RESUMO
Complete separation of the trans-enantiomers of the two most abundant, persistent polar metabolites of metolachlor, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOXA), was achieved using UPLC equipped with a reverse phase chiral column and trace detection with an electrospray triple quadrupole mass spectrometer. Various conditions that influenced the separation and instrumental signal were investigated to achieve the optimum separation and instrument response within an analysis time of less than 30 minutes. Different eluting solvent compositions for each metabolite were required for optimized separation of of the 4 enantiomers. Standard curves were responsive to less than 13 ng/mL and 8 ng/mL for the least plentiful MOXA and MESA enantiomers, respectively with a linear coefficient of determination greater than 0.998. Suitability of the method for quantification of the 4 mixed enantiomers of each was demonstrated using natural surface water samples collected from the Choptank River watershed in Eastern Maryland.â¢LC chiral separation parameters were varied to achieve optimal separation of the major enantiomers of the two metolachlor metabolites.â¢LC/MS-MS parameters were adjusted to maximize response and minimize analysis time.â¢Finished methods were used to quantitate enantiomers in archived stream water extracts from agricultural watersheds with corn/soybean production.
RESUMO
An important component of assessing the hazards of anticoagulant rodenticides to non-target wildlife is observations in exposed free-ranging individuals. The objective of this study was to determine whether environmentally realistic, sublethal first-generation anticoagulant rodenticide (FGAR) exposures via prey can result in direct or indirect adverse effects to free-flying raptors. We offered black-tailed prairie dogs (Cynomys ludovicianus) that had fed on Rozol® Prairie Dog Bait (Rozol, 0.005% active ingredient chlorophacinone, CPN) to six wild-caught red-tailed hawks (RTHA, Buteo jamaicensis), and also offered black-tailed prairie dogs that were not exposed to Rozol to another two wild-caught RTHAs for 7 days. On day 6, blood was collected to determine CPN's effects on blood clotting time. On day 7, seven of the eight RTHAs were fitted with VHF radio telemetry transmitters and the RTHAs were released the following day and were monitored for 33 days. Prothrombin time (PT) and Russell's viper venom time confirmed that the CPN-exposed RTHAs were exposed to and were adversely affected by CPN. Four of the six CPN-exposed RTHAs exhibited ptiloerection, an indication of thermoregulatory dysfunction due to CPN toxicity, but no signs of intoxication were observed in the reference hawk or the remaining two CPN-exposed RTHAs. Of note is that PT values were associated with ptiloerection duration and frequency; therefore, sublethal CPN exposure can directly or indirectly evoke adverse effects in wild birds. Although our sample sizes were small, this study is a first to relate coagulation times to adverse clinical signs in free-ranging birds.
Assuntos
Falcões , Rodenticidas , Animais , Animais Selvagens , Anticoagulantes/toxicidade , Aves , Fígado , Rodenticidas/toxicidade , SciuridaeRESUMO
We previously discovered a method to estimate the groundwater mean residence time using the changes in the enantiomeric ratio of metolachlor ethanesulfonic acid (MESA), (2-[(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxoethanesulfonic acid), a metabolite of the herbicide metolachlor. However, many grab samples would be needed for each watershed over an extended period, and this is not practical. Thus, we examined the use of a polar organic chemical integrative sampler (POCIS) deployed for 28 days combined with a modified liquid chromatography-mass spectrometry LC-MS/MS method to provide a time-weighted average of the MESA enantiomeric ratio. POCISs equipped with hydrophilic-lipophilic-balanced (HLB) discs were deployed at five sites across the United States where metolachlor was used before and after 1999 and compared the effectiveness of the POCIS to capture MESA versus grab samples. In addition, an in situ POCIS sampling rate (Rs) for MESA was calculated (0.15 L/day), the precision of MESA extraction from stored POCIS discs was determined, and the effectiveness of HLB to extract MESA was examined. Finally, using molecular modeling, the influence of the asymmetric carbon of metolachlor degradation on the MESA enantiomeric ratio was predicted to be negligible. Results of this work will be used in projects to discern the groundwater mean residence times, to evaluate the delivery of nitrate-N from groundwater to surface waters under various soil, agronomic, and land use conditions, and to examine the effectiveness of conservation practices.
Assuntos
Acetamidas/química , Alcanossulfonatos/química , Monitoramento Ambiental/métodos , Água Subterrânea/química , Herbicidas/química , Compostos Orgânicos/química , Poluentes Químicos da Água/química , Cromatografia Líquida de Alta Pressão/métodos , Estereoisomerismo , Espectrometria de Massas em Tandem/métodosRESUMO
The fate of four phthalate plasticizers during wastewater treatment processes at six different wastewater treatment plants (WWTPs) was investigated. Concentrations of benzyl butyl phthalate (BBP), di(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DiNP), and diisodecyl phthalate (DiDP) were determined prior to either aerobic or anaerobic (conventional and advanced) treatment, after treatment, and in final, dewatered solids. Despite their elevated use worldwide, the fate of DiNP and DiDP during wastewater treatment have not been well characterized. DEHP was readily degraded during aerobic treatments while anaerobic digestion resulted in either no significant change in concentrations or an increase in concentration, in the case of more advanced anaerobic processes (thermal hydrolysis pretreatment and a two-phase acid/gas process). Impacts of the various treatment systems on DiNP, DiDP, and BBP concentrations were more varied - anaerobic digestion led to significant decreases, increases, or no significant change for these compounds, depending on the treatment facility, while aerobic treatment was generally effective at degrading the compounds. Additionally, thermal hydrolysis pretreatment of sludge prior to anaerobic digestion resulted in increases in DiNP, DiDP, and BBP concentrations. The predicted environmental concentrations for all four compounds in soils after a single biosolids application were calculated and the risk quotients for DEHP in soils were determined. The estimated toxicity risk for DEHP in soils treated with a single application of sludge from any of the six studied WWTPs is lower than the level of concern for acute and chronic risk, as defined by the US EPA.
Assuntos
Ácidos Ftálicos , Plastificantes , Esgotos/química , Águas Residuárias/química , Poluentes Químicos da Água , Purificação da Água/métodos , Dietilexilftalato/química , Dietilexilftalato/isolamento & purificação , Dietilexilftalato/farmacocinética , Humanos , Ácidos Ftálicos/química , Ácidos Ftálicos/isolamento & purificação , Ácidos Ftálicos/farmacocinética , Plastificantes/química , Plastificantes/isolamento & purificação , Plastificantes/farmacocinética , Instalações de Eliminação de Resíduos , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificação , Poluentes Químicos da Água/farmacocinéticaRESUMO
Triclocarban [N-(4-chlorophenyl)-N-(3,4-dichlorophenyl) urea] (TCC) is an antimicrobial agent utilized in a variety of consumer products. It is commonly released into domestic wastewaters and upon treatment, it is known to accumulate in biosolids. This study examines the occurrence of TCC in biosolids and its long-term fate in biosolid-treated soils. TCC levels in the biosolids from a large waste water treatment plant (WWTP) over 2 years showed little variability at 18,800 ± 700 ng g-1 dry wt. (mean ± SEM). Surface soil samples (top 10 cm) were collected from 26 commercial farms located in northern VA, US that had received biosolid applications from the WWTP. Samples were grouped as farms receiving no biosolids, farms with a single biosolid application, and those receiving multiple biosolid applications from 1992 to 2006. Our results illustrate that TCC soil residues remained years after biosolid application. The two most important parameters controlling TCC topsoil concentrations were the biosolid application rate and the period since the last application. No TCC removal was observed in farms where the time since biosolid application was between 7 and 9 months. TCC concentration analyzed 7 and 8 years after biosolid applications were 45.8 ± 6.1 and 72.4 ± 15.3 ng g-1 dry wt., respectively, showing its persistence in soils and build-up upon multiple biosolid applications. A soil TCC half-life of 287.5 ± 45.5 days was estimated.
Assuntos
Agricultura/métodos , Carbanilidas/análise , Monitoramento Ambiental/métodos , Poluentes do Solo/análise , Solo/química , Águas Residuárias/química , Estados UnidosRESUMO
Benchtop bioreactors were run aerobically with activated sludge samples collected from a large municipal wastewater treatment plant (WWTP) to understand how increased hydraulic retention time (HRT), sludge retention time (SRT), and varying treatment temperatures (21°C and 30°C) impact concentrations of the endocrine disrupting antimicrobials triclosan (TCS), triclocarban (TCC), and their transformation products. Samples from the reactors were collected periodically over a 122-196h period and the solid and liquid fraction were separately quantitated for TCS, TCC, and methyltriclosan (MeTCS) and scanned qualitatively for six other transformation products. Results indicated that TCS, TCC and MeTCS were predominately associated with the solids fraction of the activated sludge with only nominal concentrations in the liquids fraction. TCS was degraded in the solids fraction, with increased rates at 30°C (-0.0224 ± 0.007h-1) when compared to reactors run at 21°C (- 0.0170 ± 0.003h-1). Conversely, TCC concentrations did not significantly change in solids samples from reactors run at 21°C, while an increase in reactor temperature to 30°C resulted in TCC degradation at an average rate of - 0.0158 ± 0.012h-1. Additionally, MeTCS formation in the solids fraction was observed in three out of four reactors run - indicating a notable transformation of TCS. Qualitative appearance of 2,4-dichlorophenol and 4-chloroanaline was observed in the liquids fraction of all reactor samples. The remaining four qualitatively scanned compounds were not detected. These experiments demonstrate that increased HRT, SRT, and temperature result in enhanced removal of TCS and TCC from wastewater during the activated sludge process. Furthermore, a substantial formation of TCS into MeTCS was observed.
Assuntos
Reatores Biológicos , Carbanilidas , Triclosan , Carbanilidas/química , Esgotos , Triclosan/químicaRESUMO
The growing concern worldwide regarding the presence of emerging contaminants in biosolids calls for a better understanding of how different treatment technologies at water resource recovery facilities (WRRFs) can influence concentrations prior to biosolids land application. This study focuses on the influence of solids treatment via the Cambi Thermal Hydrolysis Process™ in conjunction with anaerobic digestion (TH-AD) on concentrations of triclosan (TCS), triclocarban (TCC), and their transformation products in biosolids and sludges. Concentrations of the target analytes in biosolids from the TH-AD process (Class A), sludges from the individual TH-AD treatment steps, and limed biosolids (Class B) from the same WRRF were compared. TCC concentrations were significantly lower in Class A biosolids than those in the Class B product - a removal that occurred during thermal hydrolysis. Concentrations of TCS, methyl triclosan, and 2,4-dichlorophenol, conversely, increased during anaerobic digestion, leading to significantly higher concentrations of these compounds in Class A biosolids when compared to Class B biosolids. Implementation of the TH-AD process had mixed effect on contaminant concentrations.
Assuntos
Carbanilidas/análise , Clorofenóis/análise , Triclosan/análise , Eliminação de Resíduos Líquidos/métodos , Anaerobiose , Compostos de Cálcio , Carbanilidas/química , Carbanilidas/metabolismo , Clorofenóis/química , Clorofenóis/metabolismo , Temperatura Alta , Hidrólise , Óxidos , Triclosan/análogos & derivados , Triclosan/química , Triclosan/metabolismo , Águas ResiduáriasRESUMO
UNLABELLED: To better address how much groundwater contributes to the loadings of pollutants from agriculture we developed a specific dating tool for groundwater residence times. This tool is based on metolachlor ethane sulfonic acid, which is a major soil metabolite of metolachlor. The chiral forms of metolachlor ethane sulfonic acid (MESA) and the chiral forms of metolachlor were examined over a 6-year period in samples of groundwater and water from a groundwater-fed stream in a riparian buffer zone. This buffer zone bordered cropland receiving annual treatments with metolachlor. Racemic (rac) metolachlor was applied for two years in the neighboring field, and subsequently S-metolachlor was used which is enriched by 88% with the S-enantiomer. Chiral analyses of the samples showed an exponential increase in abundance of the S-enantiomeric forms for MESA as a function of time for both the first order riparian buffer stream (R(2)=0.80) and for groundwater within the riparian buffer (R(2)=0.96). However, the S-enrichment values for metolachlor were consistently high indicating different delivery mechanisms for MESA and metolachlor. A mean residence time of 3.8years was determined for depletion of the initially-applied rac-metolachlor. This approach could be useful in dating groundwater and determining the effectiveness of conservation measures. ONE SENTENCE SUMMARY: A mean residence time of 3.8years was calculated for groundwater feeding a first-order stream by plotting the timed-decay for the R-enantiomer of metolachlor ethane sulfonic acid.
Assuntos
Acetamidas/análise , Monitoramento Ambiental/métodos , Água Subterrânea/química , Herbicidas/análise , Ácidos Sulfônicos/análise , Poluentes Químicos da Água/análise , Agricultura , Etano/análiseRESUMO
Culture medium from an isolate of the fungus Aspergillus candidus was extracted, fractionated and examined to discover compounds antagonistic to plant-parasitic nematodes that are important pathogens of agricultural crops. Column, thin layer and preparative chromatographies and spectral and elemental analyses, were used to isolate and identify two major constituents of an active fraction (Fraction F) obtained from the medium. Compound 1 was identified as 2-hydroxypropane-1, 2, 3-tricarboxylic acid (citric acid). Compound 2 was identified as 3-hydroxy-5-methoxy-3-(methoxycarbonyl)-5-oxopentanoic acid, an isomer of 1, 2-dimethyl citrate. Compound 1 and a citric acid standard, each tested at 50 mg mL(-1) in water, decreased hatch from eggs of the plant-parasitic nematode Meloidogyne incognita by more than 94%, and completely immobilized second-stage juveniles after 4-6 days exposure. Fraction F and Compounds 1 and 2 decreased the mobility of adults of the plant-parasitic nematode Ditylenchus destructor in vitro. Fraction F (25 mg mL(-1)) inhibited mobility >99% at 72 hrs. Compounds 1 and 2 (50 mg mL(-1)) each inhibited mobility more than 25% at 24 hr and more than 50% at 72 hr. This is the first assignment of nematode-antagonistic properties to specifically identified A. candidus metabolites.
Assuntos
Aspergillus/metabolismo , Ácido Cítrico/análogos & derivados , Ácido Cítrico/farmacologia , Praguicidas/farmacologia , Tylenchoidea/efeitos dos fármacos , Agricultura , Animais , Aspergillus/patogenicidade , Citratos/farmacologia , Ácido Cítrico/química , Meios de Cultivo Condicionados/farmacologia , Praguicidas/química , Praguicidas/isolamento & purificação , Doenças das Plantas/parasitologiaRESUMO
While the recycling of wastewater biosolids via land-application is a sustainable practice for nutrient recovery and soil reclamation that has become increasingly common worldwide, concerns remain that this practice may become a source of toxic, persistent organic pollutants to the environment. This study concentrates on assessing the presence and the temporal trends of 12 perfluoroalkyl substances (PFASs), pollutants of global consequence, in limed Class B biosolids from a municipal water resource recovery facility (WRRF), also know as a wastewater treatment plant. PFASs are of significant concern due to their extensive presence and persistence in environmental and biotic samples worldwide, most notably human blood samples. Class B biosolids were collected from the WRRF, prior to land-application, approximately every two to three months, from 2005 to 2013. Overall, this study found that concentrations of the 7 detectable PFAS compounds remained unchanged over the 8-year period, a result that is consistent with other temporal studies of these compounds in sewage sludges. From these analyzed compounds, the highest mean concentrations observed over the study period were 25.1 ng/g dw, 23.5 ng/g dw, and 22.5 ng/g dw for perfluorononanoic acid (PFNA), perfluorooctanoic acid (PFOA), and perfluorooctanesulfonic acid (PFOS), respectively, and these compounds were detected at concentrations 2.5-5 times higher than the remaining, detectable PFASs. Furthermore, it was observed that PFOS, while demonstrating no overall change during the study, exhibited a visible spike in concentration from late 2006 to early 2007. This study indicates that concentrations of PFASs in WRRFs have been stagnant over time, despite regulation. This study also demonstrates that the use of glass jars with polytetrafluoroethylene-lined lids, a common storage method for environmental samples, will not influence PFOA and PFNA concentrations in archived biosolids samples.
Assuntos
Ácidos Alcanossulfônicos/análise , Caprilatos/análise , Poluentes Ambientais/análise , Fluorocarbonos/análise , Eliminação de Resíduos Líquidos/métodos , Resíduos/análise , Compostos de Cálcio , Monitoramento Ambiental/métodos , Humanos , Mid-Atlantic Region , Óxidos , Esgotos , Solo , Manejo de Espécimes/métodos , Recursos HídricosRESUMO
Urban streams are an integral part of the municipal water cycle and provide a point of discharge for wastewater treatment plant (WWTP) effluents, allowing additional attenuation through dilution and transformation processes, as well as a conduit for transporting contaminants to downstream water supplies. Domestic and commercial activities dispose of wastes down-the-drain, resulting in wastewater containing complex chemical mixtures that are only partially removed during treatment. A key issue associated with WWTP effluent discharge into streams is the potential to cause endocrine disruption in fish. This study provides a long-term (1999-2009) evaluation of the occurrence of alkylphenolic endocrine disrupting chemicals (EDCs) and other contaminants discharged from WWTPs into streams in the Great Lakes and Upper Mississippi River Regions (Indiana, Illinois, Michigan, Minnesota, and Ohio). The Greater Metropolitan Chicago Area Waterways, Illinois, were evaluated to determine contaminant concentrations in the major WWTP effluents and receiving streams, and assess the behavior of EDCs from their sources within the sewer collection system, through the major treatment unit processes at a WWTP, to their persistence and transport in the receiving stream. Water samples were analyzed for alkylphenolic EDCs and other contaminants, including 4-nonylphenol (NP), 4-nonylphenolpolyethoxylates (NPEO), 4-nonylphenolethoxycarboxylic acids (NPEC), 4-tert-octylphenol (OP), 4-tert-octylphenolpolyethoxylates (OPEO), bisphenol A, triclosan, ethylenediaminetetraacetic acid (EDTA), and trace elements. All of the compounds were detected in all of the WWTP effluents, with EDTA and NPEC having the greatest concentrations. The compounds also were detected in the WWTP effluent dominated rivers. Multiple fish species were collected from river and lake sites and analyzed for NP, NPEO, NPEC, OP, and OPEO. Whole-body fish tissue analysis indicated widespread occurrence of alkylphenolic compounds, with the highest concentrations occurring in streams with the greatest WWTP effluent content. Biomarkers of endocrine disruption in the fish indicated long-term exposure to estrogenic chemicals in the wastewater impacted urban waterways.
Assuntos
Disruptores Endócrinos/análise , Peixes/metabolismo , Eliminação de Resíduos Líquidos , Poluentes Químicos da Água/análise , Animais , Chicago , Disruptores Endócrinos/metabolismo , Monitoramento Ambiental , Illinois , Indiana , Lagos/química , Michigan , Minnesota , Ohio , Rios/química , Águas Residuárias/química , Poluentes Químicos da Água/metabolismoRESUMO
In the US, land application of biosolids has been utilized in government-regulated programs to recycle valuable nutrients and organic carbon that would otherwise be incinerated or buried in landfills. While many benefits have been reported, there are concerns that these practices represent a source of organic micropollutants to the environment. In this study, biosolids samples from a wastewater treatment plant in the Mid-Atlantic region of the US were collected approximately every 2 months over a 7-year period and analyzed for brominated diphenyl ethers (BDE-47, BDE-99, and BDE-209), triclosan, and triclocarban. During the collection period of 2005-2011, concentrations of the brominated diphenyl ethers BDE-47+BDE-99 decreased by 42%, triclocarban decreased by 47%, but BDE-209 and triclosan remained fairly constant. Observed reductions in contaminant concentrations could not be explained by different seasons or by volumetric changes of wastewaters arriving at the treatment plant and instead may be the result of the recent phaseout of BDE-47 and BDE-99 as well as potential reductions in the use of triclocarban.
Assuntos
Carbanilidas/análise , Éteres Difenil Halogenados/análise , Esgotos/análise , Triclosan/análise , Poluentes Químicos da Água/análise , Monitoramento Ambiental , Mid-Atlantic Region , Eliminação de Resíduos LíquidosRESUMO
Although most composting studies report pathogen concentrations, little is known about the fate of Endocrine Disruptor Chemicals (EDCs) during composting. In this study, a positively aerated polyethylene bag composting system was filled with a mixture of woodchips and limed biosolids from a large Waste Water Treatment Plant (WWTP) to study the removal efficiency of two different groups of EDCs. Two antibacterial compounds, Triclocarban (TCC) and Triclosan (TCS), and a TCS byproduct, Methyltriclosan (MeTCS), as well as seven congeners of flame retardants known as PBDEs (Polybrominated Diphenyl Ethers) were studied during two phases of composting: 1) a thermophilic phase, in which positive mechanical aeration, pushing air into and through the materials matrix, was conducted for 2 months; and 2) a curing and stabilization phase in which no mechanical aeration was provided and the bag was opened to ambient passive aeration to simulate storage conditions for seven months. Our results showed that while TCC concentrations remained constant, TCS degradation took place during both phases. The degradation of TCS was corroborated by the formation of MeTCS in both phases. The TCS concentrations decreased from 18409 ± 1,877 to 11955 ± 288 ng g(-1) dry wt. during the thermophilic phase and declined from 11,955 ± 288 to 7,244 ± 909. ng g(-1) dry wt. by the end of the curing phase. Thus, slightly greater TCS transformation occurred during the second than during the first (35.1 vs. 39.4%). MeTCS concentrations increased from 189.3 ± 8.6 to 364.6 ± 72.5 ng g(-1) dry wt. during the first phase and reached 589.0 ± 94.9 ng g(-1) dry wt. at the end of the second phase. PBDEs concentrations were below quantification limits for all but two of the congeners analyzed (BDE-47 and BDE-99). PBDE concentrations were measured at the end of the first phase only and were comparable to initial concentrations.
Assuntos
Disruptores Endócrinos/análise , Esgotos/química , Solo/química , Águas Residuárias/química , Purificação da Água/métodos , Carbanilidas/análise , Disruptores Endócrinos/isolamento & purificação , Retardadores de Chama/análise , Éteres Difenil Halogenados/análise , Silagem , Poluentes do Solo/análise , Triclosan/análise , Águas Residuárias/microbiologiaRESUMO
Endosulfan (6,7,8, 9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) is a broad-spectrum, organochlorine insecticide used on numerous crops since the 1950s. It is has been identified as a persistent organic pollutant (POP) due to its persistence, bioaccumulation, long-range transport, and adverse effects to human health and aquatic ecosystems; it will be phased out in the United States in 2016. Endosulfan consists of two diastereomers, α and ß; α-endosulfan exists as two asymmetrical, twist-chair enantiomers which interchange, while ß-endosulfan has a symmetrical-chair conformation. ß-Endosulfan has been shown to isomerize to α-endosulfan. Here we document the previously proposed isomerization mechanism using temperature-dependent Raman (TDR) spectroscopy. The bending frequencies in the fingerprint region were assigned to specific bonds. Changes in the signal intensity as a function of temperature were used to identify detailed ring movements and thus conversion of ß to α. These movements cannot occur simultaneously nor symmetrically, precluding conversion of α-endosulfan to ß-endosulfan.
Assuntos
Endossulfano/química , Inseticidas/química , Isomerismo , Estrutura Molecular , Análise Espectral RamanRESUMO
Over 50% of streams in the Chesapeake Bay watershed have been rated as poor or very poor based on the index of biological integrity. The Choptank River estuary, a Bay tributary on the eastern shore, is one such waterway, where corn and soybean production in upland areas of the watershed contribute significant loads of nutrients and sediment to streams. We adopted a novel approach utilizing the relationship between the concentration of nitrate-N and the stable, water-soluble herbicide degradation product MESA {2-[2-ethyl-N-(1-methoxypropan-2-yl)-6-methylanilino]-2-oxoethanesulfonic acid} to distinguish between dilution and denitrification effects on the stream concentration of nitrate-N in agricultural subwatersheds. The ratio of mean nitrate-N concentration/(mean MESA concentration * 1000) for 15 subwatersheds was examined as a function of percent cropland on hydric soil. This inverse relationship (R(2)=0.65, p<0.001) takes into consideration not only dilution and denitrification of nitrate-N, but also the stream sampling bias of the croplands caused by extensive drainage ditch networks. MESA was also used to track nitrate-N concentrations within the estuary of the Choptank River. The relationship between nitrate-N and MESA concentrations in samples collected over three years was linear (0.95 ≤ R(2) ≤ 0.99) for all eight sampling dates except one where R(2)=0.90. This very strong correlation indicates that nitrate-N was conserved in much of the Choptank River estuary, that dilution alone is responsible for the changes in nitrate-N and MESA concentrations, and more importantly nitrate-N loads are not reduced in the estuary prior to entering the Chesapeake Bay. Thus, a critical need exists to minimize nutrient export from agricultural production fields and to identify specific conservation practices to address the hydrologic conditions within each subwatershed. In well drained areas, removal of residual N within the cropland is most critical, and practices such as cover crops which sequester the residual N should be strongly encouraged. In poorly drained areas where denitrification can occur, wetland restoration and controlled drained structures that minimize ditch flow should be used to maximize denitrification.
Assuntos
Acetamidas/análise , Monitoramento Ambiental , Herbicidas/análise , Nitratos/análise , Rios/química , Poluentes Químicos da Água/análise , Agricultura , EstuáriosRESUMO
The atmosphere is an important transport route for semi-volatile pesticides like endosulfan. Deposition, which depends on physical-chemical properties, use patterns, and climatic conditions, can occur at local, regional, and global scales. Adverse human and ecological impact may result. We measured endosulfan wet deposition in precipitation over a 4-year period within an area of high agricultural use in Southern Florida (USA) and in nearby Biscayne and Everglades National Parks. Endosulfan's two isomers and degradate, endosulfan sulfate, were detected at high frequency with the order of detection and concentration being ß-endosulfan>α-endosulfan>endosulfan sulfate. Within the agricultural area, detection frequency (55 to 98%) mean concentrations (5 to 87 ng L(-1)) and total daily deposition (200 ng m(-2) day(-1)) exceeded values at other sites by 5 to 30-fold. Strong seasonal trends were also observed with values at all monitored sites significantly higher during peak endosulfan use periods when vegetable crops were produced. Relatively high deposition in the crop production area and observations that concentrations exceeded aquatic life toxicity thresholds at all sites indicated that endosulfan volatilization and wet deposition are of ecotoxicological concern to the region. This study emphasizes the need to include localized volatilization and deposition of endosulfan and other semi-volatile pesticides in risk assessments in Southern Florida and other areas with similar climatic and crop production profiles.
Assuntos
Endossulfano/análise , Inseticidas/análise , Chuva/química , Poluentes Químicos da Água/análise , FloridaRESUMO
Triclocarban (TCC) and Triclosan (TCS) are two antibacterial chemicals present in household and personal care products. Methyltriclosan is a biodegradation product of TCS formed under aerobic conditions. TCC and TCS are discharged to Waste Water Treatment Plants (WWTP) where they are removed from the liquid phase mainly by concentrating in the solids. This study presents a thorough investigation of TCC, TCS and MeTCS concentrations in the liquid phase (dissolved + particulate) as well as solid phases within a single, large WWTP in the U.S. Total TCC and TCS concentrations decreased by >97% with about 79% of TCC and 64% of TCS transferred to the solids. The highest TCC and TCS removal rates from the liquid phase were reached in the primary treatment mainly though sorption and settling of solids. The TCC mass balances showed that TCC levels remain unchanged through the secondary treatment (activated sludge process) and about an 18% decrease was observed through the nitrification-denitrification process. On the other hand, TCS levels decreased in both processes (secondary and nitrification-denitrification) by 10.4 and 22.6%, respectively. The decrease in TCS levels associated with observed increased levels of MeTCS in secondary and nitrification-denitrification processes providing evidence of TCS biotransformation. Dissolved-phase concentrations of TCC and TCS remained constant during filtration and disinfection. TCC and TCS highest sludge concentrations were analyzed in the primary sludge (13.1 ± 0.9 µg g(-1) dry wt. for TCC and 20.3 ± 0.9 µg g(-1) dry wt. for TCS) but for MeTCS the highest concentrations were analyzed in the secondary sludge (0.25 ± 0.04 µg g(-1) dry wt.). Respective TCC, TCS and MeTCS concentrations of 4.15 ± 0.77; 5.37 ± 0.97 and 0.058 ± 0.003 kg d(-1) are leaving the WWTP with the sludge and 0.13 ± 0.01; 0.24 ± 0.07 and 0.021 ± 0.002 kg d(-1) with the effluent that is discharged.
Assuntos
Carbanilidas/isolamento & purificação , Esgotos/química , Triclosan/análogos & derivados , Triclosan/isolamento & purificação , Águas Residuárias/química , Purificação da Água/métodos , Marcação por Isótopo , Limite de Detecção , Controle de QualidadeRESUMO
This study analyzes the effect of liming on levels of triclocarban (TCC), triclosan (TCS), estrone (E1), and progesterone (P), two antimicrobial agents and two natural hormones, respectively. Factors studied include lime particle size, mixing time, and overall lime contact time. The study results suggest that coarse lime may be more active than fine lime due to less interaction with surrounding air. Both TCS and TCC concentrations were lower in coarse limed samples versus unlimed samples and the decrease was a function of time. A similar, but statistically insignificant trend in TCC and TCS levels was observed in fine lime samples with respect to unlimed samples. Liming was also found to decrease apparent E1 levels, with more notable decreases in samples amended with coarse lime. P-levels significantly increased after 1-day of contact time, stabilizing over the next 14 days of the study period. This increase and stabilization of P-levels was attributed to the pH and moisture-driven conversion of more chemically complex steroids into P.
Assuntos
Antibacterianos/análise , Compostos de Cálcio/química , Fertilizantes/análise , Hormônios/química , Óxidos/química , Águas Residuárias , Antibacterianos/química , Carbanilidas/análise , Carbanilidas/química , Estrona/análise , Estrona/química , Hormônios/análise , Concentração de Íons de Hidrogênio , Tamanho da Partícula , Progesterona/análise , Progesterona/química , Fatores de Tempo , Triclosan/análise , Triclosan/química , Águas Residuárias/análise , Águas Residuárias/químicaRESUMO
Black-tailed prairie dogs (BTPDs), Cynomys ludovicianus, are an important prey for raptors; therefore, the use of the rodenticide Rozol (0.005% chlorophacinone active ingredient) to control BTPDs raises concern for secondary poisonings resulting from the consumption of contaminated prey by raptors. In the present study, the authors observed Rozol exposure and adverse effects to mammalian prey on 11 of 12 search days of the study. Mammalian hepatic chlorophacinone residues ranged from 0.44 to 7.56 µg/g. Poisoned prey availability was greater than previously reported.