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James F. Pankow

Publications and source records attributed to James F. Pankow.

8 recordsLinked to original sources
USGS2020

Daily stream samples reveal highly complex pesticide occurrence and potential toxicity to aquatic life

Transient, acutely toxic concentrations of pesticides in streams can go undetected by fixed-interval sampling programs. Here we compare temporal patterns in occurrence of current-use pesticides in daily composite samples to those in weekly composite and weekly discrete samples of surface water from 14 small stream sites. Samples were collected over 10–14 weeks at 7 stream sites in each of the Midwestern and Southeastern United States. Samples were analyzed for over 200 pesticides and degradates by direct aqueous injection liquid chromatography with tandem mass spectrometry. Nearly 2 and 3 times as many unique pesticides were detected in daily samples as in weekly composite and weekly discrete samples, respectively. Based on exceedances of acute-invertebrate benchmarks (AIB) and(or) a Pesticide Toxicity Index (PTI) >1, potential acute-invertebrate toxicity was predicted at 11 of 14 sites from the results for daily composite samples, but was predicted for only 3 sites from weekly composites and for no sites from weekly discrete samples. Insecticides were responsible for most of the potential invertebrate toxicity, occurred transiently, and frequently were missed by the weekly discrete and composite samples. The number of days with benthic-invertebrate PTI ≥0.1 in daily composite samples was inversely related to Ephemeroptera, Plecoptera, and Trichoptera (EPT) richness at the sites. The results of the study indicate that short-term, potentially toxic peaks in pesticides frequently are missed by weekly discrete sampling, and that such peaks may contribute to degradation of invertebrate community condition in small streams. Weekly composite samples underestimated maximum concentrations and potential acute-invertebrate toxicity, but to a lesser degree than weekly discrete samples, and provided a reasonable approximation of the 90th percentile total concentrations of herbicides, insecticides, and fungicides, suggesting that weekly composite sampling may be a compromise between assessment needs and cost.

Science of the Total Environment↗
USGS2014

The atmosphere can be a source of certain water soluble volatile organic compounds in urban streams

Surface water and air volatile organic compound (VOC) data from 10 U.S. Geological Survey monitoring sites were used to evaluate the potential for direct transport of VOCs from the atmosphere to urban streams. Analytical results of 87 VOC compounds were screened by evaluating the occurrence and detection levels in both water and air, and equilibrium concentrations in water (C w s ) based on the measured air concentrations. Four compounds (acetone, methyl tertiary butyl ether, toluene, and m - & p -xylene) were detected in more than 20% of water samples, in more than 10% of air samples, and more than 10% of detections in air were greater than long-term method detection levels (LTMDL) in water. Benzene was detected in more than 20% of water samples and in more than 10% of air samples. Two percent of benzene detections in air were greater than one-half the LTMDL in water. Six compounds (chloroform, p-isopropyltoluene, methylene chloride, perchloroethene, 1,1,1-trichloroethane, and trichloroethene) were detected in more than 20% of water samples and in more than 10% of air samples. Five VOCs, toluene, m - & p -xylene, methyl tert-butyl ether (MTBE), acetone, and benzene were identified as having sufficiently high concentrations in the atmosphere to be a source to urban streams. MTBE, acetone, and benzene exhibited behavior that was consistent with equilibrium concentrations in the atmosphere.

Journal of the American Water Resources Associatio↗
USGS2007

Comparison of downhole and surface sampling for the determination of volatile organic compounds (VOCs) in ground water

The relative precision and accuracy of sampling and analysis methods for the determination of trace concentrations of volatile organic compounds (VOCs) in ground water were compared. Samples were collected from a well containing nanogram‐per‐liter (ng/L) to microgram‐per‐liter (μg/L) levels of VOCs. A Keck helical rotor submersible pump was used to collect samples at the surface for analysis by purge and trap (P&T) and for analysis by adsorption/thermal desorption (ATD). Downhole samples were collected by passing water through an ATD cartridge. Although slight spontaneous bubble outgassing occurred when the water was brought to the surface, the relative precisions and comparabilities of the surface and downhole methods were generally found to be equivalent from a statistical point of view. A main conclusion of this study is that bringing sample water to the surface for placement in VOC vials (and subsequent analysis by P&T) can be done reliably under many circumstances. However, care must still be taken to prevent adsorption losses and cross contamination. Samples subject to strong bubble outgassing will need to be handled in a special fashion (e.g., by downhole ATD) to minimize volatilization losses. Additionally, the higher sensitivity of the ATD method allows lower detection limits than are possible with P&T. For example, several compounds present at the ng/L level could be determined with confidence by ATD, but not by P&T.

New Jersey↗
USGS2007

Effects of sample isolation and handling on the recovery of purgeable organic compounds

This report compares the recovery of purgeable organic compounds (POCs) obtained by using a downhole isobaric sampler developed by the U.S. Geological Survey, a helical-rotor submersible pump, and a point source bailer to collect and isolate samples of ground water from three wells in Now York and New Jersey: the samples contained a total of 13 PCX's delectable at concentrations ranging from 0.5 μg/L to about 400 μg/L. This report also compares the effects of sample handling, specifically the differences in PCX concentration recovery when an isobaric sample container is filled at land surface vs. when it is filled downhole. and when samples art taken using a bailer with and without a bottom-emptying device. These case studies are used to quantify the possible effects of different sample-isolation find sample-handling techniques on POC recovery. The relative effectiveness of the three devices varied by site and by compound. Overall, the POC recoveries achieved by using the helical-rotor submersible pump and the downlink isobaric sampler were not significantly different at the 95 percent confidence, level. POC recovery obtained by using the point source bailer was 11 percent lower overall. The downhole isobaric sampler results exhibited smaller coefficients of variation than did the helical-rotor submersible pump or the point-source bailer results. However, the differences between the coefficients of variation of the downhole isobaric sampler and those of the helical-rotor submersible pump were not significant at the 95 percent confidence level. The nonsignificant smaller coefficient of variation of the downhole isobaric sampler apparently resulted from two fewer sample handling steps that exposed the sample water to ambient air. An independent experiment performed with a different downhole sampler at one of the wells used in this investigation produced a similar statistical result. Also, the POC recovery obtained by pouring sample water out the lop of a point source bailer into 40-mL vials was S percent lower than that obtained by filling vials from a bailer with a bottom-emptying device.

Ground Water Monitoring and Remediation↗
USGS2007

Fate of MTBE relative to benzene in a gasoline-contaminated aquifer (1993-98):

Methyl tert -butyl ether (MTBE) and benzene have been measured since 1993 in a shallow, sandy aquifer contaminated by a mid-1980s release of gasoline containing fuel oxygenates. In wells downgradient of the release area, MTBK was detected before benzene, reflecting a chromatographic-like separation of these compounds in the direction of ground water flow. Higher concentrations of MTBE and benzene were measured in the deeper sampling ports of multilevel sampling wells located near the release area, and also up to 10 feet (3 m) below the water table surface in nested wells located farther from the release area. This distribution of higher concentrations at depth is caused by recharge events that deflect originally horizontal ground water flowlines. In the laboratory, microcosms containing aquifer material incubated with uniformly labeled 14 C-MTBE under aerobic and anaerobic. Fe(III)-reducing conditions indicated a low but measurable biodegradation potential (<3% 14 C-MTBW as 14 CO 2 ) after a seven-month incubation period, Tert -butyl alcohol (TBA), a proposed microbial-MTBE transformation intermediate, was detected in MTBE-contaminated wells, but TBA was also measured in unsaturated release area sediments. This suggests that TBA may have been present in the original fuel spilled and does not necessarily reflect microbial degradation of MTBE. Combined, these data suggest that milligram per liter to microgram per liter decreases in MTBE concentrations relative to benzene are caused by the natural attenuation processes of dilution and dispersion with less-contaminated ground water in the direction of flow rather than biodegradation at this point source gasoline release site.

Groundwater Monitoring & Remediation↗
USGS1999

Hydrolysis of tert-butyl formate: Kinetics, products, and implications for the environmental impact of methyl tert-butyl ether

Asessing the environmental fate of methyl tert -butyl ether (MTBE) has become a subject of renewed interest because of the large quantities of this compound that are being used as an oxygenated additive in gasoline. Various studies on the fate of MTBE have shown that it can be degraded to tert -butyl formate (TBF), particularly in the atmosphere. Although it is generally recognized that TBF is subject to hydrolysis, the kinetics and products of this reaction under environmentally relevant conditions have not been described previously. In this study, we determined the kinetics of TBF hydrolysis as a function of pH and temperature. Over the pH range of 5 to 7, the neutral hydrolysis pathway predominates, with k N = (1.0 ± 0.2) × 10 −6 /s. Outside this range, strong pH effects were observed because of acidic and basic hydrolyses, from which we determined that k A = (2.7 ± 0.5) × 10 −3 /(M·s) and k B = 1.7 ± 0.3/(M·s). Buffered and unbuffered systems gave the same hydrolysis rates for a given pH, indicating that buffer catalysis was not significant under the conditions tested. The activation energies corresponding to k N , k A , and k B were determined to be 78 ± 5, 59 ± 4, and 88 ±11 kJ/mol, respectively. In all experiments, tert -butyl alcohol was found at concentrations corresponding to stoichiometric formation from TBF. Based on our kinetics data, the expected half-life for hydrolysis of TBF at pH = 2 and 4°C (as per some standard preservation protocols for water sampling) is 6 h. At neutral pH and 22°C, the estimated half-life is 5 d, and at pH = 11 and 22°C, the value is only 8 min.

Environmental Toxicology and Chemistry↗
USGS1996

Environmental behavior and fate of methyl tert-butyl ether (MTBE)

When gasoline that has been oxygenated with methyl tert-butyl ether (MTBE) comes in contact with water, large amounts of MTBE can dissolve; at 25 degrees Celsius the water solubility of MTBE is about 5,000 milligrams per liter for a gasoline that is 10 percent MTBE by weight. In contrast, for a nonoxygenated gasoline, the total hydrocarbon solubility in water is typically about 120 milligrams per liter. MTBE sorbs only weakly to soil and aquifer materials; therefore, sorption will not significantly retard MTBE's transport by ground water. In addition, MTBE generally resists degradation in ground water. The half-life of MTBE in the atmosphere can be as short as 3 days in a regional airshed. MTBE in the air tends to partition into atmospheric water, including precipitation. However, washout of gas-phase MTBE by precipitation would not, by itself, greatly alter the gas-phase concentration of the compound in the air. The partitioning of MTBE to precipitation is nevertheless strong enough to allow for up to 3 micrograms per liter or more inputs of MTBE to surface and ground water.

Fact Sheet↗