Arsenite sequestration at the surface of nano-Fe(OH)2, ferrous-carbonate hydroxide, and green-rust after bioreduction of arsenic-sorbed lepidocrocite by Shewanella putrefaciens

X-ray Absorption Fine Structure (XAFS) spectroscopy was used in combination with high resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), X-ray energy dispersive spectroscopy (XEDS), X-ray powder diffraction, and Mössbauer spectroscopy to obtain detailed information on arsenic and iron speciation in the products of anaerobic reduction of pure and As(V)- or As(III)-adsorbed lepidocrocite (γ-FeOOH) by Shewanella putrefaciens ATCC 12099. We found that this strain of S. putrefaciens is capable of using Fe(III) in lepidocrocite and As(V) in solution or adsorbed on lepidocrocite surfaces as electron acceptors. Bioreduction of lepidocrocite in the absence of arsenic resulted in the formation of hydroxycarbonate green rust 1 [Fe^II₄Fe^III₂(OH)₁₂CO₃: GR1(CO₃)], which completely converted into ferrous-carbonate hydroxide (Fe^II₂(OH)₂CO₃: FCH) over nine months. This study thus provides the first evidence of bacterial reduction of stoichiometric GR1(CO₃) into FCH. Bioreduction of As(III)-adsorbed lepidocrocite also led to the formation of GR1(CO₃) prior to formation of FCH, but the presence of As(III) slows down this transformation, leading to the co-occurrence of both phases after 22-month of aging. At the end of this experiment, As(III) was found to be adsorbed on the surfaces of GR1(CO₃) and FCH. After five months, bioreduction of As(V)-bearing lepidocrocite led directly to the formation of FCH in association with nanometer-sized particles of a minor As-rich Fe(OH)₂ phase, with no evidence for green rust formation. In this five-month experiment, As(V) was fully converted to As(III), which was dominantly sorbed at the surface of the Fe(OH)₂ nanoparticles as oligomers binding to the edges of Fe(OH)₆ octahedra at the edges of the octahedral layers of Fe(OH)₂. These multinuclear As(III) surface complexes are characterized by As-As pairs at a distance of 3.32 ± 0.02 Å and by As-Fe pairs at a distance of 3.50 ± 0.02 Å and represent a new type of As(III) surface complex. Chemical analyses show that the majority of As(III) produced in the experiments with As present is associated with iron-bearing hydroxycarbonate or hydroxide solids, reinforcing the idea that, at least under some circumstances, bacterial reduction can promote As(III) sequestration instead of mobilizing it into solution.     

Evaluation of snow water equivalent datasets over the Saint‐Maurice river basin region of southern Québec

A 10‐km gridded snow water equivalent (SWE) dataset is developed over the Saint‐Maurice River basin region in southern Québec from kriging of observed snow survey data for evaluation of SWE products. The gridded SWE dataset covers 1980–2014 and is based on manual gravimetric snow surveys carried out on February 1, March 1, March 15, April 1, and April 15 of each snow season, which captures the annual maximum SWE (SWEM) with a mean interpolation error of ±19%. The dataset is used to evaluate SWEM from a range of sources including satellite retrievals, reanalyses, Canadian regional climate models, and the Canadian Meteorological Centre operational snow depth analysis. We also evaluate a number of solid precipitation datasets to determine their contribution to systematic errors in estimated SWEM. None of the evaluated datasets is able to provide estimates of SWEM that are within operational requirements of ±15% error, and insufficient solid precipitation is determined to be one of the main reasons. The Climate System Forecast Reanalysis is the only dataset where snowfall is sufficiently large to generate SWEM values comparable to observations. Inconsistencies in precipitation are also found to have a strong impact on year‐to‐year variability in SWEM dataset performance and spread. Version 3.6.1 of the Canadian Land Surface Scheme land surface scheme driven with ERA‐Interim output downscaled by Version 5.0.1 of the Canadian Regional Climate Model was the best physically based model at explaining the observed spatial and temporal variability in SWEM (root‐mean‐square error [RMSE] = 33%) and has potential for lower error with adjusted precipitation. Operational snow products relying on the real‐time snow depth observing network performed poorly due to a lack of real‐time data and the strong local scale variability of point snow depth observations. The results underscore the need for more effort to be invested in improving solid precipitation estimates for use in snow hydrology applications.     

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.     

Summer temperature variability across four urban neighborhoods in Knoxville,Tennessee, USA

The urban heat island (UHI) is a well-documented effect of urbanization on local climate, identified by higher temperatures compared to surrounding areas, especially at night and during the warm season. The details of a UHI are city-specific, and microclimates may even exist within a given city. Thus, investigating the spatiotemporal variability of a city’s UHI is an ongoing and critical research need. We deploy ten weather stations across Knoxville, Tennessee, to analyze the city’s UHI and its differential impacts across urban neighborhoods: two each in four neighborhoods, one in more dense tree cover and one in less dense tree cover, and one each in downtown Knoxville and Ijams Nature Center that serve as control locations. Three months of temperature data (beginning 2 July 2014) are analyzed using paired-sample t tests and a three-way analysis of variance. Major findings include the following: (1) Within a given neighborhood, tree cover helps negate daytime heat (resulting in up to 1.19 ^°C lower maximum temperature), but does not have as large of an influence on minimum temperature; (2) largest temperature differences between neighborhoods occur during the day (0.38–1.16 ^°C difference), but larger differences between neighborhoods and the downtown control occur at night (1.04–1.88 ^°C difference); (3) presiding weather (i.e., air mass type) has a significant, consistent impact on the temperature in a given city, and lacks the differential impacts found at a larger-scale in previous studies; (4) distance from city center does not impact temperature as much as land use factors. This is a preliminary step towards informing local planning with a scientific understanding of how mitigation strategies may help minimize the UHI and reduce the effects of extreme weather on public health and well-being.     

Clitellate worms (Annelida) in lateglacial and Holocene sedimentary DNA records from the Polar Urals and northern Norway

While there are extensive macro‐ and microfossil records of a range of plants and animals from the Quaternary, earthworms and their close relatives amongst annelids are not preserved as fossils and therefore the knowledge of their past distributions is limited. This lack of fossils means that clitellate worms (Annelida) are currently underused in palaeoecological research, even though they can provide valuable information about terrestrial and aquatic environmental conditions. Their DNA might be preserved in sediments, which offers an alternative method for detection. Here we analyse lacustrine sediments from lakes in the Polar Urals, Arctic Russia, covering the period 24 000–1300 cal. a BP, and NE Norway, covering 10 700–3300 cal. a BP, using a universal mammal 16S rDNA marker. While mammals were recorded using the marker (reindeer was detected twice in the Polar Urals core at 23 000 and 14 000 cal. a BP, and four times in the Norwegian core at 11 000 cal. a BP and between 3600–3300 cal. a BP), worm extracellular DNA ‘bycatch’ was rather high. In this paper we present the first reported worm detection from ancient DNA. Our results demonstrate that both aquatic and terrestrial clitellates can be identified in late‐Quaternary lacustrine sediments, and the ecological information retrievable from this group warrants further research with a more targeted approach.     

Spatial and Temporal Variations in <Emphasis Type="Italic">Pyrodinium bahamense</Emphasis> Cyst Concentrations in the Sediments of Bioluminescent Mangrove Lagoon,St. Croix,USVI

Mangrove Lagoon, located on the island of St. Croix, US Virgin Islands (USVI), is one of few actively bioluminescent lagoons in a location experiencing significant anthropogenic impacts. The bioluminescence is due to an abundance of the dinoflagellate Pyrodinium bahamense in the water column. We recovered surface sediments and sediment cores from Mangrove Lagoon to analyze the spatial distribution and temporal variability of P. bahamense cysts in this system. Surface sediment P. bahamense cyst concentrations ranged from 0 to 466 cysts g^?1 dry sediment, with higher abundances associated with elevated surface water nutrient concentrations and a mixed terrestrial–marine organic matter source regime. In combination with available bioassay data, we hypothesize that phytoplankton utilize nutrients rapidly and subsequent decay of organic matter makes nutrients available for dinoflagellates at the sediment–water interface in the eastern and northern quadrants of the lagoon. However, the nutrients are rapidly exhausted during counterclockwise lagoon circulation resulting in the decline of primary productivity and dinoflagellate abundance in the western quadrants. Downcore profiles suggest that P. bahamense blooms have been occurring for decades, declining in recent years. No cysts were present in sediments predating dredging activities of the 1960s that created Mangrove Lagoon. Recent reductions in cyst abundance may be the result of limited primary productivity caused by restricted water exchange with Salt River Bay due to shallowing of a sill at the mouth of the lagoon. This research highlights the need for more comprehensive geochemical and fossil analyses to better understand long-term ecological variability and inform conservation efforts of these unique habitats.     

Submerged vegetation of the Rotorua and Waikato lakes

Five plant communities in Lake Rotoiti, North Island, New Zealand (38° 02’ S, 176° 24’ E) are described. In shallow water (0–2 m depth) partly protected from the prevailing westerly winds, some indigenous species form characteristic mounds. From 2 to 6 m depth the exotic macrophyte Lagarosiphon major (Ridley) Moss is the dominant and forms dense beds which appear to have completely replaced any native vegetation. Elodea canadensis Michx., a longer‐established exotic, may form a minor component of this zone, but may become the dominant species in water above and below the Lagarosiphon zone. Lagarosiphon appears to be primarily restricted to silty sand, but on pure silt areas it is replaced by Elodea and/or Nitella hookeri A. Braun. These zonations are probably static rather than successional. On underwater cliff faces and boulder shores a seasonal succession of algae was the major vegetation. Only filamentous cyanophytes grew within 1–2m of geothermal springs in the lake.