The influence of edge sites on the development of surface charge on goethite nanoparticles: A molecular dynamics investigation

Large-scale molecular simulation of proton accumulations were carried out on (i) (110) and (021) slabs immersed in aqueous solution and (ii) a series of model goethite nanoparticles of dimension 2 to 8 nm with systematically varying acicularity and (110)/(021) surface areas. In the slab systems, the (021) surface exhibits 15% more proton charge per unit area than the (110) surface. In the particulate systems, the acicular particles having the highest (110)/(021) ratio accumulate the most charge, opposite to the trend expected from the slab simulations, indicating that, at length scales on the order of 10 nm, the slab results are not a good indicator of the overall charging behavior of the particles. The primary reason for the discrepancy between the particulate systems and slab systems is the preferential accumulation of protons at acute (110)-(110) intersections. Charge accumulates preferentially in this region because excess proton charge at an asperity is more effectively solvated than at a flat interface.     

Compositions of group IVB iron meteorites and their parent melt

The concentrations of P, V, Cr, Fe, Co, Ni, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in the group IVB iron meteorites Cape of Good Hope, Hoba, Skookum, Santa Clara, Tawallah Valley, Tlacotepec, and Warburton Range have been measured by laser ablation inductively coupled plasma mass spectrometry. The data were fitted to a model of fractional crystallization of the IVB parent body core, from which the composition of the parent melt and metal/melt distribution coefficients for each element in the system were determined, for a chosen value of D(Ni). Relative to Ni and chondritic abundances, the parent melt was enriched in refractory siderophiles, with greatest enrichment of 5× chondritic in the most refractory elements, and was strongly volatile-depleted, down to 0.00014× chondritic in Ge. Comparison to an equilibrium condensation sequence from a gas of solar composition indicates that no single temperature satisfactorily explains the volatility trend in the IVB parent melt; a small (<1%) complement of ultrarefractory components added to metal that is volatile-depleted but otherwise has nearly chondritic abundances (for Fe, Co and Ni) best explains the volatility trend. In addition to this volatility processing, which probably occurred in a nebular setting, there was substantial oxidation of the metal in the IVB parent body, leading to loss of Fe and other moderately siderophile elements such as Cr, Ga, and W, and producing the high Ni contents that are observed in the IVB irons. By assuming that the entire IVB parent body underwent a similar chemical history as its core, the composition of the silicate that is complementary to the IVB parent melt was also estimated, and appears to be similar to that of the angrite parent.     

Facies of slurry-flow deposits, Britannia Formation (Lower Cretaceous), North Sea: implications for flow evolution and deposit geometry

ABSTRACT Mud‐rich sandstone beds in the Lower Cretaceous Britannia Formation, UK North Sea, were deposited by sediment flows transitional between debris flows and turbidity currents, termed slurry flows. Much of the mud in these flows was transported as sand‐ and silt‐sized grains that were approximately hydraulically equivalent to suspended quartz and feldspar. In the eastern Britannia Field, individual slurry beds are continuous over long distances, and abundant core makes it possible to document facies changes across the field. Most beds display regular areal grain‐size changes. In this study, fining trends, especially in the size of the largest grains, are used to estimate palaeoflow and palaeoslope directions. In the middle part of the Britannia Formation, stratigraphic zones 40 and 45, slurry flows moved from south‐west and south towards the north‐east and north. Most zone 45 beds lens out before reaching the northern edge of the field, apparently by wedging out against the northern basin slope. Zone 40 and 45 beds show downflow facies transitions from low‐mud‐content, dish‐structured and wispy‐laminated sandstone to high‐mud‐content banded units. In zone 50, at the top of the formation, flows moved from north to south or north‐west to south‐east, and their deposits show transitions from proximal mud‐rich banded and mixed slurried beds to more distal lower‐mud‐content banded and wispy‐laminated units. The contrasting facies trends in zones 40 and 45 and zone 50 may reflect differing grain‐size relationships between quartz and feldspar grains and mud particles in the depositing flows. In zones 40 and 45, quartz grains average 0·30–0·32 mm in diameter, ≈ 0·10 mm coarser than in zone 50. The medium‐grained quartz in zones 40 and 45 flows may have been slightly coarser than the associated mud grains, resulting in the preferential deposition of quartz in proximal areas and downslope enrichment of the flows in mud. In zone 50 flows, mud was probably slightly coarser than the associated fine‐grained quartz, resulting in early mud sedimentation and enrichment of the distal flows in fine‐grained quartz and feldspar. Mud particles in all flows may have had an effective grain size of ≈ 0·25 mm. Both mud content and suspended‐load fallout rate played key roles in the sedimentation of Britannia slurry flows and structuring of the resulting deposits. During deposition of zones 40 and 45, the area of the eastern Britannia Field in block 16/26 may have been a locally enclosed subbasin within which the depositing slurry flows were locally ponded. Slurry beds in the eastern Britannia Field are ‘lumpy’ sheet‐like bodies that show facies changes but little additional complexity. There is no thin‐bedded facies that might represent waning flows analogous to low‐density turbidity currents. The dominance of laminar, cohesion‐dominated shear layers during sedimentation prevented most bed erosion, and the deposystem lacked channel, levee and overbank facies that commonly make up turbidity current‐dominated systems. Britannia slurry flows, although turbulent and capable of size‐fractionating even fine‐grained sediments, left sand bodies with geometries and facies more like those deposited by poorly differentiated laminar debris flows.     

Analytical perspective on trace element species of interest in exploration

Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH₂OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH₂OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.     

A review of paired catchment studies for determining changes in water yield resulting from alterations in vegetation

Paired catchment studies have been widely used as a means of determining the magnitude of water yield changes resulting from changes in vegetation. This review focuses on the use of paired catchment studies for determining the changes in water yield at various time scales resulting from permanent changes in vegetation. The review considers long term annual changes, adjustment time scales, the seasonal pattern of flows and changes in both annual and seasonal flow duration curves. The paired catchment studies reported in the literature have been divided into four broad categories: afforestation experiments, deforestation experiments, regrowth experiments and forest conversion experiments. Comparisons between paired catchment results and a mean annual water balance model are presented and show good agreement between the two methodologies. The results highlight the potential underestimation of water yield changes if regrowth experiments are used to predict the likely impact of permanent alterations to a catchment's vegetation. An analysis of annual water yield changes from afforestation, deforestation and regrowth experiments demonstrates that the time taken to reach a new equilibrium under permanent land use change varies considerably. Deforestation experiments reach a new equilibrium more quickly than afforestation experiments. The review of papers reporting seasonal changes in water yield highlights the proportionally larger impact on low flows. Flow duration curve comparison provides a potential means of gaining a greater understanding of the impact of vegetation on the distribution of daily flows.     

A Method for Estimating the Cost of CO2 Mitigation through Afforestation

The Kyoto Protocol allows Annex I countries to use afforestation (theconversion of non-forest landto forest) to meet emissions reduction targets. We present a new method forestimating the cost of CO₂mitigation through afforestation based on econometric models of land use. Landuse models are developed from dataon observed land allocation decisions and quantify the relationship betweenthe share of land in forest and the netreturns to forestry, among other land use determinants. The econometricapproach measures the actual responsesby landowners to observed changes in net returns, in contrast to earlierstudies in which landowner responses aredictated by the researcher. Models are estimated for Maine, South Carolina,and Wisconsin. The estimated modelsare used to simulate subsidies for afforestation, which imply increases inforest area and net reductions inatmospheric CO₂ concentrations. Average cost measures – totalsubsidies divided by total carbon sequestered –are derived for afforestation programs with and without timber harvesting. Theuse of econometric land use modelsin integrated assessments of climate change is explored. We model the effectson land use patterns and the costsof CO₂ mitigation of changes in the net returns to agricultureinduced by climate change.     

The Vulnerability of the Australian Beef Industry to Impacts of the Cattle Tick (Boophilus microplus) under Climate Change

An integrated assessment is presented of the potential impacts of the cattle tick (Boophilus microplus Canestrini) on the Australian beefindustry under climate change. The project was carried out as a case study to test an impact assessment approach that was designed to integrate biological, production and socio-economic impacts on managed and natural systems. A climate-driven, tick population model was run for European, zebu and crossbred cattle breeds having different levels of resistance to cattle ticks. A geographical information system (GIS) was used to organise spatial data on climate scenarios and industry statistics and to undertake regional analyses.A comparison was made of the two available approaches to conducting impact assessments, namely a bottom-up approach using sensitivity analysis and a top-down approach using climate change scenarios from a global circulation model (GCM) (CSIRO, 1996). The output, in terms of the abundance of tick populations and reductions in cattle productivity for each breed showed significant expansions in potential geographical impacts. In the absence of any adaptation measures, the results indicated changes in the losses in live weight gain of cattle tick ranging from 7780 tonnes per year by 2030 to 21637 tonnes per year by 2100, in comparison with estimates for current losses of 6594 tonnes per year.The principal adaptation options available to the beef industry are to switch to breeds that are more resistant to cattle ticks, or to increase the frequency of treatments with various tick control products. In this paper we focus on switching breeds as an adaptive measure when appropriate damage thresholds are triggered under the climate change scenarios. When adaptation measures were put in place, the losses ranged from 4962 tonnes in 2030 to 5619 tonnes in 2100 compared with 2636 tonnes at present if all producers adopted the optimal breed structure. Optimal breed structure was defined as one that would prevent tick numbers per animal exceeding 100 ticks per animal for European and 700 ticks per animal for crossbred breeds of cattle in any week of the year under a tick control strategy that was suitable for present climatic conditions. The lower threshold for European breeds reflects their vulnerability to explosive increases in numbers because of their low resistance to ticks. The results of the analyses using the GCM scenarios were used in an economic model to calculate costs of lost live-weight gain for 2030, 2070 and 2100. The greatest increases in costs were incurred in the southern parts of the current distribution in Queensland and potentially in northern New South Wales if the present quarantine barrier failed.Given the great uncertainty of the nature of possible regional changes in climate, analyses of the sensitivity of losses in live weight gain to changes in climatic variables were also undertaken. The analyses included a measure of likely impacts of cattle tick on the beef cattle industry, in the absence of adaptation measures, as a baseline measure of sensitivity. The likely impacts on crossbred cattle were insensitive to the climatic variables.When adaptive breed changes were allowed, the economic impacts on the industry were insensitive to the GCM scenarios. This suggests that, at least in this instance, reducing the uncertainties in climate change scenarios is not a priority if the adaptation strategies can be implemented in a cost-effective manner. Finally we made a qualitative assessment of the sustainability and robustness of alternative approaches to adaptation and assessed regional vulnerability to cattle tick under climate change. The conclusions were so strongly dependent on assumptions about the future of other global changes, in particular the ability to maintain quarantine barriers and to retain effective acaricides at comparable costs to the present, that we strongly recommend that risk assessments of climate change extend to all relevant variables in involved in global change where possible.     

High spatial resolution hyperspectral mapping of in-stream habitats, depths, and woody debris in mountain streams

This article evaluates the potential of 1-m resolution, 128-band hyperspectral imagery for mapping in-stream habitats, depths, and woody debris in third- to fifth-order streams in the northern Yellowstone region. Maximum likelihood supervised classification using principal component images provided overall classification accuracies for in-stream habitats (glides, riffles, pools, and eddy drop zones) ranging from 69% for third-order streams to 86% for fifth-order streams. This scale dependency of classification accuracy was probably driven by the greater proportion of transitional boundary areas in the smaller streams. Multiple regressions of measured depths (y) versus principal component scores (x₁, x₂,…, x_n) generated R² values ranging from 67% for high-gradient riffles to 99% for glides in a fifth-order reach. R² values were lower in third-order reaches, ranging from 28% for runs and glides to 94% for pools. The less accurate depth estimates obtained for smaller streams probably resulted from the relative increase in the number of mixed pixels, where a wide range of depths and surface turbulence occurred within a single pixel. Matched filter (MF) mapping of woody debris generated overall accuracies of 83% in the fifth-order Lamar River. Accuracy figures for the in-stream habitat and wood mapping may have been misleadingly low because the fine-resolution imagery captured fine-scale variations not mapped by field teams, which in turn generated false “misclassifications” when the image and field maps were compared.The use of high spatial resolution hyperspectral (HSRH) imagery for stream mapping is limited by the need for clear water to measure depth, by any tree cover obscuring the stream, and by the limited availability of airborne hyperspectral sensors. Nonetheless, the high accuracies achieved in northern Yellowstone streams indicate that HSRH imagery can be a powerful tool for watershed-wide mapping, monitoring, and modeling of streams.     

Long lifetimes of β-glucosidase,leucine aminopeptidase,and phosphatase in Arctic seawater

The active lifetime of extracellular enzymes is a critical determinant of the effectiveness of enzyme production as a means for heterotrophic marine microbes to obtain organic substrates. Here, we report lifetimes of three classes of extracellular enzyme in Arctic seawater. We also investigated the relative importance of photochemical processes and particle-associated processes in inactivating extracellular enzymes. Enzyme inactivation in filtered seawater was slow, with apparent half-lives of enzyme activities on the order of hundreds of hours. The presence of particles (including cells) did not significantly change inactivation rates, suggesting that the long half-lives observed in filtered seawater were realistic for enzymes in unfiltered seawater. Phosphatase and leucine aminopeptidase were susceptible to photoinactivation, but only under high intensity UV-B and UV-C illumination; there was no evidence for increased inactivation rates under natural illumination at our study site in Ny Ålesund, Svalbard. Comparison of inactivation rates of commercially-obtained enzymes from non-marine sources with the extracellular enzymes naturally present in Arctic seawater suggests that the natural enzymes contain structural features that confer longer lifetimes, consistent with observations reported by others from a range of field sites that cell-free enzymes can contribute a substantial fraction of total hydrolytic activity in the water column.