Simultaneous determination of in situ vertical transitions of color, pore-water metals, and visualization of infaunal activity in marine sediments

The vertical color transition from brown to gray-green in marine sediments is linked to the Fe redox boundary and is commonly used as a proxy for biogeochemical state. We combine time-lapse sediment profile imaging with diffusive gradient thin (DGT) gels to obtain simultaneous in situ measurements of sediment color profiles, pore-water Fe and Mn profiles, and qualitative estimates of faunal activity at the Oyster Ground and North Dogger (North Sea). Analysis of Fe and Mn profiles using generalized additive modeling reveals that high variability between profiles within the sites makes it difficult to determine any intersite differences in trace metal behavior. At the Oyster Ground, the depth of sediment color transition (4.78 +/- 0.76 cm) was not significantly different from the Fe redox boundary (7.67 +/- 4.04 cm). At the North Dogger, there was a significant discrepancy between the depth of the sediment color transition (2.86 +/- 0.78 cm) and the Fe redox boundary (10.17 +/- 1.04 cm), which most likely results from high sulfate reduction rates at the North Dogger, leading to complexation of reduced iron to a form not available to the DGT technique. The differences in the coupling of sediment color and the Fe redox boundary between stations is likely to be related to variations in recent infaunal bioturbation activity, rather than variations in sediment source or fundamental differences in bulk sediment chemistry. Our results highlight the importance of the infaunal community in mediating Fe and Mn cycles, which are key pathways in the degradation of organic matter, and suggest that descriptions of bulk chemistry alone may be insufficient to understand the dynamics of biogeochemical cycling

Atmospheric Deposition: A Potential Source of Trace Metal Organic Complexing Ligands to the Marine Environment

The present study confirms the existence of rainwater and seawater soluble metal (Cu, Pb, Cd, Ni and Co) complexing organic ligands associated with end-member aerosol populations. The end member aerosols being representative of a European urban aerosol population (LUAP ¿ Liverpool Urban Aerosol Population), and an aerosol population representative of crustal dominated material (Mesh Saharan dust, collected off the west African coast). The investigations carried out by ACSV (adsorptive cathodic stripping voltammetry) clearly indicated that these end-members were a source of organic complexing ligands for all the considered metals. For LUAP Cu 26%, Pb 55%, Cd 36%, Ni 26% and Co 27% of the total seawater soluble fraction was ACSVnon-labile (i.e. that fraction of the dissolved metal which is released after UV irradiation) compared to the corresponding values for Saharan dust (Cu 59%, Pb 23%, Cd 56%, Ni 66%, Co 23%). From these studies it was apparent that the dissolution for all metals and their respective fractions in both seawater and artificial rainwater was a rapid process with no further release after ca. 30 minutes. The studies displayed for a number of the metals re-adsorption of ACSVnon-labile metal to the aerosol particulate surface (Co and Pb - Saharan / seawater; Co and Cd - LUAP / seawater) implying that different geochemical pathways are taken by different metal speciation fractions leading to potential differences in their marine residence times. Conditional formation stability constants and complexing capacities for Ni were determined for seawater after being equilibrated with both end member aerosols. Log K\u27NiL detected were 18.3 - 0.3 and 19.26 - 0.4 for LUAP and Saharan dust respectively. The equivalent complexing capacities were 1.0 - 0.1 nmol mg-1 and 0.038 - 0.005 nmol mg-1 respectively

Evaluation of diffusive gradients in thin-films using a Diphonix® resin for monitoring dissolved uranium in natural waters

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 Ca2+ (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 1 M NaOH/1 M H2O2, eluting 90% of the uranium from the resin. Uptake of uranium was linear (R2 = 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 (U235/U238) 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 application of passive sampler (DGT) technology for improved understanding of metal behaviour at a marine disposal site

Metal behaviour and availability at a contaminated dredge material disposal site within UK waters has been investigated using Diffusive Gradient in Thin films (DGT) passive sampling technology. Three stations representing contrasting history and presence of maintenance dredge disposal, including a control station outside the disposal site, have been studied and depth profiles of fluxes of different metals (Fe, Mn, Pb, Cu, Cd, Cr, Ni, Zn) to the binding gel (Chelex 100) have been derived. Higher flux rates and shallower mobilisation of metals (Mn and Fe) to the binding gel were observed at the disposal stations compared to the control station. Here we describe metal mobilization at different depths, linking the remobilization of Fe2+ and Mn2+ to the sediment (re)supply of other heavy metals of interest with a focus on Cd, Ni and Pb and as they are on the Water Framework Directive (WFD) list of priority substances and OSPAR list of priority pollutants. Results showed that Cd, Pb and Ni exhibited signs of resupply at the sediment-water interface (SWI). There was a potential increased mobilisation and source to the water column of Pb and Ni at the disposal site stations, but there was no Cd source, despite higher total loadings. This information has the potential to improve our current understanding of metal cycles at disposal sites. This work can be used as an indication of likely metal bioavailability and also assist in determining whether the sites act as sources or sinks of heavy metals. This information could assist disposal site monitoring and dredge material licensing

Calibration and field application of an innovative passive sampler for monitoring groundwater quality

International audienc

Using high-frequency phosphorus monitoring for water quality management: a case study of the upper River Itchen, UK

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