Cultivation and human impact at 6000 cal yr B.P. in tropical lowland forest at Niah, Sarawak, Malaysian Borneo

This paper describes palynological evidence for what appears to be comparatively large-scale human impact in the catchment of the Sungai Niah in the wet tropical lowland swamp forests of Sarawak, Malaysian Borneo close to the Great Cave of Niah. Pollen associated with cleared landscapes and rice cultivation is evident in the sedimentary record from before 6000 cal yr B.P. Human activity seems to have been associated with changes in sedimentary regime, with peat-dominated environments being replaced diachronously by clay-dominated deposition. This may reflect anthropogenic soil erosion in the catchment of the Sungai Niah.     

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.     

Uranium and Thorium Concentration and Isotopic Composition in Five Glass (BHVO‐2G,BCR‐2G,NKT‐1G,T1‐G,ATHO‐G) and Two Powder (BHVO‐2, BCR‐2) Reference Materials

Here we report uranium and thorium isotopic ratios and elemental concentrations measured in solid reference materials from the USGS (BHVO‐2G, BCR‐2G, NKT‐1G), as well as those from the MPI‐DING series (T1‐G, ATHO‐G). Specifically created for microanalysis, these naturally‐sourced glasses were fused from rock powders. They cover a range of compositions, elemental concentrations and expected isotopic ratios. The U‐Th isotopic ratios of two powdered source materials (BCR‐2, BHVO‐2) were also characterised. These new measurements via multi‐collector thermal ionisation mass spectrometry and multi‐collector inductively coupled plasma‐mass spectrometry can now be used to assess the relative performance of techniques and facilitate comparison of U‐Th data amongst laboratories in the geoscience community for in situ and bulk analyses.     

Rare Earth Element and yttrium compositions of Archean and Paleoproterozoic Fe formations revisited: New perspectives on the significance and mechanisms of deposition

The ocean and atmosphere were largely anoxic in the early Precambrian, resulting in an Fe cycle that was dramatically different than today’s. Extremely Fe-rich sedimentary deposits—i.e., Fe formations—are the most conspicuous manifestation of this distinct Fe cycle. Rare Earth Element (REE) systematics have long been used as a tool to understand the origin of Fe formations and the corresponding chemistry of the ancient ocean. However, many earlier REE studies of Fe formations have drawn ambiguous conclusions, partially due to analytical limitations and sampling from severely altered units. Here, we present new chemical analyses of Fe formation samples from 18 units, ranging in age from ca. 3.0 to 1.8 billion years old (Ga), which allow a reevaluation of the depositional mechanisms and significance of Precambrian Fe formations. There are several temporal trends in our REE and Y dataset that reflect shifts in marine redox conditions. In general, Archean Fe formations do not display significant shale-normalized negative Ce anomalies, and only Fe formations younger than 1.9 Ga display prominent positive Ce anomalies. Low Y/Ho ratios and high shale-normalized light to heavy REE (LREE/HREE) ratios are also present in ca. 1.9 Ga and younger Fe formations but are essentially absent in their Archean counterparts. These marked differences in Paleoproterozoic versus Archean REE + Y patterns can be explained in terms of varying REE cycling in the water column.Similar to modern redox-stratified basins, the REE + Y patterns in late Paleoproterozoic Fe formations record evidence of a shuttle of metal and Ce oxides across the redoxcline from oxic shallow seawater to deeper anoxic waters. Oxide dissolution—mainly of Mn oxides—in an anoxic water column lowers the dissolved Y/Ho ratio, raises the light to heavy REE ratio, and increases the concentration of Ce relative to the neighboring REE (La and Pr). Fe oxides precipitating at or near the chemocline will capture these REE anomalies and thus evidence for this oxide shuttle. In contrast, Archean Fe formations do not display REE + Y patterns indicative of an oxide shuttle, which implies an absence of a distinct Mn redoxcline prior to the rise of atmospheric oxygen in the early Paleoproterozoic. As further evidence for reducing conditions in shallow-water environments of the Archean ocean, REE data for carbonates deposited on shallow-water Archean carbonate platforms that stratigraphically underlie Fe formations also lack negative Ce anomalies. These results question classical models for deposition of Archean Fe formations that invoke oxidation by free oxygen at or above a redoxcline. In contrast, we add to growing evidence that metabolic Fe oxidation is a more likely oxidative mechanism for these Fe formations, implying that the Fe distribution in Archean oceans could have been controlled by microbial Fe uptake rather than the oxidative potential of shallow-marine environments.     

Surface structure effects on direct reduction of iron oxides by Shewanella oneidensis

The atomic and electronic structure of mineral surfaces affects many environmentally important processes such as adsorption phenomena. They are however rarely considered relevant to dissimilatory bacterial reduction of iron and manganese minerals. In this regard, surface area and thermodynamics are more commonly considered. Here we take a first step towards understanding the nature of the influence of mineral surface structure upon the rate of electron transfer from Shewanella oneidensis strain MR-1 outer membrane proteins to the mineral surface and the subsequent effect upon cell “activity.” Cell accumulation has been used as a proxy for cell activity at three iron oxide single crystal faces; hematite (001), magnetite (111) and magnetite (100). Clear differences in cell accumulation at, and release from the surfaces are observed, with significantly more cells accumulating at hematite (001) compared to either magnetite face whilst relatively more cells are released into the overlying aqueous phase from the two magnetite faces than hematite. Modeling of the electron transfer process to the different mineral surfaces from a decaheme (protoporphyrin rings containing a central hexacoordinate iron atom), outer membrane-bound cytochrome of S. oneidensis has been accomplished by employing both Marcus and ab initio density functional theories. The resultant model of electron transfer to the three oxide faces predicts that over the entire range of expected electron transfer distances the highest electron transfer rates occur at the hematite (001) surface, mirroring the observed cell accumulation data. Electron transfer rates to either of the two magnetite surfaces are slower, with magnetite (111) slower than hematite (001) by approximately two orders of magnitude. A lack of knowledge regarding the structural details of the heme-mineral interface, especially in regards to atomic distances and relative orientations of hemes and surface iron atoms and the conformation of the protein envelope, precludes a more thorough analysis. However, the results of the modeling concur with the empirical observation that mineral surface structure has a clear influence on mineral surface-associated cell activity. Thus surface structure effects must be accounted for in future studies of cell-mineral interactions.     

An Atomic Force Microscopy study of the growth of calcite in the presence of sodium sulfate

In situ atomic force microscopy (AFM) has been used to compare the growth of pure calcite and the growth of calcite in the presence of sulfate ions from aqueous solutions at a constant value of supersaturation (S.I. = 0.89) with respect to calcite. The effect of sulfate ions on calcite growth rates is determined and a potential incorporation of sulfate ions is identified in the calcite during growth. Solutions supersaturated with respect to calcite with solution concentration ratio of one and a constant pH of 10.2, were prepared and sulfate was added as Na₂SO₄ aqueous solution. The solution composition was readjusted in order to keep the supersaturation and pH constant. PHREEQC was used to determine relevant solution concentrations. In situ AFM experiments of calcite growth were performed using a fluid cell and flowing solutions passed over a freshly cleaved calcite surface. Growth rates were determined from the closure of the rhombohedral etch pits induced by initial dissolution with pure water. The spreading rate of 2-dimensional nuclei was also measured. At low concentrations of sulfate (≤ 0.5 mM), no effect on the growth rate of the calcite was observed. At higher concentrations (2 to 3 mM) of sulfate, the growth rate increased, possibly because a higher concentration of calcium and carbonate was necessary to maintain the supersaturation constant. At much higher concentrations of additional sulfate (up to 60 mM) the growth rate of the calcite was substantially decreased, despite the fact that a further increase of calcium and carbonate was required. The morphology of 2-dimensional growth nuclei became increasingly elongated with increasing sulfate content. Measurements of step height showed that newly grown steps were approximately 1 Å higher when grown in high sulfate concentrations, compared to steps grown in sulfate-free solutions. At sulfate concentrations above 5 mM the growth mechanism changes from layer growth to surface roughening. These observations suggest that the new growth has incorporated sulfate into the calcite surface.     

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.     

Adsorption of copper (II) on mesoporous silica: the effect of nano-scale confinement

Nano-scale spatial confinement can alter chemistry at mineral–water interfaces. These nano-scale confinement effects can lead to anomalous fate and transport behavior of aqueous metal species. When a fluid resides in a nanoporous environments (pore size under 100 nm), the observed density, surface tension, and dielectric constant diverge from those measured in the bulk. To evaluate the impact of nano-scale confinement on the adsorption of copper (Cu²⁺), we performed batch adsorption studies using mesoporous silica. Mesoporous silica with the narrow distribution of pore diameters (SBA-15; 8, 6, and 4 nm pore diameters) was chosen since the silanol functional groups are typical to surface environments. Batch adsorption isotherms were fit with adsorption models (Langmuir, Freundlich, and Dubinin–Radushkevich) and adsorption kinetic data were fit to a pseudo-first-order reaction model. We found that with decreasing pore size, the maximum surface area-normalized uptake of Cu²⁺ increased. The pseudo-first-order kinetic model demonstrates that the adsorption is faster as the pore size decreases from 8 to 4 nm. We attribute these effects to the deviations in fundamental water properties as pore diameter decreases. In particular, these effects are most notable in SBA-15 with a 4-nm pore where the changes in water properties may be responsible for the enhanced Cu mobility, and therefore, faster Cu adsorption kinetics.     

Heterogeneous effects of warming and drought on selected wheat variety yields

Climate change is likely to significantly impact agricultural production in the Great Plains region of the Central United States. This study estimated the impact of changes in temperature and precipitation on wheat (triticum aestivum) variety yield distributions using the moment-based maximum entropy (MBME) model. This approach allows for quantification of potential weather impacts on the yield distribution, and allows these effects to vary across varieties. The unique data set matches wheat variety trial data for 1985 to 2011 with weather data from the exact trial site for 11 locations throughout Kansas. Ten widely-planted varieties with a range of biotic and abiotic characteristics were included for comparison. Weather scenarios were simulated for baseline, increased temperature (one-degree Celsius warming), decreased precipitation (tenth-percentile rainfall outcome), and a combination warming and drought scenario. Warming resulted in an 11 % yield reduction, drought a 22 % reduction, and warming and drought a cumulative 33 % reduction. These effects vary across varieties. Alternative measures of yield risk (e.g. yield variance and coefficient of variation) were also constructed under each scenario and a similar pattern of heterogeneous impacts emerges. The key findings are that (i) exposure to warming and drought lead to mean yield reductions coupled with increased yield risk for all varieties, and (ii) newer (post 2005) seed varieties have a yield advantage over older varieties, however this advantage is reduced under warming and drought conditions.