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The effect of chronic chromium exposure on the health of Chinook salmon (Oncorhynchus tshawytscha)

This study was designed to determine fish health impairment of Chinook salmon ( Oncorhynchus tshawytscha ) exposed to chromium. Juvenile Chinook salmon were exposed to aqueous chromium concentrations (0–266 μg l −1 ) that have been documented in porewater from bottom sediments and in well waters near salmon spawning areas in the Columbia River in the northwestern United States. After Chinook salmon parr were exposed to 24 and 54 μg Cr l −1 for 105 days, neither growth nor survival of parr was affected. On day 105, concentrations were increased from 24 to 120 μg Cr l −1 and from 54 to 266 μg Cr l −1 until the end of the experiment on day 134. Weight of parr was decreased in the 24/120 μg Cr l −1 treatment, and survival was decreased in the 54/266 μg Cr l −1 treatment. Fish health was significantly impaired in both the 24/120 and 54/266 μg Cr l −1 treatments. The kidney is the target organ during chromium exposures through the water column. The kidneys of fish exposed to the greatest concentrations of chromium had gross and microscopic lesions (e.g. necrosis of cells lining kidney tububules) and products of lipid peroxidation were elevated. These changes were associated with elevated concentrations of chromium in the kidney, and reduced growth and survival. Also, variations in DNA in the blood were associated with pathological changes in the kidney and spleen. These changes suggest that chromium accumulates and enters the lipid peroxidation pathway where fatty acid damage and DNA damage (expressed as chromosome changes) occur to cause cell death and tissue damage. While most of the physiological malfunctions occurred following parr exposures to concentrations ≥120 μg Cr l −1 , nuclear DNA damage followed exposures to 24 μg Cr l −1 , which was the smallest concentration tested. The abnormalities measured during this study are particularly important because they are associated with impaired growth and reduced survival at concentrations ≥120 μg Cr l −1 . Therefore, these changes can be used to investigate the health of resident fish in natural waters with high chromium concentrations as well as provide insight into the mechanisms of chromium toxicity.

Aquatic Toxicology↗

Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr(VI) and Cr(VI) adsorbed onto γ-Al 2 O 3 and goethite is less than 0.04‰ ( 53 Cr/ 52 Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53 Cr/ 52 Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO 4 - and CrO 4 2 - was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in δ 53 Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

Environmental Science & Technology↗

Book review: Proceedings of the First International Snakehead Symposium

Snakehead fishes (family Channidae) are among the most maligned aquatic invasive species in the USA and some other countries where they have been introduced outside of their native range in Asia and Africa. Nevertheless, snakeheads continue to be widely exploited in the live‐food trade in aquaculture and wild‐capture fisheries, are highly sought by anglers, and are also popular in the aquarium trade (Courtenay and Williams 2004). The Northern Snakehead Channa argus is the most widespread of the three channid species that are currently naturalized in the USA. This species has generated much concern and controversy, a situation that is partly fueled by sensational media coverage and B‐grade science fiction horror films, such as “Frankenfish,” “Snakehead Terror,” and “Snakehead Swamp.” Media reports of snakehead introductions are often replete with provocative terms, such as “vicious,” “villain,” “voracious,” “monster,” “diabolical,” and even “ecological Armageddon.” When snakeheads first appeared in natural waters of the USA, fisheries professionals became increasingly interested in their status. Established populations rapidly expanded in the mid‐Atlantic region and Arkansas, with scattered reports of introduced snakeheads from isolated locations in Hawaii, California, North Carolina, Florida, the Upper Midwest, and New England. In 2002, snakeheads were added to the list of injurious fishes under the Lacey Act, thereby prohibiting their importation or transport across state lines without a permit. This symposium was conceived by the editors and other concerned fisheries professionals of the Mississippi River Basin Panel on Aquatic Invasive Species. The mission of the symposium, held in Alexandria, Virginia, in July 2018, was to bring together experts on snakehead biology and ecology and to synthesize existing information into summary papers. In this book, 35 authors contributed to 15 peer‐reviewed articles that detail the current state of knowledge about snakehead introductions in the USA. Additionally, 16 abstracts are included from meeting presentations that were not accompanied by full‐length manuscripts. Also included is a summary of a facilitated symposium panel discussion featuring eight experts representing state and federal natural resource agencies and private fishing organizations. The book is organized into six sections. In the first section (Distribution), three papers provide an overview of the Channa species introduced into the USA and historical accounts of occurrence and dispersal of the Northern Snakehead in the mid‐Atlantic region and Arkansas. The second section (Biology/Ecology) consists of two articles that examine growth and energetics of Northern Snakehead populations and two papers that investigate diet, diel feeding activity, and movement of this species in the Potomac River drainage. The third section (Monitoring/Response) includes a paper that models range expansion of the Northern Snakehead in the southeastern USA based on occurrence data and environmental conditions. Also included in this section is a paper summarizing an environmental DNA study to assess the status and range of the Bullseye Snakehead C. marulius in southern Florida. The fourth section (Management/Control) is comprised of four papers that address harvest, age and growth, and development of a stock–recruitment model to inform management decisions regarding control and mitigation for Northern Snakehead populations in the greater Chesapeake Bay area. The fifth section (Perspectives) includes a paper on the history of snakehead introductions in Japan and a thought‐provoking social commentary on the human dimensions of Northern Snakehead management. Abstracts in the final section provide brief summaries of a diversity of snakehead studies, including aspects of distribution, ecology, behavior, control and monitoring efforts, public outreach, and pathology. The summary of the panel discussion is an engaging dialogue about the challenges of snakehead management in the context of conflicts regarding snakeheads as injurious versus their value as game and food species. Most of this book is focused on the Northern Snakehead. Much has been done to document snakehead distributions and certain aspects of snakehead biology, such as diets, age, and growth. Less research has been devoted to understanding the ecological impacts of snakeheads to native aquatic communities and ecosystems. This book would have benefited from a chapter summarizing the current systematics and diversity of the Channidae to inform fisheries biologists about the morphological characteristics of the family, approximate numbers of genera and species, and taxonomic instability. Exemplifying the latter, recent molecular and morphological evidence indicates uncertainty regarding identification of the feral snakehead population in Florida (Adamson and Britz 2019). Those authors suggest that this population may have originated from western Thailand, a possibility that could have implications for understanding historical pathways of snakehead introductions into the USA. In comparison with many published AFS symposia, this volume is relatively narrow in scope and lacks cohesive integration. It will primarily be of interest to those fisheries professionals engaged in the study of snakeheads as well as other nonnative species for which there are contrasting social values regarding their management: whether to monitor and attempt control or eradication efforts or to maintain populations for harvest as game or food species. The book should serve to identify information gaps and guide future research.

Transactions of the American Fisheries Society↗

Biogeochemical aspects of uranium mineralization, mining, milling, and remediation

Natural uranium (U) occurs as a mixture of three radioactive isotopes: 238 U, 235 U, and 234 U. Only 235 U is fissionable and makes up about 0.7% of natural U, while 238 U is overwhelmingly the most abundant at greater than 99% of the total mass of U. Prior to the 1940s, U was predominantly used as a coloring agent, and U-bearing ores were mined mainly for their radium (Ra) and/or vanadium (V) content; the bulk of the U was discarded with the tailings (Finch et al., 1972). Once nuclear fission was discovered, the economic importance of U increased greatly. The mining and milling of U-bearing ores is the first step in the nuclear fuel cycle, and the contact of residual waste with natural water is a potential source of contamination of U and associated elements to the environment. Uranium is mined by three basic methods: surface (open pit), underground, and solution mining (in situ leaching or in situ recovery), depending on the deposit grade, size, location, geology and economic considerations (Abdelouas, 2006). Solid wastes at U mill tailings (UMT) sites can include both standard tailings (i.e., leached ore rock residues) and solids generated on site by waste treatment processes. The latter can include sludge or “mud” from neutralization of acidic mine/mill effluents, containing Fe and a range of coprecipitated constituents, or barium sulfate precipitates that selectively remove Ra (e.g., Carvalho et al., 2007). In this chapter, we review the hydrometallurgical processes by which U is extracted from ore, the biogeochemical processes that can affect the fate and transport of U and associated elements in the environment, and possible remediation strategies for site closure and aquifer restoration. This paper represents the fourth in a series of review papers from the U.S. Geological Survey (USGS) on geochemical aspects of UMT management that span more than three decades. The first paper (Landa, 1980) in this series is a primer on the nature of tailings and radionuclide mobilization from them. The second paper (Landa, 1999) includes coverage of research carried out under the U.S. Department of Energy’s Uranium Mill Tailings Remedial Action Program (UMTRA). The third paper (Landa, 2004) reflects the increased focus of researchers on biotic effects in UMT environs. This paper expands the focus to U mining, milling, and remedial actions, and includes extensive coverage of the increasingly important alkaline in situ recovery and groundwater restoration.

Applied Geochemistry↗

Land use and land cover, 1972-77, Culpeper Basin, Virginia-Maryland

Land use refers to man's activities that relate directly to the land. Lover cover describes the land surface- vegetation, water, naturally- occurring soil and rock, and artificial constructions. In showing land use and land cover in the Culpeper Basin, this map features a consistent level of detail and standardization of categories. The use of the 1:125,000 compilation scale is appropriate, because this type of data is used frequently for different purposes by people representing several disciplines- land use planners, land managers, resource managemnet planners, and others. For example, maps and data similar to this publication have been used for river basin planning, for analysis of land use and land cover changes relative to recreation, for river quality assessment, for preparation of environmental impact statements, and for studies on urbanization. These efforts have been made at the multicounty regional, State, and Federal levels.

Maryland↗

Simultaneous determination of Cr(iii) and Cr(vi) using reversed-phased ion-pairing liquid chromatography with dynamic reaction cell inductively coupled plasma mass spectrometry

A method for the simultaneous determination of Cr(iii) and Cr(vi) species in waters, soil leachates and synthetic bio-fluids is described. The method uses reversed-phase ion-pairing liquid chromatography to separate the chromium species and a dynamic reaction cell (DRC??) equipped ICP-MS for detection of chromium. Separation of the chromium species is carried out in less than 2 min. Cr(iii) is complexed with ethylenediaminetetraacetic acid (EDTA) prior to separation by mixing samples with the mobile phase containing 2.0 mM tetrabutylammonium hydroxide (TBAOH), 0.5 mM EDTA (dipotassium salt), and 5% (vol/vol) methanol, adjusted to pH 7.6. The interfering 40Ar 12C+ background peak at mass 52 was reduced by over four orders of magnitude to less than 200 cps by using 0.65 mL min-1 ammonia as a reaction gas and an RPq setting on the DRC of 0.75. Method detection limits (MDLs) of 0.09 ??g L-1 for Cr(iii) and 0.06 ??g L-1 for Cr(vi) were obtained based on peak areas at mass 52 for 50 ??L injections of low level spikes. Reproducibility at 2 ??g L-1 was 3% RSD for 5 replicate injections. The tolerance of the method to various levels of common cations and anions found in natural waters and to matrix constituents found in soil leachates and simulated gastric and lung fluids was tested by performing spike recovery calculations for a variety of samples. ?? The Royal Society of Chemistry.

Journal of Analytical Atomic Spectrometry↗

Potential sources of analytical bias and error in selected trace element data-quality analyses

Potential sources of analytical bias and error associated with laboratory analyses for selected trace elements where concentrations were greater in filtered samples than in paired unfiltered samples were evaluated by U.S. Geological Survey (USGS) Water Quality Specialists in collaboration with the USGS National Water Quality Laboratory (NWQL) and the Branch of Quality Systems (BQS). Causes for trace-element concentrations in filtered samples to exceed those in associated unfiltered samples have been attributed to variability in analytical measurements, analytical bias, sample contamination either in the field or laboratory, and (or) sample-matrix chemistry. These issues have not only been attributed to data generated by the USGS NWQL but have been observed in data generated by other laboratories. This study continues the evaluation of potential analytical bias and error resulting from matrix chemistry and instrument variability by evaluating the performance of seven selected trace elements in paired filtered and unfiltered surface-water and groundwater samples collected from 23 sampling sites of varying chemistries from six States, matrix spike recoveries, and standard reference materials. Filtered and unfiltered samples have been routinely analyzed on separate inductively coupled plasma-mass spectrometry instruments. Unfiltered samples are treated with hydrochloric acid (HCl) during an in-bottle digestion procedure; filtered samples are not routinely treated with HCl as part of the laboratory analytical procedure. To evaluate the influence of HCl on different sample matrices, an aliquot of the filtered samples was treated with HCl. The addition of HCl did little to differentiate the analytical results between filtered samples treated with HCl from those samples left untreated; however, there was a small, but noticeable, decrease in the number of instances where a particular trace-element concentration was greater in a filtered sample than in the associated unfiltered sample for all trace elements except selenium. Accounting for the small dilution effect (2 percent) from the addition of HCl, as required for the in-bottle digestion procedure for unfiltered samples, may be one step toward decreasing the number of instances where trace-element concentrations are greater in filtered samples than in paired unfiltered samples. The laboratory analyses of arsenic, cadmium, lead, and zinc did not appear to be influenced by instrument biases. These trace elements showed similar results on both instruments used to analyze filtered and unfiltered samples. The results for aluminum and molybdenum tended to be higher on the instrument designated to analyze unfiltered samples; the results for selenium tended to be lower. The matrices used to prepare calibration standards were different for the two instruments. The instrument designated for the analysis of unfiltered samples was calibrated using standards prepared in a nitric:hydrochloric acid (HNO 3 :HCl) matrix. The instrument designated for the analysis of filtered samples was calibrated using standards prepared in a matrix acidified only with HNO 3 . Matrix chemistry may have influenced the responses of aluminum, molybdenum, and selenium on the two instruments. The best analytical practice is to calibrate instruments using calibration standards prepared in matrices that reasonably match those of the samples being analyzed. Filtered and unfiltered samples were spiked over a range of trace-element concentrations from less than 1 to 58 times ambient concentrations. The greater the magnitude of the trace-element spike concentration relative to the ambient concentration, the greater the likelihood spike recoveries will be within data control guidelines (80–120 percent). Greater variability in spike recoveries occurred when trace elements were spiked at concentrations less than 10 times the ambient concentration. Spike recoveries that were considerably lower than 90 percent often were associated with spiked concentrations substantially lower than what was present in the ambient sample. Because the main purpose of spiking natural water samples with known quantities of a particular analyte is to assess possible matrix effects on analytical results, the results of this study stress the importance of spiking samples at concentrations that are reasonably close to what is expected but sufficiently high to exceed analytical variability. Generally, differences in spike recovery results between paired filtered and unfiltered samples were minimal when samples were analyzed on the same instrument. Analytical results for trace-element concentrations in ambient filtered and unfiltered samples greater than 10 and 40 μg/L, respectively, were within the data-quality objective for precision of ±25 percent. Ambient trace-element concentrations in filtered samples greater than the long-term method detection limits but less than 10 μg/L failed to meet the data-quality objective for precision for at least one trace element in about 54 percent of the samples. Similarly, trace-element concentrations in unfiltered samples greater than the long-term method detection limits but less than 40 μg/L failed to meet this data-quality objective for at least one trace-element analysis in about 58 percent of the samples. Although, aluminum and zinc were particularly problematic, limited re-analyses of filtered and unfiltered samples appeared to improve otherwise failed analytical precision. The evaluation of analytical bias using standard reference materials indicate a slight low bias for results for arsenic, cadmium, selenium, and zinc. Aluminum and molybdenum show signs of high bias. There was no observed bias, as determined using the standard reference materials, during the analysis of lead.

Scientific Investigations Report↗

Culturing Selenastrum capricornutum (Chlorophyta) in a synthetic algal nutrient medium with defined mineral particulates

Algal nutrient studies in chemically-defined media typically employ a synthetic chelator to prevent iron hydroxide precipitation. Micronutrient-particulate interactions may, however, significantly affect chemical speciation and hence biovailability of these nutrients in natural waters. A technique is described by which Selenastrum capricornutum Printz (Chlorophyta) may be cultured in a medium where trace metal speciation (except iron) is controlled, not by organic chelation, but by sorption onto titanium dioxide. Application of this culturing protocol in conjunction with results from sorption studies of nutrient ions on mineral particles provides a means of studying biological impacts of sorptive processes in aquatic environments.

Hydrobiologia↗

Uptake of methoxychlor from food and water by the American toad (Bufo americanus)

Various studies (Mulla et al. 1963; Ferguson and Gilbert 1967; Cooke 1973) have examined the effects of pesticides on anuran amphibians, but the routes of contaminant uptake by transformed amphibians have not been evaluated. The need of frogs and toads to imbibe water from natural surface water would seem to make them vulnerable to uptake from this source. Fish are known to accumulate pesticides from both food and water (Jarvinen et al. 1977). Toads are more terrestrial and tend to lose water less readily than most other amphibians (Thorson and Svihla 1943); hence they should he a conservative estimator of the potential for uptake of pesticides from water. Methoxychlor is an analogue of DDT and has been widely used to replace it. It is a good model of many pesticides in current use in its low persistence in animal tissues (Gardner and Bailey 1975), and its long half life in water (Wolfe et al. 1977). It is also suitable for study because of its relatively low toxicity to amphibians (Kaplan and Overpeck 1964) and its easily detected residues. In the present study we measured the accumulation of methoxychlor from food and water in a preliminary evaluation of the two routes of exposure.

Bulletin of Environmental Contamination and Toxico↗

Deep geothermal brine near Salton Sea, California

A well drilled for geothermal power near Salton Sea in Imperial Valley, Calif., is 5,232 feet deep; it is the deepest well in the world (1962) in a high-temperature hot spring area. In the lower half of the hole temperatures are too high to measure with available equipment, but are at loast 270°C, and may be as much as 370°C. For comparison, maximum temperature heretofore reported at depth (1962) for hot spring areas is 295°C. The well taps a very saline brine of Na-Ca-K-Cl type (about 185,000 ppm Cl) with exceptionally high potassium, and with the highest content of minor alkali elements known for natural waters; Fe, Mn, Zn, Pb, Cu, Ag, and some other metals are also exceptionally high. This brine may be connate, but present evidence favors a source in the magma chamber at depth that supplied late Quaternary rhyolite domes of the area. If the latter is correct, the brine is an undiluted magmatic water that is residual from the separation of a more volatile phase high in CO 2 , H 2 S, and with some alkali halides. Elsewhere, the hypothesized volatile phase may account for near-surface hot spring activity of most thermal areas of volcanic association. The residual brine of high salinity may ordinarily remain relatively deep in the volcanic systems because of high specific gravity and low content of volatiles, seldom appearing at the surface except in a greatly diluted form. The hot springs of Arima, Japan, may be a rare example of this type of magmatic water discharging at the surface in moderate concentration (Cl as much as 42,000 ppm). Independent evidence from fluid inclusions in minerals of high-temperature base-metal deposits also favors the existence of magmatic water high in Na, Ca, and Cl, and low in CO 2 and other volatile components. During a three-month production test several tons of material precipitated in the horizontal discharge pipe from the well. Amorphous silica with iron and manganese, and bornite are the dominant recognized components. This material contains the astonishingly high contents of about 20 percent copper, 2 percent silver, and notable sulfur, arsenic, bismuth, lead, antimony, and some other minor elements. Total quantities of all elements in the original whole brine are not yet known, but calculated amounts corresponding to 1 to 3 ppm of copper and 0.1 to 0.3 ppm of silver were precipitated from the brine to form the pipe deposits. The brine, therefore, may be man’s first sample of an « active » ore solution. Equally fascinating to many geologists is the possibility that in the lower part of the hole temperatures are so high and pressures are sufficient for young sedimentary rocks to be undergoing transformation into rocks with mineral assemblages of the greenschist facies of metamorphism. Drill cores from 4,400 to 5,000 feet in depth contain chlorite, albite, K-feldspar, epidote, mica, and quartz, with some indication of increase in metamorphic grade downward. Regional geological and geophysical studies favor a depth of about 20,000 feet to pre-Tertiary basement rocks in the general area. A shallow basement or local upfaulting of old metamorphic rocks are not likely possibilities for the thermal area.

California↗

The next decade in geochemistry

The purpose, associations, functions; and activities of the Geochmical Society are reviewed briefly. Work on the Colorado Plateau uranium deposits is described as an example of what geochemical research, in conjunction with detailed field work, mineralogical studies, and related techniques can contribute to the understanding of a type of deposit. It is pointed out that not only have these studies given a great deal of information about the origin of the ores, but they have brought about directly a manifold increase in production and reserves of uranium in the United States. Indirectly, they aided the discovery of the tremendous deposits of the Blind River area in Ontario. It is suggested that similar broad cooperative attacks could not only yield comparable results with other types of mineral deposits, such as laterites and Mississippi Valley type lead-zinc deposits, but could also advance our knowledge and understanding of such diverse problems of geology and cosmology as the origin of granites, origin and geologic implications of meteorites (including tektites), origin and search for petroleum, and geochemical relations and interpretations of natural waters. For each of these problems methods of approach are outlined and for some of them, specific projects and correlative problems are mentioned. It is further suggested that the broad cooperative attack needed for most of these problems might be fostered most effectively by a programme comparable to that of the I.G.Y., even though for most types of geochemical research synoptic sampling and observations are not as important as they are for many projects in geophysics.

Geochimica et Cosmochimica Acta↗

Complexation of trace metals by adsorbed natural organic matter

The adsorption behavior and solution speciation of Cu(II) and Cd(II) were studied in model systems containing colloidal alumina particles and dissolved natural organic matter. At equilibrium a significant fraction of the alumina surface was covered by adsorbed organic matter. Cu(II) was partitioned primarily between the surface-bound organic matter and dissolved Cu-organic complexes in the aqueous phase. Complexation of Cu2+ with the functional groups of adsorbed organic matter was stronger than complexation with uncovered alumina surface hydroxyls. It is shown that the complexation of Cu(II) by adsorbed organic matter can be described by an apparent stability constant approximately equal to the value found for solution phase equilibria. In contrast, Cd(II) adsorption was not significantly affected by the presence of organic matter at the surface, due to weak complex formation with the organic ligands. The results demonstrate that general models of trace element partitioning in natural waters must consider the presence of adsorbed organic matter.

Geochimica et Cosmochimica Acta↗

Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C

Dissolution of synthetic strontianite-aragonite solid solutions was followed analytically to stoichiometric saturation using large solid to solution ratios in CO 2 -H 2 O solution at 25 and 76°C. The compositional dependence of the equilibrium constant was calculated from the composition of saturated (stoichiometric) solutions and used to calculate the activities and activity coefficients of CaCO 3 and SrCO 3 in the solid Ca (1− x ) Sr x CO 3 at 25 and 76°C. The results show that the solid-solution is not regular but unsymmetrical. The excess free energy of mixing is closely modeled for all compositions by the relation where A 0 is 8.49 ± 0.30 and 7.71 ± 0.20 KJ/mole and A 1 is −4.51 ± 0.20 and −3.36 ± 0.40 KJ/mole at 25 and 76°C, respectively. The equilibrium constant is denned as a function of the SrCO 3 mole fraction, x , by the relation where R is the gas constant, T is in Kelvins and K A and K S are the aragonite and strontianite equilibrium constants. The experimental results indicate the Henry's law coefficients of SrCO 3 in aragonites containing 0 to 6 mole percent SrCO 3 are approximately 91± 8 and 23 ± 1 at 25 and 76°C, respectively and for strontianites the Henry's law coefficients and applicable compositional ranges are approximately 7.3 ± 0.3 (0.84 ≤ x ≤ 1.00) and 3.3 ± 0.5 (0.50 ≤ x ≤ 1.00) at 25 and 76°C, respectively. Substitution of small amounts of Sr in aragonite and Ca in strontianite initially increases the stability of the solid. The most stable aragonites and strontianites contain 0.58 ± 0.03 and 12.5 ± 1.1 mole percent SrCO 3 and CaCO 3 at 25°C and 3.1 ± 0.3 and 17.2 ± 1.1 mole percent SrCO 3 and CaCO 3 at 76°C, respectively. The spinode occurs over the regions 0.065 ± 0.001 ≤ x ≤ 0.620 ± 0.014 at 25°C and 0.103 ± 0.007 ≤ x ≤ 0.585 ± 0.019 at 76°C where all compositions are unstable. A miscibility gap occurs over the compositional ranges 0.0058 ± 0.0003 ≤ x ≤ 0.875 ± 0.011 at 25°C and 0.031 ± 0.003 ≤ x ≤ 0.828 ± 0.011 at 76°C and is in reasonable agreement with reported compositions of natural aragonites and strontianites. Marine aragonites are neither at equilibrium nor stoichiometric saturation with surface seawater. The experimentally observed distribution coefficient of Sr in aragonite is 12 times larger than the calculated equilibrium value (0.095) at 25°C. Naturally occurring strontianites contain large amounts of calcium primarily because Ca/Sr ratios in natural waters are typically large. Neither equilibrium nor stoichiometric saturation is observed at 76°C during laboratory recrystallization of strontianite-aragonite solid solutions even after apparent 100 percent conversion to a narrow secondary composition and demonstration of a nearly constant composition system for periods of 300 hours.

Geochimica et Cosmochimica Acta↗

Surface chemistry of ferrihydrite: Part 2. Kinetics of arsenate adsorption and coprecipitation

The kinetics of As(V) adsorption by ferrihydrite was investigated in coprecipitation and postsynthesis adsorption experiments conducted in the pH range 7.5-9.0. In coprecipitation experiments, As(V) was present in solution during the hydrolysis and precipitation of iron. In adsorption experiments, a period of rapid (<5 min) As(V) uptake from solution was followed by continued uptake for at least eight days, as As(V) diffused to adsorption sites on ferrihydrite surfaces within aggregates of colloidal particles. The time dependence of As(V) adsorption is well described by a general model for diffusion into a sphere if a subset of surface sites located near the exterior of aggregates is assumed to attain adsorptive equilibrium rapidly. The kinetics of As(V) desorption after an increase in pH were also consistent with diffusion as a rate-limiting process. Aging of pure ferrihydrite prior to As(V) adsorption caused a decrease in adsorption sites on the precipitate owing to crystallite growth. In coprecipitation experiments, the initial As(V) uptake was significantly greater than in post-synthesis adsorption experiments, and the rate of uptake was not diffusion limited because As(V) was coordinated by surface sites before crystallite growth and coagulation processes could proceed. After the initial adsorption, As(V) was slowly released from coprecipitates for at least one month, as crystallite growth caused desorption of As(V). Adsorption densities as high as 0.7 mole As(V) per mole of Fe were measured in coprecipitates, in comparison to 0.25 mole As(V) per mole of Fe in post-synthesis adsorption experiments. Despite the high Concentration of As(V) in the precipitates, EXAFS spectroscopy (Waychunas et al., 1993) showed that neither ferric arsenate nor any other As-bearing surface precipitate or solid solution was formed. The high adsorption densities are possible because the ferrihydrite particles are extremely small, approaching the size of small dioctahedral chains at the highest As(V) adsorption density. The results suggest that the solid solution model proposed by Fox (1989, 1992) for control of arsenate and phosphate concentrations in natural waters may be invalid.

Geochimica et Cosmochimica Acta↗

Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite

Although solid solutions play important roles in controlling the concentrations of minor metal ions in natural waters, uncertainties regarding their compositions, thermodynamics, and kinetics usually prevent them from being considered. A range of precipitation rates was used here to study the nonequilibrium and equilibrium partitioning behaviors of Sr2+, Ba2+, and Cd2+ to calcite (CaCO3(s)). The distribution coefficient of a divalent metal ion Me2+ for partitioning from an aqueous solution into calcite is given by DMe = (XMeCO3(s)/[Me2+])/(XCaCO3(s)/[Ca 2+]). The X values are solid-phase mole fractions; the bracketed values are the aqueous molal concentrations. In agreement with prior work, at intermediate to high precipitation rates R (nmol/mg-min), DSr, DBa, and DCd were found to depend strongly on R. At low R, the values of DSr, DBa, and DCd became constant with R. At 25??C, the equilibrium values for DSr, DBa, and DCd for dilute solid solutions were estimated to be 0.021 ?? 0.003, 0.012 ?? 0.005, and 1240 ?? 300, respectively. Calculations using these values were made to illustrate the likely importance of partitioning of these ions to calcite in groundwater systems. Due to its large equilibrium DMe value, movement of Cd2+ will be strongly retarded in aquifers containing calcite; Sr2+ and Ba2+ will not be retarded nearly as much.

Geochimica et Cosmochimica Acta↗

Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

Molybdenum K-edge EXAFS (extended X-ray absorption fine structure) spectra yield new structural information about the chemical environment of Mo in high-Mo black shales and sediments. Two spectral types are found. The less common one, associated with Mo ores developed in shale in China, is that of a MoS2 phase, possibly X-ray amorphous jordisite. The other, associated with Cretaceous deep sea sediments and with other black shales, is characterized by short Mo-O distances (1.69-1.71 A??), by Mo-S distances of 2.30-2.38 A??, and in some cases by second shell Mo and Fe interactions, which suggests that some Mo resides in transition metal-rich phases. EXAFS spectra of synthetic amorphous materials, prepared by scavenging Mo from HS solutions with Fe(II), FeOOH, and humic acid, suggest that the second spectral type arises from Mo present chiefly in two forms. One is a compact, Mo-Fe-S "cubane" type compound with Mo-S distances of ???2.36 A?? and Mo-Fe distances of ???2.66 A??, while the other is probably an organic form containing some Mo-O double bonds (???1.69 A??). Laboratory products, that were prepared by scavenging dissolved Mo from sulfidic solutions with humic acid, yield spectra quite similar to the second spectral type observed in shales and sediments, including unexpected indications of Mo-Fe interactions. Molybdenum L-edge spectra indicate that the mean oxidation state in the sediments and shales lies between IV and VI. This work demonstrates the merit of EXAFS for obtaining structural information on natural materials containing X-ray amorphous components which defeat conventional mineralogical characterization. The implications of these findings regarding Mo scavenging from sulfidic natural waters are considered. We introduce the concept of a geochemical switch, in which HS- transforms the marine behavior of Mo from that of a conservative element to that of a particle reactive element. The action point of the HS- switch is calculated to be, aHS- = 10-3.6 - 10-4.3. When aHS- approaches the action point, Mo becomes reactive to particles containing transition metals (e.g., Fe). We conjecture that thiols, including humic-bound thiol groups, also switch Mo behavior. In contrast to previous ideas, our model for Mo scavenging deemphasizes the role of reduction from Mo(VI) to Mo(V) as the initial step in scavenging; instead, we emphasize the ease with which Mo forms covalent bonds to transition metals and organic molecules via S bridges.

Geochimica et Cosmochimica Acta↗

Bromine incorporation factors for trihalomethane formation for the Mississippi, Missouri, and Ohio Rivers

The bromine incorporation factor describes the distribution of the four trihalomethane compounds in the mixture formed when a natural water is chlorinated. This factor was determined for the Mississippi, Missouri, and Ohio Rivers by chlorinating water samples at three levels each of pH and free chlorine concentration. Samples were collected during the summer, fall, and spring seasons of the year at 12 sites on the Mississippi River from Minneapolis, MN, to New Orleans, LA, and on the Missouri and Ohio Rivers 1.6 kilometers upstream from their confluences with the Mississippi. The bromine incorporation factor increased as the bromide concentration increased, and decreased as the pH, initial free-chlorine and dissolved organic-carbon concentrations increased. Variation of the bromine incorporation factor with distance along the Mississippi River approximately paralleled the variation of the bromide concentration with distance along the river, with the Missouri River samples having the highest bromine incorporation factors for all combinations of pH and free-chlorine concentration.

Science of the Total Environment↗

A study of metal ion adsorption at low suspended-solid concentrations

A procedure for conducting adsorption studies at low suspended solid concentrations in natural waters (<50 mg l −1 ) is described. Methodological complications previously associated with such experiments have been overcome. Adsorption of zinc ion onto synthetic colloidal titania (TiO 2 ) was studied as a function of pH, supporting electrolyte (NaCl) concentration (0·1-0·002 m ) and particle concentration (2–50 mg l −1 ). The lack of success of the Davis Leckie site bonding model in describing Zn(II) adsorption emphasizes the need for further studies of adsorption at low suspended-solid concentrations.

Estuarine, Coastal and Shelf Science↗