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1.
Arch Environ Contam Toxicol ; 76(2): 231-245, 2019 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-30361942

RESUMEN

Triclosan is widely used in personal care products (skin creams, toothpastes, soaps, deodorants, body spray) and cleaning products (dishwashing detergent and all-purpose cleaners) (Halden in Environ Sci Technol 48:3603-3611, 2014). In 2001, it was selected for screening-level risk assessment under the Canadian Environmental Protection Act (HC and EC in Preliminary assessment. Triclosan. Chemical abstracts Service Number 3380-34-5, 2012. http://www.ec.gc.ca/ese-ees/default.asp?lang=En&n=6EF68BEC-1 ), and its physicochemical and toxicological characteristics indicate that there may be a risk to aquatic environments due to releases of the chemical in Canada. A surveillance initiative across Canada has included sampling at 44 sites from July 2012 to March 2018. Triclosan was detected in 226 of 918 samples; concentrations ranged from less than 6 to 874 ng L-1, and the detections averaged 54.23 ng L-1 (standard deviation; 97.6 ng L-1). However, using the entire dataset (including censored data estimated with the Kaplan-Meier model), the mean triclosan concentration was 17.95 ng L-1, and the standard deviation was 52.84 ng L-1. Three samples at Wascana Creek (downstream), Saskatchewan, had concentrations above the Federal Environmental Quality Guidelines of 470 ng L-1, indicating a potential risk to the aquatic ecosystem. In this study, triclosan in samples collected downstream from municipal wastewater treatment plant discharges usually demonstrated higher concentrations than upstream samples. Based on the results of this study, it is hypothesized that triclosan concentration have fluctuated between years of this study but not in an overall or significant increase or decreasing trend. Triclosan concentrations and detections also are more prevalent in urban than in rural or mixed development rivers. Performance evaluation of triclosan concentrations in the Canadian environment is scheduled to be reassessed by 2024. Therefore, a 3-year sampling program should be in place across Canada by 2021.


Asunto(s)
Agua Dulce/análisis , Triclosán/análisis , Contaminantes Químicos del Agua/análisis , Canadá , Monitoreo del Ambiente
2.
Chemosphere ; 169: 516-523, 2017 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-27894057

RESUMEN

The widespread use of neonicotinoid insecticides and recent increased regulatory scrutiny requires the generation of monitoring data with sufficient scope and resolution to provide decision makers with a better understanding of occurrence and distribution in the environment. This study presents a wide-scale investigation of neonicotinoid insecticides used across the range of agricultural activities from fifteen surface water sites in southern Ontario. Using statistical analysis, the correlation of individual compounds with land use was investigated, and the relationship between neonicotinoid occurrence and hydrologic parameters in calibrated water courses was also assessed. Of the five neonicotinoids studied, imidacloprid, clothianidin and thiamethoxam exhibited detection rates above 90% at over half the sites sampled over a three year period (2012-2014). At two sites in southwestern Ontario, the Canadian Federal freshwater guideline value for imidacloprid (230 ng/L) was exceeded in roughly 75% of the samples collected. For some watersheds, there were correlations between the occurrence of neonicotinoids and precipitation and/or stream discharge. Some watersheds exhibited seasonal maxima in concentrations of neonicotinoids in spring and fall, particularly for those areas where row crop agriculture is predominant; these seasonal patterns were absent in some areas characterized by a broad range of agricultural activities.


Asunto(s)
Guanidinas/análisis , Imidazoles/análisis , Insecticidas/análisis , Nitrocompuestos/análisis , Oxazinas/análisis , Ríos/química , Tiazoles/análisis , Contaminantes Químicos del Agua/análisis , Agricultura , Guanidinas/química , Imidazoles/química , Insecticidas/química , Neonicotinoides , Nitrocompuestos/química , Ontario , Oxazinas/química , Estaciones del Año , Solubilidad , Tiametoxam , Tiazoles/química , Contaminantes Químicos del Agua/química , Tiempo (Meteorología)
3.
Pest Manag Sci ; 72(10): 1862-72, 2016 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-26732707

RESUMEN

BACKGROUND: The objective of this study was to investigate the occurrence of glyphosate residues (glyphosate and its metabolite AMPA) in shallow groundwater in a catchment dominated by agriculture, and to examine the potential for this groundwater to store and transmit these compounds to surface waters. RESULTS: Glyphosate residues were found in some of the groundwater samples collected in riparian (surface seeps), upland (mostly <20 m below ground) and wetland settings (<3 m below ground). Overall, glyphosate and AMPA were detected in 10.5 and 5.0%, respectively, of the groundwater samples analyzed as part of this study. All concentrations of glyphosate were well below Canadian guidelines for drinking water quality and for protection of aquatic life. Seasonal differences in concentrations in riparian seeps were possibly related to cycles of weather, herbicide application and degradation of glyphosate. Highest concentrations were at upland sites (663 ng L(-1) of glyphosate, 698 ng L(-1) of AMPA), apparently related to localized applications. Most glyphosate detections in wetlands were >0.5 km distant from possible areas of application, and, combined with other factors, suggest an atmospheric transport and deposition delivery mechanism. In both upland and wetland settings, highest glyphosate concentrations were sometimes not at the shallowest depths, indicating influence of hydrological factors. CONCLUSION: The glyphosate/AMPA detections in riparian seeps demonstrated that these compounds are persistent enough to allow groundwater to store and transmit glyphosate residues to surface waters. Detections in the wetlands support earlier evidence that atmospheric transport and deposition may lead to glyphosate contamination of environments not intended as targets of applications. This interpretation is further supported by detections of both glyphosate and AMPA in precipitation samples collected in the same watershed. © 2016 Her Majesty the Queen in Right of Canada Pest Management Science © 2016 Society of Chemical Industry.


Asunto(s)
Glicina/análogos & derivados , Agua Subterránea/química , Monitoreo del Ambiente , Glicina/análisis , Herbicidas/análisis , Ontario , Residuos de Plaguicidas/análisis , Contaminantes Químicos del Agua/análisis , Humedales , Glifosato
4.
Bull Environ Contam Toxicol ; 96(4): 423-31, 2016 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-26754544

RESUMEN

Surface water sampling in 2007-2010 measured the occurrence of carbamates and metalaxyl during base flow conditions and wet weather events in southern Ontario surface waters. Carbaryl, metalaxyl and pirimicarb were the most frequently detected compounds. In 2008 these three compounds were detected in over 50 % of the samples. Overall mean concentrations of carbaryl and metalaxyl over the course of the study (2007-2010) were 15 and 18 ng/L, respectively. Elevated concentrations of carbaryl (~100 to ~950 ng/L) appeared associated with wet weather (high flow) events, while highest concentrations of metalaxyl (~20-1330 ng/L) were correlated with base flow conditions. We attributed these observations as the result of runoff of carbaryl from the watershed during rain events, while metalaxyl contamination may have resulted primarily from spray drift.


Asunto(s)
Alanina/análogos & derivados , Carbamatos/análisis , Carbaril/análisis , Agua Dulce/química , Plaguicidas/análisis , Pirimidinas/análisis , Contaminantes Químicos del Agua/análisis , Alanina/análisis , Monitoreo del Ambiente , Agua Dulce/análisis , Ontario , Lluvia
5.
Environ Toxicol Chem ; 35(5): 1224-38, 2016 May.
Artículo en Inglés | MEDLINE | ID: mdl-26436714

RESUMEN

In situ exposures with Hyalella azteca were used to assess impacts of current-use pesticides in Southern Ontario, Canada. Exposures were conducted over 2 growing seasons within areas of high pesticide use: 1 site on Prudhomme Creek and 3 sites on Twenty Mile Creek. Three sites on Spencer Creek, an area of low pesticide use, were added in the second season. Surface water samples were collected every 2 wk to 3 wk and analyzed for a suite of pesticides. Hyalella were exposed in situ for 1 wk every 4 wk to 6 wk, and survival and acetylcholinesterase (AChE) activity were measured. Pesticides in surface waters reflected seasonal use patterns: lower concentrations in spring and fall and higher concentrations during summer months. Organophosphate insecticides (chlorpyrifos, azinphos methyl, diazinon) and acid herbicides (2,4-dichlorophenoxyacetic acid [2,4-D], mecoprop) were routinely detected in Prudhomme Creek, whereas neutral herbicides (atrazine, metolachlor) dominated the pesticide signature of Twenty Mile Creek. Spencer Creek contained fewer pesticides, which were measured at lower concentrations. In situ effects also followed seasonal patterns: higher survival and AChE activity in spring and fall, and lower survival and AChE activity during summer months. The highest toxicity was observed at Prudhomme Creek and was primarily associated with organophosphates. The present study demonstrated that current-use pesticides in Southern Ontario were linked to in situ effects and identified sites of concern requiring further investigation.


Asunto(s)
Anfípodos/efectos de los fármacos , Plaguicidas/toxicidad , Ácido 2,4-Diclorofenoxiacético/toxicidad , Ácido 2-Metil-4-clorofenoxiacético/análogos & derivados , Ácido 2-Metil-4-clorofenoxiacético/toxicidad , Acetamidas/toxicidad , Acetilcolinesterasa/metabolismo , Anfípodos/enzimología , Animales , Atrazina/toxicidad , Azinfosmetilo/toxicidad , Cloropirifos/toxicidad , Diazinón/toxicidad , Herbicidas/toxicidad , Insecticidas/toxicidad , Ontario , Estaciones del Año
6.
Environ Int ; 59: 183-200, 2013 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-23831544

RESUMEN

In Canada, perfluoroalkyl acids (PFAAs) have been the focus of several monitoring programs and research and surveillance studies. Here, we integrate recent data and perform a multi-media assessment to examine the current status and ongoing trends of PFAAs in Canada. Concentrations of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and other long-chain perfluorocarboxylates (PFCAs) in air, water, sediment, fish, and birds across Canada are generally related to urbanization, with elevated concentrations observed around cities, especially in southern Ontario. PFOS levels in water, fish tissue, and bird eggs were below their respective Draft Federal Environmental Quality Guidelines, suggesting there is low potential for adverse effects to the environment/organisms examined. However, PFOS in fish and bird eggs tended to exceed guidelines for the protection of mammalian and avian consumers, suggesting a potential risk to their wildlife predators, although wildlife population health assessments are needed to determine whether negative impacts are actually occurring. Long-term temporal trends of PFOS in suspended sediment, sediment cores, Lake Trout (Salvelinus namaycush), and Herring Gull (Larus argentatus) eggs collected from Lake Ontario increased consistently from the start of data collection until the 1990s. However, after this time, the trends varied by media, with concentrations stabilizing in Lake Trout and Herring Gull eggs, and decreasing and increasing in suspended sediment and the sediment cores, respectively. For PFCAs, concentrations in suspended sediment, sediment cores, and Herring Gulls generally increased from the start of data collection until present and concentrations in Lake Trout increased until the late 1990s and subsequently stabilized. A multimedia comparison of PFAA profiles provided evidence that unexpected patterns in biota of some of the lakes were due to unique source patterns rather than internal lake processes. High concentrations of PFAAs in the leachate and air of landfill sites, in the wastewater influent/effluent, biosolids, and air at wastewater treatment plants, and in indoor air and dust highlight the waste sector and current-use products (used primarily indoors) as ongoing sources of PFAAs to the Canadian environment. The results of this study demonstrate the utility of integrating data from different media. Simultaneous evaluation of spatial and temporal trends in multiple media allows inferences that would be impossible with data on only one medium. As such, more co-ordination among monitoring sites for different media is suggested for future sampling, especially at the northern sites. We emphasize the importance of continued monitoring of multiple-media for determining future responses of environmental PFAA concentrations to voluntary and regulatory actions.


Asunto(s)
Ácidos Alcanesulfónicos/análisis , Caprilatos/análisis , Monitoreo del Ambiente , Fluorocarburos/análisis , Contaminantes Químicos del Agua/análisis , Animales , Aves , Huevos/análisis , Peces , Lagos/química , Ontario , Instalaciones de Eliminación de Residuos
7.
Chemosphere ; 86(6): 565-71, 2012 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-22137558

RESUMEN

Water quality monitoring programs rely on residue data that are frequently left censored, due to some observations occurring below the Method Detection Limit (MDL). Our objective was to determine the influence the MDL has on the interpretation of pesticide residues in surface waters. Water samples from tributaries in southern and central Ontario were collected by Environment Canada from 2003 to 2008 and were analyzed for 27 pesticides, with MDLs that averaged 7.02 ng(-1) L (range 0.39-25.1 ng(-1) L). We then simulated MDLs ranging from 25 to 1700 ng(-1) L, to determine the impact this would have on the reporting of pesticide concentrations and detections. The mean number of pesticides detected simultaneously declined with increasing, i.e. less sensitive MDLs, from 5.02 pesticides (native MDL) to 0.08 pesticides detected (MDL<1700 ng(-1) L). We compared the proportion of sites where pesticides were detected in surface waters under five MDL scenarios for 13 selected pesticides. The proportions decreased sharply with increasing MDLs. We calculated detection probabilities in an effort to compensate for higher MDLs using maximum likelihood; while adjusting for detection probabilities generally improved estimates of the presence of pesticides, as the MDLs increased the ability to compensate for detection probabilities deteriorated and became unviable at high MDLs. Depending on the method of substitution for observations below MDL (replacement with ½ × or 0 × MDL), the mean and median pesticide residues became increasingly over- and underestimated, respectively, at higher MDLs. Although monitoring programs that are focused on exceedences of water quality guidelines may not require low MDLs, the achievable goals of monitoring programs oriented towards other ecological and toxicological objectives may be limited by higher MDLs.


Asunto(s)
Ecotoxicología/métodos , Límite de Detección , Residuos de Plaguicidas/análisis , Contaminación Química del Agua/análisis , Agua/química , Canadá , Probabilidad , Calidad del Agua
8.
Environ Sci Pollut Res Int ; 19(3): 821-34, 2012 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-21948131

RESUMEN

INTRODUCTION: Public and scientific concern has grown over the last decade in Canada over the cosmetic use of pesticides in urban centers. With this in mind, a national survey was designed to monitor eight commonly used herbicides in urban rivers and streams across Canada. MATERIALS AND METHODS: To coordinate sample collections across the country, samples were collected monthly on one of two predetermined dates from April to September, 2007 from 19 sites within 16 watersheds, including 15 sites downstream of urban lands and two reference sites. Water samples were also collected approximately three times from each watershed during or after precipitation events. All samples were collected using a common sampling protocol and all were analyzed using the same analytical laboratories. RESULTS AND DISCUSSION: The herbicides 2,4-D, mecoprop, dicamba, glyphosate and its major metabolite aminomethylphosphonic acid (AMPA) were most frequently detected. Using either herbicide concentrations upstream/downstream of urban centers or bromoxynil and clopyralid as indictors of agricultural inputs of herbicides to streams, it was clear that environmental concentrations of these herbicides downstream of urban areas were linked to urban use in Canada. Herbicide concentrations in streams draining urban areas were greater during or after significant rainfall events and, with the exception of glyphosate, were significantly greater in the Province of Ontario. Herbicide concentrations were not correlated to the proportion of the watersheds in urban land use. Also, there was no difference in seasonal patterns of herbicide concentrations across urban centers when grouped in five geographic areas. None of the herbicide concentrations measured exceeded existing Canadian Water Quality Guidelines for the protection of aquatic life. CONCLUSIONS: This is the first time a national survey of pesticides in urban rivers has been carried out in a consistent fashion across Canada. Concentrations of 2,4-D, mecoprop, dicamba, glyphosate, and AMPA were linked to urban use and frequently detected in all geographic areas. However, geographic differences in concentration suggested differences in usage or stream connectivity patterns among urban centers. Some jurisdictions in Canada have recently restricted cosmetic use of pesticides and it would be interesting to determine whether such restrictions will lead to reduced pesticide concentrations in urban streams.


Asunto(s)
Glicina/análogos & derivados , Herbicidas/análisis , Ríos/química , Contaminantes Químicos del Agua/análisis , Ácido 2,4-Diclorofenoxiacético/análisis , Ácido 2-Metil-4-clorofenoxiacético/análogos & derivados , Ácido 2-Metil-4-clorofenoxiacético/análisis , Canadá , Fenómenos Químicos , Dicamba/análisis , Glicina/análisis , Herbicidas/química , Concentración de Iones de Hidrógeno , Isoxazoles , Organofosfonatos/análisis , Proyectos Piloto , Estaciones del Año , Tetrazoles , Urbanización , Contaminantes Químicos del Agua/química , Calidad del Agua , Glifosato
9.
Bull Environ Contam Toxicol ; 87(4): 420-5, 2011 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-21792538

RESUMEN

Surface water sampling in 2006-2008 measured the occurrence of sulfonylureas and related herbicides (SUs) during base flow conditions and wet weather events. Flumetsulam (29.2%), diuron (36.5%) and fomesafen (25.3%) were most frequently detected over the course of the study. Typical SU concentrations were in the low parts per trillion range; however, maximum concentrations of fomesafen (873 ng/L), linuron (856 ng/L) and diuron (2,900 ng/L) approached or exceeded 1 µg/L. The temporal trend in SUs showed a correlation with application periods. In general, detections of SUs were more frequent where rotation of row crops was more intense. Sampling during wet-weather events indicated potential for a range of SUs to be flushed into surface waters at relatively high concentrations.


Asunto(s)
Agua Dulce/química , Herbicidas/análisis , Compuestos de Sulfonilurea/análisis , Contaminantes Químicos del Agua/análisis , Benzamidas/análisis , Canadá , Diurona/análisis , Monitoreo del Ambiente , Linurona/análisis , Pirimidinas/análisis , Sulfonamidas/análisis , Contaminación Química del Agua/estadística & datos numéricos
10.
Environ Int ; 37(5): 821-8, 2011 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-21458072

RESUMEN

A model formulation based on "aquivalence", as defined in terms of activity is presented to estimate the multimedia fate of ionizing chemicals. The aquivalence approach is analogous to fugacity but aquivalence is applicable to neutral and ionizing compounds, and has been applied previously to speciating chemicals, notably metals. The new aquivalence-based mass-balance model treats ionizing organic compounds that exist as interconverting neutral and ionic species which are subject to fate processes at differing rates. The model is illustrated by application to four ionizing pharmaceuticals in Hamilton Harbour, Lake Ontario. At the system pH of 7.9-8.5, ibuprofen, gemfibrozil, and naproxen are expected to be almost entirely ionic and triclosan split between ionic and neutral forms. Measured seasonal surface water concentrations, which were 2-10 times lower in the late summer and fall than during spring, were used to solve for unknown values of chemical half-life in the water column due to degradation (photo- and bio-) of the ionizing and neutral forms and secondarily, ionic sorption coefficients of the ionizing forms. Model estimates of half-lives in the habour's water ranged from 11 to 77, 11 to 147 and 10 to 37 for ionic ibuprofen, gemfibrozil, and naproxen, respectively; and 4-22 days and 2-9 days for ionic and neutral triclosan, respectively, with the shortest half-lives in spring and the longest in summer.


Asunto(s)
Monitoreo del Ambiente/métodos , Agua Dulce/química , Modelos Químicos , Preparaciones Farmacéuticas/química , Contaminantes Químicos del Agua/química , Biodegradación Ambiental , Semivida , Concentración de Iones de Hidrógeno , Iones/análisis , Iones/química , Ontario , Preparaciones Farmacéuticas/análisis , Procesos Fotoquímicos , Estaciones del Año , Movimientos del Agua , Contaminantes Químicos del Agua/análisis
11.
Chemosphere ; 82(8): 1155-60, 2011 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-21215422

RESUMEN

Concerns regarding the impacts of pesticides on aquatic species and drinking water sources have increased demands on water quality monitoring programs; however the costs of sample analysis can be prohibitive. In this study we investigated enzyme-linked immunosorbent assay (ELISA) as a cost-effective, high through-put method for measuring pesticide concentrations in surface waters. Seven hundred and thirty-nine samples from 158 locations throughout Ontario were analysed for atrazine and metolachlor from April to October 2007. Concentrations ranged from <0.1 to 3.91 µg L(-1) (median=0.12 µg L(-1)) for atrazine and from <0.1 to 1.83 µg L(-1) (median=0.09 µg L(-1)) for metolachlor. Peak concentrations occurred in late spring/early summer, in rural agricultural locations, and decreased over the remainder of the growing season for both herbicides. About 3% of the samples that had ELISA results occurring above the limit of quantification (0.10 µg L(-1)) were evaluated against gas chromatography-mass spectrometry (GC-MS). Linear regression analysis revealed a R(2) value of 0.88 and 0.39, for atrazine and metolachlor, respectively. ELISA tended to overestimate concentrations for atrazine and metolachlor, most likely because the ELISA kits also detect their metabolites. Atrazine data suggest that ELISA may be used complementary with GC-MS analysis to enhance the spatial and temporal resolution of a water quality monitoring study. The commercially available metolachlor ELISA kit requires further investigation. ELISA may be used to detect atrazine and metolachlor in surface water samples, but it is not recommended as a quantitative replacement for traditional analytical methods.


Asunto(s)
Acetamidas/análisis , Atrazina/análisis , Monitoreo del Ambiente/métodos , Herbicidas/análisis , Contaminantes Químicos del Agua/análisis , Acetamidas/química , Atrazina/química , Ensayo de Inmunoadsorción Enzimática , Agua Dulce/química , Cromatografía de Gases y Espectrometría de Masas , Herbicidas/química , Ontario , Estaciones del Año , Contaminantes Químicos del Agua/química
12.
Environ Pollut ; 158(5): 1842-9, 2010 May.
Artículo en Inglés | MEDLINE | ID: mdl-19962221

RESUMEN

Mecoprop, dichlorprop and metolachlor concentrations and enantiomer signatures were determined in Ontario streams in 2006-2007 and compared to results from 2003 to 2004. Median concentrations of dichlorprop and metolachlor were not significantly different between the two campaigns, but mecoprop was higher in 2006-2007. Concentrations of mecoprop and dichlorprop in Lake Ontario surface water were 1-2 orders of magnitude lower than stream averages. Enantiomer fractions (EFs) > 0.5 of mecoprop in high-concentration stream water samples during 2006-2007 were related to replacement of racemic mecoprop by single (+) enantiomer mecoprop-P after 2004. EFs <0.5 in low-concentration samples suggested enantioselective degradation and/or interconversion. Metolachlor profiles were expressed as SF, the fraction of herbicidally active/(active + inactive) stereoisomers. Samples with higher concentrations of metolachlor had SFs similar to S-metolachlor which is enriched in the active stereoisomers. Low concentrations were associated with lower and more variable SFs, suggesting mixed input of racemic and S-metolachlor or stereoselective degradation.


Asunto(s)
Ácido 2,4-Diclorofenoxiacético/análogos & derivados , Ácido 2-Metil-4-clorofenoxiacético/análogos & derivados , Acetamidas/química , Herbicidas/química , Ríos/química , Contaminantes Químicos del Agua/química , Ácido 2,4-Diclorofenoxiacético/química , Ácido 2-Metil-4-clorofenoxiacético/química , Monitoreo del Ambiente , Ontario , Estereoisomerismo
13.
Environ Sci Technol ; 42(22): 8452-8, 2008 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-19068831

RESUMEN

Concentrations of mecoprop, dichlorprop, and metolachlor were investigated in 393 samples from Ontario streams in 2003-2004. Maximum concentrations of mecoprop, dichlorprop, and metolachlor were 1900, 6.62, and 1560 ng L(-1), respectively in 2003, and 103,000, 110, and 5290 ng L(-1), respectively, in 2004. Concentrations of metolachlor in agricultural watersheds were significantly (p < 0.0001) higher than those in urban watersheds, whereas concentrations of mecoprop did not differ (p > 0.1) between the two watershed types. Enantiomer fractions (EFs) of the acid herbicide mecoprop ranged from 0.236 to 0.928 and for dichlorprop EFs ranged from 0.152 to 0.549. EFs of mecoprop did not differ significantly (p > 0.1) between agricultural and urban land usage. Mecoprop EFs > or = 0.5 were found in 54% of samples, a situation expected during the transition years when racemic mecoprop was replaced by mecoprop-P, consisting of only the R(+) enantiomer. However, EFs < 0.5 were found in 46% of samples, which suggests preferential degradation of R(+) or conversion of R(+) to S(-). The four stereopluisomers of metolachlor were separated by HPLC and are reported as the ratio of the two herbicidally active stereoisomers (aS,1'S and aR,1'S) to the two inactive stereoisomers (aS,1'R and aR,1'R). The average S/R of metolachlor in streams was 6.73 +/- 2.28 and ranged from 1.08 to 12.7. Samples with higher concentrations of metolachlor had S/R ratios similar to the S/R of S-metolachlor (enriched in aS,1'S and aR,1'S stereoisomers) whereas samples with lower concentrations display lower S/R ratios with greater variability, suggesting mixed input of racemic and S-metolachlor or stereoselective degradation. S/R values were significantly higher (p < 0.001) in agricultural than urban watersheds. Streamwater from row crop areas showed higher S/R ratios than streamwater from fruit growing areas (p = 0.036).


Asunto(s)
Herbicidas/química , Ríos/química , Contaminantes Químicos del Agua/química , Animales , Estructura Molecular , Estaciones del Año , Estereoisomerismo
14.
Environ Sci Technol ; 42(16): 6052-7, 2008 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-18767665

RESUMEN

Concerns have been raised in the scientific community regarding the environmental implications of a dramatic increase in corn-based ethanol production and associated increases in pesticide use. The use of glyphosate, a broad-spectrum herbicide, for corn production has increased considerably in recent years in Canada and the United States. The cost of measuring concentrations of organic contaminants in the environment using traditional wet chemistry methods can be prohibitive; especiallywhen large numbers of samples are required to quantify the spatial and temporal variability in contaminant concentrations. The goal of our study was to evaluate a cost-effective method to measure glyphosate concentrations in surface waters. The reliability of enzyme-linked immunosorbent assay (ELISA) results was evaluated against liquid chromatography tandem mass spectrometry, and linear regression results for 30 water samples from urban watersheds revealed a strong relationship (R2 = 0.88). These results suggest that ELISA methods, used in conjunction with traditional methods, represent a cost-effective approach to enhance the spatial and temporal resolution of a water quality monitoring study. Additionally, we measured a total of 739 surface water samples from over 150 sampling locations throughout Ontario using ELISA from April to October 2007. Concentrations exceeded the method detection limit of 0.1 microg/L in 33% of the samples, with a maximum concentration of 12.0 microg/L. Glyphosate showed a bimodal temporal distribution with peak concentrations occurring in late spring/early summer and fall, and did not exceed the Canadian Council of Ministers of the Environment (CCME) guideline for the protection of aquatic life (65 microg/L) in any of the samples.


Asunto(s)
Monitoreo del Ambiente/métodos , Ensayo de Inmunoadsorción Enzimática , Agua Dulce/química , Glicina/análogos & derivados , Herbicidas/química , Contaminantes Químicos del Agua/química , Fuentes de Energía Bioeléctrica , Glicina/química , Factores de Tiempo , Glifosato
15.
Aquat Toxicol ; 88(4): 230-42, 2008 Jul 30.
Artículo en Inglés | MEDLINE | ID: mdl-18582957

RESUMEN

Intensive row crop agriculture (IRCA) for corn and soybean production is predominant in eastern and central North America. IRCA relies heavily on pesticide and nutrient inputs to maximize production under conventional systems. In 2003-2005, we assessed the occurrence of a suite of potential endocrine effects in amphibians inhabiting farm ponds and agricultural drains in IRCA areas of southwestern Ontario. Effects were compared to amphibians from two agricultural reference sites as well as four non-agricultural reference sites. Pesticide and nutrient concentrations were also determined in water samples from those sites. Atrazine and metolachlor were detected in most samples, exceeding 1 microg L(-1) at some sites. Blood samples were taken from northern leopard frogs (Rana pipiens) and green frogs (Rana clamitans) for analysis of circulating sex steroids and vitellogenin-like protein (Vtg-lp), a biomarker of exposure to environmental estrogens. Gonads were histologically examined for evidence of abnormalities. Some evidence of exposure to endocrine disrupting compounds was apparent from the data. The occurrence of testicular ovarian follicles (TOFS) in male R. pipiens was significantly higher (42%; p<0.05) at agricultural sites, particularly those in Chatham county compared to frogs from reference sites (7%). There was no difference in circulating sex steroid levels between frogs from agricultural and reference sites and sex steroid levels did not correlate with pesticide concentrations in the environment. No differences were detected in the gonadosomatic indices or stage of spermatogenesis between frogs from agricultural and non-agricultural regions (p>0.05). Plasma Vtg-lp was detected in only one male R. pipiens from an agricultural site. Neither gonad size, gonad maturity nor sex steroid levels differed between normal males and those with testicular oocytes. Although the proportion of testicular oocytes did not correlate directly with atrazine concentrations, it did correlate with a mixture of pesticides and nutrients, particularly atrazine and nitrate, while the number of pesticides detected at each site was also important.


Asunto(s)
Ecosistema , Disruptores Endocrinos/toxicidad , Plaguicidas/toxicidad , Ranidae/metabolismo , Maduración Sexual/efectos de los fármacos , Contaminantes Químicos del Agua/toxicidad , Agricultura , Análisis de Varianza , Animales , Disruptores Endocrinos/análisis , Femenino , Hormonas Esteroides Gonadales/sangre , Masculino , Ontario , Folículo Ovárico/efectos de los fármacos , Plaguicidas/análisis , Maduración Sexual/fisiología , Especificidad de la Especie , Testículo/efectos de los fármacos , Contaminantes Químicos del Agua/análisis
16.
Bull Environ Contam Toxicol ; 80(4): 378-84, 2008 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-18320130

RESUMEN

Glyphosate in surface waters of southern Ontario (Canada) was studied over a 2-year period. A small percentage of samples exhibited glyphosate concentrations greater than the analytical limit of quantitation (17 microg a.e./L), and the maximum concentration of glyphosate measured was 40.8 microg/L. No samples of roughly 500 analyzed exceeded the Canadian Water Quality Guideline of 65 microg a.e./L considered protective of aquatic life. Typical concentrations of glyphosate in amphibian habitats were well below a range of toxicity thresholds for aquatic organisms, and were thus judged to be unlikely to pose a substantial risk to either sensitive amphibian larvae or other aquatic biota.


Asunto(s)
Glicina/análogos & derivados , Herbicidas/análisis , Residuos de Plaguicidas/análisis , Contaminantes Químicos del Agua/análisis , Animales , Anuros/metabolismo , Cromatografía de Gases , Exposición a Riesgos Ambientales/análisis , Agua Dulce , Glicina/análisis , Glicina/toxicidad , Herbicidas/toxicidad , Isoxazoles , Dosificación Letal Mediana , Ontario , Organofosfonatos/análisis , Control de Calidad , Tetrazoles , Glifosato
18.
J Environ Sci Health B ; 38(3): 257-73, 2003 May.
Artículo en Inglés | MEDLINE | ID: mdl-12716044

RESUMEN

An integrated model, the Pesticide Runoff Model (PeRM), has been developed to predict pesticide losses due to runoff by considering the emission, degradation, adsorption and desorption of pesticides, as well as their movement in dissolved and adsorbed phases. The developed modeling system has been used to calculate the losses of atrazine from agricultural lands in the Kintore Creek Watershed, Ontario, Canada between 1988 and 1992. The modeling outputs have been verified against actual monitoring data, which were obtained from a water quality monitoring project carried out in the same watershed over the same period of time.


Asunto(s)
Modelos Químicos , Plaguicidas/análisis , Contaminantes Químicos del Agua/análisis , Agricultura , Atrazina/análisis , Monitoreo del Ambiente/métodos , Herbicidas/análisis , Ontario , Lluvia , Movimientos del Agua
19.
Environ Toxicol Chem ; 22(12): 2881-9, 2003 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-14713027

RESUMEN

Prescription and nonprescription drugs have been detected in rivers and streams in Europe and the United States. Sewage treatment plants (STPs) are an important source of these contaminants, but few data exist on the spatial distribution of drugs in surface waters near STPs. Samples of surface water were collected in the summer and fall of 2000 at open-water sites in the lower Great Lakes (Lake Ontario and Lake Erie), at sites near the two STPs for the city of Windsor (ON, Canada), and at sites in Hamilton Harbour (ON, Canada), an embayment of western Lake Ontario that receives discharges from several STPs. In a follow-up study in the summer of 2002, samples of surface water and final effluent from adjacent STPs were collected from sites in Hamilton Harbour and Windsor. In addition, surface water and STP effluent samples were collected in Peterborough (ON, Canada). All samples of surface water and STP effluents were analyzed for selected acidic and neutral drugs. In the survey of Hamilton Harbour and Windsor conducted in 2000, acidic drugs and the antiepileptic drug carbamazepine were detected at ng/L concentrations at sites that were up to 500 m away from the STP, but the hydrological conditions of the receiving waters strongly influenced the spatial distribution of these compounds. Drugs were not detected at open-water locations in western Lake Erie or in the Niagara River near the municipality of Niagara-on-the-Lake (ON, Canada). However, clofibric acid, ketoprofen, fenoprofen, and carbamazepine were detected in samples collected in the summer of 2000 at sites in Lake Ontario and at a site in the Niagara River (Fort Erie, ON, Canada) that were relatively remote from STP discharges. Follow-up studies in the summer of 2002 indicated that concentrations of acidic and neutral drugs in surface waters near the point of sewage discharge into the Little River (ON, Canada) STP were approximately equal to the concentrations in the final effluent from the STP. Caffeine and cotinine, a metabolite of nicotine, were generally present in STP effluents and surface waters contaminated by drugs. The antidepressant fluoxetine and the antibiotic trimethoprom were also detected in most STP effluents and some surface water samples. For the first time, the lipid regulating drug atorvastatin was detected in samples of STP effluent and surface water.


Asunto(s)
Prescripciones de Medicamentos , Medicamentos sin Prescripción/análisis , Aguas del Alcantarillado/química , Contaminantes Químicos del Agua/análisis , Ácidos/análisis , Canadá , Great Lakes Region , Ríos , Estaciones del Año , Eliminación de Residuos Líquidos , Movimientos del Agua
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