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At least 73 records · Page 4Linked to original sources

Indirect spectrophotometric determination of traces of bromide in water

A rapid, accurate, and sensitive indirect spectrophotometric method for the determination of bromide in natural waters is based on the catalytic effect of bromide on the oxidation of iodine to iodate by potassium permanganate in sulfuric acid solution. The method is applicable to concentrations ranging from 1 to 100 μ g. of bromide per liter, but may be modified to extend the concentration range. Most ions commonly occurring in water do not interfere. The standard deviation is 2.9 at bromide concentrations of 100 μ g. per liter and less at lower concentrations. The determination of bromide in samples containing known added amounts gave values ranging from 99 to 105% of the concentration calculated to be present.

Analytical Chemistry↗

The 25 October 2010 Mentawai tsunami earthquake, from real-time discriminants, finite-fault rupture, and tsunami excitation

The moment magnitude 7.8 earthquake that struck offshore the Mentawai islands in western Indonesia on 25 October 2010 created a locally large tsunami that caused more than 400 human causalities. We identify this earthquake as a rare slow‐source tsunami earthquake based on: 1) disproportionately large tsunami waves; 2) excessive rupture duration near 125 s; 3) predominantly shallow, near‐trench slip determined through finite‐fault modeling; and 4) deficiencies in energy‐to‐moment and energy‐to‐duration‐cubed ratios, the latter in near‐real time. We detail the real‐time solutions that identified the slow‐nature of this event, and evaluate how regional reductions in crustal rigidity along the shallow trench as determined by reduced rupture velocity contributed to increased slip, causing the 5–9 m local tsunami runup and observed transoceanic wave heights observed 1600 km to the southeast.

Mentawai Islands↗

Bait preference by the Argentine ant (Hymenoptera: Formicidae) in Haleakala National Park, Hawaii

The Argentine ant, Linepithema humile (Mayr), has proven to be a threat to native arthropod species in Haleakala National Park, Maui, HI, and is also a potential threat to the park's native flora. As it continues to expand its range, an effort has been undertaken to eradicate it, or at the least, control its spread. The 1st part of this effort focused on finding a bait carrier for subsequent toxicant-based control tests. A year-long bait preference test was implemented at each of the ant's 2 infestation sites in Haleakala National Park, in which 6 solid baits and 2 liquid baits were assessed for attractiveness and feasibility for large scale control. At both sites, a toxicant-free formulation of Maxforce, a protein-based granular bait made from ground silkworm, Bombyx mori (L.), pupae, and a 25% sugar water solution were the most attractive baits. Ants took more Maxforce (without toxicant) and sugar water than all other baits, including honey granules and a fish protein bait. Sugar water, however, is difficult to distribute over large natural areas. Maxforce was therefore concluded to be the best bait carrier for toxicant-based control at Haleakala National Park because of its attractiveness and its ease for large scale broadcast dispersal.

Hawaii↗

Molybdenum isotope fractionation during adsorption to organic matter

Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2–170 h) and pH (2–7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ 98 Mo solution-IHA ) was 1.39‰ (± 0.16‰, 2σ, based on 98 Mo/ 95 Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ 98 Mo solution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

Geochimica et Cosmochimica Acta↗

Effects of karst and geologic structure on the circulation of water and permeability in carbonate aquifers

The results of the natural processes caused by solution and leaching of limestone, dolomite, gypsum, salt and other soluble rocks, is known as karst. Development of karst is commonly known as karstification, which may have a pronounced effect on the topography, hydrology and environment, especially where such karst features as sinkholes and vertical solution shafts extend below the land surface and intersect lateral solution passages, cavities, caverns and other karst features in carbonate rocks. Karst features may be divided into two groups: (1) surficial features that do not extend far below the surface; and (2) karst features such as sinkholes that extend below the surface and affect the circulation of water below. The permeability of the most productive carbonate aquifers is due chiefly to enlargement of fractures and other openings by circulation of water. Important controlling factors responsible for the development of karst and permeability in carbonate aquifers include: (1) climate, topography, and presence of soluble rocks; (2) geologic structure; (3) nature of underground circulation; and (4) base level. Another important factor is the condition of the surface of the carbonate rocks at the time they are exposed to meteoric water. A carbonate rock surface, with soil or relatively permeable, less soluble cover, is more favorable for initiation of karstification and solution than bare rocks. Water percolates downward through the cover to the underlying carbonate rocks instead of running off on the surface. Also, the water becomes more corrosive as it percolates through the permeable cover to the underlying carbonate rocks. Where there is no cover or the cover has been removed, the carbonate rocks become case hardened and resistant to erosion. However, in regions underlain not only by carbonate rocks but also by beds of anhydrite, gypsum and salt, such as the Hueco Plateau in southeastern New Mexico, subsurface solution may occur where water without natural acids moves down from bare rock surfaces through cracks to the beds that are more soluble than carbonate rocks. For example, in the area of Carlsbad Caverns in southeastern New Mexico, much of the water responsible for solution that formed the caverns apparently entered the groundwater system through large open fractures and did not form sinkhole topography. East of the Carlsbad Caverns, however, in the Pecos River Valley where the carbonate rocks are overlain by the less soluble Ogallala Formation of Late Tertiary age, solution began along escarpments as the Pecos River and its tributaries cut through the less soluble cover. As these escarpments retreated, sinkholes and other karst features developed. Joints or fractures are essential for initiation of downward percolation of water in compact carbonate rocks such as some Paleozoic limestone in which there is no intergranular permeability. Also joints or fractures and bedding planes may be essential in the initiation of lateral movement of water in the zone of saturation. Where conditions of recharge and discharge are favorable, groundwater may move parallel to the dip. However, the direction of movement of water in most carbonate rocks is not necessarily down dip or parallel to the dip. The general direction of movement of both surface and groundwater may be parallel to the strike in a breached anticline. Faults may restrict the lateral movement of water, especially if water-bearing beds are faulted against relatively impervious beds. Conversely, some fault may serve as avenues through which water may move as, for example, in the Cretaceous Edwards aquifer in the San Antonio area, Texas. Karst aquifers, chiefly carbonate rocks, may be placed in three groups according to water-bearing capacity. Water in aquifers of group 1 occurs chiefly in joints, fractures, and other openings that have not been enlarged by solution. The yield of wells is small. Aquifers in group 2 , with low to intermediate yields, are those in which water occurs in joints and fractures with some cavities and channels enlarged by solution. Aquifers in group 3 are those in which the yield of wells and springs range from intermediate to very large. This group includes five of the most productive aquifers in the U.S.A. The water-bearing beds of all of these productive aquifers, except the Biscayne aquifer in southeastern Florida, contain buried paleokarst in which the permeability has been reactivated and enlarged by the present circulation system.

Journal of Hydrology↗

Constraints on the Pleistocene chronology of sediments from the Lomonosov Ridge

Despite its importance in the global climate system, age-calibrated marine geologic records reflecting the evolultion of glacial cycles through the Pleistocene are largely absent from the central Arctic Ocean. This is especially true for sediments older than 200 ka. Three sites cored during the Integrated Ocean Drilling Program's Expedition 302, the Arctic Coring Expedition (ACEX), provide a 27 m continuous sedimentary section from the Lomonosov Ridge in the central Arctic Ocean. Two key biostratigraphic datums and constraints from the magnetic inclination data are used to anchor the chronology of these sediments back to the base of the Cobb Mountain subchron (1215 ka). Beyond 1215 ka, two best fitting geomagnetic models are used to investigate the nature of cyclostratigraphic change. Within this chronology we show that bulk and mineral magnetic properties of the sediments vary on predicted Milankovitch frequencies. These cyclic variations record "glacial" and "interglacial" modes of sediment deposition on the Lomonosov Ridge as evident in studies of ice-rafted debris and stable isotopic and faunal assemblages for the last two glacial cycles and were used to tune the age model. Potential errors, which largely arise from uncertainties in the nature of downhole paleomagnetic variability, and the choice of a tuning target are handled by defining an error envelope that is based on the best fitting cyclostratigraphic and geomagnetic solutions. Copyright 2008 by the American Geophysical Union.

Paleoceanography↗

Hydrogeomorphology of the hyporheic zone: stream solute and fine particle interactions with a dynamic streambed

Hyporheic flow in streams has typically been studied separately from geomorphic processes. We investigated interactions between bed mobility and dynamic hyporheic storage of solutes and fine particles in a sand-bed stream before, during, and after a flood. A conservatively transported solute tracer (bromide) and a fine particles tracer (5 μm latex particles), a surrogate for fine particulate organic matter, were co-injected during base flow. The tracers were differentially stored, with fine particles penetrating more shallowly in hyporheic flow and retained more efficiently due to the high rate of particle filtration in bed sediment compared to solute. Tracer injections lasted 3.5 h after which we released a small flood from an upstream dam one hour later. Due to shallower storage in the bed, fine particles were rapidly entrained during the rising limb of the flood hydrograph. Rather than being flushed by the flood, we observed that solutes were stored longer due to expansion of hyporheic flow paths beneath the temporarily enlarged bedforms. Three important timescales determined the fate of solutes and fine particles: (1) flood duration, (2) relaxation time of flood-enlarged bedforms back to base flow dimensions, and (3) resulting adjustments and lag times of hyporheic flow. Recurrent transitions between these timescales explain why we observed a peak accumulation of natural particulate organic matter between 2 and 4 cm deep in the bed, i.e., below the scour layer of mobile bedforms but above the maximum depth of particle filtration in hyporheic flow paths. Thus, physical interactions between bed mobility and hyporheic transport influence how organic matter is stored in the bed and how long it is retained, which affects decomposition rate and metabolism of this southeastern Coastal Plain stream. In summary we found that dynamic interactions between hyporheic flow, bed mobility, and flow variation had strong but differential influences on base flow retention and flood mobilization of solutes and fine particulates. These hydrogeomorphic relationships have implications for microbial respiration of organic matter, carbon and nutrient cycling, and fate of contaminants in streams.

Journal of Geophysical Research: Biogeosciences↗

Simulation of less‐mobile porosity dynamics in contrasting sediment water interface porous media

Considering heterogeneity in porous media pore size and connectivity is essential to predicting reactive solute transport across interfaces. However, exchange with less‐mobile porosity is rarely considered in surface water/groundwater recharge studies. Previous research indicates that a combination of pore‐fluid sampling and geoelectrical measurements can be used to quantify less‐mobile porosity exchange dynamics using the time‐varying relation between fluid and bulk electrical conductivity. For this study, we use macro‐scale (10 s of cm) advection–dispersion solute transport models linked with electrical conduction in COMSOL Multiphysics to explore less‐mobile porosity dynamics in two different types of observed sediment water interface porous media. Modeled sediment textures contrast from strongly layered streambed deposits to poorly sorted lakebed sands and cobbles. During simulated ionic tracer perturbations, a lag between fluid and bulk electrical conductivity, and the resultant hysteresis, is observed for all simulations indicating differential loading of pore spaces with tracer. Less‐mobile exchange parameters are determined graphically from these tracer time series data without the need for inverse numerical model simulation. In both sediment types, effective less‐mobile porosity exchange parameters are variable in response to changes in flow direction and fluid flux. These observed flow‐dependent effects directly impact local less‐mobile residence times and associated contact time for biogeochemical reaction. The simulations indicate that for the sediment textures explored here, less‐mobile porosity exchange is dominated by variable rates of advection through the domain, rather than diffusion of solute, for typical low‐to‐moderate rate (approximately 3–40 cm/day) hyporheic fluid fluxes. Overall, our model‐based results show that less‐mobile porosity may be expected in a range of natural hyporheic sediments and that changes in flowpath orientation and magnitude will impact less‐mobile exchange parameters. These temporal dynamics can be assessed with the geoelectrical experimental tracer method applied at laboratory and field scales.

Hydrological Processes↗

Radioactive disequilibria in mineralised fracture samples from two uranium occurrences in northern Sweden

Mineralised fractures from two uranium occurrences in northern Sweden were examined mineralogically and isotopically to establish the presence or absence of radioactive equilibrium that may indicate recent rock-water interaction processes based on the natural mobility of uranium (i.e.; during the last 0.5 Ma). The results show evidence of radioactive disequilibrium in six of the nine samples investigated. Disequilibria are attributable to solution to solid 234U recoil gain (weakly mineralised zones adjacent to the main mineralisation) and solid to solution 234U recoil loss (moderate to highly mineralised zones). The absence of significant 238U loss in the samples emphasises the reducing conditions at the sampled depths. ?? 1984.

LITHOS↗

Weathering rates as a function of flow through an alpine soil

The effect of flow on release rates of solutes from soil in a 39-m2 alpine catchment in the Colorado Rockies was measured during the summers of 1990-1994. Flow rates through the soil were varied by augmenting natural rainfall with deionized irrigation water. Daily water inputs averaged between 96 and 216 1 day-1 during the five field seasons, and mean discharge (inputs minus evapotranspiration) varied from 35 to 175 1 day-1. Volume-weighted mean concentrations of base cations and silica decreased only moderately in response to the increased water inputs. Input fluxes of solutes in precipitation were similar in each of the study seasons, but output fluxes of base cations and silica in surface outflow increased substantially in conjunction with the average water input rate for the season. Weathering rates calculated from the chemical fluxes increased substantially in response to increases in water input rates. The increases appear to be largely attributable to enhanced transport of solutes from the soil matrix under high flow conditions. At high flow, physical flushing of micropores presumably occurs to a greater extent than during low-flow periods because of greater soil wetness and higher hydrologic head. Increased flushing would also cause an increased rate of diffusion of solutes from microcracks in mineral surfaces and constricted pore spaces in response to an increased concentration gradient between those regions and adjacent areas in the soil matrix. Another consequence of the increased flushing that occurs during periods of high flow is that concentrations throughout the soil matrix tend to be lower, which might increase chemical weathering rates of some silicate minerals such as microcline, which are relatively close to saturation. Decreased Si concentrations under high-flow conditions appear to promote dissolution of amorphous aluminosilicates or desorption of Si from mineral surfaces, buffering Si concentrations in the soil solutions. Thus, both physical transport of solutes and subsequent chemical effects appear to be responsible for the positive relation observed between fluxes of weathering products and water input rates.

Chemical Geology↗

Arsenic in groundwater in the North Carolina Eastern slate belt (Esb): Nash and halifax counties, north carolina

Naturally occurring arsenic-contaminated groundwater is present within the Eastern Slate Belt (ESB) of North Carolina. Long-term, integrated geologic and geo-chemical investigations havedetermined the presence of arsenic by analyzing precipitates from first and second order streams under base flow conditions. When groundwater discharges into streams, arsenic and other metals are precipitated from solution, due to redox changes between the subsurface and surface environments. Analyses (As, base metals, Fe and Mn) were determined following chemical extraction ofnaturally occurring manganese-iron oxide-coatings, which had precipitated from solution onto stream-bed cobbles. Additionally, artificial redox fronts were produced by placing ceramic tilesin streambeds to collect and analyze oxide precipitates. Thermochemical plots from these data, as well as information from respective stream water measurements (pH and Eh), water sampling, and rock chemical analyses indicate mobile arsenic in predicted stability fields. Initial results show that naturally occurring arsenic-contaminated groundwater is present within the study area. However, the resulting oxidation and pre-cipitation within streams appreciably removes thiscontaminant from surface water solution.

North Carolina↗

Drawdown and stream depletion produced by pumping in the vicinity of a partially penetrating stream

Commonly used analytical approaches for estimation of pumping-induced drawdown and stream depletion are based on a series of idealistic assumptions about the stream-aquifer system. A new solution has been developed for estimation of drawdown and stream depletion under conditions that are more representative of those in natural systems (finite width stream of shallow penetration adjoining an aquifer of limited lateral extent). This solution shows that the conventional assumption of a fully penetrating stream will lead to a significant overestimation of stream depletion (> 100 %) in many practical applications. The degree of overestimation will depend on the value of the stream leakance parameter and the distance from the pumping well to the stream. Although leakance will increase with stream width, a very wide stream will not necessarily be well represented by a model of a fully penetrating stream. The impact of lateral boundaries depends upon the distance from the pumping well to the stream and the stream leakance parameter. In most cases, aquifer width must be on the order of hundreds of stream widths before the assumption of a laterally infinite aquifer is appropriate for stream-depletion calculations. An important assumption underlying this solution is that stream-channel penetration is negligible relative to aquifer thickness. However, an approximate extension to the case of nonnegligible penetration provides reasonable results for the range of relative penetrations found in most natural systems (up to 85%). Since this solution allows consideration of a much wider range of conditions than existing analytical approaches, it could prove to be a valuable new tool for water management design and water rights adjudication purposes.

Ground Water↗

Salinity and total dissolved solids measurements for natural waters: An overview and a new salinity method based on specific conductance and water type

The total concentration of dissolved constituents in water is routinely quantified by measurements of salinity or total dissolved solids (TDS). However, salinity and TDS are operationally defined by their analytical methods and are not equivalent for most waters. Furthermore, multiple methods are available to determine salinity and TDS, and these methods have inherent differences. TDS is defined as the mass of anhydrous residue remaining in a sample vessel after evaporation and subsequent oven drying at a defined temperature. Salinity is a measure of the mass of dissolved salts in a given mass of solution. In addition, there are approaches that quantify the total solute (TS) concentration, including gases. The purpose of this study is to develop a proxy method using specific conductance and major-ion water type to reliably predict salinity, TDS, and/or TS. Thus, we compared several methods to calculate salinity, TDS, and TS for 6391 surface water samples and conclude the following: TDS measurements are best suited for studies of anhydrous residue (e.g., evaporites); salinity determined by summing the speciated ion concentrations, termed S ∑spec , is the most comprehensive method to represent the concentration of dissolved constituents in natural waters; and TS determinations are useful if dissolved CO 2 and other gases are of interest. Thus, we utilized S ∑spec to compare differences between the various salinity, TDS, and TS methods, and to develop a new proxy method to predict salinity based on specific conductance (SC) and major ion water type, termed S SC_WT . For the surface waters used in this study, the median difference between TDS and S ∑Spec was between −19% and −24%, depending on the method. The median difference between S SC_WT and S ∑Spec was −2.4% for the samples in this study. The S SC_WT approach is cost effective, rapid, and capable of providing reliable real-time salinity determinations at surface water sites where SC data are available and water type is known.

Applied Geochemistry↗

Reactive solute-transport simulation of pre-mining metal concentrations in mine-impacted catchments: Redwell Basin, Colorado, USA

With the increased importance of water resources in the western United States and many areas worldwide, the remediation of impacts from historical mining becomes ever more important. A possible process of making decisions about remediation for a catchment might include identification of principal sources of metals in the catchment, classification of the sources as natural or anthropogenic, and simulations to evaluate different options for removal of anthropogenic sources. The application of this process is based on understanding the pre-mining conditions in the catchment, so that remediation goals appropriately correct for the impacts of mining. A field experiment in Redwell Basin, Colorado, provided a setting to demonstrate this process and to evaluate pre-mining concentrations through reactive solute-transport modeling. The field experiment provided spatially detailed stream and inflow samples that were the basis for model calibration. Only two inflows along the study reach were affected by mining or mine exploration. To simulate pre-mining conditions, these inflows were removed from the model calibration; the result was a simulation of the stream with all the non-mining inputs. At a point downstream from the two mining inflows, the simulated pre-mining pH would have been 5.1, up from the measured 3.8. At the higher pH, the streambed likely would have been coated with Al precipitate. Simulated pre-mining Zn and Cu would have been 1300 µg/L and 18 µg/L, lower than the measured concentrations of 3340 and 93 µg/L. Despite these changes, the pre-mining conditions would not have met aquatic-life standards.

Colorado↗

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

Organic Geochemistry↗

On the air-scattering of gamma rays from thick uranium sources

Semiquantative interpretation of data from airborne radioactivity surveying requires detailed knowledge of air-scattered gamma-ray intensity at considerable air distances from natural, thick uranium sources. Based on the concept of an elementary source of infinite thickness rather than on the classical point source, semi-empirical expressions, are developed for measured gamma-radiation intensities from . the two extreme types of natural, thick uranium sources, the elementary (point) and t-he broad (semi-infinite) source. These expressions agree both with extensive experimental data and with the form and structure of theory. Theoretical computations based on published solutions of the Boltzmann equation for ga.m.ma-ray transport in one medium agree closely with experimental measurements. The calculated value for primary, scattered, and total intensities from thick uranium sources show that at considerable air distances the scattered intensities are more than half of the total intensities for energies above 0.4 Mev and become considerably more than half as the lower limit of detector energy response is decreased below 0.4 Mev.

Trace Elements Investigations↗

Model coupling intraparticle diffusion/sorption, nonlinear sorption, and biodegradation processes

Diffusion, sorption and biodegradation are key processes impacting the efficiency of natural attenuation. While each process has been studied individually, limited information exists on the kinetic coupling of these processes. In this paper, a model is presented that couples nonlinear and nonequilibrium sorption (intraparticle diffusion) with biodegradation kinetics. Initially, these processes are studied independently (i.e., intraparticle diffusion, nonlinear sorption and biodegradation), with appropriate parameters determined from these independent studies. Then, the coupled processes are studied, with an initial data set used to determine biodegradation constants that were subsequently used to successfully predict the behavior of a second data set. The validated model is then used to conduct a sensitivity analysis, which reveals conditions where biodegradation becomes desorption rate-limited. If the chemical is not pre-equilibrated with the soil prior to the onset of biodegradation, then fast sorption will reduce aqueous concentrations and thus biodegradation rates. Another sensitivity analysis demonstrates the importance of including nonlinear sorption in a coupled diffusion/sorption and biodegradation model. While predictions based on linear sorption isotherms agree well with solution concentrations, for the conditions evaluated this approach overestimates the percentage of contaminant biodegraded by as much as 50%. This research demonstrates that nonlinear sorption should be coupled with diffusion/sorption and biodegradation models in order to accurately predict bioremediation and natural attenuation processes. To our knowledge this study is unique in studying nonlinear sorption coupled with intraparticle diffusion and biodegradation kinetics with natural media.

Journal of Contaminant Hydrology↗

Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite I: X-ray absorption extended fine structure spectroscopy analysis

“Two-line” ferrihydrite samples precipitated and then exposed to a range of aqueous Zn solutions (10 −5 to 10 −3 M), and also coprecipitated in similar Zn solutions (pH 6.5), have been examined by Zn and Fe K-edge X-ray absorption spectroscopy. Typical Zn complexes on the surface have Zn-O distances of 1.97(.02) Å and coordination numbers of about 4.0(0.5), consistent with tetrahedral oxygen coordination. This contrasts with Zn-O distances of 2.11(.02) Å and coordination numbers of 6 to 7 in the aqueous Zn solutions used in sample preparation. X-ray absorption extended fine structure spectroscopy (EXAFS) fits to the second shell of cation neighbors indicate as many as 4 Zn-Fe neighbors at 3.44(.04) Å in coprecipitated samples, and about two Zn-Fe neighbors at the same distance in adsorptionsamples. In both sets of samples, the fitted coordination number of second shell cations decreases as sorption density increases, indicating changes in the number and type of available complexing sites or the onset of competitive precipitation processes. Comparison of our results with the possible geometries for surface complexes and precipitates suggests that the Zn sorption complexes are inner sphere and at lowest adsorption densities are bidentate, sharing apical oxygens with adjacent edge-sharing Fe(O,OH) 6 octahedra. Coprecipitation samples have complexes with similar geometry, but these are polydentate, sharing apices with more than two adjacent edge-sharing Fe(O,OH) 6 polyhedra. The results are inconsistent with Zn entering the ferrihydrite structure (i.e., solid solution formation) or formation of other Zn-Fe precipitates. The fitted Zn-Fe coordination numbers drop with increasing Zn density with a minimum of about 0.8(.2) at Zn/(Zn + Fe) of 0.08 or more. This change appears to be attributable to the onset of precipitation of zinc hydroxide polymers with mainly tetrahedral Zn coordination. At the highest loadings studied, the nature of the complexes changes further, and a second type of precipitate forms. This has a structure based on a brucite layer topology, with mainly octahedral Zn coordination. Amorphous zinc hydroxide samples prepared for comparison had a closely similar local structure. Analysis of the Fe K-edge EXAFS is consistent with surface complexation reactions and surface precipitation at high Zn loadings with little or no Fe-Zn solid solution formation. The formation of Zn-containing precipitates at solution conditions two or more orders of magnitude below their solubility limit is compared with other sorption and spectroscopic studies that describe similar behavior.

Geochimica et Cosmochimica Acta↗