarine waters by using a readily available metal speciation model (Visual MINTEQ).

Orthophosphate-P in the nutrient impacted River Taw and its catchment (SW England) between 1990 and 2013.

Excess dissolved phosphorus (as orthophosphate-P) contributes to reduced river water quality within Europe and elsewhere. This study reports results from analysis of a 23 year (1990-2013) water quality dataset for orthophosphate-P in the rural Taw catchment (SW England). Orthophosphate-P and river flow relationships and temporal variations in orthophosphate-P concentrations indicate the significant contribution of sewage (across the catchment) and industrial effluent (upper R. Taw) to orthophosphate-P concentrations (up to 96%), particularly during the low flow summer months when maximum algal growth occurs. In contrast, concentrations of orthophosphate-P from diffuse sources within the catchment were more important (>80%) at highest river flows. The results from a 3 end-member mixing model incorporating effluent, groundwater and diffuse orthophosphate-P source terms suggested that sewage and/or industrial effluent contributes ≥50% of the orthophosphate-P load for 27-48% of the time across the catchment. The Water Framework Directive (WFD) Phase 2 standards for reactive phosphorus, introduced in 2015, showed the R. Taw to be generally classified as Poor to Moderate Ecological Status, with a Good Status occurring more frequently in the tributary rivers. Failure to achieve Good Ecological Status occurred even though, since the early-2000s, riverine orthophosphate-P concentrations have decreased (although the mechanism(s) responsible for this could not be identified). For the first time it has been demonstrated that sewage and industrial effluent sources of alkalinity to the river can give erroneous boundary concentrations of orthophosphate-P for WFD Ecological Status classification, the extent of which is dependent on the proportion of effluent alkalinity present. This is likely to be a European - wide issue which should be examined in more detail.

Can polychlorinated biphenyl (PCB) signatures and enantiomer fractions be used for source identification and to age date occupational exposure?

Detailed polychlorinated biphenyl (PCB) signatures and chiral Enantiomer Fractions (EFs) of CB-95, CB-136 and CB-149 were measured for 30 workers at a transformer dismantling plant. This was undertaken to identify sources of exposure and investigate changes to the PCB signature and EFs over different exposure periods. Approximately 1.5 g of serum was extracted and PCB signatures were created through analysis by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) and EFs calculated following analysis by gas chromatography with high resolution mass spectrometry (GC-HRMS). A total of 84 PCBs were identified in the serum samples with concentrations of the 7 indicator PCBs ranging from 11-350 ng g(-1) of serum (1.2-39 µg g(-1) lipid). The PCB signatures were interpreted using principal component analysis (PCA) which was able to distinguish workers with background or recent minimal exposure from those with prolonged occupational exposure. Occupationally exposed individuals had a similar PCB profile to Aroclor A1260. However, individuals with prolonged exposure had depleted proportions of several PCB congeners that are susceptible to metabolism (CB-95, CB-101 and CB-151) and elevated proportions of PCBs that are resistant to metabolism (CB-74, CB-153, CB-138 and CB-180). The results also identified a third group of workers with elevated proportions of CB-28, CB-60, CB-66, CB-74, CB-105 and CB-118 who appeared to have been exposed to an additional source of PCBs. The results show near complete removal of the CB-95 E2 enantiomer in some samples, indicating that bioselective metabolism or preferential excretion of one enantiomer occurs in humans. By considering PCB concentrations along with detailed congener specific signatures it was possible to identify different exposure sources, and gain an insight into both the magnitude and duration of exposure.

Combined uncertainty estimation for the determination of the dissolved iron amount content in seawater using flow injection with chemiluminescence detection.

This work assesses the components contributing to the combined uncertainty budget associated with the measurement of the Fe amount content by flow injection chemiluminescence (FI-CL) in <0.2 µm filtered and acidified seawater samples. Amounts of loaded standard solutions and samples were determined gravimetrically by differential weighing. Up to 5% variations in the loaded masses were observed during measurements, in contradiction to the usual assumptions made when operating under constant loading time conditions. Hence signal intensities (V) were normalised to the loaded mass and plots of average normalised intensities (in V kg-1) vs. values of the Fe amount content (in nmol kg-1) added to a "low level" iron seawater matrix were used to produce the calibration graphs. The measurement procedure implemented and the uncertainty estimation process developed were validated from the agreement obtained with consensus values for three SAFe and GEOTRACES reference materials (D2, GS, and GD). Relative expanded uncertainties for peak height and peak area based results were estimated to be around 12% and 10% (coverage factor k = 2), respectively. The most important contributory factors were the uncertainty on the sensitivity coefficient (i.e., calibration slope) and the within-sequence-stability (i.e., the signal stability over several hours of operation; here 32 h). For GD, using peak height measurements, these factors contributed respectively 69.7% and 21.6% while the short-term repeatability accounted for only 7.9%. Therefore, an uncertainty estimation based on the intensity repeatability alone, as is often done in FI-CL studies, is not a realistic estimation of the overall uncertainty of the procedure.

Uncertainty contributions to the measurement of dissolved Co, Fe, Pb and V in seawater using flow injection with solid phase preconcentration and detection by collision/reaction cell-quadrupole ICP-MS.

A flow injection manifold incorporating a solid phase chelating resin (Toyopearl AF-Chelate-650) is reported for the preconcentration of dissolved metals from seawater, with a focus on investigating the effect of the loading pH, wash solution composition and wash time. Cobalt, iron, lead and vanadium have been used as target analytes with contrasting oceanographic behaviour. Quadrupole ICP-MS has been used for detection to make the approach accessible to most laboratories and a collision/reaction cell has been incorporated to minimise polyatomic interferences. Results for the seawater CRM NASS-6 and two GEOTRACES reference materials were in good agreement with the certified/consensus values, demonstrating the suitability of the approach for the determination of trace metals in seawater. The experimental design used allowed a thorough investigation of the uncertainty contribution from each method parameter to the overall expanded uncertainty of the measurement. The results showed that the parameters making the largest contributions were the precision of the peak area measurement and the uncertainty associated with the slope of the calibration curve. Therefore, these are the critical parameters that should be targeted in order to reduce the overall measurement uncertainty. For iron, the wash blank also gave a measureable contribution.

Identifying the provenance of Leach's storm petrels in the North Atlantic using polychlorinated biphenyl signatures derived from comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

PCB signatures can be used for source identification, exposure studies, age dating and bio-monitoring. This study uses comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-ToFMS) to produce a PCB signature comprised of over 80 PCBs for individual Leach's storm petrels (Oceanodroma leucorhoa). The Leach's storm petrel is a relatively small, elusive, understudied pelagic bird, which only returns to remote islands under darkness during the breeding season. Samples were obtained from 25 Leach's storm petrels found dead in Canada and the UK following storm events in 2006 and 2009. Tissue samples were extracted and analysed by GCxGC-ToFMS and results showed that 83 PCB congeners were present in >60% of samples. An assessment of the PCB signature in four different tissue types showed that it did not vary greatly in samples obtained from the gut, heart, liver and stomach. Multivariate statistical analysis identified a distinctive PCB signature in birds from Canada and Europe which was used to identify the regional provenance and transatlantic movement of individual birds. The findings showcase the ability of GCxGC-ToFMS to provide the high quality congener specific analysis that is necessary for PCB fingerprinting, as well as highlighting the potential of PCB signatures for use in ecological studies of movement, foraging and behaviour.

Fingerprinting polychlorinated biphenyls in environmental samples using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

A GC × GC-TOFMS installed with a Rtx-PCB (60 m × 0.18 mm × 0.18 µm) in the first dimension and Rxi- 17 (1.5 m × 0.1 mm × 0.1 µm) column in the second dimension was used to separate 188 out of 209 congeners. A further 12 congeners were identified through additional data processing resulting in the identification of a total of 200 congeners. However, caution is advised if these 12 congeners were to be used in quantitative assessments. The remaining 9 co-eluting congeners were three doublets (CB65 + CB62, CB160 + CB163 and CB201 + CB204) and one triplet (CB20 + CB21 + CB33). This method was tested on five Aroclors and resulted in the separation of all congeners present in the heavier Aroclor mixtures A1254 and A1260. The suitability of this method for applications in biological matrices was demonstrated on extracted whiting and guillemot liver samples which resulted in the identification of 137 individual PCBs in the whiting liver sample and 120 in the guillemot sample. Fingerprinting was able to show clear differences in the PCB signature of the two animals. This highlights the potential of this method for PCB fingerprinting in environmental forensics studies and other assessments that require congener specific analysis.

Flow injection analysis as a tool for enhancing oceanographic nutrient measurements--a review.

Macronutrient elements (C, N and P) and micronutrient elements (Fe, Co, Cu, Zn and Mn) are widely measured in their various physico-chemical forms in open ocean, shelf sea, coastal and estuarine waters. These measurements help to elucidate the biogeochemical cycling of these elements in marine waters and highlight the ecological and socio-economic importance of the oceans. Due to the dynamic nature of marine waters in terms of chemical, biological and physical processes, it is advantageous to make these measurements in situ and in this regard flow injection analysis (FIA) provides a suitable shipboard platform. This review, therefore, discusses the role of FIA in the determination of macro- and micro-nutrient elements, with an emphasis on manifold design and detection strategies for the reliable shipboard determination of specific nutrient species. The application of various FIA manifolds to oceanographic nutrient determinations is discussed, with an emphasis on sensitivity, selectivity, high throughput analysis and suitability for underway analysis and depth profiles. Strategies for enhancing sensitivity and minimizing matrix effects, e.g. refractive index (schlieren) effects and the important role of uncertainty budgets in underpinning method validation and data quality are discussed in some detail.

Export of dissolved organic carbon and nitrate from grassland in winter using high temporal resolution, in situ UV sensing.

Co-deployment of two reagentless UV sensors for high temporal resolution (15 min) real time determination of wintertime DOC and nitrate-N export from a grassland lysimeter plot (North Wyke, Devon, UK) is reported. They showed rapid, transient but high impact perturbations of DOC (5.3-23 mg CL(-1)) and nitrate-N export after storm/snow melt which discontinuous sampling would not have observed. During a winter freeze/thaw cycle, DOC export (1.25 kg Cha(-1)d(-1)) was significantly higher than typical UK catchment values (maximum 0.25 kg Chad(-1)) and historical North Wyke data (0.7 kg Cha(-1)d(-1)). DOC concentrations were inversely correlated with the key DOC physico-chemical drivers of pH (January r=-0.65), and conductivity (January r=-0.64). Nitrate-N export (0.8-1.5 mg NL(-1)) was strongly correlated with DOC export (r ≥ 0.8). The DOC:NO3-N molar ratios showed that soil microbial N assimilation was not C limited and therefore high N accrual was not promoted in the River Taw, which is classified as a nitrate vulnerable zone (NVZ). The sensor was shown to be an effective sentinel device for identifying critical periods when rapid ecosystem N accumulation could be triggered by a shift in resource stoichiometry. It is therefore a useful tool to help evaluate land management strategies and impacts from climate change and intensive agriculture.

Elucidating the structural properties that influence the persistence of PCBs in humans using the National Health and Nutrition Examination Survey (NHANES) dataset.

In human exposure studies involving Polychlorinated Biphenyls (PCBs), it is useful to establish when an individual was potentially exposed. Age dating PCB exposure is complex but assessments can be made because different PCB congeners have different residence times in the human body. The less chlorinated congeners generally tend to have shorter residence times because they are biotransformed and eliminated faster than more chlorinated congeners. Therefore, the presence of high proportions of less chlorinated congeners is often indicative of recent exposure. The 2003-04 National Health and Nutrition Examination Survey (NHANES) dataset contains results for the concentration of 37 PCBs in a sub-sample of the US population. Multivariate statistical analysis of the NHANES data showed that less chlorinated congeners are not always biotransformed faster than higher chlorinated compounds. For example, PCB 28 (a tri-chlorobiphenyl) appears to be more resistant to biotransformation than PCB 101 and 110 (penta-chlorobiphenyls). Using statistical analysis of the NHANES data in conjunction with previously published studies on PCB persistence in humans, it was possible to identify the structural relationships that determine if a PCB is likely to be from a recent exposure (termed 'episodic') or from steady state exposure. Congeners with chlorine atoms in the 2,5- and 2,3,6-positions appear to be more susceptible to biotransformation whereas congeners with chlorine bonds in the 2,3,4- 2,4,5- 3,4,5- and 2,3,4,5-positions appear to be more persistent. This work shows that future investigations to date PCB exposure would benefit from the analysis of a wide range of congeners, including the selection of key congeners based not only on the degree of chlorination but also on the positions of the chlorine atoms on the biphenyl.

Fate of 90Sr and U(VI) in Dounreay sediments following saline inundation and erosion.

There is concern that sea level rise associated with projected climate change will lead to the inundation, flooding and erosion of soils and sediments contaminated with radionuclides at coastal nuclear sites, such as Dounreay (UK), with seawater. Here batch and column experiments were designed to simulate these scenarios and sequential extractions were used to identify the key radionuclide solid phase associations. Strontium was exchangeable and was mobilised rapidly by ion exchange with seawater Mg(2+) in both batch and column experiments. In contrast, U was more strongly bound to the sediments and mobilisation was initially limited by the influence of the sediment on the pH of the water. Release was only observed when the pH increased above 6.9, suggesting that the formation of soluble U(VI)-carbonate species was important. Under dynamic flow conditions, long term release was significant (47%), but controlled by slow desorption kinetics from a range of binding sites.