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.

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.

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.

The safe use of lipid-based drug delivery agents requires fast and sensitive qualitative and quantitative assessment of their cellular interactions. Many mass spectrometry (MS) based analytical platforms can achieve such task with varying capabilities. Therefore, four novel high-throughput MS-based quantitative methods were evaluated for the analysis of a small organic gene delivery agent: N,N-bis(dimethylhexadecyl)-1,3-propane-diammonium dibromide (G16-3). Analysis utilized MS instruments that detect analytes using low-resolution tandem MS (MS/MS) analysis (i.e. QTRAP or linear ion trap in this work) or high-resolution MS analysis (i.e. time of flight (ToF) or Orbitrap). Our results indicate that the validated fast chromatography (FC)-QTRAP-MS/MS, FC- LTQ-Orbitrap-MS, desorption electrospray ionization-collision-induced dissociation (CID)-MS/MS and matrix assisted laser desorption ionization-ToF/ToF-MS MS methods were superior in the area of method development and sample analysis time to a previously developed liquid chromatography (LC)-CID-MS/MS. To our knowledge, this is the first evaluation of the abilities of five MS-based quantitative methods that target a single pharmaceutical analyte. Our findings indicate that, in comparison to conventional LC-CID-MS/MS, the new MS-based methods resulted in a (1) substantial reduction in the analysis time, (2) reduction in the time required for method development and (3) production of either superior or comparable quantitative data. The four new high-throughput MS methods, therefore, were faster, more efficient and less expensive than a conventional LC-CID-MS/MS for the quantification of the G16-3 analyte within tissue culture. When applied to cellular lysate, no significant change in the concentration of G16-3 gemini surfactant within PAM212 cells was observed between 5 and 53h, suggesting the absence of any metabolism/excretion from PAM212 cells. Copyright (c) 2014 John Wiley & Sons, Ltd.

Some imidazolinone herbicides have been shown to be mobile in soil, raising concern about their possible movement to ground water. Three imidazolinone herbicides (imazamethabenz-methyl, 497 g ha(-1); imazethapyr, 14.7 g ha(-1); and imazamox, 14.7 g ha(-1)) commonly used in crop production on the Canadian prairies were applied to a tile-drained field to assess their susceptibility to leach when subjected to sprinkler irrigation using a center pivot. Tile-drain flow began when the water table rose above tile-drain depth, and peak flow rates corresponded to the greatest depths of ground water above the tile drains. Interception of irrigation water by the tile drains in each quadrant of the field varied from ∼11 to 20% of the water applied. Under a worst-case scenario in which irrigation began the day after herbicide application and irrigation water was applied at 25 mm d(-1) for 12 d, there was evidence of preferential flow of all three herbicides and hydrolysis of imazamethabenz-methyl to imazamethabenz in the initial samples of tile-drain effluent. In subsequent samples, concentrations (analysis by LC-MS-MS) of the summation of imazamethabenz-methyl (25-24,000 ng L(-1)) plus its hydrolysis product imazamethabenz (63-26,500 ng L(-1)) greatly exceeded those of imazethapyr (<13-1260 ng L) and imazamox (19-599 ng L(-1)), thus reflecting relative application rates. In contrast, estimates of total transport of each herbicide from the root zone, which varied in each quadrant and ranged from 0.06 to 2.3% for imazamethabenz-methyl plus imazamethabenz, 0.71 to 3.1% for imazethapyr, and 0.61 to 2.8% for imazamox, did not reflect application rates. In shallow ground water (piezometer samples), there was inconsistent and infrequent detection all four compounds. With the frequency and amount of rainfall typically encountered in the prairie region of Canada, contamination of shallow ground water with detectable concentrations of the three imidazolinone herbicides would be unlikely.

Mineralogical Magazine | www.minersoc.org 1827 Canadian oil sands; a window on the deep petroleum biosphere IAN M. HEAD1 *, NEIL D. GRAY1, ANGELA SHERRY1, MICHAEL J. MAGUIRE1, RUSSELL J. GRANT, CASEY R.J. HUBERT1, CAROLYN AITKEN1, D. MARTIN JONES1, THOMAS OLDENBURG2, BARRY BENNETT2 AND STEVE LARTER2 NRG, School of Civil Engineering and Geosciences, U. Newcastle, Newcastle upon Tyne, UK. i.m.head@ncl.ac.uk (* presenting author) PRG Dept Geosciences, U. Calgary, Calgary, Canada., slarter@ucalgary.ca

Pesticides can be present in the atmosphere either as vapours and/or in association with suspended particles. High-volume air sampling, in which air is aspirated first through a glass fibre filter to capture pesticides associated with atmospheric particulates and then polyurethane foam (PUF), often in combination with an adsorbent resin such as XAD-2, to capture pesticides present as vapours, is generally employed during atmospheric monitoring for pesticides. However, the particulate fraction may be underestimated because some pesticides may be stripped or desorbed from captured particulates due to the pressure drop created by the high flow of air through the filter. This possibility was investigated with ten herbicide active ingredients commonly used on the Canadian prairies (dimethylamine salts of 2,4-D, MCPA and dicamba, 2,4-D 2-ethylhexyl ester, bromoxynil octanoate, diclofop methyl ester, fenoxaprop ethyl ester, trifluralin, triallate and ethalfluralin) and seven hydrolysis products (2,4-D, MCPA, dicamba, bromoxynil, diclofop, clopyralid and mecoprop). Finely ground heavy clay soil fortified with active ingredients/hydrolysis products was evenly distributed on the glass fibre filters of high-volume air samplers and air aspirated through the samplers at a flow rate of 12.5 m3/h for a 7-day period. The proportion desorbed as vapour from the fortified soil was determined by analysis of the PUF/XAD-2 resin composite cartridges. The extent of desorption from the fortified soil applied to the filters varied from 0% for each of the dimethylamine salts of 2,4-D, MCPA and dicamba to approximately 50% for trifluralin, triallate and ethalfluralin.

Sulfonylurea herbicides are widely applied on the Canadian prairies to control weeds in a variety of crops. Several sulfonylurea herbicides are mobile in soil, and there is concern about their possible movement to ground water. This study was performed to assess the susceptibility of three sulfonylurea herbicides commonly used in prairie crop production to leach under a worst-case scenario. Thifensulfuron-methyl, tribenuron-methyl, and rimsulfuron were applied to a 9-ha tile-drained field, and then approximately 300 mm of irrigation water were applied over a 2-wk period using a center pivot. The commencement of tile-drain flow corresponded to the rise of the water table above tile-drain depth, and peak flow rates corresponded to the greatest depths of ground water above the tile drains. The volume of irrigation water intercepted by the tile drains in each quadrant was determined by site hydrology and represented <10% of the irrigation water applied. Concentrations of thifensulfuron-methyl, tribenuron-methyl, and rimsulfuron in the tile-drain effluent ranged (analysis by liquid chromatography/tandem mass spectrometry) from 2.0 to 248 ng L(-1), not detected (nd) to 55 ng L(-1), and nd to 497 ng L(-1), respectively. Total herbicide transport from the root zone in each quadrant was estimated at <0.5% of the amount of each sulfonylurea herbicide applied. Thifensulfuron-methyl was the only herbicide detected in ground water, with concentrations ranging from 1.2 to 2.5 ng L(-1). With the frequency and amount of rainfall typically encountered in the prairie region of Canada, detectable concentrations (>1 ng L(-1)) of these sulfonylurea herbicides in ground water would be unlikely.

Sulfonylurea herbicides are applied at relatively low rates (3 to 40 g ha(-1)) to control weeds in a variety of crops across the Canadian prairies. Because of their high phytotoxicity and the likelihood of their transport in surface runoff, there is concern about their possible impact to aquatic ecosystems. Little is known, however, about their persistence and behavior in aquatic ecosystems. To assess persistence in aquatic ecosystems, three prairie farm dugouts (ponds) were fortified with either thifensulfuron-methyl {methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylate}, ethametsulfuron-methyl {methyl 2-[[[[[4-ethoxy-6-(methylamino)-1,3,5-triazin-2-yl]amino]carbonyl]amino]sulfonyl]benzoate} or metsulfuron-methyl {methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazinyl)amino]carbonyl]amino]sulfonyl]benzoate}. The decreasing order of persistence of environmentally relevant concentrations (1 to 4.6 microg L(-1)) of these herbicides in dugout water over the June to October period was metsulfuron-methyl>ethametsulfuron-methyl>thifensulfuron-methyl. The corresponding dissipation half-lives (DT(50)) of 84, 30, and 16 d, respectively, are in the same relative order as the recropping intervals for these herbicides. Thifensulfuron-methyl showed a biphasic dissipation with slower dissipation during the winter months. In contrast, the dissipation of metsulfuron-methyl, the sulfonylurea herbicide with the longest DT(50), was somewhat enhanced under winter conditions. One of the major routes of sulfonylurea herbicide dissipation was removal from the water column when dugout water was lost during hydrological discharge. The relatively long persistence of these herbicides in water indicates that partitioning into sediments was minimal, the sulfonylurea and methyl ester linkages in these compounds were resistant to hydrolysis in weakly alkaline waters, and that microbial and photolytic degradation in dugout waters were slow.