Experimental analysis of arsenic precipitation during microbial sulfate and iron reduction in model aquifer sediment reactors

Microbial SO₄²⁻ reduction limits accumulation of aqueous As in reducing aquifers where the sulfide that is produced forms minerals that sequester As. We examined the potential for As partitioning into As- and Fe-sulfide minerals in anaerobic, semi-continuous flow bioreactors inoculated with 0.5% (g mL⁻¹) fine-grained alluvial aquifer sediment. A fluid residence time of three weeks was maintained over a ca. 300-d incubation period by replacing one-third of the aqueous phase volume of the reactors with fresh medium every seven days. The medium had a composition comparable to natural As-contaminated groundwater with slightly basic pH (7.3) and 7.5 μM aqueous As(V) and also contained 0.8 mM acetate to stimulate microbial activity. Medium was delivered to a reactor system with and without 10 mmol L⁻¹ synthetic goethite (α-FeOOH). In both reactors, influent As(V) was almost completely reduced to As(III). Pure As-sulfide minerals did not form in the Fe-limited reactor. Realgar (As₄S₄) and As₂S₃(am) were undersaturated throughout the experiment. Orpiment (As₂S₃) was saturated while sulfide content was low (∼50 to 150 μM), but precipitation was likely limited by slow kinetics. Reaction-path modeling suggests that, even if these minerals had formed, the dissolved As content of the reactor would have remained at hazardous levels. Mackinawite (Fe_1 + xS; x ? 0.07) formed readily in the Fe-bearing reactor and held dissolved sulfide at levels below saturation for orpiment and realgar. The mackinawite sequestered little As (<0.1 wt.%), however, and aqueous As accumulated to levels above the influent concentration as microbial Fe(III) reduction consumed goethite and mobilized adsorbed As. A relatively small amount of pyrite (FeS₂) and greigite (Fe₃S₄) formed in the Fe-bearing reactor when we injected a polysulfide solution (Na₂S₄) to a final concentration of 0.5 mM after 216, 230, 279, and 286 days. The pyrite, and to a lesser extent the greigite, that formed did sequester As from solution, containing 0.84 and 0.23 wt.% As on average, respectively. Our results suggest that As precipitation during Fe-sulfide formation in nature occurs mainly in conjunction with pyrite formation. Our findings imply that the effectiveness of stimulating microbial SO₄²⁻ reduction to remediate As contamination may be limited by the rate and extent of pyrite formation and the solubility of As-sulfides.     

The potential origins and palaeoenvironmental implications of high temporal resolution δO heterogeneity in coral skeletons

δ¹⁸O was determined at high spatial resolution (beam diameter ∼30 μm) by secondary ion mass spectrometry (SIMS) across 1-2 year sections of 2 modern Porites lobata coral skeletons from Hawaii. We observe large (>2‰) cyclical δ¹⁸O variations that typically cover skeletal distances equivalent to periods of ∼20-30 days. These variations do not reflect seawater temperature or composition and we conclude that skeletal δ¹⁸O is principally controlled by other processes. Calcification site pH in one coral record was estimated from previous SIMS measurements of skeletal δ¹¹B. We model predicted skeletal δ¹⁸O as a function of calcification site pH, DIC residence time at the site and DIC source (reflecting the inputs of seawater and molecular CO₂ to the site). We assume that oxygen isotopic equilibration proceeds at the rates observed in seawater and that only the aqueous carbonate ion is incorporated into the precipitating aragonite. We reproduce successfully the observed skeletal δ¹⁸O range by assuming that DIC is rapidly utilised at the calcification site (within 1 h) and that ∼80% of the skeletal carbonate is derived from seawater. If carbonic anhydrase catalyses the reversible hydration of CO₂ at the calcification site, then oxygen isotopic equilibration times may be substantially reduced and a larger proportion of the skeletal carbonate could be derived from molecular CO₂. Seasonal skeletal δ¹⁸O variations are most pronounced in the skeleton deposited from late autumn to winter (and coincide with the high density skeletal bands) and are dampened in skeleton deposited from spring to summer. We observed no annual pattern in sea surface temperature or photosynthetically active radiation variability which could potentially correlate with the coral δ¹⁸O. At present we are unable to resolve an environmental cue to drive seasonal patterns of short term skeletal δ¹⁸O heterogeneity.     

Lithogeochemical localisation of disseminated gold in the White River area, Yukon, Canada

Gold mineralisation in the White River area, 80 km south of the highly productive Klondike alluvial goldfield, is hosted in amphibolite facies gneisses in the same Permian metamorphic pile as the basement for the Klondike goldfield. Hydrothermal fluid which introduced the gold was controlled by fracture systems associated with middle Cretaceous to early Tertiary extensional faults. Gold deposition occurred where highly fractured and chemically reactive rocks allowed intense water–rock interaction and hydrothermal alteration, with only minor development of quartz veins. Felsic gneisses were sericitised with recrystallisation of hematite and minor arsenic mobility, and extensively pyritised zones contain gold and minor arsenic (ca 10 ppm). Graphitic quartzites (up to 5 wt.% carbon) caused chemical reduction of mineralising fluids, with associated recrystallisation of metamorphic minerals (graphite, pyrrhotite, pyrite, chalcopyrite) in host rocks and veins, and introduction of arsenic (up to 1 wt.%) to form arsenopyrite in veins and disseminated through host rock. Veins have little or no hydrothermal quartz, and up to 19 wt.% carbon as graphite. Late-stage oxidation of arsenopyrite in some graphitic veins has formed pharmacosiderite. Gold is closely associated with disseminated and vein sulphides in these two rock types, with grades of up to 3 ppm on the metre scale. Other rock types in the White River basement rocks, including biotite gneiss, hornblende gneiss, pyroxenite, and serpentinite, have not developed through-going fracture systems because of their individual mineralogical and rheological characteristics, and hence have been little hydrothermally altered themselves, have little hydrothermal gold, and have restricted flow of fluids through the rock mass. Some small post-metamorphic quartz veins (metre scale) have been intensely fractured and contain abundant gold on fractures (up to 40 ppm), but these are volumetrically minor. The style of gold mineralisation in the White River area is younger than, and distinctly different from, that of the Klondike area. Some of the mineralised zones in the White River area resemble, mineralogically and geochemically, nearby coeval igneous-hosted gold deposits, but this resemblance is superficial only. The White River mineralisation is an entirely new style of Yukon gold deposit, in which host rocks control the mineralogy and geochemistry of disseminated gold, without quartz veins.     

An in situ investigation of the preservation and alteration of presolar silicates in the Miller Range 07687 chondrite

Dust grains that formed around ancient stars and in stellar explosions seeded the early solar protoplanetary disk. While most of such presolar grains were destroyed during solar system formation, a fraction of such grains were preserved in primitive materials such as meteorites. These grains can provide constraints on stellar origins and secondary processing such as aqueous alteration and thermal metamorphism on their parent asteroids. Here, we report on the nature of aqueous alteration in the Miller Range (MIL) 07687 chondrite through the analysis of four presolar silicates and their surrounding material. The grains occur in the Fe-rich and Fe-poor lithologies, reflecting relatively altered and unaltered material, respectively. The O-isotopic compositions of two grains, one each from the Fe-rich and Fe-poor matrix, are consistent with formation in the circumstellar envelopes of low-mass Asymptotic Giant Branch (AGB)/Red Giant Branch (RGB) stars. The other two grains, also one each from the Fe-rich and Fe-poor matrix, have O-isotopic compositions consistent with formation in the ejecta of type-II supernovae (SNe). The grains derived from AGB/RGB stars include two polycrystalline pyroxene grains that contain Fe-rich rims. The SNe grains include a polycrystalline Ca-bearing pyroxene and a polycrystalline assemblage consistent with a mixture of olivine and pyroxene. Ferrihydrite is observed in all focused ion beam sections, consistent with parent-body aqueous alteration of the fine-grained matrix under oxidizing conditions. The Fe-rich rims around presolar silicates in this study are consistent with Fe-diffusion into the grains resulting from early-stage hydrothermal alteration, but such alteration was not extensive enough to lead to isotopic equilibration with the surrounding matrix.     

Glacial and periglacial buzzsaws: fitting mechanisms to metaphors

The buzzsaw hypothesis refers to the potential for glacial and periglacial processes to rapidly denude mountains at and above glacier Equilibrium Line Altitudes (ELAs), irrespective of uplift rates, rock type or pre-existing topography. Here the appropriateness of the buzzsaw metaphor is examined alongside questions of the links between glacial erosion and ELAs, and whether the glacial system can produce low-relief surfaces or limit summit heights. Plateau fragments in mountains on both active orogens and passive margins that have been cited as products of glacial and periglacial buzzsaw erosion instead generally represent dissected remnants of largely inherited, pre-glacial relief. Summit heights may correlate with ELAs but no causal link need be implied as summit erosion rates are low, cirque headwalls may not directly abut summits and, on passive margins, cirques are cut into pre-existing mountain topography. Any simple links between ELAs and glacial erosion break down on passive margins due to topographic forcing of ice-sheet growth, and to the km-scale vertical swaths through which ELAs have shifted through the Quaternary. Glaciers destroy rather than create low-relief rock surfaces through the innate tendency for ice flow to be faster, thicker and warmer along valleys. The glacial buzzsaw cuts down.     

Understanding processes of sediment bleaching in glacial settings using a portable OSL reader

Analysis of a high‐resolution suite of modern glacial sediments from Jostedalen, southern Norway, using a portable optically stimulated luminescence (OSL) reader, provides insights into the processes of sediment bleaching in glacial environments at the catchment scale. High‐magnitude, low‐frequency processes result in the least effective sediment bleaching, whereas low‐magnitude, high‐frequency events provide greater bleaching opportunities. Changes in sediment bleaching can also be identified at the scale of individual bar features: tails of braid‐bars and side‐attached bar deposits have the lowest portable reader signal intensities, as well as the smallest conventional OSL residual doses. In addition to improving our understanding of the processes of sediment bleaching, portable reader investigations can also facilitate more rapid and comprehensive modern analogue investigations, which are commonly used to confirm that the OSL signals of modern glacial sediments are well bleached.     

分支河流体系河网形态演变规律——以格尔木河流扇为例

为了探索分支河流体系河网分布规律,为创建储层建模训练图像提供知识库信息。利用Google Earth、Global Mapper、91卫图助手等现代地理信息软件,系统测量了现代格尔木河流扇表面河道分叉特征,应用Horton定律和分形方法建立了河流扇的河网形态模型。结果表明：①格尔木河流扇从顶点到入湖段共识别出26级河道,882个节点和2162个河道段,泉线上、下的河道表现出不同的河网形态;②泉线上部共发育64个节点,每级河道数目增长是上一级河道的RB=1.8900倍,每级河道平均长度是下一级河道的RL=1.0095倍,即河网形态特征参数RB=1.8900和RL=1.0095;泉线下部共发育818个节点,每级河道数目增长是上一级河道的RB=1.0279倍,每级河道平均长度是下一级河道的RL=0.9899倍,即河网形态特征参数是RB=1.0279和RL=0.9899;③河网形态特征参数受坡度影响变化较大,坡度较大则河网形态特征参数较大,坡度较小则河网形态特征参数较小。河网形态特征参数定量表征促进了分支河流体系沉积学发展,为开展陆相盆地储层建模和砂体预测提供了新的知识库信息