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Geology topics

E. Michael Thurman

Publications and source records attributed to E. Michael Thurman.

At least 19 recordsLinked to original sources

Wildfires: Identification of a new suite of aromatic polycarboxylic acids in ash and surface water

Ash and surface water samples collected after wildfires in four different geographical locations (California, Colorado, Kansas and Alberta) were analyzed. The ash samples were leached with deionized water, and leachates were concentrated by solid phase extraction and analyzed by liquid chromatography/time-of-flight mass spectrometry. In addition, three surface water samples and a lysimeter water sample were collected from watersheds recently affected by fire in California and Colorado, and analyzed in similar fashion. A suite of benzene polycarboxylic acids (BPCAs), with two and three carboxyl groups and their corresponding isomers were identified for the first time in both ash leachates and water samples. Also found was a pyridine carboxylic acid (PCA), 3,5-pyridine dicarboxylic acid. Furthermore, putative identifications were made for other carboxylated aromatic acids: quinolinic, naphthalenic, and benzofuranoic acid carboxylates. The wildfire ashes, a controlled wood ash, and post-fire surface water samples suggest that burned woody material, along with surface plant-material and heated o-horizon soil organic matter, contribute to both BPCAs and PCAs in runoff. This study is the first of its kind to identify this suite of aromatic acids in wildfire ash and surface water samples. These data make an important contribution to the nature of dissolved organic matter from wildfire and are useful to better understand the impact of wildfire on water quality and drinking water sources.

Science of the Total Environment

Organic chemical characterization and mass balance of a hydraulically fractured well: From fracturing fluid to produced water over 405 days

A long-term field study (405 days) of a hydraulically fractured well from the Niobrara Formation in the Denver-Julesburg Basin was completed. Characterization of organic chemicals used in hydraulic fracturing and their changes through time, from the preinjected fracturing fluid to the produced water, was conducted. The characterization consisted of a mass balance by dissolved organic carbon (DOC), volatile organic analysis by gas chromatography/mass spectrometry, and nonvolatile organic analysis by liquid chromatography/mass spectrometry. DOC decreased from 1500 mg/L in initial flowback to 200 mg/L in the final produced water. Only ∼11% of the injected DOC returned by the end of the study, with this 11% representing a maximum fraction returned since the formation itself contributes DOC. Furthermore, the majority of returning DOC was of the hydrophilic fraction (60–85%). Volatile organic compound analysis revealed substantial concentrations of individual BTEX compounds (0.1–11 mg/L) over the 405-day study. Nonvolatile organic compounds identified were polyethylene glycols (PEGs), polypropylene glycols (PPG), linear alkyl-ethoxylates, and triisopropanolamine (TIPA). The distribution of PEGs, PPGs, and TIPA and their ubiquitous presence in our samples and the literature illustrate their potential as organic tracers for treatment operations or in the event of an environmental spill.

Environmental Science & Technology

Characterization of hydraulic fracturing flowback water in Colorado: Implications for water treatment

A suite of analytical tools was applied to thoroughly analyze the chemical composition of an oil/gas well flowback water from the Denver–Julesburg (DJ) basin in Colorado, and the water quality data was translated to propose effective treatment solutions tailored to specific reuse goals. Analysis included bulk quality parameters, trace organic and inorganic constituents, and organic matter characterization. The flowback sample contained salts (TDS = 22,500 mg/L), metals (e.g., iron at 81.4 mg/L) and high concentration of dissolved organic matter (DOC = 590 mgC/L). The organic matter comprised fracturing fluid additives such as surfactants (e.g., linear alkyl ethoxylates) and high levels of acetic acid (an additives' degradation product), indicating the anthropogenic impact on this wastewater. Based on the water quality results and preliminary treatability tests, the removal of suspended solids and iron by aeration/precipitation (and/or filtration) followed by disinfection was identified as appropriate for flowback recycling in future fracturing operations. In addition to these treatments, a biological treatment (to remove dissolved organic matter) followed by reverse osmosis desalination was determined to be necessary to attain water quality standards appropriate for other water reuse options (e.g., crop irrigation). The study provides a framework for evaluating site-specific hydraulic fracturing wastewaters, proposing a suite of analytical methods for characterization, and a process for guiding the choice of a tailored treatment approach.

Colorado

Widespread occurrence of neuro-active pharmaceuticals and metabolites in 24 Minnesota rivers and wastewaters

Concentrations of 17 neuro-active pharmaceuticals and their major metabolites (bupropion, hydroxy-bupropion, erythro-hydrobupropion, threo-hydrobupropion, carbamazepine, 10,11,-dihydro-10,11,-dihydroxycarbamazepine, 10-hydroxy-carbamazepine, citalopram, N -desmethyl-citalopram, fluoxetine, norfluoxetine, gabapentin, lamotrigine, 2-N-glucuronide-lamotrigine, oxcarbazepine, venlafaxine and O-desmethyl-venlafaxine), were measured in treated wastewater and receiving surface waters from 24 locations across Minnesota, USA. The analysis of upstream and downstream sampling sites indicated that the wastewater treatment plants were the major source of the neuro-active pharmaceuticals and associated metabolites in surface waters of Minnesota. Concentrations of parent compound and the associated metabolite varied substantially between treatment plants (concentrations ± standard deviation of the parent compound relative to its major metabolite) as illustrated by the following examples; bupropion and hydrobupropion 700 ± 1000 ng L − 1 , 2100 ± 1700 ng L − 1 , carbamazepine and 10-hydroxy-carbamazepine 480 ± 380 ng L − 1 , 360 ± 400 ng L − 1 , venlafaxine and O -desmethyl-venlafaxine 1400 ± 1300 ng L − 1 , 1800 ± 2300 ng L − 1 . Metabolites of the neuro-active compounds were commonly found at higher or comparable concentrations to the parent compounds in wastewater effluent and the receiving surface water. Neuro-active pharmaceuticals and associated metabolites were detected only sporadically in samples upstream from the effluent outfall. Metabolite to parent ratios were used to evaluate transformation, and we determined that ratios in wastewater were much lower than those reported in urine, indicating that the metabolites are relatively more labile than the parent compounds in the treatment plants and in receiving waters. The widespread occurrence of neuro-active pharmaceuticals and metabolites in Minnesota effluents and surface waters indicate that this is likely a global environmental issue, and further understanding of the environmental fate and impacts of these compounds is warranted.

Minnesota

Endocrine active chemicals, pharmaceuticals, and other chemicals of concern in surface water, wastewater-treatment plant effluent, and bed sediment, and biological characteristics in selected streams, Minnesota: Design, methods, and data, 2009

This report presents the study design, environmental data, and quality-assurance data for an integrated chemical and biological study of selected streams or lakes that receive wastewater-treatment plant effluent in Minnesota. This study was a cooperative effort of the U.S. Geological Survey, the Minnesota Pollution Control Agency, St. Cloud State University, the University of St. Thomas, and the University of Colorado. The objective of the study was to identify distribution patterns of endocrine active chemicals, pharmaceuticals, and other organic and inorganic chemicals of concern indicative of wastewater effluent, and to identify biological characteristics of estrogenicity and fish responses in the same streams. The U.S. Geological Survey collected and analyzed water, bed-sediment, and quality-assurance samples, and measured or recorded streamflow once at each sampling location from September through November 2009. Sampling locations included surface water and wastewater-treatment plant effluent. Twenty-five wastewater-treatment plants were selected to include continuous flow and periodic release facilities with differing processing steps (activated sludge or trickling filters) and plant design flows ranging from 0.002 to 10.9 cubic meters per second (0.04 to 251 million gallons per day) throughout Minnesota in varying land-use settings. Water samples were collected from the treated effluent of the 25 wastewater-treatment plants and at one point upstream from and one point downstream from wastewater-treatment plant effluent discharges. Bed-sediment samples also were collected at each of the stream or lake locations. Water samples were analyzed for major ions, nutrients, trace elements, pharmaceuticals, phytoestrogens and pharmaceuticals, alkylphenols and other neutral organic chemicals, carboxylic acids, and steroidal hormones. A subset (25 samples) of the bed-sediment samples were analyzed for carbon, wastewater-indicator chemicals, and steroidal hormones; the remaining samples were archived. Biological characteristics were determined by using an in-vitro bioassay to determine total estrogenicity in water samples and a caged fish study to determine characteristics of fish from experiments that exposed fish to wastewater effluent in 2009. St. Cloud State University deployed and processed caged fathead minnows at 13 stream sites during September 2009 for the caged fish study. Measured fish data included length, weight, body condition factor, and vitellogenin concentrations.

Minnesota

Gas chromatographic–mass spectrometric fragmentation study of phytoestrogens as their trimethylsilyl derivatives: Identification in soy milk and wastewater samples

An analytical method for the identification of eight plant phytoestrogens (biochanin A, coumestrol, daidzein, equol, formononetin, glycitein, genistein and prunetin) in soy products and wastewater samples was developed using gas chromatography coupled with ion trap mass spectrometry (GC/MS–MS). The phytoestrogens were derivatized as their trimethylsilyl ethers with trimethylchlorosilane (TMCS) and N,O- bis (trimethylsilyl)trifluoroacetamide (BSTFA). The phytoestrogens were isolated from all samples with liquid–liquid extraction using ethyl acetate. Daidzein-d 4 and genistein-d 4 labeled standards were used as internal standards before extraction and derivatization. The fragmentation patterns of the phytoestrogens were investigated by isolating and fragmenting the precursor ions in the ion-trap and a typical fragmentation involved the loss of a methyl and a carbonyl group. Two characteristic fragment ions for each analyte were chosen for identification and confirmation. The developed methodology was applied to the identification and confirmation of phytoestrogens in soy milk, in wastewater effluent from a soy-milk processing plant, and in wastewater (influent and effluent) from a treatment plant. Detected concentrations of genistein ranged from 50,000 μg/L and 2000 μg/L in soy milk and in wastewater from a soy-plant, respectively, to 20 μg/L and <1 μg/L for influent and effluent from a wastewater treatment plant, respectively.

Journal of Chromatography A

Water-quality data for pharmaceuticals and other organic wastewater contaminants in ground water and in untreated drinking water sources in the United States, 2000-01

This report presents water-quality data from two nationwide studies on the occurrence and distribution of organic wastewater contaminants. These data are part of the continuing effort of the U.S. Geological Survey Toxic Substances Hydrology Program to collect baseline information on the environmental occurrence of pharmaceuticals and other organic wastewater contaminants. In 2000, samples were collected from 47 ambient ground-water sites (not drinking-water wells) in 18 states and analyzed for 65 organic wastewater contaminants. In the summer of 2001, samples were collected from 74 sources of raw, untreated, drinking water in 25 states and Puerto Rico and analyzed for 100 organic wastewater contaminants. These sources comprise 25 ground-water and 49 surface-water sources of drinking water serving populations ranging from one family to more than 8 million people. Site selection for both studies focused on areas known or suspected to contain sources of animal and/or human wastewater. The five most frequently detected compounds in samples collected from ambient ground-water sites are N,N-diethyltoluamide (35 percent, insect repellant), bisphenol A (30 percent, plasticizer), tri(2-chloroethy) phosphate (30 percent, fire retardant), sulfamethoxazole (23 percent, veterinary and human antibiotic), and 4-octylphenol monoethoxylate (19 percent, detergent metabolite). The five most frequently detected organic wastewater contaminants in samples of untreated drinking water from surface-water sources are cholesterol (59 percent, natural sterol), metolachlor (53 percent, herbicide), cotinine (51 percent, nicotine metabolite), &beta;-sitosterol (37 percent, natural plant sterol), and 1,7-dimethylxanthine (27 percent, caffeine metabolite). The five most frequently detected organic wastewater contaminants in samples of untreated drinking water from ground-water sources are tetrachloroethylene (24 percent, solvent), carbamazepine (20 percent, pharmaceutical), bisphenol A (20 percent, plasticizer), 1,7-dimethylxanthine (16 percent, caffeine metabolite), and tri(2-chloroethyl) phosphate (12 percent, fire retardant).

Open-File Report

Comparison of purge and trap GC/MS and purgeable organic chloride analysis for monitoring volatile chlorinated hydrocarbons

A combined field and laboratory study was conducted to compare purge and trap gas chromatography/mass spectrometry (PT‐GC/MS) and purgeable organic chloride (POC1) analysis for measuring volatile chlorinated hydro‐carbons (VCH) in ground water. Distilled‐water spike and recovery experiments using 10 VCH indicate that at concentrations greater than 1 /ig/1 recovery is more than 80 percent for both methods with relative standard deviations of about 10 percent. Ground‐water samples were collected from a site on Cape Cod, Massachusetts, where a shallow unconfined aquifer has been contaminated by VCH, and were analyzed by both methods. Results for PT‐GC/MS and POC1 analysis of the ground‐water samples were not significantly different (alpha = 0.05, paired t‐test analysis) and indicated little bias between the two methods. Similar conclusions about concentrations and distributions of VCH in the ground‐water contamination plume were drawn from the two data sets. However, only PT‐GC/MS analysis identified the individual compounds present and determined their concentrations, which was necessary for toxicological and biogeochemical evaluation of the contaminated ground water. POC1 analysis was a complimentary method for use with PT‐GC/MS analysis for identifying samples with VCH concentrations below the detection limit or with high VCH concentrations that require dilution. Use of POC1 as a complimentary monitoring method for PT‐GC/MS can result in more efficient use of analytical resources.

Ground Water

Response to comment on "Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: A national reconnaissance"

Till (1) raised concerns that several aspects of how we handled the data in our study (2) may have caused unintended bias. First, Till (1) considers the “median detectable concentrations” listed in Table 1 (2) to be misleading because “higher median concentrations than is actually the case” were suggested. We interpret this concern raised by Till (1) to be that some readers may misinterpret our median detectable concentration to be an overall median concentration. Our intention was to provide the reader with information that could not easily be determined independently. For example, by examining the frequency of detection (2), it could easily be determined that the overall median concentration was less than the reporting level for all but six compounds (those having a detection frequency of>50%). Our goal for providing a median detectable concentration was to give a better sense of the concentrations when a particular compound was detected. Thus, we felt the combination of frequency of detection (how often a compound was found), median detectable concentration (median concentration when a compound was detected), and maximum concentration (highest concentration measured) would provide the greatest benefit to the readers. In future reports, we will modify the table headings to ensure that overall median concentration and median detectable concentration are clearly differentiated.

Environmental Science & Technology

Response to comment on "Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: A national reconnaissance"

We concur with the response of Eckel to our recent publication in this Journal (1). As the author notes, the topic of emerging contaminants is currently receiving extensive media coverage and scientific notice, but there are earlier reports that foreshadow this current interest. Eckel’s comment regarding the detection of pharmaceuticals and other organic wastewater contaminants (OWC) at a Superfund landfill site (2) is well taken, as other reports confirm the presence of such compounds at waste-disposal and landfill sites (3). In fact, literature from more than 20 years ago documented the occurrence of OWCs in the environment (4-7). A significant difference between these reports and our study is that we have systematically documented the frequent presence and low concentrations of a broad suite of OWCs in a wide variety of streams across the United States.

Environmental Science & Technology

Response to comment on "Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: A national reconnaissance"

We thank Ericson et al. (1) for their careful review and thoughtful comments on the synthetic hormone data presented in our recent publication summarizing the results from the USGS nationwide reconnaissance for pharmaceuticals and other organic wastewater contaminants (2). Their efforts have helped raise the awareness of the difficulties in accurately measuring these compounds at the low concentrations that occur in the environment and reinforce the need for continued research in the area of analytical methods development for synthetic hormones

Environmental Science & Technology

Determination of alkylbenzenesulfonate surfactants in groundwater using macroreticular resins and carbon-13 nuclear magnetic resonance spectrometry

Alkylbenzenesulfonate surfactants were determined in groundwater at concentrations as low as 0.3 mg/L. The method uses XAD-8 resin for concentration, followed by elution with methanol, separation of anionic and nonionic surfactants by anion exchange, quantitation by titration, and identification by 13C nuclear magnetic resonance spectrometry. Laboratory standards and field samples containing straight-chain and branched-chain alkylbenzenesulfonates, sodium dodecyl sulfate, and alkylbenzene ethoxylates were studied. The XAD-8 extraction of surfactants from groundwater was completed in the field, which simplified sample preservation and reduced the cost of transporting samples.

Analytical Chemistry

A reconnaissance study of herbicides and their metabolites in surface water of the midwestern united states using immunoassay and gas chromatography/mass spectrometry

Preemergent herbicides and their metabolites, particularly atrazine, deethylatrazine, and metolachlor, persisted from 1989 to 1990 in the majority of rivers and streams in the midwestern United States. In spring, after the application of herbicides, the concentrations of atrazine, alachlor, and simazine were frequently 3-10 times greater than the U.S. Environmental Protection Agency maximum contaminant level (MCL). The concentration of herbicides exceeded the MCLs both singly and in combination. Two major degradation products of atrazine (deisopropylatrazine and deethylatrazine) also were found in many of the streams. The order of persistence of the herbicides and their metabolites in surface water was atrazine > deethylatrazine > metolachlor > alachlor > deisopropylatrazine > cyanazine. Storm runoff collected at several sites exceeded the MCL multiple times during the summer months as a function of stream discharge, with increased concentrations during times of increased streamflow. It is proposed that metabolites of atrazine may be used as indicators of surface-water movement into adjacent alluvial aquifers.

Environmental Science & Technology

Water-quality data for pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000

Water-quality data collected during 1999 and 2000 as part of the first nationwide reconnaissance of the occurrence of pharmaceuticals, hormones, and other organic wastewater contaminants (OWCs) are presented in this report. A network of 139 streams in 30 states were sampled and analyzed for 95 different OWCs using five new research methods developed by the U.S. Geological Survey. Site selection was biased toward streams more susceptible to OWC contamination because of proximity to urban areas or livestock production. At least one OWC was detected in 80% of the streams sampled, with 82 of the 95 analyzed OWCs determined in this study detected in at least one sample.

Open-File Report

Natural attenuation of chloroacetinilide herbicides in aquatic systems

Chloroacetanilide herbicides (e.g. alachlor and metolachlor) and their breakdown products are frequently found in agriculturally impacted and other natural waters. Although these compounds are usually present at low concentrations in aquatic systems, defining their fate and attenuation rate is important because they can be toxic at comparatively low exposure levels. This paper summarizes results from a four-year research program assessing factors that affect herbicide attenuation rates and breakdown product formation patterns in aquatic systems. Over 70 different field microcosms (11.3 m 3 cylindrical fiberglass tanks) were selectively manipulated (in replicate) to create nine unique aquatic ecosystems for this study. Alachlor and/or metolachlor were added to these units and transformations were observed over time. Alachlor half-lives ranged from 6.0 days to more than 100 days depending upon the temperature, oxygen conditions, and the nutrient conditions in the microcosm waters. The highest rates of alachlor decay were observed in warm, nutrient-rich, anaerobic water columns, whereas the lowest alachlor decay rates were observed under cooler, aerobic, oligotrophic water conditions. Similar relationships were observed for metolachlor, although metolachlor decay rates were about 40% slower. Our data suggest that herbicides will decay rapidly in waters that are high in nutrients possibly resulting from human activities. Alternately, low nutrient or pristine waters will have the lowest rates of herbicide decay. On a policy level, all efforts should be made to prevent exposure of comparatively pristine waters to herbicide inputs.

Conference Paper