Accuracy of self-reported distance to nearest unconventional oil and gas well in Pennsylvania, Ohio, and West Virginia residents and implications for exposure assessment.

Self-reported distances to industrial sources have been used in epidemiology as proxies for exposure to environmental hazards and indicators of awareness and perception of sources. Unconventional oil and gas development (UOG) emits pollutants and has been associated with adverse health outcomes. We compared self-reported distance to the nearest UOG well to the geographic information system-calculated distance for 303 Pennsylvania, Ohio, and West Virginia residents using Cohen's Weighted Kappa. Agreement was low (Kappa = 0.18), and self-reports by Ohioans (39% accuracy) were more accurate than West Virginians (22%) or Pennsylvanians (13%, both p < 0.05). Of the demographic characteristics studied, only educational attainment was related to reporting accuracy; residents with 12-16 years of education were more accurate (31.3% of group) than those with <12 or >16 years (both 16.7%). Understanding differences between objective and subjective measures of UOG proximity could inform studies of perceived exposures or risks and may also be relevant to adverse health effects. IMPACT: We compared objective and self-reported measures of distance to the nearest UOG well for 303 Appalachian Basin residents. We found that residents' self-reported distance to the nearest UOG well had limited agreement with the true calculated distance category. Our results can be used to inform the collection and contextualize the use of self-reported data in communities exposed to UOGD. Self-reported metrics can be used in conjunction with objective assessments and can be informative regarding how potentially exposed populations perceive environmental exposures or risks and could provide insights into awareness of distance-related policies, such as setbacks.

Predictors of early life residential mobility in urban and rural Pennsylvania children with acute lymphoblastic leukemia and implications for environmental exposure assessment.

BACKGROUND: Residential mobility can introduce exposure misclassification in pediatric epidemiology studies using birth address only. OBJECTIVE: We examined whether residential mobility varies by sociodemographic factors and urbanicity/rurality among children with cancer. METHODS: Our study included 400 children born in Pennsylvania during 2002-2015 and diagnosed with leukemia at ages 2-7 years. Addresses were obtained from state registries at birth and diagnosis. We considered three aspects of mobility between birth and diagnosis: whether a child moved, whether a mover changed census tract, and distance moved. We evaluated predictors of these aspects in urban- and rural-born children using chi-square, t-tests, and regression analyses. RESULTS: Overall, 58% of children moved between birth and diagnosis; suburban/rural-born children were more likely to move than urban-born children (67% versus 57%). The mean distance moved was 16.7 km in suburban/rural-born and 14.8 km in urban-born movers. In urban-born children, moving between birth and diagnosis was associated with race, education, participation in the Nutrition Program for Women, Infants and Children (WIC), and census tract-level income (all χ2 p < 0.01). Urban-born movers tended to be born in a census tract with a higher Social Vulnerability Index than non-movers (t-test p < 0.01). No factors were statistically significantly associated with any of the residential mobility metrics in suburban/rural-born children, although the sample size was small. IMPACT STATEMENT: In this study of a vulnerable population of children with cancer, we found that rural-born children were more likely to move than urban-born children, however, the frequency of movers changing census tracts was equivalent. Mobility in urban-born children, but not rural-born, was associated with several social factors, although the sample size for rural-born children was small. Mobility could be an important source of misclassification depending on the spatial heterogeneity and resolution of the exposure data and whether the social factors are related to exposures or health outcomes. Our results highlight the importance of considering differences in mobility between urban and rural populations in spatial research.

Investigation of Sources of Fluorinated Compounds in Private Water Supplies in an Oil and Gas-Producing Region of Northern West Virginia.

Per- and polyfluoroalkyl substances (PFASs) are a class of toxic organic compounds that have been widely used in consumer applications and industrial activities, including oil and gas production. We measured PFAS concentrations in 45 private wells and 8 surface water sources in the oil and gas-producing Doddridge, Marshall, Ritchie, Tyler, and Wetzel Counties of northern West Virginia and investigated relationships between potential PFAS sources and drinking water receptors. All surface water samples and 60% of the water wells sampled contained quantifiable levels of at least one targeted PFAS compound, and four wells (8%) had concentrations above the proposed maximum contaminant level (MCL) for perfluorooctanoic acid (PFOA). Individual concentrations of PFOA and perfluorobutanesulfonic acid exceeded those measured in finished public water supplies. Total targeted PFAS concentrations ranged from nondetect to 36.8 ng/L, with surface water concentrations averaging 4-fold greater than groundwater. Semiquantitative, nontargeted analysis showed concentrations of emergent PFAS that were potentially higher than targeted PFAS. Results from a multivariate latent variable hierarchical Bayesian model were combined with insights from analyses of groundwater chemistry, topographic characteristics, and proximity to potential PFAS point sources to elucidate predictors of PFAS concentrations in private wells. Model results reveal (i) an increased vulnerability to contamination in upland recharge zones, (ii) geochemical controls on PFAS transport likely driven by adsorption, and (iii) possible influence from nearby point sources.

Conventional Fossil Fuel Extraction, Associated Biogeochemical Processes, and Topography Influence Methane Groundwater Concentrations in Appalachia.

The production of fossil fuels, including oil, gas, and coal, retains a dominant share in US energy production and serves as a major anthropogenic source of methane, a greenhouse gas with a high warming potential. In addition to directly emitting methane into the air, fossil fuel production can release methane into groundwater, and that methane may eventually reach the atmosphere. In this study, we collected 311 water samples from an unconventional oil and gas (UOG) production region in Pennsylvania and an oil and gas (O&G) and coal production region across Ohio and West Virginia. Methane concentration was negatively correlated to distance to the nearest O&G well in the second region, but such a correlation was shown to be driven by topography as a confounding variable. Furthermore, sulfate concentration was negatively correlated with methane concentration and with distance to coal mining in the second region, and these correlations were robust even when considering topography. We hypothesized that coal mining enriched sulfate in groundwater, which in turn inhibited methanogenesis and enhanced microbial methane oxidation. Thus, this study highlights the complex interplay of multiple factors in shaping groundwater methane concentrations, including biogeochemical conversion, topography, and conventional fossil extraction.

Social Vulnerability and Groundwater Vulnerability to Contamination From Unconventional Hydrocarbon Extraction in the Appalachian Basin.

Unconventional oil and gas (UOG) development, made possible by horizontal drilling and high-volume hydraulic fracturing, has been fraught with controversy since the industry's rapid expansion in the early 2000's. Concerns about environmental contamination and public health risks persist in many rural communities that depend on groundwater resources for drinking and other daily needs. Spatial disparities in UOG risks can pose distributive environmental injustice if such risks are disproportionately borne by marginalized communities. In this paper, we analyzed groundwater vulnerability to contamination from UOG as a physically based measure of risk in conjunction with census tract level sociodemographic characteristics describing social vulnerability in the northern Appalachian Basin. We found significant associations between elevated groundwater vulnerability and lower population density, consistent with UOG development occurring in less densely populated rural areas. We also found associations between elevated groundwater vulnerability and lower income, higher proportions of elderly populations, and higher proportion of mobile homes, suggesting a disproportionate risk burden on these socially vulnerable groups. We did not find a statistically significant association between elevated groundwater vulnerability and populations of racial/ethnic minorities in our study region. Household surveys provided empirical support for a relationship between sociodemographic characteristics and capacity to assess and mitigate exposures to potentially contaminated water. Further research is needed to probe if the observed disparities translate to differences in chemical exposure and adverse health outcomes.

Residential proximity to unconventional oil and gas development and birth defects in Ohio.

BACKGROUND: Chemicals used or emitted by unconventional oil and gas development (UOGD) include reproductive/developmental toxicants. Associations between UOGD and certain birth defects were reported in a few studies, with none conducted in Ohio, which experienced a thirty-fold increase in natural gas production between 2010 and 2020. METHODS: We conducted a registry-based cohort study of 965,236 live births in Ohio from 2010 to 2017. Birth defects were identified in 4653 individuals using state birth records and a state surveillance system. We assigned UOGD exposure based on maternal residential proximity at birth to active UOG wells and a metric specific to the drinking-water exposure pathway that identified UOG wells hydrologically connected to a residence ("upgradient UOG wells"). We estimated odds ratios (ORs) and 95% confidence intervals (CIs) for all structural birth defects combined and specific birth defect types using binary exposure metrics (presence/absence of any UOG well and presence/absence of an upgradient UOG well within 10 km), adjusting for confounders. Additionally, we conducted analyses stratified by urbanicity, infant sex, and social vulnerability. RESULTS: The odds of any structural defect were 1.13 times higher in children born to mothers living within 10 km of UOGD than those born to unexposed mothers (95%CI: 0.98-1.30). Odds were elevated for neural tube defects (OR: 1.57, 95%CI: 1.12-2.19), limb reduction defects (OR: 1.99, 95%CI: 1.18-3.35), and spina bifida (OR 1.93; 95%CI 1.25-2.98). Hypospadias (males only) was inversely related to UOGD exposure (OR: 0.62, 95%CI: 0.43-0.91). Odds of any structural defect were greater in magnitude but less precise in analyses using the hydrological-specific metric (OR: 1.30; 95%CI: 0.85-1.90), in areas with high social vulnerability (OR: 1.27, 95%CI: 0.99-1.60), and among female offspring (OR: 1.28, 95%CI: 1.06-1.53). CONCLUSIONS: Our results suggest a positive association between UOGD and certain birth defects, and findings for neural tube defects corroborate results from prior studies.

Unconventional Oil and Gas Development Exposure and Risk of Childhood Acute Lymphoblastic Leukemia: A Case-Control Study in Pennsylvania, 2009-2017.

BACKGROUND: Unconventional oil and gas development (UOGD) releases chemicals that have been linked to cancer and childhood leukemia. Studies of UOGD exposure and childhood leukemia are extremely limited. OBJECTIVE: The objective of this study was to evaluate potential associations between residential proximity to UOGD and risk of acute lymphoblastic leukemia (ALL), the most common form of childhood leukemia, in a large regional sample using UOGD-specific metrics, including a novel metric to represent the water pathway. METHODS: We conducted a registry-based case-control study of 405 children ages 2-7 y diagnosed with ALL in Pennsylvania between 2009-2017, and 2,080 controls matched on birth year. We used logistic regression to estimate odds ratios (ORs) and 95% confidence intervals (CIs) for the association between residential proximity to UOGD (including a new water pathway-specific proximity metric) and ALL in two exposure windows: a primary window (3 months preconception to 1 y prior to diagnosis/reference date) and a perinatal window (preconception to birth). RESULTS: Children with at least one UOG well within 2km of their birth residence during the primary window had 1.98 times the odds of developing ALL in comparison with those with no UOG wells [95% confidence interval (CI): 1.06, 3.69]. Children with at least one vs. no UOG wells within 2km during the perinatal window had 2.80 times the odds of developing ALL (95% CI: 1.11, 7.05). These relationships were slightly attenuated after adjusting for maternal race and socio-economic status [odds ratio (OR) =1.74 (95% CI: 0.93, 3.27) and OR=2.35 (95% CI: 0.93, 5.95)], respectively). The ORs produced by models using the water pathway-specific metric were similar in magnitude to the aggregate metric. DISCUSSION: Our study including a novel UOGD metric found UOGD to be a risk factor for childhood ALL. This work adds to mounting evidence of UOGD's impacts on children's health, providing additional support for limiting UOGD near residences. https://doi.org/10.1289/EHP11092.

Regional Scale Assessment of Shallow Groundwater Vulnerability to Contamination from Unconventional Hydrocarbon Extraction.

Concerns over unconventional oil and gas (UOG) development persist, especially in rural communities that rely on shallow groundwater for drinking and other domestic purposes. Given the continued expansion of the industry, regional (vs local scale) models are needed to characterize groundwater contamination risks faced by the increasing proportion of the population residing in areas that accommodate UOG extraction. In this paper, we evaluate groundwater vulnerability to contamination from surface spills and shallow subsurface leakage of UOG wells within a 104,000 km2 region in the Appalachian Basin, northeastern USA. We test a computationally efficient ensemble approach for simulating groundwater flow and contaminant transport processes to quantify vulnerability with high resolution. We also examine metamodels, or machine learning models trained to emulate physically based models, and investigate their spatial transferability. We identify predictors describing proximity to UOG, hydrology, and topography that are important for metamodels to make accurate vulnerability predictions outside their training regions. Using our approach, we estimate that 21,000-30,000 individuals in our study area are dependent on domestic water wells that are vulnerable to contamination from UOG activities. Our novel modeling framework could be used to guide groundwater monitoring, provide information for public health studies, and assess environmental justice issues.

Assessing Exposure to Unconventional Oil and Gas Development: Strengths, Challenges, and Implications for Epidemiologic Research.

PURPOSE OF REVIEW: Epidemiologic studies have observed elevated health risks in populations living near unconventional oil and gas development (UOGD). In this narrative review, we discuss strengths and limitations of UOG exposure assessment approaches used in or available for epidemiologic studies, emphasizing studies of children's health outcomes. RECENT FINDINGS: Exposure assessment challenges include (1) numerous potential stressors with distinct spatiotemporal patterns, (2) critical exposure windows that cover long periods and occur in the past, and (3) limited existing monitoring data coupled with the resource-intensiveness of collecting new exposure measurements to capture spatiotemporal variation. All epidemiologic studies used proximity-based models for exposure assessment as opposed to surveys, biomonitoring, or environmental measurements. Nearly all studies used aggregate (rather than pathway-specific) models, which are useful surrogates for the complex mix of potential hazards. Simple and less-specific exposure assessment approaches have benefits in terms of scalability, interpretability, and relevance to specific policy initiatives such as set-back distances. More detailed and specific models and metrics, including dispersion methods and stressor-specific models, could reduce exposure misclassification, illuminate underlying exposure pathways, and inform emission control and exposure mitigation strategies. While less practical in a large population, collection of multi-media environmental and biological exposure measurements would be feasible in cohort subsets. Such assessments are well-suited to provide insights into the presence and magnitude of exposures to UOG-related stressors in relation to spatial surrogates and to better elucidate the plausibility of observed effects in both children and adults.

Groundwaters in Northeastern Pennsylvania near intense hydraulic fracturing activities exhibit few organic chemical impacts.

Horizontal drilling with hydraulic fracturing (HDHF) relies on the use of anthropogenic organic chemicals in proximity to residential areas, raising concern for groundwater contamination. Here, we extensively characterized organic contaminants in 94 domestic groundwater sites in Northeastern Pennsylvania after ten years of activity in the region. All analyzed volatile and semi-volatile compounds were below recommended United States Environmental Protection Agency maximum contaminant levels, and integrated concentrations across two volatility ranges, gasoline range organic compounds (GRO) and diesel range organic compounds (DRO), were low (0.13 ± 0.06 to 2.2 ± 0.7 ppb and 5.2-101.6 ppb, respectively). Following dozens of correlation analyses with distance-to-well metrics and inter-chemical indicator correlations, no statistically significant correlations were found except: (1) GRO levels were higher within 2 km of violations and (2) correlation between DRO and a few inorganic species (e.g., Ba and Sr) and methane. The correlation of DRO with inorganic species suggests a potential high salinity source, whereas elevated GRO may result from nearby safety violations. Highest-concentration DRO samples contained bis-2-ethylhexyl phthalate and N,N-dimethyltetradecylamine. Nevertheless, the overall low rate of contamination for the analytes could be explained by a spatially-resolved hydrogeologic model, where estimated transport distances from gas wells over the relevant timeframes were short relative to the distance to the nearest groundwater wells. Together, the observations and modeled results suggest a low probability of systematic groundwater organic contamination in the region.

Assessing Unconventional Oil and Gas Exposure in the Appalachian Basin: Comparison of Exposure Surrogates and Residential Drinking Water Measurements.

Health studies report associations between metrics of residential proximity to unconventional oil and gas (UOG) development and adverse health endpoints. We investigated whether exposure through household groundwater is captured by existing metrics and a newly developed metric incorporating groundwater flow paths. We compared metrics with detection frequencies/concentrations of 64 organic and inorganic UOG-related chemicals/groups in residential groundwater from 255 homes (Pennsylvania n = 94 and Ohio n = 161). Twenty-seven chemicals were detected in ≥20% of water samples at concentrations generally below U.S. Environmental Protection Agency standards. In Pennsylvania, two organic chemicals/groups had reduced odds of detection with increasing distance to the nearest well: 1,2-dichloroethene and benzene (Odds Ratio [OR]: 0.46, 95% confidence interval [CI]: 0.23-0.93) and m- and p-xylene (OR: 0.28, 95% CI: 0.10-0.80); results were consistent across metrics. In Ohio, the odds of detecting toluene increased with increasing distance to the nearest well (OR: 1.48, 95% CI: 1.12-1.95), also consistent across metrics. Correlations between inorganic chemicals and metrics were limited (all |ρ| ≤ 0.28). Limited associations between metrics and chemicals may indicate that UOG-related water contamination occurs rarely/episodically, more complex metrics may be needed to capture drinking water exposure, and/or spatial metrics in health studies may better reflect exposure to other stressors.

Groundwater Methane in Northeastern Pennsylvania Attributable to Thermogenic Sources and Hydrogeomorphologic Migration Pathways.

Conflicting evidence exists as to whether or not unconventional oil and gas (UOG) development has enhanced methane transport into groundwater aquifers over the past 15 years. In this study, recent groundwater samples were collected from 90 domestic wells and 4 springs in Northeastern Pennsylvania located above the Marcellus Shale after more than a decade of UOG development. No statistically significant correlations were observed between the groundwater methane level and various UOG geospatial metrics, including proximity to UOG wells and well violations, as well as the number of UOG wells and violations within particular radii. The δ13C and methane-to-higher chain hydrocarbon signatures suggested that the elevated methane levels were not attributable to UOG development nor could they be explained by using simple biogenic-thermogenic end-member mixing models. Instead, groundwater methane levels were significantly correlated with geochemical water type and topographical location. Comparing a subset of contemporary methane measurements to their co-located pre-drilling records (n = 64 at 49 distinct locations) did not indicate systematic increases in methane concentration but did reveal several cases of elevated concentration (n = 12) across a spectrum of topographies. Multiple lines of evidence suggested that the high-concentration groundwater methane could have originated from shallow thermogenic methane that migrated upward into groundwater aquifers with Appalachian Basin brine.

Community concern and government response: Identifying socio-economic and demographic predictors of oil and gas complaints and drinking water impairments in Pennsylvania.

Oil and gas development has led to environmental hazards and community concerns, particularly in relation to water supply issues. Filing complaints with state agencies enables citizens to register concerns and seek investigations. We evaluated associations between county-level socio-economic and demographic factors, oil and gas drilling, and three outcomes in Pennsylvania between 2004-2016: number of oil and gas complaints filed, and both the number and proportion of state investigations of water supply complaints yielding a confirmed water supply impairment (i.e., "positive determination"). We used hierarchical Bayesian Poisson and binomial regression analyses. From 2004-2016, 9,404 oil and gas-related complaints were filed, of which 4,099 were water supply complaints. Of those, 3,906 received investigations, and 215 yielded positive determinations. We observed a 47% increase in complaints filed per $10,000 increase in annual median household income (MHI) (Rate Ratio [RR]: 1.47, 95% credible interval [CI]: 1.09-1.96) and an 18% increase per 1% increase in educational attainment (RR: 1.18, 95% CI: 1.11-1.26). While the number of complaints filed did not vary by race/ethnicity, the odds of a complaint yielding a positive determination were 0.81 times lower in counties with a higher proportion of marginalized populations (Odds Ratio [OR]: 0.81 per 1% increase in percent Black, Asian, and Native American populations combined, 95% CI: 0.64-0.99). The odds of positive determinations were also lower in areas with higher income (OR per $10,000 increase in MHI: 0.35, 95% CI: 0.09-0.96). Our results suggest these relationships are complex and may indicate potential environmental and procedural inequities, warranting further investigation.

Elucidating Environmental Fingerprinting Mechanisms of Unconventional Gas Development through Hydrocarbon Analysis.

Hydraulic fracturing is an increasingly common technique for the extraction of natural gas entrapped in shale formations. This technique has been highly criticized due to the possibility of environmental contamination, underscoring the need for method development to identify chemical factors that could be utilized in point-source identification of environmental contamination events. Here, we utilize comprehensive two-dimensional gas chromatography (GC × GC) coupled to high-resolution time-of-flight (HRT) mass spectrometry, which offers a unique instrumental combination allowing for petroleomics hydrocarbon fingerprinting. Four flowback fluids from Marcellus shale gas wells in geographic proximity were analyzed for differentiating factors that could be exploited in environmental forensics investigations of shale gas impacts. Kendrick mass defect (KMD) plots of these flowback fluids illustrated well-to-well differences in heteroatomic substituted hydrocarbons, while GC × GC separations showed variance in cyclic hydrocarbons and polyaromatic hydrocarbons among the four wells. Additionally, generating plots that combine GC × GC separation with KMD established a novel data-rich visualization technique that further differentiated the samples.

Unconventional Oil and Gas Spills: Risks, Mitigation Priorities, and State Reporting Requirements.

Rapid growth in unconventional oil and gas (UOG) has produced jobs, revenue, and energy, but also concerns over spills and environmental risks. We assessed spill data from 2005 to 2014 at 31 481 UOG wells in Colorado, New Mexico, North Dakota, and Pennsylvania. We found 2-16% of wells reported a spill each year. Median spill volumes ranged from 0.5 m3 in Pennsylvania to 4.9 m3 in New Mexico; the largest spills exceeded 100 m3. Seventy-five to 94% of spills occurred within the first three years of well life when wells were drilled, completed, and had their largest production volumes. Across all four states, 50% of spills were related to storage and moving fluids via flowlines. Reporting rates varied by state, affecting spill rates and requiring extensive time and effort getting data into a usable format. Enhanced and standardized regulatory requirements for reporting spills could improve the accuracy and speed of analyses to identify and prevent spill risks and mitigate potential environmental damage. Transparency for data sharing and analysis will be increasingly important as UOG development expands. We designed an interactive spills data visualization tool ( http://snappartnership.net/groups/hydraulic-fracturing/webapp/spills.html ) to illustrate the value of having standardized, public data.

Unconventional oil and gas spills: Materials, volumes, and risks to surface waters in four states of the U.S.

Extraction of oil and gas from unconventional sources, such as shale, has dramatically increased over the past ten years, raising the potential for spills or releases of chemicals, waste materials, and oil and gas. We analyzed spill data associated with unconventional wells from Colorado, New Mexico, North Dakota and Pennsylvania from 2005 to 2014, where we defined unconventional wells as horizontally drilled into an unconventional formation. We identified materials spilled by state and for each material we summarized frequency, volumes and spill rates. We evaluated the environmental risk of spills by calculating distance to the nearest stream and compared these distances to existing setback regulations. Finally, we summarized relative importance to drinking water in watersheds where spills occurred. Across all four states, we identified 21,300 unconventional wells and 6622 reported spills. The number of horizontal well bores increased sharply beginning in the late 2000s; spill rates also increased for all states except PA where the rate initially increased, reached a maximum in 2009 and then decreased. Wastewater, crude oil, drilling waste, and hydraulic fracturing fluid were the materials most often spilled; spilled volumes of these materials largely ranged from 100 to 10,000L. Across all states, the average distance of spills to a stream was highest in New Mexico (1379m), followed by Colorado (747m), North Dakota (598m) and then Pennsylvania (268m), and 7.0, 13.3, and 20.4% of spills occurred within existing surface water setback regulations of 30.5, 61.0, and 91.4m, respectively. Pennsylvania spills occurred in watersheds with a higher relative importance to drinking water than the other three states. Results from this study can inform risk assessments by providing improved input parameters on volume and rates of materials spilled, and guide regulations and the management policy of spills.

Hydrological and biogeochemical controls on watershed dissolved organic matter transport: pulse-shunt concept.

Hydrological precipitation and snowmelt events trigger large "pulse" releases of terrestrial dissolved organic matter (DOM) into drainage networks due to an increase in DOM concentration with discharge. Thus, low-frequency large events, which are predicted to increase with climate change, are responsible for a significant percentage of annual terrestrial DOM input to drainage networks. These same events are accompanied by marked and rapid increases in headwater stream velocity; thus they also "shunt" a large proportion of the pulsed DOM to downstream, higher-order rivers and aquatic ecosystems geographically removed from the DOM source of origin. Here we merge these ideas into the "pulse-shunt concept" (PSC) to explain and quantify how infrequent, yet major hydrologic events may drive the timing, flux, geographical dispersion, and regional metabolism of terrestrial DOM. The PSC also helps reconcile long-standing discrepancies in C cycling theory and provides a robust framework for better quantifying its highly dynamic role in the global C cycle. The PSC adds a critical temporal dimension to linear organic matter removal dynamics postulated by the river continuum concept. It also can be represented mathematically through a model that is based on stream scaling approaches suitable for quantifying the important role of streams and rivers in the global C cycle. Initial hypotheses generated by the PSC include: (1) Infrequent large storms and snowmelt events account for a large and underappreciated percentage of the terrestrial DOM flux to drainage networks at annual and decadal time scales and therefore event statistics are equally important to total discharge when determining terrestrial fluxes. (2) Episodic hydrologic events result in DOM bypassing headwater streams and being metabolized in large rivers and exported to coastal systems. We propose that the PSC provides a framework for watershed biogeochemical modeling and predictions and discuss implications to ecological processes.

Box-Counting Dimension Revisited: Presenting an Efficient Method of Minimizing Quantization Error and an Assessment of the Self-Similarity of Structural Root Systems.

Fractal dimension (FD), estimated by box-counting, is a metric used to characterize plant anatomical complexity or space-filling characteristic for a variety of purposes. The vast majority of published studies fail to evaluate the assumption of statistical self-similarity, which underpins the validity of the procedure. The box-counting procedure is also subject to error arising from arbitrary grid placement, known as quantization error (QE), which is strictly positive and varies as a function of scale, making it problematic for the procedure's slope estimation step. Previous studies either ignore QE or employ inefficient brute-force grid translations to reduce it. The goals of this study were to characterize the effect of QE due to translation and rotation on FD estimates, to provide an efficient method of reducing QE, and to evaluate the assumption of statistical self-similarity of coarse root datasets typical of those used in recent trait studies. Coarse root systems of 36 shrubs were digitized in 3D and subjected to box-counts. A pattern search algorithm was used to minimize QE by optimizing grid placement and its efficiency was compared to the brute force method. The degree of statistical self-similarity was evaluated using linear regression residuals and local slope estimates. QE, due to both grid position and orientation, was a significant source of error in FD estimates, but pattern search provided an efficient means of minimizing it. Pattern search had higher initial computational cost but converged on lower error values more efficiently than the commonly employed brute force method. Our representations of coarse root system digitizations did not exhibit details over a sufficient range of scales to be considered statistically self-similar and informatively approximated as fractals, suggesting a lack of sufficient ramification of the coarse root systems for reiteration to be thought of as a dominant force in their development. FD estimates did not characterize the scaling of our digitizations well: the scaling exponent was a function of scale. Our findings serve as a caution against applying FD under the assumption of statistical self-similarity without rigorously evaluating it first.

Colloid Mobilization in a Fractured Soil: Effect of Pore-Water Exchange between Preferential Flow Paths and Soil Matrix.

Exchange of water and solutes between contaminated soil matrix and bulk solution in preferential flow paths has been shown to contribute to the long-term release of dissolved contaminants in the subsurface, but whether and how this exchange can affect the release of colloids in a soil are unclear. To examine this, we applied rainfall solutions of different ionic strength on an intact soil core and compared the resulting changes in effluent colloid concentration through multiple sampling ports. The exchange of water between soil matrix and the preferential flow paths leading to each port was characterized on the basis of the bromide (conservative tracer) breakthrough time at the port. At individual ports, two rainfalls of a certain ionic strength mobilized different amounts of colloids when the soil was pre-exposed to a solution of lower or higher ionic strength. This result indicates that colloid mobilization depended on rainfall solution history, which is referred as colloid mobilization hysteresis. The extent of hysteresis was increased with increases in exchange of pore water and solutes between preferential flow paths and matrix. The results indicate that the soil matrix exchanged the old water from the previous infiltration with new infiltrating water during successive infiltration and changed the pore water chemistry in the preferential flow paths, which in turn affected the release of soil colloids. Therefore, rainfall solution history and soil heterogeneity must be considered to assess colloid mobilization in the subsurface. These findings have implications for the release of colloids, colloid-associated contaminants, and pathogens from soils.

Characterization and Analysis of Liquid Waste from Marcellus Shale Gas Development.

Hydraulic fracturing of shale for gas production in Pennsylvania generates large quantities of wastewater, the composition of which has been inadequately characterized. We compiled a unique data set from state-required wastewater generator reports filed in 2009-2011. The resulting data set, comprising 160 samples of flowback, produced water, and drilling wastes, analyzed for 84 different chemicals, is the most comprehensive available to date for Marcellus Shale wastewater. We analyzed the data set using the Kaplan-Meier method to deal with the high prevalence of nondetects for some analytes, and compared wastewater characteristics with permitted effluent limits and ambient monitoring limits and capacity. Major-ion concentrations suggested that most wastewater samples originated from dilution of brines, although some of our samples were more concentrated than any Marcellus brines previously reported. One problematic aspect of this wastewater was the very high concentrations of soluble constituents such as chloride, which are poorly removed by wastewater treatment plants; the vast majority of samples exceeded relevant water quality thresholds, generally by 2-3 orders of magnitude. We also examine the capacity of regional regulatory monitoring to assess and control these risks.