Study region: Santa Barbara County, California, USA. Study focus: To analyze a wide array of newly collected chemical, isotopic, dissolved gas, and age dating tracers in conjunction with historical data from groundwater and oil wells to determine if water and/or thermogenic gas from oil-bearing formations have mixed with groundwater in the Orcutt Oil Field and surrounding area. New hydrological insights for the region: Three of 15 groundwater samples had compositions indicating potential mixing with water and/or thermogenic gas from oil-bearing formations. Relevant indicators included salinity tracers (TDS, Cl, Br), NH3, DOC, enriched delta C-13-DIC, delta H-2-CH4, delta C-13-CH4, and delta C-13-C2H6 values, and trace amounts of C-3-C-5 gas. The potential sources/ pathways for oil-bearing formation water and/or thermogenic gas in groundwater overlying and adjacent to the Orcutt Oil Field include: (1) upward movement from formations developed for oil production due to: (a) natural migration; or (b) anthropogenic activity such as injection and/or movement along wellbores; and (2) oil and gas shows in overlying non-producing oil-bearing formations. Groundwater age tracers, elevated He-4 concentrations, and isotopic compositions of noble gases indicated legacy produced water ponds were not a source. This phase of the study relied on samples and data from existing infrastructure. Additional data on potential end-member compositions from new and existing wells and assessments of potential vertical head gradients and pathways between oil and groundwater zones may yield additional insight.

Relative risks of groundwater-quality degradation near selected California oil fields are estimated by examining spatial and temporal patterns in chemical and isotopic data in the context of groundwater-age categories defined by tritium and carbon-14. In the Coastal basins, western San Joaquin Valley (SJV), and eastern SJV; 82, 76, and 0% of samples are premodern (pre-1953 recharge), respectively; and 3, 0, and 31% are modern (recharged during or after 1953), respectively. Carbon-14 and helium-4 data indicate most premodern samples are 1000 to 10,000 (33%) or >10,000 (50%) years old. Organic chemicals that could be associated with deeper hydrocarbon reservoirs (e.g. thermogenic gases and benzene) occur most frequently in premodern groundwater, suggesting premodern groundwater has a higher risk of degradation from upward migration of hydrocarbons than modern and mixed-age groundwater. Low sulfate concentrations in some premodern groundwater containing high thermogenic-methane concentrations (>28 mg/L) indicate methane attenuation associated with sulfate reduction can be limited in premodern groundwater. The more common occurrence of manufactured compounds, like tetrachloroethene, in modern and mixed-age groundwater than in premodern groundwater indicates modern and mixed-age groundwater has a higher risk of degradation from land-surface sources than premodern groundwater. Time-series data for chloride in groundwater affected by disposal of oil-field water in unlined ponds indicate some modern and mixed-age groundwater are susceptible to chemical migration within 2-3 km of surface sources. Timescales for diluting chloride concentrations in groundwater with fresh recharge once disposal ponds are decommissioned are shorter in mixed-age groundwater with large fractions of modern water (9-14 years in one example) than in mixed-age groundwater with large fractions of premodern water (no evidence of dilution after 12 years of monitoring in one example). The presence of predominantly premodern groundwater in the Coastal basins and western SJV indicates these areas have relatively high risk from upward migration of hydrocarbons, reduced methane attenuation capacity, and long dilution times, whereas predominantly modernand mixed-age groundwater in the eastern SJV indicates this area has relatively high risk from chemical migration from land-surface sources and subsequent extensive spreading. Age-based characterizations of relative risk could inform the design of groundwater-monitoring programs near oil fields in terms of the spatial distribution of monitoring points relative to source areas and monitoring frequency and duration.

Geochemical evaluation of the sources and movement of saline groundwater in coastal aquifers can aid in the initial mapping of the subsurface when geological information is unavailable. Chloride concentrations of groundwater in a coastal aquifer near San Diego, California, range from about 57 to 39,400 mg/L. On the basis of relative proportions of major‐ions, the chemical composition is classified as Na‐Ca‐Cl‐SO4, Na‐Cl, or Na‐Ca‐Cl type water. δ2H and δ18O values range from −47.7‰ to −12.8‰ and from −7.0‰ to −1.2‰, respectively. The isotopically depleted groundwater occurs in the deeper part of the coastal aquifer, and the isotopically enriched groundwater occurs in zones of sea water intrusion. 87Sr/86Sr ratios range from about 0.7050 to 0.7090, and differ between shallower and deeper flow paths in the coastal aquifer. 3H and 14C analyses indicate that most of the groundwater was recharged many thousands of years ago. The analysis of multiple chemical and isotopic tracers indicates that the sources and movement of saline groundwater in the San Diego coastal aquifer are dominated by: (1) recharge of local precipitation in relatively shallow parts of the flow system; (2) regional flow of recharge of higher‐elevation precipitation along deep flow paths that freshen a previously saline aquifer; and (3) intrusion of sea water that entered the aquifer primarily during premodern times. Two northwest‐to‐southeast trending sections show the spatial distribution of the different geochemical groups and suggest the subsurface in the coastal aquifer can be separated into two predominant hydrostratigraphic layers.

Oocysts of the protozoan pathogen Cryptosporidium parvum are of particular concern for riverbank filtration (RBF) operations because of their persistence, ubiquity, and resistance to chlorine disinfection. At the Russian River RBF site (Sonoma County, CA), transport of C. parvum oocysts and oocyst-sized (3 μm) carboxylate-modified microspheres through poorly sorted (sorting indices, σ(1), up to 3.0) and geochemically heterogeneous sediments collected between 2 and 25 m below land surface (bls) were assessed. Removal was highly sensitive to variations in both the quantity of extractable metals (mainly Fe and Al) and degree of grain sorting. In flow-through columns, there was a log-linear relationship (r(2) = 0.82 at p < 0.002) between collision efficiency (α, the probability that colloidal collisions with grain surfaces would result in attachment) and extractable metals, and a linear relationship (r(2) = 0.99 at p < 0.002) between α and σ(1). Collectively, variability in extractable metals and grain sorting accounted for ∼83% of the variability in α (at p < 0.0002) along the depth profiles. Amendments of 2.2 mg L(-1) of Russian River dissolved organic carbon (DOC) reduced α for oocysts by 4-5 fold. The highly reactive hydrophobic organic acid (HPOA) fraction was particularly effective in re-entraining sediment-attached microspheres. However, the transport-enhancing effects of the riverine DOC did not appear to penetrate very deeply into the underlying sediments, judging from high α values (∼1.0) observed for oocysts being advected through unamended sediments collected at ∼2 m bls. This study suggests that in evaluating the efficacy of RBF operations to remove oocysts, it may be necessary to consider not only the geochemical nature and size distribution of the sediment grains, but also the degrees of sediment sorting and the concentration, reactivity, and penetration of the source water DOC.

Laboratory-scale virus transport experiments were conducted in columns packed with sand under saturated and unsaturated conditions. The viruses employed were the male-specific RNA coliphage, MS2, and the Salmonella typhimurium phage, PRD1. The mathematical model developed by Sim and Chrysikopoulos (Water Resour Res 36:173–179, 2000) that accounts for processes responsible for removal of viruses during vertical transport in one-dimensional, unsaturated porous media was used to fit the data collected from the laboratory experiments. The liquid to liquid–solid and liquid to air–liquid interface mass transfer rate coefficients were shown to increase for both bacteriophage as saturation levels were reduced. The experimental results indicate that even for unfavorable attachment conditions within a sand column (e.g., phosphate-buffered saline solution; pH = 7.5; ionic strength = 2 mM), saturation levels can affect virus transport through porous media.

Carboxylated microspheres were employed as surrogates to assess the transport potential of Cryptosporidium parvumoocysts during forced- and natural-gradient tests conducted in July and October 2004. The tests involved poorly-sorted, near-surface sediments where groundwater is pumped from an alluvial aquifer underlying the Russian River, Sonoma County, CA. In an off channel infiltration basin and within the river, a mixture (2-, 3-, and 5- μm diameters) of fluorescently-labeled carboxylated microspheres and bromide tracers were used in two injection and recovery tests to assess sediment removal efficiency for the microspheres. Bottom sediments varied considerably in their filtration efficiency for Cryptosporidium.

Static and dynamic batch experiments were conducted to study the effects of temperature and the presence of sand on the inactivation of bacteriophage MS2 and PRD1. The experimental data suggested that the inactivation process can be satisfactorily represented by a pseudo-first-order expression with time-dependent rate coefficients. The time-dependent rate coefficients were used to determine pertinent thermodynamic properties required for the analysis of the molecular processes involved in the inactivation of each bacteriophage. A combination of high temperature and the presence of sand appears to produce the greatest disruption to the surrounding protein coat of MS2. However, the lower activation energies for PRD1 indicate a weaker dependence of the inactivation rate on temperature. Instead, the presence of air-liquid and air-solid interfaces appears to produce the greatest damage to specific viral components that are related to infection. These results indicate the importance of using thermodynamic parameters based on the time-dependent inactivation model to better predict the inactivation of viruses in groundwater.

A field-scale experiment was conducted at a research site using bacterial viruses (bacteriophage) MS2 and PRD1 as surrogates for human viruses, bromide as a conservative tracer, and tertiary-treated municipal wastewater (recycled water) to investigate the fate and transport of viruses during artificial recharge. Observed virus concentrations were fitted using a mathematical model that simulates virus transport in one-dimensional, homogeneous, water-saturated porous media accounting for virus sorption (or filtration), virus inactivation, and time-dependent source concentration. The fitted time-dependent clogging rate constants were used to estimate the collision efficiencies for bacteriophage MS2 and PRD1 during vertical fully saturated flow. Furthermore, the corresponding time-dependent collision efficiencies for both bacteriophage asymptotically reached similar values at the various sampling locations. These results can be used to develop an optimal management scenario to maximize the amount of recycled water that can be applied to the spreading grounds while still maintaining favorable attachment conditions for virus removal.

Total and fecal coliform bacteria distributions in subsurface water samples collected at a research field site in Los Angeles County were found to increase from nondetectable levels immediately before artificial recharge using tertiary-treated municipal wastewater (recycled water). This rapid increase indicates that bacteria can move through the soil with the percolating recycled water over intervals of a few days and vertical and horizontal distances of about 3 meters. This conclusion formed the basis for three field-scale experiments using bacterial viruses (bacteriophage) MS2 and PRD1 as surrogates for human enteric viruses and bromide as a conservative tracer to determine the fate and transport of viruses in recycled water during subsurface transport under actual recharge conditions. The research field site consists of a test basin constructed adjacent to a large recharge facility (spreading grounds) located in the Montebello Forebay of Los Angeles County, California. The soil beneath the test basin is predominantly medium to coarse, moderately sorted, grayish-brown sand. The three tracer experiments were conducted during August 1997, August-September 1998, and August 2000. For each experiment, prepared solutions of bacteriophage and bromide were sprayed on the surface of the water in the test basin and injected, using peristaltic pumps, directly into the feed pipe delivering the recycled water to the test basin. Extensive data were obtained for water samples collected from the test basin itself and from depths of 0.3, 0.6, 1.0, 1.5, 3.0, and 7.6 meters below the bottom of the test basin. The rate of bacteriophage inactivation in the recycled water, independent of any processes occurring in the subsurface, was determined from measurements on water samples from the test basin. Regression analysis of the ratios of bacteriophage to bromide was used to determine the attenuation rates for MS2 and PRD1, defined as the logarithmic reduction in the ratio during each experiment. Although the inactivation rates increased during the third tracer experiment, they were nearly two orders of magnitude less than the attenuation rates. Therefore, adsorption, not inactivation, is the predominant removal mechanism for viruses during artificial recharge. Using the colloid-filtration model, the collision efficiency was determined for both bacteriophage during the second and third field-scale tracer experiments. The collision efficiency confirms that more favorable attachment conditions existed for PRD1, especially during the third tracer experiment. The different collision efficiencies between the second and third tracer experiments possibly were due to changing hydraulic conditions at the research field site during each experiment. The field data suggest that an optimal management scenario might exist to maximize the amount of recycled water that can be applied to the spreading grounds while still maintaining favorable attachment conditions for virus removal and thereby ensuring protection of the ground-water supply.

A number of studies have reported on the successful use of intravenous glycoprotein IIb/IIIa receptor antagonists in patients with unstable angina or undergoing percutaneous interventions. The promise of interrupting the aggregation of platelets in the setting of unstable plaques on a chronic basis had led to the evaluation of several oral agents for longer-term administration. The development program of two of these agents, xemilofiban and orbofiban, will be reviewed and evaluated to understand the selection process of therapeutic targets for use based upon complex pharmacokinetic and pharmacodynamic responses. A review of the pivotal phase III trial results will also be provided along with insights into the potential reasons for the lack of significant benefit shown with these agents to date.

Clinical trials have demonstrated the efficacy of glycoprotein (GP) IIb/IIIa antagonists in preventing the thrombotic end points of death, myocardial infarction, and urgent revascularization when they are administered at the time of percutaneous coronary revascularization (PTCR). It has been postulated that prolongation of receptor blockade beyond acute intervention would extend the clinical benefit of these agents. The Evaluation of Oral Xemilofiban in Controlling Thrombotic Events (EXCITE) study was a multicenter, international, randomized placebo‐controlled trial of the oral GP IIb/IIIa antagonist Xemilofiban administered prior to and after PTCR. The study was designed to assess the efficacy and safety of continuing oral xemilofiban for 6 months to prevent these primary thrombotic end points. More than 7,200 patients were randomized in 29 countries to receive placebo or one of two doses of xemilofiban. Stenting was performed at the discretion of the operator. All patients received aspirin and periprocedural heparin; all stented patients received continuous xemilofiban, or ticlopidine for 2–4 weeks followed by xemilofiban‐placebo. Most patients were also evaluated 1 month after conclusion of the study drug treatment. Clinical data from up to 6 months of drug treatment and 1 month posttreatment were used to evaluate the acute and long‐term efficacy and safety of xemilofiban. Secondary end points included the need for any revascularization, repeat hospitalization for unstable angina, and nonhemorrhagic stroke. The cumulative incidence of bleeding events and effects of xemilofiban in stented and nonstented patients were evaluated. The efficacy of continuing xemilofiban and aspirin therapy as the sole antithrombotic medications following stent deployment was assessed against a ticlopidine and aspirin control group. The incremental clinical benefit of long‐term receptor blockade over acute receptor antagonism was evaluated.

Tertiary-treated municipal wastewater (recycled water) has been used to replenish the Central Basin in Los Angeles County for over 40 years. Therefore, this area provides an excellent location to investigate (1) the fate and transport of wastewater constituents as they travel from the point of recharge to points of withdrawal, and (2) the long-term effects that artificial recharge using recycled water has on the quality of the ground-water basin. The U.S. Geological Survey has been conducting such investigations in this area for about 10 years, beginning in 1992. For this investigation, a variety of inorganic, organic, and isotopic constituents were analyzed in samples from 23 production wells within 500 feet of the San Gabriel and Rio Hondo Coastal Basin Spreading Grounds, and tritium/helium-3, chlorofluorocarbons, dissolved gases, and nitrogen isotopes were analyzed in five multiple-well monitoring sites along a 10-mile flow path extending from just upgradient of the spreading grounds southward through the Central Basin. Spearman rank-order correlation coefficients and level of significance calculated for about 40 water-quality indicators and several physical features show significant correlations between numerous inorganic and organic constituents that indicate the presence of wastewater. On the basis of a simple two-member mixing model, chloride, boron, ultraviolet absorbance at 254 nanometers, and excitation-emission fluorescence yielded the most reasonable estimates of wastewater percentages in the production wells. Tritium/helium-3 age determinations indicated that samples of ground water tested range in age from less than 2 to more than 50 years. Chloride and boron concentrations, along with tritium/helium-3 age determinations, indicate more rapid recharge and (or) displacement of pre-existing ground water at the San Gabriel Coastal Basin Spreading Grounds than at the Rio Hondo Coastal Basin Spreading Grounds. Nitrogen-15 enrichment of the ground-water nitrate and dissolved nitrogen indicates that denitrification, an important process for the removal of nitrate at the shallower depths beneath the spreading grounds, continues to occur at distances of several miles from the spreading grounds and over a period of many years. Analysis of dissolved gases shows that areas that contain recycled water have no detectable methane, whereas methane is present in the native ground water older than 50 years. The absence of methane in the younger ground water suggests that artificial recharge using recycled water has the desirable effect of increasing slightly the redox potential of the ground-water basin. Finally, measured chlorofluorocarbon concentrations and tritium/helium-3 age determinations indicate that chlorofluorocarbon concentrations are markedly elevated above atmosphere-water equilibrium in ground water older than about 20 years but still young enough to contain recycled water.