An exploratory study of air emissions associated with shale gas development and production in the Barnett Shale

Information regarding air emissions from shale gas extraction and production is critically important given production is occurring in highly urbanized areas across the United States. Objectives of this exploratory study were to collect ambient air samples in residential areas within 61 m (200 feet) of shale gas extraction/production and determine whether a “fingerprint” of chemicals can be associated with shale gas activity. Statistical analyses correlating fingerprint chemicals with methane, equipment, and processes of extraction/production were performed. Ambient air sampling in residential areas of shale gas extraction and production was conducted at six counties in the Dallas/Fort Worth (DFW) Metroplex from 2008 to 2010. The 39 locations tested were identified by clients that requested monitoring. Seven sites were sampled on 2 days (typically months later in another season), and two sites were sampled on 3 days, resulting in 50 sets of monitoring data. Twenty-four-hour passive samples were collected using summa canisters. Gas chromatography/mass spectrometer analysis was used to identify organic compounds present. Methane was present in concentrations above laboratory detection limits in 49 out of 50 sampling data sets. Most of the areas investigated had atmospheric methane concentrations considerably higher than reported urban background concentrations (1.8–2.0 ppm_v). Other chemical constituents were found to be correlated with presence of methane. A principal components analysis (PCA) identified multivariate patterns of concentrations that potentially constitute signatures of emissions from different phases of operation at natural gas sites. The first factor identified through the PCA proved most informative. Extreme negative values were strongly and statistically associated with the presence of compressors at sample sites. The seven chemicals strongly associated with this factor (o-xylene, ethylbenzene, 1,2,4-trimethylbenzene, m- and p-xylene, 1,3,5-trimethylbenzene, toluene, and benzene) thus constitute a potential fingerprint of emissions associated with compression.

Implications: Information regarding air emissions from shale gas development and production is critically important given production is now occurring in highly urbanized areas across the United States. Methane, the primary shale gas constituent, contributes substantially to climate change; other natural gas constituents are known to have adverse health effects. This study goes beyond previous Barnett Shale field studies by encompassing a wider variety of production equipment (wells, tanks, compressors, and separators) and a wider geographical region. The principal components analysis, unique to this study, provides valuable information regarding the ability to anticipate associated shale gas chemical constituents.     

Matrix Diffusion Modeling Applied to Long‐Term Pump‐and‐Treat Data: 2. Results From Three Sites

The data mining/groundwater modeling methodology developed in McDade et al. (2013) was performed to determine if matrix diffusion is a plausible explanation for the lower‐concentration but persistent chlorinated solvent plumes in the groundwater‐bearing units at three different pump‐and‐treat systems. Capture‐zone maps were evaluated, and eight wells were identified that did not draw water from any of the historical source areas but captured water from the sides of the plume. Two groundwater models were applied to study the persistence of the plumes in the absence of contributions from the historical source zones. In the wells modeled, the observed mass discharge generally decreased by about one order of magnitude or less over 4 to 10 years of pumping, and 1.8 to 17 pore volumes were extracted. In five of the eight wells, the matrix diffusion model fit the data much better than the advection dispersion retardation model, indicating that matrix diffusion better explains the persistent plume. In the three other wells, confounding factors, such as a changing capture zone over time (caused by changes in pumping rates in adjacent extraction wells); potential interference from a high‐concentration unremediated source zone; and limited number of pore volumes removed made it difficult to confirm that matrix diffusion processes were active in these areas. Overall, the results from the five wells indicate that mass discharge rates from the pumping wells will continue to show a characteristic “long tail'' of mass removal from zones affected by active matrix diffusion processes. Future site management activities should include matrix diffusion processes in the conceptual site models for these three sites. © 2013 Wiley Periodicals, Inc.     

The electron density distribution in pyridinium and bipyridylium compounds and its relevance to their adsorption by expanding lattice clays

Abstract

Charge distributions in 1, 1'‐ethylene‐2, 2'‐bipyridylium (diquat), 1,1'‐dimethyl‐4,4'‐bipyridylium (paraquat) and 1‐methylpyridinium organocations were calculated by a Complete Neglect of Differential Overlap semi‐empirical quantum mechanical procedure. The data show that the positive charges in the organocations are distributed around the molecules and are greatest in the positions ortho and para to the heterocyclic nitrogen atoms. Earlier interpretations of the mechanisms of adsorption of paraquat and diquat by soils and clays assumed that the charges were located in the heterocyclic nitrogen atoms. Here some consideration is given to the influence of the charge delocalizations on the processes of adsorption by montmorillonite and vermiculite clay preparations.     

Phosmet residues in an orchard and adjacent recreational area 1

Abstract

Two cover sprays of phosmet were applied to an orchard adjoining a camping area and a bird sanctuary with a resident goose population. Insecticide residues were monitored on orchard leaves, orchard ground cover, ground cover in the camp‐site and along the adjacent lakeshore. Despite attempts to minimize drift, significant spray residues were found outside the target area. Residues on ground cover and leaves were reduced by sprinkler irrigation subsequent to spray application.     

Integrating economic and biophysical data in assessing cost-effectiveness of buffer strip placement

The European Union Water Framework Directive (WFD) requires Member States to set water quality objectives and identify cost-effective mitigation measures to achieve "good status" in all waters. However, costs and effectiveness of measures vary both within and between catchments, depending on factors such as land use and topography. The aim of this study was to develop a cost-effectiveness analysis framework for integrating estimates of phosphorus (P) losses from land-based sources, potential abatement using riparian buffers, and the economic implications of buffers. Estimates of field-by-field P exports and routing were based on crop risk and field slope classes. Buffer P trapping efficiencies were based on literature metadata analysis. Costs of placing buffers were based on foregone farm gross margins. An integrated optimization model of cost minimization was developed and solved for different P reduction targets to the Rescobie Loch catchment in eastern Scotland. A target mean annual P load reduction of 376 kg to the loch to achieve good status was identified. Assuming all the riparian fields initially have the 2-m buffer strip required by the General Binding Rules (part of the WFD in Scotland), the model gave good predictions of P loads (345-481 kg P). The modeling results show that riparian buffers alone cannot achieve the required P load reduction (up to 54% P can be removed). In the medium P input scenario, average costs vary from ￡38 to ￡176 kg P at 10% and 54% P reduction, respectively. The framework demonstrates a useful tool for exploring cost-effective targeting of environmental measures.     

Temporal patterns of atmospheric mercury species in northern Mississippi during 2011–2012: Influence of sudden population swings

Gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate bound mercury (PBM) were measured on the University of Mississippi campus from July 2011 to June 2012. It is believed to be the first time that concentrations of atmospheric mercury species have been documented in northern Mississippi, and at a location with relatively large and sudden swings in population. The mean concentration (±1SD) of GEM was 1.54 ± 0.32 ng m⁻³; levels were lower and generally more stable during the winter (1.48 ± 0.22) and spring (1.46 ± 0.27) compared with the summer (1.56 ± 0.32) and fall (1.63 ± 0.42). Mean concentrations for GOM and PBM were 3.87 pg m⁻³ and 4.58 pg m⁻³, respectively; levels tended to be highest in the afternoon and lowest in the early morning hours. During the fall and spring academic semesters concentrations and variability of GOM and PBM both increased, possibly from vehicle exhaust. There were moderate negative correlations with wind speed (all species) and humidity (GOM and PBM). Backward air mass trajectory modeling for the ten highest peaks for each mercury species revealed that the majority of these events occurred from air masses that passed through the northern continental US region. Overall, this study illustrates the complexity of temporal fluctuations of airborne mercury species, even in a small town environment.     

Sexual difference in PCB congener distributions of burbot (Lota lota) from Lake Erie

Concentrations of 86 congeners of polychlorinated biphenyls (PCBs) were determined for 25 adult female and 25 adult male burbot (Lota lota) from Lake Erie. Significant differences in mean proportions of total PCB concentration between males and females ages 14–17 were found for 26 congeners. Males generally had higher mean proportions of hexachloro congeners, whereas females had higher mean proportions of more highly chlorinated congeners. In contrast, only four congeners exhibited differences between males and females ages 6–13 in mean proportions of total PCB. Therefore, the sexual difference in PCB congener distribution widened for older burbot. Males ages 14–17 also had higher proportions of certain hexachloro congeners than the other three demographic groups (males ages 6–13, females ages 6–13, and females ages 14–17) we examined. The reverse was true for more highly chlorinated congeners. The results supported a previous hypothesis that older male burbot spent a substantial amount of time feeding in the vicinity of mouths of rivers with sediment contaminated with PCBs. However, additional studies are needed to clarify and corroborate this apparent “hot spot” effect, such as seasonal movements, spatial distributions, and diet of burbot; and PCB congener distributions of various species of prey fishes captured at various locations throughout the eastern basin of Lake Erie and at different locations in the contaminated rivers.     

Development and field validation of an indicator to assess the relative mobility and risk of pesticides in the Lourens River catchment,South Africa

A GIS based pesticide risk indicator that integrates exposure variables (i.e. pesticide application, geographic, physicochemical and crop data) and toxicity endpoints (using species sensitivity distributions) was developed to estimate the Predicted Relative Exposure (PREX) and Predicted Relative Risk (PRRI) of applied pesticides to aquatic ecosystem health in the Lourens River catchment, Western Cape, South Africa. Samples were collected weekly at five sites from the beginning of the spraying season (October) till the beginning of the rainy season (April) and were semi quantitatively analysed for relevant pesticides applied according to the local farmers spraying programme. Monitoring data indicate that physicochemical data obtained from international databases are reliable indicators of pesticide behaviour in the Western Cape of South Africa. Sensitivity analysis identified K_OC as the most important parameter influencing predictions of pesticide loading derived from runoff. A comparison to monitoring data showed that the PREX successfully identified hotspot sites, gave a reasonable estimation of the relative contamination potential of different pesticides at a site and identified important routes of exposure (i.e. runoff or spray drift) of different pesticides at different sites. All pesticides detected during a monitored runoff event, were indicated as being more associated with runoff than spray drift by the PREX. The PRRI identified azinphos-methyl and chlorpyrifos as high risk pesticides towards the aquatic ecosystem. These results contribute to providing increased confidence in the use of risk indicator applications and, in particular, could lead to improved utilisation of limited resources for monitoring and management in resource constrained countries.     

Detecting Temporal Change in Watershed Nutrient Yields

Meta-analyses reveal that nutrient yields tend to be higher for watersheds dominated by anthropogenic uses (e.g., urban, agriculture) and lower for watersheds dominated by natural vegetation. One implication of this pattern is that loss of natural vegetation will produce increases in watershed nutrient yields. Yet, the same meta-analyses also reveal that, absent land-cover change, watershed nutrient yields vary from one year to the next due to many exogenous factors. The interacting effects of land cover and exogenous factors suggest nutrient yields should be treated as distributions, and the effect of land-cover change should be examined by looking for significant changes in the distributions. We compiled nutrient yield distributions from published data. The published data included watersheds with homogeneous land cover that typically reported two or more years of annual nutrient yields for the same watershed. These data were used to construct statistical models, and the models were used to estimate changes in the nutrient yield distributions as a result of land-cover change. Land-cover changes were derived from the National Land Cover Database (NLCD). Total nitrogen (TN) yield distributions increased significantly for 35 of 1550 watersheds and decreased significantly for 51. Total phosphorus (TP) yield distributions increased significantly for 142 watersheds and decreased significantly for 17. The amount of land-cover change required to produce significant shifts in nutrient yield distributions was not constant. Small land-cover changes led to significant shifts in nutrient yield distributions when watersheds were dominated by natural vegetation, whereas much larger land-cover changes were needed to produce significant shifts when watersheds were dominated by urban or agriculture. We discuss our results in the context of the Clean Water Act.     

Matrix based fertilizers reduce nitrogen and phosphorus leaching in three soils

We compared the efficacy of matrix based fertilizers (MBFs) formulated to reduce NO3-, NH4+, and total phosphorus (TP) leaching, with Osmocoate 14-14-14, a conventional commercial slow release fertilizer (SRF) and an unamended control in three different soil textures in a greenhouse column study. The MBFs covered a range of inorganic N and P in compounds that are relatively loosely bound (MBF 1) to more moderately bound (MBF 2) and more tightly bound compounds (MBF 3) mixed with Al(SO4)3H2O and/or Fe2(SO4)3 and with high ionic exchange compounds starch, chitosan and lignin. When N and P are released, the chemicals containing these nutrients in the MBF bind N and P to a Al(SO4)3H2O and/or Fe2(SO4)3 starch-chitosan-lignin matrix. One milligram (8000 spores) of Glomus intradices was added to all formulations to enhance nutrient uptake. In all three soil textures the SRF leachate contained a higher amount of NH4+, NO3- and TP than leachate from all other fertilizers. In all three soils there were no consistent differences in the amount of NH4+, NO3- and TP in the MBF leachates compared to the control leachate. Plants growing in soils receiving SRF had greater shoot, root and total biomass than all MBFs regardless of Al(SO4)3H2O or Fe2(SO4)3 additions. Arbuscular mycorrhizal infection in plant roots did not consistently differ among plants growing in soil receiving SRF, MBFs and control treatments. Although the MBFs resulted in less plant growth in this experiment they may be applied to soils growing plants in areas that are at high risk for nutrient leaching to surface waters.