Redox-sensitive Metals Research Articles

Spatial and temporal variability in the chemical properties of the oxic and suboxic layers of the Black Sea

The Black Sea, a land-locked deep basin with sulfide bearing waters below 150–200m, has been subject to anthropogenic pressures since the 1970s. Large inputs of nutrients (nitrate — N, phosphate — P, silicate — Si) with high N/P but low Si/N ratios and subsequent development of intensive eutrophication over the basin have changed vertical distributions and inventories of nutrients and redox-sensitive metals in the oxic, suboxic and anoxic layers. Chemical data sets obtained between 1988 and 2010, and older data from before 1970 were evaluated to assess spatial/temporal variations of the dissolved oxygen (O2), nutrients and dissolved/particulate manganese (Mnd, Mnp) in the water column from the lower salinity, oxygenated surface waters through the SubOxic Layer (SOL; O2<20μM; H2S<1μM) to the anoxic, sulfidic water interface. Correlations were observed between salinity and nutrients (nitrate, silicate) in the nearshore waters off the Danube delta and in the southwestern (SW) coastal waters which had low Si/N ratios. Surface waters from the western central gyre were consistently depleted in nitrate and phosphate with low N/P but higher Si/N molar ratios throughout the year. Chemical profiles obtained recently in the Rim Current and western central gyre displayed very similar vertical features through the halocline to the sulfidic water interface. However, in the SW coastal margin, lateral intrusion of O2 and nutrients by the Bosporus Plume resulted in formation of secondary maxima of nitrate, nitrite and O2 in the SOL, and local deepening of the first appearance of anoxic, sulfidic waters. Before the mid 1960s, nitrate-enriched major rivers fed the Black Sea with high N/P ratios (>50). The surface waters over the basin were rich in silicate (25–70μM), but poor in nitrate (<0.1μM) and phosphate (0.05–0.3μM), resulting in very high Si/N (>500) but very low N/P (<1.0) ratios. After the mid 1970s, construction of dams, especially on the Danube River, resulted in lower Si concentrations. At this time the increased loads of anthropogenic nitrate and phosphate by the major rivers resulted in lower Si/N, but still high N/P molar ratios, which enhanced eutrophication (production of particulate organic matter, POM) drastically in the coastal waters. This led to reductions in the surface Si/N ratio by up to 500-fold in the western basin while the N/P ratio increased. The enhanced POM export increased the nitrate inventory and thus N/P ratios of the NW shelf waters spreading over the whole basin. The increased export of POM decreased the Si inventory of the upper layer down to the boundary of sulfidic waters. This export also increased O2 consumption and removal of nitrate to N2 form by denitrification in the oxic/suboxic interface, leading to seasonal/decadal changes in the boundaries of the nitracline and main oxycline and changes in the slopes of the nitrate-phosphate and Apparent Oxygen Utilization (AOU)-nitrate regressions in the steep oxycline down to the SOL. These slopes are much smaller than those observed in the lower layer of Marmara Sea fed by the Black Sea outflow. The enlargement of SOL by ~15–20m after the 1970s modified the vertical features of nitrate, phosphate and manganese (Mnd, Mnp) species in the redox gradient zone.

Atmospheric oxygenation three billion years ago

It is widely assumed that atmospheric oxygen concentrations remained persistently low (less than 10(-5) times present levels) for about the first 2 billion years of Earth's history. The first long-term oxygenation of the atmosphere is thought to have taken place around 2.3 billion years ago, during the Great Oxidation Event. Geochemical indications of transient atmospheric oxygenation, however, date back to 2.6-2.7 billion years ago. Here we examine the distribution of chromium isotopes and redox-sensitive metals in the approximately 3-billion-year-old Nsuze palaeosol and in the near-contemporaneous Ijzermyn iron formation from the Pongola Supergroup, South Africa. We find extensive mobilization of redox-sensitive elements through oxidative weathering. Furthermore, using our data we compute a best minimum estimate for atmospheric oxygen concentrations at that time of 3 × 10(-4) times present levels. Overall, our findings suggest that there were appreciable levels of atmospheric oxygen about 3 billion years ago, more than 600 million years before the Great Oxidation Event and some 300-400 million years earlier than previous indications for Earth surface oxygenation.

Vanadium bioavailability and toxicity to soil microorganisms and plants

Vanadium, V, is a redox-sensitive metal that in solution, under aerobic conditions, prevails as the oxyanion vanadate(V). There is little known regarding vanadium toxicity to soil biota, and the present study was set up to determine the toxicity of added vanadate to soil organisms and to investigate the relationship between toxicity and vanadium sorption in soils. Five soils with contrasting properties were spiked with 7 different doses (3.2-3200 mg V kg(-1)) of dissolved vanadate, and toxicity was measured with 2 microbial and 3 plant assays. The median effective concentration (EC50) thresholds of the microbial assays ranged from 28 mg added V kg(-1) to 690 mg added V kg(-1), and the EC50s in the plant assays ranged from 18 mg added V kg(-1) to 510 mg added V kg(-1). The lower thresholds were in the concentration range of the background vanadium in the untreated control soils (15-58 mg V kg(-1)). The vanadium toxicity to plants decreased with a stronger soil vanadium sorption strength. The EC50 values for plants expressed on a soil solution basis ranged from 0.8 mg V L(-1) to 15 mg V L(-1) and were less variable among soils than corresponding values based on total vanadium in soil. It is concluded that sorption decreases the toxicity of added vanadate and that soil solution vanadium is a more robust measure to determine critical vanadium concentrations across soils.

Sediment geochemistry of the Thetis hypersaline anoxic basin (eastern Mediterranean Sea)

The Thetis basin is a deep hypersaline anoxic basin in the western part of the Mediterranean Ridge (eastern Mediterranean Sea). It is characterised by highly sulphidic NaCl-saturated brine with one of the highest values of salinity reported from similar basins (S ~348‰). The strong pycnocline at the seawater–brine interface induces permanent anoxic bottom conditions driving depositional processes and distribution patterns of redox-sensitive metals in the sediments. This work presents a high-resolution dataset of sedimentological, mineralogical and geochemical features and planktonic foraminifera distribution, derived from the exploration of a 52cm long box-core sampled in the Thetis sediments. Basing on direct comparisons with available data from other hypersaline records and ancient anoxic organic-rich deep-sea records (sapropels and black shales), we aim to explore the potential of these anoxic basins as natural laboratories to better understand the mechanisms driving geochemical patterns in recent/ancient anoxic sediments.

Co-variation of nitrogen isotopes and redox states through glacial–interglacial cycles in the Black Sea

In all aquatic environments, nitrogen cycling within the water column is strongly influenced by oxygen. We hypothesize that the nitrogen isotopic composition (δ15N) of organic matter deposited in the sediments is a proxy for the redox state of the water column at the time of deposition. We tested the hypothesis by measuring the bulk sedimentary δ15N values in a drill core from the Black Sea, a basin that alternates between oxic, less saline conditions and anoxic, marine conditions on glacial–interglacial time scales. We reconstructed these changes in Black Sea redox conditions using sedimentary δ15N, total organic carbon (TOC), total nitrogen (TN), redox-sensitive metals, and micropaleontological data from a deep-sea core (DSDP Site 380). The sedimentary data reveal that during the transitions between oxic and anoxic conditions, δ15N values increased relative to the preceding and succeeding quasi-steady-state oxic and anoxic periods. The results indicate that the reciprocal transitional states from anoxic to oxic conditions were accompanied by intense denitrification; during the quasi-stable oxic and anoxic states (characterized by glacial fresh water and interglacial marine conditions) nitrification and complete nitrate utilization, respectively, dominate the nitrogen cycle. While other factors may influence the δ15N record, our results support the hypothesis that the variations in nitrogen isotopic composition of organic matter are strongly influenced by changes in redox state in the Black Sea subphotic zone on glacial–interglacial time scales, and can be explained by a relatively simple model describing the effects of oxygen on the microbial processes that drive the nitrogen cycle in marine ecosystems. Our model suggests that the nitrogen isotopic composition of marine sediments, on geological time scales, can be used to reconstruct the redox state of the overlying water column.

Changing Climate and Sea Level Alter Hg Mobility at Lake Tulane, Florida, U.S.

Between 45,000 cal years BP and the beginning of the Holocene, the accumulation rate for Hg in sediments of Lake Tulane, Florida ranged from ≈2 to 10 μg m(-2) yr(-1), compared with 53 μg Hg m(-2) yr(-1) in the 1985-1990 period of anthropogenic input. The locality experienced regional draw-down of the water table during the Wisconsinan glaciation, which lowered global sea level by nearly 130 m. Natural atmospheric deposition of Hg to the surrounding area resulted in long-term (ca. 100,000 years) sequestration of this atmospheric flux of Hg, primarily by adsorption in the oxic Al- and Fe-hydroxide-rich sandy subsoil. Global sea level rise during deglaciation led to a rising regional water table, flooding the oxidized soils surrounding Tulane. Iron and adsorbed Hg were mobilized by reductive dissolution and transported by groundwater flow to Lake Tulane and ultimately to the accumulating sediment. The accumulation rate of Hg (and Fe) increased rapidly about 16,000 cal years BP, peaked at nearly 60 μg Hg m(-2) yr(-1) ca. 13,000-14,000 cal years BP, declined sharply during the Younger Dryas, and then increased sharply to a second 60 μg Hg m(-2) yr(-1) peak about 5000 cal years BP. Thereafter, it declined nearly to background by 900 cal years BP. In similar geologic situations, rapid modern sea level rise will initiate this process globally, and may mobilize large accumulations of Hg and lesser amounts of As, and other redox sensitive metals to groundwater and surface water.

Ocean oxygenation in the wake of the Marinoan glaciation

Metazoans are likely to have their roots in the Cryogenian period, but there is a marked increase in the appearance of novel animal and algae fossils shortly after the termination of the late Cryogenian (Marinoan) glaciation about 635 million years ago. It has been suggested that an oxygenation event in the wake of the severe Marinoan glaciation was the driving factor behind this early diversification of metazoans and the shift in ecosystem complexity. But there is little evidence for an increase in oceanic or atmospheric oxygen following the Marinoan glaciation, or for a direct link between early animal evolution and redox conditions in general. Models linking trends in early biological evolution to shifts in Earth system processes thus remain controversial. Here we report geochemical data from early Ediacaran organic-rich black shales (∼635-630 million years old) of the basal Doushantuo Formation in South China. High enrichments of molybdenum and vanadium and low pyrite sulphur isotope values (Δ(34)S values ≥65 per mil) in these shales record expansion of the oceanic inventory of redox-sensitive metals and the growth of the marine sulphate reservoir in response to a widely oxygenated ocean. The data provide evidence for an early Ediacaran oxygenation event, which pre-dates the previous estimates for post-Marinoan oxygenation by more than 50 million years. Our findings seem to support a link between the most severe glaciations in Earth's history, the oxygenation of the Earth's surface environments, and the earliest diversification of animals.

Geochemical, mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquifer

► U, sulfate, and Fe reduction has occurred in a zone of naturally reduced sediment. ► Reduced U has accumulated in the naturally reduced sediment. ► Reduction is likely stimulated by increased organic matter and lower permeability. ► U(IV) persists in the naturally reduced lenses even under oxidizing conditions. ► Zones of natural reduction may seasonally act as a U source or sink to the aquifer. Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology and redox processes that occur in these zones, several cores from a region of naturally occurring reducing conditions in a U-contaminated aquifer (Rifle, CO) were examined. Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for U and Fe content, oxidation state, and mineralogy; reduced S phases; and solid-phase organic C content using a suite of analytical and spectroscopic techniques on bulk sediment and size fractions. Solid-phase U concentrations were higher in the naturally reduced zone, with a high proportion of the U present as U(IV). The sediments were also elevated in reduced S phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and SO 4 reduction has occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentrations of solid-phase organic C and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic C concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic C for maintaining reducing conditions and U immobilization.

MMPH-0 (Enterobacter aerogenes)에 의한 6가 크롬 오염 지하수의 생지화학적 정화

오염환경에 서식하는 토착미생물은 환경정화에 중요한 역할을 담당하며 이 연구는 6가 크롬 오염 지하수에서 분리한 미생물을 이용해 반응성, 이동성, 발암성 높은 6가 크롬을 당대사 조효소인 3가 크롬으로 환원/침전시켜 경제적, 친환경적, 생지화학적 정화의 효율성을 알아보았다. 미생물 농화배양과 조성분석, 호기와 혐기환경의 6가 크롬 환원과 내성, 전자공여체별 6가 크롬 환원, 지화학적 변화, 미생물 외형과 Cr((III) 침전물의 광물특성을 연구한 결과, 분리한 MMPH-0(Enterobacter aerogenes)는 혐기/호기환경에서 6가 크롬 내성과 환원능(유기산 주입 1주 후 70%, 주입 안한 경우 4주 후 10 ~ 20%)이 있고, Eh는 미생물의 유기산 산화로 생성된 전자에 의해 산화에서 환원환경, pH는 중성에서 약산성으로 변화되어 <TEX>$Cr(OH)_3$</TEX>/Cr(III)침전물이 형성되었다. SEM/TEM-EDS 결과 <TEX>$2{\sim}5{\mu}m$</TEX> 막대형 미생물과 세포 밖 Cr(III) 침전물은 지화학적 환경변화와 유기산 산화에 따른 전자공여에 의한 환원의 근거가 된다. 지화학적 촉매제 토착미생물의 활성화로 산화환원에 민감한 중금속 오염 지하수 정화에 효율적 기술 응용이 기대된다. Indigenous bacteria isolated from contaminated sites play important roles to remediate contaminated groundwater. Chromium has the most stable oxidation states. Cr(VI) is toxic, carcinogenic, and mobile, but Cr(III) is less toxic and immobile. In this study, indigenous microorganism (MMPH-0) was enriched from Cr(VI) contaminated groundwater, and identified by 16S rRNA gene analysis. Using MMPH-0, the effect of stimulating with e-donors (glucose, lactate, acetate, and no e-donor control), respiration conditions, biomass, tolerance, and geochemical changes on Cr(VI) reduction were investigated in batch experiments for 4 weeks. The changes of Cr(VI) concentration and geochemical conditions were monitored using UV-vis-spectrophotometer and Eh-pH meter. And the morphological and chemical characteristics of MMPH-0 and precipitates in the effluents were characterized by TEM-EDS and SEM-EDS analyses. MMPH-0 (Enterobacter aerogenes) was able to tolerate up to 2000 mg/L Cr(VI) and reduce Cr(VI) under aerobic and anaerobic conditions. MMPH-0 performed faster and higher efficiency of Cr(VI) reduction with electron donors (over 70% after 1 week with e-donor, 10-20% after 4 weeks without e-donor). The changes of Eh-pH in effluents showing the tendency from oxidizing to reducing condition and a bit of acidic change in pH due to microbial oxidation of organic matters donating electrons and protons suggested the roles of MMPH-0 on Cr(VI) in the contaminated water catalyzing to transit geochemical stable zone for more stable <TEX>$Cr(OH)_3$</TEX> or Cr(III) precipitates. TEM/SEM-EDS analyses of MMPH-0 and precipitates indicate direct and indirect Cr(VI) reduction: extracellular polymers capturing Cr component outside cells. These results suggested diverse indigenous bacteria and their biogeochemical reactions might enhance more effective and feasible remediation technology of redox sensitive heavy metals in metal-contaminated in groundwater.

Arctic Bay Formation, Borden Basin, Nunavut (Canada): Basin evolution, black shale, and dissolved metal systematics in the Mesoproterozoic ocean

The Arctic Bay Formation (Nunavut, Canada) represents a late Mesoproterozoic muddy terrigenous ramp and contains >200m of black shale. The formation was studied in order to decipher the tectonostratigraphic and geochemical evolution of the basin, address the origin of metal enrichment, and determine whether this frontier basin has the potential to host sedimentary-exhalative or polymetallic black shale deposits. Samples were analysed in the laboratory for major and trace elements, total organic carbon (TOC), 4-step loss-on-ignition (LOI), and Pb isotopes. Non-calcareous black shale exhibits neither Ce nor Y anomalies, reflecting euxinia in the lower water column, whereas slightly dolomitic black shale has both Ce and Y anomalies, reflecting the dolomite's probable origin as a precipitate in the upper water column. The stratigraphic distribution of the rare earth elements (REEs) indicates an evolving sediment provenance, and Pb isotopic data indicate that the source of clay in the black shale was dominated by weathered, juvenile, mantle-derived material. Base metals and redox-sensitive metals, expressed as enrichment ratios relative to conservative lithophile elements, are elevated and exhibit coherent covariations in the black shale. Enrichment in the redox-sensitive elements, such as Mo and U, correlates with dolomite content of the shale, rather than with organic C or Fepy. From a deep-time ocean evolution perspective, this important observation suggests that enrichment in these metals cannot necessarily be attributed to metal incorporation at an interface between sediment and euxinic water. Instead, in Arctic Bay Formation black shale, the metals were either scavenged onto dolomite as it precipitated in the water column, or secondarily re-distributed within the sediment according to its dolomite content. The base metals that are concentrated in the black shale (e.g., Zn) were probably sourced from diffuse hydrothermal venting, and although there is no evidence at the studied location for a nearby point source of metals (vent), persistent bottom-water euxinia would have ensured the effective scavenging of any dissolved metals supplied, and so the basin has at the very minimum a hypothetical potential for SEDEX and polymetallic mineralisation. Whole-rock U–Th–Pb isotope analysis of black shale yielded a date of 1092±59Ma, which is considered to be the Arctic Bay Formation's depositional age.

Molybdenum evidence for expansive sulfidic water masses in ~ 750 Ma oceans

The Ediacaran appearance of large animals, including motile bilaterians, is commonly hypothesized to reflect a physiologically enabling increase in atmospheric and oceanic oxygen abundances (pO 2). To date, direct evidence for low oxygen in pre-Ediacaran oceans has focused on chemical signatures in the rock record that reflect conditions in local basins, but this approach is both biased to constrain only shallower basins and statistically limited when we seek to follow the evolution of mean ocean chemical state through time. Because the abundance and isotopic composition of molybdenum (Mo) in organic-rich euxinic sediments can vary in response to changes in global redox conditions, Mo geochemistry provides independent constraints on the global evolution of well-oxygenated environments. Here, we establish a theoretical framework to access global marine Mo cycle in the past from the abundance and isotope composition of ancient seawater. Further, we investigate the ~ 750 Ma Walcott Member of the Chuar Group, Grand Canyon, which accumulated in a rift basin with open connection to the ocean. Iron speciation data from upper Walcott shales indicate that local bottom waters were anoxic and sulfidic, consistent with their high organic content (up to 20 wt.%). Similar facies in Phanerozoic successions contain high concentrations of redox-sensitive metals, but in the Walcott Member, abundances of Mo and U, as well as Mo/TOC (~ 0.5 ppm/wt.%) are low. δ 98 Mo values also fall well below modern equivalents (0.99 ± 0.13‰ versus ~ 2.35‰ today). These signatures are consistent with model predictions where sulfidic waters cover ~ 1–4% of the global seafloor, corresponding to a ~ 20–80 fold increase compared to the modern ocean. Therefore, our results suggest globally expansive sulfidic water masses in mid-Neoproterozoic oceans, bridging a nearly 700 million-year gap in previous Mo data. We propose that anoxic and sulfidic (euxinic) conditions governed Mo cycling in the oceans even as ferruginous subsurface waters re-appeared 800–750 Ma, and we interpret this anoxic ocean state to reflect a markedly lower atmospheric and oceanic O 2 level, consistent with the hypothesis that pO 2 acted as an evolutionary barrier to the emergence of large motile bilaterian animals prior to the Ediacaran Period.

Early diagenesis of redox-sensitive trace metals in the Peru upwelling area – response to ENSO-related oxygen fluctuations in the water column

Pore water and solid phase data for redox-sensitive metals (Mn, Fe, V, Mo and U) were collected on a transect across the Peru upwelling area (11°S) at water depths between 78 and 2025 m and bottom water oxygen concentrations ranging from ∼0 to 93 μM. By comparing authigenic mass accumulation rates and diffusive benthic fluxes, we evaluate the respective mechanisms of trace metal accumulation, retention and remobilization across the oxygen minimum zone (OMZ) and with respect to oxygen fluctuations in the water column related to the El Niño Southern Oscillation (ENSO). Sediments within the permanent OMZ are characterized by diffusive uptake and authigenic fixation of U, V and Mo as well as diffusive loss of Mn and Fe across the benthic boundary. Some of the dissolved Mn and Fe in the water column re-precipitate at the oxycline and shuttle particle-reactive trace metals to the sediment surface at the lower and upper boundary of the OMZ. At the lower boundary, pore waters are not sufficiently sulfidic as to enable an efficient authigenic V and Mo fixation. As a consequence, sediments below the OMZ are preferentially enriched in U which is delivered via both in situ precipitation and lateral supply of U-rich phosphorites from further upslope. Trace metal cycling on the Peruvian shelf is strongly affected by ENSO-related oxygen fluctuations in bottom water. During periods of shelf oxygenation, surface sediments receive particulate V and Mo with metal (oxyhydr)oxides that derive from both terrigenous sources and precipitation at the retreating oxycline. After the recurrence of anoxic conditions, metal (oxyhydr)oxides are reductively dissolved and the hereby liberated V and Mo are authigenically removed. This alternation between supply of particle-reactive trace metals during oxic periods and fixation during anoxic periods leads to a preferential accumulation of V and Mo compared to U on the Peruvian shelf. The decoupling of V, Mo and U accumulation is further accentuated by the varying susceptibility to re-oxidation of the different authigenic metal phases. While authigenic U and V are readily re-oxidized and recycled during periods of shelf oxygenation, the sequestration of Mo by authigenic pyrite is favored by the transient occurrence of oxidizing conditions. Our findings reveal that redox-sensitive trace metals respond in specific manner to short-term oxygen fluctuations in the water column. The relative enrichment patterns identified might be useful for the reconstruction of past OMZ extension and large-scale redox oscillations in the geological record.

Trace and rare earth element geochemistry of black shale and kerogen in the early Cambrian Niutitang Formation in Guizhou province, South China: Constraints for redox environments and origin of metal enrichments

Early Cambrian black shales of South China not only host important sponge, arthropod and other soft-bodied fossils that have helped to trace early metazoan diversification, but also show extreme enrichments of a number of trace metals in particular Ni, Mo and V. In this study, we use a new approach by analyzing rare earth elements in kerogen extracted from the black shales, together with a number of redox-sensitive trace element compositions and total organic carbon (TOC) concentrations in an early Cambrian black shale sequence in Zunyi, Guizhou province, South China, to place better constraints on the oceanic redox conditions and the origin of the extreme metal enrichment.Our data show significant negative Ce anomalies (Ce/Ce* as low as 0.4) occurring in kerogen, which indicate an oxygenated surface environment of primary productivity in consistent with the concept that the organic matter is mainly derived from organisms in the euphotic zone. Mass balance calculation suggests that the kerogen-associated REE can dominate the measured black shale REE budget, while similarity between our measured REE patterns and those of similarly aged phosphorites indicates that the REE content of ancient phosphorites may have also derived initially from organic matter.The redox-sensitive trace elements, such as U, V, Mo, and their ratios of U/Al, V/Al and Mo/Al in black shales show different correlation patterns with TOC contents. The upper black shales show a good metal/TOC correlation, but such a correlation is absent in the lower part. The lower black shales exhibit much higher metal enrichments compared to Black Sea sulphidic (euxinic) sediment. This is taken to indicate the presence of sulphidic bottom waters during the deposition of the lower black shales, including the Ni–Mo ore layer. In contrast, anoxic, non-sulphidic conditions occurred during the deposition of the upper black shales.Taking all these geochemical data together, we suggest that the early Cambrian South China seaway was strongly stratified and stagnant, and that euxinic bottom water conditions may have led to enrichment of the redox-sensitive metals such as U, V and Mo in the lower black shales, and in one case the occurrence of a polymetallic Ni–Mo sulphide ore bed bearing an extraordinarily extreme metal enrichment, which, according to the Mo/TOC and Ni/TOC ratios and much other geochemical evidence, may have been additionally influenced by hydrothermal input of metals within the rift basin as suggested by a number of previous studies.

Natural and Post-Urbanization Signatures of Hypoxia in Two Basins of Puget Sound: Historical Reconstruction of Redox Sensitive Metals and Organic Matter Inputs

Hypoxia has been observed in Hood Canal, Puget Sound, WA, USA since the 1970s. Four long sediment cores were collected in 2005 and age-dated to resolve natural and post-urbanization signatures of hypoxia and organic matter (OM) sources in two contrasting basins of Puget Sound: Main Basin and Hood Canal. Paleoecological indicators used for sediment reconstructions included pollen, stable carbon and nitrogen isotopes (δ13C and δ15N), biomarkers of terrestrial OM (TOM), biogenic silica (BSi), and redox-sensitive metals (RSM). The sedimentary reconstructions illustrated a gradient in RSM enrichment factors as Hood Canal > Main Basin, southern > northern cores, and pre-1900s > 1900–2005. The urbanization of Puget Sound watersheds during the 1900s was reflected as shifts in all the paleoecological signatures. Pollen distributions shifted from predominantly old growth conifer to successional alder, dominant OM signatures recorded a decrease in the proportion of marine OM (MOM) concomitant with an increase in the proportion of TOM, and the weight % of BSi decreased. However, these shifts were not coincidental with an overall increase in the enrichment of RSM or δ15N signatures indicative of cultural eutrophication. The increased percentage of TOM was independently verified by both the elemental ratios and lignin yields. In addition, isotopic signatures, BSi, and RSMs all suggest that OM shifts may be due to a reduction in primary productivity rather than an increase in OM regeneration in the water column or at the sediment/water interface. Therefore, the reconstructions suggested the Hood Canal has been under a more oxygenated “stance” during the twentieth century compared to prior periods. However, these 2005 cores and their resolutions do not encompass the period of high resolution water column measurements that showed short-lived hypoxia events and fish kills in Hood Canal during the early twenty-first century. The decoupling between the increased watershed-scale anthropogenic alterations recorded in the OM signatures and the relatively depleted RSM during the twentieth century suggests that physical processes, such as deep-water ventilation, may be responsible for the historical variation in oxygen levels. Specifically, climate oscillations may influence the ventilation and/or productivity of deep water in Puget Sound and particularly their least mixed regions.

REE geochemical characteristics and depositional environment of the black shale-hosted Baiguoyuan Ag-V deposit in Xingshan, Hubei Province, China

By means of techniques such as inductively coupled plasma-mass spectrometry (ICP-MS) and X-ray fluorescence spectrometry (XRF), REE geochemical characteristics and depositional environment of the black shales in Baiguoyuan Ag-V deposit, Xingshan, Hubei Province, were studied in this work. The black shales in a typical TC5 profile of Doushantuo Formation of upper Sinian period were obviously enriched in REE, especially in LREE. The REE patterns of the investigated samples normalized by Post Archean Australian Shale (PAAS) showed a flat or slight rightward inclination. The characteristic elements, their ratio and correlation diagrams showed that it should be hot-water deposit and the black shale in the study area was of a sedimentary origin. Redox sensitive metal elements pattern, trace elements index measurement in anoxic environment, Ce anomaly and δEu negative anomaly showed that the deposit environment of the black shales was a reducing and anoxic one and a slight change of the sea level could be identified. The samples relatively focused on the superimposed area of sedimentary rock and basalt in the diagram of La/Yb-ΣREE and La/Yb-Ce/La. So there might be accession of hot-water sedimentation during the period of the formation of the black rock series, mostly in normal terrigenous sedimentation with the participation of deep hot-water deposit.

Humic acid model substances with pronounced redox functionality for the study of environmentally relevant interaction processes of metal ions in the presence of humic acid

Humic acid (HA) model substances with pronounced redox functionality were synthesized by oxidation of hydroquinone or catechol in the presence of glycine or glutamic acid and characterized concerning their elemental, structural and functional properties. In order to characterize the redox properties of the synthetic products, formal redox potentials and Fe(III) reducing capacities were determined and compared to purified Aldrich HA (AHA). Furthermore, the reduction of U(VI) in the presence of HA was studied. The synthetic products show elemental, functional and structural properties comparable to natural HA, however, they are characterized by high amounts of phenolic/acidic OH groups (5.3–6.6 meq/g). Furthermore, the synthetic HA show significantly higher reducing capacities for Fe 3+ and [Fe(CN) 6] 3− at pH 3.0 (8.8–14.5 meq/g) and at pH 9.2 (27.5–36.9 meq/g), respectively, than AHA (pH 3.0: 1.2 ± 0.1 meq/g; pH 9.2: 7.2 ± 1.9 meq/g). The highest reducing capacities were obtained for HA Cat-Gly (pH 3.0: 14.5 ± 1.6 meq/g; pH 9.2: 36.9 ± 0.2 meq/g), an oxidation product from catechol and glycine, which is characterized by the lowest formal redox potential (E 0⁎ = 517 ± 12 mV) of all studied HA (E 0⁎ = 517–571 mV). Indications for a slight reduction of U(VI) in the presence of HA were observed, whereby, HA Cat-Gly exhibits again the highest reducing capacity (pH 6: 0.065 ± 0.002 meq/g). Using modified HA with blocked phenolic/acidic OH groups the importance of these functional groups for the redox behavior of HA was confirmed. Synthetic HA with pronounced redox functionality can be used to study the redox behavior of HA and the redox stability of metal ions in the presence of HA and furthermore, to stabilize redox-sensitive metal ions against oxidation in complexation and transport studies with HA. This contributes to a better understanding of interaction processes of metal ions with humic substances in soils, sediments and waters.

Selenium isotopes trace the source and redox processes in the black shale-hosted Se-rich deposits in China

We analyzed the Se isotopic composition of black shales and related kerogen and sulfide fractions from the Zunyi Ni–Mo–Se deposit, the La’erma Se–Au deposit and the Yutangba Se deposit in southern China to constrain metal sources and accumulation processes, both subjects of disagreement in the scientific community. Se at the Zunyi Ni–Mo–Se polymetallic deposit displayed a restricted range of δ 82Se values (−1.6‰ to 2.4‰ with a mean of 0.6‰) suggesting a major hydrothermal origin where aqueous Se was probably transported as H 2Se, along with H 2S, and precipitated directly as selenides or in sulfides. Se at the La’erma Se–Au deposit covers a larger range in δ 82Se values (−3.8‰ to 5.4‰ with a mean of 0.3‰), suggesting Se redistribution following redox transformations, leading to kinetic isotopic fractionation. The largest Se isotopic variation so far in natural terrestrial samples was found in the Yutangba Se deposit, with δ 82Se values varying from −12.77‰ to 4.93‰. On the basis of variations in Se isotopes in the deposit, along with other geological and geochemical evidence, the “redox model” (supergene alteration) explains the occurrence of native Se in the deposit. Overall, hydrothermal systems may be a potentially important Se source to form economic deposits in comparison to seawater sources. Significantly, our study indicates that either secondary hydrothermal or supergene alteration is a key factor in Se enrichment in black shales. Redistribution of Se, and probably other redox-sensitive metals like Mo, Cr and V, leads to isotopic fractionation which may be used to fingerprint such alteration/precipitation processes.

Site-specific accentuation of heavy metals in groundwaters from Ankaleshwar industrial estate, India

The seasonal behavior of environmentally sensitive polymetallic contaminants in groundwaters from Ankaleshwar industrial estate (AIE) India was studied. The potentially toxic elements (Co, Cr, Cu, Mn, Fe, Mo and Ni) demonstrated accentuated enrichment signatures during post-monsoon, besides colossal spatial variability on temporal scale. GIS-based accrual factor raster mapping facilitated the spot-specific quantitative and comparative appraisal of metallic distensions during post-monsoon with a decreasing hierarchy of seasonal augmentation Ni > Cu > Mn > Fe > Co > Mo > Cr. High inconsistencies and spot (pixel) strict exceedingly high accrual factors over these maps concur with diverse land use and surface-polluting sources. Inter-annual adiabatic extension of heavy metals in groundwaters implies their widespread availability in soil and atmospheric backgrounds in the region. Dissimilar performance with contrasting accretion patterns of redox-sensitive metals (Fe and Mo) is revealed by three-component color composites. Heavy metal hyper-accrual realms warrant an immediate demand for upgrading the existing waste management methodologies and aquifer remediation, as the region is highly cultivated and groundwater is the sole source of water supply for drinking, agricultural and other purposes.

A deeper respired carbon pool in the glacial equatorial Pacific Ocean

Atmospheric pCO 2 was approximately 80 ppm lower during the last glacial period than during pre-industrial times. Identifying the fate of that carbon has been one of the great challenges in paleoceanography. We present evidence from ten equatorial Pacific Ocean sediment cores to show that the deep Pacific Ocean likely stored more carbon during the last glacial period than the Holocene. The concentration of the redox-sensitive metal uranium (U) in sediments was systematically greater during the last glacial period than during the Holocene, indicating more reducing conditions in glacial-age sediments. Reconstructions of biogenic opal flux indicate that changes in U distribution were not the result of changes in biological productivity and the ensuing rain of organic carbon to the sea floor, which also affects the redox conditions of the sediments. Together, these results lead to the interpretation that bottom water in the equatorial Pacific during the glacial period had significantly lower oxygen concentration than during the Holocene, and a correspondingly greater level of respired CO 2. This conclusion is supported by evidence for greater preservation of brassicasterol, a biomarker produced by diatoms, in glacial-age sediments of the eastern equatorial Pacific. The presence of additional respired CO 2 in the glacial deep ocean would have lowered atmospheric pCO 2 by 1) increasing the total storage of CO 2 in the glacial ocean and 2) increasing ocean alkalinity following a transient carbonate dissolution event. Our results are consistent with recently published data from the North Pacific Ocean; this suggests that increased carbon storage in the glacial deep Pacific Ocean was a basin-wide phenomenon, consistent with a large-scale transfer of carbon to the deep ocean during glacial periods.

Electrospray ionization mass spectrometry of a cerium(III) phosphomolybdate complex: Condensed and gas-phase cluster chemistry

Electrospray ionization quadrupole ion trap mass spectrometry (ESI-QIT/MS) of the ammonium cerium(III) phosphomolybdate complex (NH 4) 11[Ce(III)(PMo 11O 39) 2] in aqueous media has revealed a concentration-dependent behavior. Under fixed instrumental parameters, the Ce-containing polyoxomolybdate complexes H 2Ce(III)P 2Mo 22O 75 3− and Ce(III)PMo 11O 38 2− are the primary species present at 11 mM (pH = 4.3); at 0.7 mM (pH = 3.6), Ce(III)PMo 10O 35 2− is the predominant species, Ce(III)PMo 11O 38 2− is quite diminished, and H 2Ce(III)P 2Mo 22O 75 3− is absent. As a result of the complex isotopic fingerprints from multiple molybdenums, compositions of such ions are difficult to assign—successive collision induced dissociation (CID) of large ions produced smaller ions for which calculated and experimental isotopic patterns could be compared. The oxidation state of Ce and the number of counter cations on negative complexes was discerned from spectra of ions containing 1H + and 7Li +. The overall result is an ESI method applicable to phosphomolybdate complexes containing redox sensitive f-block metal ions such as Ce(IV) and Pu(III/IV). Dissociation studies also gave insight into favored fragmentation pathways, and generated gas ions with empirical formulae similar to known condensed-phase ions. Deconvolution of concentration- and pH-dependent solution behavior via ESI/MS and 31P NMR spectroscopy showed speciation dependent on solution concentration, not on pH.