Surface complexation modeling for predicting solid phase arsenic concentrations in the sediments of the Mississippi River Valley alluvial aquifer, Arkansas, USA

The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6 m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21-36.6 m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory.     

An Algorithm for the Determination of All Significant Pathways in Chemical Reaction Systems

When the output of a complex chemical model is analysed, a typical topic isthe determination of pathways, i.e., reaction sequences, that produce ordestroy a chemical species of interest.A representative example is the investigation of catalytic ozone destruction cycles in the stratosphere.An algorithm for the automatic determination of pathways in any given reactionsystem is presented. Under the assumption that reaction rates are known, it finds all significant pathways, i.e., all pathways with a rate above a prescribed threshold.The algorithm forms pathways step by step, starting from single reactions.The chemical species in the system are consecutively considered as `branching points'.For every branching-point species, each pathway producing it is connected witheach pathway consuming it.Rates proportional to `branching probabilities' are calculated.Pathways with a rate that is smaller than a prescribed threshold arediscarded.If a newly formed pathway contains sub-pathways, e.g., null cycles, it is split into these simpler pathways.In order to demonstrate the performance of the algorithm, it has been applied to the determination of catalytic ozone destruction cycles and methaneoxidation pathways in the stratosphere.     

Sediment budgeting: A case study in the Katiorin drainage basin,Kenya

The primary objective of this study was to compute a detailed budget for a small semiarid tropical drainage basin in Kenya. Results indicated that transfer of sediments (‘inputs’) from primary source areas was minor in comparison to changes in storage. The major sediment source area within the Katiorin drainage basin was the colluvial hillslope zone. The net change in storage within this zone was approximately 2100 Mg yr^?1. Surface wash and rilling were the dominant transport processes responsible for the remobilization of colluvial sediments. Sediment storage within the in-channel reservoir increased by 60 Mg yr^?1, which was minor when compared to the total store of sediment in this reservoir. During 1986, the channel network stored only a small fraction ( < 3 per cent) of the sediment delivered from the hillslope subsystem. Therefore, the in-channel reservoir had limited influence on sediment conveyance to the basin outlet. These data indicate that a static equilibrium condition cannot be assumed within the Katiorin drainage basin. Such an assumption would result in erosion estimates of approximately 5.5 mm yr^?1 for the entire basin (based on a sediment output of 7430 Mg km^?2 yr^?1 and a measured bulk density of 1.35 Mg m^?3). However, this masked the actual rates of 1.2 to 7.1 mm yr^?1 in subbasin primary source areas, and rates of 0.6 to 17 mm yr^?1 for colluvial material in the various subbasins. The extreme accelerated erosion rates resulted from minimal ground vegetation, steep slopes, soil crust formation, an erodible substrate, and a well-integrated drainage network for rapid conveyance of sediments from the hillslope subsystem to the basin outlet.     

Estimates of CO2 from wood fuel based on forest harvest data

Wood continues to be a major fuel source for vast numbers of the world's people. Even in the highly industrialized countries, use of wood and wood wastes as fuel produces a small (in comparison to fossil fuels) but non-negligible amount of CO₂. Although information on the worldwide harvest and use of wood is not as complete or as reliable as fossil fuel data, this paper uses what is available and develops annual estimates of CO₂ emissions for the period 1968–1983. Woods are separated into two types, coniferous and non-coniferous, and average content and carbon amounts are estimated for each type. Wood utilization is divided into several categories, e.g., fuelwood, lumber, poles, and use of wood wastes as fuels in the lumber and paper industries is included. Results are given for major world regions. In recent years the worldwide CO₂ emissions from wood used as fuels is estimated to be about one-tenth as much as CO₂ emissions from fossil fuels. This does not include fires in the forests, either associated with forest clearing or those from natural causes.     

Boundary-Layer Similarity Under an Axisymmetric,Gradient Wind Vortex

We present similarity solutions for the mean boundary-layer profiles under an axisymmetric vortex that is in gradient wind balance; the similarity model includes the nonlinear momentum advection and curvature terms. These solutions are a generalization of the Ekman layer mean flow, which is the canonical boundary-layer basic state under a uniform, geostrophically-balanced flow. Near-surface properties such as inflow angle, surface wind factor, diffusive transport of kinetic energy into the surface layer and dissipational heating are calculated and shown to be sensitive to the choice of turbulence parameterization.     

Quantifying and modelling the carbon sequestration capacity of seagrass meadows – A critical assessment

Seagrasses are among the planet’s most effective natural ecosystems for sequestering (capturing and storing) carbon (C); but if degraded, they could leak stored C into the atmosphere and accelerate global warming. Quantifying and modelling the C sequestration capacity is therefore critical for successfully managing seagrass ecosystems to maintain their substantial abatement potential. At present, there is no mechanism to support carbon financing linked to seagrass. For seagrasses to be recognised by the IPCC and the voluntary C market, standard stock assessment methodologies and inventories of seagrass C stocks are required. Developing accurate C budgets for seagrass meadows is indeed complex; we discuss these complexities, and, in addition, we review techniques and methodologies that will aid development of C budgets. We also consider a simple process-based data assimilation model for predicting how seagrasses will respond to future change, accompanied by a practical list of research priorities.     

The use of meiofauna as an indicator of benthic organic enrichment associated with salmonid aquaculture

Sediment chemistry and meiofaunal samples were collected in the Broughton Archipelago, British Columbia, to examine the relationship between sediment variables and meiofauna diversity across near- and far-field gradients surrounding several finfish aquaculture operations. The sediment variables examined consisted of free sulfide concentrations, redox potential (E(NHE)), organic content, and sediment grain size. A strong trend between sediment texture and organic content was observed across all sampling locations, which reflected a wide range of sediment types (sand-silt) that exist within the Broughton Archipelago. The abundance of certain meiofaunal groups (kinorhynchs, crustaceans, polychaetes) declined in an asymptotic fashion with increasing free sulfide concentrations, an indicator of benthic organic enrichment. Within these relationships, low meiofaunal abundances occurred in fine sediments associated with higher organic contents. Although other groups (nematodes, foraminifera) showed a slight decline in abundance with increasing organic enrichment, a high amount of variability in abundance was observed at high free sulfide concentrations, rendering these groups not suitable as indicators of organic enrichment. This study reports both horizontal and vertical trends in meiofaunal distributions relative to free sulfide concentrations. The abundance of nematode and crustacean taxa decreased with sediment depth as well as increasing sulfide concentration, while polycheate abundance increased with increasing free sulfide concentration. The ratio of nematodes to copepods was also shown to represent the degree of organic loading associated with aquaculture operations and its application as an indicator of benthic impact is discussed.