Molecular weight of dissolved organic matter-napropamide complex transported through soil columns

Soil-derived dissolved organic matter (DOM) has been shown to form stable complexes with the herbicide napropamide [2-(alpha-naphthoxy-N,N-diethylpropionamide] capable of enhancing the transport of napropamide through soil columns. Two soils, one containing sewage sludge-derived organic matter (SS) and the other having only natural organic matter (NoSS) were treated with napropamide and allowed to dry to promote complex formation. Soil columns were prepared by packing a 10-cm layer of untreated, dry, sieved soil followed by an overlying 5-cm layer of napropamide-treated soil. Columns were irrigated and the effluent collected and placed in dialysis chambers. After equilibration napropamide concentrations were determined on both sides of the membrane and complex and quantified based on the amount of napropamide unable to cross the membrane. it was found that for the SS soil 7% and for the NoSS 2.4% of the applied napropamide underwent facilitated transport. In addition, most of the complex transported through the columns had a molecular weight between 500 and 1000 Daltons (Da). The solutions from the SS soil were also found to have formed at least two distinct complexes that were resolved after passing through the untreated soil layer. The results obtained were in agreement with other published results and the techniques used offer a way to separate and concentrate DOM complexes from column effluents for further characterization.     

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.     

Coupled effects of treated effluent irrigation and wetting-drying cycles on transport of triazines through unsaturated soil columns

The physical and chemical parameters controlling the movement of atrazine (6-chloro-N2-ethyl-N4-isopropyl-l,3,5-triazine-2,4-diamine; 98.8%) and prometryn [N,N'-bis(1-methylethyl)-6-(methylthio)-l,3,5triazine-2,4-diamine; 99.5%] were investigated in columns infiltrated with treated effluent under unsaturated transient conditions and subjected to drying events at 22 or 60 degrees C followed by rewetting. Three soils varying in soil pH and texture and three solutions were used. The infiltrating solutions consisted of either a CaCl2 matrix (CC), a swine waste-derived lagoon effluent (SW), or a simulated buffer solution (SB) representative of the element composition and pH of the SW but with no dissolved organic matter. Several parameters were monitored including leachate triazine concentrations, pH, dissolved organic carbon (DOC), inorganic carbon, and flow rates. Compared with CC, application of SW and SB increased column leachate pH, enhanced dissolution of organic carbon and particle dispersion, and decreased average flow rates, which allowed for increased desorption time. The coupled effect of these processes enhanced movement of triazines in some cases, with SW generally having the greatest effect. The individual effect of increased pH was more pronounced for prometryn (pKa=4.05) versus atrazine (pKa=1.66), and most dramatic for the soil with the lowest initial pH. High-temperature drying, which simulated intensive evaporation, further enhanced the dissolution of soil organic matter and the reduction in leachate flow rates with SW and SB applications; however, the net effect under the experimental conditions employed varied with soil type. Relative to low-temperature drying, high-temperature drying in the silty clay loam-packed columns reduced pesticide migration.     

Virus retention and transport as influenced by different forms of soil organic matter

Organic materials are widespread in natural soil and aquatic environments. Their effect on virus transport is very important in assessing the risk for contamination of ground water by viruses. This study aimed to determine how different forms (mineral-associated and dissolved) of natural organic matter influence the retention and transport of two bacteriophages (MS-2 and phiX174) in two porous media (a sand and a soil). We found that mineral-associated organic matter significantly promoted the transport of one virus (MS-2) but not the other (phiX174) in a phosphate-buffered saline solution. Similarly, MS-2 was retained less in sand columns with increasing concentrations of dissolved humic acid, while little effect was observed for phiX174 under the same conditions. The two viruses have different surface properties and thus exhibited different reactivity to the metal oxides present on sand particles and were affected differently by organic matter. Because the organic matter used in the study was negatively charged and hydrophilic, blocking of virus sorption sites and increasing of virus-medium electrostatic repulsion arising from modification of the sand and virus surface by organic matter are probably responsible for the facilitated transport. For dissolved humic acid, its competition for sorption sites with viruses was an additional mechanism involved. This study suggests that the effect of organic matter varied depending on the organic material properties and the type of viruses involved. As a general trend, the effect of organic matter was dominated by electrostatic rather than hydrophobic interactions.     

Sorptive and desorptive fractionation of dissolved organic matter by mineral soil matrices

Interactions of dissolved organic matter (DOM) with soil minerals, such as metal oxides and clays, involve various sorption mechanisms and may lead to sorptive fractionation of certain organic moieties. While sorption of DOM to soil minerals typically involves a degree of irreversibility, it is unclear which structural components of DOM correspond to the irreversibly bound fraction and which factors may be considered determinants. To assist in elucidating that, the current study aimed at investigating fractionation of DOM during sorption and desorption processes in soil. Batch DOM sorption and desorption experiments were conducted with organic matter poor, alkaline soils. Fourier-transform infrared (FTIR) and UV-Vis spectroscopy were used to analyze bulk DOM, sorbed DOM, and desorbed DOM fractions. Sorptive fractionation resulted mainly from the preferential uptake of aromatic, carboxylic, and phenolic moieties of DOM. Soil metal-oxide content positively affected DOM sorption and binding of some specific carboxylate and phenolate functional groups. Desorptive fractionation of DOM was expressed by the irreversible-binding nature of some carboxylic moieties, whereas other bound carboxylic moieties were readily desorbed. Inner-sphere, as opposed to outer-sphere, ligand-exchange complexation mechanisms may be responsible for these irreversible, as opposed to reversible, interactions, respectively. The interaction of aliphatic DOM constituents with soil, presumably through weak van der Waals forces, was minor and increased with increasing proportion of clay minerals in the soil. Revealing the nature of DOM-fractionation processes is of great importance to understanding carbon stabilization mechanisms in soils, as well as the overall fate of contaminants that might be associated with DOM.     

Interactions of carbamazepine in soil: effects of dissolved organic matter

Pharmaceutical compounds (PCs) and dissolved organic matter (DOM) are co-introduced into soils by irrigation with reclaimed wastewater. We targeted carbamazepine (CBZ) as a model compound to study the tertiary interactions between relatively polar PCs, DOM, and soil. Sorption-desorption behavior of CBZ was studied with bulk clay soil and the corresponding clay size fraction in the following systems: (i) without DOM, (ii) co-introduced with DOM, and (iii) pre-adsorption of DOM before CBZ introduction. Sorption of the DOM to both sorbents was irreversible and exhibited pronounced sorption-desorption hysteresis. Carbamazepine exhibited higher sorption affinity and nonlinearity, and a higher degree of desorption hysteresis with the bulk soil than the corresponding clay size fraction. This was probably due to specific interactions with polar soil organic matter fractions that are more common in the bulk soil. Co-introduction of CBZ and DOM to the soil did not significantly affect the sorption behavior of CBZ; however, following pre-adsorption of DOM by the bulk soil, an increase in sorption affinity and decrease in sorption linearity were observed. In this latter treatment, desorption hysteresis of CBZ was significantly increased for both sorbents. We hypothesize that this was due to either strong chemical interactions of CBZ with the adsorbed DOM or physical encapsulation of CBZ in DOM-clay complexes. Based on this study, we suggest that DOM facilitates stronger interactions of polar PCs with the solid surface. This mechanism can reduce PC desorption ability in soils.     

Sorption and fractionation of dissolved organic matter and associated phosphorus in agricultural soil

Mobility of dissolved organic matter (DOM) strongly affects the export of nitrogen (N) and phosphorus (P) from soils to surface waters. To study the sorption and mobility of dissolved organic C and P (DOC, DOP) in soil, the pH-dependent sorption of DOM to samples from Ap, EB, and Bt horizons from a Danish agricultural Humic Hapludult was investigated and a kinetic model applicable in field-scale models tested. Sorption experiments of 1 to 72 h duration were conducted at two pH levels (pH 5.0 and 7.0) and six initial DOC concentrations (0-4.7 mmol L(-1)). Most sorption/desorption occurred during the first few hours. Dissolved organic carbon and DOP sorption decreased strongly with increased pH and desorption dominated at pH 7, especially for DOC. Due to fractionation during DOM sorption/desorption at DOC concentrations up to 2 mmol L(-1), the solution fraction of DOM was enriched in P indicating preferred leaching of DOP. The kinetics of sorption was expressed as a function of how far the solution DOC or DOP concentrations deviate from "equilibrium." The model was able to simulate the kinetics of DOC and DOP sorption/desorption at all concentrations investigated and at both pH levels making it useful for incorporation in field-scale models for quantifying DOC and DOP dynamics.     

Impact of dissolved organic matter on copper mobility in aquifer material

Naturally occurring dissolved organic matter (DOM) and biosolids-derived DOM have been implicated in the mobility of metals in soils and aquifer materials. To investigate the effect of DOM on copper mobility in aquifer material, DOM derived from sewage biosolids was separated into two apparent molecular-weight (MW) fractions, 500 to 3500 Da (LMW) and > 14 000 Da (HMW). In each MW fraction, the DOM was further fractionated into hydrophilic, hydrophobic acid, and hydrophobic neutral compounds by an XAD-8 chromatography technique. The mobility of these DOM components and their influences on copper transport in a sesquioxide-coated, sandy aquifer material were examined with column transport experiments. The LMW DOM was found to be highly mobile, whereas the HMW DOM had a greater tendency to be retained by the aquifer material. Within the same MW fraction, the mobility of DOM followed the order of hydrophilic DOM > hydrophobic acid DOM > hydrophobic neutral DOM. Copper breakthrough curves in the presence of various DOM components showed that, except for the HMW hydrophilic fraction, DOM components enhanced Cu transport through the aquifer columns at early stages of transport (the first 75 pore volumes). In the later stages, however, all the DOM components substantially inhibited Cu mobility. We hypothesize that several mechanisms could account for retardation of Cu movement in the presence of the DOM fractions, including the formation of ternary complexes between the aquifer material, Cu, and DOM; changes in the electrostatic potential at the solid-phase surface; and pH buffering by DOM.     

Sorption and biodegradability of sludge bacterial extracellular polymers in soil and their influence on soil copper behavior

Bacterial extracellular polymers (BEP) affect the translocation and fate of organic and inorganic pollutants in terrestrial and aquatic ecosystems. In this study, BEP from activated sludge was compared with sludge dissolved organic matter (DOM) in terms of behavior and effects on the mobilization and bioavailability of Cu in a well-aged Cu-contaminated orchard sandy loam. Addition of sludge BEP (10-200 mg dissolved organic carbon [DOC] L(-1)) to the soil resulted in 1.6- to 12.8-fold-higher soil soluble Cu concentration over the control and 1.3- to 2.2-fold over sludge DOM of the same concentration. Consequently, the Cu uptake by the ryegrass (Lolium perenne L., cv. Target) grown in the soil was increased by 31% due to interval watering of 100 mg DOC L(-1) of sludge BEP solution in a 35-d period. The influence of sludge BEP on mobilizing soil Cu could be maintained as long as 60 d or more, depending on BEP biodegradation status. The findings that sludge BEP promoted Cu mobilization and bioavailability could be attributed to less adsorption of BEP by soil, slow degradation, and higher affinity with Cu. For example, after 3 wk of aerobic incubation, the soluble Cu present in the sludge DOM-treated soil was reduced to about the level of the control, while the concentration of soluble Cu in BEP-treated soil was 6.2 times higher than that in the control. Therefore, sludge BEP could act as a facilitated-transport carrier of Cu. The environmental risk of Cu should receive much attention if BEP is incorporated into soils.     

Determination of polyacrylamide in soil waters by size exclusion chromatography

Determination of polyacrylamide (PAM) concentration in soil waters is important in improving the efficiency of PAM application and understanding the environmental fate of applied PAM. In this study, concentrations of anionic PAM with high molecular weight in soil waters containing salts and dissolved organic matter (DOM) were determined quantitatively by size exclusion chromatography (SEC) with ultraviolet (UV) absorbance detection. Polyacrylamide was separated from interferential salts and DOM on a polymeric gel column eluted with an aqueous solution of 0.05 M KH2PO4 and then detected at a short UV wavelength of 195 nm. Analysis of PAM concentrations in soil sorption supernatants, soil leachates, and water samples from irrigation furrow streams showed that SEC is an effective approach for quantifying low concentrations (0-10 mg L(-1)) of PAM in waters containing soil DOM and salts. The method has a lower detection limit of 0.02 microg and a linear response range of 0.2 to 80 mg L(-1). Precision studies gave coefficients of variation of < 1.96% (n = 4) for > 10 mg L(-1) PAM and < 12% (n = 3) for 0.2 to 3 mg L(-1) PAM.     

Metal immobilization in soils using synthetic zeolites

In situ immobilization of heavy metals in contaminated soils is a technique to improve soil quality. Synthetic zeolites are potentially useful additives to bind heavy metals. This study selected the most effective zeolite in cadmium and zinc binding out of six synthetic zeolites (mordenite-type, faujasite-type, zeolite X, zeolite P, and two zeolites A) and one natural zeolite (clinoptilolite). Zeolite A appeared to have the highest binding capacity between pH 5 and 6.5 and was stable above pH 5.5. The second objective of this study was to investigate the effects of zeolite addition on the dissolved organic matter (DOM) concentration. Since zeolites increase soil pH and bind Ca, their application might lead to dispersion of organic matter. In a batch experiment, the DOM concentration increased by a factor of 5 when the pH increased from 6 to 8 as a result of zeolite A addition. A strong increase in DOM was also found in the leachate of soil columns, particularly in the beginning of the experiment. This resulted in higher metal leaching caused by metal-DOM complexes. In contrast, the free ionic concentration of Cd and Zn strongly decreased after the addition of zeolites, which might explain the reduction in metal uptake observed in plant growth experiments. Pretreatment of zeolites with acid (to prevent a pH increase) or Ca (to coagulate organic matter) suppressed the dispersion of organic matter, but also decreased the metal binding capacity of the zeolites due to competition of protons or Ca.     

Influence of decomposition on chemical properties of plant- and manure-derived dissolved organic matter and sorption to goethite

Sorption of dissolved organic matter (DOM) plays an important role in maintaining the fertility and quality of soils in agricultural ecosystems. Few studies have examined the effects of decomposition on DOM sorption and chemical characteristics. This study investigated the sorption to goethite (alpha-FeOOH) of fresh and decomposed hydrophilic (HPL) and hydrophobic (HPB) DOM fractions extracted from the shoots and roots of crimson clover (Trifolium incarnatum L.), corn (Zea mays L.), soybean [Glycine max (L.) Merr.], hairy vetch (Vicia villosa L.), and dairy and poultry manures. Sorption was positively related to apparent molecular weight (MWAP), aromaticity as measured by absorptivity at 280 nm, and phenolic acid content. A 10-d laboratory microbial decomposition of the source organic matter generally increased the sorption of the extracted DOM onto goethite. The decomposition effect on sorption was greater for the HPL fractions than for the HPB fractions. There was a decrease in the MWAP values of the DOM samples following sorption to goethite. In many cases the reduction in MWAP was large, indicating a strong preference by goethite for the higher MWAP DOM fractions. The results of this laboratory-based research demonstrate that microbial processes affect the chemical characteristics of DOM which may affect the distribution of soil organic C pools.     

Effect of dissolved organic matter from sludge and sludge compost on soil copper sorption

Interaction of Cu with dissolved organic matter (DOM) is an important physicochemical process affecting Cu mobility in soils. The aim of this study was to investigate the effects of DOM from anaerobically digested dewatered sludge and sludge compost on the sorption of Cu on an acidic sandy loam and a calcareous clay loam. In the presence of DOM, Cu sorption capacity decreased markedly for both soils, especially for the calcareous soil. The Cu sorption isotherms could be well described by the Freundlich equation (r2 = 0.99), and the binding intensity parameter of soils in the presence of sludge DOM was lower than compost DOM. An increase in DOM concentration significantly reduced the sorption of Cu by both soils. Within the Cu and DOM concentration range studied, the decrease in Cu sorption caused by sludge DOM was consistently greater than that of compost DOM. This might be attributed to the greater amount of hydrophobic fraction of DOM in the compost. Moreover, the reduction of Cu sorption caused by DOM was more obvious in the soil with higher pH. In addition, the sorption of Cu increased with an increase in pH for both soils without the addition of DOM, while Cu sorption in the presence of DOM was unexpectedly decreased with an increase in pH at a pH >6.8. This implied that DOM produced by sludge or other C-enriched organic wastes heavily applied on calcareous soils might facilitate the leaching loss of Cu because of the formation of soluble DOM-metal complexes.     

Colloid mobilization and arsenite transport in soil columns: effect of ionic strength

Colloid generation and transport in soils is of significance because of suspected colloid-facilitated transport of contaminants to the groundwater. In this study, colloid mobilization and its effect on the transport of arsenite [As(III)] were investigated in Olivier (fine-silty, mixed, active, thermic Aquic Fraglossudalfs) and Windsor (mixed, mesic typic Udipsamments) soil columns. Input solution of 10 mg L(-1) As(III) in 0.01 M NaCl was applied to water-saturated columns, and followed by leaching with deionized water (DIW). Flow interruptions were performed during the As(III) input and DIW leaching phases. Turbidity, electrical conductivity (EC), and pH of column effluents were monitored with time. Total and dissolved concentrations of As, Fe, and Al were analyzed. Effluent results demonstrated that colloid-facilitated transport contributed little to arsenic movement when the solution ionic strength was maintained constant. Mobilization of colloidal amorphous material and enhanced transport of As(III) were observed as a result of changes in ionic strength of the input solution. The peak of colloid generation coincided with peak concentrations of Fe, suggesting mobilization of Fe oxides and facilitated transport of As(III) adsorbed on oxide surfaces. Colloid mobilization was enhanced due to flow interruption in the Olivier column, which suggests slow dissociation of aggregated colloidal particles. Moreover, effluent results indicate significant effect of organic matter in stabilizing aggregates of colloidal particles.     

Dissolved oxygen and its response to eutrophication in a tropical black water river

The Siak is a typical, nutrient-poor, well-mixed, black water river in central Sumatra, Indonesia, which owes its brown color to dissolved organic matter (DOM) leached from surrounding, heavily disturbed peat soils. We measured dissolved organic carbon (DOC) and oxygen concentrations along the river, carried out a 36-h experiment in the province capital Pekanbaru and quantified organic matter and nutrient inputs from urban wastewater channels into the Siak. In order to consider the complex dynamic of oxygen in rivers, a box-diffusion model was used to interpret the measured data. The results suggest that the decomposition of soil derived DOM was the main factor influencing the oxygen concentration in the Siak which varied between ～100 and 140 μmol l^?1. Additional DOM input caused by wastewater discharges appeared to reduce the oxygen concentrations by ～20 μmol l^?1 during the peak-time in household water use in the early morning and in the early evening. Associated enhanced nutrient inputs appear to reduce the impact of the anthropogenic DOM by favoring the photosynthetic production of oxygen in the morning. A reduction of 20 μmol l^?1, which although perhaps not of great significance in Pekanbaru, has strong implications for wastewater management in the fast developing areas downstream Pekanbaru where oxygen concentrations rarely exceed 20 μmol l^?1.     

Environmental fate of triasulfuron in soils amended with municipal waste compost

The amendment of soil with compost may significantly influence the mobility and persistence of pesticides and thus affect their environmental fate. Factors like adsorption, kinetics, and rate of degradation of pesticides could be altered in amended soils. The aim of this study was to determine the effects of the addition of compost made from source-separated municipal waste and green waste, on the fate of triasulfuron [(2-(2-chloroethoxy)-N-[[4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide], a sulfonylurea herbicide used in postemergence treatment of cereals. Two native soils with low organic matter content were used. A series of analyses was performed to evaluate the adsorption and degradation of the herbicide in soil and in solution after the addition of compost and compost-extracted organic fractions, namely humic acids (HA), fulvic acids (FA), and hydrophobic dissolved organic matter (HoDOM). Results have shown that the adsorption of triasulfuron to soil increases in the presence of compost, and that the HA and HoDOM fractions are mainly responsible for this increase. Hydrophobic dissolved organic matter applied to the soils underwent sorption reactions with the soils, and in the sorbed state, served to increase the adsorption capacity of the soil for triasulfuron. The rate of hydrolysis of triasulfuron in solution was significantly higher at acidic pH and the presence of organic matter fractions extracted from compost also slightly increased the rate of hydrolysis. The rate of degradation in amended and nonamended soils is explained by a two-stage degradation kinetics. During the initial phase, although triasulfuron degradation was rapid with a half-life of approximately 30 d, the presence of compost and HoDOM was found to slightly reduce the rate of degradation with respect to that in nonamended soil.     

Reactivity of litter leachates from California oak woodlands in the formation of disinfection by-products

Litter materials from forested watersheds can be a significant source of dissolved organic matter (DOM) to surface waters that can contribute to the formation of carcinogenic disinfection by-products (DBPs) during drinking-water chlorination. This study characterized the reactivity of DOM from litter leachates of representative vegetation in oak woodlands, a major plant community in the Foothill Region of California. Leachates from fresh and decomposed litter (duff) from two oak species, pine, and annual grasses were collected for an entire rainy season to evaluate their reactivity to form DBPs on chlorination. Relationships among specific ultraviolet absorbance (SΔUVA), fluorescence index (FI), specific differential ultraviolet absorbance (SΔUVA), specific chlorine demand (SCD), and the dissolved organic carbon:dissolved organic nitrogen (DOC:DON) ratio to the specific DBP formation potential (SDBP-FP) were examined. The DOM derived from litter materials had considerable reactivity in forming trihalomethanes (THMs) (1.80-3.49 mmol mol), haloacetic acid (HAAs) (1.62-2.76 mmol mol(-1)), haloacetonitriles (HANs) (0.12-0.37 mmol mol(-1)), and chloral hydrate (CHD) (0.16-0.28 mmol mol). These values are comparable to other identified watershed sources of DBP precursors reported for the California Delta, such as wetlands and organic soils. Vegetation type and litter decomposition stage (fresh litter versus 1-5 yr-old duff) were key factors that determined characteristics of DOM and their reactivity to form DBPs. Pine litter had significantly lower specific THM formation potential compared with oak and grass, and decomposed duff had a greater DON content, which is a precursor of HANs and other nitrogenous DBPs. The SΔUVA and SDBP-FP were temporally variable and dependent on vegetation type, degree of decomposition, and environmental conditions. Among the optical properties of DOM, SΔUVA was the only parameter that was consistently correlated with SDBP-FP.     

Cadmium binding by fractions of dissolved organic matter and humic substances from municipal solid waste compost

The agricultural practice of amending soils with composted municipal solid waste (MSW) adds significant amounts of organic matter and trace metals, including Cd. Under these conditions, soluble organic complexes of Cd formed in the compost may be more significant than previously thought, due to Cd bioavailability and mobility in the soil environment. To study the relative importance of different types of organic ligands in MSW compost for the binding of Cd, six fractions of the dissolved organic matter (DOM) in addition to humic acid (HA) and fulvic acid (FA) were extracted and their complexation of Cd quantified at pH 7 using an ion-selective electrode (ISE). The highest complexing capacities (CC) for Cd were found for the most humified ligands: HA (2386 micromol Cd g(-1) C of ligand), predialyzed FA (2468 micromol Cd g(-1) C), and HoA, a fulvic-type, easily soluble fraction (1042 micromol Cd g(-1) C). The differences in CC for Cd of the various organic ligands were not directly related to total acid-titratable or carboxylic groups, indicating the importance of sterical issues and other functional groups. The strength of association between Cd and the organic ligands was characterized by calculating stability constants for binding at the strongest sites (pK(int)) and modeling the distribution of binding site strengths. The pK(int) values of the DOM fractions ranged between 6.93 (HiN: polysaccharides) and 8.11 (HiB: proteins and aminosugars), compared with 10.05 for HA and 7.98 for FA. Hence, the highly complex and only partially soluble organic molecules from compost such as HA and FA demonstrated the highest capacity to sequester Cd. However, strong Cd binding of organic ligands containing N-functional groups (HiB) in addition to a high CC of soluble, humified ligands like HoA indicated the relevance of these fractions for the organic complexation of Cd in solution.     

Relationships Between Nitrogen Transformation Rates and Gene Abundance in a Riparian Buffer Soil

Denitrification is a critical biogeochemical process that results in the conversion of nitrate to volatile products, and thus is a major route of nitrogen loss from terrestrial environments. Riparian buffers are an important management tool that is widely utilized to protect water from non-point source pollution. However, riparian buffers vary in their nitrate removal effectiveness, and thus there is a need for mechanistic studies to explore nitrate dynamics in buffer soils. The objectives of this study were to examine the influence of specific types of soluble organic matter on nitrate loss and nitrous oxide production rates, and to elucidate the relationships between these rates and the abundances of functional genes in a riparian buffer soil. Continuous-flow soil column experiments were performed to investigate the effect of three types of soluble organic matter (citric acid, alginic acid, and Suwannee River dissolved organic carbon) on rates of nitrate loss and nitrous oxide production. We found that nitrate loss rates increased as citric acid concentrations increased; however, rates of nitrate loss were weakly affected or not affected by the addition of the other types of organic matter. In all experiments, rates of nitrous oxide production mirrored nitrate loss rates. In addition, quantitative polymerase chain reaction (qPCR) was utilized to quantify the number of genes known to encode enzymes that catalyze nitrite reduction (i.e., nirS and nirK) in soil that was collected at the conclusion of column experiments. Nitrate loss and nitrous oxide production rates trended with copy numbers of both nir and 16s rDNA genes. The results suggest that low-molecular mass organic species are more effective at promoting nitrogen transformations than large biopolymers or humic substances, and also help to link genetic potential to chemical reactivity.     

Solubilization of mixed polycyclic aromatic hydrocarbons through a rhamnolipid biosurfactant

The solubilization of phenanthrene (PHE) and pyrene (PYR) by rhamnolipid biosurfactant was systematically investigated. The solubilities of both polycyclic aromatic hydrocarbons (PAHs) were increased linearly with the biosurfactant concentration at above critical micelle concentration. A competitive effect was observed between PHE and PYR. The solubility of PHE in a mixed system was lower than that in a single PAH system, whereas the solubility of PYR in a mixed system was enhanced. This is because the hydrophobicity of PYR is higher than that of PHE, so PYR is favored in the competitive solubilization. The combined effect of biosurfactant and dissolved organic matter (DOM) on PAH solubilization was also examined. Two kinds of DOM (derived from soil and from compost) were used. There was an obvious enhancement of solubility for PHE and PYR in systems with concurrence of DOM and biosurfacrant compared with systems with only DOM or biosurfactant; however, the enhancement in the mixed system was less than their additive. This could be explained as the formation of a DOM-biosurfactant complex. In addition, the solubility enhancement of PAHs in a compost-DOM system was higher than that in a soil-DOM system. This could be explained as functional group differences of two DOM types.