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Agricultural drainage ditches help remove excess water from fields and provide habitat for wildlife. Drainage ditch management, which includes various forms of vegetation clearing and sediment dredging, can variably affect the ecological function of these systems. To determine whether ditch conditions following dredging/vegetation clearing management affected the survival, growth, and development of embryos and tadpoles of northern leopard frogs (Lithobates pipiens), we conducted three field studies using in situ cages over 2 years. We measured nutrients, pesticides, and other water quality properties in vegetated/unmanaged (i.e., no clearing or dredging) and newly cleared/dredged (i.e., treeless, then dredged), clay-bottomed drainage ditches in a river basin in Eastern Ontario, Canada. Nutrients, atrazine, and total neonicotinoid concentrations were generally lower at the cleared/dredged sites, whereas glyphosate was at higher concentrations. In contrast, water-quality variables measured in situ, particularly temperature, dissolved oxygen, and turbidity, tended to be higher in the cleared/dredged sites. Total phosphorous and total organic carbon concentrations at all sites were above the recommended limits for amphibian assays. No significant differences were detected in the survival, hatching success, or development of embryos among the ditch management treatments, but premature hatching was observed at one vegetated/unmanaged site where high specific conductivity may have been formative. We found the cleared/dredged sites supported earlier tadpole growth and development, likely as a result of the higher water temperatures. Increased temperature may have offset other growth/development stressors, such as those related to water chemistry. However, the long-term consequences of these differences on amphibian populations requires further study.

Non-targeted analysis (NTA) workflows using mass spectrometry are gaining popularity in many disciplines, but universally accepted reporting standards are nonexistent. Current guidance addresses limited elements of NTA reporting-most notably, identification confidence-and is insufficient to ensure scientific transparency and reproducibility given the complexity of these methods. This lack of reporting standards hinders researchers' development of thorough study protocols and reviewers' ability to efficiently assess grant and manuscript submissions. To overcome these challenges, we developed the NTA Study Reporting Tool (SRT), an easy-to-use, interdisciplinary framework for comprehensive NTA methods and results reporting. Eleven NTA practitioners reviewed eight published articles covering environmental, food, and health-based exposomic applications with the SRT. Overall, our analysis demonstrated that the SRT provides a valid structure to guide study design and manuscript writing, as well as to evaluate NTA reporting quality. Scores self-assigned by authors fell within the range of peer-reviewer scores, indicating that SRT use for self-evaluation will strengthen reporting practices. The results also highlighted NTA reporting areas that need immediate improvement, such as analytical sequence and quality assurance/quality control information. Although scores intentionally do not correspond to data/results quality, widespread implementation of the SRT could improve study design and standardize reporting practices, ultimately leading to broader use and acceptance of NTA data.

Understanding the environmental fate, transport, and occurrence of pesticides and pharmaceuticals in aquatic environments is of utmost concern to regulators. Traditionally, monitoring of environmental contaminants in surface water has consisted of liquid chromatography-tandem mass spectrometry analyses for a set of targeted compounds in discrete samples. These targeted approaches are limited by the fact that they only provide information on compounds within a target list present at the time and location of sampling. To address these limitations, there has been considerable interest in suspect screening and nontargeted analysis (NTA), which allow for the detection of all ionizable compounds in the sample with the added benefit of data archiving for retrospective mining. Even though NTA can detect a large number of contaminants, discrete samples only provide a snapshot perspective of the chemical disposition of an aquatic environment at the time of sampling, potentially missing episodic events. We evaluated two types of passive chemical samplers for nontargeted analysis in mixed-use watersheds. Nontargeted data were processed using MS-DIAL to screen against our in-house library and public databases of more than 1300 compounds. The data showed that polar organic chemicals integrative samplers (POCIS) were able to capture the largest number of analytes with better reproducibility than organic compound-diffusive gradients in thin film (o-DGT), resulting from the greater amount of binding sorbent. We also showed that NTA combined with passive sampling gives a more representative picture of the contaminants present at a given site and enhances the ability to identify the nature of point and nonpoint pollution sources and ecotoxicological impacts. Environ Toxicol Chem 2022;41:1131-1143. © 2021 Her Majesty the Queen in Right of Canada Environmental Toxicology and Chemistry © 2021 SETAC. Reproduced with the permission of the Minister of Agriculture and Agri-Food Canada.

Agricultural drainage ditches help remove excess water from fields and provide habitat for wildlife. Drainage ditch management, which includes various forms of vegetation clearing and sediment dredging, can variably affect the ecological function of these systems. To determine whether ditch conditions following dredging/vegetation clearing management affected the survival, growth, and development of embryos and tadpoles of northern leopard frogs (Lithobates pipiens), we conducted three field studies using in situ cages over 2 years. We measured nutrients, pesticides, and other water quality properties in vegetated/unmanaged (i.e., no clearing or dredging) and newly cleared/dredged (i.e., treeless, then dredged), clay-bottomed drainage ditches in a river basin in Eastern Ontario, Canada. Nutrients, atrazine, and total neonicotinoid concentrations were generally lower at the cleared/dredged sites, whereas glyphosate was at higher concentrations. In contrast, water-quality variables measured in situ, particularly temperature, dissolved oxygen, and turbidity, tended to be higher in the cleared/dredged sites. Total phosphorous and total organic carbon concentrations at all sites were above the recommended limits for amphibian assays. No significant differences were detected in the survival, hatching success, or development of embryos among the ditch management treatments, but premature hatching was observed at one vegetated/unmanaged site where high specific conductivity may have been formative. We found the cleared/dredged sites supported earlier tadpole growth and development, likely as a result of the higher water temperatures. Increased temperature may have offset other growth/development stressors, such as those related to water chemistry. However, the long-term consequences of these differences on amphibian populations requires further study.

In this study, the fate of several micropollutants (MPs) in wastewater due to coagulation using both fresh and recovered aluminum and iron coagulants was determined. 18 MPs from different groups such as antibiotics, food additives, and surfactants were selected and spiked into the primary influent collected from a local wastewater plant. The distribution of MPs in the recovered coagulant and treated effluent after coagulation was determined for both fresh and recycled coagulants. The distribution of MPs in wastewater and the removal during coagulation were compound specific; MPs with log Kow 2.5 were sorbed on the coagulated sludge. The distribution ratio (Kd) of all the MPs (diclofenac, clarithromycin, etc.) with log Kow > 2.5 was determined along with their extent of accumulation in sludge due to the recycling of coagulants. Compounds such as sulfamethoxazole, erythromycin and sulfathiazole, showed low removal during coagulation. The tetracycline group of compounds showed possible chelation with iron and aluminum. Only 2.5 was being recycled with the recovered coagulant, thus alleviating the concern of accumulation of the MPs during recycle of the coagulants.

In many jurisdictions sludge recovered from the sewage treatment process is a valued fertilizer for crop production. Pre-treatment of sewage sludge prior to land application offers the potential to abate enteric microorganisms that carry genes conferring resistance to antibiotics. Pre-treatment practices that accomplish this should have the desirable effect of reducing the risk of contamination of crops or adjacent water with antibiotic resistance genes carried in these materials. In the present study, we obtained municipal sludge that had been subjected to one of five treatments. There were, anaerobic-digestion or aerobic-digestion, in both instances with and without dewatering; and heat-treatment and pelletization. Each of the five types of biosolids was applied to an agricultural field at commercial rates, following which lettuce, carrots and radishes were planted. Based on qPCR, the estimated antibiotic gene loading rates were comparable with each of the five biosolids. However, the gene abundance in soil following application of the pelletized biosolids was anomalously lower than expected. Following application, the abundance of antibiotic resistance genes decreased in a generally coherent fashion, except sul1 which increased in abundance during the growing season in the soil fertilized with pelletized biosolids. Based on qPCR and high throughput sequencing evidence for transfer of antibiotic resistance genes from the biosolids to the vegetables at harvest was weak. Clostridia were more abundant in soils receiving any of the biosolids except the pelletized. Overall, the behavior of antibiotic resistance genes in soils receiving aerobically or anaerobically-digested biosolids was consistent and coherent with previous studies. However, dynamics of antibiotic resistance genes in soils receiving the heat treated pelletized biosolids were very different, and the underlying mechanisms merit investigation.

Manuring ground used for crop production is an important agricultural practice. Should antibiotic-resistant enteric bacteria carried in the manure be transferred to crops that are consumed raw, their consumption by humans or animals will represent a route of exposure to antibiotic resistance genes. Treatment of manures prior to land application is a potential management option to reduce the abundance of antibiotic resistance genes entrained with manure application. In this study, dairy manure that was untreated, anaerobically digested, mechanically dewatered or composted was applied to field plots that were then cropped to lettuce, carrots and radishes. The impact of treatment on manure composition, persistence of antibiotic resistance gene targets in soil following application, and distribution of antibiotic resistance genes and bacteria on vegetables at harvest was determined. Composted manure had the lowest abundance of antibiotic resistance gene targets compared to the other manures. There was no significant difference in the persistence characteristics of antibiotic resistance genes following land application of the various manures. Compared to unmanured soil, antibiotic resistance genes were detected more frequently in soil receiving raw or digested manure, whereas they were not in soil receiving composted manure. The present study suggests that vegetables grown in ground receiving raw or digested manure are at risk of contamination with manure-borne antibiotic resistant bacteria, whereas vegetables grown in ground receiving composted manure are less so.

Acesulfame potassium (ACE) is a widely used artificial sweetener that has consistently been detected in wastewater and surface waters. The high-valent iron-based green oxidant known as ferrate(VI) (potassium ferrate(VI); Fe(VI)) had low reactivity with ACE (i.e. 4 h (or 240 min) contact time removed only ∼ 67% ACE) at a molar ratio of 6.0 ([Fe(VI)]:[ACE]). Comparatively, it took 60 s (or 1 min) to remove ∼94% ACE when HCl (786 μM) was added to a mixture of Fe(VI)-ACE at the same molar ratio of 6.0 (or acid-activated Fe(VI)). Significantly, the final pH (i.e. 7.6–8.1) was similar for Fe(VI) and acid-activated Fe(VI). An empirical model using response surface methodology was developed that could describe reasonably well the removal efficiency of ACE. Inorganic constituents of wastewater (Cl−, Na+, Ca2+, and Mg2+) had no significant effect on the oxidation of ACE by acid-activated Fe(VI). The degradation efficiency of ACE decreased in the presence of 10 mg/L of natural organic matter (NOM) but remained unchanged at 5 mg NOM/L. Sulfamic acid as the oxidized product of ACE was identified by liquid chromatography high resolution mass spectrometry method. Reaction pathways include ring opening of ACE through hydrolytic transformation. Acid-activated Fe(VI) has advantage of rapid removal of ACE under mild alkaline conditions of wastewater treatment plants compared to other oxidation processes such as chlorination, ozonation, and light-based processes.

The macrolide antibiotics erythromycin, clarithromycin and azithromycin are very important in human and animal medicine, and can be entrained onto agricultural ground through application of sewage sludge or manures. In the present study, a series of replicated field plots were left untreated or received up to five annual spring applications of a mixture of three drugs to achieve a nominal concentration for each of 10 or 0.1mgkg(-1) soil; the latter an environmentally relevant concentration. Soil samples were incubated in the laboratory, and supplemented with antibiotics to establish the dissipation kinetics of erythromycin and clarithromycin using radioisotope methods, and azithromycin using HPLC-MS/MS. All three drugs were dissipated significantly more rapidly in soils with a history of field exposure to 10mgkg(-1) macrolides, and erythromycin and clarithromycin were also degraded more rapidly in field soil exposed to 0.1mgkg(-1) macrolides. Rapid mineralization of (14)C-labelled erythromycin and clarithromycin are consistent with biodegradation. Analysis of field soils revealed no carryover of parent compound from year to year. Azithromycin transformation products were detected consistent with removal of the desosamine and cladinose moieties. Overall, these results have revealed that following several years of exposure to macrolide antibiotics these are amenable to accelerated degradation. The potential accelerated degradation of these drugs in soils amended with manure and sewage sludge should be investigated as this phenomenon would attenuate environmental exposure and selection pressure for clinically relevant resistance.

In many jurisdictions land application of municipal biosolids is a valued source of nutrients for crop production. The practice must be managed to ensure that crops and adjacent water are not subject to contamination by pharmaceuticals or other organic contaminants. The broad spectrum antimicrobial agents triclosan (TCS) and triclocarban (TCC), the anti-epileptic drug carbamazepine (CBZ), and the nonsteroidal anti-inflammatory drug naproxen (NAP) are widely used and are carried in biosolids. In the present study, the effect of biosolids and depth of placement in the soil profile on the rates of TCS, TCC, CBZ, and NAP dissipation were evaluated under semi-field conditions. Aggregates of dewatered municipal biosolids (DMBs) supplemented with (14)C-labeled residues were applied either on the soil surface or in the subsurface of the soil profile, and incubated over several months under ambient outdoor conditions. The dissipation of TCS, TCC and NAP was significantly faster in sub-surface than surface applied biosolid aggregates. In contrast the dissipation rate for CBZ was the same in surface applied and incorporated aggregates. Overall, the present study has determined a significant effect of depth of placement on the dissipation rate of biodegradable molecules.

Antibiotics are frequently introduced into agricultural soils with the application of sewage sludge or farm organic fertilizers. Repeated exposure of soils to a pollutant can enrich for microbial populations that metabolize the chemical, reducing its environmental persistence. In London, Canada, soils from a long-term field experiment have received different concentrations of antibiotics annually for several years. The purpose of the present study was to assess the bioavailability of sulfamethazine, erythromycin, or ciprofloxacin through aqueous extractions with borax or EDTA solutions and their biodegradation following different soil exposure scenarios. Control soils and soils treated annually in the field with 10 mg antibiotics per kg were sampled, supplemented in the laboratory with radiolabeled antibiotic either added directly or carried in dairy manure. Sulfamethazine and erythromycin were initially more bioavailable than ciprofloxacin, with aqueous extractabilities representing 60, 36, and 8%, respectively. Sulfamethazine and erythromycin were degraded in soils, with a larger fraction mineralized in the long-term exposed soil (20 and 65%, respectively) than in control soil (0.4 and 3%, respectively) after 7 days of incubation. In contrast, ciprofloxacin was not mineralized neither in control nor long-term exposed soils. The mineralized fractions were similar for antibiotics added directly to soil or carried in dairy manure.

Advances in high-resolution mass spectrometers have allowed for the development of nontargeted screening methods, where data sets can be archived and retrospectively mined as new environmental contaminants are identified. We have developed a spectral counting approach to calculate the selectivities of LC-MS acquisition modes taking mass accuracy, sample matrix, and the analyte properties into account. The selectivities of high-resolution MS (HRMS) alone or in combination with all-ion-fragmentation (AIF), data-independent-acquisition (DIA), and data-dependent-acquisition (DDA) modes, performed on a Q-Exactive Orbitrap were compared by retrospectively screening surface water samples for 95 pharmaceuticals. Samples were reanalyzed using targeted LC-MS/MS to confirm the accuracy of each acquisition method and to quantitate the 29 putatively detected drugs. LC-HRMS provided the lowest calculated selectivities and accordingly produced the highest number of false positives (6). In contrast, DDA provided the highest selectivities, yielding only one false positive; however, it was bias toward the most intense signals resulting in the detection of only 10 compounds. AIF had lower selectivities than traditional LC-MS/MS, produced one false positive and did not detect 6 confirmed compounds. Because of the high-quality archived data, DIA selectivities were better than traditional LC-MS/MS, showed no bias toward the most intense signals, achieved low limits of detection, and confidently detected the greatest number of pharmaceuticals (22) with only one false positive. This spectral counting method can be used across different instrument platforms or samples and provides a robust and empirical estimation of selectivities to give more confident detection of trace analytes.

Consumption of vegetables represents a route of direct human exposure to bacteria found in soil. The present study evaluated the complement of bacteria resistant to various antibiotics on vegetables often eaten raw (tomato, cucumber, pepper, carrot, radish, lettuce) and how this might vary with growth in soil fertilized inorganically or with dairy or swine manure. Vegetables were sown into field plots immediately following fertilization and harvested when of marketable quality. Vegetable and soil samples were evaluated for viable antibiotic-resistant bacteria by plate count on Chromocult medium supplemented with antibiotics at clinical breakpoint concentrations. DNA was extracted from soil and vegetables and evaluated by PCR for the presence of 46 gene targets associated with plasmid incompatibility groups, integrons, or antibiotic resistance genes. Soil receiving manure was enriched in antibiotic-resistant bacteria and various antibiotic resistance determinants. There was no coherent corresponding increase in the abundance of antibiotic-resistant bacteria enumerated from any vegetable grown in manure-fertilized soil. Numerous antibiotic resistance determinants were detected in DNA extracted from vegetables grown in unmanured soil. A smaller number of determinants were additionally detected on vegetables grown only in manured and not in unmanured soil. Overall, consumption of raw vegetables represents a route of human exposure to antibiotic-resistant bacteria and resistance determinants naturally present in soil. However, the detection of some determinants on vegetables grown only in freshly manured soil reinforces the advisability of pretreating manure through composting or other stabilization processes or mandating offset times between manuring and harvesting vegetables for human consumption.

Sewage sludge recovered from wastewater treatment plants contains antibiotic residues and is rich in antibiotic resistance genes, selected for and enriched in the digestive tracts of human using antibiotics. The use of sewage sludge as a crop fertilizer constitutes a potential route of human exposure to antibiotic resistance genes through consumption of contaminated crops. Several gene targets associated with antibiotic resistance (catA1, catB3, ereA, ereB, erm(B), str(A), str(B), qnrD, sul1, and mphA), mobile genetic elements (int1, mobA, IncW repA, IncP1 groups -α, -β, -δ, -γ, -ε), and bacterial 16S rRNA (rrnS) were quantified by qPCR from soil and vegetable samples obtained from unamended and sludge-amended plots at an experimental field in London, Ontario. The qPCR data reveals an increase in abundance of gene targets in the soil and vegetables samples, indicating that there is potential for additional crop exposure to antibiotic resistance genes carried within sewage sludge following field application. It is therefore advisable to allow an appropriate delay period before harvesting of vegetables for human consumption.

Clotrimazole is a broad-spectrum antimycotic drug used for the treatment of dermatological and gynecological infections; it is incompletely broken down during sewage treatment and could potentially reach agricultural land through the application of municipal biosolids or wastewater. In the absence of any environmental fate data, we evaluated the persistence and dissipation pathways of 3H-clotrimazole during laboratory incubations of agricultural soils. Clotrimazole was removed from a loam (time to dissipate 50% = 68 d), a sandy loam (time to dissipate 50% = 36 d), and a clay loam (time to dissipate 50% = 55 d), with formation of nonextractable residues being the major sink for 3H. Their parent compound had no significant mineralization, as evidenced by the lack of formation of 3H2O. Up to 15% of the applied radioactivity was recovered in the form of [3H]-(2-chlorophenyl)diphenyl methanol. The rate of clotrimazole dissipation in the loam soil did not vary with moisture content, but it was slower at a lower temperature (number of days to dissipate 50% = 275.6 d at 4°C). Addition of municipal biosolids to the loam soil did not vary the clotrimazole dissipation rate. In summary, the present study has established that clotrimazole is dissipated in soil, at rates that varied with soil texture and temperature. Clotrimazole dissipation was accompanied by the formation of nonextractable residues and detectable extractable residues of the transformation product (2-chlorophenyl)diphenyl methanol. Environ. Toxicol. Chem. 2011; 30:582–587. © 2010 SETAC

Diclofenac, 2-[2-[(2,6-dichlorophenyl)amino]phenyl]acetic acid, is an important non-steroidal anti-inflammatory drug widely used for human and animals to reduce inflammation and pain. Diclofenac could potentially reach agricultural lands through the application of municipal biosolids or wastewater, and in the absence of any environmental fate data, we evaluated its persistence in agricultural soils incubated in the laboratory. (14)C-Diclofenac was rapidly mineralized without a lag when added to soils varying widely in texture (sandy loam, loam, clay loam). Over a range of temperature and moisture conditions extractable (14)C-diclofenac residues decreased with half lives

Tenofovir (9-(R)-(2-phosphonylmethoxypropyl)-adenine) is an antiretroviral drug widely used for the treatment of human immunodeficiency virus (HIV-1) and Hepatitis B virus (HBV) infections. Tenofovir is extensively and rapidly excreted unchanged in the urine. In the expectation that tenofovir could potentially reach agricultural lands through the application of municipal biosolids or wastewater, and in the absence of any environmental fate data, we evaluated its persistence in selected agricultural soils. Less than 10% of [adenine-8-(14)C]-tenofovir added to soils varying widely in texture (sand, loam, clay loam) was mineralized in a 2-month incubation under laboratory conditions. Tenofovir was less readily extractable from clay soils than from a loam or a sandy loam soil. Radioactive residues of tenofovir were removed from the soil extractable fraction with DT(50)s ranging from 24±2 to 67+22days (first order kinetic model) or 44+9 to 127+55days (zero order model). No extractable transformation products were detectable by HPLC. Tenofovir mineralization in the loam soil increased with temperature (range 4°C to 30°C), and did not occur in autoclaved soil, suggesting a microbial basis. Mineralization rates increased with soil moisture content, ranging from air-dried to saturated. In summary, tenofovir was relatively persistent in soils, there were no extractable transformation products detected, and the response of [adenine-8-(14)C]-tenofovir mineralization to soil temperature and heat sterilization indicated that the molecule was biodegraded by aerobic microorganisms. Sorption isotherms with dewatered biosolids suggested that tenofovir residues could potentially partition into the particulate fraction during sewage treatment.

Municipal biosolids are a useful source of nutrients for crop production, and commonly used in agriculture. In this field study, we applied dewatered municipal biosolids at a commercial rate using broadcast application followed by incorporation. Precipitation was simulated at 1, 3, 7, 21 and 34 days following the application on 2 m(2) microplots to evaluate surface runoff of various pharmaceuticals and personal care products (PPCPs), namely atenolol, carbamazepine, cotinine, caffeine, gemfibrozil, naproxen, ibuprofen, acetaminophen, sulfamethoxazole, triclosan and triclocarban. There was little temporal coherence in the detection of PPCPs in runoff, various compounds being detected maximally on days 1, 3, 7 or 36. Maximum concentrations in runoff ranged from below detection limit (gemfibrozil) to 109.7 ng L(-1) (triclosan). Expressing the total mass exported as a percentage of that applied, some analytes revealed little transport potential (1% exported; triclocarban, triclosan, sulfamethoxazole, ibuprofen, naproxen and gemfibrozil) whereas others were readily exported (1% exported; acetaminophen, carbamazepine, caffeine, cotinine, atenolol). Those compounds with little transport potential had log K(ow) values of 3.18 or greater, whereas those that were readily mobilized had K(ow) values of 2.45 or less. Maximal concentrations of all analytes were below toxic concentrations using a variety of endpoints available in the literature. In summary, this study has quantified the transport potential in surface runoff of PPCPs from land receiving biosolids, identified that log K(ow) may be a determinant of runoff transport potential of these analytes, and found maximal concentrations of all chemicals tested to be below toxic concentrations using a variety of endpoints.

Municipal biosolids are a source of nutrients for crop production. Beneficial Management Practices (BMPs) can be used to minimize the risk of contamination of adjacent water resources with chemical or microbial agents that are of public or environmental health concern. In this field study, we applied biosolids slurry at a commercial rate using either subsurface injection or broadcast application followed by incorporation. Precipitation was simulated at 1, 3, 7, 22, 36 and 266 days post-application on 2 m(2) microplots to evaluate surface runoff of 9 model pharmaceuticals and personal care products (PPCPs), atenolol, carbamazepine, cotinine, gemfibrozil, naproxen, ibuprofen, acetaminophen, sulfamethoxazole and triclosan. In runoff from the injected plots, concentrations of the model PPCPs were generally below the limits of quantitation. In contrast, in the broadcast application treatment, the concentrations of atenolol, carbamazepine, cotinine, gemfibrozil, naproxen, sulfamethoxazole and triclosan on the day following application ranged from 70-1477 ng L(-1) in runoff and generally declined thereafter with first order kinetics. The total mass of PPCPs mobilized in surface runoff per m(2) of the field ranged from 0.63 microg for atenolol to 21.1 microg for ibuprofen. For ibuprofen and acetaminophen, concentrations in runoff first decreased and then increased, suggesting that these drugs were initially chemically or physically sequestered in the biosolids slurry, and subsequently released in the soil. Carbamazepine and triclosan were detected at low concentrations in a runoff event 266 days after broadcast application. Overall, this study showed that injection of biosolids slurry below the soil surface could effectively eliminate surface runoff of PPCPs.

This paper focuses on calibration and validation of a dual-permeability soil water flow model, MACRO, to simulate liquid municipal biosolid (LMB) and precipitation induced vadose zone flow to a monitored tile drain system in a structured silt-loam soil, in southern Ontario Canada. The model was calibrated primarily on the basis of site-measured soil hydraulic parameters (encompassing tillage effects associated with LMB application), and field-monitored soil water content, soil water tension, and tile drain discharge for fall site conditions. LMB application for calibration data sets were carried out using an AerWay SSD system. Overall, daily tile drain discharge, soil water content, and soil water tension were well predicted by the following model calibration of primarily soil hydraulic parameters (specifically soil porosity, saturated hydraulic conductivity and van Genuchten soil desorption curve factors). The calibrated model was then validated using two additional daily data sets for two spring/summer study periods, both employing an LMB application. The modeling results were evaluated in part via statistical measures (i.e. average error and root mean square error); which indicated excellent agreement between daily simulated and measured tile drain discharges, soil water content and soil water tension. Overall, for certain LMB applications the modeling approach that was taken slightly under-predicted the degree of immediate application-induced macropore flow in the top 0.4 m of the soil. Generally, MACRO was found to be less adept at handling what was considered to be true bypass flow as a result of soil cracking during the drier soil conditions.

The consumption of crops fertilized with human waste represents a potential route of exposure to antibiotic-resistant fecal bacteria. The present study evaluated the abundance of bacteria and antibiotic resistance genes by using both culture-dependent and molecular methods. Various vegetables (lettuce, carrots, radish, and tomatoes) were sown into field plots fertilized inorganically or with class B biosolids or untreated municipal sewage sludge and harvested when of marketable quality. Analysis of viable pathogenic bacteria or antibiotic-resistant coliform bacteria by plate counts did not reveal significant treatment effects of fertilization with class B biosolids or untreated sewage sludge on the vegetables. Numerous targeted genes associated with antibiotic resistance and mobile genetic elements were detected by PCR in soil and on vegetables at harvest from plots that received no organic amendment. However, in the season of application, vegetables harvested from plots treated with either material carried gene targets not detected in the absence of amendment. Several gene targets evaluated by using quantitative PCR (qPCR) were considerably more abundant on vegetables harvested from sewage sludge-treated plots than on vegetables from control plots in the season of application, whereas vegetables harvested the following year revealed no treatment effect. Overall, the results of the present study suggest that producing vegetable crops in ground fertilized with human waste without appropriate delay or pretreatment will result in an additional burden of antibiotic resistance genes on harvested crops. Managing human exposure to antibiotic resistance genes carried in human waste must be undertaken through judicious agricultural practice.

Animal manures recycled onto crop production land carry antibiotic-resistant bacteria. The present study evaluated the fate in soil of selected genes associated with antibiotic resistance or genetic mobility in field plots cropped to vegetables and managed according to normal farming practice. Referenced to unmanured soil, fertilization with swine or dairy manure increased the relative abundance of the gene targets sul1 , erm (B), str (B), int1 , and IncW repA . Following manure application in the spring of 2012, gene copy number decayed exponentially, reaching background levels by the fall of 2012. In contrast, gene copy number following manure application in the fall of 2012 or spring of 2013 increased significantly in the weeks following application and then declined. In both cases, the relative abundance of gene copy numbers had not returned to background levels by the fall of 2013. Overall, these results suggest that under conditions characteristic of agriculture in a humid continental climate, a 1-year period following a commercial application of raw manure is sufficient to ensure that an additional soil burden of antibiotic resistance genes approaches background. The relative abundance of several gene targets exceeded background during the growing season following a spring application or an application done the previous fall. Results from the present study reinforce the advisability of treating manure prior to use in crop production systems.

a Agriculture and Agri-Food Canada, London, ON, Canada N5V 4T3 b Health Canada, New Substances Assessment and Control Bureau, Ottawa, Canada K1A 0K9 c Department of Biology, University of Western Ontario, London, ON, Canada N6A 5B7 d Ontario Ministry of the Environment, Toronto, ON, Canada M4V 1M2 e Agriculture and Agri-Food Canada, Ottawa, Canada K1A 0C6 f Worsfold Water Qualify Centre, Trent University, Peterborough, ON, Canada K9J 7B8 g Ontario Ministry of Food, Agriculture and Rural Affairs, Stratford, ON, Canada N5A 5T8

Joanette and Goulet ( Neuropsychologia , 1986, 24, 875–879) reported that right-handed patients suffering from a right-hemisphere stroke were impaired on semantic but not on orthographic criteria when they were submitted to a word fluency task. The interpretation of this dissociation was that the right hemisphere would subtend a particular contribution to the semantic component of word processing in right handers. The goal of the research reported here was to challenge this dissociation. In contrast with the first study, the production criteria were presented randomly and their level of productivity was a controlled factor. The semantic-orthographic dissociation was not replicated under these conditions.

International audience; The World Health Organization has identified antibiotic resistance as one of the top three threats to global health. There is concern that the use of antibiotics as growth promoting agents in livestock production contributes to the increasingly problematic development of antibiotic resistance. Many antibiotics are excreted at high rates, and the land application of animal manures represents a significant source of environmental exposure to these agents. To evaluate the long-term effects of antibiotic exposure on soil microbial populations, a series of field plots were established in 1999 that have since received annual applications of a mixture of sulfamethazine (SMZ), tylosin (TYL), and chlortetracycline (CTC). During the first 6 yr (1999-2004) soils were treated at concentrations of 0, 0.01 0.1, and 1.0 mg kg(-1) soil, in subsequent years at concentrations of 0, 0.1, 1.0, and 10 mg kg(-1) soil. The lower end of this concentration range is within that which would result from an annual application of manure from medicated swine. Following ten annual applications, the fate of the drugs in the soil was evaluated. Residues of SMZ and TYL, but not CTC were removed much more rapidly in soil with a history of exposure to 10 mg/kg drugs than in untreated control soil. Residues of C-14-SMZ were rapidly and thoroughly mineralized to (CO2)-C-14 in the historically treated soils, but not in the untreated soil. A SMZ-degrading Microbacterium sp. was isolated from the treated soil. Overall, these results indicate that soil bacteria adapt to long-term exposure to some veterinary antibiotics resulting in sharply reduced persistence. Accelerated biodegradation of antibiotics in matrices exposed to agricultural, wastewater, or pharmaceutical manufacturing effluents would attenuate environmental exposure to antibiotics, and merits investigation in the context of assessing potential risks of antibiotic resistance development in environmental matrices.

The widely used antihistamine diphenhydramine is present in municipal biosolids, and is detected in runoff from agricultural land fertilized with biosolids. In the present study the kinetics and major pathways of diphenhydramine dissipation in a loam, sandy loam, and clay loam soil were determined in laboratory incubations. The time to dissipate 50% (DT(50)) of (14)C-diphenhydramine residues at 30 °C ranged from 88 ± 28 days in the clay loam to 335 ± 145 days in the loam soil. Mineralization of (14)C was insignificant, and diphenhydramine-N-oxide was the only detected extractable transformation product elucidated by radioisotope and HPLC-MS methods. There were no significant effects of municipal biosolids on the kinetics or pathways of removal. Overall, diphenhydramine is quite persistent in soils, and formation of non-extractable soil-bound residues is the major mechanism of diphenhydramine dissipation.

The broad spectrum antimicrobial agents triclosan (TCS) and triclocarban (TCC) are widely used in many personal care products. Knowledge concerning the fate of these two compounds in different environmental matrices is scarce. In this study, the fate of TCS and TCC in soil following direct addition, or when residues were applied via either liquid municipal biosolids (LMB) or dewatered municipal biosolids (DMB) was investigated in laboratory dissipation experiments and under outdoor conditions using radioisotope methods. In laboratory incubations, (14)C-TCC or (14)C-TCS was added to microcosms containing a loam soil and the rate of (14)CO(2) accumulation and loss of solvent-extractable (14)C were determined during incubation at 30 degrees C. Compared to when TCC or TCS was added directly to soil, both chemicals were mineralized more rapidly when applied in LMB, and both were mineralized more slowly when applied in DMB. The application matrix had no effect on the rate of removal of extractable residues. In field experiments, parent compounds were incorporated directly in soil, incorporated via LMB, or a single aggregate of amended DMB was applied to the soil surface. During the experiment soil temperatures ranged from 20 degrees C to 10 degrees C. Dissipation was much slower in the field than in the laboratory experiments. Removal of non-extractable residues was faster in the presence of LMB than the other treatments. Recovery of extractable and non-extractable residues suggested that there was little atmospheric loss of (14)C. Triclocarban readily formed non-extractable residues with DMB whereas TCS did not. Overall, this study has identified that both the pathways and the kinetics of TCS and TCC dissipation in soil are different when the chemicals are carried in biosolids compared to when these chemicals are added directly to the soil.

This study examined bacteria and nutrient quality in tile drainage and shallow ground water resulting from a fall land application of liquid municipal biosolids (LMB), at field application rates of 93,500 L ha(-1), to silt-clay loam agricultural field plots using two different land application approaches. The land application methods were a one-pass AerWay SSD approach (A), and surface spreading plus subsequent incorporation (SS). For both treatments, it took between 3 and 39 min for LMB to reach tile drains after land application. The A treatment significantly (p0.1) reduced application-induced LMB contamination of tile drains relative to the SS treatment, as shown by mass loads of total Kjeldahl N (TKN), NH(4)-N, Total P (TP), PO(4)-P, E. coli., and Clostridium perfringens. E. coli contamination resulting from application occurred to at least 2.0-m depth in ground water, but was more notable in ground water immediately beneath tile depth (1.2 m). Treatment ground water concentrations of selected nutrients and bacteria for the study period ( approximately 46 d) at 1.2-m depth were significantly higher in the treatment plots, relative to control plots. The TKN and TP ground water concentrations at 1.2-m depth were significantly (p0.1) higher for the SS treatment, relative to the A treatment, but there were no significant (p0.1) treatment differences for the bacteria. For the macroporous field conditions observed, pre-tillage by equipment such as the AerWay SSD, will reduce LMB-induced tile and shallow ground water contamination compared to surface spreading over non-tilled soil, followed by incorporation.

The MACRO soil water flow model adequately predicted liquid municipal biosolid (LMB) application and precipitation induced tile discharges. LMB was applied via two different application methods; AerWay SSD (Sub Surface Deposition) and a Kongskilde Vibro-Shank-type injection system. The model was able to satisfactorily simulate wetting-front movement through soil profiles. The model, however, could not reproduce the observed tile discharge values under dry, cracking soil conditions. Modeling results showed that LMB induced flow moved instantaneously through the soil profile to tile drains for the injection method. Tile discharge changes for the AerWay method were not notably detected. Bacteria concentrations in tile water were evaluated for each application approach, and tended to decrease over time presumably due to macropore flushing and dilution effects.

With increasing application of liquid municipal biosolids (LMB) on farm lands, a better understanding of the transport mechanisms by which contaminants reach water sources is required. For this purpose, a onedimensional transport model, MACRO, was used to understand soil water transport mechanisms under macroporous soils. Field measured data were used for calibration purposes. The model predicted that macropore flow dominated tile flow; bacteria transport was also found to be predominately macropore driven. Modeling helped to elucidate: the LMB application rates that reduce the risk of application induced macropore flow of LMB to tiles, the surface soil water contents required to minimize application induced tile contamination from LMB, and tile discharge contributing area. Although cursory at this stage, this modeling exercise was found to be promising with respect to providing information that can be used towards the development of Best Management Practices (BMPs) for land application of LMB.

Selection of appropriate liquid sewage, or liquid municipal biosolid (LMB), land application options can be assisted by modeling LMB transport in the vadose zone. The dual-permeability soil water flow model (MACRO) was used to simulate vadose zone flow and tile drain discharge resulting from LMB application (at 93,500 L ha-1) to agricultural field plots for three seasons using a rolling-tine aeration (AerWay® SSD) slurry deposition system (surface apply over aerator-tilled soil), furrow-based slurry injection system, and surface spread (broadcast) on un-tilled soil followed by incorporation methods. Given the total solid content of the LMB (0.02 to 0.05 g mL-1), we assumed that it behaved, for modeling purposes, as water. The AerWay SSD system, which surface applies LMB immediately over aerator-tilled soil, did not cause measurable or simulated changes in tile drain discharge during any study period condition. For the broadcast + incorporation experiment, preferential flow of LMB to tile occurred within 0.5 h post-application. Modeling did not simulate the small increase in application-induced discharge observed. This discrepancy was likely due to the existence of bypass flow in un-tilled soil. For the injection method, we simulated vadose zone flow processes associated discretely with the application furrow. While the furrow modeling approach adequately reflected tile breakthrough times, there were some overestimations of peak discharge (100%). Mass loads of bacteria associated with the different application methods did not show, nevertheless, marked or consistent treatment effects. Overall, it was felt that the physically based modeling approach employed here could be used to inform water quality risks associated with different methods to land apply LMB.