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.     

Determining sources of dissolved organic carbon and disinfection byproduct precursors to the McKenzie River, Oregon

This study was conducted to determine the main sources of dissolved organic carbon (DOC) and disinfection byproduct (DBP) precursors to the McKenzie River, Oregon (USA). Water samples collected from the mainstem, tributaries, and reservoir outflows were analyzed for DOC concentration and DBP formation potentials (trihalomethanes [THMFPs] and haloacetic acids [HAAFPs]). In addition, optical properties (absorbance and fluorescence) of dissolved organic matter (DOM) were measured to provide insight into DOM composition and assess whether optical properties are useful proxies for DOC and DBP precursor concentrations. Optical properties indicative of composition suggest that DOM in the McKenzie River mainstem was primarily allochthonous--derived from soils and plant material in the upstream watershed. Downstream tributaries had higher DOC concentrations than mainstem sites (1.6 +/- 0.4 vs. 0.7 +/- 0.3 mg L(-1)) but comprised < 5% ofmainstem flows and had minimal effect on overall DBP precursor loads. Water exiting two large upstream reservoirs also had higher DOC concentrations than the mainstem site upstream of the reservoirs, but optical data did not support in situ algal production as a source of the added DOC during the study. Results suggest that the first major rain event in the fall contributes DOM with high DBP precursor content. Although there was interference in the absorbance spectra in downstream tributary samples, fluorescence data were strongly correlated to DOC concentration (R2 = 0.98), THMFP (R2 = 0.98), and HAAFP (R2 = 0.96). These results highlight the value of using optical measurements for identifying the concentration and sources of DBP precursors in watersheds, which will help drinking water utilities improve source water monitoring and management programs.     

Changes in the quality of chromophoric dissolved organic matter leached from senescent leaf litter during the early decomposition

Chromophoric dissolved organic matter (CDOM) leached from leaf litter is a major source of humus in mineral soil of forest ecosystems. While their functions and refractoriness depend on the physicochemical structure, there is little information on the quality of CDOM, especially for that leached in the very early stages of litter decomposition when a large amount of dissolved organic matter (DOM) is leached. This study aimed to better understand the variations/changes in the composition of CDOM leached from senescent leaf litter from two tree species during the early stage of decomposition. Leaf litter from a conifer tree (Japanese cedar, D. Don) and a deciduous broad-leaved tree (Konara oak, Thunb.) were incubated in columns using simulated rainfall events periodically for a total of 300 d at 20°C. The quality of CDOM was investigated based on the fluorescence properties by using a combination of excitation-emission matrix fluorescence (EEM) and parallel factor analysis (PARAFAC). In addition, the phenolic composition of DOM was investigated at a molecular level by thermally assisted hydrolysis and methylation-gas chromatography-mass spectrometry (THM-GC-MS) in the presence of tetramethylammonium hydroxide (TMAH). The EEM was statistically decomposed into eight fluorescence components (two tannin/peptide-like peaks, one protein-like peak, and five humic-like peaks). A significant contribution of tannin/peptide-like peaks was observed at the beginning of incubation, but these peaks decreased quickly and humic-like peaks increased within 1 mo of incubation. The composition of humic-like peaks was different between tree species and changed over the incubation period. Since tannin-derived phenolic compounds were detected in the DOM collected after 254 d of incubation on THM-GC-MS, it was suggested that tannins partially changed its structure, forming various humic-like peaks during the early decomposition.     

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.     

LEAF LITTER BREAKDOWN IN A RECENTLY IMPOUNDED RESERVOIR1

ABSTRACT: The impoundment of Richard B. Russell Lake resulted in the inundation of 3490 ha of forested area or 33 percent of the total area of the lake. Estimates of the total inundated leaf litter biomass were combined with a leaf litter decomposition study to determine the nutrient load and dissolved oxygen demand to the reservoir. Hickory leaf bags broke down most rapidly at the 3-m and 28-rn depths, followed by short-needle pine, white oak, a hardwood litter mixture, beech, and red oak. Leaf bags incubated at the 3-m depth exhibited significantly higher breakdown rates than those at the 28-m depth for most leaf types, due to differences in dissolved oxygen and temperature. Respiration rates of litter were also higher at the 3-m depth. Most leaf types accumulated nitrogen and phosphorus and lost organic carbon after an initial leaching period. Richard B. Russell Lake exhibited extensive anoxia and the buildup of total organic carbon, nitrogen, and phosphorus during summer stratification. Leaf litter breakdown accounted for 64 percent of the organic carbon increase but acted as a sink for nitrogen and phosphorus. The dissolved oxygen demand of the litter accounted for over 50 percent of the demand incurred in the lake.     

Dissolved organic nitrogen regulation in freshwaters

Dissolved organic nitrogen (DON) has been hypothesized to play a major role in N cycling in a variety of ecosystems. Our aim was to assess the seasonal and concentration relationships between dissolved organic carbon (DOC), DON, and NO3- within 102 streams and 16 lakes within catchments of differing complexity situated in Wales. Further, we aimed to assess whether patterns of land use, soil type, and vegetation gave consistent trends in DON and dissolved inorganic nitrogen (DIN) relationships over a diverse range of catchments. Our results reinforce that DON constitutes a significant component of the total dissolved N pool typically representing 40 to 50% of the total N in streams and lakes but sometimes representing greater than 85% of the total dissolved N. Generally, the levels of DON were inversely correlated with the concentration of DIN. In contrast to DIN concentrations, which showed distinct seasonality, DON showed no consistent seasonal trend. We hypothesize that this reflects differences in the bioavailability of these two N types. The amount of DON, DOC, and DIN was significantly related to soil type with higher DON export from Histosol-dominated catchments in comparison with Spodosol-dominated watersheds. Vegetation cover also had a significant effect on DON concentrations independent of soil type with a nearly twofold decrease in DON export from forested catchments in comparison with nonforested watersheds. Due to the diversity in catchment DON behavior, we speculate that this will limit the adoption of DON as a broad-scale indicator of catchment condition for use in monitoring and assessment programs.     

Dissolved organic carbon and disinfection by-product precursor release from managed peat soils

A wetland restoration demonstration project examined the effects of a permanently flooded wetland on subsidence of peat soils. The project, started in 1997, was done on Twitchell Island, in the Sacramento-San Joaquin Delta of California. Conversion of agricultural land to a wetland has changed many of the biogeochemical processes controlling dissolved organic carbon (DOC) release from the peat soils, relative to the previous land use. Dissolved organic C in delta waters is a concern because it reacts with chlorine, added as a disinfectant in municipal drinking waters, to form carcinogenic disinfection byproducts (DBPs), including trihalomethanes (THMs) and haloacetic acids (HAAs). This study explores the effects of peat soil biogeochemistry on DOC and DBP release under agricultural and wetland management. Results indicate that organic matter source, extent of soil organic matter decomposition, and decomposition pathways all are factors in THM formation. The results show that historical management practices dominate the release of DOC and THM precursors. However, within-site differences indicate that recent management decisions can contribute to changes in DOC quality and THM precursor formation. Not all aromatic forms of carbon are highly reactive and certain environmental conditions produce the specific carbon structures that form THMs. Both HAA and THM precursors are elevated in the DOC released under wetland conditions. The findings of this study emphasize the need to further investigate the roles of organic matter sources, microbial decomposition pathways, and decomposition status of soil organic matter in the release of DOC and DBP precursors from delta soils under varying land-use practices.     

The impact of alum addition on organic P transformations in poultry litter and litter-amended soil

Poultry litter treatment with alum (Al(2)(SO(4))(3) . 18H(2)O) lowers litter phosphorus (P) solubility and therefore can lower litter P release to runoff after land application. Lower P solubility in litter is generally attributed to aluminum-phosphate complex formation. However, recent studies suggest that alum additions to poultry litter may influence organic P mineralization. Therefore, alum-treated and untreated litters were incubated for 93 d to assess organic P transformations during simulated storage. A 62-d soil incubation was also conducted to determine the fate of incorporated litter organic P, which included alum-treated litter, untreated litter, KH(2)PO(4) applied at 60 mg P kg(-1) of soil, and an unamended control. Liquid-state (31)P nuclear magnetic resonance indicated that phytic acid was the only organic P compound present, accounting for 50 and 45% of the total P in untreated and alum-treated litters, respectively, before incubation and declined to 9 and 37% after 93 d of storage-simulating incubation. Sequential fractionation of litters showed that alum addition to litter transformed 30% of the organic P from the 1.0 mol L(-1) HCl to the 0.1 mol L(-1) NaOH extractable fraction and that both organic P fractions were more persistent in alum-treated litter compared with untreated litter. The soil incubation revealed that 0.1 mol L(-1) NaOH-extractable organic P was more recalcitrant after mixing than was the 1.0 mol L(-1) HCl-extractable organic P. Thus, adding alum to litter inhibits organic P mineralization during storage and promotes the formation of alkaline extractable organic P that sustains lower P solubility in the soil environment.     

Characterization of brewery wastewater with spectrofluorometry analysis

The wastewater treatment systems from the three local breweries consist of upflow anaerobic sludge blanket (UASB) and activated sludge (AS) connected in series for which the influent and effluent from each treatment step were collected and determined for their dissolved organic matter (DOM) surrogate parameters including dissolved organic carbon (DOC), UV(254) and SUVA(254). The analyses suggested that the influent wastewater contained a high level of aromatic organic content classified as humic substances with high average molecular weight. Organic removal mostly occurred in the UASBs where DOC and UV(254) were reduced by 24-58% and 38-50%, respectively. Spectrofluorometry analysis (fluorescent excitation-emission matrix: FEEM) was reasonably accurate in evaluating DOM reduction during the treatment course. A total of eight fluorescent peaks were detected by the FEEM technique comprising (A) 230 nm(Ex)/315 nm(Em), (B) 275 nm(Ex)/315 nm(Em), (C) 230 nm(Ex)/365 nm(Em), (D) 285 nm(Ex)/365 nm(Em), (E) 290 nm(Ex)/400 nm(Em), (F) 335-355 nm(Ex)/405-465 nm(Em), (G) 255 nm(Ex)/455 nm(Em), and (H) 500 nm(Ex)/525 nm(Em). Peaks 'A and B' and 'C and D' were associated with tyrosine-like, tryptophan-like substances, respectively, whilst each individual peak E, F and G was associated with humic and fulvic acid-like substances. Peaks C, D, F and H were always found in the influent wastewater from all the breweries, whereas the effluents only exhibited Peak F. The origin of Peak H had not been recognized elsewhere and was not identified in this work. This suggested that FEEM could not only be used to monitor the reduction in DOM, but it could also provide details on the organic composition of the wastewater.     

Differences in Dissolved Organic Carbon and Nitrogen Responses to Storm‐Event and Ground‐Water Conditions in a Forested,Glaciated Watershed in Western New York1

Abstract: Differences in the storm‐event responses of dissolved organic carbon (DOC) and nitrogen (DON) in streamflow and ground water were evaluated for a glaciated forested watershed in western New York. Eight to ten storm events with varying rainfall amounts, intensities, and antecedent moisture conditions were studied for three catchments (1.6, 3.4, and 696 ha) over a three‐year period (2003‐2005). Concentrations of DOC in streamflow exiting the catchments were significantly higher for storm events following a dry period, whereas no similar response was observed for DON. Highest DON concentrations in streamflow were typically associated with storm events following wet antecedent moisture conditions. In addition to antecedent moisture conditions, DOC concentrations were also positively correlated with precipitation amounts, while DON did not reveal a consistent pattern. Streamwater and ground‐water concentrations of DOC during storm events were also strongly correlated with riparian ground‐water depths but a similar relationship was not observed for DON. Ground‐water DON concentrations were also more variable than DOC. We hypothesized that the differences in DOC and DON responses stemmed from the differences in catchment sources of these solutes. This study suggests that while DOC and DON are intrinsically linked as components of dissolved organic matter, their dynamics and exports from watersheds may be regulated by a different set of mechanisms and factors. Identifying these differences is critical for developing more reliable and robust models for transport of dissolved organic matter.     

Effects of dissolved organic matter from animal waste effluent on chlorpyrifos sorption by soils

The increased use of animal waste-derived effluents for irrigation could result in the enhanced movement of pesticides through complexation with dissolved organic materials. Batch equilibrium studies were conducted to measure the interaction among soil, chlorpyrifos [O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate], and dissolved organic matter (DOM) from poultry, swine, and cow waste-derived lagoon effluents. All DOM was found to have a strong affinity for chlorpyrifos, resulting in reduced sorption of chlorpyrifos by soil, thus the potential for DOM-enhanced mobility. Effluent DOM was observed to sorb to soils. Thus, for increasingly higher soil mass to solution volume ratios, the effect of chlorpyrifos association with water-borne DOM on sorption decreases significantly. For high soil mass to solution volume ratios typical of soil profiles in the landscape, the potential for DOM-enhanced transport will be greatly attenuated. Dissolved organic matter concentration and the nonpolar nature of DOM in the lagoon effluent decreased with increasing residence time in the cells of the lagoon system, thus reducing the potential for DOM-enhanced transport.     

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.     

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.     

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.     

Interactions of organic compounds with wastewater dissolved organic matter: role of hydrophobic fractions

The role of structural fractions of dissolved organic matter (DOM) from wastewater in the sorption process of hydrophobic organic compounds is still not clear. In this study, DOM from two wastewater treatment plants (Lachish and Netanya, Israel) was fractionated to hydrophobic acid (HoA) and hydrophobic neutral (HoN) fractions. The fractions were characterized and their sorptive capabilities for s-triazine herbicides and polycyclic aromatic hydrocarbons (PAHs) were studied. For all sorbates, the binding to the HoN fractions was much higher than to HoA fractions. The HoA fractions were more polar than the HoN fractions, containing a higher level of carboxylic functionalities. However the higher binding coefficients of atrazine (2-chloro-4-ethylamine-6-isopropylamino-s-triazine) and ametryn [2-(ethylamino)-4-isopropylamino-6-methyl-thio-s-triazine] obtained for the HoN fractions suggest that their sorption is governed by hydrophobic-like interactions rather than H bonding. The values of binding coefficients of PAHs measured for the HoN fractions were within the range reported for humic acids and much higher than other fractions, suggesting that this fraction plays an important role in the overall sorption of these compounds by DOM. Higher sorption coefficients were measured for the Netanya DOM sample containing higher level of hydrophobic fractions (HoA + HoN) than the Lachish DOM, suggesting that the sorption of hydrophobic organic compounds by DOM is governed by the level of these structural substances. The evaluation of mobility of organic pollutants by wastewater irrigation requires not only assessment of the total carbon concentration but also, more importantly, the content of the hydrophobic fractions.     

Land management impacts on dairy-derived dissolved organic carbon in ground water

Dairy operations have the potential to elevate dissolved organic carbon (DOC) levels in ground water, where it may interact with organic and inorganic contaminants, fuel denitrification, and may present problems for drinking water treatment. Total and percent bioavailable DOC and total and carbon-specific trihalomethane (THM) formation potential (TTHMFP and STHMFP, respectively) were determined for shallow ground water samples from beneath a dairy farm in the San Joaquin Valley, California. Sixteen wells influenced by specific land management areas were sampled over 3 yr. Measured DOC concentrations were significantly elevated over the background as measured at an upgradient monitoring well, ranging from 13 to 55 mg L(-1) in wells downgradient from wastewater ponds, 8 to 30 mg L(-1) in corral wells, 5 to 12 mg L(-1) in tile drains, and 4 to 15 mg L(-1) in wells associated with manured fields. These DOC concentrations were at the upper range or greatly exceeded concentrations in most surface water bodies used as drinking water sources in California. DOC concentrations in individual wells varied by up to a factor of two over the duration of this study, indicating a dynamic system of sources and degradation. DOC bioavailability over 21 d ranged from 3 to 10%, comparable to surface water systems and demonstrating the potential for dairy-derived DOC to influence dissolved oxygen concentrations (nearly all wells were hypoxic to anoxic) and denitrification. TTHMFP measurements across all management units ranged from 141 to 1731 microg L(-1), well in excess of the maximum contaminant level of 80 microg L(-1) established by the Environmental Protection Agency. STHMFP measurements demonstrated over twofold variation ( approximately 4 to approximately 8 mmol total THM/mol DOC) across the management areas, indicating the dependence of reactivity on DOC composition. The results indicate that land management strongly controls the quantity and quality of DOC to reach shallow ground water and hence should be considered when managing ground water resources and in any efforts to mitigate contamination of ground water with carbon-based contaminants, such as pesticides and pharmaceuticals.     

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.     

Leachate chemistry of field-weathered spent mushroom substrate

Passive leaching by rainfall and snowmelt is a popular method to treat piles of spent mushroom substrate (SMS) before its reuse. During this field weathering process, leachate percolates into the underlying soils. A field study was conducted to examine the chemistry of SMS leachate and effects of infiltration. Two SMS piles were deposited (90 and 150 cm in height) over a Typic Hapludult and weathered for 24 mo. Leachate was collected biweekly using passive capillary samplers. The SMS leachate contained high concentrations of dissolved organic carbon (DOC; 0.8-11.0 g L(-1)), dissolved organic nitrogen (DON; 0.1-2 g L(-1)), and inorganic salts. The pH, electrical conductivity, and acid neutralizing capacity were 6.6 to 9.0, 21 to 66 ds m(-1), and 10 to 75 mmolc L(-1), respectively. Inorganic chemistry of the leachate was dominated by K+, Cl-, and SO24-. Leachate DOC was predominantly low molecular weight (<1000 Da) organic acids. During 2 yr of weathering, the 90-cm SMS pile released (per cubic meter of SMS) 3.0 kg of DOC, 1.6 kg of dissolved N, and 26.6 kg of inorganic salts. The 150-cm pile released (per cubic meter of SMS) 2.8 kg of DOC, 0.7 kg of dissolved N, and 13.6 kg of inorganic salts. The 150 cm pile retained more water and exhibited lower net nitrification compared with the 90-cm pile. The top 90 cm of soil retained 20 to 89% of the leachate solutes. Weathering of SMS in piles of 90 cm depth or greater may adversely affect ground water quality.     

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.     

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.