Reactions of nitrite with goethite and surface Fe(II)-goethite complexes.

Chemodenitrification-the abiotic (chemical) reduction of nitrite (NO2-) by iron (II)-plays an important role in nitrogen cycling due in part to this process serving as a source of nitrous oxide (N2O). Questions remain about the fate of NO2- in the presence of mineral surfaces formed during chemodenitrification, such as iron(III) (hydr) oxides, particularly relative to dissolved iron(II). In this study, stirred-batch kinetic experiments were conducted under anoxic conditions (to mimic iron(III)-reducing conditions) from pH 5.5-8 to investigate NO2- reactivity with goethite (FeOOH(s)) and Fe(II)-treated goethite using wet chemical and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Nitrite removal from solution by goethite was more rapid at pH 5.5 than at pH 7 and 8. Spectral changes upon nitrite adsorption imply an inner-sphere surface interaction (monodentate and bidentate) at pH 5.5 based on ATR-FTIR spectra of the nitrite-goethite interface over time. In iron(II)-amended experiments at pH 5.5 with high aqueous Fe(II) in equilibrium with goethite, nitrous oxide was generated, indicating that nitrite removal involved a combination of sorption and reduction processes. The presence of a surface complex resembling protonated nitrite (HONO) with an IR peak near ~1258 cm-1 was observed in goethite-only and iron(II)-goethite experiments, with a greater abundance of this species observed in the latter treatment. These results might help explain gaseous losses of nitrogen where nitrite and iron(II)/goethite coexist, with implications for nutrient cycling and release of atmospheric air pollutants.

Fragipan horizon fragmentation in slaking experiments with amendment materials and ryegrass root tissue extracts.

Slaking experiments were conducted of fragipan clods immersed in solutions of poultry manure, aerobically digested biosolid waste (ADB), fluidized bed combustion byproduct (FBC), D-H2O, CaCO3, NaF, Na-hexa-metaphosphate, and ryegrass root biomass. The fragipan clods were sampled from the Btx horizon of an Oxyaquic Fragiudalf in Kentucky. Wet sieving aggregate analysis showed significantly better fragmentation in the NaF, Na-hexa-metaphosphate, and ryegrass root solutions with a mean weight diameter range of 15.5-18.8 mm compared to the 44.2-47.9 mm of the poultry manure, ADB, and FBC treatments. Dissolved Si, Al, Fe, and Mn levels released in solution were ambiguous. The poor efficiency of the poultry manure, ADB, and FBC treatments was attributed to their high ionic strength, while the high efficiency of the NaF, Na-hexa-metaphosphate, and rye grass root solutions to their high sodium soluble ratio (SSR). A slaking mechanism is proposed suggesting that aqueous solutions with high SSR penetrate faster into the fragipan capillaries and generate the critical swelling pressure and shearing stress required to rupture the fragipan into several fragments. Additional fragmentation occurs in a followup stage during which potential Si, Al, Fe, and Mn binding agents may be released into solution. Field experiments testing these findings are in progress.

Nitrite reactivity with magnetite.

Under Fe(3+)-reducing conditions, soil Fe(2+) oxidation has been shown to be coupled with nitrate (NO3(-)) reduction. One possible secondary reaction is the involvement of NO3(-) and nitrite (NO2(-)) with magnetite, a mixed valence Fe(2+)/Fe(3+) mineral found in many natural environments. Currently, little information exists on NO3(-) and NO2(-) reactivity with magnetite. This study investigates NO3(-) and NO2(-) reactivity with magnetite under anoxic conditions using batch kinetic experiments across a range of pH values (5.5-7.5) and in the presence of added dissolved Fe(2+). Solid phase products were characterized using X-ray diffraction (XRD), Mössbauer spectroscopy, and scanning electron microscopy (SEM). Nitrate removal by magnetite was much slower when compared with NO2(-). There was a pH-dependence in the reduction of NO2(-) by magnetite; the initial rate of NO2(-) removal was two times faster at pH 5.5 than at pH 7.5. The influence of pH was explained by the binding of NO2(-) to positively charged sites on magnetite (≡ S-OH2(+)) and to neutral sites (≡ S-OH(0)). As NO2(-) was removed from solution, nitric oxide (NO) and nitrous oxide (N2O) were identified as products confirming that nitrite was reduced. Structural Fe(2+) in magnetite was determined to be the reductant of NO2(-) based on the lack of measurable dissolved Fe(2+) release to solution coupled with Mössbauer spectra and XRD analysis of solid phase products. Addition of dissolved Fe(2+) to magnetite slurries resulted in adsorption and an acceleration in the rate of nitrite reduction at a given pH value. In summary, findings reported in this study demonstrate that if magnetite is present in Fe(3+)-reducing soil and NO2(-) is available, it can remove NO2(-) from solution and reduce a portion of it abiotically to NO and subsequently to N2O by a heterogeneous electron transfer process.

Reduction of copper(II) by iron(II).

Laboratory and field investigations have clearly demonstrated the important role of reduced iron (Fe(II)) in reductive transformations of first-row transition metal species. However, interactions of Fe(II) and copper (Cu) are not clearly understood. This study examined the reduction of Cu(II) by Fe(II) in stirred-batch experiments at pH 5.2 and 5.5 as influenced by chloride (Cl-) concentration (0.002-0.1 M), initial metal concentration (0.1-9.1 mM), and reaction time (1-60 min) under anoxic conditions. Reduction of Cu(II) to Cu(I) by dissolved Fe(II) was rapid under all experimental conditions and the stability of the products explains the driving force for the redox reaction. Under conditions of low [Cl-] and high initial metal concentration, >40% of total Cu and Fe were removed from solution after 1 min, which accompanied formation of a brownish-red precipitate. X-ray diffraction (XRD) patterns of the precipitates revealed the presence of cuprite (Cu2O), a Cu(I) mineral, based on d-spacings located at 0.248, 0.215, 0.151, and 0.129 nm. Fourier transform infrared (FTIR) spectroscopy corroborated XRD data for the presence of Cu2O, with features located at 518, 625, and 698 cm(-1). Increasing [Cl-] stabilized the dissolved Cu(I) product against Cu2O precipitation and resulted in more Fe precipitated from solution (relative to Cu) that appears to be present as poorly crystalline lepidocrocite (gamma-FeOOH). This process may be important in anoxic soil environments, where dissolved Fe(II) levels can accumulate.

Biosolid colloid-mediated transport of copper, zinc, and lead in waste-amended soils.

Increasing land applications of biosolid wastes as soil amendments have raised concerns about potential toxic effects of associated metals on the environment. This study investigated the ability of biosolid colloids to transport metals associated with organic waste amendments through subsurface soil environments with leaching experiments involving undisturbed soil monoliths. Biosolid colloids were fractionated from a lime-stabilized, an aerobically digested, and a poultry manure organic waste and applied onto the monoliths at a rate of 0.7 cm/h. Eluents were monitored for Cu, Zn, Pb, and colloid concentrations over 16 to 24 pore volumes of leaching. Mass-balance calculations indicated significantly higher (up to 77 times) metal elutions in association with the biosolid colloids in both total and soluble fractions over the control treatments. Eluted metal loads varied with metal, colloid, and soil type, following the sequences Zn = Cu > Pb, and ADB > PMB > LSB colloids. Colloid and metal elution was enhanced by decreasing pH and colloid size, and increasing soil macroporosity and organic matter content. Breakthrough curves were mostly irregular, showing several maxima and minima as a result of preferential macropore flow and multiple clogging and flushing cycles. Soil- and colloid-metal sorption affinities were not reliable predictors of metal attenuation/elution loads, underscoring the dynamic nature of transport processes. The findings demonstrate the important role of biosolid colloids as contaminant carriers and the significant risk they pose, if unaccounted, for soil and ground water contamination in areas receiving heavy applications of biosolid waste amendments.

Reactivity of Pb(II) at the Mn(III,IV) (oxyhydr)oxide--water interface.

In this study, the reactivity of lead (Pb(II)) on naturally occurring Mn(III,IV) (oxyhydr)oxide minerals was evaluated using kinetic, thermodynamic, and spectroscopic investigations. Aqueous Pb(II) was more strongly adsorbed to birnessite (delta-MnO1.7) than to manganite (gamma-MnOOH) under all experimental conditions. The isoteric heat of Pb adsorption (delta HT) or birnessite was 94 kJ mol-1 at a surface loading of 1.1 mmol g-1, and decreased with increasing adsorption density. This indicated that adsorption was an endothermic process and that birnessite possessed heterogeneous sites of reactivity for Pb. X-ray absorption fine structure (XAFS) spectra revealed that Pb was adsorbed as inner-sphere complexes on both birnessite and manganite with no evidence to suggest oxidation as an operative sorption mechanism. Lead appeared to coordinate to vacancy sites in the birnessite layer structure with concurrent release of Mn to solution, which resulted in a greater number of second shell Mn scatterers in Pb-birnessite when compared to Pb-manganite samples. The difference in Pb coordination apparently explained the contrasting desorption behavior between the two Mn minerals. These results have significant implications for Pb partitioning in soil environments containing solid-phase Mn(III,IV) (oxyhydr)oxides.

Mobility of the herbicide pyrithiobac through intact soil columns.

The relative mobility of pyrithiobac [sodium 2-chloro-6-(4, 6-dimethoxypyrimidin-2-ylthio)benzoate], a new herbicide used for postemergence control of broadleaf weeds in cotton (Gossypium hirsutum), was evaluated and compared against that of bromide (Br(-)) tracer on four soils representative of cotton-growing regions using intact soil columns under saturated flow conditions. Pyrithiobac breakthrough curves were asymmetrical in shape with significant tailing and displaced to the left of 1 pore volume in the Houston Black clay (fine, montmorillonitic, thermic Udic Pellustert), Orelia fine sandy clay loam (fine-loamy, mixed, hyperthermic Typic Ochraqualfs), and Ships silty clay (very-fine, mixed, thermic Udic Chromustert) soils. Breakthrough of pyrithiobac in the Hidalgo sandy loam soil (fine-loamy, mixed, hyperthermic Typic Calciustoll) was delayed and more symmetrical, with peak pyrithiobac concentration reached after 1.2 pore volumes. The immobile pore water (IPW) fractions estimated from the Br(-) breakthrough curves ranged from 20 to 87% of total pore water. The IPW values demonstrated that soils with the greatest amount of IPW (Ships with IPW = 87.3%) exhibited the most rapid movement of pyrithiobac (peak concentration after 0.04 pore volume). The experimentally determined pyrithiobac breakthrough curves confirmed the high mobility of this herbicide in these alkaline and predominantly smectitic soils. These results indicate that pyrithiobac mobility was influenced by soil type and preferential flow processes when leached through intact soil columns.