Veterinary antimicrobials in cattle feedlot environs and irrigation conveyances in a high-intensity agroecosystem in southern Alberta, Canada.

The South Saskatchewan River Basin (SSRB) is considered one of the most intensively farmed regions in Canada, with high densities of livestock and expansive areas of irrigated cropland. We measured concentrations of seven veterinary antimicrobials (VAs) in 114 surface water samples from feedlot environs and 219 samples from irrigation conveyances in the SSRB. Overall, detection frequencies in feedlot environs were 100% for chlortetracycline (CTC) and tetracycline (TC), 94% for monensin (MON), 84% for tylosin (TYL), 72% for lincomycin (LIN), 66% for erythromycin (ERY), and 23% for sulfamethazine (SMZ). For irrigation conveyances, detection frequencies for CTC and TC remained high (94-100%), but dropped to 18% for ERY, 15% for TYL, 10% for MON, and 4% for SMZ. Lincomycin was not detected in irrigation conveyance water. Maximum concentrations of VAs ranged from 1384 µg L-1 (TC) to 17 ng L-1 (SMZ) in feedlot environs while those in irrigation conveyances were 155 ng L-1 (TC) to 29 ng L-1 (ERY). High detection frequencies and median concentrations of VAs in both feedlot environs and irrigation conveyances were associated with high amounts of precipitation. However, an irrigation district (ID) with high livestock density (Lethbridge Northern) did not exhibit higher concentrations of VAs compared to IDs with less livestock, while levels of VAs in irrigation conveyances were less influenced by the degree of surface runoff. The ubiquity of CTC and TC in our study is likely a reflection of its widespread use in intensive livestock operations. Additional investigation is required to link environmental concentrations of VAs with livestock densities and increase our understanding of potential antimicrobial resistance in high-intensity agroecosystems.

Degradation of antimicrobial resistance genes within stockpiled beef cattle feedlot manure.

Degradation of antimicrobial resistance genes (ARG) in manure from beef cattle administered (kg-1 feed) 44 mg of chlortetracycline (CTC), 44 mg of chlortetracycline plus sulfamethazine (CTCSMZ), 11 mg of tylosin (TYL), or no antimicrobials (Control) was examined. Manure was stockpiled and quantitative PCR (qPCR) was used to assess tetracycline [tet(C), (L), (M), (W)], erythromycin [erm(A), (B), (F), (X)], and sulfamethazine [sul(1), (2)] ARG and 16S rDNA. After 102 d, copies of all ARG decreased by 0.3 to 1.5 log10 copies (g dry matter)-1. Temperature in the interior of piles averaged ≥ 55 °C for 10 d, except for CTCSMZ, but did not reach 55 °C at pile exteriors. Compared to Control, CTCSMZ increased (P < 0.05) tet(C), tet(M), tet(W), sul(1), and sul(2) in stockpiled manure. Copies of 16S rDNA remained higher (P < 0.05) in CTCSMZ than Control for the first 26 d. Levels of most ARG did not differ between the interior and exterior of stockpiles. Our results suggest that stockpiled manure would still introduce ARG to land upon manure application, but at levels lower than if manure was applied fresh.

Persistence of the antimicrobials lincomycin, chlortetracycline, and sulfamethazine in prairie wetlands.

Antimicrobials used in livestock production can be present in manure via excretion in the feces and/or urine. Application of raw or processed (composted or stockpiled) manure to crop and pasture land as a plant nutrient source can result in antimicrobial transport to surface waters via rainfall or snowmelt runoff. Little is known regarding antimicrobial persistence in aquatic ecosystems. Consequently, dissipation of environmentally relevant concentrations of three veterinary antimicrobials (lincomycin, chlortetracycline, and sulfamethazine) was studied in three wetlands on the Canadian Prairies. Study wetlands were fortified in the fall to simulate antimicrobial transport via rainfall runoff from fall manure applications to the wetland catchments. After fortification, water column concentrations of all three antimicrobials decreased through September and October. Plotting natural logarithm values of antimicrobial concentration against time resulted in linear relationships for all three antimicrobials, indicating that the summation of all dissipation processes for each antimicrobial could be described by first-order kinetics. The slopes of the three plots were significantly different, indicating that the order of dissipation was lincomycin < sulfamethazine < chlortetracycline. Consequently, the dissipation DT50 (time required for 50% antimicrobial dissipation) values for lincomycin (14.0 d), sulfamethazine (7.0 d), and chlortetracycline (3.3 d) were significantly different. The longer DT50 values of lincomycin and sulfamethazine suggest that environmentally relevant concentrations of these antimicrobials may affect bacterial production in prairie wetlands.

Isomerization of chlortetracycline in prairie wetland water.

Chlortetracycline (CTC), an antimicrobial administered as a feed additive to cattle, swine, and poultry, is present in the corresponding manure. Land application of raw or processed (composted or stockpiled) manure provides a mechanism by which CTC (and other antimicrobials) enters the environment and becomes available for transport to surface receiving waters via rainfall or snowmelt runoff. Chlortetracycline has been detected in Canadian surface waters, but little has been reported on its fate in aquatic ecosystems. To address this knowledge gap, the dissipation of CTC-enol was monitored in deionized water and water typical of wetlands within the prairie region of Canada. In deionized water, CTC-enol tautomerized to CTC-keto, and both tautomers epimerized to 4-epi-CTC-enol and 4-epi-CTC-keto, respectively. Irreversible isomerization to iso-CTC occurred, which then epimerized to 4-epi-iso-CTC. In wetland water, although tauterization of CTC-enol to CTC-keto occurred, there was no evidence of the formation of the 4-epimers of either CTC-enol or CTC-keto. The major product formed in the wetland water was iso-CTC, some of which epimerized to 4-epi-iso-CTC. Although CTC-enol was shown to tautomerize to CTC-keto, the concentration of CTC-keto remained low in both deionized and wetland water, suggesting that the isomerization of CTC-enol to iso-CTC most likely occurred via CTC-keto. The dissipation of CTC-enol in wetland water was described by pseudo first-order kinetics with a DT50 (time required for 50% dissipation) value of 4.8 h. The short DT50 value of CTC and reduced antimicrobial activity of iso-CTC and 4-epi-iso-CTC suggest a lower probability for selection for CTC-resistant bacteria in Canadian Prairie aquatic ecosystems.

Concentrations of Herbicides in Wetlands on Organic and Minimum-Tillage Farms.

Wetlands are abundant throughout the agricultural landscape of central Saskatchewan, Canada, and the biota present in these wetlands may be vulnerable to the toxic effects of pesticides used on nearby crops. We hypothesized that herbicide concentrations would be higher in wetlands on minimum-tillage farms than on organic (no herbicide use) farms, and that the principal transport mechanisms of runoff versus atmospheric deposition could be identified based on the concentrations in these two wetland types. To test these hypotheses, 29 herbicides were monitored for 5 yr in 16 wetlands on minimum-tillage farms and in seven wetlands on organic farms. Twenty herbicides were detected in wetlands on minimum-tillage farms versus 12 in wetlands on organic farms. Clopyralid, MCPA, 2,4-D, bromoxynil, dichlorprop, and dicamba were detected at a >50% frequency in wetlands on both minimum-tillage and organic farms. Concentrations of clopyralid were significantly higher in wetlands on minimum-tillage farms than in those on organic farms, whereas no significant difference was observed for any of the other five herbicides. Glyphosate, including its degradation product AMPA, was detected in >50% frequency only in wetlands on minimum-tillage farms where the mean concentration (1278 ng L) was higher than the concentration of other herbicides. Mass applied, vapor pressure, and water solubility were important determinants of herbicide concentrations and detections in wetlands. Herbicide concentrations in all but two samples were less than their respective Canadian guideline for protection of aquatic life, suggesting that, overall, individual herbicide concentrations in the wetlands were not toxic to biota.

Dissipation of antimicrobial resistance genes in compost originating from cattle manure after direct oral administration or post-excretion fortification of antimicrobials.

Dissipation of antimicrobial resistance genes (ARG) during composting of cattle manure generated through fortification versus administration of antimicrobials in feed was compared. Manure was collected from cattle fed diets containing (kg-1) dry matter (DM): (1) 44 mg chlortetracycline (CTC), (2) a mixture of 44 mg each of chlortetracycline and sulfamethazine (CTCSMZ), (3) 11 mg tylosin (TYL) or (4) Control, no antimicrobials. Manures were composted for 30 d with a single mixing after 16 d to generate the second heating cycle. Quantitative PCR (qPCR) was used to measure 16S rDNA and tetracycline (tet), erythromycin (erm) and sulfamethazine (sul) genes. Temperature peaks ranged from 48 to 68°C across treatments in the first composting cycle, but except for the control, did not exceed 55°C in the second cycle. Copy numbers of 16S rDNA decreased (P < 0.05) during composting, but were not altered by antimcrobials. Except tet(L), all ARG decreased by 0.1-1.6 log10 g DM-1 in the first cycle, but some genes (tet[B], tet[L], erm[F], erm[X]) increased (P < 0.05) by 1.0-3.1 log10 g DM-1 in the second. During composting, levels of tet(M) and tet(W) in CTC, erm(A), erm(B) and erm(X) in TYL, and sul(1) in CTCSMZ remained higher (P < 0.05) in fed than fortified treatments. The dissipation of ARG during composting of manure fortified with antimicrobials differs from manure generated by cattle that are administered antimicrobials in feed, and does not always align with the dissipation of antimicrobial residues.

Dissipation of Antimicrobials in a Seasonally Frozen Soil after Beef Cattle Manure Application.

Land application of manure containing antimicrobials results in the dispersion of the antimicrobials in agro-ecosystems. Dissipation of excreted antimicrobials in seasonally frozen agricultural soils has not been fully characterized under field conditions. This study investigated the field dissipation kinetics of chlortetracycline, sulfamethazine, and tylosin over a 10-mo period after fall application of manure from cattle () administered 44 mg chlortetracycline (chlortetracycline treatment [CTC]), 44 mg each of chlortetracycline and sulfamethazine (CTCSMZ), or 11 mg tylosin per kg feed daily. Antimicrobial concentrations in manured soil reflected the same relative concentrations in manure: chlortetracycline > sulfamethazine > tylosin. The first-order dissipation half-life (DT) for chlortetracycline from the CTCSMZ treatment was 77 d during the growing season and 648 d during the nongrowing season when the soil was frozen for an extended period. By comparison, dissipation of chlortetracycline added alone (treatment CTC) did not differ significantly between the two seasons (mean DT, 121 d). During the nongrowing season, chlortetracycline from CTC dissipated faster ( = 0.004) than that from the CTCSMZ treatment, indicating that the presence of sulfamethazine may have altered the dissipation of chlortetracycline. Dissipation kinetics for sulfamethazine and tylosin were not determined due to low detection in the manure-amended soil. Sulfamethazine was detected (up to 16 ± 10 µg kg) throughout the 10-mo monitoring period. Tylosin concentration was ≤11 ± 6.6 µg kg and gradually dissipated. Chlortetracycline was detectable 10 mo after application in the seasonally frozen soil, indicating a risk for residue build-up in the soil and subsequent offsite contamination.

Transport of Three Antimicrobials in Runoff from Windrows of Composting Beef Cattle Manure.

Rain runoff from windrowed or stockpiled manure may contain antimicrobials with the potential to contaminate surface and ground water. To quantify the concentration of antimicrobials transported in runoff from windrowed manure, antimicrobials were administered continuously in feed to beef cattle () as follows: 44 mg of chlortetracycline kg feed (dry weight), a 1:1 mixture of 44 mg of chlortetracycline and 44 mg sulfamethazine kg feed, and 11 mg of tylosin kg feed. Cattle in a fourth treatment group received no antimicrobials (control). Manure from the cattle was used to construct two windrows per treatment. On Days 2 and 21 of composting, a portable Guelph Rainfall Simulator II was used to apply deionized water at an intensity of 127 mm h to each windrow, and the runoff was collected. Manure samples were collected before rain simulations on Days 2 and 21 of composting for antimicrobial analysis. On Day 2, average concentrations of chlortetracycline, sulfamethazine, and tylosin in manure were 2580, 450, and 120 µg kg, respectively, with maximum concentrations in runoff of 2740, 3600, and 4930 µg L, respectively. Concentrations of all three antimicrobials in runoff were higher ( < 0.05) on Day 2 than on Day 21, reflecting the higher concentrations in manure on Day 2. Maximum estimated masses of chlortetracycline, sulfamethazine, and tylosin that could be transported in runoff from a windrow (3 m long, 2.5 m wide, 1.5 m high) were approximately 0.87 to 0.94, 1.57, and 1.23 g, respectively. This study demonstrates the importance of windrow composting in reducing antimicrobial concentrations in manure. The runoff from windrows can be a source of antimicrobials and demonstrates the need for containment of runoff from composting facilities to mitigate antimicrobial contamination of surface and groundwater resources.

Dissipation of Antimicrobials in Feedlot Manure Compost after Oral Administration versus Fortification after Excretion.

Fortification of manure with antimicrobials is one approach to studying their dissipation. However, fortified antimicrobials may not accurately model dissipation that occurs after antimicrobials have been administered to livestock in feed and excreted in manure. This study examined the dissipation of antimicrobials excreted in manure versus those added directly to manure (fortified). Steers were fed a diet containing (kg feed) (i) 44 mg chlortetracycline, (ii) 44 mg each of chlortetracycline and sulfamethazine, (iii) 11 mg tylosin, and (iv) no antimicrobials (control). Fortified antimicrobial treatments were prepared by adding antimicrobials to control manure. Manure was composted for 30 d, sampled every 2 to 3 d, and analyzed for antimicrobials and compost properties. Antimicrobial dissipation followed first-order kinetics. The dissipation rate constant was significantly greater (based on 95% confidence limit) for excreted (0.29-0.54 d) than for fortified chlortetracycline (0.11-0.13 d). In contrast, dissipation rate constants were significantly greater for fortified sulfamethazine (0.47 d) and tylosin (0.31 d) than when the same antimicrobials were excreted (0.08 and 0.07 d, respectively). On average, 85 to 99% of the initial antimicrobial concentrations in manure were dissipated after 30 d of composting. The degree of dissipation was greater ( < 0.0001) for fortified (99%) than for excreted tylosin (85%). Composting can be used to reduce environmental loading of antimicrobials before field application of beef cattle manure. Dissipation rates of fortified antimicrobials during manure composting may not accurately reflect those of antimicrobials that are consumed and excreted by cattle.

Dissipation of Antimicrobial Resistance Determinants in Composted and Stockpiled Beef Cattle Manure.

Windrow composting or stockpiling reduces the viability of pathogens and antimicrobial residues in manure. However, the impact of these manure management practices on the persistence of genes coding for antimicrobial resistance is less well known. In this study, manure from cattle administered 44 mg of chlortetracycline kg feed (dry wt. basis) (CTC), 44 mg of CTC and 44 mg of sulfamethazine kg feed (CTCSMZ), 11 mg of tylosin kg feed (TYL), and no antimicrobials (control) were composted or stockpiled over 102 d. Temperature remained ≥55°C for 35 d in compost and 2 d in stockpiles. Quantitative PCR was used to measure levels of 16S rRNA genes and tetracycline [(B), (C), (L), (M), (W)], erythromycin [(A), (B), (F), (X)], and sulfamethazine [(1), (2)] resistance determinants. After 102 d, 16S rRNA genes and all resistance determinants declined by 0.5 to 3 log copies per gram dry matter. Copies of 16S rRNA genes were affected ( < 0.05) by antimicrobials with the ranking of control > CTC = TYL > CTCSMZ. Compared with the control, antimicrobials did not increase the abundance of resistance genes in either composted or stockpiled manure, except (M) and (2) in CTCSMZ ( < 0.05). The decline in 16S rRNA genes and resistance determinants was higher ( < 0.05) in composted than in stockpiled manure. We conclude that composting may be more effective than stockpiling in reducing the introduction of antimicrobial resistance genes into the environment before land application of manure.

Mineralisation and degradation of 2,4-dichlorophenoxyacetic acid dimethylamine salt in a biobed matrix and in topsoil.

BACKGROUND: Biobeds are used for on-farm bioremediation of pesticides in sprayer rinsate and from spills during sprayer filling. Using locally sourced materials from Saskatchewan, Canada, a biobed matrix was evaluated for its effectiveness for mineralising and degrading 2,4-dichlorophenoxyacetic acid dimethylamine salt (2,4-D DMA) compared with the topsoil used in the biobed matrix. RESULTS: Applying 2,4-D DMA to the biobed matrix caused a 2-3 day lag in CO2 production not observed when the herbicide was applied to topsoil. Despite the initial lag, less residual 2,4-D was measured in the biobed (0%) matrix than in the topsoil (57%) after a 28 day incubation. When the herbicide was applied 5 times to the biobed matrix, net CO2 increased immediately after each 2,4-D DMA application. Mineralisation of 2,4-D DMA was 61.9% and residual 2,4-D in the biobed matrix was 0.3% after 60 days, compared with corresponding values of 32.9 and 70.9% in topsoil. CONCLUSION: The biobed matrix enhanced the mineralisation and degradation of 2,4-D DMA, indicating the potential for successful implementation of biobeds under Canadian conditions. The biobed matrix was more effective for mineralising and degrading the herbicide compared with the topsoil used in the biobed matrix. By correcting for biobed matrix and formulation blank, CO2 evolution was a reliable indicator of 2,4-D DMA mineralisation. © 2016 Society of Chemical Industry.

Persistence of the Sulfonylurea Herbicides Sulfosulfuron, Rimsulfuron, and Nicosulfuron in Farm Dugouts (Ponds).

Sulfonylurea herbicides are applied at relatively low rates (3-40 g ha) to control weeds in a variety of crops grown in the prairie pothole region of south-central Canada. Because of their high phytotoxicity and the likelihood of their transport in surface runoff, there is concern about impacts of sulfonylurea herbicides to wetland ecosystems embedded in agricultural landscapes. In a previous study, dissipation half-lives (DT values) were determined for three sulfonylurea herbicides (thifensulfuron-methyl, ethametsulfuron-methyl, and metsulfuron-methyl), each possessing a hydrolyzable methyl ester linkage. In the current study, persistence of three sulfonylurea herbicides without a methyl ester linkage was determined in prairie farm dugouts (ponds). The dugouts were fortified with environmentally relevant concentrations (3.3-6.5 µg L) of either sulfosulfuron, rimsulfuron, or nicosulfuron. The order of persistence of these herbicides in dugout water from May and June to November and December was nicosulfuron > sulfosulfuron > rimsulfuron, with DT values of 75, 44, and 10 d, respectively. The lack of a methyl ester linkage in these herbicides did not significantly affect their overall persistence relative to those with the ester linkage. In all three dugouts, the decrease in herbicide mass in the water column from water loss via hydrological discharge to groundwater was minimal. The relatively long persistence of these herbicides in the water column of the dugouts reflects the stability of the sulfonylurea linkage to hydrolysis in weakly alkaline waters and indicates not only that microbial and photolytic degradation were low but also that there was little partitioning into sediments.

Transport of three veterinary antimicrobials from feedlot pens via simulated rainfall runoff.

Veterinary antimicrobials are introduced to wider environments by manure application to agricultural fields or through leaching or runoff from manure storage areas (feedlots, stockpiles, windrows, lagoons). Detected in manure, manure-treated soils, and surface and ground water near intensive cattle feeding operations, there is a concern that environmental contamination by these chemicals may promote the development of antimicrobial resistance in bacteria. Surface runoff and leaching appear to be major transport pathways by which veterinary antimicrobials eventually contaminate surface and ground water, respectively. A study was conducted to investigate the transport of three veterinary antimicrobials (chlortetracycline, sulfamethazine, tylosin), commonly used in beef cattle production, in simulated rainfall runoff from feedlot pens. Mean concentrations of veterinary antimicrobials were 1.4 to 3.5 times higher in surface material from bedding vs. non-bedding pen areas. Runoff rates and volumetric runoff coefficients were similar across all treatments but both were significantly higher from non-bedding (0.53Lmin(-1); 0.27) than bedding areas (0.40Lmin(-1); 0.19). In keeping with concentrations in pen surface material, mean concentrations of veterinary antimicrobials were 1.4 to 2.5 times higher in runoff generated from bedding vs. non-bedding pen areas. Water solubility and sorption coefficient of antimicrobials played a role in their transport in runoff. Estimated amounts of chlortetracycline, sulfamethazine, and tylosin that could potentially be transported to the feedlot catch basin during a one in 100-year precipitation event were 1.3 to 3.6ghead(-1), 1.9ghead(-1), and 0.2ghead(-1), respectively. This study demonstrates the magnitude of veterinary antimicrobial transport in feedlot pen runoff and supports the necessity of catch basins for runoff containment within feedlots.

Effects of a herbicide mixture on primary and bacterial productivity in four prairie wetlands with varying salinities: an enclosure approach.

Wetlands in the Prairie pothole region of Saskatchewan and Manitoba serve an important role in providing wildlife habitat, water storage and water filtration. They display a wide range of water quality parameters such as salinity, nutrients and major ions with sulfate as the dominant ion for the most saline wetlands. The differences in these water quality parameters among wetlands are reflected in the composition of aquatic plant communities and their productivity. Interspersed within an intensely managed agricultural landscape where pesticides are commonly used, mixtures of herbicides are often detected in these wetlands as well as in rivers, and drinking water reservoirs. One freshwater and three wetlands of varying salinity in the St. Denis National Wildlife Area, Saskatchewan, Canada were selected to study the effects of a mixture of eight herbicides (2,4-D, MCPA, dicamba, clopyralid, bromoxynil, mecoprop, dichlorprop, and glyphosate) on wetland microbial communities using an outdoor enclosure approach. Six enclosures (three controls and three treatments) were installed in each wetland and the herbicide mixture added to the treatment enclosures. The concentration of each herbicide in the enclosure water was that which would have resulted from a direct overspray of a 0.5-m deep wetland at its recommended field application rate. After herbicide addition, primary and bacterial productivity, and algal biomass were measured in both planktonic and benthic communities over 28 days. The herbicide mixture had a stimulatory effect on primary productivity in the nutrient-sufficient freshwater wetland while no stimulatory effect was observed in the nutrient-deficient saline wetlands. The differences observed in the effects of the herbicide mixture appear to be related to the nutrient bioavailability in these wetlands.

Widespread use and frequent detection of neonicotinoid insecticides in wetlands of Canada's Prairie Pothole Region.

Neonicotinoids currently dominate the insecticide market as seed treatments on Canada's major Prairie crops (e.g., canola). The potential impact to ecologically significant wetlands in this dominantly agro-environment has largely been overlooked while the distribution of use, incidence and level of contamination remains unreported. We modelled the spatial distribution of neonicotinoid use across the three Prairie Provinces in combination with temporal assessments of water and sediment concentrations in wetlands to measure four active ingredients (clothianidin, thiamethoxam, imidacloprid and acetamiprid). From 2009 to 2012, neonicotinoid use was increasing; by 2012, applications covered an estimated ∼11 million hectares (44% of Prairie cropland) with >216,000 kg of active ingredients. Thiamethoxam, followed by clothianidin, were the dominant seed treatments by mass and area. Areas of high neonicotinoid use were identified as high density canola or soybean production. Water sampled four times from 136 wetlands (spring, summer, fall 2012 and spring 2013) across four rural municipalities in Saskatchewan similarly revealed clothianidin and thiamethoxam in the majority of samples. In spring 2012 prior to seeding, 36% of wetlands contained at least one neonicotinoid. Detections increased to 62% in summer 2012, declined to 16% in fall, and increased to 91% the following spring 2013 after ice-off. Peak concentrations were recorded during summer 2012 for both thiamethoxam (range:

A coupled stochastic/deterministic model to estimate the evolution of the risk of water contamination by pesticides across Canada.

Periodic assessments of the risk of water contamination by pesticides help decision makers improve the sustainability of agricultural management practices. In Canada, when evaluating the risk of water contamination by pesticides, 2 main constraints arise. First, because the area of interest is large, a pesticide transport model with low computational running time is mandatory. Second, some relevant input data for simulations are not known, and most are known only at coarse scale. This study aims to develop a robust methodology to estimate the evolution of the risk of water contamination by pesticides across Canada. To circumvent the 2 aforementioned issues, we constructed a stochastic model and coupled it to the 1-dimensional pesticide fate model Pesticide Root Zone Model (PRZM). To account for input data uncertainty, the stochastic model uses a Monte Carlo approach to generate several pesticide application scenarios and to randomly select PRZM parameter values. One hundred different scenarios were simulated for each of over 2000 regions (Soil Landscapes of Canada [SLC] polygons) for the years 1981 and 2006. Overall, the results indicated that in those regions in which the risk increased from 1981 to 2006, the increase in risk was mainly attributable to the increased area treated by pesticides or an increase in the number of days with runoff. More specifically, this work identifies the areas at higher risk, where further analyses with finer-scale input data should be performed. The model is specific for Canadian data, but the framework could be adapted for other large countries.

Sulfonylurea herbicides in an agricultural catchment basin and its adjacent wetland in the St. Lawrence River basin.

The use of sulfonylurea herbicides (SU) has increased greater than 100 times over the past 30 years in both Europe and North America. Applied at low rates, their presence, persistence and potential impacts on aquatic ecosystems remain poorly studied. During late-spring to early fall in 2009-2011, concentrations of 9 SU were assessed in two agricultural streams and their receiving wetland, an enlargement of the St. Lawrence River (Canada). Six SU in concentrations >LOQ (10 ng L(-1)) were detected in 10% or less of surface water samples. Rimsulfuron was detected each year, sulfosulfuron and nicosulfuron in two years and the others in one year only, suggesting that application of specific herbicides varied locally between years. Detection frequency and concentrations of SU were not significantly associated with total precipitation which occurred 1 to 5d before sampling. Concentrations and fate of SU differed among sites due to differences in stream dynamics and water quality characteristics. The persistence of SU in catchment basin streams reflected the dissipation effects associated with stream discharge. Maximum concentrations of some SU (223 and 148 ng L(-1)) were occasionally above the baseline level (100 ng L(-1)) for aquatic plant toxicity, implying potential toxic stress to flora in the streams. Substantially lower concentrations (max 55 ng L(-1)) of SU were noted at the downstream wetland site, likely as a result from dilution and mixing with St. Lawrence River water, and represent less toxicological risk to the wetland flora. Sporadic occurrence of SU at low concentrations in air and rain samples indicated that atmospheric deposition was not an important source of herbicides to the study area.

Runoff losses of excreted chlortetracycline, sulfamethazine, and tylosin from surface-applied and soil-incorporated beef cattle feedlot manure.

Veterinary antimicrobials in land-applied manure can move to surface waters via rain or snowmelt runoff, thus increasing their dispersion in agro-environments. This study quantified losses of excreted chlortetracycline, sulfamethazine, and tylosin in simulated rain runoff from surface-applied and soil-incorporated beef cattle ( L.) feedlot manure (60 Mg ha, wet wt.). Antimicrobial concentrations in runoff generally reflected the corresponding concentrations in the manure. Soil incorporation of manure reduced the concentrations of chlortetracycline (from 75 to 12 µg L for a 1:1 mixture of chlortetracycline and sulfamethazine and from 43 to 17 µg L for chlortetracycline alone) and sulfamethazine (from 3.9 to 2.6 µg L) in runoff compared with surface application. However, there was no significant effect of manure application method on tylosin concentration (range, 0.02-0.06 µg L) in runoff. Mass losses, as a percent of the amount applied, for chlortetracycline and sulfamethazine appeared to be independent of their respective soil sorption coefficients. Mass losses of chlortetracycline were significantly reduced with soil incorporation of manure (from 6.5 to 1.7% when applied with sulfamethazine and from 6.5 to 3.5% when applied alone). Mass losses of sulfamethazine (4.8%) and tylosin (0.24%) in runoff were not affected by manure incorporation. Although our results confirm that cattle-excreted veterinary antimicrobials can be removed via surface runoff after field application, the magnitudes of chlortetracycline and sulfamethazine losses were reduced by soil incorporation of manure immediately after application.

Dissipation of Three Veterinary Antimicrobials in Beef Cattle Feedlot Manure Stockpiled over Winter.

Dissipation of veterinary antimicrobials is known to occur during aerated windrow composting of beef cattle manure. However, it is unclear if a similar dissipation occurs during stockpiling. Chlortetracycline, tylosin, and sulfamethazine are three of the most commonly used veterinary antimicrobials in beef cattle production in western Canada. Their dissipation in stockpiled manure was investigated over 140 d during winter in Alberta, Canada. Beef cattle housed in pens were administered 44 mg of chlortetracycline kg feed (dry weight), 44 mg of chlortetracycline + 44 mg sulfamethazine kg feed, 11 mg of tylosin kg feed, or feed without antimicrobials (control). Manure samples were extracted using pressurized liquid extraction, and the extracts were analyzed for chlortetracycline, sulfamethazine, and tylosin by LC-MS-MS. Dissipation of all three antimicrobials in the manure was explained by exponential decay kinetics. Times for 50% dissipation (DT) were 1.8 ± 0.1 d for chlortetracycline alone or 6.0 ± 0.8 d when mixed with sulfamethazine, 20.8 ± 3.8 d for sulfamethazine, and 4.7 ± 1.2 d for tylosin. After 77 d, <1% of initial chlortetracycline and <2% of sulfamethazine remained. Tylosin residues were more variable, decreasing to approximately 12% of initial levels after 28 d, with 20% present after 77 d and 13% after 140 d. Temperatures within stockpiles reached maximum values within 6 d of establishment and varied with location (bottom, 62.5°C; middle, 63.8°C; and top, 42.9°C). Antimicrobials in the manure did not inhibit microbial activity, as indicated by temperature and mass losses of carbon (C) and nitrogen (N). The C/N ratio in the manure decreased over the stockpiling period, indicating decomposition of manure to a more stable state. Dissipation of excreted residues with DT values 1.8 to 20.8 d showed that stockpiling can be as effective as windrow composting in mitigating the transfer of these three veterinary antimicrobials into the environment during land application of processed manure.

Can nutrients mask community responses to insecticide mixtures?

The ecological effect of simultaneous exposure to two nutrient gradients, three insecticides and different predator intensities was investigated over a 3-week period in 80 outdoor, artificial streams using field-collected benthic invertebrates. The experimental design consisted of a 2 × 5 factorial structure with two nutrient levels (oligotrophic or mesotrophic) and five concentrations of the ternary insecticide mixture consisting of the insecticides (chlorpyrifos, dimethoate and imidacloprid). Equivalent toxic unit doses were summed to create a ternary insecticide dose (e.g., 0.1 + 0.1 + 0.1 = 0.3 TU) resulting in a range of ternary insecticide mixture toxicity (i.e., control groundwater, 0.3, 0.6, 0.9 and 1.2 TU). Two genera of insect predators, Gomphus spp. (Odonata) and Agnetina spp. (Plecoptera) were also added into each replicate stream, at densities and sizes comparable to those found at our collection site, to evaluate how the contribution of predators may change in nutrient limited (oligotrophic) versus amended (mesotrophic) systems. We describe a causal mechanism whereby the combined action of nutrients and insecticides reshaped aquatic community structure by interacting through multiple pathways. Specifically, mesotrophic conditions reduced the toxic effects of ternary insecticide mixtures for aquatic insects which, in some cases, appeared to increase abundance of aquatic insects. However, higher levels of insecticides in mesotrophic streams negated this effect and were even more toxic; for example, to aquatic insect grazers than the same insecticide doses in oligotrophic treatment levels. Effects of predators were only significant in oligotrophic streams. Evidence is provided as to how nutrient and contaminant interactions can greatly complicate the assessment of community level responses to insecticide mixtures due to direct and indirect effects of the resulting changes in the density of different genera and functional feeding groups within a community.