Brian L. Barber

Sources and transport of contaminants of emerging concern: A two-year study of occurrence and spatiotemporal variation in a mixed land use watershed

The occurrence and spatiotemporal variation of 26 contaminants of emerging concern (CECs) were evaluated in 68 water samples in 2011-2012 in the Zumbro River watershed, Minnesota, U.S.A. Samples were collected across a range of seasonal/hydrological conditions from four stream sites that varied in associated land use and presence of an upstream wastewater treatment plant (WWTP). Selected CECs included human/veterinary pharmaceuticals, personal care products, pesticides, phytoestrogens, and commercial/industrial compounds. Detection frequencies and concentrations varied, with atrazine, metolachlor, acetaminophen, caffeine, DEET, and trimethoprim detected in more than 70% of samples, acetochlor, mecoprop, carbamazepine, and daidzein detected in 30%-50% of samples, and 4-nonylphenol, cotinine, sulfamethoxazole, erythromycin, tylosin, and carbaryl detected in 10%-30% of samples. The remaining target CECs were not detected in water samples. Three land use-associated trends were observed for the detected CECs. Carbamazepine, 4-nonylphenol, erythromycin, sulfamethoxazole, tylosin, and carbaryl profiles were WWTP-dominated, as demonstrated by more consistent loading and significantly greater concentrations downstream of the WWTP and during low-flow seasons. In contrast, acetaminophen, trimethoprim, DEET, caffeine, cotinine, and mecoprop patterns demonstrated both seasonally-variable non-WWTP-associated and continual WWTP-associated influences. Surface water studies of CECs often target areas near WWTPs. This study suggests that several CECs often characterized as effluent-associated have additional important sources such as septic systems or land-applied biosolids. Finally, agricultural herbicide (atrazine, acetochlor, and metolachlor) profiles were strongly influenced by agricultural land use and seasonal application-runoff, evident by significantly greater concentrations and loadings at upstream sites and in early summer when application and precipitation rates are greatest. Our results indicate that CEC monitoring studies should consider a range of land uses, seasonality, and transport pathways in relation to concentrations and loadings. This knowledge can augment CEC monitoring programs to result in more accurate source, occurrence, and ecological risk characterizations, more precisely targeted mitigation initiatives, and ultimately, enhanced environmental decision-making.

Contaminants of Emerging Concern: Mass Balance and Comparison of Wastewater Effluent and Upstream Sources in a Mixed-Use Watershed

Understanding the sources, transport, and spatiotemporal variability of contaminants of emerging concern (CECs) is important for understanding risks and developing monitoring and mitigation strategies. This study used mass balances to compare wastewater treatment plant (WWTP) and upstream sources of 16 CECs to a mixed-use watershed in Minnesota, under different seasonal and hydrological conditions. Three distinct CEC groups emerged with respect to their source proportionality and instream behavior. Agricultural herbicides and daidzein inputs were primarily via upstream routes with the greatest loadings and concentrations during high flows. Trimethoprim, mecoprop, nonprescription pharmaceuticals, and personal care products entered the system via balanced/mixed pathways with peak loadings and concentrations in high flows. Carbaryl, 4-nonylphenol, and the remaining prescription pharmaceuticals entered the system via WWTP effluent with relatively stable loadings across sampling events. Mass balance analysis based on multiple sampling events and sites facilitated CEC source comparisons and may therefore prove to be a powerful tool for apportioning sources and exploring mitigation strategies.

Isolation of mesotrione-degrading bacteria from aquatic environments in Brazil

Mesotrione is a benzoylcyclohexane-1,3-dione herbicide that inhibits 4-hydroxyphenyl pyruvate dioxygenase in target plants. Although it has been used since 2000, only a limited number of degrading microorganisms have been reported. Mesotrione-degrading bacteria were selected among strains isolated from Brazilian aquatic environments, located near corn fields treated with this herbicide. Pantoea ananatis was found to rapidly and completely degrade mesotrione. Mesotrione did not serve as a sole C, N, or S source for growth of P. ananatis, and mesotrione catabolism required glucose supplementation to minimal media. LC-MS/MS analyses indicated that mesotrione degradation produced intermediates other than 2-amino-4-methylsulfonyl benzoic acid or 4-methylsulfonyl-2-nitrobenzoic acid, two metabolites previously identified in a mesotrione-degrading Bacillus strain. Since P. ananatis rapidly degraded mesotrione, this strain might be useful for bioremediation purposes.

Sediment-water distribution of contaminants of emerging concern in a mixed use watershed.

This study evaluated the occurrence and distribution of 15 contaminants of emerging concern (CECs) in stream water and sediments in the Zumbro River watershed in Minnesota and compared these with sub-watershed land uses. Sixty pairs of sediment and water samples were collected across all seasons from four stream sites for over two years and analyzed for selected personal care products, pesticides, human and veterinary medications, and phytoestrogens. Spatial and temporal analyses indicate that pharmaceuticals and personal care products (urban/residential CECs) are significantly elevated in water and/or sediment at sites with greater population density (>100 people/km(2)) and percentage of developed land use (>8% of subwatershed area) than those with less population density and land area under development. Significant spatial variations of agricultural pesticides in water and sediment were detectable, even though all sites had a high percentage of agricultural land use. Seasonality in CEC concentration was observed in water but not in sediment, although sediment concentrations of three CECs did vary between years. Average measured non-equilibrium distribution coefficients exceeded equilibrium hydrophobic partitioning-based predictions for 5 of the 7 detected CECs by at least an order of magnitude. Agreement of measured and predicted distribution coefficients improved with increasing hydrophobicity and in-stream persistence. The more polar and degradable CECs showed greater variability in measured distributions across different sampling events. Our results confirm that CECs are present in urban and agricultural stream sediments, including those CECs that would typically be thought of as non-sorptive based on their log Kow values. These results and the observed patterns of sediment and water distributions augment existing information to improve prediction of CEC fate and transport, leading to more accurate assessments of exposure and risk to surface water ecosystems.

Ultrasonic decomposition of atrazine and alachlor in water.

Abstract The collapse of ultrasonically‐generated cavitation bubbles can result in sonochemical reactions. The kinetics of sonochemical decomposition of alachlor and atrazine in water were determined using a sonicator operating in the continuous mode at maximum output. Alachlor and atrazine solutions, 3.1 nmol L‐1, were kept at constant temperature during the sonication. Decomposition at 30°C followed first‐order kinetics: k = 8.01 × 10‐3 min‐1 and 2.10 × 10‐3 min‐1 for alachlor and atrazine, respectively. It is not clear from the product analysis whether the decomposition was due to a thermal or free radical reaction. However, regardless of the decomposition mechanisms, the extrapolated half‐lives (86 and 330 min for alachlor and atrazine, respectively) support the potential development of ultrasonic waves to decompose herbicides in contaminated water.

Propiconazole Distribution and Effects on Ceratocystis fagacearum Survival in Roots of Treated Red Oaks

We investigated the interaction between the oak wilt pathogen (Ceratocystis fagacearum) and propiconazole in lower stems and roots of Quercus rubra to better understand published reports of fungicide failure after 2 years. Propiconazole was infused into mature oaks in July 2004 and roots were inoculated with pathogen endoconidia 1.0 m from injection sites at ±2 weeks of fungicide treatment. Pathogen presence in wood samples was determined by isolation and fungicide concentrations measured using gas chromatography-mass spectrometry. Propiconazole was detected in the roots (≤1.0 m from injection sites) of all treated trees at 2, 12, and 24 months. Propiconazole was detected in all samples (n=68) at 2 and 12 months and in 93% of samples (n=72) at 24 months with concentrations ranging from 815 ppm (12 months in lower stem) to 0.7 ppm (24 months in most distal root segment). Although pathogen isolation incidence was lower in treated than disease control trees at 2 and 12 months, at no time did an infused oak fail to yield the fungus upon isolation. The results document basipetal movement and degradation of propiconazole, as well as the survival of the pathogen, over time in roots and lower stems of infused red oaks.

Low Sorption and Fast Dissipation of the Herbicide Saflufenacil in Surface Soils and Subsoils of an Eroded Prairie Landscape

Saflufenacil partitioning and dissipation were evaluated in soils from an eroded prairie landscape to provide information on its expected environmental fate. Saflufenacil K(d) values followed trends in soil organic carbon content. In surface soils, K(d) values ranged from 0.05 to 0.2 L kg(-1) in the depositional lower slope and from 0.02 to 0.06 L kg(-1) in the eroded upper slope. In subsurface soils, K(d) values were an order of magnitude higher in the lower slope (mean 0.1 L kg(-1)) than in the upper slope (mean 0.01 L kg(-1)). Sorption was slightly higher in samples aged 1-8 weeks compared to freshly spiked soils. Mean dissipation half-lives (DT(50)) were 13 d in surface soils and 32 d in subsurface soils. The observed low sorption and relatively rapid dissipation of saflufenacil suggest that this herbicide will be readily available for degradation or plant uptake in the root zone.

Rapid and complete degradation of the herbicide picloram by Lipomyces kononenkoae.

An enrichment culture approach was used to isolate a pure culture of the yeast Lipomyces kononenkoae, which had the ability to grow on the herbicide picloram. The yeast rapidly and completely degraded 50 microg mL(-1) picloram by 48 h of growth. While L. kononenkoae was found to use both N atoms of picloram as a sole nitrogen source for growth, it failed to mineralize the herbicide or use it as a sole C source. Product analysis done using LC-ESI-MS indicated that biodegradation of picloram by L. kononenkoae proceeds via a didechlorinated, dihydroxylated, pyridinecarboxylic acid derivative. Our results are consistent with the hypothesis that the majority of picloram degradation in the soil is likely due to microbial catabolic processes.

Sorption and Leaching Potential of Isoproturon and Atrazine in Low Organic Carbon Soil of Pakistan Under a Wheat-Maize Rotation

Abstract Pesticide leaching is a great threat in low organic carbon soils when subjected to improper irrigation scheduling. Limited data are available on the sorption and leaching potential of pesticides in agricultural soils of Pakistan with low soil organic carbon (SOC). Lysimeter and field studies were conducted with and without manure application at two irrigation levels in a wheat-fallow-maize rotation in Faisalabad, Punjab, Pakistan. Isoproturon was applied to wheat 55 d after sowing at 1 kg active ingredient (a.i.) ha−1, while atrazine was sprayed on maize 30 d after sowing at 0.774 kg a.i. ha−1. Soil was sampled from three depths (0–35, 35–70, and 70–110 cm) for the field study and four depths (0–35, 35–70, 70–115, and 115–160 cm) for the lysimeter study, 280 and 65 d after application of isoproturon and atrazine, respectively. The soil-water partition coefficients (Kd) of isoproturon and atrazine ranged from 0.3 to 1.2 and 0.4 to 1.5 L kg−1, respectively, and increased linearly with increase in SOC contents. The organic carbon-normalized soil-water partition coefficient (Koc) of isoproturon and atrazine averaged 246.1 and 184.9 L kg−1, respectively, being higher with low spiking concentration. Isoproturon residues measured 280 d after application ranged from 2.1% to 3.6% of the applied mass in the lysimeter study and from 1.5% to 3.1% under field conditions. Atrazine residues 65 d after application ranged from only 0.62% to 0.78% and from 0.88% to 0.82% in the lysimeter and field studies, respectively. The lowest levels of residues for both pesticides were observed with frequent irrigation applied to manure-amended soil. A pesticide leaching risk screening tool, the ground water ubiquity score (GUS), indicated that in the absence of manure under both irrigation levels, isoproturon has a leaching potential (GUS = 2.8), while with the application of manure it has a very low leaching risk. Atrazine GUS ranged from 1.7 to 1.9, indicating a very low risk of leaching.

Chemical application strategies to protect water quality

Management of turfgrass on golf courses and athletic fields often involves application of plant protection products to maintain or enhance turfgrass health and performance. However, the transport of fertilizer and pesticides with runoff to adjacent surface waters can enhance algal blooms, promote eutrophication and may have negative impacts on sensitive aquatic organisms and ecosystems. Thus, we evaluated the effectiveness of chemical application setbacks to reduce the off-site transport of chemicals with storm runoff. Experiments with water soluble tracer compounds confirmed an increase in application setback distance resulted in a significant increase in the volume of runoff measured before first off-site chemical detection, as well as a significant reduction in the total percentage of applied chemical transported with the storm runoff. For example, implementation of a 6.1 m application setback reduced the total percentage of an applied water soluble tracer by 43%, from 18.5% of applied to 10.5% of applied. Evaluation of chemographs revealed the efficacy of application setbacks could be observed with storms resulting in lesser (e.g. 100 L) and greater (e.g. > 300 L) quantities of runoff. Application setbacks offer turfgrass managers a mitigation approach that requires no additional resources or time inputs and may serve as an alternative practice when buffers are less appropriate for land management objectives or site conditions. Characterizing potential contamination of surface waters and developing strategies to safeguard water quality will help protect the environment and improve water resource security. This information is useful to grounds superintendents for designing chemical application strategies to maximize environmental stewardship. The data will also be useful to scientists and regulators working with chemical transport and risk models.