Re-Os and Mo isotope systematics of black shales from the Middle Proterozoic Velkerri and Wollogorang Formations, McArthur Basin, northern Australia

Joint application of the Mo isotope paleoredox proxy and Re-Os deposition-age geochronometer to euxinic black shales has potential for tracing the evolution of ocean redox chemistry over geological time. Here, we report new Re-Os and Mo isotope data for the Mesoproterozoic Velkerri Formation (Roper Group) and Paleoproterozoic Wollogorang Formation (Tawallah Group), McArthur Basin, northern Australia. New Re-Os ages of 1361 ± 21 Ma (2σ, n = 14, mean square of weighted deviates [MSWD] = 1.3, Model 1) and 1417 ± 29 Ma (2σ, n = 12, MSWD = 1.3, Model 1) constrain the depositional age of the Velkerri Formation and its contained biomarkers, as well as acritarchs and microfossils from the Roper Group. Black shales from the upper Velkerri Formation have high Mo abundances (105-119 ppm) and degree of pyritization [DOP] values (0.90-0.92) implying quantitative conversion of molybdate (MoO₄²⁻) to thiomolybdate (MoS₄²⁻) in overlying bottom waters. The average δ^97/95Mo (0.72 ± 0.10‰, 2σ, n = 6) of these shales is consistent with previous data, but represents a significantly more precise determination for global seawater δ^97/95Mo at 1.4 Ga. This value is lighter than present-day seawater by ∼0.85‰ and reflects expanded strongly euxinic deep ocean conditions ([H₂S]_aq > 11 μM) relative to oxic, suboxic, and weakly/intermittently euxinic ([H₂S]_aq < 11 μM) marine deposition in the 1.4 Ga oceans. Mass-balance modelling suggests Mo removal into strongly euxinic and oxic sediments may have comprised 30-70% and less than 15%, respectively, of the oceanic Mo sink at 1.4 Ga as opposed to 5% and 35% today, respectively.The Re-Os radioisotope system in organic-rich shales serves as a test for post-depositional alteration that could affect the usefulness of paleoredox tracers such as Mo stable isotopes. Re-Os isotope data for the Wollogorang Formation black shales are scattered and yield a highly imprecise date of 1359 ± 150 Ma (2σ, n = 21, MSWD = 85, Model 3). This age is younger than U-Pb zircon ages from interbedded tuffs that constrain the age of deposition at ca. 1730 Ma. In conjunction with previous petrological, geochemical, and paleomagnetic data, the Re-Os isotope data suggest hydrothermal fluid flow through the Wollogorang Formation, possibly associated with formation of the ca. 1640 Ma McArthur River Pb-Zn-Ag sedimentary exhalative deposit, resulted in post-depositional mobilization of Re and Os. Based on the degree of deviation of the Re-Os data from a 1730 Ma reference line, open-system behavior of Re and Os was greatest near the base of the black shale unit. Wollogorang Formation black shales are enriched in Mo (41-58 ppm), but are characterized by variable δ^97/95Mo (0.3-0.8‰) and DOP (0.57-0.92). The lightest δ^97/95Mo values occur near the base of the black shale unit. Based on the Re-Os systematics, hydrothermal fluids have probably overprinted the authigenic δ^97/95Mo signature in those shales. However, the heaviest δ^97/95Mo values in the Wollogorang Formation come from stratigraphically higher shales, and are similar to those observed for the Velkerri Formation, and thus may reflect seawater δ^97/95Mo at 1.73 Ga.     

Molybdenum isotope evidence for mild environmental oxygenation before the Great Oxidation Event

We use the molybdenum isotope paleoredox proxy to look for evidence of small amounts of O₂ in the environment ∼50 Ma before the Great Oxidation Event (GOE) in a high resolution profile from the ∼2.5 Ga Mt. McRae Shale. The molybdenum isotope compositions (δ^98/95Mo) from samples throughout the sequence span a range from 0.99‰ to 1.86‰. All samples have heavier δ^98/95Mo compared to average upper continental crust. In addition, the upper (S1) and lower (S2) black shale units within the Mt. McRae Shale exhibit systematic differences in average isotopic compositions and distinct patterns of δ^98/95Mo variation. Heavier δ^98/95Mo values occur in the S1 unit, where δ^98/95Mo correlates with Mo enrichments. In the S2 unit, δ^98/95Mo is not as heavy and is relatively invariant.Based on sedimentary Fe proxies we infer that S1 sediments were deposited under euxinic conditions, so that Mo removal from bottom waters was likely quantitative. Thus, δ^98/95Mo in this interval likely records coeval seawater. The lighter δ^98/95Mo values in the S2 unit may indicate a less fractionated ocean Mo inventory relative to the S1 unit. However, sedimentary Fe proxies suggest that S2 sediments accumulated under a water column that was ferruginous rather than euxinic, raising the possibility of non-quantitative Mo scavenging and hence an expressed δ^98/95Mo fractionation relative to coeval seawater. Because any associated fractionations during this process would have favored the light isotope in sediments, the lighter δ^98/95Mo values in the S2 unit represent a lower limit on the value in contemporaneous seawater.After evaluating a range of hypotheses, we conclude that the isotopically heavy δ^98/95Mo values seen throughout the Mt. McRae Shale likely reflect the effects of oxidative weathering and adsorption of Mo to oxide mineral surfaces on land or in surface oceans. The extent of environmental oxygenation in either unit is difficult to assess due to uncertainties in the global Mo isotope budget. Because of the small ocean Mo inventory in the Late Archean, documented by low concentrations of Mo and low Mo/TOC, the extent of oxygenation required to account for the observed fractionations is much smaller than in modern oceans. However, when juxtaposed against the record of δ^98/95Mo through time, our findings provide further evidence of the onset of environmental oxygenation before the GOE.     

On the generation of drought events using an alternating renewal-reward model

This research study focused on the hypothesis that extreme drought and high streamflow events come from different independent populations with different probability distributions which need to be studied separately, rather than considering the streamflow population as a whole. The inability of traditional streamflow generator models to consistently reproduce the frequency of occurrence of severe droughts observed in the historical record has been questioned by many researchers. Our study focused on the development of astochastic event generator model which would be capable of doing so. This was accomplished in a two-step process by first generating the drought event, and then deriving the streamflows which comprised that event. The model considered for this analysis was an alternating renewal-reward procedure that cycles between eventon andoff times, and is representative of drought or high streamflow event duration. The reward gained while the event ison oroff represents drought severity or high streamflow surplus. Geometric and gamma distributions were considered for drought duration and deficit respectively. Model validation was performed using calculated required capacities from the sequent peak algorithm.     

天然实验流域降雨径流现象发生的悖论

作为滁州水文实验系统一部分的1号天然实验流域,面积7897m2,以安山岩为基底,上覆平均厚度2.46m的第四系沉积物。实测了包括地面径流和地面下径流的各种降雨径流响应,后者包括来自非饱和带的壤中流和饱和带的地下水径流。表明这些径流成分有着复杂的组合类型,主要是以地面径流为主的SR型和以地面下径流为主的SSR型,以及中间的和演化的类型。SR型实例中的地面径流量可占总径流的65%,而SSR实例中的地面下径流量可有90%。主要降水的7月,地面下贡献占54.5%,其中地下水径流即占33%。大部分地面径流与降水的18O组成有不小的差异,比较了同时进行测验的3个实验流域,在1400min的降水径流过程中,降水的平均δ18O为-1.210%,而同期地面径流的平均δ18O,2号水文山流域(512m2)为-1.132%,1号南大洼天然流域为-1.065%,3号只有薄层风化碎屑的牵牛花流域(4573m2)为-0.801%。这质疑了现行同位素流量过程线划分方法8个假定中的两个:地面径流的同位素组成不同于降水,天然流域尤其如此;各种水源在汇集过程中的同位素分馏影响并非都可忽略不计。实验流域因降水而产生径流,但所产生的径流却有着非本次降水的组分,这一降水径流悖论发生于各个实验流域。SR型和SSR型总的非本次降水组分分别达16%和64%。     

Predictors of species richness in the deep-benthic fauna of the northern Gulf of Mexico

Species richness in macrofauna and megafauna collected with box cores and trawls from 35 standard stations over a depth range of 175–3720 m in the northern Gulf of Mexico was examined in terms of two primary questions: (1) are observed patterns random? and (2) if not, what environmental factors might account for the patterns? A null model tested whether richness vs. depth distributions were random. Groups with species that had broad vertical depth ranges fit the null model better than groups with small ranges, but for almost all phyla a non-random pattern was indicated. With randomness as a proximal explanation ruled out, further examination of the relationship between richness and environmental factors was justified. A generalized linear model (GLM) showed that a suite of 18 factors categorized as food-related, habitat-related, pollution-related and location-related were significantly related to richness patterns, but that different mixes of factors applied to different phyla. No one factor accounted for any observed patterns. Thus, each taxonomic group needs to be examined individually, and no generally applicable explanation for the causes of richness patterns may exist. Nonetheless, mapping richness itself indicates valuable areas in the Mississippi Trough that must receive special consideration and possible protection.     

Detection of multiple fracture sets using observations of shear‐wave splitting in microseismic data

The hydrocarbon industry is moving increasingly towards tight sandstone and shale gas resources – reservoirs that require fractures to be produced economically. Therefore, techniques that can identify sets of aligned fractures are becoming more important. Fracture identification is also important in the areas of coal bed methane production, carbon capture and storage (CCS), geothermal energy, nuclear waste storage and mining. In all these settings, stress and pore pressure changes induced by engineering activity can generate or reactivate faults and fractures. P‐ and S‐waves are emitted by such microseismic events, which can be recorded on downhole geophones. The presence of aligned fracture sets generates seismic anisotropy, which can be identified by measuring the splitting of the S‐waves emitted by microseismic events. The raypaths of the S‐waves will have an arbitrary orientation, controlled by the event and geophone locations, meaning that the anisotropy system may only be partly illuminated by the available arrivals. Therefore to reliably interpret such splitting measurements it is necessary to construct models that compare splitting observations with modelled values, allowing the best fitting rock physics parameters to be determined. Commonly, splitting measurements are inverted for one fracture set and rock fabrics with a vertical axis of symmetry. In this paper we address the challenge of identifying multiple aligned fracture sets using splitting measured on microseismic events. We analyse data from the Weyburn CCS‐EOR reservoir, which is known to have multiple fracture sets, and from a hydraulic fracture stimulation, where it is believed that only one set is present. We make splitting measurements on microseismic data recorded on downhole geophone arrays. Our inversion technique successfully discriminates between the single and multiple fracture cases and in all cases accurately identifies the strikes of fracture sets previously imaged using independent methods (borehole image logs, core samples, microseismic event locations). We also generate a synthetic example to highlight the pitfalls that can be encountered if it is assumed that only one fracture set is present when splitting data are interpreted, when in fact more than one fracture set is contributing to the anisotropy.     

Impacts of projected climate change on sediment yield and dredging costs

Changes in climate may significantly affect how sediment moves through watersheds into harbours and channels that are dredged for navigation or flood control. Here, we applied a hydrologic model driven by a large suite of climate change scenarios to simulate both historical and future sediment yield and transport in two large, adjacent watersheds in the Great Lakes region. Using historical dredging expenditure data from the U.S. Army Corps of Engineers, we then developed a pair of statistical models that link sediment discharge from each river to dredging costs at the watershed outlet. Although both watersheds show similar slight decreases in streamflow and sediment yield in the near‐term, by Mid‐Century, they diverge substantially. Dredging costs are projected to change in opposite directions for the two watersheds; we estimate that future dredging costs will decline in the St. Joseph River by 8–16% by Mid‐Century but increase by 1–6% in the Maumee River. Our results show that the impacts of climate change on sediment yield and dredging may vary significantly by watershed even within a region and that agricultural practices will play a large role in determining future streamflow and sediment loads. We also show that there are large variations in responses across climate projections that cause significant uncertainty in sediment and dredging projections.     

Controls on old and new water contributions to stream flow at some nested catchments in Vermont,USA

Factors controlling the partitioning of old and new water contributions to stream flow were investigated for three events in four catchments (three of which were nested) at Sleepers River Research Watershed in Danville, Vermont. In the 1993 snowmelt period, two‐component isotopic hydrograph separations showed that new water (meltwater) inputs to the stream ranged widely from 41 to 74%, and increased with catchment size (41 to 11 125 ha) (with one exception) and with open land cover (0–73%). Peak dissolved organic carbon concentrations and relative alkalinity dilution in stream water ranked in the same order among catchments as the new water fractions, suggesting that new water followed shallow flow paths. During the 1994 snowmelt, despite similar timing and magnitude of melt inputs, the new‐water contribution to stream flow ranged only from 30 to 36% in the four catchments. We conclude that the uncommonly high and variable new water fractions in streamwater during the 1993 melt were caused by direct runoff of meltwater over frozen ground, which was prevalent in open land areas during the 1993 winter. In a high‐intensity summer rainstorm in 1993, new water fractions were smaller relative to the 1993 snowmelt, ranging from 28 to 46%, but they ranked in the identical catchment order. Reconciliation of the contrasting patterns of new–old water partitioning in the three events appears to require an explanation that invokes multiple processes and effects, including:

• 1. topographically controlled increase in surface‐saturated area with increasing catchment size;
• 2. direct runoff over frozen ground;
• 3. low infiltration in agriculturally compacted soils;
• 4. differences in soil transmissivity, which may be more relevant under dry antecedent conditions.

These data highlight some of the difficulties faced by catchment hydrologists in formulating a theory of runoff generation at varying basin scales. Copyright © 2002 John Wiley & Sons, Ltd.     

Emplacement of massive deposits by sheet flow

Turbidity current and coastal storm deposits are commonly characterized by a basal sandy massive (structureless) unit overlying an erosional surface and underlying a parallel or cross-laminated unit. Similar sequences have been recently identified in fluvial settings as well. Notwithstanding field, laboratory and numerical studies, the mechanisms for emplacement of these massive basal units are still under debate. It is well accepted that the sequence considered here can be deposited by waning-energy flows, and that the parallel-laminated units are deposited under transport conditions corresponding to upper plane bed at the dune–antidune transition. Thus, transport conditions that are more intense than those at the dune–antidune transition should deposit massive units. This study presents experimental, open-channel flow results showing that sandy massive units can be the result of gradual deposition from a thick bedload layer of colliding grains called sheet flow layer. When this layer forms with relatively coarse sand, the non-dimensional bed shear stress associated with skin friction, the Shields number, is larger than a threshold value approximately equal to 0·4. For values of the Shields number smaller than 0·4 the sheet flow layer disappeared, sediment was transported by a standard bedload layer one or two grain diameters thick, and the bed configuration was characterized by downstream migrating antidunes and washed out dunes. Parallel laminae were found in deposits emplaced with standard bedload transport demonstrating that the same dilute flow can gradually deposit the basal and the parallel-laminated unit in presence of traction at the depositional boundary. Further, the experiments suggested that two different types of upper plane bed conditions can be defined, one associated with standard bedload transport at the dune–antidune transition, and the other associated with bedload transport in sheet flow mode at the transition between upstream and downstream migrating antidunes.