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.

The Effects of Salinity on the Herbivorous Crop Pest Tetranychus urticae (Trombidiformes: Tetranychidae) on Soybean and Corn.

Many environmental factors, including soil characteristics, are critical for plants, herbivorous arthropods, and their interactions. Despite increasing evidence that soil salinity drastically impacts plants, little is known about how salinity affects the herbivorous arthropod pests feeding on those plants. We investigated how soil salinity affects the twospotted spider mite (Tetranychus urticae Koch) feeding on corn (Zea mays L.) and soybean (Glycine max L.). We performed two greenhouse studies, one focusing on the impact of salinity on individual mite fecundity over a period of 3 d and the other focusing on population growth of T. urticae over 7 d. Both experiments were performed across varying salinity levels; electrical conductivity values ranged from 0.84 to 8.07 dS m-1. We also performed the 3-d fecundity experiment in the field, across naturally varying saline conditions. Overall, the twospotted spider mite performed better as salinity increased; both fecundity and population growth tended to have a positive linear correlation with salinity. These studies suggest that salinity can be important for herbivores, just as it is for plants. Moreover, the negative effects of soil salinity on crop plants in agroecosystems may be further compounded by a greater risk of pest problems. Salinity may be another important environmental stressor that can directly influence crop production while also indirectly influencing herbivorous pests.

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.

Ractopamine up take by alfalfa (Medicago sativa) and wheat (Triticum aestivum) from soil.

Ractopamine is a beta adrenergic agonist used as a growth promoter in swine, cattle and turkeys. To test whether ractopamine has the potential to accumulate in plants grown in contaminated soil, a greenhouse study was conducted with alfalfa (Medicago sativa) and wheat (Triticum aestivum) grown in two soils having different concentrations of organic matter (1.3% and 2.1%), amended with 0, 0.5, and 10 µg/g of ractopamine. Plant growth ranged from 2.7 to 8.8 g dry weight (dw) for alfalfa, and 8.7 to 40 g dw for wheat and was generally greater in the higher organic matter content soil. The uptake of ractopamine in plant tissues ranged from non-detectable to 897 ng/g and was strongly dependent on soil ractopamine concentration across soil and plant tissue. When adjusted to the total fortified quantities, the amount of ractopamine taken up by the plant tissue was low, <0.01% for either soil.

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.

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.

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.

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.