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A comparison of two methods for determining copper partitioning in oxidized sediments

Model estimations of the proportion of Cu in oxidized sediments associated with extractable organic materials show some agreement with the proportion of Cu extracted from those sediments with ammonium hydroxide. Data were from 17 estuaries of widely differing sediment chemistry. The modelling and extraction methods agreed best where concentrations of organic materials were either in very high concentrations, relative to other sediment components, or in very low concentrations. In the range of component concentrations where the model predicted Cu should be distributed among a variety of components, agreement between the methods was poor. Both approaches indicated that Cu was predominantly partitioned to organic materials in some sediments, and predominantly partitioned to other components (most probably iron oxides and manganese oxides) in other sediments, and that these differences were related to the relative abundances of the specific components in the sediment. Although the results of the two methods of estimating Cu partitioning to organics correlated significantly among 24 stations from the 17 estuaries, the variability in the relationship suggested refinement of parameter values and verification of some important assumptions were essential to the further development of a reasonable model.

Marine Chemistry↗

The release of dissolved actinium to the ocean: A global comparison of different end-members

The measurement of short-lived 223Ra often involves a second measurement for supported activities, which represents 227Ac in the sample. Here we exploit this fact, presenting a set of 284 values on the oceanic distribution of 227Ac, which was collected when analyzing water samples for short-lived radium isotopes by the radium delayed coincidence counting system. The present work compiles 227Ac data from coastal regions all over the northern hemisphere, including values from ground water, from estuaries and lagoons, and from marine end-members. Deep-sea samples from a continental slope off Puerto Rico and from an active vent site near Hawaii complete the overview of 227Ac near its potential sources. The average 227Ac activities of nearshore marine end-members range from 0.4??dpm m- 3 at the Gulf of Mexico to 3.0??dpm m- 3 in the coastal waters of the Korean Strait. In analogy to 228Ra, we find the extension of adjacent shelf regions to play a substantial role for 227Ac activities, although less pronounced than for radium, due to its weaker shelf source. Based on previously published values, we calculate an open ocean 227Ac inventory of 1.35 * 1018??dpm 227Acex in the ocean, which corresponds to 37??moles, or 8.4??kg. This implies a flux of 127??dpm m-2 y- 1 from the deep-sea floor. For the shelf regions, we obtain a global inventory of 227Ac of 4.5 * 1015??dpm, which cannot be converted directly into a flux value, as the regional loss term of 227Ac to the open ocean would have to be included. Ac has so far been considered to behave similarly to Ra in the marine environment, with the exception of a strong Ac source in the deep-sea due to 231Paex. Here, we present evidence of geochemical differences between Ac, which is retained in a warm vent system, and Ra, which is readily released [Moore, W.S., Ussler, W. and Paull, C.K., 2008-this issue. Short-lived radium isotopes in the Hawaiian margin: Evidence for large fluid fluxes through the Puna Ridge. Marine Chemistry]. Another potential mechanism of producing deviations in 227Ac/228Ra and daughter isotope ratios from the expected production value of lithogenic material is observed at reducing environments, where enrichment in uranium may occur. The presented data here may serve as a reference for including 227Ac in circulation models, and the overview provides values for some end-members that contribute to the global Ac distribution. ?? 2007 Elsevier B.V. All rights reserved.

Marine Chemistry↗

Flow and geochemistry of groundwater beneath a back-barrier lagoon: The subterranean estuary at Chincoteague Bay, Maryland, USA

To better understand large-scale interactions between fresh and saline groundwater beneath an Atlantic coastal estuary, an offshore drilling and sampling study was performed in a large barrier-bounded lagoon, Chincoteague Bay, Maryland, USA. Groundwater that was significantly fresher than overlying bay water was found in shallow plumes up to 8 m thick extending more than 1700 m offshore. Groundwater saltier than bay surface water was found locally beneath the lagoon and the barrier island, indicating recharge by saline water concentrated by evaporation prior to infiltration. Steep salinity and nutrient gradients occur within a few meters of the sediment surface in most locations studied, with buried peats and estuarine muds acting as confining units. Groundwater ages were generally more than 50 years in both fresh and brackish waters as deep as 23 m below the bay bottom. Water chemistry and isotopic data indicate that freshened plumes beneath the estuary are mixtures of water originally recharged on land and varying amounts of estuarine surface water that circulated through the bay floor, possibly at some distance from the sampling location. Ammonium is the dominant fixed nitrogen species in saline groundwater beneath the estuary at the locations sampled. Isotopic and dissolved-gas data from one location indicate that denitrification within the subsurface flow system removed terrestrial nitrate from fresh groundwater prior to discharge along the western side of the estuary. Similar situations, with one or more shallow semi-confined flow systems where groundwater geochemistry is strongly influenced by circulation of surface estuary water through organic-rich sediments, may be common on the Atlantic margin and elsewhere.

Marine Chemistry↗

The release of dissolved nutrients and metals from coastal sediments due to resuspension

Coastal sediments in many regions are impacted by high levels of contaminants. Due to a combination of shallow water depths, waves, and currents, these sediments are subject to regular episodes of sediment resuspension. However, the influence of such disturbances on sediment chemistry and the release of solutes is poorly understood. The aim of this study is to quantify the release of dissolved metals (iron, manganese, silver, copper, and lead) and nutrients due to resuspension in Boston Harbor, Massachusetts, USA. Using a laboratory-based erosion chamber, a range of typical shear stresses was applied to fine-grained Harbor sediments and the solute concentration at each shear stress was measured. At low shear stress, below the erosion threshold, limited solutes were released. Beyond the erosion threshold, a release of all solutes, except lead, was observed and the concentrations increased with shear stress. The release was greater than could be accounted for by conservative mixing of porewaters into the overlying water, suggesting that sediment resuspension enhances the release of nutrients and metals to the dissolved phase. To address the long-term fate of resuspended particles, samples from the erosion chamber were maintained in suspension for 90. h. Over this time, 5-7% of the particulate copper and silver was released to the dissolved phase, while manganese was removed from solution. Thus resuspension releases solutes both during erosion events and over a longer timescale due to reactions of suspended particles in the water column. The magnitude of the annual solute release during erosion events was estimated by coupling the erosion chamber results with a record of bottom shear stresses simulated by a hydrodynamic model. The release of dissolved copper, lead, and phosphate due to resuspension is between 2% and 10% of the total (dissolved plus particulate phase) known inputs to Boston Harbor. Sediment resuspension is responsible for transferring a significant quantity of solid phase metals to the more bioavailable and mobile dissolved phase. The relative importance of sediment resuspension as a source of dissolved metals to Boston Harbor is expected to increase as continuing pollutant control decreases the inputs from other sources. ?? 2010 Elsevier B.V.

Marine Chemistry↗

Polyphenyl fluorides

Studies related to the chemistry of aromatic fluorine compounds have been carried out at the Illinois State Geological Survey since 1933. In our reference collection we have several compounds that have not previously been described. This communication records data on 18 biphenyl, three terphenyl and some benzene fluorinated derivatives that were obtained as by-products and/or by specific synthesis. ?? 1973.

Journal of Fluorine Chemistry↗

Determination of δ 18 O and δ 15 N in Nitrate

The analyses of both O and N isotopic compositions of nitrate have many potential applications in studies of nitrate sources and reactions in hydrology, oceanography, and atmospheric chemistry, but simple and precise methods for these analyses have yet to be developed. Testing of a new method involving reaction of potassium nitrate with catalyzed graphite (C + Pd + Au) at 520 °C resulted in quantitative recovery of N and O from nitrate as free CO 2 , K 2 CO 3 , and N 2 . The δ 18 O values of nitrate reference materials were obtained by analyzing both the CO 2 and K 2 CO 3 from catalyzed graphite combustion. Provisional values of δ 18 O VSMOW for the internationally distributed KNO 3 reference materials IAEA-N3 and USGS-32 were both equal to +22.7 ± 0.5‰. Because the fraction of free CO 2 and the isotopic fractionation factor between CO 2 and K 2 CO 3 were constant in the combustion products, the δ 18 O value of KNO 3 could be calculated from measurements of the δ 18 O of free CO 2 . Thus, δ 18 O KNO 3 = a δ 18 O free CO 2 − b , where a and b were equal to 0.9967 and 3.3, respectively, for the specific conditions of the experiments. The catalyzed graphite combustion method can be used to determine δ 18 O of KNO 3 from measurements of δ 18 O of free CO 2 with reproducibility on the order of ±0.2‰ or better if local reference materials are prepared and analyzed with the samples. Reproducibility of δ 15 N was ±0.1‰ after trace amounts of CO were removed.

Analytical Chemistry↗

The effects of phosphatization on the mineral associations and speciation of Pb in ferromanganese crusts

The older layers of thick ferromanganese (FeMn) crusts from the central Pacific Ocean have undergone diagenetic phosphatization, during which carbonate fluorapatite (CFA) filled fractures and pore space and replaced carbonates. The effects of phosphatization on individual trace metal concentrations, speciation, and phase associations in FeMn crusts remain poorly understood yet may be important to metal enrichment mechanisms, paleoceanography, and extractive metallurgy. This study examines the concentrations, speciation, and mineral phase associations of Pb in phosphatized and nonphosphatized layers within three Pacific Ocean crusts using standard chemical and mineralogical techniques, in addition to bulk X-ray absorption spectroscopy (XAS) and microfocused X-ray fluorescence (μ-XRF) mapping. Our findings challenge the conclusions of previous works, which reported that most Pb in phosphatized crusts was associated with the CFA-dominated residual phase after sequential leaching experiments. These results were interpreted as an indication of Pb transfer from the oxide phases to diagenetic CFA during phosphatization. However, our results reveal an inverse correlation of Pb with Ca and P in the μ-XRF mapping of in situ FeMn crust sections and bulk chemistry. Furthermore, XAS measurements reveal that Pb speciation in bulk phosphatized FeMn crust layers is very similar to nonphosphatized layers, indicating only minor, if any, change in speciation during diagenetic phosphatization. Small differences in the EXAFS spectra for one highly phosphatized layer indicate that minor amounts of Pb may have been altered during phosphatization, but the new Pb-bearing phase was not unequivocally identified. Taken together, our results demonstrate that Pb speciation is not significantly affected by phosphatization.

Earth and Space Chemistry↗

Attenuation of barium, strontium, cobalt, and nickel plumes formed during microbial iron-reduction in a crude-oil-contaminated aquifer

We assessed the spatial distribution of 35 elements in aquifer sediments and groundwater of a crude-oil-contaminated aquifer and show evidence of the dissolution of barium (Ba), strontium (Sr), cobalt (Co), and nickel (Ni) during hydrocarbon oxidation coupled to historic microbial Fe(III)-reduction near the oil. Trace element plumes occur in the crude-oil-contaminated aquifer, where 50% Co, 47% Ni, 24% Ba, and 15% Sr have been mobilized from the sediment near the oil into groundwater, resulting in dissolved masses >33, 18, three, and two times greater than estimated dissolved masses prior to contamination, respectively. Ba 2+ and Ni 2+ concentrations exceeded the World Health Organization’s drinking-water guidelines of 700 and 20 μg/L, respectively. Sediments attenuate trace element plumes in two geochemically distinct zones, resulting in <0.01% total trace element masses dissolved in groundwater, despite the substantial mobilization near the oil body. Geochemical modeling of the modern Fe(III)-reducing zone suggests trace elements are likely attenuated via coprecipitation with/without sorption on iron carbonate precipitates. In the suboxic transition zone at the leading edge of the plume, Fe(III)-hydroxides sorb Ba 2+ , Sr 2+ , Co 2+ , and Ni 2+ . This study emphasizes that slow but persistent biogeochemical activity can substantially alter aquifer chemistry over decadal timeframes, a phenomenon we term biogeochemical gradualism.

Minnesota↗

History of the recommended atomic-weight values from 1882 to 1997: A comparision of differences from current values to the estimated uncertainties of earlier values

International commissions and national committees for atomic weights (mean relative atomic masses) have recommended regularly updated, best values for these atomic weights as applicable to terrestrial sources of the chemical elements. Presented here is a historically complete listing starting with the values in F. W. Clarke's 1882 recalculation, followed by the recommended values in the annual reports of the American Chemical Society's Atomic Weights Commission. From 1903, an International Commission published such reports and its values (scaled to an atomic weight of 16 for oxygen) are here used in preference to those of national committees of Britain, Germany, Spain, Switzerland, and the U.S.A. We have, however, made scaling adjustments from Ar(16O) to Ar(12C) where not negligible. From 1920, this International Commission constituted itself under the International Union of Pure and Applied Chemistry (IUPAC). Since then, IUPAC has published reports (mostly biennially) listing the recommended atomic weights, which are reproduced here. Since 1979, these values have been called the "standard atomic weights" and, since 1969, all values have been published, with their estimated uncertainties. Few of the earlier values were published with uncertainties. Nevertheless, we assessed such uncertainties on the basis of our understanding of the likely contemporary judgement of the values' reliability. While neglecting remaining uncertainties of 1997 values, we derive "differences" and a retrospective index of reliability of atomic-weight values in relation to assessments of uncertainties at the time of their publication. A striking improvement in reliability appears to have been achieved since the commissions have imposed upon themselves the rule of recording estimated uncertainties from all recognized sources of error.

Pure and Applied Chemistry↗

Isotope-abundance variations of selected elements (IUPAC technical report)

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

Pure and Applied Chemistry↗

Atomic weights of the elements. Review 2000 (IUPAC Technical Report)

A consistent set of internationally accepted atomic weights has long been an essential aim of the scientific community because of the relevance of these values to science and technology, as well as to trade and commerce subject to ethical, legal, and international standards. The standard atomic weights of the elements are regularly evaluated, recommended, and published in updated tables by the Commission on Atomic Weights and Isotopic Abundances (CAWIA) of the International Union of Pure and Applied Chemistry (IUPAC). These values are invariably associated with carefully evaluated uncertainties. Atomic weights were originally determined by mass ratio measurements coupled with an understanding of chemical stoichiometry, but are now based almost exclusively on knowledge of the isotopic composition (derived from isotope-abundance ratio measurements) and the atomic masses of the isotopes of the elements. Atomic weights and atomic masses are now scaled to a numerical value of exactly 12 for the mass of the carbon isotope of mass number 12. Technological advances in mass spectrometry and nuclear-reaction energies have enabled atomic masses to be determined with a relative uncertainty of better than 1 ×10−7 . Isotope abundances for an increasing number of elements can be measured to better than 1 ×10−3 . The excellent precision of such measurements led to the discovery that many elements, in different specimens, display significant variations in their isotope-abundance ratios, caused by a variety of natural and industrial physicochemical processes. While such variations increasingly place a constraint on the uncertainties with which some standard atomic weights can be stated, they provide numerous opportunities for investigating a range of important phenomena in physical, chemical, cosmological, biological, and industrial processes. This review reflects the current and increasing interest of science in the measured differences between source-specific and even sample-specific atomic weights. These relative comparisons can often be made with a smaller uncertainty than is achieved in the best calibrated “absolute ” (=SI-traceable) atomic-weight determinations. Accurate determinations of the atomic weights of certain elements also influence the values of fundamental constants such as the Avogadro, Faraday, and universal gas constants. This review is in two parts: the first summarizes the development of the science of atomic-weight determinations during the 20th century; the second summarizes the changes and variations that have been recognized in the values and uncertainties of atomic weights, on an element-by-element basis, in the latter part of the 20th century.

Pure and Applied Chemistry↗

Isotopic compositions of the elements 2013 (IUPAC Technical Report)

The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) of the International Union of Pure and Applied Chemistry (iupac.org) has revised the Table of Isotopic Compositions of the Elements (TICE). The update involved a critical evaluation of the recent published literature. The new TICE 2013 includes evaluated data from the “best measurement” of the isotopic abundances in a single sample, along with a set of representative isotopic abundances and uncertainties that accommodate known variations in normal terrestrial materials.

Pure and Applied Chemistry↗

Standard atomic weights of the elements 2021 (IUPAC Technical Report)

Following the reviews of atomic-weight determinations and other cognate data in 2015, 2017, 2019 and 2021, the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) reports changes of standard atomic weights. The symbol A r °(E) was selected for standard atomic weight of an element to distinguish it from the atomic weight of an element E in a specific substance P, designated A r (E, P). The CIAAW has changed the values of the standard atomic weights of five elements based on recent determinations of terrestrial isotopic abundances: Ar (argon): from 39.948 ± 0.001 to [39.792, 39.963] Hf (hafnium): from 178.49 ± 0.02 to 178.486 ± 0.006 Ir (iridium): from 192.217 ± 0.003 to 192.217 ± 0.002 Pb (lead): from 207.2 ± 0.1 to [206.14, 207.94] Yb (ytterbium): from 173.054 ± 0.005 to 173.045 ± 0.010 The standard atomic weight of argon and lead have changed to an interval to reflect that the natural variation in isotopic composition exceeds the measurement uncertainty of A r (Ar) and A r (Pb) in a specific substance. The standard atomic weights and/or the uncertainties of fourteen elements have been changed based on the Atomic Mass Evaluations 2016 and 2020 accomplished under the auspices of the International Union of Pure and Applied Physics (IUPAP). A r ° of Ho, Tb, Tm and Y were changed in 2017 and again updated in 2021: Al (aluminium), 2017: from 26.981 5385 ± 0.000 0007 to 26.981 5384 ± 0.000 0003 Au (gold), 2017: from 196.966 569 ± 0.000 005 to 196.966 570 ± 0.000 004 Co (cobalt), 2017: from 58.933 194 ± 0.000 004 to 58.933 194 ± 0.000 003 F (fluorine), 2021: from 18.998 403 163 ± 0.000 000 006 to 18.998 403 162 ± 0.000 000 005 (Ho (holmium), 2017: from 164.930 33 ± 0.000 02 to 164.930 328 ± 0.000 007) Ho (holmium), 2021: from 164.930 328 ± 0.000 007 to 164.930 329 ± 0.000 005 Mn (manganese), 2017: from 54.938 044 ± 0.000 003 to 54.938 043 ± 0.000 002 Nb (niobium), 2017: from 92.906 37 ± 0.000 02 to 92.906 37 ± 0.000 01 Pa (protactinium), 2017: from 231.035 88 ± 0.000 02 to 231.035 88 ± 0.000 01 Pr (praseodymium), 2017: from 140.907 66 ± 0.000 02 to 140.907 66 ± 0.000 01 Rh (rhodium), 2017: from 102.905 50 ± 0.000 02 to 102.905 49 ± 0.000 02 Sc (scandium), 2021: from 44.955 908 ± 0.000 005 to 44.955 907 ± 0.000 004 (Tb (terbium), 2017: from 158.925 35 ± 0.000 02 to 158.925 354 ± 0.000 008) Tb (terbium), 2021: from 158.925 354 ± 0.000 008 to 158.925 354 ± 0.000 007 (Tm (thulium), 2017: from 168.934 22 ± 0.000 02 to 168.934 218 ± 0.000 006) Tm (thulium), 2021: from 168.934 218 ± 0.000 006 to 168.934 219 ± 0.000 005 (Y (yttrium), 2017: from 88.905 84 ± 0.000 02 to 88.905 84 ± 0.000 01) Y (yttrium), 2021: from 88.905 84 ± 0.000 01 to 88.905 838 ± 0.000 002

Pure and Applied Chemistry↗

Minimum requirements for publishing hydrogen, carbon, nitrogen, oxygen and sulfur stable-isotope delta results (IUPAC Technical Report)

Stable hydrogen, carbon, nitrogen, oxygen and sulfur (HCNOS) isotope compositions expressed as isotope-delta values are typically reported relative to international standards such as Vienna Standard Mean Ocean Water (VSMOW), Vienna Peedee belemnite (VPDB) or Vienna Cañon Diablo Troilite (VCDT). These international standards are chosen by convention and the calibration methods used to realise them in practice undergo occasional changes. To ensure longevity and reusability of published data, a comprehensive description of (1) analytical procedure, (2) traceability, (3) data processing, and (4) uncertainty evaluation is required. Following earlier International Union of Pure and Applied Chemistry documents on terminology and notations, this paper proposes minimum requirements for publishing HCNOS stable-isotope delta results. Each of the requirements are presented with illustrative examples.

Pure and Applied Chemistry↗

Genotoxicity in native fish associated with agricultural runoff events

The primary objective of the present study was to test whether agricultural chemical runoff was associated with in-stream genotoxicity in native fish. Using Sacramento sucker (Catostomus occidentalis), we combined field-caging experiments in an agriculturally dominated watershed with controlled laboratory exposures to field-collected water samples, and we coupled genotoxicity biomarker measurements in fish with bacterial mutagenicity analysis of water samples. We selected DNA strand breakage as a genotoxicity biomarker and Ames Salmonella mutagenicity tests as a second, supporting indicator of genotoxicity. Data from experiments conducted during rainfall runoff events following winter application of pesticides in 2000 and 2001 indicated that DNA strand breaks were significantly elevated in fish exposed to San Joaquin River (CA, USA) water (38.8, 28.4, and 53.6% DNA strand breakage in year 2000 field, year 2000 lab, and year 2001 field exposures, respectively) compared with a nearby reference site (15.4, 8.7, and 12.6% DNA strand breakage in year 2000 field, year 2000 lab, and year 2001 field exposures, respectively). Time-course measurements in field experiments supported a linkage between induction of DNA strand breakage and the timing of agricultural runoff. San Joaquin River water also caused significant reversion mutation in two Ames Salmonella tester strains. Salmonella mutagenicity corroborated in-stream effects, further strengthening a causal relationship between runoff events and genotoxicity. Potentially responsible agents are discussed in the context of timing of runoff events in the field, concordance between laboratory and field exposures, pesticide application patterns in the drainage, and analytical chemistry data.

Environmental Toxicology and Chemistry↗

Subchronic effects of methylmercury on plasma and organ biochemistries in great egret nestlings

In recent years, high concentrations of mercury have been found in wading birds in Florida, USA. Great egret ( Ardea alba ) chicks (2 weeks old) were dosed orally daily with the equivalent of 0, 0.5, or 5 μg/g Hg as methylmercury chloride in the diet for up to 12 weeks. Weakness of the legs or paralysis occurred in all high-dosed birds. Geometric mean blood Hg concentrations were 0.17, 10.3, and 78.5 μg/g (wet wt), respectively. Mercury concentrations for organs (μg/g wet wt), including brain (0.22, 3.4, and 35, respectively), liver (0.34, 15.1, 138, respectively), and kidney (0.28, 8.1, and 120, respectively), increased in a dose-dependent manner. Total glutathione (GSH) peroxidase activity was significantly lower in the plasma, brain, liver, and kidney of the high-dosed group. Plasma aspartate aminotransferase activity increased with mercury treatment, whereas lactate dehydrogenase activity decreased. Four other plasma chemistries were decreased significantly in the high-dosed group and included uric acid, total protein, albumin, and inorganic phosphorus. Lipid peroxidation increased in liver (low and high dose) and brain (high dose). Tissue changes in concentrations of reduced thiols included decreased total thiols and protein-bound thiols in liver, decreased protein-bound thiols in kidney, and increased GSH in kidney and brain. Activities of GSH S -transferase and oxidized glutathione reductase increased in liver. In kidney, GSH S -transferase and glucose-6-phosphate dehydrogenase activities increased with mercury dose. These findings, including apparent compensatory changes, are compared to other Hg studies where oxidative stress was reported in egrets, herons, and diving ducks in the field and mallards in the laboratory.

Environmental Toxicology and Chemistry↗

Apparent tolerance of turkey vultures (Cathartes aura) to the non-steroidal anti-inflammatory drug diclofenac

The nonsteroidal anti‐inflammatory drug diclofenac is extremely toxic to Old World Gyps vultures (median lethal dose ∼0.1–0.2 mg/kg), evoking visceral gout, renal necrosis, and mortality within a few days of exposure. Unintentional secondary poisoning of vultures that fed upon carcasses of diclofenac‐treated livestock decimated populations in the Indian subcontinent. Because of the widespread use of diclofenac and other cyclooxygenase‐2 inhibiting drugs, a toxicological study was undertaken in turkey vultures ( Cathartes aura ) as an initial step in examining sensitivity of New World scavenging birds. Two trials were conducted entailing oral gavage of diclofenac at doses ranging from 0.08 to 25 mg/kg body weight. Birds were observed for 7 d, blood samples were collected for plasma chemistry (predose and 12, 24, and 48 h and 7 d postdose), and select individuals were necropsied. Diclofenac failed to evoke overt signs of toxicity, visceral gout, renal necrosis, or elevate plasma uric acid at concentrations greater than 100 times the estimated median lethal dose reported for Gyps vultures. For turkey vultures receiving 8 or 25 mg/kg, the plasma half‐life of diclofenac was estimated to be 6 h, and it was apparently cleared after several days as no residues were detectable in liver or kidney at necropsy. Differential sensitivity among avian species is a hallmark of cyclooxygenase‐2 inhibitors, and despite the tolerance of turkey vultures to diclofenac, additional studies in related scavenging species seem warranted.

Environmental Toxicology and Chemistry↗

The Asian clam Corbicula fluminea as a biomonitor of trace element contamination: Accounting for different sources of variation using an hierarchical linear model

In the present study, specimens of the invasive clam, Corbicula fluminea, were collected above and below possible sources of potentially toxic trace elements (As, Cd, Cr, Cu, Hg, Pb, and Zn) in the Altamaha River system (Georgia, USA). Bioaccumulation of these elements was quantified, along with environmental (water and sediment) concentrations. Hierarchical linear models were used to account for variability in tissue concentrations related to environmental (site water chemistry and sediment characteristics) and individual (growth metrics) variables while identifying the strongest relations between these variables and trace element accumulation. The present study found significantly elevated concentrations of Cd, Cu, and Hg downstream of the outfall of kaolin-processing facilities, Zn downstream of a tire cording facility, and Cr downstream of both a nuclear power plant and a paper pulp mill. Models of the present study indicated that variation in trace element accumulation was linked to distance upstream from the estuary, dissolved oxygen, percentage of silt and clay in the sediment, elemental concentrations in sediment, shell length, and bivalve condition index. By explicitly modeling environmental variability, the Hierarchical linear modeling procedure allowed the identification of sites showing increased accumulation of trace elements that may have been caused by human activity. Hierarchical linear modeling is a useful tool for accounting for environmental and individual sources of variation in bioaccumulation studies. ?? 2009 SETAC.

Environmental Toxicology and Chemistry↗