Jonathan D. Karr

Increased stray gas abundance in a subset of drinking water wells near Marcellus shale gas extraction

Horizontal drilling and hydraulic fracturing are transforming energy production, but their potential environmental effects remain controversial. We analyzed 141 drinking water wells across the Appalachian Plateaus physiographic province of northeastern Pennsylvania, examining natural gas concentrations and isotopic signatures with proximity to shale gas wells. Methane was detected in 82% of drinking water samples, with average concentrations six times higher for homes <1 km from natural gas wells (P = 0.0006). Ethane was 23 times higher in homes <1 km from gas wells (P = 0.0013); propane was detected in 10 water wells, all within approximately 1 km distance (P = 0.01). Of three factors previously proposed to influence gas concentrations in shallow groundwater (distances to gas wells, valley bottoms, and the Appalachian Structural Front, a proxy for tectonic deformation), distance to gas wells was highly significant for methane concentrations (P = 0.007; multiple regression), whereas distances to valley bottoms and the Appalachian Structural Front were not significant (P = 0.27 and P = 0.11, respectively). Distance to gas wells was also the most significant factor for Pearson and Spearman correlation analyses (P < 0.01). For ethane concentrations, distance to gas wells was the only statistically significant factor (P < 0.005). Isotopic signatures (δ13C-CH4, δ13C-C2H6, and δ2H-CH4), hydrocarbon ratios (methane to ethane and propane), and the ratio of the noble gas 4He to CH4 in groundwater were characteristic of a thermally postmature Marcellus-like source in some cases. Overall, our data suggest that some homeowners living <1 km from gas wells have drinking water contaminated with stray gases.

Mapping urban pipeline leaks: methane leaks across Boston.

Natural gas is the largest source of anthropogenic emissions of methane (CH(4)) in the United States. To assess pipeline emissions across a major city, we mapped CH(4) leaks across all 785 road miles in the city of Boston using a cavity-ring-down mobile CH(4) analyzer. We identified 3356 CH(4) leaks with concentrations exceeding up to 15 times the global background level. Separately, we measured δ(13)CH(4) isotopic signatures from a subset of these leaks. The δ(13)CH(4) signatures (mean = -42.8‰ ± 1.3‰ s.e.; n = 32) strongly indicate a fossil fuel source rather than a biogenic source for most of the leaks; natural gas sampled across the city had average δ(13)CH(4) values of -36.8‰ (± 0.7‰ s.e., n = 10), whereas CH(4) collected from landfill sites, wetlands, and sewer systems had δ(13)CH(4) signatures ~20‰ lighter (μ = -57.8‰, ± 1.6‰ s.e., n = 8). Repairing leaky natural gas distribution systems will reduce greenhouse gas emissions, increase consumer health and safety, and save money.

Stable carbon and oxygen isotope ratios of otoliths differentiate juvenile winter flounder (Pseudopleuronectes americanus) habitats

The use of natural tags for identifying the source locations of individuals recruited to fish populations has become an important area of research in fisheries science. We used stable carbon (δ13C) and oxygen (δ18O) isotope ratios in otoliths to differentiate juvenile winter flounder (Pseudopleuronectes americanus) collected from locations along the coast of Rhode Island, USA. Sagittal otoliths from the flounder were analysed for δ13C and δ18O using isotope ratio mass spectrometry. Plots of δ13C v. δ18O and discriminant function analysis (DFA) indicated differences among samples from Narragansett Bay, the coastal ponds and the Narrow River. Separations were observed among fish from the upper, middle and lower portions of Narragansett Bay and along the salinity gradient in Narrow River. Otoliths from sites grouped on the basis of low, medium and high salinities also showed differences according to DFA. Correlation analysis indicated a significant negative relationship (r = –0.60, P = 0.009) between seawater temperature and δ18O, and a significant positive relationship (r = 0.93, P < 0.001) between salinity and δ18O for the combined dataset. These results indicate that δ13C and δ18O values of juvenile winter flounder otoliths may prove useful for differentiating individuals from various juvenile habitats.

N 2 fixation estimates in real-time by cavity ring-down laser absorption spectroscopy

The most common currency for estimating N2 fixation is acetylene reduction to ethylene. Real-time estimates of nitrogen fixation are needed to close the global nitrogen budget and these remain a critical gap in both laboratory and field experiments. We present a new method for continuous real-time measurements of ethylene production: Acetylene Reduction Assays by Cavity ring-down laser Absorption Spectroscopy (ARACAS). In ARACAS, air in the headspace of an incubation chamber is circulated with a diaphragm pump through a cavity ring-down ethylene spectrometer and back to the incubation chamber. This paper describes the new approach and its benefits compared to the conventional detection of ethylene by flame ionization detector gas chromatography. First, the detection of acetylene reduction to ethylene is non-intrusive and chemically non-destructive, allowing for real-time measurements of nitrogenase activity. Second, the measurements are made instantaneously and continuously at ppb levels, allowing for observation of real-time kinetics on time intervals as short as a few seconds. Third, the instrument can be automated for long time periods of measurement. Finally, the technique will be widely accessible by the research community as it can be readily adapted to most existing acetylene reduction protocols and is based on a modestly priced, commercially available instrument. We illustrate its use for measuring N2 fixation using two species, the diazotrophic bacterium Azotobacter vinelandii and the lichen Peltigera praetextata. We also discuss potential limitations of the approach, primarily the implications of leaks in the analyzer, as well as future improvements.

Spatial and temporal trends in stable carbon and oxygen isotope ratios of juvenile winter flounder otoliths

Isotopic ratios of fish otoliths have been used in numerous studies as natural tags or markers to aid in the study of connectivity among fish populations. We investigated the use of spatial and temporal changes in the stable carbon and oxygen isotope ratios of otoliths to differentiate juvenile habitats of winter flounder (Pseudopleuronectes americanus). Young-of-the-year (YOY) juvenile winter flounder were collected annually over a three-year period from 18 stations along the coast of Rhode Island, USA. Sagittal otoliths were removed from fish and analyzed for stable carbon (13C/12C or δ13C) and oxygen (18O/16O or δ18O) isotope ratios using continuous flow isotope ratio mass spectrometry. Differences in isotope ratios were observed among stations and along salinity gradients in the Narragansett Bay estuary and an estuarine river system (Narrow River). Overall, the isotope ratio patterns observed among stations were consistent over the three sampling years; however, differences were noted in isotope ratios and the magnitude of the isotope ratio gradients among years. Significant positive correlations were noted between salinity and δ13C for two of the three years. For each of the three years sampled there was a highly significant positive correlation (2002, r = 0.93, P < 0.01; 2003, r = 0.85, P < 0.01; 2004, r = 0.97, P < 0.01) between δ18O and the salinity of the collection site. Also, there was a significant negative correlation between the number of months of above average river flow and δ18O for the three sampling years (r = 0.99, P < 0.05). These findings suggest that yearly changes in the volume of freshwater inputs to these estuarine habitats may be related to the differences observed in otolith δ18O isotope ratios. Because of these year-to-year differences, sampling of each cohort may be necessary in order to use this isotopic technique for winter flounder connectivity studies.