The Safe Drinking Water Act ensures that public systems provide water that meets health standards. However, no such protection exists for millions of Americans who obtain water from private wells. Concern for safety is warranted as most wells draw from underground aquifers, and studies demonstrate that groundwater is affected by a range of contaminants, most often nitrate. Oregon's Domestic Well Testing Act (DWTA) links well testing to property sales, enabling continuous data collection by the State. This research addresses a need for identifying datasets for characterizing exposure to private well contaminants by evaluating DWTA data for use in a sentinel surveillance system. Validation of DWTA data was accomplished by developing a land use regression (LUR) model based on agricultural nitrogen inputs and soil leachability to predict nitrate concentrations in well water. Geographic information systems (GIS) were used to advance methods for high resolution spatial modeling of fertilizer and manure nitrogen with statewide coverage. Hazard mapping with these datasets suggests that nearly half of recently drilled wells are susceptible to nitrate contamination. Spearman's rank correlation demonstrated a significant correlation between LUR-predicted nitrate levels and levels reported in the DWTA dataset. These results suggest that DWTA data is valid for use in a sentinel surveillance system, such that evidence of nitrate contamination in a single well may indicate an area-wide health hazard. However, a low fraction of variance explained by the LUR model highlighted the need for specific improvements to datasets crucial for understanding nitrate contamination in well water, including the DWTA. / Graduation date: 2012

Excessive nitrates in drinking water pose a human health threat, especially to infants. Methemoglobinemia, or blue-baby syndrome, is a potentially fatal condition that inhibits the ability of red blood cells to bind and transport oxygen. Nitrates/nitrites have also been linked to such conditions as cancer, birth defects, and behavioral and developmental abnormalities. Nitrates are frequently found in wells in rural farming areas because synthetic fertilizers (containing nitrates) leach from the soil into the groundwater. The Lower Umatilla Basin (LUB) in Morrow and Umatilla counties of Oregon represents an intensively farmed and irrigated area in which relatively high amounts of nitrates are present in the groundwater and domestic well water. This study investigated population demographics for the rural Lower Umatilla Basin, comparing these data to identified well-water nitrate levels for the purpose of estimating nitrate exposures and potential risk of adverse health effects in the survey area. Results of the investigation revealed that 25 percent of the domestic-use wells in the survey area had nitrate levels that were in excess of the 10 ppm nN MCL for drinking water, as established by the U.S. Environmental Protection Agency. From access to these wells, 23 percent of the surveyed population was exposed to nitrate concentrations in excess of the MCL standard. However, resident infants were neither exposed to well-water nitrates in excess of the standard, nor were they exposed to illness that could have increased the risk of methemoglobinemia. The LUB survey population was generally older than the populations from cities in the LUB or the combined populations of rural areas of Morrow and Umatilla counties. The population included few women of childbearing age, and it was not subject to an appreciable increase in the proportion of younger to older families. These factors reduced the likelihood of a significant increase in the infant population, which also minimized the risk of methemoglobinemia to this population. Even though the risk of methemoglobinemia to infants was low in the LUB area, it is recommended that exposures to well-water nitrates be prevented, if possible even for adults, to reduce the potential for chronic, adverse health effects from excess nitrate ingestion. Continued monitoring of private wells by state agencies is recommended, with attention directed at domesticuse wells with nitrate levels in excess of 10 ppm nN. This information should be shared with local health departments for follow-up, investigation, and educational efforts as needed. Future studies by the Oregon DEQ, or other agencies which seek to document the sources of well-water nitrate contamination in the LUB, should include an investigation of the influence of local sources of nitrate contamination. / Graduation date: 1993

Technologies such as horizontal wells and multi-stage hydraulic fracturing have made ultra-low permeability shale and tight gas reservoirs productive but the industry is still on the learning curve when it comes to addressing various production issues. Some of the problems encountered while hydraulically fracturing these reservoirs are the absence of frac barriers, thinner shales and the increased presence of geological hazards. Induced vertical fractures sometimes extend to an underlying aquifer and become a conduit to the well. We have developed a low-concentration, low-viscosity and delayed-crosslink polymeric gel system as a water shutoff agent for hydraulically-fractured tight gas and shale reservoirs, where some fractures might connect to water rich zones. The system also is a significant improvement over traditional flowing gels for fracture water shutoff in conventional reservoirs because of these features. The gel uses high molecular weight hydrolyzed polyacrylamide (HPAM) at low polymer concentrations with a delayed organic crosslinker. This crosslinker is more environmentally benign and provides much longer gelation time and stronger final gels than comparable polymer loadings with chromium carboxylate crosslinkers at higher temperatures. The low viscosity system allows low-pressure extrusion of gelant into the narrow-aperture fractures present in unconventional gas reservoirs. The gelant can be pumped at low pressures due to lower polymer concentrations and delayed gelation point. This allows the potential to seal problem zones that are producing excess water even when the fractures conducting water have very narrow apertures. By impeding water production, the gel system developed here can effectively delay water loading thereby avoiding abandonment or installation of expensive equipment with increased operational costs, thus extending life and reserves of unconventional gas wells.

Solid-phase microextraction (SPME) coupled with gas chromatography/mass spectrometry (GC/MS) is routinely used to analyze polycyclic aromatic hydrocarbons (PAHs) in water. A common SPME-GC/MS approach quantifies target analytes using isotopically labeled standards (IISs); one IIS is needed for each target analyte. This approach is challenging, even prohibitive since IISs are often expensive; moreover, they are generally not available for each analyte of interest. This study developed a novel SPME-GC/MS approach for the quantification of PAHs in water. The new method, which employs only a small number of IISs, uses relative response factor (RRF) (i.e., analyte corresponding to IIS) to quantify PAHs in water. Possible matrix dependency of RRFs values was examined using water that was modified concerning different physical-chemical characteristics (i.e., ionic strength, pH, suspended solids, humic acid, and biological organic carbon represented by hemoglobin). The results revealed that RRFs are not noticeably affected by changing ionic strength and pH; the other three parameters did affect the RRFs. However, the results also showed that the effect is minimal when the solution is dilute (i.e., low concentrations of suspended solids, humic acid or hemoglobin). Relatively stable RRFs for dilute water solutions indicates that this approach can be used for routine quantification of water that does not contain prohibitive amounts of suspended solids, humic acid, and biological organic matter. The developed method was employed to quantify trace levels of PAHs in three different types of water, namely river water, well water, and bottled water. PAH levels in every kind of water were less than 100 ng/L level (i.e., 0.1 ppb). Analyses of spiked water samples containing 2 ng PAHs revealed correlations between calculated RRFs and the physical-chemical properties of the PAHs investigated (i.e., vapor pressure, boiling point, octanol/water partition coefficient, octanol/air partition coefficient, GC retention time). This implies that RRFs for PAHs not examined in this study can be predicted. Overall, the results presented herein constitute a meaningful contribution to the development of SPME-GC/MS methods for quantitative analysis of PAHs and other chemicals in dilute aqueous solutions. Moreover, the development of methods that alleviate the need for IISs corresponding to each target analyte.