Geochemical processes controlling arsenic mobility in groundwater: A case study of arsenic mobilization and natural attenuation

The behavior of As in the subsurface environment was examined along a transect of groundwater monitoring wells at a Superfund site, where enhanced reductive dechlorination (ERD) is being used for the remediation of groundwater contaminated with chlorinated solvents. The transect was installed parallel to the groundwater flow direction through the treatment area. The ERD technology involves the injection of organic C (OC) to stimulate in situ microbial dechlorination processes. A secondary effect of the ERD treatment at this site, however, is the mobilization of As, as well as Fe and Mn. The concentrations of these elements are low in groundwater collected upgradient of the ERD treatment area, indicating that, in the absence of the injected OC, the As that occurs naturally in the sediment is relatively immobile. Batch experiments conducted using sediments from the site inoculated with an Fe(III)- and As(V)-reducing bacterium and amended with lactate resulted in mobilization of As, Fe and Mn, suggesting that As mobilization in the field is due to microbial processes.     

Arsenic in an alkaline AMD treatment sludge: Characterization and stability under prolonged anoxic conditions

Lime treatment of acid mine drainage (AMD) generates large volumes of neutralization sludge that are often stored under water covers. The sludge consists mainly of calcite, gypsum and a widespread ferrihydrite-like Fe phase with several associated species of metal(loid) contaminants. The long-term stability of metal(loid)s in this chemically ill-defined material remains unknown. In this study, the stability and speciation of As in AMD sludge subjected to prolonged anoxic conditions is determined. The total As concentration in the sludge is 300 mg kg⁻¹. In the laboratory, three distinct water cover treatments were imposed on the sludge to induce different redox conditions (100%N₂, 100%N₂ + glucose, 95%N₂:5%H₂). These treatments were compared against a control of oxidized, water-saturated sludge. Electron micro-probe (EMP) analysis and spatially resolved synchrotron X-ray fluorescence (SXRF) results indicate that As is dominantly associated with Fe in the sludge. In all treatments and throughout the experiment, measured concentrations of dissolved As were less than 5 μg L⁻¹. Dissolved Mn concentration in the N₂ + glucose treatment increased significantly compared to other treatments. Manganese and As K-edge X-ray absorption near edge structure spectroscopy (XANES) analyses showed that Mn was the redox-active element in the solid-phase, while As was stable. Arsenic(V) was still the dominant species in all water-covered sludges after 9 months of anoxic treatments. In contrast, Mn(IV) in the original sludge was partially reduced into Mn(II) in all water-covered sludges. The effect was most pronounced in the N₂ + glucose treatment, suggesting microbial reduction. Micro-scale SXRF and XANES analysis of the treated sludge showed that Mn(II) accumulated in areas already enriched in Fe and As. Overall, the study shows that AMD sludges remain stable under prolonged anoxic conditions. External sources of chemical reductants or soluble C were needed to induce lower redox state in the systems, and even under these imposed treatments, only weakly reducing conditions (Mn threshold) developed. The results suggest that As(V) in AMD sludge will remain stable under prolonged anoxic conditions as long as Mn(IV) is present and organic matter accumulation is negligible.     

Geochemical and mineralogical evidence for Sahara and Sahel dust additions to Quaternary soils on Lanzarote,eastern Canary Islands,Spain

Africa is the most important source of dust in the world today, and dust storms are frequent on the nearby Canary Islands. Previous workers have inferred that the Sahara is the most important source of dust to Canary Islands soils, with little contribution from the Sahel region. Soils overlying a late Quaternary basalt flow on Lanzarote, Canary Islands, contain, in addition to volcanic minerals, quartz and mica, exotic to the island’s bedrock. Kaolinite in the soils also likely has an exotic origin. Trace‐element geochemistry shows that the soils are derived from varying proportions of locally derived basalt and African dust. Major‐element geochemistry, clay mineralogy and interpretation of satellite imagery suggest that dust additions to the Canary Islands come not only from the Sahara Desert, but also from the Sahel region.     

Phosphorus Speciation in Stream Bed Sediments from an Agricultural Watershed: Solid-Phase Associations and Sorption Behavior

The sorption behavior and solid-phase associations of phosphorus (P) in fine-grained sediments (<63 μm) from two upstream tributaries and one downstream main stem site of the Spoon River in west-central Illinois were characterized to better understand phosphorus bioavailability in this agriculturally dominated watershed. The P sorption affinities, as indicated by linear distribution coefficients (K _d), of all sediments were 330–5,150 L/kg, and negatively correlated with equilibrium phosphorus concentration (EPC_o) values, which ranged between 0.2 and 2.2 μM. pH values measured at the conclusion of the sorption experiments varied only slightly (7.45–8.10) but were nonetheless strongly positively correlated to EPC_o values, and negatively correlated to K _d values, suggesting the importance of pH to the observed sorption behavior. K _d values were generally lower and EPC_o values higher at the main stem site than at the upstream tributary sites, suggesting dissolved reactive P (DRP) bioavailability (specifically orthophosphate) increased downstream. The solid phase associations of P were operationally assessed with the streamlined SEDEX (sedimentary extraction) procedure, and most sediment P (≥50%) was released during the step designed to determine iron oxide–associated P. On average, 70–90% of the total sediment P pool was potentially bioavailable, as estimated by the sum of the iron oxide-, authigenic carbonate-, and organic-associated P fractions. Considerable calcium was also extracted from some sediments during the step designed to specifically remove iron oxide–associated P. It is hypothesized that the severe drought conditions that persisted between April and October, 2005 allowed authigenic carbonates (perhaps partly amorphous) to accumulate, and that these carbonates dissolved during the iron oxide extraction step. The extensive benthic algal populations also present may have aided carbonate precipitation, which under more normal hydrologic conditions would be periodically flushed downstream and replaced by fresh sediment. This suggests antecedent hydrologic conditions played a dominant role in the P sorption and solid phase associations identified.     

Patterns and Scales of Phytoplankton Variability in Estuarine–Coastal Ecosystems

Phytoplankton variability is a primary driver of chemical and biological dynamics in the coastal zone because it directly affects water quality, biogeochemical cycling of reactive elements, and food supply to consumer organisms. Much has been learned about patterns of phytoplankton variability within individual ecosystems, but patterns have not been compared across the diversity of ecosystem types where marine waters are influenced by connectivity to land. We extracted patterns from chlorophyll-a series measured at 84 estuarine–coastal sites, using a model that decomposes time series into an annual effect, mean seasonal pattern, and residual “events.” Comparisons across sites revealed a large range of variability patterns, with some dominated by a recurrent seasonal pattern, others dominated by annual (i.e., year-to-year) variability as trends or regime shifts and others dominated by the residual component, which includes exceptional bloom events such as red tides. Why is the partitioning of phytoplankton variability at these three scales so diverse? We propose a hypothesis to guide next steps of comparative analysis: large year-to-year variability is a response to disturbance from human activities or shifts in the climate system; strong seasonal patterns develop where the governing processes are linked to the annual climate cycle; and large event-scale variability occurs at sites highly enriched with nutrients. Patterns of phytoplankton variability are therefore shaped by the site-specific relative importance of disturbance, annual climatology, and nutrient enrichment.     

SPASE 2.0: a standard data model for space physics

SPASE—for Space Physics Archive Search and Extract—is a group with a charter to promote collaboration and sharing of data for the Space Plasma Physics community. A major activity is the definition of the SPASE Data Model which defines the metadata necessary to describe resources in the broader heliophysics data environment. The SPASE Data Model is primarily a controlled vocabulary with hierarchical relationships and with the ability to form associations between described resources. It is the result of many years of effort by an international collaboration (see http://www.spase-group.org) to unify and improve on existing Space and Solar Physics data models. The genesis of the SPASE group can be traced to 1998 when a small group of individuals saw a need for a data model. Today SPASE has a large international participation from many of the major space research organizations. The design of the data model is based on a set of principles derived from evaluation of the existing heliophysics data environment. The development guidelines for the data model are consistent with ISO-2788 (expanded in ANSI/NISO Z39.19) and the administration for the data model is comparable to that described in the ISO standards ISO-11179 and ISO-20943. Since the release of version 1.0 of the data model in 2005, the model has undergone a series of evolutions. SPASE released version 2.0 of its data model in April 2009. This version presents a significant change from the previous release. It includes the capability to describe a wider range of data products and to describe expert annotations which can be associated with a resource. Additional improvements include an enhanced capability to describe resource associations and a more unified approach to describing data products. Version 2.0 of the SPASE Data Model provides a solid foundation for continued integration of worldwide research activities and the open sharing of data.     

Multi-zone fusion crust formation and classification of the 2004 Auckland meteorite (L6, S5, and W0)

On June 12, 2004, a meteorite passed through Earth's atmosphere and landed under the television in the living room of a house in Auckland, New Zealand. Textural characteristics, the chemistry of olivine (Fa_23–24) and orthopyroxene (Fs_20.7), and the bulk rock triple oxygen isotopes (δ¹⁷O + 3.1; δ¹⁸O + 4.2‰) from the interior of the completely unweathered (W0) 1.3 kg meteorite, hereafter referred to as Auckland, suggest it to be a strongly metamorphosed fragment from the interior of a low iron ordinary chondrite (L6) parent asteroid. The occurrence of maskelynite but shock fracturing of olivine and pyroxene indicates Auckland experienced extreme shock metamorphism (S5), likely during Ordovician fragmentation of the asteroid parent. The fusion crust consists of three zones: (1) an innermost zone containing narrow Fe-Ni-S-bearing veins that migrated along pre-existing shock fractures in olivine and pyroxene; (2) a middle zone in which the meteorite partially melted to form a silicate glass and immiscible blebs of metal and troilite, and is accompanied by unmelted silicate minerals; and (3) an approximately 0.1 mm wide vesicular-rich outermost layer that largely melted, volatilizing sulfides, before quenching to form glass and olivine. Oxygen isotope values of the bulk rock and/or maskelynite of melted rim and modified substrate are 2–3‰ greater than the meteorite interior and indicate that up to 19% of terrestrial atmospheric O₂ was incorporated into the fusion crust during the formation. The fusion crust migrated inwards as ablation occurred, enabling melting, migration, and re-precipitation ± loss of sulfide and metal components, with the prominent glassy rim therefore forming from an already chemically modified zone.     

Human capital requirements in Singapore's international financial centre

International financial centres (IFCs) are regarded as important nodes in governing global flows of money and capital. With increased globalization and rapid technological changes, the rivalry among IFCs has further intensified competition for financial labour—as a concentrated pool of highly skilled finance workers in an open and flexible labour market is crucial to sustaining the competitive dynamics of these urban financial hotspots. This study investigates the importance of different skills and tasks in financial work. Based on surveys and interviews conducted among Singapore's IFC workers, the findings show that cognitive, interpersonal communication and managerial-leadership skills and tasks are more important in financial work, whereas programming, mathematics and systems-based skills are perceived to be less important. Additionally, a network visualization of finance occupational skills obtained from Singapore's national skills database reinforces the importance of cognitive and relational skills in that sector. Higher-order cognitive and relational skills are expected to become even more critical as the financial sector undergoes rapid digital transformation, reinforcing the importance of IFCs as agglomerations of skilled finance talent.     

Temporal stability of apparent soil electrical conductivity measured by electromagnetic induction techniques

Assessing and managing the spatial variability of hydropedological properties are important in environmental,agricultural,and geological sciences.The spatial variability of soil apparent electrical conductivity（ECa） measured by electromagnetic induction（EMI） techniques has been widely used to infer the spatial variability of hydrological and pedological properties.In this study,temporal stability analysis was conducted for measuring repeatedly soil ECa in an agricultural landscape in 2008.Such temporal stability was statistically compared with the soil moisture,terrain indices（slope,topographic wetness index（TWI）,and profile curvature）,and soil properties（particle size distribution,depth to bedrock,Mn mottle content,and soil type）.Locations with great and temporally unstable soil ECa were also associated with great and unstable soil moisture,respectively.Soil ECa were greater and more unstable in the areas with great TWI（TWI 〉 8）,gentle and concave slope（slope 〈 3%; profile curvature 〉 0.2）.Soil ECa exponentially increased with depth to bedrock,and soil profile silt and Mn mottle contents（R2= 0.57）,quadratically（R2 = 0.47）,and linearly（R 2 = 0.47）,respectively.Soil ECa was greater and more unstable in Gleysol and Nitosol soils,which were distributed in areas with low elevation（〈 380 m）,thick soil solum（〉 3 m）,and fluctuated water table（shallow in winter and spring but deep in summer and fall）.In contrast,Acrisol,Luvisol,and Cambisol soils,which are distributed in the upper slope areas,had lower and more stable soil ECa.Through these observations,we concluded that the temporal stability of soil ECa can be used to interpret the spatial and temporal variability of these hydropedological properties.