Influence of sediment redox conditions on uranium mobilisation during saline intrusion

This research was funded by the Natural Environment Research Council (grant NE/C506799/1: Studentship NE/H527116/1)

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 (<i>Mytilus</i> 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)

A tale of two gyres: Contrasting distributions of dissolved cobalt and iron in the Atlantic Ocean during an Atlantic Meridional Transect (AMT-19).

Cobalt (Co) and iron (Fe) are essential for phytoplankton nutrition, and as such constitute a vital link in the marine biological carbon pump. Atmospheric deposition is an important, and in some places the dominant, source of trace elements (TEs) to the global ocean. Dissolved cobalt (dCo) and iron (dFe) were determined along an Atlantic Meridional Transect (AMT-19; Oct/Nov 2009) between 50°N and 40°S in the upper 150 m in order to investigate the behaviour and distribution of these two essential, bioactive TEs. During AMT-19, large differences in the distributions of dCo and dFe were observed. In the North Atlantic gyre provinces, extremely low mixed layer dCo concentrations (23 ± 9 pM) were observed, which contrasts with the relatively high mixed layer dFe concentrations (up to 1.0 nM) coincident with the band of highest atmospheric deposition (∼5–30°N). In the South Atlantic gyre, the opposite trend was observed, with relatively high dCo (55 ± 18 pM) observed throughout the water column, but low dFe concentrations (0.29 ± 0.08 nM). Given that annual dust supply is an order of magnitude greater in the North than the South Atlantic, the dCo distribution was somewhat unexpected. However, the distribution of dCo shows similarities with the distribution of phosphate (PO43−) in the euphotic zone of the Atlantic Ocean, where the North Atlantic gyre is characterised by chronically low PO4, and higher concentrations are observed in the South Atlantic gyre (Mather et al., 2008), suggesting the potential for a similar biological control of dCo distributions. Inverse correlations between dCo and Prochlorococcus abundance in the North Atlantic gyre provinces, combined with extremely low dCo where nitrogen fixation rates were highest (∼20–28°N), suggests the dominance of biological controls on dCo distributions. The contrasting dCo and dFe distributions in the North and South Atlantic gyres provides insights into the differences between the dominant controls on the distribution of these two bioactive trace metals in the central Atlantic Ocean

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 normalized intensities (in V kg-1) versus 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% (k=2) respectively. The most important contributory factors were the uncertainty on the sensitivity coefficient (i.e. calibration slope) and within-sequence-stability (i.e. the signal stability measured over several hours of operation; in this case 32 h). 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.JRC.D.2-Standards for Innovation and sustainable Developmen

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

© 2019 Elsevier B.V. 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 ± 0.1% to 16.9 ± 3.5%

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

publisher: Elsevier articletitle: Mixtures of tritiated water, zinc and dissolved organic carbon: Assessing interactive bioaccumulation and genotoxic effects in marine mussels, Mytilus galloprovincialis journaltitle: Journal of Environmental Radioactivity articlelink: https://doi.org/10.1016/j.jenvrad.2017.12.018 content_type: article copyright: © 2018 Elsevier Ltd. All rights reserved

Determination and prediction of zinc speciation in estuaries

Lowering of the estuarine Environmental Quality Standard for zinc in the UK to 121 nM reflects rising concern regarding zinc in ecosystems and is driving the need to better understand its fate and behaviour and to develop and parameterise speciation models to predict the metal species present. For the first time, an extensive dataset has been gathered for the speciation of zinc within an estuarine system with supporting physico-chemical characterisation, in particular dissolved organic carbon. WHAM/Model VII and Visual MINTEQ speciation models were used to simulate zinc speciation, using a combination of measured complexation variables and available defaults. Data for the five estuarine transects from freshwater to seawater endmembers showed very variable patterns of zinc speciation depending on river flows, seasons, and potential variations in metal and ligand inputs from in situ and ex situ sources. There were no clear relationships between free zinc ion concentration [Zn2+] and measured variables such as DOC concentration, humic and biological indices. Simulations of [Zn2+] carried out with both models at high salinities or by inputting site specific complexation capacities were successful, but overestimated [Zn2+] in low salinity waters, probably owing to an underestimation of the complexation strength of the ligands present. Uncertainties in predicted [Zn2+] are consistently smaller than standard deviations of the measured values, suggesting that the accuracy of the measurements is more critical than model uncertainty in evaluating the predictions

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 (MSSFCL) 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

Impact of surface ocean conditions and aerosol provenance on the dissolution of aerosol manganese, cobalt, nickel and lead in seawater

© 2017. Atmospheric deposition is an important pathway by which bioactive trace metals are delivered to the surface ocean. The proportions of total aerosol trace metals that dissolve in seawater, and thus become available to biota, are not well constrained and are therefore a key uncertainty when estimating atmospheric fluxes of these elements to surface waters. The aim of this study was to elucidate the main physico-chemical controls on the dissolution of the bioactive trace metals manganese (Mn), cobalt (Co), nickel (Ni) and lead (Pb). To this end, aerosol and surface seawater samples were collected in the Sargasso Sea and subsequently used in sequential seawater leach dissolution experiments to assess the role of aerosol source, seawater temperature, pH, and concentrations of dissolved oxygen and organic ligands, on aerosol trace metal dissolution.Results reveal that changes in key physico-chemical parameters in seawater leaches had little effect on the proportions of Mn, Co, Ni and Pb released from aerosols, although organic ligand amendments impacted the size distribution of aerosol-derived Mn in solution. Conversely, aerosol source and composition had the most significant effect on the dissolution of aerosol Co and Pb, with the most 'anthropogenic' aerosol samples displaying the highest fractional solubilities in seawater (up to 58% for Co and 112% for Pb).Fractional solubilities over the range of samples and conditions tested were in the range of 50-104% for Mn, 29-58% for Co, 40-85% for Ni and 67-112% for Pb. A large proportion (36-100%, median 89%) of the total dMn, dCo, dNi and dPb was mobilised rapidly during the first leaching step (5. min), with less dTM being released in leaches 2 through 4. Furthermore, investigation of the size distribution of the aerosol-derived trace metals in seawater showed that dissolved Pb was mostly colloidal (0.02-0.4. μm), dissolved Mn and Co were mostly soluble ( < . 0.02. μm), and dissolved Ni displayed a mixed size distribution. Good empirical relationships were observed between enrichment factors for aerosol antimony (Sb) and the fractional solubilities of aerosol Fe, Co and Pb, suggesting total aerosol Sb can be useful in estimating and modelling the fractional solubility of these metals using total aerosol trace metal concentrations from historical data