Methane flux from flowback operations at a shale gas site.

We report measurements of methane (CH4) mixing ratios and emission fluxes derived from sampling at a monitoring station at an exploratory shale gas extraction facility in Lancashire, England. Elevated ambient CH4 mixing ratios were recorded in January 2019 during a period of cold-venting associated with a nitrogen lift process at the facility. These processes are used to clear the well to stimulate flow of natural gas from the target shale. Estimates of CH4 flux during the emission event were made using three independent modeling approaches: Gaussian plume dispersion (following both a simple Gaussian plume inversion and the US EPA OTM 33-A method), and a Lagrangian stochastic transport model (WindTrax). The three methods yielded an estimated peak CH4 flux during January 2019 of approximately 70 g s-1. The total mass of CH4 emitted during the six-day venting period was calculated to be 2.9, 4.2 ± 1.4(1σ) and 7.1 ± 2.1(1σ) tonnes CH4 using the simple Gaussian plume model, WindTrax, and OTM-33A methods, respectively. Whilst the flux approaches all agreed within 1σ uncertainty, an estimate of 4.2 (± 1.4) tonnes CH4 represents the most confident assessment due to the explicit modeling of advection and meteorological stability permitted using the WindTrax model. This mass is consistent with fluxes calculated by the Environment Agency (in the range 2.7 to 6.8 tonnes CH4), using emission data provided by the shale site operator to the regulator. This study provides the first CH4 emission estimate for a nitrogen lift process and the first-reported flux monitoring of a UK shale gas site, and contributes to the evaluation of the environmental impacts of shale gas operations worldwide. This study also provides forward guidance on future monitoring applications and flux calculation in transient emission events. Implications: This manuscript discusses atmospheric measurements near to the UK's first hydraulic fracturing facility, which has very high UK public, media, and policy interest. The focus of this manuscript is on a single week of data in which a large venting event at the shale gas site saw emissions of ~4 tonnes of methane to atmosphere, in breach of environmental permits. These results are likely to beresults are likely to be reported by the media and may influence future policy decisions concerning the UK hydraulic fracturing industry.

Assessing the utility of dissolved organic matter photoreactivity as a predictor of in situ methylmercury concentration.

Methylmercury (MeHg) bioaccumulation is a growing concern in ecosystems worldwide. The absorption of solar radiation by dissolved organic matter (DOM) and other photoreactive ligands can convert MeHg into less toxic forms of mercury through photodemethylation. In this study, spectral changes and photoreactivity of DOM were measured to assess the potential to control photoreactions and predict in situ MeHg concentration. Water samples collected from a series of lakes in southwestern Nova Scotia in June, August, and September were exposed to controlled ultraviolet-A (UV-A) radiation for up to 24hr. Dissolved organic matter photoreactivity, measured as the loss of absorbance at 350nm at constant UV-A irradiation, was positively dependent on the initial DOM concentration in lake waters (r2=0.94). This relationship was consistent over time with both DOM concentration and photoreactivity increasing from summer into fall across lakes. Lake in situ MeHg concentration was positively correlated with DOM concentration and likely catchment transport in June (r=0.77) but not the other sampling months. Despite a consistent seasonal variation in both DOM and Fe, and their respective correlations with MeHg, no discernable seasonal trend in MeHg was observed. However, a 3-year dataset from the 6 study lakes revealed a positive correlation between DOM concentration and both Fe (r=0.91) and MeHg concentrations (r=0.51) suggesting a more dominant landscape mobility control on MeHg. The DOM-MeHg relationships observed in these lakes highlights the need to examine DOM photoreactivity controls on MeHg transport and availability in natural waters particularly given future climate perturbations.

Quantifying the effects of photoreactive dissolved organic matter on methylmercury photodemethylation rates in freshwaters.

The present study examined potential effects of seasonal variations in photoreactive dissolved organic matter (DOM) on methylmercury (MeHg) photodemethylation rates in freshwaters. A series of controlled experiments was carried out using natural and photochemically preconditioned DOM in water collected from 1 lake in June, August, and October. Natural DOM concentrations doubled between June and August (10.2-21.2 mg C L-1 ) and then remained stable into October (19.4 mg C L-1 ). Correspondingly, MeHg concentrations peaked in August (0.42 ng L-1 ), along with absorbances at 350 nm and 254 nm. Up to 70% of MeHg was photodemethylated in the short 48-h irradiation experiments, with June having significantly higher rates than the other sampling months (p < 0.001). Photodemethylation rate constants were not affected by photoreactive DOM, nor were they affected by initial MeHg concentrations (p > 0.10). However, MeHg photodemethylation efficiencies (quantified in moles MeHg lost/moles photon absorbed) were higher in treatments with less photoreactive DOM. Congruently, MeHg photodemethylation efficiencies also decreased over summer by up to 10 times across treatments in association with increased photoreactive DOM, and were negatively correlated with DOM concentration. These results suggest that an important driver of MeHg photodemethylation is the interplay between MeHg and DOM, with greater potential for photodemethylation in freshwaters with more photobleached DOM and lower DOM content. Environ Toxicol Chem 2017;36:1493-1502. © 2016 SETAC.