2D simultaneous measurement of the oxyanions of P, V, As, Mo, Sb, W and U.

Previous work used the sampling technique diffusive gradients in thin-films analysed by laser ablation mass spectrometry to measure sulphide, P, V and As at a microniche of reactive organic carbon in a freshwater sediment. Here we present new developments of this technique. The number of analytes has been extended and we demonstrate the technique for depth profiling of analytes in both one and two dimensions. The physical dimensions of the cell in the laser ablation unit restrict the maximum length of gel that can be analysed. We address this problem by proposing a method for obtaining better data continuity when analysing multiple segments of gel from the same probe. 13C is used as the internal standard for each gel segment. For the cross standardisation of different gel segments 58Fe signals are obtained from ablation of a small piece of standard ferrihydrite gel analysed during the same run as the sample gel. As the ferrihydrite gel is a subsection of a much larger gel (i.e. the Fe concentration is consistent for all subsection), then any difference in signal can be attributed to changes in detector sensitivity and gels across different runs and performed on different days can be standardised

Small-scale heterogeneity in sediments:experimental and modelling investigations

This thesis consists of several studies relating to small-scale heterogeneity in sediments. The principal aim was to further our understanding of processes occurring at microniches. The individual studies consist of: 1) a critical review of previous studies of microniches that used probes with high spatial resolution and modelling approaches; 2) an experimental study of analysis of oxyanions in sediment at high resolution that applied a newly developed preparation method for a combined AgI/FeOOH binding phase, to investigating processes occurring at a sulphidic microniche within a freshwater sediment; 3) analysis of the relationship between trace metal (cobalt) and iron and manganese in a marine sediment using DGT, although this is not directly related to microniches, these data are useful in modelling the release of microniche trace metal from authigenic oxides; 4) the development and application of a three-dimensional diagenetic model to investigate conceptually the geochemical behaviour of microniches under different conditions, and to interpret modelled observations in terms of data from the literature and known trace element geochemistry. The key results/conclusions from both the laboratory and modelling studies are: 1) for a freshwater sediment, depletions in anions (of P, V, As) at a microniche of elevated sulphide were observed and the behaviour of phosphate at this niche was attributed to uptake associated with elevated activity of sulphate reducing bacteria; 2) modelled scenarios, with varying microniche properties, were shown to be relevant to experimental observations reported in the literature. The preferential deposition of FeS at the edge of microniches (with lifetimes of 2.5-5 days), forming ‘crustal’ deposits was demonstrated. The modelled data indicated that microniches may be significant in terms of the formation of some trace element sulphides. This thesis also contains an assessment of the significance of microniche processes and a discussion of priorities for future work

Formation of iron sulfide at faecal pellets and other microniches within suboxic surface sediment.

Faecal pellet deposition and bioturbation may lead to heterogeneously distributed particles of localized highly reactive organic matter (microniches) being present below the oxygen penetration depth. Where O2, NO3-, and Fe/Mn oxyhydroxides become depleted within these microniches or where they exist in zones of sulfate reduction, significant localized peaks in sulfide concentration can occur. These discrete zones of sulfide evolution can cause formation of iron sulfides that would not be predicted by analysis of the ‘bulk’ sediment. Using a reaction-transport model developed specifically for investigating spherical microniches, and incorporating 3D diffusion, we investigated how the rate constants of organic matter (OM) degradation, particle porosity and niche lifetime, affect dissolved sulfide and iron concentrations, and formation of iron sulfide at such niches. For all of the modelled scenarios the saturation index for iron sulfide is positive, indicating favourable conditions for FeS precipitation in all niches. Those simulations within the microniche lifetime range of 2.5 to 5 days gave comparable concentration ratios of sulfide to iron in solution within the niche to experimentally observed values. Our model results provide insight into the mechanisms of preservation of OM, including soft tissue, in the paleo record, by predicting the conditions that result in preferential deposition of precipitates at the edge of microniches. Decreases in porosity, shorter niche lifetimes and increases in OM degradation rate constants, all tend to increase the likelihood that FeS precipitation will preferentially occur at the edges of a niche, rather than uniformly throughout the niche volume

The association of cobalt with iron and manganese (oxyhydr)oxides in marine sediment.

Formation and dissolution of authigenic Fe and Mn (oxyhydr)oxides influence cycling of trace metals in oxic/suboxic surface sediments.We used the diffusive gradients in thin films technique (DGT) to estimate the association of cobalt with iron and manganese oxides. We compared Co, Fe and Mn maxima measured by DGT in the pore waters of fresh and aged marine sediment cores and estimated the Co/Fe and Co/Mn ratios in the metal oxides. A Mn maximum was not visible in DGT concentration profiles of freshly collected sediment cores, but after ageing the sediment we observed a distinct Mn peak, presumably due to broadening of the depth range over which the various electron acceptors occur. Estimated Co/Mn ratios from both experiments are within the range of literature values for marine sediments, but the value from the aged experiment is at the lower end of the range. This is attributed to stimulation of sulphate reduction and precipitation of cobalt sulfides. The good correlation between Co and Fe maxima in the fresh sediments is attributed to the similarity of their reactions with sulphide rather than Co being released during authigenic Fe oxide reduction

WHAM-FTOXβ – An aquatic toxicity model based on intrinsic metal toxic potency and intrinsic species sensitivity

We developed a model that quantifies aquatic cationic toxicity by a combination of the intrinsic toxicities of metals and protons and the intrinsic sensitivities of the test species. It is based on the WHAM-FTOX model, which combines the calculated binding of cations by the organism with toxicity coefficients (αH, αM) to estimate the variable FTOX, a measure of toxic effect; the key parameter αM,max (applying at infinite time) depends upon both the metal and the test species. In our new model, WHAM-FTOXβ, values of αM,max are given by the product αM* × β, where αM* has a single value for each metal, and β a single value for each species. To parameterise WHAM-FTOXβ, we assembled a set of 2182 estimates of αM,max obtained by applying the basic model to laboratory toxicity data for 76 different test species, covering 15 different metals, and including results for metal mixtures. Then we fitted the log10 αM,max values with αM* and β values (a total of 91 parameters). The resulting model accounted for 72% of the variance in log10 αM,max. The values of αM* increased markedly as the chemical character of the metal changed from hard (average αM* = 4.4) to intermediate (average αM* = 25) to soft (average αM* = 560). The values of log10 β were normally distributed, with a 5–95 percentile range of -0.73 to +0.56, corresponding to β values of 0.18 to 3.62. The WHAM-FTOXβ model entails the assumption that test species exhibit common relative sensitivity, i.e. the ratio αM,max / αM* is constant across all metals. This was tested with data from studies in which the toxic responses of a single organism towards two or more metals had been measured (179 examples for the most-tested metals Ni, Cu, Zn, Ag, Cd, Pb), and statistically-significant (p < 0.003) results were obtained

Viromes of one year old infants reveal the impact of birth mode on microbiome diversity

peer-reviewedEstablishing a diverse gut microbiota after birth is being increasingly recognised as important for preventing illnesses later in life. It is well established that bacterial diversity rapidly increases post-partum; however, few studies have examined the infant gut virome/phageome during this developmental period. We performed a metagenomic analysis of 20 infant faecal viromes at one year of age to determine whether spontaneous vaginal delivery (SVD) or caesarean section (CS) influenced viral composition. We find that birth mode results in distinctly different viral communities, with SVD infants having greater viral and bacteriophage diversity. We demonstrate that CrAssphage is acquired early in life, both in this cohort and two others, although no difference in birth mode is detected. A previous study has shown that bacterial OTU’s (operational taxonomic units) identified in the same infants could not discriminate between birth mode at 12 months of age. Therefore, our results indicate that vertical transmission of viral communities from mother to child may play a role in shaping the early life microbiome, and that birth mode should be considered when studying the early life gut virome