Photochemical fate of solvent constituents of Corexit oil dispersants.

In 2010, an estimated 1.87 million gallons (7079 cubic meters) of chemical dispersants were applied to open ocean waters in the Gulf of Mexico as part of the response to the Deepwater Horizon blowout. This unprecedented volume of dispersant application highlighted the importance of dispersant chemical formulations, raising questions of dispersant fate and transport in the open ocean and spurring research into formulation improvements. The research presented here elucidates the contribution of photolytic processes to the degradation of two solvent constituents of these dispersant mixtures: propylene glycol (PG) and 2-butoxyethanol (2-BE). A series of photodegradation experiments were conducted to determine the contribution of direct photolysis and indirect photolysis via hydroxyl radical (HO) to compound degradation. Experiments were performed using both deep UV light sources (low pressure (LP) and medium pressure (MP) mercury vapor ultraviolet (UV) lamps) and a solar simulator. Sample matrices included ultrapure water, nitrate amended water, hydrogen peroxide (H2O2) spiked water, Gulf of Mexico seawater, and a surface water from Boulder, CO. Experiments included determination of the molar absorption coefficients (ε) and the HO reaction rate constants (kHO) of the individual compounds. Data illustrated that significant direct photolysis of either PG or 2-BE from sunlight is unlikely. The kHO for PG and 2-BE were determined to be 6.15 × 10(8) M(-1) s(-1) and 1.15 × 10(9) M(-1) s(-1), respectively. Solar simulation and UV experiments indicate that in natural systems, neither PG nor 2-BE is expected to undergo significant, rapid degradation due to direct or indirect photolysis. PG and 2-BE are effectively degraded through indirect photolysis in the presence of high HO concentrations, suggesting UV/H2O2 is a feasible possibility for the treatment of waters containing PG and 2-BE.

Analysis of trenbolone acetate metabolites and melengestrol in environmental matrices using gas chromatography-tandem mass spectrometry.

Studies demonstrate that exposure to steroid hormones in receiving waters can adversely impact reproduction of aquatic organisms. In particular, exogenous steroid hormones widely used as growth promoters in animal agriculture are of high concern, yet no gas chromatography-tandem mass spectrometry (GC/MS/MS) analytical methods for the detection of these compounds in complex environmental matrices is described in the literature. This study utilizes analytical methods based upon N-methyl-N-(trimethylsilyl)trifluoro-acetamide-iodine (MSTFA-I(2)) derivatization for the analysis of metabolites of trenbolone acetate (TBA), including 17α-trenbolone, 17ß-trenbolone, and trendione, and melengestrol acetate in receiving waters and surface soils associated with animal agriculture. Results suggest method detection levels of 0.5-1 ng/L for the trenbolone metabolites, while detection of melengestrol is qualitative only. Isotope dilution methods employing d3-17ß-trenbolone were used to improve steroid quantification. Method recoveries in spiked samples collected from a variety of representative receiving waters generally ranged from 80-120% with consistent and low standard deviation (generally<10%) for replicate analysis. Analysis of a storm water runoff sample from a commercial confined animal feeding operation (CAFO) that used TBA implants detected 17ß-trenbolone and trendione at concentrations of 31 and 52 ng/L, respectively. Analysis of surface soils at a commercial CAFO using TBA implants detected 17α-trenbolone at concentrations between 4-6 ng/g dry weight. Method development efforts suggested that the concentration of I(2) in MSTFA, the removal of I(2) from sample extracts after derivatization, and the use of Florisil clean-up to reduce organic matter matrix were vital aspects of steroid hormone quantification at low (<30ng/L) concentrations in complex environmental matrices.

Occurrence of trenbolone acetate metabolites in simulated confined animal feeding operation (CAFO) runoff.

Metabolites of androgenic synthetic growth promoters used at confined animal feeding operations (CAFOs) pose a demonstrated ecological risk. To evaluate the transport of trenbolone acetate (TBA) metabolites from beef cattle CAFOs, rainfall simulation experiments were conducted at the University of California, Davis, research CAFO. Steroid concentrations in solid and aqueous samples from the research CAFO and solids samples from a commercial CAFO were analyzed by gas chromatography-tandem mass spectrometry. The data indicate that 17α-trenbolone (17α-TBOH), 17ß-trenbolone (17ß-TBOH), and trendione (TBO), the three primary TBA metabolites, occur in soils and runoff. Soils at the research CAFO contained up to 8.2 (±1.1) ng/g-dw of 17α-TBOH and 1.2 (±0.1) ng/g-dw of 17ß-TBOH, with slightly higher (~20 ng/g-dw) 17α-TBOH concentrations observed in commercial CAFO soils. In simulated runoff, 17α-TBOH concentrations of 1-350 ng/L and TBO concentrations from 1-170 ng/L were observed. The metabolite 17ß-TBOH intermittently occurred in runoff samples at 5-26 ng/L and may be correlated to anaerobic soils. Metabolite concentrations observed in CAFO runoff correspond to 5-15% of potential maximum steroid concentrations predicted by mass balances. First order transformation rates of 0.028/day (25 day half-life) were estimated for 17α-TBOH in CAFO soils. Results suggest that ecologically relevant concentrations of TBA metabolites can be mobilized from CAFO surfaces in storm runoff and may lead to receiving water concentrations at or above ecological effects thresholds for a very limited number of discharge scenarios.