A nitrogen isotopic shift in fish otolith-bound organic matter during the Late Cretaceous.

The nitrogen isotopes of the organic matter preserved in fossil fish otoliths (ear stones) are a promising tool for reconstructing past environmental changes. We analyzed the N/N ratio (δN) of fossil otolith-bound organic matter in Late Cretaceous fish otoliths (of , and sp.) from three deposits along the US east coast, with two of Campanian (83.

Bromine contamination and risk management in terrestrial and aquatic ecosystems.

Bromine (Br) is widely distributed through the lithosphere and hydrosphere, and its chemistry in the environment is affected by natural processes and anthropogenic activities. While the chemistry of Br in the atmosphere has been comprehensively explored, there has never been an overview of the chemistry of Br in soil and aquatic systems. This review synthesizes current knowledge on the sources, geochemistry, health and environmental threats, remediation approaches, and regulatory guidelines pertaining to Br pollution in terrestrial and aquatic environments.

Potentially Massive and Global Non-Pyrogenic Production of Condensed "Black" Carbon through Biomass Oxidation.

With the increased occurrences of wildfires worldwide, there has been an increase in scientific interest surrounding the chemistry of fire-derived "black" carbon (BC). Traditionally, wildfire research has assumed that condensed aromatic carbon (ConAC) is produced via combustion, and thus, ConAC is equated to BC. However, the lack of correlations between ConAC in soils or rivers and wildfire history suggests that ConAC may be produced non-pyrogenically.

Carbonate Coprecipitation for Cd and Zn Treatment and Evaluation of Heavy Metal Stability Under Acidic Conditions.

Mining wastes or combustion ash are materials of high carbon sequestration potential but are also known for their toxicity in terms of heavy metal content. To utilize such waste materials for engineered carbon mineralization purposes, there is a need to investigate the fate and mobility of toxic metals. This is a study of the coprecipitation of metals with calcium carbonate for environmental heavy metal mitigation.

Uptake and speciation of zinc in edible plants grown in smelter contaminated soils.

Heavy metal accumulation in edible plants grown in contaminated soils poses a major environmental risk to humans and grazing animals. This study focused on the concentration and speciation of Zn in different edible plants grown in soils contaminated with smelter wastes (Spelter, WV, USA) containing high levels of the metals Zn, Cu, Pb, Cd. Their accumulation was examined in different parts (roots, stem, and leaves) of plants and as a function of growth stage (dry seed, sprouting seed, cotyledon, and leaves) in the root vegetables radish, the leafy vegetable spinach and the legume clover.

Impact of bromide exposure on natural organochlorine loss from coastal wetland soils in the Winyah Bay, South Carolina.

Naturally formed halogenated organic compounds are common in terrestrial and marine environments and play an important role in the halogen cycle. Among these halogenated compounds, chlorinated organic compounds are the most common halogenated species in all soils and freshwater sediments. This study evaluated how a previously observed phenomenon of bromination of organic matter in coastal soils due to salt-water intrusion impacts the stability and fate of natural organochlorine (org-Cl) in coastal wetland soils.

Cellular Mercury Coordination Environment, and Not Cell Surface Ligands, Influence Bacterial Methylmercury Production.

The conversion of inorganic mercury (Hg(II)) to methylmercury (MeHg) is central to the understanding of Hg toxicity in the environment. Hg methylation occurs in the cytosol of certain obligate anaerobic bacteria and archaea possessing the gene cluster. However, the processes involved in Hg(II) biouptake and methylation are not well understood.

High Energy Resolution-X-ray Absorption Near Edge Structure Spectroscopy Reveals Zn Ligation in Whole Cell Bacteria.

Identifying the zinc (Zn) ligation and coordination environment in complex biological and environmental systems is crucial to understand the role of Zn as a biologically essential but sometimes toxic metal. Most studies on Zn coordination in biological or environmental samples rely on the extended X-ray absorption fine structure (EXAFS) region of a Zn K-edge X-ray absorption spectroscopy (XAS) spectrum. However, EXAFS analysis cannot identify unique nearest neighbors with similar atomic number (i.

Chemistry of Natural Organic Matter-The Next Step: Commentary on a Humic Substances Debate.

Natural organic matter (NOM) is ubiquitous on the Earth surface and influences every biogeochemical reaction wherever it is present, and its impact on reactions varies with its abundance, structure, and chemistry. Because of decades of field and laboratory studies conducted on NOM in different environments, we are moving away from treating it as a black box to developing molecular structure-based approaches in investigations of soil, sediment, and aquatic systems and are beginning to make major advances in the detailed understanding of the molecular and structural characteristics of NOM, which in turn are helping in deciphering the biochemical processes involved in its evolution in the environment. Yet, many questions remain: How does NOM exist in different soil and aquatic environments? How should we obtain NOM from a sample, and does the isolated NOM represent the NOM in a sample? Do the geochemical reactions explored with extracted NOM represent the reality? How can we study NOM in situ? Here I present a synopsis of critical perspectives on the state of NOM research and a commentary on the reviews and debate presented in this special section on the NOM nomenclature, extraction procedures, and studies involving NOM in different environmental processes.

Phosphate enhanced abiotic and biotic arsenic mobilization in the wetland rhizosphere.

Although abiotic process of competitive sorption between phosphate (P) and arsenate (As(V)), especially onto iron oxides, are well understood, P-mediated biotic processes of Fe and As redox transformation contributing to As mobilization and speciation in wetlands remain poorly defined. To gain new insights into the effects of P on As mobility, speciation, and bioavailability in wetlands, well-controlled greenhouse experiments were conducted. As expected, increased P levels contributed to more As desorption, but more interestingly the interactions between P and wetland plants played a synergistic role in the microbially-mediated As mobilization and enhanced As uptake by plants.

Effect of dissimilatory iron and sulfate reduction on arsenic dynamics in the wetland rhizosphere and its bioaccumulation in wetland plants (Scirpus actus).

Microbial redox transformations of arsenic (As) are coupled to dissimilatory iron and sulfate reduction in the wetlands, however, the processes involved are complex and poorly defined. In this study, we investigated the effect of dissimilatory iron and sulfate reduction on As dynamics in the wetland rhizosphere and its bioaccumulation in plants using greenhouse mesocosms. Results show that high Fe (50μM ferrihydrite/g solid medium) and SO (5mM) treatments are most favorable for As sequestration in the presence of wetland plants (Scirpus actus), probably because root exudates facilitate the microbial reduction of Fe(III), SO, and As(V) to sequester As(III) by incorporation into iron sulfides and/or plant uptake.

Nanoscale Transforming Mineral Phases in Fresh Nacre.

Nacre, or mother-of-pearl, the iridescent inner layer of many mollusk shells, is a biomineral lamellar composite of aragonite (CaCO3) and organic sheets. Biomineralization frequently occurs via transient amorphous precursor phases, crystallizing into the final stable biomineral. In nacre, despite extensive attempts, amorphous calcium carbonate (ACC) precursors have remained elusive.

Novel apatite-based sorbent for defluoridation: synthesis and sorption characteristics of nano-micro-crystalline hydroxyapatite-coated-limestone.

Elevated levels of fluoride (F(-)) in groundwaters of granitic and basaltic terrains pose a major environmental problem and are affecting millions of people all over the world. Hydroxyapatite (HA) has been shown to be a strong sorbent for F(-); however, low permeability of synthetic HA results in poor sorption efficiency. Here we provide a novel method of synthesizing nano- to micrometer sized HA on the surfaces of granular limestone to improve the sorption efficiency of the HA-based filter.

Estimation of reactive thiol concentrations in dissolved organic matter and bacterial cell membranes in aquatic systems.

Organic thiols are highly reactive ligands and play an important role in the speciation of several metals and organic pollutants in the environment. Although small thiols can be isolated and their concentrations can be estimated using chromatographic and derivatization techniques, estimating concentrations of thiols associated with biomacromolecules and humic substances has been difficult. Here we present a fluorescence-spectroscopy-based method for estimating thiol concentrations in biomacromolecules and cell membranes using one of the soluble bromobimanes, monobromo(trimethylammonio)bimane (qBBr).

Natural niche for organohalide-respiring Chloroflexi.

The phylum Chloroflexi contains several isolated bacteria that have been found to respire a diverse array of halogenated anthropogenic chemicals. The distribution and role of these Chloroflexi in uncontaminated terrestrial environments, where abundant natural organohalogens could function as potential electron acceptors, have not been studied. Soil samples (116 total, including 6 sectioned cores) from a range of uncontaminated sites were analyzed for the number of Dehalococcoides-like Chloroflexi 16S rRNA genes present.

X-ray absorption spectroscopy of aqueous aluminum-organic complexes.

Aqueous-phase X-ray absorption near-edge structure (XANES) spectra were collected on dissolved Al complexes with organic ligands, including desferrioxamine B, EDTA, acetohydroxamate, malate, oxalate, and salicylate. Spectral interpretations were made using the density functional theory-based modeling package StoBe. The goals of this work were to study the geometric and electronic structural characteristics of these complexes relative to Al(H(2)O)(6)(3+) and to examine the utility of the aqueous Al XANES technique as a tool for probing Al speciation and structure.

Geometric and electronic structure of the aqueous Al(H2O)6(3+) complex.

The bonding environment of the aqueous Al(H2O)6(3+) complex was studied using X-ray absorption near-edge structure (XANES) spectroscopy at the Al K-edge, with spectral interpretations based on density functional theory (DFT). Calculations for a highly symmetric complex (T(h) symmetry) indicate electron transitions into Al3 p-O 2s and Al3 p-O 2p antibonding orbitals, with a split O 2p contribution that appears to be due to a weak pi-interaction of the Al 3p orbitals with water ligands off-axis (equatorial) with respect to the Al 3p axis. Calculations were performed with several hypothetical structures to assess the effects of Al-O bond length, orientation of water ligands in the first coordination shell, and the presence of a second solvation shell on the XANES spectrum.

Complexation of oxoanions and cationic metals by the biscatecholate siderophore azotochelin.

Azotochelin is a biscatecholate siderophore produced by the nitrogen-fixing soil bacterium Azotobacter vinelandii. The complexation properties of azotochelin with a series of oxoanions [Mo(VI), W(VI) and V(V)] and divalent cations [Cu(II), Zn(II), Co(II) and Mn(II)] were investigated by potentiometry, UV-vis and X-ray spectroscopy. Azotochelin forms a strong 1:1 complex with molybdate (log K=7.

Near edge X-ray absorption fine structure spectroscopy of bacterial hydroxamate siderophores in aqueous solutions.

X-ray absorption spectroscopy (XAS) is widely used to explore the coordination environments and structures of metal complexes in aqueous solutions and disordered phases. Although soft-XAS studies on gaseous phases, solid phases and their interfaces have shown that XAS is a versatile tool in studying the functional group composition of organic molecules, the application of XAS to studying aqueous solutions is seriously limited because of experimental difficulties. In this report, using a modified synchrotron endstation geometry, we show how soft-XAS was used to study the changes in electronic states of reactive functional groups in a bacterial macromolecule, desferrioxamine B (desB, a hydroxamate siderophore) and its structural analogue (acetohydroxamic acid (aHa)).

Quantitative determination of absolute organohalogen concentrations in environmental samples by X-ray absorption spectroscopy.

An in situ procedure for quantifying total organic and inorganic Cl concentrations in environmental samples based on X-ray absorption near-edge structure (XANES) spectroscopy has been developed. Cl 1s XANES spectra reflect contributions from all Cl species present in a sample, providing a definitive measure of total Cl concentration in chemically heterogeneous samples. Spectral features near the Cl K-absorption edge provide detailed information about the bonding state of Cl, whereas the absolute fluorescence intensity of the spectra is directly proportional to total Cl concentration, allowing for simultaneous determination of Cl speciation and concentration in plant, soil, and natural water samples.

X-ray absorption spectroscopy study of the hydrogen bond network in the bulk water of aqueous solutions.

We utilized X-ray absorption spectroscopy (XAS) and X-ray Raman scattering (XRS) in order to study the ion solvation effect on the bulk hydrogen bonding structure of water. The fine structures in the X-ray absorption spectra are sensitive to the local environment of the probed water molecule related to the hydrogen bond length and angles. By varying the concentration of ions, we can distinguish between contributions from water in the bulk and in the first solvation sphere.

Hard and soft X-ray absorption spectroscopic investigation of aqueous Fe(III)-hydroxamate siderophore complexes.

Microorganisms release organic macromolecules, such as siderophores, to obtain Fe(III) from natural systems. While the relative stabilities of Fe(III)-siderophore complexes are well-studied, the structural environments of Fe(III) and ligands in the complex are not well-understood. Using the X-ray absorption spectroscopy (XAS) at the Fe- and N-K absorption edges, we characterized the nature of Fe(III) interactions with a hydroxamate siderophore, desferrioxamine B (desB), and its small structural analogue, acetohydroxamic acid (aHa), as a function of pH (1.

The local structure of protonated water from x-ray absorption and density functional theory.

We present a combined x-ray absorption spectroscopy/computational study of water in hydrochloric acid (HCl) solutions of varying concentration to address the structure and bonding of excess protons and their effect on the hydrogen bonding network in liquid water. Intensity variations and energy shifts indicate changes in the hydrogen bonding structure in water as well as the local structure of the protonated complex as a function of the concentration of protons. In particular, in highly acidic solutions we find a dominance of the Eigen form, H(3)O(+), while the proton is less localized to a specific water under less acidic conditions.

Effect of soil fulvic acid on nickel(II) sorption and bonding at the aqueous-boehmite (gamma-AIOOH) interface.

The influence of soil-derived fulvic acid (SFA) on Ni(II) sorption and speciation in aqueous boehmite (gamma-AIOOH) suspensions was evaluated using a combination of sorption experiments and Ni K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy measurements. Co-sorption of SFA at the aqueous-boehmite interface modifies both the extent of Ni(II) sorption as well as the local structure of the sorbing Ni(II) ions. In SFA-free suspensions, Ni(II) sorbs by forming inner-sphere bidentate mononuclear complexes with surface aluminol groups.

Speciation of iron and sulfate in acid waters: aqueous clusters to mineral precipitates.

Acid mine drainage (AMD) contaminates surface water bodies, groundwater, soils, and sediments at innumerable locations around the world. AMD usually originates by weathering of pyrite (FeS2) and is rich in Fe and sulfate. In this study, we investigated speciation of FeII, FeIII, and SO4 in acid waters by Fourier transform infrared and X-ray absorption spectroscopy.