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Geology topics

G. R. Aiken

Publications and source records attributed to G. R. Aiken.

At least 37 records · Page 2Linked to original sources
USGS2007

DOM in recharge waters of the Santa Ana River Basin

Assessment of the composition, reactivity, and potential health effects of dissolved organic matter (DOM) is an important issue in the regulation and operation of groundwater recharge projects. The composition of DOM in various natural surface waters and reclaimed waters used to recharge the alluvial aquifers of the lower Santa Ana River Basin in California was derived primarily from terpenoid hydrocarbons and amino sugars. Lesser amounts of aromatic sulfonate and alkylphenol polyethoxylate metabolites of anionic and neutral surfactants were detected in reclaimed water, and these metabolites persisted in waters of the Santa Ana River, the Prado Wetland, and the recharge basins. Only small amounts of humic substances derived from tannins and lignins were deposited during storm flow periods in the Prado Wetland, but these amounts were responsible for significant increases in disinfection by-product formation potential in these waters. Colloids composed of bacterial cell wall fragments showed large percentage increases in all waters during storm flow periods.

California↗
USGS2006

Evidence for the aquatic binding of arsenate by natural organic matter-suspended Fe(III)

Dialysis experiments with arsenate and three different NOM samples amended with Fe(III) showed evidence confirming the formation of aquatic arsenate-Fe(III)-NOM associations. A linear relationship was observed between the amount of complexed arsenate and the Fe(III) content of the NOM. The dialysis results were consistent with complex formation through ferric iron cations acting as bridges between the negatively charged arsenate and NOM functional groups and/or a more colloidal association, in which the arsenate is bound by suspended Fe(III)-NOM colloids. Sequential filtration experiments confirmed that a significant proportion of the iron present at all Fe/C ratios used in the dialysis experiments was colloidal in nature. These colloids may include larger NOM species that are coagulated by the presence of chelated Fe(III) and/or NOM-stabilized ferric (oxy)hydroxide colloids, and thus, the solution-phase arsenate-Fe(III)-NOM associations are at least partially colloidal in nature. ?? 2006 American Chemical Society.

Environmental Science & Technology↗
USGS2005

A decrease in discharge-normalized DOC export by the Yukon River during summer through autumn

Climate warming is having a dramatic effect on the vegetation distribution and carbon cycling of terrestrial subarctic and arctic ecosystems. Here, we present hydrologic evidence that warming is also affecting the export of dissolved organic carbon and bicarbonate (DOC and HCO 3 − ) at the large basin scale. In the 831,400 km 2 Yukon River basin, water discharge (Q) corrected DOC export significantly decreased during the growing season from 1978–80 to 2001–03, indicating a major shift in terrestrial to aquatic C transfer. We conclude that decreased DOC export, relative to total summer through autumn Q, results from increased flow path, residence time, and microbial mineralization of DOC in the soil active layer and groundwater. Counter to current predictions, we argue that continued warming could result in decreased DOC export to the Bering Sea and Arctic Ocean by major subarctic and arctic rivers, due to increased respiration of organic C on land.

Geophysical Research Letters↗
USGS2005

Inhibition of calcite precipitation by natural organic material: Kinetics, mechanism, and thermodynamics

The inhibition of calcite precipitation by natural organic material (NOM) in solutions seeded with calcite was investigated using a pH-stat system. Experiments were carried out using three NOMs with different physical/chemical properties. For each of the materials, inhibition was found to be more effective at lower carbonate/calcium ratios and lower pH values. The reduction in the precipitation rate could be explained by a Langmuir adsorption model using a conditional equilibrium constant. By identification of the type of site on the NOM molecules that is involved in the adsorption reaction, the "conditional" equilibrium constants obtained at different solution compositions converged to a single "nonconditional" value. The thermodynamic data determined at 25??C and 1 atm suggest that the interaction between NOM molecules and the calcite surface is chemisorptive in nature and that adsorption is an endothermic reaction driven by the entropy change. The greatest degree of inhibition was observed for the NOM with the highest molecular weight and aromatic carbon content. For a given type of NOM, the degree of inhibition of calcite precipitation was dictated by the balance between the enthalpy change and the entropy change of the adsorption reaction. ?? 2005 American Chemical Society.

Environmental Science & Technology↗
USGS2005

Dissolution of cinnabar (HgS) in the presence of natural organic matter

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 × 10 −13 to 7.16 × 10 −12 mol Hg (mg C) −1 m −2 s −1 . Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R 2 = 0.88), aromaticity (R 2 = 0.80), and molecular weight (R 2 = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface.

Geochimica et Cosmochimica Acta↗
USGS2005

Effect of humic substance photodegradation on bacterial growth and respiration in lake water

This study addresses how humic substance (HS) chemical composition and photoreactivity affect bacterial growth, respiration, and growth efficiency (BGE) in lake water. Aqueous solutions of HSs from diverse aquatic environments representing different dissolved organic matter sources (autochthonous and allochthonous) were exposed to artificial solar UV radiation. These solutions were added to lake water passed through a 0.7-??m-pore-size filter (containing grazer-free lake bacteria) followed by dark incubation for 5, 43, and 65 h. For the 5-h incubation, several irradiated HSs inhibited bacterial carbon production (BCP) and this inhibition was highly correlated with H 2O2 photoproduction. The H2O2 decayed in the dark, and after 43 h, nearly all irradiated HSs enhanced BCP (average 39% increase relative to nonirradiated controls, standard error = 7.5%, n = 16). UV exposure of HSs also increased bacterial respiration (by ???18%, standard error = 5%, n = 4), but less than BCP, resulting in an average increase in BGE of 32% (standard error = 10%, n = 4). Photoenhancement of BCP did not correlate to HS bulk properties (i.e., elemental and chemical composition). However, when the photoenhancement of BCP was normalized to absorbance, several trends with HS origin and extraction method emerged. Absorbance-normalized hydrophilic acid and humic acid samples showed greater enhancement of BCP than hydrophobic acid and fulvic acid samples. Furthermore, absorbance-normalized autochthonous samples showed ???10-fold greater enhancement of BCP than allochthonous-dominated samples, indicating that the former are more efficient photoproducers of biological substrates. Copyright ?? 2005, American Society for Microbiology. All Rights Reserved.

Applied and Environmental Microbiology↗
USGS2003

Binding of mercury(II) to aquatic humic substances: Influence of pH and source of humic substances

Conditional distribution coefficients ( K DOM ‘) for Hg(II) binding to seven dissolved organic matter (DOM) isolates were measured at environmentally relevant ratios of Hg(II) to DOM. The results show that K DOM ‘ values for different types of samples (humic acids, fulvic acids, hydrophobic acids) isolated from diverse aquatic environments were all within 1 order of magnitude (10 22.5 ± 1.0 −10 23.5 ± 1.0 L kg - 1 ), suggesting similar Hg(II) binding environments, presumably involving thiol groups, for the different isolates. K DOM ‘ values decreased at low pHs (4) compared to values at pH 7, indicating proton competition for the strong Hg(II) binding sites. Chemical modeling of Hg(II)−DOM binding at different pH values was consistent with bidentate binding of Hg(II) by one thiol group (p K a = 10.3) and one other group (p K a = 6.3) in the DOM, which is in agreement with recent results on the structure of Hg(II)−DOM bonds obtained by extended X-ray absorption fine structure spectroscopy (EXAFS).

Environmental Science & Technology↗
USGS2002

Binding of mercury(II) to dissolved organic matter: The role of the mercury-to-DOM concentration ratio

The binding of Hg(II) to dissolved organic matter (DOM; hydrophobic acids isolated from the Florida Everglades by XAD-8 resin) was measured at a wide range of Hg-to-DOM concentration ratios using an equilibrium dialysis ligand exchange method. Conditional distribution coefficients ( K DOM ‘) determined by this method were strongly affected by the Hg/DOM concentration ratio. At Hg/DOM ratios below approximately 1 μg of Hg/mg of DOM, we observed very strong interactions ( K DOM ‘ = 10 23.2 ± 1.0 L kg - 1 at pH = 7.0 and I = 0.1), indicative of mercury−thiol bonds. Hg/DOM ratios above approximately 10 μg of Hg/mg of DOM, as used in most studies that have determined Hg−DOM binding constants, gave much lower K DOM ‘ values (10 10.7 ± 1.0 L kg - 1 at pH = 4.9−5.6 and I = 0.1), consistent with Hg binding mainly to oxygen functional groups. These results suggest that the binding of Hg to DOM under natural conditions (very low Hg/DOM ratios) is controlled by a small fraction of DOM molecules containing a reactive thiol functional group. Therefore, Hg/DOM distribution coefficients used for modeling the biogeochemical behavior of Hg in natural systems need to be determined at low Hg/DOM ratios.

Environmental Science & Technology↗
USGS2002

Influence of natural organic matter on the adsorption of metal ion onto clay particles

The influence of natural organic matter (NOM) on the adsorption of Al, Fe, Zn, and Pb onto clay minerals was investigated. Adsorption experiments were carried out at pH = 5 and pH = 7 in the presence and absence of NOM. In general, the presence of NOM decreased the adsorption of metal ions onto the clay particles. Al and Fe were strongly influenced by NOM, whereas Zn and Pb adsorption was only slightly altered. The interaction of the metal ions with the minerals and the influence of NOM on this interaction was investigated by coupling SdFFF with an inductively coupled plasma mass spectrometer (ICPMS) or an inductively coupled plasma atomic emission spectrometer (ICPAES). Quantitative atomization of the clay particles in the ICP was confirmed by comparing elemental content determined by direct injection of the clay into the ICPMS with values from acid digestion. Particle sizes of the clays were found to be between 0.1 and 1 μm by sedimentation field-flow fractionation (SdFFF) with UV detection. Aggregation of particles due to metal adsorption was observed using SdFFF-ICPMS measurements. This aggregation was dependent on the specific metal ion and decreased in the presence of NOM and at higher pH value.

Environmental Science & Technology↗
USGS2002

Prediction of capacity factors for aqueous organic solutes adsorbed on a porous acrylic resin

The capacity factors of 20 aromatic, allphatic, and allcycllc organic solutes with carboxyl, hydroxyl, amine, and methyl functional groups were determined on Amberlite XAD-8, a porous acrylic resin. The logarithm of the capacity factor, k' , correlated inversely with the logarithm of the aqueous molar solubility with significance of less than 0.001. The log k' -log solubility relationship may be used to predict the capacity of any organic solute for XAD-8 using only the solubility of the solute. The prediction is useful as a guide for determining the proper ratio of sample to column size In the preconcentration of organic solutes from water. The inverse relationship of solubility and capacity is due to the unfavorable entropy of solution of organic solutes which affects both solubility and sorption.

Analytical Chemistry↗
USGS2002

Comparison of XAD macroporous resins for the concentration of fulvic acid from aqueous solution

Five macroreticular, nonlonlc AmberlHe XAD resins were evaluated for concentration and Isolation of fulvlc acid from aqueous solution. The capacity of each resin for fulvlc acid was measured by both batch and column techniques. Elution efficiencies were determined by desorptlon with 0.1 N NaOH. Highest recoveries were obtained with the acrylic ester resins which proved to be most efficient for both adsorption and elution of fulvlc acid. Compared to the acrylic ester resins, usefulness of the styrene dvlnybenzene resins to remove fulvlc acid is limited because of slow diffusion-controlled adsorption and formation of charge-transfer complexes, which hinders elution.

Analytical Chemistry↗
USGS2002

Evaluation of ultrafiltration for determining molecular weight of fulvic acid

Two commonly used ultrafiltration membranes are evaluated for the determination of molecular weights of humic substances. Polyacrylic acids of Mr 2000 and 5000 and two well-characterized fulvic acids are used as standards. Molecular size characteristics of standards, as determined by small-angle X-ray scattering, are presented. Great care in evaluating molecular weight data obtained by ultrafiltration is needed because of broad nominal cutoffs and membrane-solute interactions.

Environmental Science & Technology↗
USGS2002

A comparison of surface water natural organic matter in raw filtered water samples, XAD, and reverse osmosis isolates

This research compared raw filtered waters (RFWs), XAD resin isolates (XAD-8 and XAD-4), and reverse osmosis (RO) isolates of several surface water samples from McDonalds Branch, a small freshwater fen in the New Jersey Pine Barrens (USA). RO and XAD-8 are two of the most common techniques used to isolate natural organic matter (NOM) for studies of composition and reactivity; therefore, it is important to understand how the isolates differ from bulk (unisolated) samples and from one another. Although, any comparison between the isolation methods needs to consider that XAD-8 is specifically designed to isolate the humic fraction, whereas RO concentrates a broad range of organic matter and is not specific to humics. The comparison included for all samples: weight average molecular weight ( M w ), number average molecular weight ( M n ), polydispersity ( ρ ), absorbance at 280 nm normalized to moles C ( ε 280 ) (RFW and isolates); and for isolates only: elemental analysis, % carbon distribution by 13 C NMR, and aqueous FTIR spectra. As expected, RO isolation gave higher yield of NOM than XAD-8, but also higher ash content, especially Si and S. M w decreased in the order: RO>XAD-8>RFW>XAD-4. The M w differences of isolates compared with RFW may be due to selective isolation (fractionation), or possibly in the case of RO to condensation or coagulation during isolation. 13 C NMR results were roughly similar for the two methods, but the XAD-8 isolate was slightly higher in ‘aromatic’ C and the RO isolate was slightly higher in heteroaliphatic and carbonyl C. Infrared spectra indicated a higher carboxyl content for the XAD-8 isolates and a higher ester:carboxyl ratio for the RO isolates. The spectroscopic data thus are consistent with selective isolation of more hydrophobic compounds by XAD-8, and also with potential ester hydrolysis during that process, although further study is needed to determine whether ester hydrolysis does indeed occur. Researchers choosing between XAD and RO isolation methods for NOM need to consider first the purpose of the isolation; i.e., whether humic fractionation is desirable. Beyond that, they should consider the C yield and ash content, as well as the potential for alteration of NOM by ester hydrolysis (XAD) or condensation/coagulation (RO). Furthermore, the RO and XAD methods produce different fractions or isolates so that researchers should be careful when comparing the compositions and reactivities of NOM samples isolated by these two different techniques.

Water Research↗
USGS2001

Constants for mercury binding by organic matter isolates from the Florida Everglades

Dissolved organic matter (DOM) has been implicated as an important complexing agent for Hg that can affect its mobility and bioavailability in aquatic ecosystems. However, binding constants for natural Hg-DOM complexes are not well known. We employed a competitive ligand approach to estimate conditional stability constants for Hg complexes with DOM isolates collected from Florida Everglades surface waters. The isolates examined were the hydrophobic fraction of DOM from a eutrophic, sulfidic site (F1-HPoA) and the hydrophilic fraction from an oligotrophic, low-sulfide site (2BS-HPiA). Our experimental determinations utilized overall octanol-water partitioning coefficients (D ow ) for 203 Hg at 0.01 M chloride and across pH and DOM concentration gradients. Use of this radioisotope allowed rapid determinations of Hg concentrations in both water and octanol phases without problems of matrix interference. Conditional stability constants (I = 0.06, 23°C) were log K′ = 11.8 for F1-HPoA and log K′ = 10.6 for 2BS-HPiA. These are similar to previously published stability constants for Hg binding to low-molecular-weight thiols. Further, F1-HPoA showed a pH-dependent decline in D ow that was consistent with models of Hg complexation with thiol groups as the dominant Hg binding sites in DOM. These experiments demonstrate that the DOM isolates are stronger ligands for Hg than chloride ion or ethylenediamine-tetraacetic acid. Speciation calculations indicate that at the DOM concentrations frequently measured in Everglades, 20 to 40 μM, significant complexation of Hg by DOM would be expected in aerobic (sulfide-free) surface waters.

Florida↗
USGS2001

Progression of natural attenuation processes at a crude-oil spill site . I. Geochemical evolution of the plume

A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho -xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe 2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume.

Journal of Contaminant Hydrology↗
USGS2000

A log-normal distribution model for the molecular weight of aquatic fulvic acids

The molecular weight of humic substances influences their proton and metal binding, organic pollutant partitioning, adsorption onto minerals and activated carbon, and behavior during water treatment. We propose a lognormal model for the molecular weight distribution in aquatic fulvic acids to provide a conceptual framework for studying these size effects. The normal curve mean and standard deviation are readily calculated from measured M(n) and M(w) and vary from 2.7 to 3 for the means and from 0.28 to 0.37 for the standard deviations for typical aquatic fulvic acids. The model is consistent with several types of molecular weight data, including the shapes of high- pressure size-exclusion chromatography (HP-SEC) peaks. Applications of the model to electrostatic interactions, pollutant solubilization, and adsorption are explored in illustrative calculations.The molecular weight of humic substances influences their proton and metal binding, organic pollutant partitioning, adsorption onto minerals and activated carbon, and behavior during water treatment. We propose a log-normal model for the molecular weight distribution in aquatic fulvic acids to provide a conceptual framework for studying these size effects. The normal curve mean and standard deviation are readily calculated from measured Mn and Mw and vary from 2.7 to 3 for the means and from 0.28 to 0.37 for the standard deviations for typical aquatic fulvic acids. The model is consistent with several type's of molecular weight data, including the shapes of high-pressure size-exclusion chromatography (HP-SEC) peaks. Applications of the model to electrostatic interactions, pollutant solubilization, and adsorption are explored in illustrative calculations.

Environmental Science & Technology↗
USGS2000

Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades

The crystallization of calcium carbonate minerals plays an integral role in the water chemistry of terrestrial ecosystems. Humic substances, which are ubiquitous in natural waters, have been shown to reduce or inhibit calcite crystal growth in experiments. The purpose of this study is to quantify and understand the kinetic effects of hydrophobic organic acids isolated from the Florida Everglades and a fulvic acid from Lake Fryxell, Antarctica, on the crystal growth of calcite (CaCO 3 ). Highly reproducible calcite growth experiments were performed in a sealed reactor at constant pH, temperature, supersaturation (Ω = 4.5), P CO 2 (10 −3.5 atm), and ionic strength (0.1 M) with various concentrations of organic acids. Higher plant-derived aquatic hydrophobic acids from the Everglades were more effective growth inhibitors than microbially derived fulvic acid from Lake Fryxell. Organic acid aromaticity correlated strongly with growth inhibition. Molecular weight and heteroatom content correlated well with growth inhibition, whereas carboxyl content and aliphatic nature did not.

Florida↗