Este trabalho teve como objetivo principal a utilização de duas variantes da técnica analítica de fluorescência de raios X, dispersiva em energia - EDXRF e reflexão total TXRF, na determinação de Pb em amostras de águas superficiais e subterrâneas, e em sedimentos em suspensão e de fundo. Cinco amostras de cada matriz foram coletadas em uma área contaminada, nas proximidades da desativada fábrica de baterias Indústria Acumuladores Ajax Ltda., localizada no km 229 da rodovia Jaú-Ipaussu, em Bauru, SP. As variantes EDXRF com pré-concentração com APDC e medida direta por TXRF mostraram resultados satisfatórios na determinação de Pb em soluções-padrão e amostra certificada de água natural SRM1640, produzida pelo NIST, obtendo-se concentrações compatíveis com os valores esperados. A primeira técnica resultou em limite de detecção da ordem de 0,70 mg L-1, com tempo de análise de 300 s, melhor que a segunda técnica (4,46 mg L-1), em 200 s. Estas duas variantes também foram utilizadas para outros elementos químicos, como o Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn e Br, onde a EDXRF mostrou também melhores limites de detecção para todos os elementos. Para Ni, Cu e Zn, importantes na indústria de baterias, foram encontrados os limites de 0,34 - 0,27 e 0,24 mg L-1, respectivamente, enquanto que por TXRF foram encontrados os valores ao redor de 1 mg L-1. Na validação destas duas metodologias para análise de água, a EDXRF mostrou resultados mais próximos aos valores esperados, enquanto que por TXRF foram superestimados na maioria das vezes, com exceção para As, Se e Pb. Este erro foi devido a uma interferência espectral ocasionada provavelmente pela presença dos elementos Ti ao Zn nos componentes metálicos do arranjo experimental, ausentes no suporte refletor de quartzo, colimador do detector ou solução do padrão interno. Sem a eliminação dessa interferência, os resultados obtidos por TXRF para estes elementos, com exceção para As, Se e Pb, só podem ser utilizados como qualitativos. Para análise de sedimentos em suspensão foi utilizada a técnica de EDXRF, assumindo a amostra como filme fino, atingindo limite de detecção da ordem de 2 mg g-1 para Pb, enquanto que para o Cu e Zn o limite de detecção foi da ordem de 5 mg g-1, em 300 s. Para sedimento de fundo foi utilizada a mesma técnica, mas admitindo a amostra como espessa, corrigindo-se o efeito matriz através do fator de absorção, validando-a pela análise de amostras certificadas de sedimento (SRM1646a/NIST) e solo (SRM2711/NIST). O limite de detecção para Pb ficou em torno de 2 mg g-1, e para outros elementos os limites foram de 3,07 mg g-1 para Ni, 2,12 mg g-1 para Cu e 1,50 mg g-1 para Zn, em 500 s. Com base nos valores máximos permitidos para Pb, estabelecidos pela Portaria 1469/00 e Resolução 20/1986 CONAMA, duas amostras de água mostraram-se contaminadas pelos resultados obtidos pela variante EDXRF, e quatro pelos resultados da TXRF. Para os outros elementos, apesar da interferência na TXRF, por esta técnica uma amostra de água ultrapassou o limite permissível para Cu e todas as cinco para Zn, e pela EDXRF uma amostra para Ni e Cu em água, e três para Zn. Na legislação brasileira não há limite máximo permitido para Pb e outros elementos em solos e sedimentos, e portanto foram adotados os limites TEL (Threshold Effect Level, nível limiar do efeito) e PEL (Probable Effect Level, nível provável do efeito), utilizados pela Agência Ambiental Canadense. As amostras de sedimento em suspensão mostraram concentrações de Pb menores que o limite de detecção, e das cinco amostras de sedimento de fundo, uma amostra apresentou valor acima do limite TEL, e outra, coletada num ponto bem ao lado da fábrica, acima do limite PEL. Para os outros elementos Ni, Cu e Zn, nenhuma das amostras de sedimento em suspensão ou de fundo não ultrapassaram os limites TEL. / This study had as main objective the use of two variants of the analytical technique of X-ray fluorescence, energy dispersive - EDXRF and total reflection - TXRF, for the determination of Pb in superficial and underground water and in suspended and bottom sediment samples. Five samples of each matrix were collected in a contaminated area near the closed battery plant, Indústria de Acumuladores Ajax Ltd., located on km 229 of the Jaú-Ipaussu highway, near the city of Bauru in São Paulo State, Brazil. The two variants – EDXRF with preconcentration with APDC and TXRF direct measurement – had shown satisfactory results in the determination of Pb in standard solutions and certified natural water sample SRM1640/NIST, obtaining compatible concentrations with the expected values. The first technique resulted in a 0.70 mg L-1 limit of detention, with 300 s analysis time, and the second one 4.46 mg L-1 in 200 s. These two variants were also used for other chemical elements, such as Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn and Br. EDXRF also showed better limits of detection for all the elements. For Ni, Cu and Zn, important in the industry of batteries, the limits of 0.34, 0.27 and 0.24 mg L-1, respectively, were found, while with TXRF the values of around 1 mg L-1 were achieved. In the validation of these two methodologies for water analysis, the EDXRF showed results nearer to the expected values, while with TXRF the results were overestimated most of the times, with the exceptions of As, Se and Pb. This error was due to a spectral interference caused probably by the presence of the elements Ti to Zn in the metallic parts of the experimental arrangement, absent in the quartz reflecting support, detector collimator or internal standard solution. Without the elimination of this interference, the results for TXRF for these elements, with the exceptions of As, Se and Pb, can only be used as qualitative results. For analysis of suspended sediments, the EDXRF technique was used, assuming the sample as thin film, the limit of detection of around 2 mg g-1 for Pb was reached, while that for Cu and Zn was around 5 mg g-1, in 300 s. For bottom sediments the same technique was used, but admitting the sample as thick, the matrix effect through the absorption factor was corrected, validating it for the analysis of certified samples of sediment (SRM1646a/NIST) and soil (SRM2711/NIST). The limit of detention for Pb was around 2 mg g-1 and for other elements the limits were 3.07, 2.12 and 1.50 mg g-1 for Ni, Cu and Zn, respectively, in 500 s. On the basis of the Brazilian allowed maximum values for Pb, established by Decree 1469/00 and Resolution 20/1986 CONAMA, two water samples were shown to be contaminated by the results gotten with variant EDXRF, and four by the results of TXRF. For the other elements from the TXRF results (despite the interference) one water sample exceeded the permissible limit for Cu and all the five for Zn, and for the EDXRF results one sample for Ni and Cu and three for Zn. In the Brazilian legislation there is no maximum limit allowed for Pb and other elements in soils and sediments; therefore, TEL (Threshold Effect Level) and PEL (Probable Effect Level) limits from the Canadian Environment Agency were adopted. The suspended sediment samples showed Pb concentrations lesser than the limit of detection. From the five bottom sediment samples, one sample presented a value above the TEL limit, and another one, collected in a point very close to the plant, above the PEL limit. For the other elements, Ni, Cu and Zn, none of the suspended or bottom sediment samples exceeded the TEL limits.

<p>Field-edge buffers are a promising way to address nonpoint source pollution from agricultural runoff, but concentrated runoff flow often renders standard fixed-width linear buffers ineffective. AgBufferBuilder (ABB) is a tool within ESRI ArcMap Geographic Information Systems software that designs and evaluates targeted, nonlinear buffers based on hydrologic modeling and other field-specific parameters. We tested ABB on n=45 Areas of Interest (AOIs) stratified based on estimated sediment loading across three sub-watersheds within Michigan’s Saginaw Bay watershed to evaluate the effectiveness of ABB relative to existing practices across a wide range of landscape conditions. We modeled tractor movement around ABB buffer designs to assess more realistic versions of the likely final designs. ABB regularly failed to deliver the desired 75% sediment capture rate using default 9 m x 9 m output raster resolution, with Proposed buffers capturing from 0% to 68.49% of sediment within a given AOI (mean=37.56%). Differences in sediment capture between Proposed and Existing buffers (measured as Proposed – Existing) ranged from -48% to 66.81% of sediment (mean=24.70%). Proposed buffers were estimated to capture more sediment than Existing buffers in 37 of 45 AOIs, representing potential for real improvements over Existing buffers across the wider landscape. In 13 of 45 AOIs, ABB buffers modified for tractor movement captured more sediment than Existing buffers using less total buffer area. We conducted a collaborative design process with three Saginaw Bay watershed farmers to assess their willingness to implement ABB designs. Feedback indicated farmers may prefer in-field erosion control practices like cover cropping and grassed waterways over field-edge ABB designs. More farmer input is needed to better assess farmer perspectives on ABB buffers and to identify preferred data-based design alternatives. Engineered drainage systems with raised ditch berms and upslope catch basins piped underground directly into ditches were encountered several times during site visits. ABB only models surface flow and does not recognize drain output flow entering waterways. Modified ABB functionality that models buffers around drain inlets would greatly improve its functionality on drained sites. This may be accomplishable through modification of user-entered AOI margins but requires further investigation. Unfortunately, the existing tool is built for outdated software and is not widely accessible to non-expert users. We suggest that an update of this tool with additional functionality and user accessibility would be a useful addition in the toolbox of conservation professionals in agricultural landscapes.</p>

<p>Current watershed-scale, nonpoint source (NPS) pollution models do not represent the processes and impacts of agricultural best management practices (BMP) on water quality with sufficient detail. To begin addressing this gap, a novel process-based, watershed-scale, water quality model (WEPP-WQ) was developed based on the Water Erosion Prediction Project (WEPP) and the Soil and Water Assessment Tool (SWAT) models. The proposed model was validated at both hillslope and watershed scales for runoff, sediment, and both soluble and particulate forms of nitrogen and phosphorus. WEPP-WQ is now one of only two models which simulates BMP impacts on water quality in ‘high’ detail, and it is the only one not based on USLE sediment predictions. Model validations indicated that particulate nutrient predictions were better than soluble nutrient predictions for both nitrogen and phosphorus. Predictions of uniform conditions outperformed nonuniform conditions, and calibrated model simulations performed better than uncalibrated model simulations. Applications of these kinds of models in real-world, historical simulations are often limited by a lack of field-scale agricultural management inputs. Therefore, a prototype tool was developed to derive management inputs for hydrologic models from remotely sensed imagery at field-scale resolution. At present, only predictions of crop, cover crop, and tillage practice inference are supported and were validated at annual and average annual time intervals based on data availability for the various management endpoints. Extraction model training and validation were substantially limited by relatively small field areas in the observed management dataset. Both of these efforts contribute to computational modeling research and applications pertaining to agricultural systems and their impacts on the environment.</p>