The hypothesis that reducing conditions exist in localized zones of high organic matter, termed microniches, was first suggested over a century ago, but only relatively recently have high-resolution techniques been available to investigate them. In any sediment containing benthic fauna, bioturbation affects the distribution of a number of redox-sensitive components. Direct faecal deposition and the death of fauna may be expected to cause particles of labile organic matter (microniches) to be distributed heterogeneously within the sediment. This review discusses the significance and future direction of microniche studies by considering, exclusively, data obtained on a sub-mm scale that provide significant evidence for the existence and properties of microniches. Microelectrodes and planar optodes have shown the significant effect of burrowing organisms on localized O 2 distributions and revealed distinct depletions in O 2 due to microniches. Localized increases in pCO 2 and decreases in pH measured by optodes were attributed to elevated activity at microniches. Diffusive gradients in thin-films have shown isolated supersaturation of metals and sulphide, providing evidence for possible simultaneous oxidation of organic matter by sulphate and iron oxides. The stochastic nature of these data and the lack of information for the same precise location hinders interpretation in terms of sediment diagenesis. If microniches are known to account for a significant proportion of organic matter degradation, re-examination of the current understanding of sedimentary diagenesis may be needed. Further investigation on the distribution and frequency of microniches is required, including a wider range of analytes, in order to estimate their cumulative effect on element diagenesis, immobilisation/remobilisation processes and ultimately pollutant fate.

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Environmental context. Chemical characterisation of sediment microniches can reveal diagenetic processes that may not be detected by larger-scale analysis. With the development of a new preparation method for a binding phase gel, the technique of diffusive gradients in thin films has been used to demonstrate links between the diagenesis of sulfide, phosphorus, vanadium and arsenic at microniches. Knowledge of these processes may improve predictions of past deposition climates where trace elements are considered as paleoredox proxies. Abstract.Recently introduced techniques that can provide two-dimensional images of solution concentrations in sediments for multiple analytes have revealed discrete sites of geochemical behaviour different from the average for that depth (microniches). We have developed a new preparation method for a binding phase, incorporated in a hydrogel, for the diffusive gradients in thin films (DGT) technique. It allows co-analysis of sulfide and the reactive forms of phosphorus, vanadium and arsenic in the porewaters at the surface of the device. This gel, when dried and analysed using laser ablation mass spectrometry, allows the acquisition of high-resolution sub-millimetre-scale data. The binding phase was deployed within a DGT device in a sediment core collected from a productive lake, Esthwaite Water (UK). Localised removal of phosphate and vanadium from the porewaters has been demonstrated at a microniche of local sulfide production. The possible removal processes, including bacterial uptake and reduction of vanadate to insoluble V III by sulfide, are discussed. Understanding processes occurring at this scale may allow improved prediction of pollutant fate and better prediction of past climates where trace metals are used as paleoredox proxies.

Acidification of airborne dust particles can dramatically increase the amount of bioavailable phosphorus (P) deposited on the surface ocean. Experiments were conducted to simulate atmospheric processes and determine the dissolution behavior of P compounds in dust and dust precursor soils. Acid dissolution occurs rapidly (seconds to minutes) and is controlled by the amount of H + ions present. For H + < 10 −4 mol/g of dust, 1-10% of the total P is dissolved, largely as a result of dissolution of surface-bound forms. At H + > 10 −4 mol/g of dust, the amount of P (and calcium) released has a direct proportionality to the amount of H + consumed until all inorganic P minerals are exhausted and the final pH remains acidic. Once dissolved, P will stay in solution due to slow precipitation kinetics. Dissolution of apatite-P (Ap-P), the major mineral phase in dust (79-96%), occurs whether calcium carbonate (calcite) is present or not, although the increase in dissolved P is greater if calcite is absent or if the particles are externally mixed. The system was modeled adequately as a simple mixture of Ap-P and calcite. P dissolves readily by acid processes in the atmosphere in contrast to iron, which dissolves more slowly and is subject to reprecipitation at cloud water pH. We show that acidification can increase bioavailable P deposition over large areas of the globe, and may explain much of the previously observed patterns of variability in leachable P in oceanic areas where primary productivity is limited by this nutrient (e.g., Mediterranean).atmospheric processing | ocean macronutrients | desert dusts

Recent estimates of nutrient budgets for the Eastern Mediterranean Sea (EMS) indicate that atmospheric aerosols play a significant role as suppliers of macro-and micro-nutrients to its Low Nutrient Low Chlorophyll water. Here we present the first mesocosm experimental study that examines the overall response of the oligotrophic EMS surface mixed layer (Cretan Sea, May 2012) to two different types of natural aerosol additions, "pure" Saharan dust (SD, 1.6 mg l −1 ) and mixed aerosols (A-polluted and desert origin, 1 mg l −1 ). We describe the rationale, the experimental set-up, the chemical characteristics of the ambient water and aerosols and the relative maximal biological impacts that resulted from the added aerosols. The two treatments, run in triplicates (3 m 3 each), were compared to control-unamended runs. Leaching of ∼2.1-2.8 and 2.2-3.7 nmol PO 4 and 20-26 and 53-55 nmol NO x was measured per each milligram of SD and A, respectively, representing an addition of ∼30% of the ambient phosphate concentrations. The nitrate/phosphate ratios added in the A treatment were twice than those added in the SD treatment. Both types of dry aerosols triggered a positive change (25-600% normalized per 1 mg l −1 addition) in most of the rate and state variables that were measured: bacterial abundance (BA), bacterial production (BP), Synechococcus (Syn) abundance, chlorophyll-a (chl-a), primary production (PP), and dinitrogen fixation (N 2 -fix), with relative changes among them following the sequence BP>PP≈N2-fix>chl-a≈BA≈Syn. Our results show that the "polluted" aerosols triggered a relatively larger biological Herut et al.Impact of Aerosols on LNLC Seawater change compared to the SD amendments (per a similar amount of mass addition), especially regarding BP and PP. We speculate that despite the co-limitation of P and N in the EMS, the additional N released by the A treatment may have triggered the relatively larger response in most of the rate and state variables as compared to SD. An implication of our study is that a warmer atmosphere in the future may increase dust emissions and influence the intensity and length of the already well stratified water column in the EMS and hence the impact of the aerosols as a significant external source of new nutrients.

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Rising concentrations of atmospheric carbon dioxide are causing acidification of the oceans. This results in changes to the concentrations of key chemical species such as hydroxide, carbonate and bicarbonate ions. These changes will affect the distribution of different forms of trace metals. Using IPCC data for pCO2 and pH under four future emissions scenarios (to the year 2100) we use a chemical speciation model to predict changes in the distribution of organic and inorganic forms of trace metals. Under a scenario where emissions peak after the year 2100, predicted free ion Al, Fe, Cu, and Pb concentrations increase by factors of up to approximately 21, 2.4, 1.5, and 2.0 respectively. Concentrations of organically complexed metal typically have a lower sensitivity to ocean acidification induced changes. Concentrations of organically complexed Mn, Cu, Zn, and Cd fall by up to 10%, while those of organically complexed Fe, Co, and Ni rise by up to 14%. Although modest, these changes may have significance for the biological availability of metals given the close adaptation of marine microorganisms to their environment.

Melting of the Greenland Ice Sheet is a leading cause of land-ice mass loss and cryosphere-attributed sea level rise. Blooms of pigmented glacier ice algae lower ice albedo and accelerate surface melting in the ice sheet’s southwest sector. Although glacier ice algae cause up to 13% of the surface melting in this region, the controls on bloom development remain poorly understood. Here we show a direct link between mineral phosphorus in surface ice and glacier ice algae biomass through the quantification of solid and fluid phase phosphorus reservoirs in surface habitats across the southwest ablation zone of the ice sheet. We demonstrate that nutrients from mineral dust likely drive glacier ice algal growth, and thereby identify mineral dust as a secondary control on ice sheet melting.