Equipping for risk: Lessons learnt from the UK shale-gas experience on assessing environmental risks for the future geoenergy use of the deep subsurface.

findings are presented from an investigation to improve understanding of the environmental risks associated with developing an unconventional-hydrocarbons industry in the UK. The EQUIPT4RISK project, funded by UK Research Councils, focused on investigations around Preston New Road (PNR), Fylde, Lancashire, and Kirby Misperton Site A (KMA), North Yorkshire, where operator licences to explore for shale gas by hydraulic fracturing (HF) were issued in 2016, although exploration only took place at PNR. EQUIPT4RISK considered atmospheric (greenhouse gases, air quality), water (groundwater quality) and solid-earth (seismicity) compartments to characterise and model local conditions and environmental responses to HF activities. Risk assessment was based on the source-pathway-receptor approach. Baseline monitoring of air around the two sites characterised the variability with meteorological conditions, and isotopic signatures were able to discriminate biogenic methane (cattle) from thermogenic (natural-gas) sources. Monitoring of a post-HF nitrogen-lift (well-cleaning) operation at PNR detected the release of atmospheric emissions of methane (4.2 ± 1.4 t CH4). Groundwater monitoring around KMA identified high baseline methane concentrations and detected ethane and propane at some locations. Dissolved methane was inferred from stable-isotopic evidence as overwhelmingly of biogenic origin. Groundwater-quality monitoring around PNR found no evidence of HF-induced impacts. Two approaches for modelling induced seismicity and associated seismic risk were developed using observations of seismicity and operational parameters from PNR in 2018 and 2019. Novel methodologies developed for monitoring include use of machine learning to identify fugitive atmospheric methane, Bayesian statistics to assess changes to groundwater quality, a seismicity forecasting model seeded by the HF-fluid injection rate and high-resolution monitoring of soil-gas methane. The project developed a risk-assessment framework, aligned with ISO 31000 risk-management principles, to assess the theoretical combined and cumulative environmental risks from operations over time. This demonstrated the spatial and temporal evolution of risk profiles: seismic and atmospheric impacts from the shale-gas operations are modelled to be localised and short-lived, while risk to groundwater quality is longer-term.

A method for screening groundwater vulnerability from subsurface hydrocarbon extraction practices.

This paper describes a new screening method for assessing groundwater vulnerability to pollution from hydrocarbon exploitation in the subsurface. The method can be used for various hydrocarbon energy sources, including conventional oil and gas, shale gas and oil, coal bed methane and underground coal gasification. Intrinsic vulnerability of potential receptors is assessed at any particular location by identifying possible geological pathways for contaminant transport. This is followed by an assessment of specific vulnerability which takes into account the nature of the subsurface hydrocarbon activity and driving heads. A confidence rating is attached to each parameter in the assessment to provide an indication of the confidence in the screening. Risk categories and associated confidence ratings are designed to aid in environmental decision making, regulation and management, highlighting where additional information is required. The method is demonstrated for conventional gas and proposed shale gas operations in northern England but can be adapted for use in any geological or hydrogeological setting and for other subsurface activities.

Global patterns of nitrate storage in the vadose zone.

Global-scale nitrogen budgets developed to quantify anthropogenic impacts on the nitrogen cycle do not explicitly consider nitrate stored in the vadose zone. Here we show that the vadose zone is an important store of nitrate that should be considered in future budgets for effective policymaking. Using estimates of groundwater depth and nitrate leaching for 1900-2000, we quantify the peak global storage of nitrate in the vadose zone as 605-1814 Teragrams (Tg). Estimates of nitrate storage are validated using basin-scale and national-scale estimates and observed groundwater nitrate data. Nitrate storage per unit area is greatest in North America, China and Europe where there are thick vadose zones and extensive historical agriculture. In these areas, long travel times in the vadose zone may delay the impact of changes in agricultural practices on groundwater quality. We argue that in these areas use of conventional nitrogen budget approaches is inappropriate.

A baseline survey of dissolved methane in aquifers of Great Britain.

Interest in dissolved methane (CH4) concentrations in aquifers in England, Scotland and Wales ('Great Britain' or GB) has grown concurrently with interest in the exploitation of unconventional gas sources (UGS). Experience, mainly from North America, has shown the importance of a pre-production baseline against which changes possibly due to UGS extraction can be compared. The British Geological Survey, aided by water utilities, private users and regulators, has compiled a unique dataset for CH4 in groundwaters of GB. This focuses principally on areas where UGS exploration is considered more likely, as indicated by the underlying geology. All the main water supply aquifers (Principal aquifers) were targeted, plus Secondary aquifers where locally important. The average dissolved CH4 concentration across GB in the aquifers sampled was 45µg/l. Out of a total of 343 sites, 96% showed dissolved CH4 concentrations <100µg/l, 80% <10µg/l, and 43%<1µg/l. No site had a CH4 concentration above the US Department of the Interior suggested risk action level of 10,000µg/l. While most sites were sampled only once, a subset was monitored quarterly to determine the magnitude of seasonal or other variations. Generally these variations were minor, with 84% of sites showing variations within the range 0.5-37µg/l, but some aquifers where the porosity was primarily fracture-related showed larger changes (0.5-264µg/l). This may have been due to the nature of sampling at these sites which, unlike the others, did not have installed pumps. Since the regulatory compliance monitoring attending UGS operations will include the measurement of parameters such as dissolved CH4, it is essential that sampling methods are tested to ensure that reliable and comparable datasets can be obtained.

Declining trends in invasive orthopedic interventions for people with hemophilia enrolled in the Universal Data Collection program (2000-2010).

INTRODUCTION: Recurrent joint hemarthroses due to hemophilia (Factor VIII and Factor IX deficiency) often lead to invasive orthopedic interventions to decrease frequency of bleeding and/or to alleviate pain associated with end-stage hemophilic arthropathy. AIM: Identify trends in invasive orthopedic interventions among people with hemophilia who were enrolled in the Universal Data Collection (UDC) program during the period 2000-2010. METHODS: Data were collected from 130 hemophilia treatment centers in the United States annually during the period 2000-2010, in collaboration with the Centers for Disease Control and Prevention (CDC). The number of visits in which an invasive orthopedic intervention was reported was expressed as a proportion of the total visits in each year of the program. Invasive orthopedic interventions consisted of arthroplasty, arthrodesis, and synovectomy. Joints included in this study were the shoulder, elbow, hip, knee, and ankle. RESULTS: A 5.6% decrease in all invasive orthopedic interventions in all joints of people with hemophilia enrolled in the UDC program over the 11-year study period was observed. CONCLUSIONS: These data reflect a declining trend in invasive orthopedic interventions in people with hemophilia. Further research is needed to understand the characteristics that may influence invasive orthopedic interventions.

The changing trend in nitrate concentrations in major aquifers due to historical nitrate loading from agricultural land across England and Wales from 1925 to 2150.

Nitrate is necessary for agricultural productivity, but can cause considerable problems if released into aquatic systems. Agricultural land is the major source of nitrates in UK groundwater. Due to the long time-lag in the groundwater system, it could take decades for leached nitrate from the soil to discharge into freshwaters. However, this nitrate time-lag has rarely been considered in environmental water management. Against this background, this paper presents an approach to modelling groundwater nitrate at the national scale, to simulate the impacts of historical nitrate loading from agricultural land on the evolution of groundwater nitrate concentrations. An additional process-based component was constructed for the saturated zone of significant aquifers in England and Wales. This uses a simple flow model which requires modelled recharge values, together with published aquifer properties and thickness data. A spatially distributed and temporally variable nitrate input function was also introduced. The sensitivity of parameters was analysed using Monte Carlo simulations. The model was calibrated using national nitrate monitoring data. Time series of annual average nitrate concentrations along with annual spatially distributed nitrate concentration maps from 1925 to 2150 were generated for 28 selected aquifer zones. The results show that 16 aquifer zones have an increasing trend in nitrate concentration, while average nitrate concentrations in the remaining 12 are declining. The results are also indicative of the trend in the flux of groundwater nitrate entering rivers through baseflow. The model thus enables the magnitude and timescale of groundwater nitrate response to be factored into source apportionment tools and to be taken into account alongside current planning of land-management options for reducing nitrate losses.

Aquatic toxicity of cationic surfactants to Daphnia magna.

Quantitative structure-activity relationship (QSAR) modelling of aquatic toxicity for cationic surfactants has received limited attention despite the fact that surfactants of this type are generally more toxic than predicted by general narcosis or polar narcosis equations. Here we report measurement of log P for three types of aromatic quaternary ammonium halides at sub-micellar concentrations, refinement of earlier rules for log P calculation, and development of a hydrophobicity based QSAR, using both calculated and measured log P values, for the aquatic toxicity of quaternary ammonium halides to Daphnia magna. The QSAR for cationics has a substantially larger intercept than the log P-based QSARs for nonionic and anionic surfactants. This is rationalised in terms of the head group interactions with membrane phospholipid in a two-dimensional partitioning model. The effect of the positive nitrogen on the log P contributions of methylene groups along alkyl chains varies, depending on the other groups bonded to the positive nitrogen. We propose a mechanistic explanation, but until these effects can be put on a more predictable quantitative basis it is recommended that, for quaternaries other than the three types discussed here, calculated log P values should not be relied on and experimental values should be determined, e.g. for prediction of toxicity by the QSAR equation reported here.

Emerging organic contaminants in groundwater: A review of sources, fate and occurrence.

Emerging organic contaminants (EOCs) detected in groundwater may have adverse effects on human health and aquatic ecosystems. This paper reviews the existing occurrence data in groundwater for a range of EOCs including pharmaceutical, personal care, 'life-style' and selected industrial compounds. The main sources and pathways for organic EOCs in groundwater are reviewed, with occurrence data for EOCs in groundwater included from both targeted studies and broad reconnaissance surveys. Nanogram-microgram per litre concentrations are present in groundwater for a large range of EOCs as well as metabolites and transformation products and under certain conditions may pose a threat to freshwater bodies for decades due to relatively long groundwater residence times. In the coming decades, more of these EOCs are likely to have drinking water standards, environmental quality standards and/or groundwater threshold values defined, and therefore a better understanding of the spatial and temporal variation remains a priority.

Practical methods for the measurement of logP for surfactants.

Hydrophobicity is a commonly used parameter in quantitative structure activity relationships. The ability to determine the octanol-water partition coefficient (logP) empirically for non-ionizing, non-surfactant type chemicals using traditional stir-flask methods has been successful and well documented. In comparison the ability to measure logP for surfactants is considered impractical due to their amphiphilic nature, which gives them a tendency to form micelles and reside at the octanol-water interface. In this study we have shown that working with compounds below their critical micelle concentrations (CMC), at the experimental concentrations, it is possible to obtain experimental logP values for a series of sulphobetaines using the stir-flask method coupled with reversed phase-high performance liquid chromatography (RP-HPLC). Until now the ability to verify calculated logP values for surfactants has been limited. Measuring logP as described here can now be applied to other surfactants to validate existing and new modifications to the fragment method.

Effect of 3M Coban Self-Adherent Wraps on edema and function of the burned hand: a case study.

Edema and limited function are common acute problems associated with hand burns. This case study examined the effects of 3M Coban Self-Adherent Wraps on edema and function in a 59-year-old male (46% TBSA flame injury) with newly skin grafted dorsally burned hands. At the time of each dressing change, circumferential measurements were taken of both hands and weekly active range of motion and grip strength measurements were recorded. The nine-hole peg test was used to appraise dexterity. During the 4-week study period, there was less edema, greater active range of motion and grip strength, and greater dexterity in the hand with 3M Coban Self-Adherent Wraps as compared with the control hand. This case study suggests that 3M Coban Self-Adherent Wraps were effective in reducing edema in the skin-grafted hand after skin grafting. It further appeared that the reduced edema may have contributed to improved hand function and that 3M Coban Self-Adherent Wraps as a compressive dressing do not impede hand function

The natural (baseline) quality of groundwater: a UK pilot study.

Knowledge of the natural baseline quality of groundwaters is an essential prerequisite for understanding pollution and for imposing regulatory limits. The natural baseline of groundwaters may show a range of concentrations depending on aquifer mineralogy, facies changes, flow paths and residence time. The geochemical controls on natural concentrations are discussed and an approach to defining baseline concentrations using geochemical and statistical tools is proposed. The approach is illustrated using a flowline from the Chalk aquifer in Berkshire, UK where aerobic and anaerobic sections of the aquifer are separately considered. The baseline concentrations for some elements are close to atmospheric values whereas others evolve through time-dependent water-rock interaction. Certain solutes (K, NH(4)(+)), often considered contaminants, reach naturally high concentrations due to geochemical controls; transition metal concentrations are generally low, although their concentrations may be modified by redox controls. It is recommended that the baseline approach be incorporated into future management strategies, notably monitoring.

Educational preparedness for physical therapists and occupational therapists in burn care.

The background of physical therapy (PT) and occupational therapy (OT) students in burn care training may be variable during their professional education. The purpose of this study was to evaluate whether professional programs in PT and OT are meeting the burn care educational needs of their students. PTs and OTs currently practicing in burn care were asked to give their opinion of the most important curricular topics related to burn care, report their perception of their own entry-level preparedness for burn care, recount therapy interns preparation for burn care internships, and recommend topics that should be included in a therapy program burn care curriculum. Therapists felt prepared in basic sciences and somewhat prepared in specific burn care practice topics. Study participants felt more prepared for burn practice if they completed an internship in burn care. Enhancing content on burn-related treatment interventions was the most common suggestion for curricular revision.

Calibration of the Periotron 8000 and 6000 by polynomial regression.

This paper reports the detailed calibration of the new Periotron 8000 with different fluids and uses the method of least squares to derive polynomial regression equations up to the 6th order, to investigate the most accurate descriptor of the resulting calibration lines. The use of a 4th order polynomial regression equation (recommended by the manufacturer) provided better coefficients of determination (R2: 0.999) and root mean square errors (RMSE = 1.6) than either linear regression (R2: 0.986, RMSE = 10.9) or quadratic models (R2: 0.998, RMSE = 3.2). Data derived using the manufacturer's MLCONVERT software program lacked accuracy and incurred large errors for volumes > 0.5 microliter. Calibrations performed on one day could be used with accuracy to derive volumes > 0.1 microliter collected on subsequent days, when using the same machine (s.d. for residuals plot = 2.49 Periotron units), but this was not the case for different machines (s.d. = 9.57 Periotron units). Varying serum protein concentration by up to 500% had a negligible effect on calculated volumes above 0.1 microliter. We conclude that the Periotron 8000 is at least as reliable a machine as the Periotron 6000, and that the calibration lines for both machines are best described using 4th order polynomial regression equations and "look-up" tables, rather than quadratic (Periotron 6000) or the manufacturer's software (Periotron 8000). Serum seems to be an acceptable GCF substitute for calibrations, which can be performed 1 day, and used on subsequent days for a given machine and for volumes above 0.1 microliter.

The synthesis of 2-substituted isoflavones for immunoassay.

Details are given of the preparation of isoflavones derivatised so that they act as haptens in the development of immunoassays for large scale screening for phytoestrogens in biological fluid. A specifically designed new cyclisation reaction allowed the direct conversion of 2-acyloxydeoxybenzoins to the required isoflavones.

Briarane diterpenes from the Indian Ocean gorgonian Gorgonella umbraculum.

Three briarane diterpenes, junceellin (1), praelolide (2), and compound 3 (of which 3 is new), were isolated from the gorgonian Gorgonella umbraculum (EII & Sol), and their structures were established on the basis of their spectral data.

Cutaneous nerve distribution in adult rat hairy skin after thermal injury--an immunohistochemical study.

Regrowth of cutaneous nerves after thermal injury was examined in rat hairy skin with use of protein gene product 9.5, which has been shown to label nerves in skin preparations. Tissue biopsies were obtained from injured and control skin at postburn days 1, 7, 14, 28, and 120, fixed in 4% paraformaldehyde, cryoprotected, sectioned, and immunostained with rhodamine conjugated goat anti-rabbit immunoglobulin G. Immunoreactivity for protein gene product 9.5 was intense and illustrated the process of nerve regrowth in rat skin after thermal injury. No nerve growth was detectable in 1- and 7-day preparations. Variable regeneration was noted in 14-day preparations. The 28- and 120-day groups produced nerve counts that were similar to control sections. Results suggest that rat hairy skin has a capacity for nerve regrowth after thermal injury. Nerves were noted to regenerate from beneath the scar. Burn wounds in rats demonstrated vigorous cutaneous nerve regeneration.

Topical agents in burn and wound care.

With any open wound infection may occur. Many factors such as age and general health status may increase the likelihood of infection, but the size and depth of the wound are critical factors in determining the chronicity of any wound. Infection greatly adds to the morbidity associated with open wounds. An infected wound not only heals more slowly, there is also the risk of systemic infection and even death. Infected wounds also scar more severely and are associated with more prolonged rehabilitation. Topical therapeutic agents have been shown to be effective in the management of open skin wounds. These agents may assist less complicated healing and decrease the conversion of a partial-thickness injury to a full-thickness injury, and thereby reduce wound-related morbidity. Common topical agents with suggestions for application are discussed in this review.

Uses of Coban self-adherent wrap in management of postburn hand grafts: case reports.

Coban wrap is a durable, elastic, self-adherent gauze that applies snugly without loosening. Coban does not stick to underlying tissue, making it excellent for early postoperative management of split- and full-thickness hand grafts. The wrap protects new grafts and decreases postoperative edema, permitting earlier mobility and facilitating accurate measurements for fitting of pressure garments. Wounds are judged suitable for Coban when the grafts are largely adherent and vascularized. Coban can be wrapped (1) directly over the graft, (2) over an ointment/adaptic dressing, or (3) over gauze padding for extra protection, or use as a "soft splint." Because of its inherent elasticity, Coban can be used to passively encourage desirable joint positions. The wrap is changed daily, and family members readily learn its use. Coban appears to encourage early, protected, active range of motion and early use of custom-fit pressure garments.

Evaluation of topical therapeutic ultrasound to improve response to physical therapy and lessen scar contracture after burn injury.

This study compared results of patients who received standard burn physical therapy and topical ultrasound with patients who received standard care alone to investigate the effect of topical therapeutic ultrasound on range of motion and pain in patients with burns. Fourteen burned extremities were studied. Eight joints were randomized to treatment with ultrasound followed by 10 minutes of passive stretching. Six joints received placebo ultrasound treatments and stretching. All treatments were performed every other day throughout a 2-week study period. Joint range of motion was measured before and after each treatment, and patients estimated the pain of the procedure. Patients and therapists were blinded to the treatment group. Analysis of the data revealed no differences in range of motion or perceived pain between the two groups. The effect of ultrasound on range of motion and pain was not predictable. We conclude that patients are not likely to improve from ultrasound treatment at our protocol parameters.