Significance of anion exchange in pentachlorophenol sorption by variable-charge soils

Sorption data and subsequent predictive models for evaluating acidic pesticide behavior on variable-charge soils are needed to improve pesticide management and environmental stewardship. Previous work demonstrated that sorption of pentachlorophenol (PCP), a model organic acid, was adequately modeled by accounting for pH-and pKa-dependent chemical speciation and using two organic carbon-normalized sorption coefficients; one each for the neutral and anionic species. Such models do not account for organic anion interaction to positively charged surface sites, which can be significant for variable-charge minerals present in weathered soils typical of tropical and subtropical regions. The role of anion exchange in sorption of ionizable chemicals by variable-charge soils was assessed by measuring sorption of PCP by several variable-charge soils from aqueous solutions of CaCl2, CaSO4, Ca(H2PO4)2 as a function of pH. Differences in sorption from phosphate and chloride electrolyte solutions were attributed to pentachlorophenolate interactions with anion exchange sites. Suppression of PCP sorption by phosphate ranged from negligible in a soil with essentially no positively charge sites, as measured by negligible anion exchange capacity, to as much as 69% for variable-charge soils. Pentachlorophenolate exchange correlated well with the ratio of pH-dependent anion exchange capacity to net surface charge. Sorption reversibility of PCP by both CaCl2 and Ca(H2PO4)2 solutions was also demonstrated. Results for PCP clearly demonstrate that sorption to anion exchange sites in variable-charge soils should be considered in assessing pesticide mobility and that phosphate fertilizer application may increase the mobility of acidic pesticides.     

Phosphorus sorption and availability in soils amended with animal manures and sewage sludge

Soils that receive large applications of animal wastes and sewage sludge are vulnerable to releasing environmentally significant concentrations of dissolved P available to subsurface flow owing to the gradual saturation of the soil's P sorption capacity. This study evaluated P sorption (calculated from Langmuir isotherms) and availability of P (as CaCl2-P and resin P) in soils incubated for 20 d with poultry litter, poultry manure, cattle slurry, municipal sewage sludge, or KH2PO4, added on a P-equivalent basis (100 mg P kg(-1)). All the P sources had a marked negative effect on P sorption and a positive effect on P availability in all soils. In the cattle slurry- and KH2PO4-treated soils, the decreases in P sorption maximum (19-66%) and binding energy (25-89%) were consistently larger than the corresponding decreases (7-41% and 11-30%) in poultry litter-, poultry manure-, and sewage sludge-treated soils. The effects of cattle slurry and KH2PO4 on P availability were, in most cases, larger than those of the other P sources. In the poultry litter, poultry manure, and sewage sludge treatments, the increase in soil solution P was inversely related (R2 = 0.75) to the input of Ca from these relatively high Ca (13.5-42 g kg(-1)) sources. Correlation analyses implied that the magnitude of the changes in P sorption and availability was not related to the water-extractable P content of the P sources. Future research on the sustainable application of organic wastes to agricultural soils needs to consider the non-P- as well as P-containing components of the waste.     

Factors controlling sorption of prosulfuron by variable-charge soils and model sorbents

Prosulfuron [1-(4-methoxy-6-methyltriazin-2-yl)-3-[2-(3,3,3-trifluoropropyl) phenylsulfonyl]-urea), a relatively new sulfonylurea herbicide, is a weak acid (pK(a) 3.76), and therefore, will undergo pH-dependent speciation and sorption. Understanding prosulfuron sorption in soils is important for predicting its environmental fate. Soil and solution factors controlling sorption were investigated by measuring prosulfuron sorption on five model sorbents (amorphous silica, alpha-alumina, CaSWy1 montmorillonite, commercial humic acid, and anion exchange resin) and 10 variable-charge soils from CaCl(2) and Ca(H(2)PO(4))(2) solutions as a function of pH and ionic strength. Anion exchange of prosulfuron accounted for up to 82% of overall sorption in the pH range from 3 to 7. The relative importance of anion exchange to prosulfuron sorption was positively correlated to the ratio of anion and cation exchange capacities. Comparison between organic carbon (OC)-normalized sorption (K(oc)) versus pH for humic acid and variable-charge soils show similar trends with sorption decreasing with increasing pH. However, K(oc) values estimated from variable-charge soils in the lower pH range where anion exchange has the greatest contribution to sorption was almost one log unit greater than that estimated from humic acid clearly exemplifying the impact of anion exchange. Similarity in K(oc)-pH curves for humic acid and variable-charge soils may result from the fact that (i) cation exchange capacity increases with increasing OC content, thus effective anion exchange capacity is reduced; and (ii) the relative contribution of hydrophobic and hydrophilic sorption mechanisms was fairly constant. Given that both hydrophilic and hydrophobic sorption of prosulfuron decrease with increasing pH, addition of fertilizer and lime amendments may enhance the potential for off-site leaching of recently applied acidic pesticides.     

The role of lipids on sorption characteristics of freshwater- and wastewater-irrigated soils

The soil lipid fraction can play an important role in the sorption of organic compounds. In this study, the impact of the lipid fraction of freshwater- and wastewater-irrigated soils on the sorption of non- and relatively polar compounds was assessed. Lipid analyses revealed a clear difference between the two lipid fractions. The lipid extract from the wastewater-irrigated soil was consistent with mainly straight paraffinic chain materials; the lipid extract from freshwater-irrigated soil, on the other hand, exhibited stronger signals of aromatics, double bonds, ester, ether, and methyl, in addition to a smaller contribution from methylene protons. Our data suggest that lipid removal induced a stronger increase in the soil's sorption affinity for solutes capable of polar interactions such as atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) and chlorotoluron (N'-(3-chloro-4-methylphenyl)-N,N-dimethylurea) as compared to phenanthrene. Moreover, the level of increase in sorption affinities due to lipid removal was much higher for the freshwater-irrigated soil than for its wastewater-irrigated counterpart, even though the level of lipids in the freshwater-irrigated soil was half that in the wastewater-irrigated one (6 vs. 11% of the total organic C). The higher level of polar functionalities, such as ether and ester moieties, in the lipid fraction from the freshwater-irrigated soil suggests that these extractable compounds compete successfully with the polar solutes (atrazine and chlorotoluron) for specific binding sites in the soil organic matter (SOM). It appears that the composition of the lipid fraction may be a key consideration in unraveling the sorption of organic molecules in soils.     

Phosphorus and nitrogen sorption to soils in the presence of poultry litter-derived dissolved organic matter

Two environmental aspects associated with land application of poultry litter that have not been comprehensively evaluated are (i) the competition of dissolved organic matter (DOM) and P for soil sorption sites, and (ii) the sorption of dissolved organic nitrogen (DON) relative to inorganic nitrogen species (e.g., NO(3)(-) and NH(4)(+)) and dissolved organic carbon (DOC). The competition between DOM and P for sorption sites has often been assumed to increase the amount of P available for plant growth; however, elevating DOM concentrations may also increase P available for transport to water resources. Batch sorption experiments were conducted to (i) evaluate soil properties governing P sorption to benchmark soils of Southwestern Missouri, (ii) elucidate the impact of poultry litter-derived DOM on P sorption, and (iii) investigate DON retention relative to inorganic N species and DOC. Soils were reacted for 24 h with inorganic P (0-60 mg L(-1)) in the presence and absence of DOM (145 mg C L(-1)) using a background electrolyte solution comparable to DOM extracts (I = 10.8 mmol L(-1); pH 7.7). Soil P sorption was positively correlated with metal oxide (r(2) = 0.70) and clay content (r(2) = 0.79) and negatively correlated with Bray-1 extractable P (r(2) = 0.79). Poultry litter-derived DOM had no significant negative impact on P sorption. Dissolved organic nitrogen was preferentially removed from solution relative to (NO(3)(-)-N + NO(2)(-)-N), NH(4)(+)-N, and DOC. This research indicates that poultry litter-derived DOM is not likely to enhance inorganic P transport which contradicts the assumption that DOM released from organic wastes increases plant-available P when organic amendments and fertilizer P are co-applied. Additionally, this work demonstrates the need to further evaluate the fate and transport of DON in agroecosystem soils receiving poultry litter applications.     

Phosphorus cycling in wetland soils: the importance of phosphate diesters

Productivity in P limited peatlands is regulated in part by the turnover of organic phosphates, which is influenced by the chemical nature of the compounds involved. We used solution 31P nuclear magnetic resonance (NMR) spectroscopy to quantify organic and inorganic phosphates in benthic floc (a mixture of plant detritus and algae) and underlying soil from sites along P gradients in hard water and soft water areas of the northern Florida Everglades, USA. Phosphorus-enriched sites were dominated by cattail (Typha spp.), while unenriched sites included sawgrass (Cladium jamaicense Crantz) ridges and open-water sloughs. Phosphorus extracted in a solution containing 0.25 M NaOH and 50 mM EDTA (ethylenediaminetetraacetate) included phosphate, phosphate monoesters, DNA, and pyrophosphate. Signals from phosphate monoesters were consistent with those from alkaline hydrolysis products of RNA and phospholipids formed during extraction and analysis, whereas phytic acid (myo-inositol hexakisphosphate), the most abundant organic phosphate in most soils, was not detected. Phosphorus composition was similar among sites, although neither DNA nor pyrophosphate were detected in extracts of benthic floc from a calcareous slough. DNA was a greater proportion of the P extracted from soil compared to benthic floc, while the opposite was true for pyrophosphate. Research on the cycling of organic phosphates in wetlands focuses conventionally on the turnover of phosphate monoesters, but our results suggest strongly that greater emphasis should be given to understanding the role of phosphate diesters and phosphodiesterase activity.     

Measuring sorption of hydrophilic organic compounds in soils by an unsaturated transient flow method

Determination of sorption of hydrophilic, weakly sorbing organic compounds in soil by conventional batch methods using a slurried suspension is often prone to considerable errors because small changes in the solution concentration on equilibration must be accurately determined. This difficulty is exacerbated for compounds susceptible to degradation, which also decreases the solution concentration. The objective of this study was to determine sorption of hydrophilic pesticides by applying an unsaturated transient flow method, which enables determination of sorption at sufficiently small solution to soil ratios. The method makes use of piston-like displacement of the antecedent solution in equilibrium with sorbed phase when pesticide-free water is infiltrated into a soil column spiked with a pesticide. Pesticide sorption and the solution concentration are inferred from a plot of total pesticide content per unit mass of soil vs. water content in a region where the antecedent solution is accumulated. Thus, extraction of solution from relative dry soil is unnecessary. We tested this method for two hydrophilic pesticides, monocrotophos [dimethyl (E)-1-methyl-2-(methyl-carbamoyl) vinyl phosphate] and dichlorvos (2,2-dichlorovinyl dimethyl phosphate). The sorption coefficient, K(d), obtained for monocrotophos was slightly lower than that by batch method (K(d) = 0.10 vs. 0.19 L kg(-1)), whereas for dichlorvos, a compound highly susceptible to degradation, the unsaturated flow method yielded a much smaller K(d) (0.19 vs. 3.22 L kg(-1)). The K(d) values for both compounds were consistent with the observed retardation in the pesticide displacement in the columns. The proposed method is more representative of field conditions and particularly suitable for weakly sorbing organic compounds in soils.     

Effect of heat treatment on sorption of polar and nonpolar compounds to montmorillonites and soils

Batch sorption isotherms of 1,3,5-trichlorobenzene, 1,3,5-trinitrobenzene, and tetracycline to organic-free montmorillonites and soils receiving heat treatment (375°C for 24 h) were compared with those to unheated sorbents. Sorption of the nonpolar 1,3,5-trichlorobenzene to soil was lowered after the removal of humus by heating, consistent with the mechanism of hydrophobic partition into organic matter. For 1,3,5-trinitrobenzene, the enhanced sorption to heated soils was attributed to specific interactions with exchangeable cations facilitated by heating-induced irreversible partial dehydration of the clay interlayer. For tetracycline, an additional mechanism for sorption enhancement could be due to increased exposure of strong complexation sites on clay minerals after removal of the humic coating. These hypotheses were supported by the sorption data to heated and unheated Na-, K-, and Cs-saturated montmorillonites. The combustion method is commonly adopted to measure the content of black carbon in soils and sediments. However, findings from the present study indicate that combustion may greatly modify the structural properties of clay minerals, leading to misinterpreted sorption contributions of different soil components to sorption of polar or ionic compounds.     

Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils

Reactions of heavy metals with soil are important in determining metal fates in the environment. Sorption characteristics of two heavy metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) from Puerto Rico were assessed at varying metal concentrations (0 to 1.2 mM) and pH values (approximately 2 to 7). All soils sorbed more Pb than Cd. Sorption maxima were obtained for each metal for the Oxisol and Ultisol soils, but not the Mollisol. Sorption appeared to depend more on soil mineralogy than organic matter content. Sorption isotherms were linear within the sorption envelope with similar slopes for each soil-metal curve, when plotting metal sorption as a function of pH. Cadmium and Pb isotherms yielded average slopes of approximately 36+/-1 and 28+/-1 units (percent increase in metal sorption per 1-unit increase in pH), respectively. Metal sorption depended more on metal type than soil composition. Cadmium sorption displayed a greater pH dependence than Pb. Cadmium sorption was less than or equal to the amount of negative surface charge except at pH values greater than the point of zero net charge (PZNC). This suggests that Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere complexation at pH > 3.7. However, the amount of Pb sorbed by the Oxisol was greater than the amount of negative surface charge, suggesting that Pb participates in inner-sphere surface reactions. Lead was sorbed more strongly than Cd in our soils and poses less of a threat to underlying ground water systems due to its lower mobility and availability.     

Phosphorus leaching in sandy outwash soils following potato-processing wastewater application

Land application of wastewater presents potential for ground water pollution if not properly managed. In situ breakthrough tests were conducted using potato (Solanum tuberosum L.)-processing wastewater and a Br tracer to characterize P leaching in seasonally frozen sandy outwash soils. In the first test, P and Br breakthrough were measured in a 7-m deep well following wastewater [2.94 mg L(-1) total P (TP); 280 mg L(-1) Br] application at the site that had 13.1 mg water-extractable P (WEP) kg(-1)and 94.4 mg Bray-1 P kg(-1). Bromide was detected in the well after approximately 0.4 pore volumes, but there was no P break-through after 7 pore volumes. In the second breakthrough test, wastewater containing 3.6 mg L(-1) TP and 259 mg L(-1) Br was applied on 1.5-m deep lysimeters at low (0.8 mg WEP kg(-1); 12.1 mg Bray-1 P kg(-1)) and high soil test P sites (104 mg WEP kg(-1); 585 mg Bray-1 P kg(-1)). Leachate TP concentration during the test remained constant (0.04 mg L(-1)) at the low P sites but increased from approximately 3.5 to 5.6 mg L(-1) at the high P sites. These results indicate no P leaching in low P soils, but leaching in high P soils, thus suggesting that most of the P leached at the high P sites was mainly due to desorption and dissolution of weakly adsorbed P from prior P applications. This was consistent with P transport simulations using the convective-dispersive equation. We conclude that P concentration in land-applied wastewater should be regulated based on soil test-P level plus wastewater P loading.     

The influence of biochar and black carbon on reduction and bioavailability of chromate in soils

The widespread use of chromium (Cr) has a deleterious impact on the environment. A number of pathways, both biotic and abiotic in character, determine the fate and speciation of Cr in soils. Chromium exists in two predominant species in the environment: trivalent [(Cr(III)] and hexavalent [Cr(VI)]. Of these two forms, Cr(III) is nontoxic and is strongly bound to soil particles, whereas Cr(VI) is more toxic and soluble and readily leaches into groundwater. The toxicity of Cr(VI) can be mitigated by reducing it to Cr(III) species. The objective of this study was to examine the effect of organic carbon sources on the reduction, microbial respiration, and phytoavailability of Cr(VI) in soils. Organic carbon sources, such as black carbon (BC) and biochar, were tested for their potential in reducing Cr(VI) in acidic and alkaline contaminated soils. An alkaline soil was selected to monitor the phytotoxicity of Cr(VI) in sunflower plant. Our results showed that using BC resulted in greater reduction of Cr(VI) in soils compared with biochar. This is attributed to the differences in dissolved organic carbon and functional groups that provide electrons for the reduction of Cr(VI). When increasing levels of Cr were added to soils, both microbial respiration and plant growth decreased. The application of BC was more effective than biochar in increasing the microbial population and in mitigating the phytotoxicity of Cr(VI). The net benefit of BC emerged as an increase in plant biomass and a decrease in Cr concentration in plant tissue. Consequently, it was concluded that BC is a potential reducing amendment in mitigating Cr(VI) toxicity in soil and plants.     

Dissolution of phosphate in a phosphorus-enriched ultisol as affected by microbial reduction

Phosphorus dissolution often increases as soils become more reduced, but the mechanisms are not fully understood. The objectives of this research were to determine rates and mechanisms of P dissolution during microbial reduction of a surface soil from the North Carolina Coastal Plain. Duplicate suspensions of silt + clay fractions from a Cape Fear sandy clay loam (fine, mixed, semiactive, thermic Typic Umbraquult) were reduced in a continuously stirred redox reactor for 40 d. We studied the effects of three treatments on P dissolution: (i) 2 g dextrose kg(-1) solids added as a microbial carbon source at time 0 d; (ii) 2 g dextrose kg(-1) solids split into three additions at 0, 12, and 26 d; and (iii) no added dextrose. After 40 d of reduction, concentrations of dissolved reactive phosphorus (DRP) were similar for all treatments and increased up to sevenfold from 1.5 to 10 mg L(-1). The initial rate of reduction and dissolution of DRP was significantly greater for the 0-d treatment. A linear relationship (R(2) = 0.79) was found between DRP and dissolved organic carbon (DOC). Dissolved Fe and Al and pH increased, suggesting the formation of aqueous Fe- and Al-organic matter complexes. Separate batch experiments were performed to study the effects of increasing pH and citrate additions on PO(4) dissolution under aerobic conditions. Increasing additions of citrate increased concentrations of DRP, Fe, and Al, while increasing pH had no effect. Results indicated that increased dissolved organic matter (DOM) during soil reduction contributed to the increase in DRP, perhaps by competitive adsorption or formation of aqueous ternary DOM-Fe-PO(4) or DOM-Al-PO(4) complexes.     

Arsenic, cadmium, and lead in California cropland soils: role of phosphate and micronutrient fertilizers

Phosphate and micronutrient fertilizers contain potentially harmful trace elements, such as arsenic (As), cadmium (Cd), and lead (Pb). We investigated if application of these fertilizer increases the As, Cd, and Pb concentrations of the receiving soils. More than 1000 soil samples were collected in seven major vegetable production regions across California. Benchmark soils (no or low fertilizer input) sampled in 1967 and re-sampled in 2001 served as a baseline. Soils were analyzed for total concentrations of As, Cd, Pb, P, and Zn. The P and Zn concentrations of the soils were indicators of P fertilizer and micronutrient inputs, respectively. Results showed that the concentrations of these elements in the vegetable production fields in some production areas of California had been shifted upward. Principal component analysis and cluster analysis showed that the seven production areas could be sorted into three categories: (i) enrichment of As, Cd, and Pb, which was associated with the enrichment of P and Zn in one of the seven areas surveyed; (ii) enrichment of As, which was associated with enrichment of Zn in two of the seven areas surveyed; and (iii) no remarkable correlation between enrichment of As, Cd, and Pb and enrichment of P and Zn in the other four areas surveyed.     

Chemical immobilization of lead, zinc, and cadmium in smelter-contaminated soils using biosolids and rock phosphate

Chemical immobilization, an in situ remediation method where inexpensive chemicals are used to reduce contaminant solubility in contaminated soil, has gained attention. We investigated the effectiveness of lime-stabilized biosolid (LSB), N-Viro Soil (NV), rock phosphate (RP), and anaerobic biosolid (AB) to reduce extractability and plant and gastrointestinal (GI) bioavailability in three Cd-, Pb-, and Zn-contaminated soils from smelter sites. Treated (100 g kg(-1) soil) and control soils were incubated at 27 degrees C and -0.033 MPa (0.33 bar) water content for 90 d. The effect of soil treatment on metal extractability was evaluated by sequential extraction, on phytoavailability by a lettuce bioassay (Lactuca sativa L.), on human GI availability of Pb from soil ingestion by the Physiologically Based Extraction Test. The largest reductions in metal extractability and phytoavailability were from alkaline organic treatments (LSB and NV). Phytotoxic Zn [1188 mg Zn kg(-1) extracted with 0.5 M Ca(NO3)2] in Blackwell soil (disturbed soil) was reduced by LSB, NV, and RP to 166, 25, and 784 mg Zn kg(-1), respectively. Rock phosphate was the only treatment that reduced GI-available Pb in both gastric and intestinal solutions, 23 and 92%, respectively. Alkaline organic treatments (LSB, NV) decreases Cd transmission through the food chain pathway, whereas rock phosphate decreases risk from exposure to Pb via the soil ingestion pathway. Alkaline organic treatments can reduce human exposure to Cd and Pb by reducing Zn phytotoxicity and revegetation of contaminated sites.     

Polyacrylamide distribution in columns of organic matter-removed soils following surface application

Knowledge of how polyacrylamide (PAM) penetrates and distributes in a soil profile after application in irrigation water is important for understanding PAM conditioning depth and evaluating its environmental effects. Little is known, however, about PAM distribution in soil because of the difficulty in quantifying PAM content in natural soils. By using a recently modified substrate-borne PAM quantification method, PAM distribution in columns of organic matter-removed soils was determined. Results showed that penetration of PAM into the soil was affected by salt level of irrigation water, soil texture, initial soil water content, water application method, and other factors. Polyacrylamide penetration depth was about one-eighth to one-half of the water penetration depth, with a particularly high PAM retention in the top few centimeters of the soil. Under different experimental conditions, the PAM retained in the top 0 to 2 cm of soil ranged from 16 to 95% of the total applied amount. More favorable solution-soil contact conditions, longer solution-soil contact time, and lower initial soil moisture caused much more PAM retention in the top few centimeters of the soil. High sorptive affinity of PAM on soil is the main reason for its low penetration into the soil. Although these results were not obtained from natural soils, they are still helpful in improving our understanding of PAM transport behavior in soils.     

Chemistry of inorganic arsenic in soils: II. Effect of phosphorus, sodium, and calcium on arsenic sorption

There are more than 10000 arsenic (As) contaminated sites in Australia. The ability of soils at these contaminated sites to sorb As is highly variable and appreciable amounts of As have been recorded in the subsurface soils. The potential risk of surface and ground water contamination by As at these sites is a major environmental concern. Factors that influence adsorption capacity of soils influence the bioavailability and subsequent mobility of As in soils. In the present study we investigated the effect of PO4(3-) and Na+ and Ca2+ on the sorption of AsV and AsIII by an Oxisol, a Vertisol, and two Alfisols. The presence of P (0.16 mmol L(-1)) greatly decreased AsV sorption by soils containing low amounts of Fe oxides (<100 mmol kg(-1)), indicating competitive adsorption between P and AsV for sorption sites. In contrast, the presence of a similar amount of P had little effect on the amount of AsV adsorbed by soils with high Fe content (>800 mmol kg(-1)). However, AsV sorption substantially decreased from 0.63 to 0.37 mmol kg(-1) as P concentration was increased from 0.16 to 3.2 mmol L(-1) in selected soils. This suggests increased competition between P and AsV for soil sorption sites, through either the higher affinity or the effect of mass action of the increasing concentration of P in solution. A similar effect of P on AsIII sorption was observed in the low sorbing Alfisol and high affinity Oxisol. However, the amount of AsIII sorbed by the Oxisol was much greater than the Alfisol for all treatments. The presence of Ca2+ increased the amount of AsV sorbed compared with that of Na+ and was manifested through changes in the surface charge characteristics of the soils. A similar trend in AsIII sorption was recorded with changes in index cation, although the effect was not as marked as recorded for AsV.     

Effects of oxide coating and selected cations on nitrate reduction by iron metal

Under anoxic conditions, zerovalent iron (Fe(0)) reduces nitrate to ammonium and magnetite (Fe3O4) is produced at near-neutral pH. Nitrate removal was most rapid at low pH (2-4); however, the formation of a black oxide film at pH 5 to 8 temporarily halted or slowed the reaction unless the system was augmented with Fe(2+), Cu(2+), or Al(3+). Bathing the corroding Fe(0) in a Fe(2+) solution greatly enhanced nitrate reduction at near-neutral pH and coincided with the formation of a black precipitate. X-ray diffractometry and scanning electron microscopy confirmed that both the black precipitate and black oxide coating on the iron surface were magnetite. In this system, ferrous iron was determined to be a partial contributor to nitrate removal, but nitrate reduction was not observed in the absence of Fe(0). Nitrate removal was also enhanced by augmenting the Fe(0)-H2O system with Fe(3+), Cu(2+), or Al(3+) but not Ca(2+), Mg(2+), or Zn(2+). Our research indicates that a magnetite coating is not a hindrance to nitrate reduction by Fe(0), provided sufficient aqueous Fe(2+) is present in the system.     

Change in soluble phosphorus in soils following fertilization is dependent on initial Mehlich-3 phosphorus

There is a lack of information on how fertilization and initial Mehlich-3 phosphorus (M3P) interact to affect water soluble P (WSP) in soils. Our objectives were to (i) quantify the relationship between WSP and M3P for four textural diverse benchmark soils of North Carolina (NC) and (ii) quantify the change in WSP concentrations following P additions to soils over a wide range of initial M3P. Soils known to represent a wide range in M3P were collected from an Autryville loamy sand (loamy, siliceous, subactive, thermic Arenic Paleudults), Wasda muck (fine-loamy, mixed, semiactive, acid, thermic Histic Humaquepts), Georgeville silt loam (fine, kaolinitic, thermic Typic Kanhapludults), and Pacolet sandy clay loam (fine, kaolinitic, thermic Typic Kanhapludults) and analyzed for M3P, Fe, Al, and WSP. An incubation study was also conducted where four samples representing a range in M3P from each series were fertilized at rates of 150 and 300 kg P ha(-1), and WSP was measured at 1, 7, and 21 d after fertilization. The Wasda muck exhibited a change point at 115 mg P kg(-1) across a broad range of M3P concentrations (60-238 mg kg(-1)) while Autryville, Georgeville, and Pacolet series (with ranges in M3P of 32-328, 119-524, 0-1034 mg P kg(-1), respectively) maintained linear relationships between WSP and M3P. For the fertilized soils, significant increases in WSP occurred regardless of P rate. Yet, WSP concentrations were greater in soils with greater initial M3P. Thus, these data suggest that shifting animal waste applications to fields of relatively lower M3P concentrations would have an immediate impact on reducing risk for P losses, if all other factors are equal.     

In situ reduction of chromium(VI) in heavily contaminated soils through organic carbon amendment

Chromium has become an important soil contaminant at many sites, and facilitating in situ reduction of toxic Cr(VI) to nontoxic Cr(III) is becoming an attractive remediation strategy. Acceleration of Cr(VI) reduction in soils by addition of organic carbon was tested in columns pretreated with solutions containing 1000 and 10 000 mg L(-1) Cr(VI) to evaluate potential in situ remediation of highly contaminated soils. Solutions containing 0,800, or 4000 mg L(-1) organic carbon in the form of tryptic soy broth or lactate were diffused into the Cr(VI)-contaminated soils. Changes in Cr oxidation state were monitored through periodic micro-XANES analyses of soil columns. Effective first-order reduction rate constants ranged from 1.4 x 10(-8) to 1.5 x 10(-7) s(-1), with higher values obtained for lower levels of initial Cr(VI) and higher levels of organic carbon. Comparisons with sterile soils showed that microbially dependent processes were largely responsible for Cr(VI) reduction, except in the soils initially exposed to 10 000 mg L(-1) Cr(VI) solutions that receive little (800 mg L(-1)) or no organic carbon. However, the microbial populations (< or = 2.1 x 10(5) g(-1)) in the viable soils are probably too low for direct enzymatic Cr(VI) reduction to be important. Thus, synergistic effects sustained in whole soil systems may have accounted for most of the observed reduction. These results show that acceleration of in situ Cr(VI) reduction with addition of organic carbon is possible in even heavily contaminated soils and suggest that microbially dependent reduction pathways can be dominant.     

Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI)

Uranium is a redox active contaminant of concern to both human health and ecological preservation. In anaerobic soils and sediments, the more mobile, oxidized form of uranium (UO(2)(2+) and associated species) may be reduced by dissimilatory metal-reducing bacteria. Despite rapid reduction in controlled, experimental systems, various factors within soils or sediments may limit biological reduction of U(VI), inclusive of competing electron acceptors and alterations in uranyl speciation. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite, and hematite) varying in free energies of formation. Observed pseudo first-order rate coefficients for U(VI) reduction vary from 12 +/- 0.60 x 10(-3) h(-1) (0 mM Ca in the presence of goethite) to 2.0 +/- 0.10 x 10(-3) h(-1) (0.8 mM Ca in the presence of hematite). Nevertheless, dissolved Ca (at concentrations from 0.2 to 0.8 mM) decreases the extent of U(VI) reduction by approximately 25% after 528 h relative to rates without Ca present. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Ferrihydrite, in contrast, acts as a competitive electron acceptor and thus, like Ca, decreases uranium reduction. However, while ferrihydrite decreases U(VI) in solutions without Ca, with increasing Ca concentrations U(VI) reduction is enhanced in the presence of ferrihydrite (relative to its absence)-U(VI) reduction, in fact, becomes almost independent of Ca concentration. The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments.