Establishing the baseline in groundwater chemistry in connection with shale-gas exploration: Vale of Pickering, UK

The baseline chemistry of groundwater from two aquifers in the Vale of Pickering, North Yorkshire, has been investigated ahead of a proposal to explore for shale gas, planning permission for which has recently been granted. Groundwater in a shallow aquifer including Quaternary and/or Jurassic Kimmeridge Clay deposits shows compositions distinct from a Corallian (Jurassic) Limestone aquifer, reflecting different lithologies and hydrogeological conditions. Corallian groundwaters along the margins of the vale are controlled by reaction with carbonate, with redox conditions varying according to degree of aquifer confinement. Superficial aquifer groundwaters are confined and strongly reducing, with some observed high concentrations of dissolved CH4 (up to 37 mg/L; Feb 2016 data). This appears to be of mixed biogenic-thermogenic origin but further work is needed to determine whether the source includes a deeper hydrocarbon reservoir contributing via fractures, or a shallower source in the Quaternary or Kimmeridge sediments. The data show a shallow aquifer with a high-CH4 baseline which pre-dates any shale-gas activity

Monitoring of methane in groundwater from the Vale of Pickering, UK: temporal variability and source discrimination

Groundwater abstracted from aquifers in the Vale of Pickering, North Yorkshire, UK and monitored over the period 2015–2022, shows evidence of variable but commonly high concentrations of dissolved CH4. Sampled groundwater from the Jurassic organic-rich Kimmeridge Clay Formation (boreholes up to 180 m depth) has concentrations up to 57 mg/L, and concentrations up to 59 mg/L are found in groundwater from underlying confined Corallian Group limestone (borehole depths 50–227 m). The high concentrations are mainly from boreholes in the central parts of the vale. Small concentrations of ethane (C2H6, up to 800 μg/L) have been found in the Kimmeridge Clay and confined Corallian groundwaters, and of propane (C3H8, up to 160 μg/L) in deeper boreholes (110–180 m) from these formations. The concentrations are typically higher in groundwater from the deeper boreholes and vary with hydrostatic pressure, reflecting the pressure control on CH4 solubility. The occurrences contrast with groundwater from shallow Quaternary superficial deposits which have low CH4 concentrations (up to 0.39 mg/L), and with the unconfined and semi-confined sections of the Corallian aquifer (up to 0.7 mg/L) around the margins of the vale. Groundwater from the Quaternary, Kimmeridge Clay formations and to a small extent the confined Corallian aquifer, supports local private-water supplies, that from the peripheral unconfined sections of Corallian also supports public supply for towns and villages across the region. Dissolved methane/ethane (C1/C2) ratios and stable-isotopic compositions (δ13C-CH4, δ2H-CH4 and δ13C-CO2) suggest that the high-CH4 groundwater from both the Kimmeridge Clay and confined Corallian formations derives overwhelmingly from biogenic reactions, the methanogenesis pathway by CO2 reduction. A small minority of groundwater samples shows a more enriched δ13C-CH4 composition (−50 to −44 ‰) which has been interpreted as due to anaerobic or aerobic methylotrophic oxidation in situ or post-sampling oxidation, rather than derivation by a thermogenic route. Few of the existing groundwater sites are proximal to abandoned or disused conventional hydrocarbon wells that exist in the region, and little evidence has been found for an influence on groundwater dissolved gases from these sites. The Vale of Pickering has also been under recent consideration for development of an unconventional hydrocarbon (shale-gas) resource. In this context, the monitoring of dissolved gases has been an important step in establishing the high-CH4 baseline of groundwaters from Jurassic deposits in the region and in apportioning their sources and mechanisms of genesis

Laboratory studies using naturally occurring 'green rust' to aid metal mine water remediation

Green rust, an Fe (II) and (III) oxyhydroxy salt, can alter the aqueous oxidation state, mobility and toxicity, of inorganic contaminants and thus could have applications in water treatment. This paper discusses a series of stirred, open batch experiments designed to evaluate green rust, and its oxidised equivalent in this context comparing it to a ferrihydrite/goethite ‘ochre’. Natural green rust was added to different mine waters as either a wet, reduced material or a dry, partially oxidised material. Experiments showed that the addition of either form accelerated the removal of potentially harmful elements from solution. Within one hour Fe, Al and Cu were completely removed from mine waters with initial concentrations of 80, 70 and 8.5 mg/L respectively, and Zn was reduced from 60 to <5mg/L. These experiments show the potential of green rust in mine water treatment, especially as it is able to remove problematic elements such as Al and Zn. The material is effective even after being dried and mostly oxidised. Changes to the pH and ORP of the mine waters and surface catalysis are the suggested mechanisms of accelerated removal of contaminants