Transformations of mercury, iron, and sulfur during the reductive dissolution of iron oxyhydroxide by sulfide

Methylmercury can accumulate in fish to concentrations unhealthy for humans and other predatory mammals. Most sources of mercury (Hg) emit inorganic species to the environment. Therefore, ecological harm occurs when inorganic Hg is converted to methylmercury. Sulfate- and iron-reducing bacteria (SRB and FeRB) methylate Hg, but the effects of processes involving oxidized and reduced forms of sulfur and iron on the reactivity of Hg, including the propensity of inorganic Hg to be methylated, are poorly understood. Under abiotic conditions, using a laboratory flow reactor, bisulfide (HS⁻) was added at 40 to 250 μM h⁻¹ to 5 g L⁻¹ goethite (α-FeOOH) suspensions to which Hg(II) was adsorbed (30-100 nmol m⁻²) at pH 7.5. Dissolved Hg initially decreased from 10³ or 10⁴ nM (depending on initial conditions) to 10⁻¹ nM, during which the concentration of Hg(II) adsorbed to goethite decreased by 80% and metacinnabar (β-HgS_(s)) formed, based on identification using Hg L_III-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The apparent coordination of oxygens surrounding Hg(II), measured with EXAFS spectroscopy, increased during one flow experiment, suggesting desorption of monodentate-bound Hg(II) while bidentate-bound Hg(II) persisted on the goethite surface. Further sulfidation increased dissolved Hg concentrations by one to two orders of magnitude (0.5 to 10 nM or 30 nM), suggesting that byproducts of bisulfide oxidation and Fe(III) reduction, primarily polysulfide and potentially Fe(II), enhanced the dissolution of β-HgS_(s) and/or desorption of Hg(II). Rapid accumulation of Fe(II) in the solid phase (up to 40 μmol g⁻¹) coincided with faster elevation of dissolved Hg concentrations. Fe(II) served as a proxy for elemental sulfur [S(0)], as S(0) was the dominant bisulfide oxidation product coupled to Fe(III) reduction, based on sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. In one experiment, dissolved Hg concentrations tracked those of all sulfide species [S(-II)]. These results suggest that S(-II) reacted with S(0) to form polysulfide, which then caused the dissolution of β-HgS_(s). A secondary Fe-bearing phase resembling poorly formed green rust was observed in sulfidized solids with scanning electron microscopy, although there was no clear evidence that either surface-bound or mineralized Fe(II) strongly affected Hg speciation. Examination of interrelated processes involving S(-II) and Fe(III) revealed new modes of Hg solubilization previously not considered in Hg reactivity models.     

Trace element partitioning between vapor, brine and halite under extreme phase separation conditions

Experiments were conducted to investigate the partitioning of Li, Br, Rb, Cs and B between vapor, brine and halite during subcritical and supercritical phase separation in the NaCl-H₂O system (388-550 °C, 250-350 bars). Results indicate that Li and Br partition preferentially into the low-salinity vapor fluids, while Rb and Cs become more enriched in the coexisting brines. Under more extreme conditions of pressure and temperature in the two-phase region, especially near the vapor-brine-halite boundary, strong salting-out effects imposed on neutral aqueous species enhance significantly partitioning of all trace elements into the low-salinity fluid. Dissolved boron is strongly affected by this and a particularly strong enrichment into vapors is observed, a trend that can be effectively correlated with changes in reduced density. Exclusion of Li, Br, Rb, Cs and B from halite, when precipitated, further increases the solubility of these species in the coexisting Cl-poor fluid. In general, the lack of distortion in the partitioning behavior of trace elements between vapor, brine and/or halite with the transition from subcritical to supercritical conditions in the NaCl-H₂O system precludes the need for special reference to the critical point of seawater when interpreting phase relations in submarine hydrothermal systems. The combination of experimentally determined trace element partitioning data with constraints imposed by mineral solubility provides a means to better understand the origin and evolution of hot spring vent fluids. For example, in Brandon hydrothermal system (21°S EPR) supercritical phase separation and subseafloor mixing appear to be the main heat and mass transport mechanisms fueled by a shallow magmatic intrusion, with boron systematics ruling out major contributions from magmatic degassing processes accompanying the near-seafloor volcanism.     

The effects of soil type and chemical treatment on nickel speciation in refinery enriched soils: A multi-technique investigation

Aerial deposition of Ni from a refinery in Port Colborne, Ontario, Canada has resulted in the enrichment of 29 km² of land with Ni concentrations exceeding the Canadian Ministry of the Environment’s remedial action level of 200 mg kg⁻¹. Several studies on these soils have shown that making the soils calcareous was effective at reducing chemically extractable Ni, as well as alleviating Ni phytotoxicity symptoms in vegetable crops grown in the vicinity of the refinery. Conversely, dolomitic limestone additions resulted in increased uptake of Ni in the Ni hyperaccumulator Alyssum murale ‘Kotodesh’, a plant whose use was proposed as a remediation strategy for this area. In this paper we use multiple techniques to directly assess the role soil type and lime treatments play in altering the speciation of Ni in the Welland loam and Quarry muck soils around the refinery and relate these findings to Ni mobility and bioavailability.Stirred-flow dissolution experiments using pH 4 HNO₃ showed that Ni release from the limed Quarry muck and Welland loam soils was reduced (∼0.10%) relative to the unlimed soils (∼2.0%). Electron microprobe analysis (EMPA) identified approximately spherical NiO and Ni metal particles, which are associated with no other metals, and range from 5 to 50 μm in diameter. Synchrotron micro-X-ray absorption fine structure and X-ray fluorescence spectroscopies showed that Ni and Al layered double hydroxide (Ni-Al LDH) phases were present in both the limed and unlimed mineral soils, with a tendency towards more stable (e.g., aged-LDH and phyllosilicate) Ni species in the limed soil, possibly aided by the solubilization of Si with increasing pH. In the muck soils, Ni-organic complexes (namely fulvic acid) dominated the speciation in both limed and unlimed soils.The results reported herein show that both soil type and treatment have a pronounced effect on the speciation of Ni in the soils surrounding the Port Colborne refinery. We provide the first evidence that Ni-Al LDH phases can form in anthropogenically enriched mineral field soils at circumneutral pH, and can lead to a reduction in Ni mobility. In the organic soils Ni is strongly complexed by soil organic matter; a property enhanced with liming. Interestingly, increased accumulation of Ni by A. murale grown in the limed muck and loam soils indicates that the plant may be capable of removing Ni from those fractions typically considered unavailable to most plants.     

Paleoenvironmental analysis of a middle Wisconsinan biota site, southwestern Virginia, U.S.A.

The Ratcliff Site in southwestern Virginia lies in a small second-order stream valley filled with approximately 3.5 m of organic-rich deposits that contain bones of mammoth, mastodon, deer (or antelope), logs, and plant macrofossils. Radiocarbon analyses indicate the age of the organic-rich sediment ranges from > 44,000 to 29,100 ¹⁴C yr BP, a time period with no fossil remains reported in this region of the Appalachians. Analyses of field observations, textural data, organic carbon content, and plant macrofossils indicate that the organic-rich sediments contain interbedded standing-water and debris-flow deposits. Up to 6 m of oxidized debris-flow sediments bury the organic-rich sediments. The presence of Rubus parviflorus (Thimble Berry) throughout the deposit indicates the site had a boreal environment from > 44,000 to 29,100 ¹⁴C yr BP. Plant macrofossil evidence indicates the uplands had stands of spruce/jack-pine forests while the valley contained ponds and associated wetlands. Three debris flows occurred at the site between approximately 38,000 and 29,000 ¹⁴C yr BP, suggesting a recurrence interval for major storms of approximately 3000 yr, even though the apparent stability of the boreal environment implies a climate not conducive to catastrophic rainstorms. This conflicting combination of features suggests that during the middle Wisconsinan this area experienced generally cool climates, dominated by polar air masses, but was punctuated by relatively brief warm periods marked by incursions of tropical air masses.     

Conservation and community in the new South Africa: A case study of the Mahushe Shongwe Game Reserve

The idealization of natural landscapes and peoples during colonialism, coupled with the popularity of sustainable development in the postcolonial era, has contributed to the expansion of conservation planning throughout the African continent. Concerns surrounding the promotion of national and international conservation agendas at the expense of local livelihood needs have generated interest in community conservation projects that attempt to include local participation and knowledge in natural resource management. The early excitement associated with community conservation has waned in light of recent assessments that it has been unsuccessful in meeting its ecological and social goals. This parallels other research that suggests communities are understood in generic or homogenous ways that influence how these initiatives are understood. Using a case study of the Mahushe Shongwe Game Reserve, this paper evaluates how rural households access environmental and economic resources to produce livelihoods, and how these access patterns impact their views of the project. It is argued that there are significant livelihood variations within the community that shape the ways households engage with, and benefit from, conservation planning. Rather than strictly viewing Mahushe Shongwe as a constraint to environmental resource access or site for limited employment, community members identify a number of benefits from its existence including education and development opportunities. Additionally, transformations in governance systems in the region impact community views of the project since younger residents are less likely to engage with the Matsamo Tribal Authority, which participates in managing the reserve. The consequence is that conservation has various impacts and meanings within a specific community that remain tied to the livelihood and governance systems being renegotiated in the post-apartheid era.     

A method for generating uniform size-segregated pyrite particle fractions

Background  

Standardized sample preparation techniques allow comparison of pyrite dissolution experiments under diverse conditions. Our objective was to assess dry and wet sieving preparation methodologies, and to develop a reproducible technique that yields uniformly size-distributed material within a limited size range of interest.     

Predation on the rocky shores of Patagonia,Argentina

Rocky intertidal communities of Argentinean Patagonia are exposed to harsh physical conditions caused by dry, strong southern trade winds (mean speed 45 km h^-1, gusts up to 140 km h^-1) that result in intense desiccation of intertidal organisms. Predator distributions in these communities were evaluated from April 2003 to December 2004 at two exposed headlands and six protected bays in Cabo dos Bahias (44°50′S, 65°40′W). Crabs and sea stars dominated the predator assemblage, with occasional scavenger snails and fish also present. During low tide, predators were never found in the open but were always associated with shelter (primarily within mussel beds and coralline algae), suggesting a strong predator dependency on foundation species to buffer them from physical stress. Few predators (mostly crabs) emerged from shelter at high tide. Unlike the larger predators found on Chilean rocky shores, invertebrate predators in this system are diminutive, generally < 2 cm. The lone exception was the newly discovered invasive green crab,Carcinus mamas. Feeding trials, gut content analyses, and visual surveys indicated that native predators feed primarily on small, soft-bodied prey.C. mamas fed on slow-moving and sessile animals, including the super abundant musselPerumytilus purpuratus, with much greater voracity than native predators. Because native intertidal organisms are dependent on mussel beds and coralline algae for shelter from desiccation, successful invasion ofC. mamas may lead to a significant decrease in native diversity by consuming foundation species. This study represents a preliminary survey of predator distributions and feeding habits on the rocky shores of Argentinean Patagonia and provides important baseline data to evaluate trophic linkages and predatory effects on Patagonian rocky shores.     

Analysis of drought determinants for the Colorado River Basin

Ongoing drought in the Colorado River Basin, unprecedented urban growth in the watershed, and numerical model simulations showing higher temperatures and lower precipitation totals in the future have all combined to heighten interest in drought in this region. In this investigation, we use principal components analysis (PCA) to independently assess the influence of various teleconnections on Basin-wide and sub-regional winter season Palmer Hydrological Drought Index (PHDI) and precipitation variations in the Basin. We find that the Pacific Decadal Oscillation (PDO) explains more variance in PHDI than El Niño-Southern Oscillation (ENSO), the Atlantic Multidecadal Oscillation (AMO), and the planetary temperature combined for the Basin as a whole. When rotated PCA is used to separate the Basin into two regions, the lower portion of the Basin is similar to the Basin as a whole while the upper portion, which contains the high-elevation locations important to hydrologic yield for the watershed, demonstrates poorly defined relationships with the teleconnections. The PHDI for the two portions of the Basin are shown to have been out of synch for much of the twentieth century. In general, teleconnection indices account for 19% of the variance in PHDI leaving large uncertainties in drought forecasting.     

Economic consequences of consideration of permanence, leakage and additionality for soil carbon sequestration projects

This paper introduces, explains, and describes methods for addressing the issues of permanence, leakage, and additionality (PLA) of agricultural soil carbon sequestration (ASCS) activities at the project level. It is important to cast these as project-level issues, because they relate to the integrity and consistency of using location-specific ASCS projects as an offset against GHG emissions generated in other sectors (e.g., energy). The underlying objective is to understand and quantify what the net carbon benefits of an ASCS project are once we account for the fact that (1) the sequestered carbon may be stored impermanently, (2) the project may displace emissions outside the project boundaries (leakage), and (3) the project’s carbon sequestration may not be entirely additional to what would have occurred anyway under business-as-usual (no project) conditions. This article evaluates methods for identifying and estimating PLA and gauges the potential magnitude of these effects on the economic returns to a project. This work reflects ongoing collaborative efforts of the authors and Bruce McCarl (Texas A&M University), Allan Sommer, Jui-Chen Yang, and Laurel Clayton (RTI International), Sandra Brown (Winrock International), Ken Andrasko and Ben DeAngelo (US EPA), and various participants in the World Resources Institute/World Business Council workgroup to develop GHG project reporting protocols. All opinions, errors and omissions are those of the authors only.