Fate of 17α-Estradiol, 17β-Estradiol, and Estrone in Agricultural Soils and Sediments

The shift to concentrated animal production facilities and increasing rural-urban migration has increased the localized land application of nearly 1 billion tons of manure and biosolids annually. Although these applications provide nutrients and contribute to soil tilth, they also serve as a source for an estimated 49 tons of the natural manure-borne estrogens, 17α-estradiol (17α-E2), 17β-estradiol (17β-E2), and estrone (E1). While these estrogens are critical to endocrine systems, the low concentrations observed in the environment can disrupt endocrine function in non-target organisms, e.g., altering secondary sex characteristics which can lead to changes in wildlife communities. Research presented here focuses on understanding natural endocrine fate, specifically: (1) the sorptive behavior of 17α-E2 and 17β-E2 on agricultural soils using batch sorption experiments on seven autoclave-sterilized soils, with a range of properties, where both solution and soil phase concentrations were measured; (2) the aerobic biodegradation of 17α-E2 and 17β-E2 in soils using aerobic soil microcosms on two soils with different taxonomic properties, sacrificed over a 3-week period; and (3) the biotransformation of 17α-E2, 17β-E2, and E1 in sediments using anaerobic microcosms under nitrate-reducing, iron-reducing, sulfate-reducing, and methanogenic conditions. For all degradation studies, sterile controls were used to discern between biotic and abiotic transformations. Water, soil, and sediment extracts were analyzed for hormones using negative electrospray ionization tandem mass spectrometry. Electron acceptor concentrations and gas production were also quantified. 17α-E2 and 17β-E2 exhibited stereospecific sorption with the highest β/α sorption ratio being 1.9. Sorption was best correlated to soil organic carbon (OC) with average log OC-normalized distribution coefficients (L kgoc-1) of 2.97 ± 0.13 for 17α-E2 and 3.14 ± 0.16 for 17β-E2. No statistical difference, however, was observed between the aerobic degradation rates of the isomers, which were relatively fast (t½ \u3c 0.5 d), with residuals persisting with time. Under all anaerobic conditions, stereospecific degradation was observed with the magnitude of t½ following 17β-E2 \u3c 17α-E2 \u3c E1. The observed t½ of 17β-E2 was rapid under all conditions (\u3c 1.5 d), while 17α-E2 exhibited higher persistence with an observed t½ of 4.3 d to 69.3 d depending on the redox condition. Interconversion between 17α-E2 and 17β-E2 was observed, as was the reversible transformation from E1 back to its E2 precursors with a preferential formation of the more potent 17β-E2 (e.g., up to 33 mol % in iron-reducing conditions within 1 d). Under both aerobic and anaerobic conditions, E1 was the primary metabolite of both isomers and sterile controls support that the observed transformations were primarily biotically mediated. The anaerobic studies mirror the trends observed in a reconnaissance field study that monitored hormone concentrations in sediments taken quarterly over a 2-year period in an agro-impacted ditch and stream network using quarterly grab samples. These findings are significant and suggest that careful attention is needed when evaluating resource and risk management strategies for these compounds. For example, given that 17α-E2 is more likely to be leached from agricultural soils than 17β-E2, assuming the isomers exhibit the same sorption behavior, as has been previously assumed, would underestimate the transport behavior for the α-isomer. Likewise, although the bulk of E2 appears to degrade within a day under aerobic conditions, using a first-order degradation model for E2 would fail to predict the residual concentrations remaining in the soil profile. In stream networks receiving hormone-containing discharge, hormones are likely to persist in anaerobic sediments. Given evidence of interconversion between 17α-E2 and 17β-E2 and the reversible transformation to E2 from E1 under reducing conditions, sediments may serve as both a source and a sink of hormones to the water column. Therefore, quantifying just the inputs into the water column from discharge and run off may not be sufficient for understanding the persistence of these compounds. This suggests that further research is needed in water and nutrient management strategies, including controlled tile drains and bioreactors, where an anaerobic environment conducive to these transformations may be an unintended consequence

Evaluating Contaminants of Emerging Concern in Commercial Biosolid-based Fertilizers

The production and popularity of commercially available biosolid-based fertilizers are increasing because of their economic, environmental, and plant nutrition benefits, particularly in urban and suburban areas. Because biosolid-based fertilizers are derived from waste water treatment plant residuals, we hypothesized that there is the potential for micropollutants to persist in these products. Their presence would be of particular concern due to their potential impact on human and ecological health and risk of bioaccumulation. This study involves quantifying contaminants of emerging concern in three biosolid-based fertilizers, and 2 non-biosolid-based fertilizers, a composted animal manure and an organic compost. Our extraction method employed ultrasonic assisted solid-liquid extraction followed by a 20 h equilibration during which samples were rotated end-over-end. Prior to analysis, all solvent extracts were concentrated under nitrogen and cleaned up with ENVI-carb to minimize matrix effects during sample analysis. High performance liquid chromatography tandem mass spectrometry (LC-MSMS) and quadrupole time of flight liquid chromatography mass spectrometry (QTOF-LCMS) were used to identify and quantify a suite of micropollutants including perfluoroalkyl substances (PFASs), hormones, parabens, pharmaceuticals, and personal care products. Variable levels of contaminants ranging from 8.22 to 11,300 ppb were found in the biosolid fertilizers, while the nonbiosolid fertilizers contained much smaller concentrations. Milorganite had 14 contaminants, OceanGRO had 13, Elite Lawn had 16, New Plant Life Composted Manure had 1, and Pro-Mix Ultimate Organic Mix had 3. Although many of these chemicals persist in commercially available biosolid-based fertilizers, future research is still needed to determine what, if any, potential risk these contaminants may pose to human or ecological health at the concentrations detected

Persistence of Trace Organic Contaminants from a Commercial Biosolids-Based Fertilizer in Aerobic Soils

Municipal biosolids are recycled as agricultural fertilizers. Recent studies have raised concerns due to the presence of emerging contaminants in municipal biosolids. Previous research suggests that these contaminants have the potential to reside in biosolids-based fertilizers that are commercially distributed. Use of these products in urban/suburban areas may provide a pathway for these contaminants to enter ecosystems and impact human and environmental health. Soils from Purdue University’s community garden and MiracleGro Potting Mix were chosen to represent commonly used urban/suburban growth media. Triclosan, triclocarban, and methyl parabens were selected as compounds of interest for this study. A heat treated commercial biosolids-based fertilizer (Milorganite) was applied to growth media at a rate twice the recommended rate. Microcosm aeration and moisture content were monitored weekly and adjusted accordingly. Microcosms were sacrificed in triplicate at 0, 3, 7, 14, and 21 days, though data will continue to be collected up to 112 days. Soils were extracted using a 1:1 methanol:acetone (v/v) mixture, were cleaned up with microcentrifugation, and analyzed via LC-MS/MS. Results demonstrate no degradation of triclocarban in either growth media, and no degradation of triclosan in Purdue University community garden soil, over 14 days. Degradation rates of triclosan in MiracleGro Potting Mix were inconclusive. This study should further our ability to assess risk and assist in guidance towards safer use of biosolids-based fertilizers

Improved survival following surgery and radiation therapy for olfactory neuroblastoma: analysis of the SEER database

<p>Abstract</p> <p>Background</p> <p>Olfactory Neuroblastoma is a rare malignant tumor of the olfactory tract. Reports in the literature comparing treatment modalities for this tumor are limited.</p> <p>Methods</p> <p>The SEER database (1973-2006) was queried by diagnosis code to identify patients with Olfactory Neuroblastoma. Kaplan-Meier was used to estimate survival distributions based on treatment modality. Differences in survival distributions were determined by the log-rank test. A Cox multiple regression analysis was then performed using treatment, race, SEER historic stage, sex, age at diagnosis, year at diagnosis and SEER geographic registry.</p> <p>Results</p> <p>A total of 511 Olfactory Neuroblastoma cases were reported. Five year overall survival, stratified by treatment modality was: 73% for surgery with radiotherapy, 68% for surgery only, 35% for radiotherapy only, and 26% for neither surgery nor radiotherapy. There was a significant difference in overall survival between the four treatment groups (p < 0.01). At ten years, overall survival stratified by treatment modality and stage, there was no significant improvement in survival with the addition of radiation to surgery.</p> <p>Conclusions</p> <p>Best survival results were obtained for surgery with radiotherapy.</p

Loss of Propiconazole and Its Four Stereoisomers from the Water Phase of Two Soil-Water Slurries as Measured by Capillary Electrophoresis

Propiconazole is a chiral fungicide used in agriculture for control of many fungal diseases on a variety of crops. This use provides opportunities for pollution of soil and, subsequently, groundwater. The rate of loss of propiconazole from the water phase of two different soil-water slurries spiked with the fungicide at 50 mg/L was followed under aerobic conditions over five months; the t1/2 was 45 and 51 days for the two soil slurries. To accurately assess environmental and human risk, it is necessary to analyze the separate stereoisomers of chiral pollutants, because it is known that for most such pollutants, both biotransformation and toxicity are likely to be stereoselective. Micellar electrokinetic chromatography (MEKC), the mode of capillary electrophoresis used for analysis of neutral chemicals, was used for analysis of the four propiconazole stereoisomers with time in the water phase of the slurries. MEKC resulted in baseline separation of all stereoisomers, while GC-MS using a chiral column gave only partial separation. The four stereoisomers of propiconazole were lost from the aqueous phase of the slurries at experimentally equivalent rates, i.e., there was very little, if any, stereoselectivity. No loss of propiconazole was observed from the autoclaved controls of either soil, indicating that the loss from active samples was most likely caused by aerobic biotansformation, with a possible contribution by sorption to the non-autoclaved active soils. MEKC is a powerful tool for separation of stereoisomers and can be used to study the fate and transformation kinetics of chiral pesticides in water and soil

Rates and Product Identification for Trenbolone Acetate Metabolite Biotransformation Under Aerobic Conditions

Trenbolone acetate metabolites are endocrine-active contaminants discharged into the aquatic environment in runoff from agricultural fields, rangelands, and concentrated animal feeding operations. To investigate the environmental fate of these compounds and their biotransformation mechanisms, the authors used inocula from a variety of different water sources and dosed biologically active microcosms with approximately 1400 ng/L of trenbolone acetate metabolites, including 17β-trenbolone, trendione, and 17α-trenbolone. To investigate aerobic biotransformation rates and interconversions between known trenbolone acetate metabolites, gas chromatography–tandem mass spectrometry was used to measure concentrations and assess product distributions as a function of time. High-resolution liquid chromatography–tandem mass spectrometry (LC-MS/MS) was used to characterize novel transformation products and potential transformation pathways. Kinetic analysis yields observed half-lives of approximately 0.9 d, 1.3 d, and 2.2 d for 17β-trenbolone, trendione, and 17α-trenbolone, respectively, at 20 °C, although colder conditions increased half-lives to 8.5 d and biphasic transformation was observed. Relative to reported faster attenuation rates in soils, trenbolone acetate metabolites are likely more persistent in aqueous systems. Product distributions indicate an enzymatic preference for biotransformation between trendione and 17β-trenbolone. The LC-MS/MS characterization indicates dehydrogenation products as the major detectable products and demonstrates that major structural elements responsible for bioactivity in steroids are likely retained during biotransformation

Management of Comorbidities in Diabetics With Renal Cell Carcinoma Past Utilization and Current Outcomes

Objectives: This study evaluated whether particular diabetes mellitus (DM), hyperlipidemia, or hypertension pharmacotherapy was associated with improved renal cell carcinoma (RCC) outcomes in diabetics with emergent RCC. Methods: All DM cases newly diagnosed with RCC at Roswell Park Cancer Institute (January 01, 2003-December 31, 2010) were included (n = 95). Baseline demographic information, clinical history, and cancer outcomes were documented after chart review. Fisher’s test was used for the analysis of categorical outcomes across different treatment groups. Univariate and multivariate analyses for the comparisons of the overall survival and progression-free survival across treatment groups were assessed using Kaplan-Meier log-rank test and Cox proportional hazards models. Results: We found that DM pharmacotherapy users, which may represent a more advanced disease as compared to those controlled by diet alone, displayed significantly greater mortality (P = .01). Additionally, we found that cholesterol-lowering pharmacotherapy use was associated with decreased RCC mortality (hazard ratio = 0.54, P = .06). Individuals receiving combined hypertension regimens had a lower chance to present with baseline metastasis; however, hypertension pharmacotherapy use added no survival benefit. Conclusion: Reinforcing guidelines compliance for hyperlipidemia management in patients with DM may provide a considerable cancer benefit if diagnosed with RCC. Studies evaluating the need for cholesterol-lowering pharmacotherapy in guidelines-noncompliant DM cases upon RCC diagnosis are currently needed

Usability Evaluation of Access Ramps in Transit Buses: Preliminary Findings

The research literature on access ramps used in transit vehicles is undermined by inconsistent methodologies used across studies, thus providing an inconclusive evidence base for proposed Federal guidelines that would impose a maximum 1:6 slope for all deployment situations. The current study assessed the usability of ramp slope for mobility aid users. Four access ramp slopes were evaluated, with 27 adults representing three populations: manual wheelchair users, power wheelchair users, and people with vision impairment who use a cane or service animal. The dependent variables included five usability measures. The 1:8 and 1:12 slopes were usable and acceptable for most participants. The data indicate that the 1:4 slope is too steep for safe unassisted boarding and disembarking. Many manual wheelchair users lacked the strength needed for unassisted ascent. Power wheelchair users and people with vision impairment expressed safety concerns about descent of steeper slopes. Conclusive interpretations should be cautiously drawn because the sample size was relatively small and did not include users of scooters or ambulation aids