Geology topics

D.L. Sparks

Publications and source records attributed to D.L. Sparks.

6 recordsLinked to original sources

USGS2005

Arsenate adsorption mechanisms at the allophane: Water interface

We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As(V)] o from 50 to 1000 μM (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0−10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline Al−As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane−water interface are attributable to ligand exchange reactions between As(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H 2 PO 4 2 - and H 2 AsO 4 2 - ) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The inner-sphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments.

Environmental Science & Technology↗

USGS2005

Phosphate reactivity in long-term poultry litter-amended southern Delaware sandy soils

Eutrophication caused by dissolved P from poultry litter (PL)-amended agricultural soils has been a serious environmental concern in the Delaware-Maryland-Virginia Peninsula (Delmarva), USA. To evaluate state and federal nutrient management strategies for reducing the environmental impact of soluble P from long-term PL-amended Delaware (DE) soils, we investigated (i) inorganic P speciation; (ii) P adsorption capacity; and (iii) the extent of P desorption. Although the electron microprobe (EMP) analyses showed a strong correlation between P and Al/Fe, crystalline Al/Fe-P precipitates were not detected by x-ray diffraction (XRD). Instead, the inorganic P fractionation analyses showed high levels of oxalate extractable P, Al, and Fe fractions (615-858, 1215-1478, and 337-752 mg kg-1, respectively), which were susceptible to slow release during the long-term (30-d) P desorption experiments at a moderately acidic soil pHwater. The labile P in the short-term (24-h) desorption studies was significantly associated with oxalate and F extractable Fe and Al, respectively. This was evident in an 80% reduction maximum in total desorbable P from NH4 oxalate/F pretreated soils. In the adsorption experiments, P was strongly retained in soils at near targeted pH of lime (???6.0), but P adsorption gradually decreased with decreasing pH near the soil pHwater (???5.0). The overall findings suggest that P losses from the can be suppressed by an increase in the P retention capacity of soils via (i) an increase in the number of lime applications to maintain soil pHwater at near targeted pH values, and/or (ii) alum/iron sulfate amendments to provide additional Al- and Fe-based adsorbents. ?? Soil Science Society of America.

Soil Science Society of America Journal↗

USGS2004

Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface

Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (??-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L-1; pH 4.5 and 6.0; I = 0.01 M NaCl). Divalent Zn adsorption on synthetic ??-MnO 2 in the absence of As(III) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 ??M. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the ??-MnO 2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.

Environmental Science & Technology↗

USGS2004

Alum amendment effects on phosphorus release and distribution in poultry litter-amended sandy soils

Increased poultry production has contributed to excess nutrient problems in Atlantic Coastal Plain soils due to land application of poultry litter (PL). Aluminum sulfate [alum, Al 2 (SO 4 ) 3 ·14H 2 O] amendment of PL effectively reduces soluble phosphorus (P) in the PL; however, the effects of these litters when added to acidic, sandy soils are not well understood. The objective of this study was to investigate the efficacy of alum-amended poultry litter in reducing P release from three Delaware Coastal Plain soils: Evesboro loamy sand (Ev; excessively drained, mesic, coated Typic Quartzipsamments), Rumford loamy sand (Ru; well drained, coarse-loamy, siliceous, subactive, thermic Typic Hapludults), and Pocomoke sandy loam (Pm; very poorly drained, coarse-loamy, siliceous, active, thermic Typic Umbraquults). Long-term (25 d) and short-term (24 h) desorption studies were conducted, in addition to chemical extractions and kinetic modeling, to observe the changes that alum-amended versus unamended PL caused in the soils. The Ev, Ru, and Pm soils were incubated with 9 Mg ha −1 of alum-amended or unamended PL. Long-term desorption (25 d) of the incubated material resulted in approximately 13.5% (Ev), 12.7% (Ru), and 13.3% (Pm) reductions in cumulative P desorbed when comparing soil treated with unamended and alum-amended PL. In addition, the P release from the soil treated with alum-amended litter was not significantly different from the control (soil alone). Short-term desorption (24 h) showed 7.3% (Ev), 15.4% (Ru), and 20% (Pm) reductions. The overall implication from this study is that the use of alum as a PL amendment is useful in coarse-textured soils of the Coastal Plain. With increased application of alum-amended PL, more significant decreases may be possible with little or no effect on soil quality. textured soils of the Coastal Plain. With increased application of alum-amended PL, more significant decreases may be possible with little or no effect on soil quality.

Delaware↗

USGS2003

Effects of dissolved carbonate on arsenate adsorption and surface speciation at the hematite-water interface

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite−water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [ P CO 2 = 10 - 3.5 atm and ∼0; CO 2 -free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L - 1 , [As(V)] 0 = 1.5 mM and I = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L - 1 , [As(V)] 0 = 0.5 mM and I = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems ( P CO 2 = 10 - 3.5 atm) than in the CO 2 -free argon system at pH 4−7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (≈2.8 Å) and bidentate binuclear (≈3.3 Å) bonding at pH 4.5−8 and loading levels of 0.46−3.10 μM m - 2 . Using the results of the pseudo-equilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the P CO 2 = 10 - 3.5 atm and the CO 2 -free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO 2 (g).

Environmental Science & Technology↗

USGS2003

Arsenic speciation and reactivity in poultry litter

Recent U.S. government action to lower the maximum concentration levels (MCL) of total arsenic (As) (10 ppb) in drinking water has raised serious concerns about the agricultural use of As-containing biosolids such as poultry litter (PL). In this study, solid-state chemical speciation, desorbability, and total levels of As in PL and long-term amended soils were investigated using novel synchrotron-based probing techniques (microfocused (μ) synchrotron X-ray fluorescence (SXRF) and μ-X-ray absorption near-edge structure (XANES) spectroscopies) coupled with chemical digestion and batch experiments. The total As levels in the PL were as high as ≈50 mg kg - 1 , and As(II/III and V) was always concentrated in abundant needle-shaped microscopic particles (≈20 μm × 850 μm) associated with Ca, Cu, and Fe and to a lesser extent with S, Cl, and Zn. Post-edge XANES features of litter particles are dissimilar to those of the organo-As(V) compound in poultry feed (i.e., roxarsone), suggesting possible degradation/transformation of roxarsone in the litter and/or in poultry digestive tracts. The extent of As desorption from the litter increased with increasing time and pH from 4.5 to 7, but at most 15% of the total As was released after 5 d at pH 7, indicating the presence of insoluble phases and/or strongly retained soluble compounds. No significant As accumulation (<15 mg kg - 1 ) was found in long-term PL-amended agricultural surface soils. This suggests that As in the PL may have undergone surface and subsurface transport processes. Our research results raise concerns about long-term PL amendment effects on As contamination in surrounding soil−water environments.

Environmental Science & Technology↗