Herbicides in the upper Poxim River, Sergipe, and the risk of contamination of water resources

Increased agricultural activity in watershed areas has been causing concern over contamination by herbicides in agricultural areas. The problem becomes more important when contamination can affect water for human consumption, as happens with water from the Poxim river, which supplies the city of Aracaju, capital of the State of Sergipe. The aim of this study was to evaluate the risk of contamination by herbicides to both surface and groundwater in the upper sub-basin of the Poxim River, and to detect the presence of the active ingredients Diuron and Ametrine up-river from the sugar-cane plantations. Risk analysis was carried out using criteria from the Environmental Protection Agency (EPA), the GUS index, and the GOSS method. It was observed that several active ingredients are at risk of leaching, demonstrating the importance of monitoring the river to control both the quality of water and the frequency and volume of herbicides used in the region. Based on the results, monitoring was carried out bi-monthly from July 2009 to July 2010 at two sampling points. Water samples were analyzed in the laboratory, where the presence of Diuron and Ametrine was noted. Water quality in the Sub-basin of the Rio Poxim is being influenced by the use of herbicides in the region. There was an increase in herbicide concentration in the surface water during the rainy season, possibly caused by soil runoff.

Nutrient reference concentrations and trophic state boundaries in subtropical reservoirs

Nutrient criteria as reference concentrations and trophic state boundaries are necessary for water management worldwide because anthropogenic eutrophication is a threat to the water uses. We compiled data on total phosphorus (TP), nitrogen (TN) and chlorophyll a (Chl a) from 17 subtropical reservoirs monitored from 2005-2009 in the Sao Paulo State (Brazil) to calculate reference concentrations through the trisection method (United States Environmental Protection Agency). By dividing our dataset into thirds we presented trophic state boundaries and frequency curves for the nutrient levels in water bodies with different enrichment conditions. TP and TN baseline concentrations (0.010 mg/L and 0.350 mg/L, respectively) were bracketed by ranges for temperate reservoirs available in the literature. We propose trophic state boundaries (upper limits for the oligotrophic category: 0.010 mg TP/L, 0.460 mg TN/L and 1.7 mu g Chl a/L; for the mesotrophic: 0.030 mg TP/L, 0.820 mg TN/L and 9.0 mu g Chl a/L). Through an example with a different dataset (from the Itupararanga Reservoir, Brazil), we encouraged the use of frequency curves to compare data from individual monitoring efforts with the expected concentrations in oligotrophic, mesotrophic and eutrophic regional systems. Such analysis might help designing recovery programs to reach targeted concentrations and mitigate the undesirable eutrophication symptoms in subtropical freshwaters.

Herbicidas no alto rio Poxim, Sergipe e os riscos de contaminação dos recursos hídricos

A crescente atividade agrícola em áreas de mananciais tem causado preocupações quanto à contaminação por herbicidas em áreas agrícolas. O problema se torna mais importante quando a contaminação pode afetar a água para uso humano, como ocorre com a água do Rio Poxim, que abastece a cidade de Aracaju, capital do Estado de Sergipe. O objetivo do estudo foi avaliar o risco de contaminação de águas superficiais e subterrâneas por herbicidas no alto da Sub-bacia do Rio Poxim e detectar a presença dos princípios ativos Diuron e Ametrina, à montante das plantações de cana-de-açúcar. A análise de risco foi realizada mediante critérios da Environmental Protection Agency (EPA), índice de GUS e método de GOSS. Observou-se que vários princípios ativos sofrem risco de lixiviação, demonstrando a importância do monitoramento do rio para controle tanto da qualidade da água como da frequência e volume de herbicidas aplicado na região. A partir do resultado, foi realizado um monitoramento bimensal de julho de 2009 a julho de 2010, em dois pontos de amostragem. As amostras de água foram analisadas em laboratório, onde se, constatou a presença de Diuron e Ametrina. A qualidade da água na Sub-bacia do Rio Poxim está sendo influenciada pelo uso de herbicidas na região. Ocorreu um aumento nas concentrações dos herbicidas na água superficial, durante o período chuvoso, provocado possivelmente pelo escoamento superficial.

L'impatto ambientale delle operazioni di bonifica delle acque sotterranee

Il lavoro di tesi è stato svolto presso l’azienda Ecosurvey® - 3000 Srl, con sede a Bologna. Ecosurvey® fornisce servizi e consulenze nel campo della geologia e delle scienze ambientali e opera in diversi ambiti, tra cui le bonifiche del suolo, del sottosuolo e delle acque sotterranee. L’inquinamento del suolo e del sottosuolo è, infatti, il contesto dello studio di questa tesi. Tale inquinamento è persistente: con riferimento ai fenomeni di contaminazione, il sottosuolo registra la storia industriale di un sito. L’approccio che tenta di coniugare i bisogni dell’uomo nella società con il rispetto dell’ambiente è lo sviluppo sostenibile, ovvero, secondo la World Commission on Environment and Development, uno sviluppo che soddisfa i bisogni del presente senza compromettere la possibilità delle generazioni future di soddisfare i propri. Tra i molti ambiti in cui si applica il concetto di sostenibilità, è da ricordare quello delle bonifiche dei siti contaminati. A tal proposito, l’United States Environmental Protection Agency nel 2008 ha introdotto il concetto di “green remediation” come la pratica del considerare tutti gli effetti ambientali di un’azione di bonifica, includendo nel processo opzioni in grado di minimizzarne l’impronta ambientale. Nel 2013 la società Battelle, con i servizi tecnici ambientali di U.S. Navy, e U.S. Army Corps of Engineers ha sviluppato un applicativo denominato SiteWiseTM per la valutazione degli impatti ambientali associati alle tecnologie di bonifica delle acque sotterranee. Nell’ambito di questa tesi, in riferimento ad un intervento di bonifica presso un impianto di produzione di bitumi in attività, contaminato da idrocarburi, idrocarburi aromatici e composti organo-clorurati, con l’applicativo sono stati esaminati i principali indicatori dell’impronta ecologica (emissioni di gas serra, di ossidi di azoto, di zolfo e di polveri sottili; consumi di acqua, suolo ed energia) per tre diverse opzioni di bonifica, effettuandone poi il confronto.

Metallic copper as an antimicrobial surface

Bacteria, yeasts, and viruses are rapidly killed on metallic copper surfaces, and the term "contact killing" has been coined for this process. While the phenomenon was already known in ancient times, it is currently receiving renewed attention. This is due to the potential use of copper as an antibacterial material in health care settings. Contact killing was observed to take place at a rate of at least 7 to 8 logs per hour, and no live microorganisms were generally recovered from copper surfaces after prolonged incubation. The antimicrobial activity of copper and copper alloys is now well established, and copper has recently been registered at the U.S. Environmental Protection Agency as the first solid antimicrobial material. In several clinical studies, copper has been evaluated for use on touch surfaces, such as door handles, bathroom fixtures, or bed rails, in attempts to curb nosocomial infections. In connection to these new applications of copper, it is important to understand the mechanism of contact killing since it may bear on central issues, such as the possibility of the emergence and spread of resistant organisms, cleaning procedures, and questions of material and object engineering. Recent work has shed light on mechanistic aspects of contact killing. These findings will be reviewed here and juxtaposed with the toxicity mechanisms of ionic copper. The merit of copper as a hygienic material in hospitals and related settings will also be discussed.

Hydrogeochemical controls on uranium in aquifers of the Jacobsville Sandstone

The occurrence of elevated uranium (U) in sandstone aquifers was investigated in the Upper Peninsula of Michigan, focusing on aquifers of the Jacobsville Sandstone. The hydrogeochemical controls on groundwater U concentrations were characterized using a combination of water sampling and spectral gamma-ray logging of sandstone cliffs and residential water wells. 235U/238U isotope ratios were consistent with naturally occurring U. Approximately 25% of the 270 wells tested had U concentrations above the U.S. Environmental Protection Agency Maximum Contaminant Level (MCL) of 30 μg/L, with elevated U generally occurring in localized clusters. Water wells were logged to determine whether groundwater U anomalies could be explained by the heterogeneous distribution of U in the sandstone. Not all wells with relative U enrichment in the sandstone produced water with U above the MCL, indicating that the effect of U enrichment in the sandstone may be modified by other hydrogeochemical factors. Well water had high redox, indicating U is in its highly soluble (VI) valence. Equilibrium modeling indicated that aqueous U is complexed with carbonates. In general, wells with elevated U concentrations had low 235U/238U activity ratios. However, in some areas U concentrations and 235U/238U activity ratios were simultaneously high, possibly indicating differences in rock-water interactions. Limited groundwater age dating suggested that residence time may also help explain variations in well water U concentrations. Low levels of U enrichment (4 to 30 ppm) in the Jacobsville sandstone may make wells in its oxidized aquifers at risk for U concentrations above the MCL. On average, U concentrations were highest in heavy mineral and clay layers and rip up conglomerates. Uranium concentrations above 4 ppm also occurred in siltstones, sandstones and conglomerates. Uranium enrichment was likely controlled by deposition processes, sorption to clays, and groundwater flow, which was controlled by permeability variations in the sandstone. Low levels of U enrichment were found at deltaic, lacustrine and alluvial fan deposits and were not isolated to specific depositional environments.

Dynamic modeling of active regeneration in catalyzed and non-catalyzed diesel particulate filters

Particulate matter (PM) emissions standards set by the US Environmental Protection Agency (EPA) have become increasingly stringent over the years. The EPA regulation for PM in heavy duty diesel engines has been reduced to 0.01 g/bhp-hr for the year 2010. Heavy duty diesel engines make use of an aftertreatment filtration device, the Diesel Particulate Filter (DPF). DPFs are highly efficient in filtering PM (known as soot) and are an integral part of 2010 heavy duty diesel aftertreatment system. PM is accumulated in the DPF as the exhaust gas flows through it. This PM needs to be removed by oxidation periodically for the efficient functioning of the filter. This oxidation process is also known as regeneration. There are 2 types of regeneration processes, namely active regeneration (oxidation of PM by external means) and passive oxidation (oxidation of PM by internal means). Active regeneration occurs typically in high temperature regions, about 500 - 600 °C, which is much higher than normal diesel exhaust temperatures. Thus, the exhaust temperature has to be raised with the help of external devices like a Diesel Oxidation Catalyst (DOC) or a fuel burner. The O2 oxidizes PM producing CO2 as oxidation product. In passive oxidation, one way of regeneration is by the use of NO2. NO2 oxidizes the PM producing NO and CO2 as oxidation products. The passive oxidation process occurs at lower temperatures (200 - 400 °C) in comparison to the active regeneration temperatures. Generally, DPF substrate walls are washcoated with catalyst material to speed up the rate of PM oxidation. The catalyst washcoat is observed to increase the rate of PM oxidation. The goal of this research is to develop a simple mathematical model to simulate the PM depletion during the active regeneration process in a DPF (catalyzed and non-catalyzed). A simple, zero-dimensional kinetic model was developed in MATLAB. Experimental data required for calibration was obtained by active regeneration experiments performed on PM loaded mini DPFs in an automated flow reactor. The DPFs were loaded with PM from the exhaust of a commercial heavy duty diesel engine. The model was calibrated to the data obtained from active regeneration experiments. Numerical gradient based optimization techniques were used to estimate the kinetic parameters of the model.

Pathology working group review of histopathologic specimens from three laboratory studies of diclofenac in trout.

While the pathology peer review/pathology working group (PWG) model has long been used in mammalian toxicologic pathology to ensure the accuracy, consistency, and objectivity of histopathology data, application of this paradigm to ecotoxicological studies has thus far been limited. In the current project, the PWG approach was used to evaluate histopathologic sections of gills, liver, kidney, and/or intestines from three previously published studies of diclofenac in trout, among which there was substantial variation in the reported histopathologic findings. The main objectives of this review process were to investigate and potentially reconcile these interstudy differences, and based on the results, to establish an appropriate no observed effect concentration (NOEC). Following a complete examination of all histologic sections and original diagnoses by a single experienced fish pathologist (pathology peer review), a two-day PWG session was conducted to allow members of a four-person expert panel to determine the extent of treatment-related findings in each of the three trout studies. The PWG was performed according to the United States Environmental Protection Agency (US EPA) Pesticide Regulation (PR) 94-5 (EPA Pesticide Regulation, 1994). In accordance with standard procedures, the PWG review was conducted by the non-voting chairperson in a manner intended to minimize bias, and thus during the evaluation, the four voting panelists were unaware of the treatment group status of individual fish and the original diagnoses associated with the histologic sections. Based on the results of this review, findings related to diclofenac exposure included minimal to slightly increased thickening of the gill filament tips in fish exposed to the highest concentration tested (1,000 μg/L), plus a previously undiagnosed finding, decreased hepatic glycogen, which also occurred at the 1,000 μg/L dose level. The panel found little evidence to support other reported effects of diclofenac in trout, and thus the overall NOEC was determined to be >320 μg/L. By consensus, the PWG panel was able to identify diagnostic inconsistencies among and within the three prior studies; therefore this exercise demonstrated the value of the pathology peer review/PWG approach for assessing the reliability of histopathology results that may be used by regulatory agencies for risk assessment.

A discourse-theoretic approach to negotiated rulemaking

In 1996 and in 1997, Congress ordered the Secretary of Health and Human Services to undertake a process of negotiated rulemaking, which is authorized under the Negotiated Rulemaking Act of 1990, on three separate rulemaking matters. Other Federal agencies, including the Environmental Protection Agency and the Occupational Health and Safety Administration, have also made use of this procedure. As part of the program to reinvent government, President Clinton has issued an executive order requiring federal agencies to engage in some negotiated rulemaking procedures. I present an analytic, interpretative and critical approach to looking at the statutory and regulatory provisions for negotiated rulemaking as related to issues of democratic governance surrounding the problem of delegation of legislative power. The paradigm of law delineated by Jürgen Habermas, which sets law the task of achieving social or value integration as well as integration of systems, provides the background theory for a critique of such processes. My research questions are two. First, why should a citizen obey a regulation which is the result of negotiation by directly interested parties? Second, what is the potential effect of negotiated rulemaking on other institutions for deliberative democracy? For the internal critique I argue that the procedures for negotiated rulemaking will not produce among the participants the agreement and cooperation which is the legislative intent. For the external critique I argue that negotiated rulemaking will not result in democratically-legitimated regulation. In addition, the practice of negotiated rulemaking will further weaken the functioning of the public sphere, as Habermas theorizes it, as the central institution of deliberative democracy. The primary implication is the need to mitigate further development of administrative agencies as isolated, self-regulating systems, which have been loosened from the controls of democratic governance, through the development of a robust public sphere in which affected persons may achieve mutual understanding. ^

A Study of Radon in Air and Water in Maine Schools

The transfer coefficient of radon from water to air was investigated in schools. Kitchens, bathrooms and locker rooms were studied for seven schools in Maine. Simulations were done in water-use rooms where radon in air detectors were in place. Quantities measured were radon in water (270-24500 F) and air (0-80 q), volume of water used, emissivities (0.01-0.99) and ventilation rates (0.012-0.066A). Variation throughout the room of the radon concentration was found. Values calculated for the transfer coefficient for kitchens and baths were ranged from 9.6 x to 2.0 x The transfer coefficient was calculated using these parameters and was also measured using concentrations of radon in water and air. This provides a means by which radon in air can be estimated using the transfer coefficient and the concentration in the water in other schools and it can be used to estimate the dose caused by radon released from water use. This project was partially funded by the United States Environmental Protection Agency (grant #X828l2 101-0) and by the State of Maine (grant #10A500178). These are the first measurements of this type to be done in schools in the United States.

Revising the National Ambient Air Quality Standards: The integration of science and policy

Under the Clean Air Act, Congress granted discretionary decision making authority to the Administrator of the Environmental Protection Agency (EPA). This discretionary authority involves setting standards to protect the public's health with an "adequate margin of safety" based on current scientific knowledge. The Administrator of the EPA is usually not a scientist, and for the National Ambient Air Quality Standard (NAAQS) for particulate matter (PM), the Administrator faced the task of revising a standard when several scientific factors were ambiguous. These factors included: (1) no identifiable threshold below which health effects are not manifested, (2) no biological basis to explain the reported associations between particulate matter and adverse health effects, and (3) no consensus among the members of the Clean Air Scientific Advisory Committee (CASAC) as to what an appropriate PM indicator, averaging period, or value would be for the revised standard. ^ This project recommends and demonstrates a tool, integrated assessment (IA), to aid the Administrator in making a public health policy decision in the face of ambiguous scientific factors. IA is an interdisciplinary approach to decision making that has been used to deal with complex issues involving many uncertainties, particularly climate change analyses. Two IA approaches are presented; a rough set analysis by which the expertise of CASAC members can be better utilized, and a flag model for incorporating the views of stakeholders into the standard setting process. ^ The rough set analysis can describe minimal and maximal conditions about the current science pertaining to PM and health effects. Similarly, a flag model can evaluate agreement or lack of agreement by various stakeholder groups to the proposed standard in the PM review process. ^ The use of these IA tools will enable the Administrator to (1) complete the NAAQS review in a manner that is in closer compliance with the Clean Air Act, (2) expand the input from CASAC, (3) take into consideration the views of the stakeholders, and (4) retain discretionary decision making authority. ^

Toxics Release Inventory facilities and childhood cancer: Geographic information systems based approach

Purpose. To examine the association between living in proximity to Toxics Release Inventory (TRI) facilities and the incidence of childhood cancer in the State of Texas. ^ Design. This is a secondary data analysis utilizing the publicly available Toxics release inventory (TRI), maintained by the U.S. Environmental protection agency that lists the facilities that release any of the 650 TRI chemicals. Total childhood cancer cases and childhood cancer rate (age 0-14 years) by county, for the years 1995-2003 were used from the Texas cancer registry, available at the Texas department of State Health Services website. Setting: This study was limited to the children population of the State of Texas. ^ Method. Analysis was done using Stata version 9 and SPSS version 15.0. Satscan was used for geographical spatial clustering of childhood cancer cases based on county centroids using the Poisson clustering algorithm which adjusts for population density. Pictorial maps were created using MapInfo professional version 8.0. ^ Results. One hundred and twenty five counties had no TRI facilities in their region, while 129 facilities had at least one TRI facility. An increasing trend for number of facilities and total disposal was observed except for the highest category based on cancer rate quartiles. Linear regression analysis using log transformation for number of facilities and total disposal in predicting cancer rates was computed, however both these variables were not found to be significant predictors. Seven significant geographical spatial clusters of counties for high childhood cancer rates (p<0.05) were indicated. Binomial logistic regression by categorizing the cancer rate in to two groups (<=150 and >150) indicated an odds ratio of 1.58 (CI 1.127, 2.222) for the natural log of number of facilities. ^ Conclusion. We have used a unique methodology by combining GIS and spatial clustering techniques with existing statistical approaches in examining the association between living in proximity to TRI facilities and the incidence of childhood cancer in the State of Texas. Although a concrete association was not indicated, further studies are required examining specific TRI chemicals. Use of this information can enable the researchers and public to identify potential concerns, gain a better understanding of potential risks, and work with industry and government to reduce toxic chemical use, disposal or other releases and the risks associated with them. TRI data, in conjunction with other information, can be used as a starting point in evaluating exposures and risks. ^

Industrial benzene emissions in Houston: Legal barriers to reducing a public health threat

Decades of research show that environmental exposure to the chemical benzene is associated with severe carcinogenic, hematoxic and genotoxic effects on the human body. As such, the Environmental Protection Agency (EPA) has designated the chemical as a Hazardous Air Pollutant and prescribed benzene air concentration guidelines that provide cities with an ideal ambient level to protect human health. However, in Houston, Texas, a city home to the top industrial benzene emitters in the US who undoubtedly contribute greatly to the potentially unsafe levels of ambient benzene, regulations beyond the EPA’s unenforceable guidelines are critical to protecting public health. Despite this, the EPA has failed to establish National Ambient Air Quality Standards (NAAQS) for benzene. States are thus left to regulate air benzene levels on their own; in the case of Texas, the Texas Commission on Environmental Quality (TCEQ) and state legislature have failed to proactively develop legally enforceable policies to reduce major source benzene emissions. This inaction continues to exacerbate a public health problem, which may only be solved through a legal framework that restricts preventable benzene emissions to protect human health and holds industrial companies accountable for violations of such regulations and standards. This analysis explores legal barriers that the City of Houston and other relevant agencies currently face in their attempt to demand and bring about such change. ^

An evaluation of the Cypress Creek watershed for inorganic chemical load as it flows into Lake Houston

Background. The Cypress Creek is one of the main tributaries of Lake Houston, which provides drinking water to 21.4 million customers. Furthermore, the watershed is being utilized for contact and non-contact recreation, such as canoeing, swimming, hiking trail, and picnics. Water along the creek is impacted by numerous wastewater outfalls from both point and non-point sources. As the creek flows into Lake Houston, it carries both organic and inorganic contaminants that may affect the drinking water quality of this important water source reservoir. Objective. This study was carried out to evaluate the inorganic chemical load of the water in Cypress Creek along its entire length, from the headwaters in Waller County and up to the drainage into Lake Houston. The purpose was to determine whether there are hazardous concentrations of metals in the water and what would be the likely sources. Method. Samples were collected at 29 sites along the creek and analyzed for 29 metals, 17 of which were on the Environmental Protection Agency priority pollution list. Public access sites primarily at bridges were used for sample collection. Samples were transported on ice to the University Of Texas School Of Public Health laboratory, spiked with 2 ml HNO3 kept overnight in the refrigerator, and the following day transported to the EPA laboratory for analysis. Analysis was done by EPA Method 200.7-ICP, Method 200.8ICP/MS and Method 245.1-CVAAS. Results. Metals were present above the detection limits at 65% of sites. Concentrations of aluminum, iron, sodium, potassium, magnesium, and calcium, were particularly high at all sites. Aluminum, sodium, and iron concentrations greatly exceeded the EPA secondary drinking water standards at all sites. ^ Conclusion. The recreational water along Cypress Creek is impacted by wastewater from both permitted and non-permitted outfalls, which deposit inorganic substances into the water. Although a number of inorganic contaminants were present in the water, toxic metals regulated by the EPA were mostly below the recommended limits. However, high concentrations of aluminum, sodium, and iron in the Cypress Creek bring forward the issue of unauthorized discharges of salt water from mining, as well as industrial and domestic wastewater.^

A standard operation procedure and a pilot water testing for herbicides in northwest Harris County, Texas

Herbicides are used to control the growth of weeds along highways, power lines, and many other urban locations. Exposure to herbicides has been linked to adverse health outcomes. This study was initiated to pretest for the presence of herbicides in multiple water sources near intersections in a corridor in the Northwest Harris County (specifically in the Highway 6/FM 1960, North Freeway 45, US 290 and S 99 corridor). Roadside water and tap water samples were collected and analyzed for herbicides using the established Environmental Protection Agency (EPA) Method 515.4: "Determination of Chlorinated Acids in Drinking Water by Liquid-Liquid Micro-extraction, Derivatization, and Fast Gas Chromatography with Electron Capture Detection." A standard operating procedure (adapted from the US EPA Method 515.4) was developed for subsequent, larger studies of environmental fate of herbicides and non-occupational exposure risks. Preliminary testing of 16 water samples was performed to pretest the existence of trace herbicides; all concentrations that were greater than the minimum reporting limits of each analyte are reported with a 99 percent confidence. This study failed to find concentrations above the limits of detection of the method in any of the samples collected on June 15, 2008. However, this does not indicate that the waters around the NW Harris County are free of herbicides and metabolites. A larger and repeated sampling in the region would be necessary to make that claim. ^