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.

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.

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.

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.

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.

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.

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 m filtered and acidified seawater samples. Amounts of loaded standard solutions and samples were determined gravimetrically by differential weighing.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Effect of organic complexing agents on the interactions of Cs(+), Sr(2+) and UO(2)(2+) with silica and natural sand.

Sorption processes play a key role in controlling radionuclide migration through subsurface environments and can be affected by the presence of anthropogenic organic complexing agents found at contaminated sites. The effect of these complexing agents on radionuclide-solid phase interactions is not well known. Therefore the aim of this study was to examine the processes by which EDTA, NTA and picolinate affect the sorption kinetics and equilibria of Cs(+), Sr(2+) and UO2(2+) onto natural sand.

Evaluation of electrospray ionisation mass spectrometry as a technique for the investigation of competitive interactions: a case study of the ternary Th-Mn-EDTA system.

Rationale: Electrospray ionisation mass spectrometry (ESI-MS) is a useful tool for exploring the speciation of solution-phase metal complexes; however, the quantification of ternary systems is challenging due to the differences in the electrospray response of different species. Here, the Th-Mn-EDTA system was investigated to evaluate the capability of ESI-MS for quantifying the species present.

Methods: Increasingly complex mixtures of Th(IV), Mn(II) and EDTA were analysed using manual flow injection of samples into an HPLC grade water mobile phase delivered to an ion trap mass spectrometer fitted with an ESI interface (ThermoQuest Finnigan Mat LCQ).

Temporal variability in nutrient concentrations and loads in the River Tamar and its catchment (SW England) between 1974 and 2004.

This study reports the results from the analyses of a 30-year (1974-2004) river water quality monitoring dataset for NO x -N (NO₃-N + NO2-N), NH₄-N, PO₄-P and SiO₂-Si at the tidal limit of the River Tamar (SW England), an agriculturally dominated and sparsely populated catchment. Annual mean concentrations of NH4-N, PO₄-P and SiO₂-Si were similar to other rural UK rivers, while annual mean concentrations of NO x -N were clearly lower. Estimated values for the 1940s were much lower than for those of post-1974, at least for NO₃-N and PO₄-P.

Mobilization of technetium from reduced sediments under seawater inundation and intrusion scenarios.

Predicted sea level rise would increase the vulnerability of low lying coastal legacy nuclear sites to inundation and intrusion with oxygenated seawater. This could have a significant impact on the mobility of redox-sensitive radionuclides such as Tc. Here, batch and column experiments were used to simulate and investigate the effect of these processes on the mobilization of Tc from sediments under a range of geochemically reduced conditions.

Determination of nitrate and nitrite in freshwaters using flow-injection with luminol chemiluminescence detection.

A simple and sensitive flow-injection (FI) method for the determination of nitrate and nitrite in natural waters, based on luminol chemiluminescence (CL) detection, is reported. Nitrate was reduced online to nitrite via a copperized cadmium (Cu-Cd) column and then reacted with acidic hydrogen peroxide to form peroxynitrous acid. CL emission was observed from the oxidation of luminol in an alkaline medium in the presence of the peroxynitrite anion.