Denitrification coupled to pyrite oxidation and changes in groundwater quality in a shallow sandy aquifer

This study focuses on denitrification in a sandy aquifer using geochemical analyses of both sediment and groundwater, combined with groundwater age dating (³H/³He). The study sites are located underneath cultivated fields and an adjacent forested area at Oostrum, The Netherlands. Shallow groundwater in the region has high nitrate concentrations (up to 8 mM) due to intense fertilizer application. Nitrate removal from the groundwater below cultivated fields correlates with sulfate production, and the release of dissolved Fe²⁺ and pyrite-associated trace metals (e.g. As, Ni, Co and Zn). These results, and the presence of pyrite in the sediment matrix within the nitrate removal zone, indicate that denitrification coupled to pyrite oxidation is a major process in the aquifer. Significant nitrate loss coupled to sulfate production is further confirmed by comparing historical estimates of regional sulfate and nitrate loadings to age-dated groundwater sulfate and nitrate concentrations, for the period 1950-2000. However, the observed increases in sulfate concentration are about 50% lower than would be expected from complete oxidation of pyrite to sulfate, possibly due to the accumulation of intermediate oxidation state sulfur compounds, such as elemental sulfur. Pollutant concentrations (NO₃, Cl, As, Co and Ni) measured in the groundwater beneath the agricultural areas in 1996 and 2006 show systematic decreases most likely due to declining fertilizer use.     

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments from Hong Kong

Concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in 14 sediment samples collected from four sites in the Mai Po Marshes Nature Reserve (within a RAMSAR Site) and from another six sites in Victoria Harbour and along the Hong Kong coastline. Elevated levels of PCDDs, and particularly OCDD, were detectable in all samples collected from the Mai Po Marshes and five of the six sites. In contrast to PCDDs, PCDFs were mainly found in sediment samples collected from industrial areas (Kwun Tong and To Kwa Wan) in Victoria Harbour. PCDD/F levels and congener profiles in the samples from the Mai Po Marshes Nature Reserve in particular show strong similarities to those reported in studies which have attributed similar elevated PCDD concentrations to nonanthropogenic PCDD sources.     

Permeability development in vesiculating magmas: implications for fragmentation

 Fragmentation, or the "coming apart" of magma during a plinian eruption, remains one of the least understood processes in volcanology, although assumptions about the timing and mechanisms of fragmentation are key parameters in all existing eruption models. Despite evidence to the contrary, most models assume that fragmentation occurs at a critical vesicularity (volume percent vesicles) of 75–83%. We propose instead that the degree to which magma is fragmented is determined by factors controlling bubble coalescence: magma viscosity, temperature, bubble size distribution, bubble shapes, and time. Bubble coalescence in vesiculating magmas creates permeability which serves to connect the dispersed gas phase. When sufficiently developed, permeability allows subsequent exsolved and expanded gas to escape, thus preserving a sufficiently interconnected region of vesicular magma as a pumice clast, rather than fully fragmenting it to ash. For this reason pumice is likely to preserve information about (a) how permeability develops and (b) the critical permeability needed to insure clast preservation. We present measurements and calculations that constrain the conditions (vesicularity, bubble size distribution, time, pressure difference, viscosity) necessary for adequate permeability to develop. We suggest that magma fragments explosively to ash when and where, in a heterogeneously vesiculating magma, these conditions are not met. Both the development of permeability by bubble wall thinning and rupture and the loss of gas through a permeable network of bubbles require time, consistent with the observation that degree of fragmentation (i.e., amount of ash) increases with increasing eruption rate. Received: 5 July 1995 / Accepted: 27 December 1995     

Abundance versus rates of accumulation in fine-grained strata of the Miocene Santa Barbara Basin,California

Although best known as a deposit rich in silica and organic matter, the Miocene Monterey Formation actually had long-term rates of silica and organic Matter accumulation equal to or lower than values in the underlying and overlying detritus-rich formations in the Santa Barbara coastal area. The factor Mainly influencing the composition of the Monterey Formation in this area was the slow accumulation of terrigenous debris. In contrast, with greater than average silica abundance within the Monterey Formation probably resulted from rapid short-term silica accumulation (of hundreds to tens of thousands years duration) rather than from especially slow accumulation of diluting debris.     

Can marine fisheries and aquaculture meet fish demand from a growing human population in a changing climate?

Expansion in the world's human population and economic development will increase future demand for fish products. As global fisheries yield is constrained by ecosystems productivity and management effectiveness, per capita fish consumption can only be maintained or increased if aquaculture makes an increasing contribution to the volume and stability of global fish supplies. Here, we use predictions of changes in global and regional climate (according to IPCC emissions scenario A1B), marine ecosystem and fisheries production estimates from high resolution regional models, human population size estimates from United Nations prospects, fishmeal and oil price estimations, and projections of the technological development in aquaculture feed technology, to investigate the feasibility of sustaining current and increased per capita fish consumption rates in 2050. We conclude that meeting current and larger consumption rates is feasible, despite a growing population and the impacts of climate change on potential fisheries production, but only if fish resources are managed sustainably and the animal feeds industry reduces its reliance on wild fish. Ineffective fisheries management and rising fishmeal prices driven by greater demand could, however, compromise future aquaculture production and the availability of fish products.     

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.