Fate and toxicity of endosulfan in Namoi River water and bottom sediment

Endosulfan (6,7,8,9,10,10,-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) sorption (standardized to 1% total organic carbon and dry weight) was significantly (P < 0.05) more concentrated on the large (>63 microm) particle fraction compared with smaller size fractions (<5 microm and 5-24 microm) of bottom sediments from the Namoi River, Australia. Following completion of the particle size fractionation (6 to 12 wk) and a sediment toxicity assessment (2 wk), the sediments showed large decreases in concentrations of alpha-endosulfan that coincided with an increase in endosulfan sulfate concentrations and minimal changes in beta-endosulfan concentrations. In the Namoi River, similar patterns were observed in the composition of total endosulfan in monthly measurements of bottom sediments and in passive samplers placed in the water column following runoff from cotton (Gossypium hirsutum L.) fields. The toxicity of endosulfan sulfate in river water indicated by the nymphs of the epibenthic mayfly Jappa kutera, was more persistent than the alpha- and beta-endosulfan parent isomers due to its longer half-life. This suggests that endosulfan sulfate would contribute most to previously observed changes in population densities of aquatic biota. Measured concentrations of total endosulfan in river water of up to 4 microg L(-1) following storm runoff, exceed the range of the 96-h median lethal concentration (LC50) values in river water for both alpha-endosulfan (LC50 = 0.7 microg L(-1); 95% confidence interval [CI] = 0.5 to 1.1) and endosulfan sulfate (LC50 = 1.2 microg L(-1); 95% CI = 0.4 to 3.3). In contrast, the 10-d LC50 value for total endosulfan in the sediment toxicity test (LC50 = 162 microg kg(-1); 95% CI = 120 to 218 microg kg(-1)) was more than threefold higher than the highest measured concentration of total endosulfan in field samples of bottom sediment (48 microg kg(-1)). This suggests that pulse exposures of endosulfan in the water column following storm runoff may be more acutely toxic to riverine biota than in contaminated bottom sediment.     

Size distribution of organic matter and associated propiconazole in agricultural runoff material

Sorption and desorption characteristics of propiconazole (1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole) to different particle/aggregate-size fractions of agricultural runoff material were investigated. Emphasis was put on clay and colloidal size fractions to evaluate their role as potential sorbents and carriers for this pesticide. The runoff material was separated into size fractions ranging from 2 mm to ca. 15 nm by wet sieving, sedimentation, centrifugation, and membrane ultrafiltration. Each fraction was characterized by its organic C content and C/N ratio. Distinctive sorption properties of clay-sized particles and colloids were investigated. The obtained size fractions differed significantly in their organic C concentration, C/N ratio, and sorption properties to propiconazole. Organic matter was mainly associated in aggregates >2 microm. Binding of propiconazole to this coarse fraction made up 80% of the sorbed propiconazole. The distribution coefficient between solid and aqueous phases increased with decreasing particle size. The colloidal fraction (<0.16 microm) exhibited the highest sorbtivity, with a distribution coefficient of 113 L kg(-1), which was more than four times higher than that in the bulk sample (27 L kg(-1)). The fraction <2 microm represented 8% of the total sample weight, but contributed to 20% of the sorbed propiconazole. Strong hysteresis was observed for the sorption-desorption of propiconazole on the runoff material. Under dilution very little sorbed propiconazole will be released into the water phase. Due to its high sorbtivity and mobility and the strong sorption-desorption hysteresis, particles in the fraction <2 microm can be important carriers of propiconazole in runoff suspensions with high sediment load.     

Carbon, nitrogen, and phosphorus distribution in particle size-fractionated separated pig and cattle slurry

Solid liquid separation of animal slurry is a method to reduce the excess nutrient loads from intensive livestock production. Five different separation technologies (sedimentation, centrifugation, pressurized filtration, polymer flocculation and drainage, and iron chloride addition + polymer flocculation and drainage) were applied to pig and cattle slurry in a laboratory study. Separation efficiencies of mass, dry matter (DM), N, and P were measured. Particle size fractionation of the solid fractions was performed by subjecting them to wet fractionation and C, organic N (N(org)), and P contents were subsequently measured. Chemical pretreatment with polymer before gravity drainage separated DM, total N, and P from raw pig and cattle slurry with the highest efficiencies. Sedimentation and centrifugation separated P from pig and cattle slurries with higher simple separation efficiencies (0.77 and 0.70, respectively) compared with pressurized filtration (0.15 and 0.37). Pressurized filtration transferred the lowest masses (14 and 18%) to the solid fractions. Solid fractions from pig slurry generally contained higher concentrations of P and C compared with cattle slurry solid fractions. The majority of C in solid fractions was present in particles > 25 microm, whereas N and P were present in larger proportions in particles < 25 microm. Chemical pretreatment increased the capture of smaller N(org)- and P-rich particles into larger particles between 25 and 1000 microm.     

RELATION OF PHYSICAL AND MINERALOGICAL PROPERTIES TO STREAMBANK STABILITY1

ABSTRACT. Alluvial streambank materials from nine unstable and six stable reaches showed little variation in physical and mineralogical properties. The bulk density of all the samples was so similar that they could be considered from the same population. Particle size distributions showed that the clay fractions were slightly, but significantly, higher for the stable reaches. The mineralogy of all samples was also quite similar. The sand-sized grains of the stable areas were less rounded than those of the unstable areas. This somewhat angular shape of the grains may have produced an interlocking between grains that added stability to the bank material. Also, clay coatings on the sand-sized grains from the stable areas may have caused cementation between grains that also strengthened the material.     

PRELIMINARY OBSERVATIONS ON WATER QUALITY OF STORM RUNOFF FROM FOUR SELECTED RESIDENTIAL ROOFS1

ABSTRACT: Storm runoff from four characteristic types of residential roofs and incident rainwater were monitored for 47 storm events over a six-month period at Nacogdoches, Texas, to study water quality conditions for 20 element and four chemical variables. The total element concentration in storm runoff from each roof type was greater than that of rainwater in the open. Differences in element concentrations in storm runoff among the four roof types were statistically significant (α≤ 0.05) with the differences for the wood shingle roof being the greatest and that for terra cotta clay roof being the least. The median concentrations of four element variables exceeded the Texas surface water quality standards, while 12 variables exceeded the standards at least one time in all samples collected. Zinc concentrations violated the Standard ranging from 85.7 percent of the samples for the wood shingle roof to 66.0 percent for the composite shingle, the greatest exceedances of all 24 variables studied. Storm characteristics and gutter maintenance level had some effects on these water quality conditions. The study suggested that roof types can be important to water pollution management programs. More detailed studies on roof water quality in major municipalities are required.     

Surface water and wastewater treatment using a new tannin-based coagulant. Pilot plant trials

A new tannin-based coagulant-flocculant (Tanfloc) was tested for water treatment at a pilot plant level. Four types of water sample were treated: surface water (collected from a river), and municipal, textile industry (simulated by a 100 mg L^?1 aqueous solution of an acid dye), and laundry (simulated by a 50 mg L^?1 aqueous solution of an anionic surfactant) wastewaters. The pilot plant process consisted of coagulation, sedimentation, and filtration. The experiments were carried out with an average coagulant dosage of 92.2 mg L^?1 (except in the case of the surface water for which the dosage was 2 mg L^?1). The efficacy of the water purification was notable in every case: total turbidity removal in the surface water and municipal wastewater, about 95% dye removal in the case of the textile industry wastewater, and about 80% surfactant removal in the laundry wastewater. Filtration improved the removal of suspended solids, both flocs and turbidity, and slightly improved the process as a whole. The efficiency of Tanfloc in these pilot studies was similar to or even better than that obtained in batch trials.     

Variation of Nitrogen Concentrations in Stormpipe Discharge in a Residential Watershed1

Abstract: Use of lawn chemicals in residential areas may contribute nonpoint source (NPS) pollutants, such as nutrients, pesticides, and herbicides to streams. We conducted a 2‐year screening study of discharge in stormwater pipes in the Wissahickon Valley Watershed (suburban Philadelphia) using nitrogen as an indicator of lawn chemical use. Stormwater samples representing first flush and composite runoff were collected approximately twice a month using automatic samplers triggered by rise in water level during storms. The runoff collected by the stormpipes was from neighborhoods with 15‐100 residences, and from 2 to 18 ha (5‐45 acres). Several factors were examined to evaluate the effects on nitrate concentration. These factors included time of sampling (season), number of homes, total area, size of the storm, and time since last storm. Nitrate levels were generally less than 5 mg/l, but still above background in typical undeveloped areas. Concentrations were slightly higher in the first summer than during a drought in the second year, but the difference was not statistically significant. There was a positive correlation between size of the neighborhood (capture area) and peak concentration of nitrate. Storm characteristics (size of storm and time since last storm) did not correlate with nitrate concentrations. The variation in both space and time suggests that a more local control may be a factor. Although individual lawn chemical applications were not monitored, they may influence the timing of increased loading. Furthermore, the variability indicates that quarterly monitoring will not capture discharge characteristics of storm basins.     

Determination of redox-sensitive phosphorus in field runoff without sediment preconcentration

Reduction-induced phosphorus (P) release from particles transported by field runoff has been poorly studied for want of a method that could be used for large surveys. To rectify this shortcoming, we modified the bicarbonate-dithionite (BD) extraction step of a sediment P speciation scheme for analyzing redox-sensitive P in runoff without sample preconcentration. The extraction comprised the addition of bicarbonate (pH buffer) and dithionite (reducing agent) into a runoff sample, 15 min of gentle shaking, filtration, and sample digestion. The samples were greatly reduced (Eh < -200 mV), and Fe and P were solubilized, but Al solubility was not increased. Phosphorus release from rock phosphates (calcium phosphates) was greater in the BD extraction than in water or bicarbonate solution, although no more than 0.2% of the total P was released. For runoff from a very fine Typic Cryaquept, the particulate phosphorus (PP) versus BD-PP relationship was linear up to a PP concentration of about 1.0 mg L(-1), but over the whole PP range studied (up to 2.6 mg L(-1)) somewhat better described by an exponential equation (BD-PP = 0.297 x PP(0.766); r2 = 0.91, n = 79). The minimum detectable value given by the method was relatively low, 0.023 mg L(-1), but reproducibility varied, with the coefficient of variation for 10 samples analyzed with 5 replicates ranging from 1.8 to 28.5%. Considering the variable reproducibility of the results and the lack of suitable reference material, the method needs further refinement and testing if it is to be used for quantitative determination of redox-sensitive P in runoff.     

TRANSPORT OF SEDIMENT-BOUND ORGANOCHLORINE PESTICIDES TO THE SAN JOAQUIN RWER,CALIFORNIA1

ABSTRACT: Suspended sediment samples were collected in west-side tributaries and the main stem of the San Joaquin River, California, in June 1994 during the irrigation season and in January 1995 during a winter storm. These samples were analyzed for 15 organochiorine pesticides to determine their occurrence and their concentrations on suspended sediment and to compare transport during the irrigation season (April to September) to transport during winter storm runoff (October to March). Ten organochiorine pesticides were detected during the winter storm runoff; seven during the irrigation season. The most frequently detected organochlorine pesticides during both sampling periods were p,p'-DDE, p,p'-DDT, p,p'-DDD, dieldrin, toxaphene, and chiordane. Dissolved samples were analyzed for three organochiorine pesticides during the irrigation season and for 15 during the winter storm. Most calculated total concentrations of p,p-DDT, chlordane, dieldrin, and toxaphene exceeded chronic criteria for the protection of freshwater aquatic life. At eight sites in common between sampling periods, suspended sediment concentrations and streamfiow were greater during the winter storm runoff - median concentration of 3,590 mg/L versus 489 mg(L and median streamfiow of 162 ft³/s versus 11 ft³/s. Median concentrations of total DDT (sum of p,p'-DDD, p,p-DDE, and p,p'-DDT), chlordane, dieldrin, and toxaphene on suspended sediment were slightly greater during the irrigation season, but instantaneous loads of organochlorine pesticides at the time of sampling were substantially greater during the winter storm. Estimated loads for the entire irrigation season exceeded estimated loads for the January 1995 storm by about 2 to 4 times for suspended transport and about 3 to 11 times for total transport. However, because the mean annual winter runoff is about 2 to 4 times greater than the runoff during the January 1995 storm, mean winter transport may be similar to irrigation season transport. This conclusion is tentative primarily because of insufficient information on long-term seasonal variations in suspended sediment and organochlorine concentrations. Nevertheless, runoff from infrequent winter storms will continue to deliver a significant load of sediment-bound organochiorine pesticides to the San Joaquin River even if irrigation-induced sediment transport is reduced. As a result, concentrations of organochlorine pesticides in San Joaquin River biota will continue to be relatively high compared to other regions of the United States.     

Headwater Influences on Downstream Water Quality

We investigated the influence of riparian and whole watershed land use as a function of stream size on surface water chemistry and assessed regional variation in these relationships. Sixty-eight watersheds in four level III U.S. EPA ecoregions in eastern Kansas were selected as study sites. Riparian land cover and watershed land use were quantified for the entire watershed, and by Strahler order. Multiple regression analyses using riparian land cover classifications as independent variables explained among-site variation in water chemistry parameters, particularly total nitrogen (41%), nitrate (61%), and total phosphorus (63%) concentrations. Whole watershed land use explained slightly less variance, but riparian and whole watershed land use were so tightly correlated that it was difficult to separate their effects. Water chemistry parameters sampled in downstream reaches were most closely correlated with riparian land cover adjacent to the smallest (first-order) streams of watersheds or land use in the entire watershed, with riparian zones immediately upstream of sampling sites offering less explanatory power as stream size increased. Interestingly, headwater effects were evident even at times when these small streams were unlikely to be flowing. Relationships were similar among ecoregions, indicating that land use characteristics were most responsible for water quality variation among watersheds. These findings suggest that nonpoint pollution control strategies should consider the influence of small upland streams and protection of downstream riparian zones alone is not sufficient to protect water quality.     

Determination of phosphorus speciation in dairy manure using XRD and XANES spectroscopy

Intensive manure application is an important source of diffuse phosphorus (P) pollution. Phosphorus availability from animal manure is influenced by its chemical speciation. The major objective of this study was to investigate the P speciation in raw and anaerobically digested dairy manure with an emphasis on the calcium (Ca) and magnesium (Mg) phosphate phases. Influent and effluent from an on-farm digester in Wisconsin were sampled and sieved, and the 25 to 53 microm size fraction was dried for X-ray powder diffraction (XRD) and P K-edge X-ray absorption near edge structure (XANES) analyses. Struvite (MgNH4PO4.6H2O) was identified in both the raw (influent) and anaerobically digested (effluent) manure using XRD. Qualitative analysis of P K-edge XANES spectra indicated that the Ca orthophosphate phases, except dicalcium phosphate anhydrous (DCPA) or monetite (CaHPO4), were not abundant in dairy manure. Linear combination fitting (LCF) of the P standard compounds showed that 57.0 and 43.0% of P was associated with DCPA and struvite, respectively, in the raw manure. In the anaerobically digested sample, 78.2% of P was present as struvite and 21.8% of P was associated with hydroxylapatite (HAp). The P speciation shifted toward Mg orthophosphates and least soluble Ca orthophosphates following anaerobic digestion. Similarity between the aqueous orthophosphate (aq-PO4), newberyite (MgHPO4.3H2O), and struvite spectra can cause inaccurate P speciation determination when dairy manure is analyzed solely using P K-edge XANES spectroscopy; however, XANES can be used in conjunction with XRD to quantify the distribution of inorganic P species in animal manure.     

Off-site movement of endosulfan from irrigated cotton in New South Wales

The fate and transport of endosulfan (6,7,8,9,10,10-hexachloro-1,5, 5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3-oxide) applied to cotton (Gossypium hirsutum L.) fields were studied throughout three consecutive years on two selected locations in New South Wales (Australia). Rates of dissipation from foliage and soil, volatilization from the field, and transport of residues in irrigation and/or storm runoff waters were measured in order to estimate a total field balance. Dissipation of endosulfan from both foliage and soil is best explained by a two-phase process rather than by a first-order decay. Half-lives of total endosulfan toxic residues (alpha- and beta-endosulfan and the sulfate product) in the first phase were 1.6 d in foliage and 7.1 d in soil, and could be explained by the rapid volatilization of the parent isomers in the first 5 d (up to 70% of endosulfan volatilizes). In the second phase, half-lives were 9.5 d in foliage and 82 d in soil, mostly due to the persistence of the sulfate product. Concentration of endosulfan residues in runoff water varied from 45 to 2.5 microg L(-1) depending on the residue levels present on field soil at the time of the irrigation or storm events. These in turn are related to the total amounts applied, the cotton canopy cover at application, and the time since last spraying. Most of the endosulfan in runoff was found in the water phase (80%), suggesting it was bound to colloidal matter. Total endosulfan residues in runoff for a whole season accounted for no more than 2% of the pesticide applied on-field.     

STORM AND SEASONAL DISTRIBUTIONS OF FECAL COLIFORMS AND CRYPTOSPORIDIUM IN A SPRING1

ABSTRACT: The transmission of disease in ground water is a topic of great concern to government agencies, ground water specialists, and the general public. The purpose of this study was to compare the temporal variability in storm flow of fecal coliform bacteria densities and Cryptosporidium parvum oocyst densities in agriculturally impacted karst ground water. Cryptosporidium parvum oocyst densities ranged from 0 to 1,050 oocysts/1, and mean storm densities ranged from 3.5 to 156.8 oocysts/1. Fecal coliform densities ranged from less than 1 CFU/100ml to more than 40,000 CFU/100ml, and geometric mean storm densities ranged from 1.7 CFU/100ml to more than 7,000 CFU/100ml. Fecal coliform densities correlated well with flow during storms, but Cryptosporidium oocyst densities exhibited a great deal of sample to sample variability and were not correlated with flow. Fecal coliform densities did not correlate positively with Cryptosporidium oocyst densities. Fecal coliform densities were greatest at storm peaks, when sediment loads were also greatest. Multiple transport mechanisms for fecal coliform bacteria and C. parvum oocysts may necessitate various agricultural land management and livestock health maintenance practices to control movement of pathogens to karst ground water.     

Chloride persistence in a deiced access road drainage system

Three years of field data, classical linear reservoir theory, and a new dissolution model confirm the hypothesis that residual chloride from highway deicing applications dissolves into precipitation throughout the year. The measured input includes 52 storm hyetographs and logs of salt and premix applications on an access road with a closed drainage system subject to runoff, interflow, and baseflow. The output data feature discharge and conductivity in an outlet weir measured continuously from February 1998 to May 2000. Individual storm hydrographs and pollutographs yield calibrated first flush dissolved chloride concentrations and residual solid chloride loads that persist at appreciable levels over the entire period of record. The storm calibrations imply a source strength w of 2.01 x 10(-6) s(-1) that accurately models chloride dissolution kinetics through three salt seasons on the access road. This w rests on physically plausible values for the depression storage depth zeta (3 mm) and porosity n (0.40) that store the residual chloride.     

Suspended sediment, nitrogen and phosphorus concentrations and exports during storm-events to the Tuross estuary, Australia

This paper presents a process for estimating pollutant loads from water quality data, to improve catchment-scale modelling in the region for resource management purposes. It describes a program to estimate suspended sediment, total and dissolved nitrogen and phosphorus loads to the Tuross estuary from the Tuross River catchment (1810 km(2)) of coastal southeast Australia. Event-based water quality sampling results obtained during storm events in 2005 are presented. Event 1, during July 2005 was the largest storm event in terms of peak flow for 3.5 years. Other events monitored were also in July, November and December 2005. The early July 2005 event had a flow-weighted mean suspended sediment (SS) concentration during the first 4 days of 63 mg L(-1). Of the events monitored, this was unusual as it was preceded by drought and had the largest SS concentrations (peaking at 180 mg L(-1)) during the rising-stage. In contrast, the November event had a much lower flow-weighted SS mean (28 mg L(-1)), even though peak flow magnitudes were similar. The July and November 2005 events had peak flows of 12,360 and 11,330 ML day(-1). Low-cost rising-stage siphon samplers were used to collect samples during the rapidly rising phase of these events. The use of such samplers and consideration of time-lead/lag flow adjustments, quantified using cross-correlation analysis to account for hysteresis effects, were incorporated into the load estimation techniques. The technique is a potentially useful approach for understanding relationships between water quality concentrations and flow for modelling catchment source strengths and transport processes.     

IMPLEMENTATION OF BIORETENTION SYSTEMS: A WISCONSIN CASE STUDY1

ABSTRACT: The implementation of various bioretention systems was analyzed, including rain gardens, vegetated swales, trenches, and infiltration basins in the St. Francis subdivision, Cross Plains, Wisconsin. Through the examination of archival data and interviews with key participants, it was found that although regulatory and political pressures encouraged the inclusion of bioretention, current standards for storm water management prevailed. The developers had to meet both existing requirements and anticipated rules requiring infiltration. As a result, bioretention systems simply supplemented, rather than replaced, traditional storm water practices. The confusion surrounding dual standards contributed to substantial delays in the negotiations among relevant stakeholders in the watershed. It is concluded that the St. Francis subdivision serves as both a cautionary tale and a bioretention success story. As a caution, this situation demonstrates the need for careful review and refinement of existing storm water ordinances to incorporate water quality improvement technologies, such as bioretention. The demonstrated success of the St. Francis development, however, is that it became a positive prototype for best management storm water practices elsewhere in the region. In addition, the water quality monitoring data from the site has contributed to development of a new county ordinance, the first in Wisconsin to address both quantity and quality of storm water runoff.     

WATER QUALITY OF STORMWATER RUNOFF FROM TEN INDUSTRIAL SITES1

ABSTRACT: This study was to designed to determine concentrations of selected metals, organic compounds, pesticides, and conventional pollutants in stormwater runoff from two North Carolina businesses in each of the following five general industrial groups: auto salvage, metal fabrication, scrap and recycling, vehicle maintenance, and wood preserving facilities. The sampling procedure involved collecting a first flush sample of runoff from a single storm event and both first flush and composite samples of runoff from three consecutive storm events. Analysis of samples collected during the first flush indicated that zinc and copper were the most common of the 13 metals included in the analysis. Additional analysis documented that several volatile organic, semi-volatile organic, or pesticide compounds including acrolein, methylene chloride, xylenes, toluene, tetrachloroethylene, trichloroethylene, pentachlorophenol, and aldrin were also found in the first flush samples. Concentrations of aggregate organics, nitrogen, phosphorus, and sediment were determined in both first flush and three-hour composite samples. Concentrations of pollutants in first flush samples were similar to those in corresponding composite samples.     

Application of a slow-release fertilizer for oil bioremediation in beach sediment

A 105-d field experiment was conducted to determine the potential of the slow-release fertilizer, Osmocote (Scotts, Marysville, OH), to stimulate the indigenous microbial biodegradation of petroleum hydrocarbons in an oil-spiked beach sediment on an intertidal foreshore in Singapore. Triplicate microcosms containing 80 kg of weathered sediment, spiked with 5% (w/w) Arabian light crude oil and 1.2% (w/w) Osmocote pellets, were established, together with control microcosms minus Osmocote. Relative to the control, the presence of the Osmocote sustained a significantly higher level of nutrients (NH(4)(+)-N, NO(3)(-)-N, and PO(4)(3-)-P) in the sediment pore water over the duration of the experiment. The metabolic activity of the indigenous microbial biomass, as measured using an intracellular dehydrogenase enzyme assay, was also significantly enhanced over the duration of the experiment in amended sediments. The loss of total recoverable petroleum hydrocarbons (TRPH) and biodegradation of total n-alkanes (C(10)-C(33)), branched alkanes (pristane and phytane), as well as total target polycyclic aromatic hydrocarbons (PAHs) (two- to six-ring), in both the control and Osmocote-amended sediments, followed a first-order biodegradation model. The first-order loss rate of total recoverable petroleum hydrocarbons was 2.57 times greater than that of the control. The hopane-normalized rate constants for total n-alkane, branched alkane, and total target PAH biodegradation in the Osmocote-treated sediments were 3.95-, 5.50-, and 2.45-fold higher than the control, respectively. Overall, the presence of Osmocote was able to significantly enhance and accelerate the biodegradation of aliphatics and PAHs in oil-contaminated sediments under natural field conditions in an intertidal foreshore environment.     

Properties of several fly ash materials in relation to use as soil amendments

Fly ash samples from five power stations in Western Australia and Queensland, and two soils used for horticulture in Western Australia, were evaluated for a series of physical and chemical properties. Soils were comprised primarily of coarse sand-sized particles, whereas most of the fly ashes were primarily fine sand- and silt-sized particles. Hydraulic conductivities in the fly ashes were 105- to 248-fold slower than in the soils. The water-holding capacities of fly ashes at "field capacity" were three times higher than those of the soils. Extractable P in the fly ashes (except Tarong and Callide) were 20- to 88-fold higher than in the soils. The pH showed considerable variation among the different sources of fly ash, with samples from Muja being the most acidic (pH = 3.8; 1:5 in CaCl2 extract) and from Gladstone the most alkaline (pH = 9.9). The toxicity characteristic leaching procedure (TCLP) values indicate that the potential for release of trace elements from the fly ashes was well below regulatory levels. When applied at sufficient rates (e.g., to achieve 10% w/w in surface layers) to sandy soils, fly ash altered texture and increased water-holding capacity. Depending on the source of fly ash used, such amendments could also provide P and aid nutrient retention by increasing the phosphorus retention index (PRI) and/or cation exchange capacity (CEC). The considerable variability in physical and chemical properties among the fly ash samples evaluated in the present study supports the notion that field trials are essential to the future development of soil amendment strategies making use of any particular source of fly ash.     

Hydrophobicity of soil colloids and heavy metal mobilization: effects of drying

Drying of soil may increase the hydrophobicity of soil and affect the mobilization of colloids after re-wetting. Results of previous research suggest that colloid hydrophobicity is an important parameter in controlling the retention of colloids and colloid-associated substances in soils. We tested the hypothesis that air-drying of soil samples increases the hydrophobicity of water-dispersible colloids and whether air-drying affects the mobilization of colloid-associated heavy metals. We performed batch experiments with field-moist and air-dried (25 degrees C) soils from a former sewage farm (sandy loam), a municipal park (loamy sand), and a shooting range site (loamy sand with 25% C(org)). The filtered suspensions (<1.2 microm) were analyzed for concentrations of dissolved and colloidal organic C and heavy metals (Cu, Cd, Pb, Zn), average colloid size, zeta potential, and turbidity. The hydrophobicity of colloids was determined by their partitioning between a hydrophobic solid and a hydrophilic aqueous phase. Drying increased hydrophobicity of the solid phase but did not affect the hydrophobicity of the dispersed colloids. Drying decreased the amount of mobilized mineral and (organo-)mineral colloids in the sewage farm soils but increased the mobilization of organic colloids in the C-rich shooting range soil. Dried samples released less colloid-bound Cd and Zn than field-moist samples. Drying-induced mobilization of dissolved organic C caused a redistribution of Cu from the colloidal to the dissolved phase. We conclude that drying-induced colloid mobilization is not caused by a change in the physicochemical properties of the colloids. Therefore, it is likely that the mobilization of colloids in the field is caused by increasing shear forces or the disintegration of aggregates.