Factors influencing the oxidation,reduction, methylation and demethylation of mercury species in coastal waters

The objective of this study was to examine the redox reactions and other transformations of mercury (Hg) species in surface waters, and the factors determining the rates of these reactions. For the redox studies completed at the Chesapeake Biological Laboratory (CBL), two isotopes (¹⁹⁹Hg^II and ²⁰²Hg⁰) were added into different types of filtered water (fresh to seawater) to examine the oxidation and reduction reactions. Further studies of both the redox reactions and methylation/demethylation reactions of Hg were conducted with unfiltered water on board research vessels during cruises in May and July 2005 on the Chesapeake Bay and shelf. While CH₃¹⁹⁹Hg^II was added to allow the examination of demethylation, ²⁰¹Hg^II was used to examine both reduction and methylation, and ²⁰²Hg⁰ was used to examine oxidation. Overall, the results showed that both Hg oxidation and reduction were simultaneously occurring and were photochemically mediated in the waters investigated. In contrast to the previously assumed “unreactive” nature of Hg⁰, the studies found that the magnitude of the rate constant for Hg⁰ oxidation was greater than that for reduction, indicating its importance in estuarine and coastal waters. In addition, both experiments at CBL and on board ship showed that Hg^II reduction was similar in magnitude, suggesting that biotic processes were relatively unimportant. While no measurable methylation occurred during the incubation period during the on board studies, concentration of CH₃¹⁹⁹Hg^II decreased over the time during the experiments. It appeared that the demethylation processes were not dominantly photochemically driven, but could be microbially mediated. Further studies are needed in order to help better understand Hg redox and transformations in natural water systems.     

Changes in survivorship,behavior, and morphology in native soft‐shell clams induced by invasive green crab predators

Many studies on invasive species show reduced native densities, but few studies measure trait‐mediated effects as mechanisms for changes in native growth rates and population dynamics. Where native prey face invasive predators, mechanisms for phenotypic change include selective predation, or induced behavioral or morphological plasticity. Invasive green crabs, Carcinus maenas, have contributed to declines in native soft‐shell clams, Mya arenaria, in coastal New England, USA. We tested the hypothesis that clam ability to detect chemical cues from predators or damaged conspecifics would induce greater burrowing depth as a refuge from invasive crabs, and greater burrowing would require increased siphon growth. To determine how crab predation affected clam survivorship and phenotypic traits in the field, clams in exclosure, open, and crab enclosure plots were compared. Crab predation reduced clam density, and surviving clams were deeper and larger, with longer siphons. To determine whether the mechanism for these results was selective predation or induced plasticity, phenotypes were compared between clams exposed to chemical cues from crab predation and clams exposed to seawater in laboratory and field experiments. In response to crab predation cues, clams burrowed deeper, with longer siphons and greater siphon mass. Overall, crab predation removed clams with shorter siphons at shallow depths, and crab predation cues induced greater burrowing depths and longer siphons. Longer siphons and greater siphon mass of deeper clams suggests clams may allocate energy to siphon growth in response to crabs. By determining native behavior and morphological changes in response to an invasive predator, this study adds to our understanding of mechanisms for invasive impacts and illustrates the utility of measuring trait‐mediated effects to investigate predator–prey dynamics.     

Evidence of space weathering in regolith breccias II: Asteroidal regolith breccias

Abstract– Space weathering products, such as agglutinates and nanophase iron‐bearing rims are easily preserved through lithification in lunar regolith breccias, thus such products, if produced, should be preserved in asteroidal regolith breccias as well. A study of representative regolith breccia meteorites, Fayetteville (H4) and Kapoeta (howardite), was undertaken to search for physical evidence of space weathering on asteroids. Amorphous or npFe⁰‐bearing rims cannot be positively identified in Fayetteville, although possible glass rims were found. Extensive friction melt was discovered in the meteorite that is difficult to differentiate from weathered materials. Several melt products, including spherules and agglutinates, as well as one irradiated rim and one possible npFe⁰‐bearing rim were identified in Kapoeta. The existence of these products suggests that lunar‐like space weathering processes are, or have been, active on asteroids.     

Measuring the significance of a divide to local drainage patterns

This article presents a framework for estimating a new topographic attribute derived from digital elevation models (DEMs) called maximum branch length (B _max). Branch length is defined as the distance travelled along a flow path initiated at one grid cell to the confluence with the flow path passing through a second cell. B _max is the longest branch length measured for a grid cell and its eight neighbours. The index provides a physically meaningful method for assessing the relative significance of drainage divides to the dispersion of materials and energy across a landscape, that is, it is a measure of ‘divide size’. B _max is particularly useful for studying divide network structure, for mapping drainage divides, and in landform classification applications. Sensitivity analyses were performed to evaluate the robustness of estimates of B _max to the algorithm used to estimate flow lengths and the prevalence of edge effects resulting from inadequate DEM extent. The findings suggest that the index is insensitive to the specific flow algorithm used but that edge effects can result in significant underestimation along major divides. Edge contamination can, however, be avoided by using an appropriately extensive DEM.     

Resident Attitudes Toward Timber Rattlesnakes (Crotalus horridus)

Abstract

Timber rattlesnakes (Crotalus horridus) are endangered throughout the northeastern United States where multiple factors contribute to population declines. Challenges exist to managing rattlesnake populations because there is little information about human dimensions of this species or other small predators that are venomous or perceived as hazardous. Our objective was to evaluate relationships between resident attitudes and behavioral intentions toward timber rattlesnakes. A mail survey (n?=?593) was used to collect data from residents who live near a rattlesnake population in central Connecticut. Two variables defined resident attitudes toward rattlesnakes: coexistence with the species and perceived threats from the species. Rattlesnake-related factors and situational factors appeared to contribute more heavily to behavioral intentions toward rattlesnakes than general wildlife value orientations. Attitudes predicted behavioral intentions toward rattlesnakes. Results will help wildlife managers incorporate human factors into appropriate management and public outreach strategies.     

The last British Ice Sheet: growth, maximum extent and deglaciation

The growth, maximum lateral extent and deglaciation of the last British Ice Sheet (BIS) has been reconstructed using sediment, faunal and stable isotope methods from a sedimentary record recovered from the Barra Fan, north-west Scotland. During a phase of ice sheet expansion postdating the early "warmth" of Marine Isotope Stage 3 (MIS 3), ice rafting events, operating with a cyclicity of approximately 1500 years, are interspersed between warm, carbonate-rich interstadials operating with a strong Dansgaard-Oeschger (D-O) cyclicity. The data suggest that the BIS expanded westwards to the outer continental shelf break shortly after 30 Ky BP (before present) and remained there until about 15 Ky BP. Within MIS 2, as the ice sheet grew to its maximum extent, the pronounced periodicities which characterize MIS 3 are lost from the record. The exact timing of the Last Glacial Maximum is difficult to define in this record; but maxima in Neogloboquadrina pachyderma (sinistral) ع⁸O are observed between 21-17 Ky BP. A massive discharge of ice-rafted detritus, coincident with Heinrich event 1, is observed at about 16 Ky BP. Deglaciation of the margin is complete by about 15 Ky BP and surface waters warm rapidly after this date.     

Heavitree Quartzite,a Neoproterozoic (ca 800–760 Ma), high‐energy,tidally influenced,ramp association,Amadeus Basin,central Australia

The Neoproterozoic Heavitree Quartzite is widespread in the Amadeus Basin and has correlatives in all of the major central Australian intracratonic basins. The origin of the formation is enigmatic, not only because of its widespread sheet‐like distribution and uniformity of composition, but also because intense silicification makes facies studies difficult. Recently discovered exposures at the eastern end of the basin are relatively free of diagenetic quartz allowing a detailed study of sedimentary structures and an understanding of the depositional architecture of the formation. The formation, which consists largely of pale‐tan or white quartzose sandstone interbedded with rare laminated mudstone and conglomerate intervals, was deposited in at least four depositional sequences. The sheet‐like nature of the sandstone results from an abundant supply of sediments deposited in a high‐energy, open, shelf‐like environment on a regionally subsiding, low‐gradient ramp. Environmental settings switched both laterally and temporally between sand waves deposited by reversing tidal flow and higher velocity unidirectional currents involving dunes and plane beds. In the early stages of deposition, mud‐dominated, tidal‐flat environments alternated with higher energy, sand‐dominated, tidally influenced settings. However, in the later stages of deposition a major eustatic sea‐level fall moved base‐level basinwards, earlier sediments were reworked by streams to form a ravinement surface, gravel was carried well into the basin and fines largely disappeared from the environment. Gravel deposition was followed by a return to high‐energy, tidally influenced deposits involving large sand waves or dunes. Towards the top of the formation sand waves deposited by reversing tidal currents gradually decline and are eventually replaced by dunes deposited by unidirectional current flow. The transition to the shallow‐marine, anoxic rocks of the Bitter Springs Formation is gradational in response to increased accommodation in a ramp setting which lacked a clearly defined shelf break. The Heavitree Quartzite was probably deposited as a direct response to the events surrounding the assembly and breakup of Rodinia, in particular peneplanation during regional uplift in response to a rising mantle plume followed by broad regional subsidence as the plume decayed prior to the breakup of the supercontinent. The large supply of quartz sand resulted from peneplanation associated with the rising plume and the lack of soil‐stabilising vascular plants, an environmental setting with no modern analogue. The ultimate disposition of fines is not known but, given the environment of deposition, it is likely that they were removed during peneplanation and bypassed the sag basin completely.     

U–Pb zircon chronostratigraphy of early-Pliocene ignimbrites from La Pacana, north Chile: implications for the formation of stratified magma chambers

High spatial resolution U–Pb dates of zircons from two consanguineous ignimbrites of contrasting composition, the high-silica rhyolitic Toconao and the overlying dacitic Atana ignimbrites, erupted from La Pacana caldera, north Chile, are presented in this study. Zircons from Atana and Toconao pumice clasts yield apparent ²³⁸U/²⁰⁶Pb ages of 4.11±0.20 Ma and 4.65±0.13 Ma (2σ), respectively. These data combined with previously published geochemical and stratigraphic data, reveal that the two ignimbrites were erupted from a stratified magma chamber. The Atana zircon U–Pb ages closely agree with the eruption age of Atana previously determined by K–Ar dating (4.0±0.1 Ma) and do not support long (>1 Ma) residence times. Xenocrystic zircons were found only in the Toconao bulk ignimbrite, which were probably entrained during eruption and transport. Apparent ²³⁸U/²⁰⁶Pb zircon ages of 13 Ma in these xenocrysts provide the first evidence that the onset of felsic magmatism within the Altiplano–Puna ignimbrite province occurred approximately 3 Myr earlier than previously documented.     

Estimation of the 3D correlation structure of an alluvial aquifer from surface-based multi-frequency ground-penetrating radar reflection data

Knowledge about the stochastic nature of heterogeneity in subsurface hydraulic properties is critical for aquifer characterization and the corresponding prediction of groundwater flow and contaminant transport. Whereas the vertical correlation structure of the heterogeneity is often well constrained by borehole information, the lateral correlation structure is generally unknown because the spacing between boreholes is too large to allow for its meaningful inference. There is, however, evidence to suggest that information on the lateral correlation structure may be extracted from the correlation statistics of the subsurface reflectivity structure imaged by surface-based ground-penetrating radar measurements. To date, case studies involving this approach have been limited to 2D profiles acquired at a single antenna centre frequency in areas with limited complementary information. As a result, the practical reliability of this methodology has been difficult to assess. Here, we extend previous work to 3D and consider reflection ground-penetrating radar data acquired using two antenna centre frequencies at the extensively explored and well-constrained Boise Hydrogeophysical Research Site. We find that the results obtained using the two ground-penetrating radar frequencies are consistent with each other, as well as with information from a number of other studies at the Boise Hydrogeophysical Research Site. In addition, contrary to previous 2D work, our results indicate that the surface-based reflection ground-penetrating radar data are not only sensitive to the aspect ratio of the underlying heterogeneity, but also, albeit to a lesser extent, to the so-called Hurst number, which is a key parameter characterizing the local variability of the fine-scale structure.     

Arsenic attenuation in tailings at a former Cu–W–As mine,SW Finland

Nearly half a century after mine closure, release of As from the Ylöjärvi Cu–W–As mine tailings in groundwater and surface water run-off was observed. Investigations by scanning electron microscopy (SEM), electron microprobe analysis (EMPA), synchrotron-based micro-X-ray diffraction (μ-XRD), micro-X-ray absorption near edge structure (μ-XANES) and micro-extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, and a sequential extraction procedure were performed to assess As attenuation mechanisms in the vadose zone of this tailings deposit. Results of SEM, EMPA, and sequential extractions indicated that the precipitation of As bearing Fe(III) (oxy)hydroxides (up to 18.4 wt.% As₂O₅) and Fe(III) arsenates were important secondary controls on As mobility. The μ-XRD, μ-XANES and μ-EXAFS analyses suggested that these phases correspond to poorly crystalline and disordered As-bearing precipitates, including arsenical ferrihydrite, scorodite, kaňkite, and hydrous ferric arsenate (HFA). The pH within 200 cm of the tailings surface averaged 5.7, conditions which favor the precipitation of ferrihydrite. Poorly crystalline Fe(III) arsenates are potentially unstable over time, and their transformation to ferrihydrite, which contributes to As uptake, has potential to increase the As adsorption capacity of the tailings. Arsenic mobility in tailings pore water at the Ylöjärvi mine will depend on continued arsenopyrite oxidation, dissolution or transformation of secondary Fe(III) arsenates, and the As adsorption capacity of Fe(III) (oxy)hydroxides within this tailings deposit.