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The potential impact of rapid development of unconventional oil and natural gas resources using hydraulic fracturing and horizontal drilling on regional groundwater quality has received significant attention. Major concerns are methane or oil/gas related hydrocarbon (such as TPHs, BTEX including benzene, toluene, ethybenzene and xylene) leaks into the aquifer due to the failure of casing and/or stray gas migration. Previously, we investigated the relationship between oil and gas activity and dissolved methane concentration in a drinking water aquifer with the major finding being the presence of thermogenic methane contamination, but did not find detectable concentrations of TPHs or BTEX. To understand if aqueous and gas phases from the producing formation were transported concurrently to drinking water aquifers without the presence of oil/gas related hydrocarbons, the ionic composition of three water groups was studied: (1) uncontaminated deep confined aquifer, (2) suspected contaminated groundwater - deep confined aquifer containing thermogenic methane, and (3) produced water from nearby oil and gas wells that would represent aqueous phase contaminants. On the basis of quantitative and spatial analysis, we identified that the "thermogenic methane contaminated" groundwater did not have similarities to produced water in terms of ionic character (e.g. Cl/TDS ratio), but rather to the "uncontaminated" groundwater. The analysis indicates that aquifer wells with demonstrated gas phase contamination have not been contacted by an aqueous phase from oil and gas operations according to the methodology we use in this study and the current groundwater quality data from COGCC. However, the research does not prove conclusively that this the case. The results may provide insight on contamination mechanisms since improperly sealed well casing may result in stray gas but not aqueous phase transport.

The purpose of this study was to quantify antibiotic resistance genes (ARG) in the sediments of the mixed-landscape Cache La Poudre River, which has previously been studied and shown to have high concentrations of antibiotics related to urban and agricultural activities. River sediments were sampled during two events (high-flow and low-flow) from five sites with varying urban and agricultural impact levels. Polymerase-chain-reaction (PCR) detection assays were conducted for four sulfonamide resistance gene families, using newly designed primers, and five tetracycline resistance gene families, using previously published primers. Sul(I), sul(II), tet(W), and tet(O) gene families were further quantified by real-time quantitative polymerase chain reaction (Q-PCR). Resistance to four classes of antibiotics (tetracyclines, sulfonamides, ionophores, and macrolides) was also investigated using a culture-based approach. The quantities of resistance genes normalized to the 16S gene copy number were significantly different between the sites, with higher resistance gene concentrations at the impacted sites than at the pristine site. Total resistant CFUs were over an order of magnitude lower at the pristine site, but differences were less apparent when normalized to the total CFUs. Six tetracyclines and six sulfonamides were also quantified in the sediments and were found to be highest at sites impacted by urban and agricultural activity, with no antibiotics detected at the pristine sit. To the knowledge of the authors, this study is the first to demonstrate a relationship between urban and agricultural activity and microbial resistance in river sediments using quantitative molecular tools.

Analytical methods for quantifying three ionophore antibiotics, monensin, salinomycin, and narasin, were developed for water and sediment matrices. Sample preparation was based on solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS) was used to separate and detect the compounds. Recoveries ranged from 83% to 117% for water and from 51% to 105% for sediment in three different concentrations with less than 10% of relative standard deviation. The statistical detection limit was 0.001-0.003 microg/L for water and 0.4-3.6 microg/kg for sediment. Ionophore antibiotics are only used to treat coccidiostats for broilers or turkeys, and to increase growth and feed efficiency for beef and dairy cattle. Since they are not used for human purposes, these compounds can act as markers for the transport of animal pharmaceuticals to the watershed. The occurrence of three ionophore compounds was determined at five sampling sites along the Cache la Poudre River in Northern Colorado representing pristine, urban, and agriculture landscapes. Statistical analysis demonstrates that the measured concentration was significantly different among sampling sites in different sampling events for both water and sediment. In addition, significant differences were observed among different sampling times at each sampling site. Furthermore, all three ionophores were found in the sediments at much higher concentrations than in water indicating the importance of this matrix when determining environmental impacts.

Antibiotics are one of a group of pharmaceutical compounds that have been found in lakes and streams throughout the world and the occurrence of these compounds in the environment has raised concerns regarding the toxicity to aquatic organisms and the emergence of strains of antibiotic-resistant bacteria. The objective of this study was to assess the use of a relatively simple coupled solid-phase extraction (SPE)/radioimmunoassay (RIA) method for screening and/or monitoring tetracycline (TC) and sulfonamide (SA) compounds in water. Cross-reactivity of TCs and SAs was used to determine the specificity of the assays. The results indicate that TC, oxytetracycline (OTC), chlortetracycline (CTC) of the investigated 5 TCs, and sulfamethazine (SMT), sulfamethoxazole (SMX), sulfadimethoxane (SDM) and sulfathiazole (STZ) of the investigated 6 SAs in water matrix cross-react to a similar degree within each family in RIA and SPE/RIA. Water samples were collected across a watershed in northern Colorado in addition to the influent and effluent of a wastewater treatment plant. SPE/RIA analysis of these samples was compared with SPE/liquid chromatography (LC)-mass spectrometry (MS) quantification of 5 TC and 6 SA compounds. Results of the study indicate that SPE/RIA can be an effective technique for monitoring antibiotic compounds in waters suspected to be contaminated with these compounds. The coupled method provides a sufficiently low detection limit (0.05 microg/L) to screen large sample sets at environmentally relevant concentrations. The method provides a semi-quantitative composite measurement of similar compounds in an antibiotic family without complex and expensive analytical equipment.

This study investigated the floc formation and re-aggregation potential for alum, polyaluminum chloride (PACl) and a blend of these coagulants. Bench-scale testing included floc morphology characterization for well-developed floc, post-shear floc, and non-settleable (filter influent) floc. Different applications of coagulants were observed to produce non-settleable floc that was morphologically different. The alum treatment had a decrease in average floc size from coagulated to non-settleable conditions, whereas the PACl and PACl/alum treatments resulted in similar sized floc between these processes. Zeta potential distribution measurements showed that the alum treatment resulted in a negative shift from coagulated to non-settleable conditions whereas the PACl and PACl/alum treatments had no significant shift. A photometric dispersion analyzer (PDA) was employed to compare the differences between coagulant treatments with respect to shear induced aggregate breakup and recovery. The PDA allowed a dynamic monitoring of initial floc aggregation and measured the degree of recovery from cyclic shearing. The degree of recovery from shearing was greatest for the PACl/alum treatment likely as a result of increased collision efficiency due to more effective charge neutralization.

A river along the semi-arid Front Range of Colorado was monitored for antibiotics including five tetracycline and six sulfonamide compounds. Existing analytical methods were adapted to measure these compounds in a surface water matrix at environmentally relevant concentrations (0.05 microg/L). Natural organic matter present in surface waters was confirmed to significantly impact the low-level analysis of tetracyclines (TCs) necessitating the use of standard addition quantification techniques. Five sites along the Cache la Poudre River were monitored for antibiotics encompassing pristine areas without anthropogenic influence, urban areas impacted by wastewater discharges and agricultural areas susceptible to non-point source contaminant runoff. The only site at which no antibiotics were detected was the pristine site in the mountains before the river had encountered urban or agricultural landscapes. By the time the river had exited the urban area, 6 of the 11 antibiotic compounds that were monitored were found in the samples. At Site 5, which had both urban and agricultural influences all five of the TCs monitored were detected indicating both urban and agricultural influences. The concentration of TCs at Site 5 ranged from 0.08 to 0.30 microg/L.

The formation of soluble microbial products (SMPs) during a drinking water ozone-biofiltration process was estimated using two approaches. First, a model was developed that related the assimilation of biodegradable organic matter (BOM) to the accumulation of biomass on filter media. The model was calibrated with data from a regularly backwashed, pilot scale biofilter that approximated a steady-state plug flow reactor. The second approach was a direct measurement of SMP concentrations, accomplished by applying a synthetic water comprised of known compounds to a bio-acclimated filter. The SMP concentration was estimated by determining the difference between known-compound removal (on a carbon basis) and dissolved organic carbon (DOC) removal. Comparable results were obtained from both approaches. SMPs were found to be important relative to the carbon removal that is typically measured (DOC), indicating that this measurement can significantly underestimate the actual BOM removal (17–33% in this research). The concentration of SMPs was negligible relative to the filter effluent DOC pool.