Free and conjugated estrogens detections in drainage tiles and wells beneath fields receiving swine manure slurry.

Although livestock manure, such as from swine (Sus scrofa domestica), have high capacity to introduce endocrine-disrupting free estrogens into the environment, the frequency of estrogen detections from reconnaissance studies suggest that these compounds are ubiquitous in the environment, perhaps resulting from historic manure inputs (e.g. cattle grazing residues, undocumented historic manure applications) or uncontrolled natural sources. Compared to free estrogens, conjugates of estrogens are innocuous but have greater mobility in the environment. Estrogen conjugates can also hydrolyze to re-form the potent free estrogens. The objective of this study was to identify the transport of free and conjugated estrogens to subsurface tile drains and groundwater beneath fields treated with swine manure slurry. Three field treatments were established, two receiving swine lagoon manure slurry and one with none. Manure slurry was injected into soils at a shallow depth (∼8 cm) and water samples from tile drains and shallow wells were sampled periodically for three years. Glucuronide and sulfate conjugates of 17ß-estradiol (E2) and estrone (E1) were the only estrogen compounds detected in the tile drains (total detects = 31; 5% detection frequency; conc. range = 3.9-23.1 ng L-1), indicating the important role conjugates played in the mobility of estrogens. Free estrogens and estrogen conjugates were more frequently detected in the wells compared to the tile drains (total detects = 70; 11% detection frequency; conc. range = 4.0-1.6 × 103 ng L-1). No correlations were found between estrogen compound detections and dissolved or colloidal organic carbon (OC) fractions or other water quality parameters. Estrogenic compounds were detected beneath both manure treated and non-treated plots; furthermore, the total potential estrogenic equivalents (i.e. estrogenicity of hydrolyzed conjugates + free estrogens) were similar between treated and non-treated plots.

Thermal remediation alters soil properties - a review.

Contaminated soils pose a risk to human and ecological health, and thermal remediation is an efficient and reliable way to reduce soil contaminant concentration in a range of situations. A primary benefit of thermal treatment is the speed at which remediation can occur, allowing the return of treated soils to a desired land use as quickly as possible. However, this treatment also alters many soil properties that affect the capacity of the soil to function. While extensive research addresses contaminant reduction, the range and magnitude of effects to soil properties have not been explored. Understanding the effects of thermal remediation on soil properties is vital to successful reclamation, as drastic effects may preclude certain post-treatment land uses. This review highlights thermal remediation studies that have quantified alterations to soil properties, and it supplements that information with laboratory heating studies to further elucidate the effects of thermal treatment of soil. Notably, both heating temperature and heating time affect i) soil organic matter; ii) soil texture and mineralogy; iii) soil pH; iv) plant available nutrients and heavy metals; v) soil biological communities; and iv) the ability of the soil to sustain vegetation. Broadly, increasing either temperature or time results in greater contaminant reduction efficiency, but it also causes more severe impacts to soil characteristics. Thus, project managers must balance the need for contaminant reduction with the deterioration of soil function for each specific remediation project.

Wheat Growth in Soils Treated by Ex Situ Thermal Desorption.

Successful remediation of oil-contaminated agricultural land may include the goal of returning the land to prespill levels of agricultural productivity. This productivity may be measured by crop yield, quality, and safety, all of which are influenced by soil characteristics. This research was conducted to determine if these metrics are affected in hard red spring wheat ( L. cultivar Barlow) when grown in soils treated by ex situ thermal desorption (TD) compared with wheat grown in native topsoil (TS). Additionally, TD soils were mixed with TS at various ratios to assess the effectiveness of soil mixing as a procedure for enhancing productivity. In two greenhouse studies, TD soils alone produced similar amounts of grain and biomass as TS, although grain protein in TD soils was 22% (±7%) lower. After mixing TS into TD soils, the mean biomass and grain yield were reduced by up to 60%, but grain protein increased. These trends are likely the result of nutrient availability determined by soil organic matter and nutrient cycling performed by soil microorganisms. Thermal desorption soil had 84% (±2%) lower soil organic carbon than TS, and cumulative respiration was greatly reduced (66 ± 2%). From a food safety perspective, grain from TD soils did not show increased uptake of polycyclic aromatic hydrocarbons. Overall, this research suggests that TD soils are capable of producing safe, high-quality grain yields.

Halogenated 17ß-Estradiol Surrogates: Synthesis, Estrogenic Activity, and Initial Investigations of Fate in Soil/Water Systems.

17ß-Estradiol (E2), a natural, endocrine-disrupting, steroid hormone, is excreted by all vertebrates and can enter the environment from domestic animal and wildlife wastes. Multiple field studies using livestock manures as E2 sources suggest significant background concentrations of E2 (e.g., wildlife sources, hydrolysis of E2 conjugates, previous inputs). To accurately understand field fate and transport processes of E2, it is necessary to address the issue of background detections. In this study, two fluorinated and three brominated surrogate compounds of E2 were synthesized and compared to native E2 using soil/water batch experiments and for estrogenic activity. Analytical difficulties presented by the two fluorinated congeners deemed these compounds to be unsuitable surrogates of E2, and further assessment was abandoned. However, the brominated congeners proved promising, with log( ) values that fell within the range previously reported for E2. Batch studies yielded similar relative aqueous concentrations and linear sorption isotherms across time for E2 and 2-bromo-17ß-estradiol; however, the relative aqueous concentrations and linear sorption isotherms of 4-bromo-17ß-estradiol and 2,4-dibromo-17ß-estradiol were different from E2 but similar to one another. All three brominated congeners possessed estrogenic activity by E-Screen assay, albeit three orders of magnitude less than native E2, putatively due to steric interference introduced by the large bromine atom on the phenolic ring, the group that mediates interaction with the estrogen receptor. The data suggest that 2-bromo-17ß-estradiol may serve as a suitable surrogate for E2 in planned field scale tracer studies designed to distinguish between antecedent and de novo inputs.

Fate and transport of the ß-adrenergic agonist ractopamine hydrochloride in soil-water systems.

The feed additive ractopamine hydrochloride was fortified at four concentrations into batch vials containing soils that differed in both biological activity and organic matter (OM). Sampling of the liquid layer for 14days demonstrated that ractopamine rapidly dissipated from the liquid layer. Less than 20% of the fortified dose remained in the liquid layer after 4hr, and recoveries of dosed ractopamine ranged from 8 to 18% in the liquid layer at 336hr. Sorption to soil was the major fate for ractopamine in soil:water systems, i.e., 42%-51% of the dose at 14days. The major portion of the sorbed fraction was comprised of non-extractables; a smaller fraction of the sorbed dose was extracted into water and acetone, portions which would be potentially mobile in the environment. Partitioning coefficients for all soils suggested strong sorption of ractopamine to soil which is governed by hydrophobic interactions and cation exchange complexes within the soil OM. Ractopamine degradation was observed, but to mostly non-polar compounds which had a higher potential than ractopamine to sorb to soil. The formation of volatiles was also suggested. Therefore, despite rapid and extensive soil sorption, these studies indicated a portion of ractopamine, present in manures used to fertilize soils, may be mobile in the environment via water-borne events.

Implications of Using Thermal Desorption to Remediate Contaminated Agricultural Soil: Physical Characteristics and Hydraulic Processes.

Given the recent increase in crude oil production in regions with predominantly agricultural economies, the determination of methods that remediate oil contamination and allow for the land to return to crop production is increasingly relevant. Ex situ thermal desorption (TD) is a technique used to remediate crude oil pollution that allows for reuse of treated soil, but the properties of that treated soil are unknown. The objectives of this research were to characterize TD-treated soil and to describe implications in using TD to remediate agricultural soil. Native, noncontaminated topsoil and subsoil adjacent to an active remediation site were separately subjected to TD treatment at 350°C. Soil physical characteristics and hydraulic processes associated with agricultural productivity were assessed in the TD-treated samples and compared with untreated samples. Soil organic carbon decreased more than 25% in both the TD-treated topsoil and the subsoil, and total aggregation decreased by 20% in the topsoil but was unaffected in the subsoil. The alteration in these physical characteristics explains a 400% increase in saturated hydraulic conductivity in treated samples as well as a decrease in water retention at both field capacity and permanent wilting point. The changes in soil properties identified in this study suggest that TD-treated soils may still be suitable for sustaining vegetation, although likely at a slightly diminished capacity when directly compared with untreated soils.

Sorption and degradation of 17ß-estradiol-17-sulfate in sterilized soil-water systems.

To identify abiotic processes that govern the fate of a sulfate conjugated estrogen, 17ß-estradiol-17-sulfate (E2-17S), soil batch experiments were conducted to investigate the dissipation, sorption, and degradation of radiolabeled E2-17S under sterilized conditions. The aqueous dissipation half-lives (DT50) for E2-17S ranged from 2.5 to 9.3h for the topsoil of high organic carbon (OC) content (1.29%), but E2-17S remained at ∼80% of applied dose in the low OC (0.26%) subsoil by 14 d. The non-linear sorption isotherms indicated limited sorption of E2-17S, and the concentration-dependent log KOC values were 2.20 and 2.45 for the topsoil and subsoil, respectively. Additionally, two types of hydroxyl E2-17S (OH-E2-17S and diOH-E2-17S) were found as major metabolites in the aqueous phase, which represented 9-25% and 6-7% of applied dose for the topsoil and subsoil at 14 d, respectively. Free estrogens, 17ß-estradiol (E2) and estrone (E1), were detected from the sorbed phase of the soil-water systems.

Modeling coupled sorption and transformation of 17ß-estradiol-17-sulfate in soil-water systems.

Animal manure is the primary source of exogenous free estrogens in the environment, which are known endocrine-disrupting chemicals to disorder the reproduction system of organisms. Conjugated estrogens can act as precursors to free estrogens, which may increase the total estrogenicity in the environment. In this study, a comprehensive model was used to simultaneously simulate the coupled sorption and transformation of a sulfate estrogen conjugate, 17ß-estradiol-17-sulfate (E2-17S), in various soil-water systems (non-sterile/sterile; topsoil/subsoil). The simulated processes included multiple transformation pathways (i.e. hydroxylation, hydrolysis, and oxidation) and mass transfer between the aqueous, reversibly sorbed, and irreversibly sorbed phases of all soils for E2-17S and its metabolites. The conceptual model was conceived based on a series of linear sorption and first-order transformation expressions. The model was inversely solved using finite difference to estimate process parameters. A global optimization method was applied for the inverse analysis along with variable model restrictions to estimate 36 parameters. The model provided a satisfactory simultaneous fit (R(2)adj=0.93 and d=0.87) of all the experimental data and reliable parameter estimates. This modeling study improved the understanding on fate and transport of estrogen conjugates under various soil-water conditions.

Potential bioactivity and association of 17ß-estradiol with the dissolved and colloidal fractions of manure and soil.

The dissolved (DF) and colloidal fractions (CF) of soil and manure play an important role in the environmental fate and transport of steroidal estrogens. The first objective of this study was to quantify the association of 17ß-estradiol (E2) with the DF and CF isolated from (i) liquid swine manure (LSM), (ii) a soil:water mixture (soil), and (iii) a LSM:soil:water mixture (Soil+LSM). The appropriate CF and DF size fractions of the Soil, Soil+LSM, and LSM media were obtained by first filtering through a 0.45 µm filter, which provided the combined DF and CF (DF/CF). The DF/CF from the three media was spiked with carbon-14 ([(14)C]) radiolabeled E2 ([(14)C]-E2), and then ultrafiltered to isolate the CF (<0.45 µm and >1 kDa) from the DF (<1 kDa). The average recoveries of the [(14)C] associated with the DF were 67%-72%, 67%-79%, and 76%-78% for the Soil, Soil+LSM and LSM, respectively. For the CF that was retained on the 1 kDa filter, organic carbon and [(14)C]-E2 were dislodged with subsequent water rinses the Soil+LSM and LSM, but not the Soil. The second objective was to evaluate whether the E2 associated with the various fractions of the different media could still bind the estrogen receptor using an E2 receptor (17ß-ER) competitor assay, which allowed E2 equivalent concentrations to be determined. The estrogen receptor assay results indicated that E2 present in the DF of the Soil and Soil+LSM solutions could still bind the estrogen receptor. Results from this study indicated that E2 preferentially associated with the DF of soil and manure, which may enhance its dissolved advective transport in surface and subsurface water. Furthermore, this study indicated that E2 associated with DF solutions in the environment could potentially induce endocrine responses through its interactions with estrogen receptor.

Fate of 17ß-estradiol in anaerobic lagoon digesters.

The fate of [C]17ß-estradiol ([C]E2) was monitored for 42 d in triplicate 10-L anaerobic digesters. Total radioactive residues decreased rapidly in the liquid layer of the digesters and reached a steady-state value of 22 to 26% of the initial dose after 5 d. High-performance liquid chromatography and liquid chromatography-tandem mass spectrometry analyses of the liquid layer of the anaerobic digesters indicated a rapid degradation of E2 to estrone (E1), which readily adsorbed to the sludge layer subsequent to its formation. Estrone was the predominant steroid identified under anaerobic digestion in the liquid layer or sorbed to sludge at 42 d. Methane formation represented 11.1 ± 5.7% of the initial E2 fortification with 0.3 to 0.5% of the starting E2 mineralized to carbon dioxide. Maximum [C]methane production appeared between Days 4 and 7. An estimate of estrogenicity of the final product based on reported estrogen equivalents for E1 and E2 was 2% of the original in active digesters. Anaerobic digestion of swine waste has several management benefits; moreover, this study demonstrated that it reduces the potential of environmental release of estrogens, which are known endocrine disruptors.

Dissipation and transformation of 17ß-estradiol-17-sulfate in soil-water systems.

In the environment, estrogen conjugates can be precursors to the endocrine-disrupting free estrogens, 17ß-estradiol (E2) and estrone (E1). Compared to other estrogen conjugates, 17ß-estradiol-17-sulfate (E2-17S) is detected at relatively high concentrations and frequencies in animal manure and surface runoff from fields receiving manure. To elucidate the lifecycle of manure-borne estrogens and their conjugates in the environment, the fate of radiolabelled E2-17S in agricultural soils was investigated using laboratory batch studies with soils of different organic carbon (OC) content (1.29% for topsoil versus 0.26% for subsoil). E2-17S was found relatively persistent in the aqueous phase throughout the duration of the 14 d experiment. The aqueous E2-17S persisted longer in the subsoil (half-lives (DT50)=64-173 h) than the topsoil (DT50=4.9-26 h), and the aqueous persistence of E2-17S depended on its initial concentration. The major transformation pathway was hydroxylation, yielding mono- and di-hydroxy-E2-17S (OH-E2-17S and diOH-E2-17S). Free estrogens, E2 and E1, were only observed in the sorbed phase of the soil at low concentrations (∼1% of applied dose), which demonstrated that deconjugation and subsequent oxidation had occurred. Although deconjugation was not a major pathway, E2-17S could be a precursor of free estrogens in the environment.

Radioassay-Based Approach to Investigate Fate and Transformation of Conjugated and Free Estrogens in an Agricultural Soil.

Estrogens, a potent group of endocrine disruptors toward aquatic species, are primarily excreted as conjugates from humans and animals. Radioassay-based approaches with detailed speciation have been frequently conducted for environmental-fate studies for pesticides; however, such techniques have not been exploited for reproductive hormones, and especially for hormone conjugates. This article describes a simple, robust, and high-mass-recovery approach to investigate the fate and transformation of a prototype estrogen conjugate, that is, 17ß-estradiol-3-glucuronide (E2-3G), and its metabolites (free estrogens) in a laboratory soil and water matrix without the need for enzymatic cleavage and/or fluorescent derivatization. E2-3G and its metabolites were baseline resolved in a single run using high-performance liquid chromatography (HPLC) and quantified by liquid scintillation counting of the HPLC effluents. Transformation of E2-3G and the disposition of its metabolites--the free estrogens 17ß-estradiol and estrone--into aqueous, sorbed, and gaseous phases, were adequately accounted for in a soil-water batch system. High mass balances ranging from 99.0% to 114.1% were obtained. Although the method gave lower sensitivity (parts per billion) than tandem mass spectrometer (parts per trillion), it offered sufficient chromatographic resolution and sensitivity to study the fate of labile estrogens in environmental matrices, using the concentration range of this study. An additional advantage of the approach was the relatively low cost of the instrumentation employed. The presented approach can be successfully applied to study the fate of conjugated hormones and their metabolites in the environment allowing simultaneous discernment of complex fate and transformation processes in soil, water, and gas.

Field-scale relationships among soil properties and shallow groundwater quality.

It is important to understand the link between land surface/soil properties and shallow groundwater quality. To that end, soil properties and near-water-table groundwater chemistry of a shallow, unconfined aquifer were measured on a 100-m grid on a 64-ha irrigated field in southeastern North Dakota. Soil properties and hydrochemistry were compared via multivariate analysis that included product-moment correlations and factor analysis/principal component analysis. Topographic low areas where the water table was in close proximity to the soil surface generally had higher apparent electrical conductivity (ECa ) and higher percent silt and clay than higher positions on the landscape. The majority of the groundwater was characterized by Ca- and Mg-HCO3 type water and was associated with topographic high areas with lower ECa and net groundwater recharge. Small topographic depressions were areas of higher ECa (net groundwater discharge) where salts that precipitated via evapotranspiration and evaporative discharge dissolved and leached to the groundwater during short-term depression-focused recharge events. At this site, groundwater quality and soil ECa were related to surface topography. High-resolution topography and EC(a) measurements are necessary to characterize the land surface/soil properties and surficial groundwater quality at the field-scale and to delineate areas where the shallow groundwater is most susceptible to contamination.

Fate and transformation of an estrogen conjugate and its metabolites in agricultural soils.

In the environment, conjugated estrogens are nontoxic but may hydrolyze to their potent unconjugated, 'free' forms. Compared to free estrogens, conjugated estrogens would be more mobile in the environment because of their higher water solubility. To identify the fate of a conjugated estrogen in natural agricultural soils, batch experiments were conducted with a (14)C labeled prototype conjugate, 17ß-estradiol-3-glucuronide (E2-3G). Initially, aqueous dissipation was dominated by biological hydrolysis of E2-3G and its oxidized metabolite, estrone glucuronide (E1-3G), both of which were transformed into the free estrogens, 17ß-estradiol (E2) and estrone (E1), respectively. Following hydrolysis, hydrophobic sorption interactions of E2 and E1 dominated. Depending on soil organic matter contents, dissolved E2-3G persisted from 1-14 d, which was much longer than what others reported for free estrogens (generally <24 h). Biodegradation rate constants of E2-3G were smaller in the subsoil (0.01-0.02 h(-1)) compared to topsoil (0.2-0.4 h(-1)). Field observations supported our laboratory findings where significant concentrations (425 ng L(-1)) of intact E2-3G were detected in groundwater (6.5-8.1 m deep) near a swine (Sus scrofa domesticus) farm. This study provides evidence that conjugate estrogens may be a significant source of free estrogens to surface water and groundwater.

Effects of field-manure applications on stratified 17ß-estradiol concentrations.

The occurrence of the manure-borne estrogen, 17ß-estradiol (E2), was investigated in laboratory and field soils. In the laboratory, E2 was applied to soil to simulate concentrations found in swine (Sus scrofa domestica) manure (5000ngL(-1)). The aqueous-extracted E2 dissipated in the soil by 98% within 1h and was not significantly different from background concentrations (18ng L(-1)) for the duration of the experiment (64h). In the field study, soil cores were taken before and several dates after swine manure application. Equivalent porewater concentrations of water-extractable E2 were determined in 0.15-m increments down to the water table (0.70-2.00m deep). The average frequency of detection for 168 samples was 38% (average=40ng L(-1) porewater equivalents). Eleven days after manure application there was no significant effect on E2 detection frequency or concentration. However, E2 concentrations significantly increased by 6 months after manure application, and appeared to be related to precipitation. Concentrations then returned to original levels by 17 months after manure application. Manure did not have an immediate effect on E2 occurrence due to the capacity of the soil to rapidly sorb E2. However, it appears that soil may act as a long-term reservoir for E2 in the environment, which may be periodically released through desorption.

An on-farm survey of spatial and temporal stratifications of 17ß-estradiol concentrations.

17ß-estradiol (E2) is a natural estrogenic hormone found in animal manure and urine, which may cause endocrine disruption in sensitive organisms. 17ß-Estradiol has been widely detected in the environment, and animal agriculture may be an important source. The objectives of this study were to investigate the potential sources and/or spatial and temporal characteristics contributing to detections of E2 at the farm-scale. Soil cores, segmented into 0.15m increments, were taken down to the water table from four locations (three potential E2 sources and one control) at or around a swine (Sus scrofa domesticus) farm on five different dates between 2006 and 2007. Estradiol was quantified in the soil-water extracts using liquid chromatography-with tandem mass spectrometry (LC/MS/MS) analysis. Estradiol detections were widespread and found in 128 out of 345 extractions (37%). Concentrations ranged from 0 to 1910 ng L⁻¹ (porewater equivalents). A location that received field application of manure had significantly lower E2 concentrations compared to other locations. Also, the spring 2007 E2 concentrations were significantly higher than all other sample dates, perhaps related to climatic and hydrological events. Results suggested E2 was not directly related to manure sources, but was widespread in this environment. Where E2 was detected, highest concentrations favored the upper profile, while the greatest frequency of detections was in the lower profile and near the water table. Detections of E2 were associated with high organic mater contents in the upper profile and high sand contents in the lower profile. The study suggests that E2 is widespread in some soil environments, raising questions as to the source and mechanisms that facilitate its transport and mobility.

Development of an ultra-high-pressure liquid chromatography-tandem mass spectrometry multi-residue sulfonamide method and its application to water, manure slurry, and soils from swine rearing facilities.

An analytical method was developed using ultra-high-pressure liquid chromatography-triple quadrupole-tandem mass spectrometry (UHPLC-TQ-MS/MS) to simultaneously analyze 14 sulfonamides (SA) in 6 min. Despite the rapidity of the assay the system was properly re-equilibrated in this time. No carryover was observed even after high analyte concentrations. The instrumental detection limit based on signal-to-noise ratio (S/N)>3, was below 1 pg/microL (5 pg on column) for all SAs except sulfachloropyridazine. Surface water, ground water, soil, and slurry manure contained in storage ponds in and around swine [Sus scrofa domesticus] rearing facilities were analyzed. Sample cleanup for ground water and surface water included using solid phase extraction (SPE) using Oasis hydrophilic-lipophilic balance (HLB) cartridges. The soil and slurry manure required tandem strong anion exchange (SAX) and HLB solid phase extraction cartridges for sample cleanup. With few exceptions, the recoveries ranged from 60 to 100% for all matrices. The minimum detectable levels were below 2.0 ng/L for water, 30 ng/L for slurry manure, and 45 ng/kg for soil except for sulfachloropyridazine. The coefficient of variation (CV) was within 20% for most of the compounds analyzed. Using this method, sulfamethazine concentrations of 2250-5060 ng/L, sulfamethoxazole concentrations of 108-1.47 x 10(6)ng/L, and sulfathiazole concentrations of 785-1700 ng/L were found in the slurry manure. Sulfadimethoxine (2.0-32 ng/L), sulfamethazine (2.0-5.1 ng/L), and sulfamethoxazole (20.5-43.0 ng/L) were found in surface water and ground water. In top soil (0-15 cm), sulfamethazine ranged 34.5-663 ng/kg dry weight in those locations that received slurry manure as a nutrient; no SAs were found in the soil depths between 46 and 61 cm. The speed makes the method practical for medium to high throughput applications. The sensitivity and positive analyte identification make the method suitable for the demanding requirements for real world applications.

A feasibility study of immobilized and free mixed culture bioaugmentation for treating atrazine in infiltrate.

A feasibility study of phosphorylated-polyvinyl alcohol immobilized and free mixed bacterial culture bioaugmentation for removing atrazine in agricultural infiltrate was conducted utilizing a sand column setup. The effects of bacterial cell loading and infiltration rate on atrazine degradation were investigated by short-term tests in which the amount of synthetic infiltrate fed through was five times of the void volume (five pore volumes) of the sand column. In addition, the loss of the inoculated atrazine-degrading cultures and the change of bacterial community were determined. Selected tests were continued for monitoring a long-term performance of the system (50 pore volumes of the sand column). The results indicated that the inoculated cells removed 42-80% of the atrazine. The infiltration rate and cell loading significantly affected the atrazine removal. In the short-term tests, the immobilized and free cells provided similar atrazine removal; however, leaching of the free cells was much greater than that of the immobilized cells. For the long-term performance, only the immobilized cells provided consistent atrazine removal efficiency throughout the test. Both immobilized and free cell systems exhibited a significant change in bacterial community structure during the atrazine degradation experiments. The infiltration rate was a significant factor for the change.

Occurrence and pathways of manure-borne 17beta-estradiol in vadose zone water.

The hormone 17beta-estradiol (E2) can cause endocrine disruption in sensitive species at part per trillion concentrations. The persistence and transport pathways of manure-borne E2 in agricultural soils were determined by comparing its occurrence with the transfer of water and the transport of non-sorbing fluorobenzoic acid (FBA) tracers. This comparison was done using capillary wick lysimeters installed 0.61m beneath three corn (Zea mays L.) plots that receive swine (Sus scrofa domesticus) manure from various sources. An additional control plot was included that received no manure. Soil water transfer was modeled to compare actual versus predicted percolation. On average, lysimeters collected 61% of the expected percolation and 8% of the FBA. There were frequent E2 detections, where there were an average of 8 detections for the 11 sample events. The average detection was 21ngL(-1) and its range was 1-245ngL(-1). 17beta-Estradiol was detected before manure was applied and also in the control plot lysimeters. Furthermore, the average mass recovery of E2 in all the lysimeters was >50%, which was greater than the FBA tracer recovery. Results indicated that tracer was transported with precipitated water infiltrating into the soil surface and percolating down through the soil profile. There was substantial evidence for antecedent E2, which was persistent and mobile. The persistence and mobility of the E2 may result from its associations with colloids, such as dissolved organic matter. Furthermore, this antecedent E2 appeared to overwhelm any observable effect of manure management on E2 fate and transport.

Atrazine removal in agricultural infiltrate by bioaugmented polyvinyl alcohol immobilized and free Agrobacterium radiobacter J14a: a sand column study.

Bench-scale sand column breakthrough experiments were conducted to examine atrazine removal in agricultural infiltrate by Agrobacterium radiobacter J14a (J14a) immobilized in phosphorylated-polyvinyl alcohol compared to free J14a cells. The effects of cell loading and infiltration rate on atrazine degradation and the loss of J14a were investigated. Four sets of experiments, (i) tracers, (ii) immobilized dead cells, (iii) immobilized cells, and (iv) free cells, were performed. The atrazine biodegradation at the cell loadings of 300, 600, and 900 mg dry cells L(-1) and the infiltration rates of 1, 3, and 6 cm d(-1) were tested for 5 column pore volumes (PV). The atrazine breakthrough results indicated that the immobilized dead cells significantly retarded atrazine transport. The atrazine removal efficiencies at the infiltration rates of 1, 3, and 6 cm d(-1) were 100%, 80-97%, and 50-70%, respectively. Atrazine degradation capacity for the immobilized cells was not significantly different from the free cells. Both infiltration rate and cell loading significantly affected atrazine removal for both cell systems. The bacterial loss from the immobilized cell system was 10-100 times less than that from the free cell system. For long-term tests at 50 PV, the immobilized cell system provided consistent atrazine removal efficiency while the atrazine removal by the free cells declined gradually because of the cell loss.