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.     

Influence of irrigated paddy fields on the fluorescence properties of fluvial dissolved organic matter

This study investigated seasonal and geographical variation in the fluorescence properties of dissolved organic matter (DOM) in a river system that includes rice paddy fields in its watershed. The river system covers a northern area of the main island of Japan, and between 6 and 45% the watershed area of the tributaries is paddy fields. Water samples were collected monthly from eight tributaries for 1 yr, and the fluorescence properties of DOM were monitored by combined excitation-emission matrix (EEM) and parallel factor analysis. The EEM was statistically decomposed into six fluorescence components with different environmental dynamics. The relative proportion of these components varied with season and geographic location, the former having a greater effect than the latter. Seasonal variation is largely attributed to changes in the source of DOM associated with irrigated rice cultivation practice. The fluorescence component composition showed a stronger autochthonous signature, which varied over a wider range during off-cropping period (October-April) than cropping period (May-September). During the cropping period, a large amount of allochthonous DOM with relatively similar quality was transported into river water from flooded paddy fields and masked the variability in the quality of DOM among tributaries. Therefore, irrigated rice cropping practices are considered to be one of major factors that influence seasonal and geographical variation of fluvial DOM composition.     

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.     

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.     

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.     

Alum treatment of poultry litter: decomposition and nitrogen dynamics

While the poultry industry is a major economic benefit to several areas in the USA, land application of poultry litter to recycle nutrients can lead to impaired surface and ground water quality. Amending poultry litter with alum [Al3(SO4)2 x 14H2O] has received considerable attention as a method of economically reducing ammonia volatilization in the poultry house and soluble phosphorus in runoff waters. The objective of this study was to characterize the effect of alum on broiler litter decomposition and N dynamics under laboratory conditions. Litter that had been amended with alum in the poultry house after each of the first four of five flock cycles (Experiment I) and litter that had been amended with alum after removal from a poultry house after the third flock cycle (Experiment II) were compared with unamended litter in separate studies. The litters in Experiment I were surface-applied to simulate application to grasslands, while the litters in Experiment II were incorporated to simulate application to conventionally tilled crops. The only statistically significant differences in decomposition due to alum occurred early in Experiment II and the differences were small. The only statistically significant differences in net N mineralization, soil inorganic N, and soil NH4+-N in either experiment was found in Experiment I after 70 d of incubation where soil inorganic N was significantly greater for the alum treatment. Thus, alum had little effect on decomposition or N dynamics. Results of many of the studies on litter not amended with alum should be applicable to litters amended with alum to reduce P availability.     

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.     

Sewage sludge effects on mesofauna and cork oak (Quercus suber L.) leaves decomposition in a Mediterranean forest firebreak

Effects of sewage sludge on litter mesofauna communities (Collembola and Acari) and cork oak (Quercus suber L.) leaf litter decomposition have been studied during 18 mo using litterbags in an in situ experimental forest firebreak in southeastern France. The sludge (2.74 t DM ha(-1) yr(-1)) was applied to fertilize and maintain a pasture created on the firebreak. Litterbag colonization had similar dynamics on both the control and fertilized plots and followed a typical Mediterranean pattern showing a greater abundance in spring and autumn and a lower abundance in summer. After 9 mo of litter colonization, Collembola and Acari, but mainly Oribatida, were more abundant on the sludge-fertilized plot. Leaf litter decomposition showed a similar pattern on both plots, but it was faster on the control plot. Furthermore, leaves from the fertilized plot were characterized by greater nitrogen content. Both chemical composition of leaves and sludges and the decomposition state of leaves have significantly affected the mesofauna community composition from each plot.     

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.     

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.     

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.     

Controlling the fate of roxarsone and inorganic arsenic in poultry litter

A growing body of literature reports 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) degradation in poultry litter (PL) to the more toxic inorganic arsenic (As). Aluminum-based drinking-water treatment residuals (WTR) present a low-cost amendment technology to reduce As availability in PL, similar to the use of alum to reduce phosphorus availability. Batch experiments investigated the effectiveness of WTR in removing roxarsone and inorganic As species from PL aqueous suspensions. Incubation experiments with WTR-amended PL evaluated the effects of WTR application rates (2.5-15% by weight) and incubation time (up to 32 d) at two incubation temperatures (23 and 35 degrees C) on As availability in PL. Batch PL aqueous experiments showed the high affinity of As(V), As(III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and roxarsone for the WTR. The 10% WTR amendment rate decreased As availability in PL by half of that of the unamended (no WTR) PL-incubated samples. The reduction in dissolved As concentrations during incubation of WTR-amended PL samples was kinetically limited, being complete within 13 d. Parallel reductions in roxarsone, As(V), and DMA concentrations were observed with liquid chromatography-inductively coupled plasma mass spectrometry, whereas As(III) and MMA concentrations were always <5% of dissolved As. Incubation temperature did not significantly (p > 0.05) influence dissolved As concentrations in the WTR-amended PL. Potential formation of a copper-containing roxarsone metabolite was considered in PL aqueous suspensions with the aid of electrospray mass spectrometry. Further experiments in the field are necessary to ensure that sorbed As is stable in WTR-amended PL.     

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.     

Transport of di(2-ethylhexyl)phthalate (DEHP) applied with sewage sludge to undisturbed and repacked soil columns

Municipal sewage sludge is often used on arable soils as a source of nitrogen and phosphorus, but it also contains organic contaminants that may be leached to the ground water. Di(2-ethylhexyl)phthalate (DEHP) is a priority pollutant that is present in sewage sludge in ubiquitous amounts. Column experiments were performed on undisturbed soil cores (20-cm depth x 20-cm diameter) with three different soil types: a sand, a loamy sand, and a sandy loam soil. Dewatered sewage sludge was spiked with 14C-labeled DEHP (60 mg kg(-1)) and bromide (5 g kg(-1)). Sludge was applied to the soil columns either as five aggregates, or homogeneously mixed with the surface layer. Also, two leaching experiments were performed with repacked soil columns (loamy sand and sandy loam soil). The DEHP concentrations in the effluent did not exceed 1.0 microg L(-1), and after 200 mm of outflow less than 0.5% of the applied amount was recovered in the leachate in all soils but the sandy loam soil with homogeneous sludge application (up to 3.4% of the applied amount recovered). In the absence of macropore flow, DEHP in the leachate was primarily sorbed to mobilized dissolved organic macromolecules (DOM, 30.3 to 81.3%), while 2.4 to 23.6% was sorbed to mobilized mineral particles. When macropore flow occurred, this changed to 16.5 to 37.4% (DOM) and 36.9 to 40.6% (mineral particles), respectively. The critical combination for leaching of considerable amounts of DEHP was homogeneous sludge application and a continuous macropore structure.     

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.     

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.     

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.     

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.     

Influence of organic matter decomposition on soluble carbon and its copper-binding capacity

Bulk and low molecular weight (LMW) (<1 kDa) water-extractable carbon were collected from fresh and microbially degraded wheat straw (Triticum aestivum L.) and crimson clover (Trifolium incarnatum L.) residues to monitor early-stage humification over an 8-wk incubation. Copper complexation parameters were determined for both bulk and LMW water-extractable C for both plant materials in a separate 1-wk incubation. Humification progressed through increasing molar absorptivity (A285) and phenolic and total acidity (TA), and through an increase in average molecular size and degree of polymerization as determined by ultrafiltration and changes in fluorescence peak locations. Such dynamic transformations demonstrate that while humification is a bulk property, with C breakdown and stabilization occurring simultaneously and continuously in soil, its early stages can be effectively monitored for fresh plant residues. Significant changes consistently occurred during the first 7 d of the incubation and were more pronounced for LMW fractions than bulk extracts. For both residues, water-extractable C extracted initially and following a 7-d incubation desorbed and complexed 0.11 to 0.55 mmol resin-bound Cu g(-1) C. Low molecular weight water-extractable C generated the higher values within this range, and values increased consistently following incubation. Potential concerns regarding LMW soluble Cu complexes include percolation through soils or runoff into adjacent water bodies as well as effects on plant root development.