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This report presents the results and interpretation for Phase 5 of an integrated environmental monitoring programme that is being undertaken around two proposed shale gas sites in England – Preston New Road, Lancashire and Kirby Misperton, North Yorkshire. The report should be read in conjunction with previous reports freely available through the project website1 . These provide additional background to the project, presentation of earlier results and the rationale for establishment of the different elements of the monitoring programme.

This report details the steps taken in the process of producing risk (hazard) maps for chemical parameters listed in the European Commission Directive 98/83/EC on the quality of water intended for human consumption and the national Water Supply (Water Quality) Regulations that implement the requirements of the directive for drinking water in England and Wales. Amendments to 98/83/EC set out in Directive 2015/1787 provide the terms for reduced monitoring requirements by European Member States for drinking water where evidence indicates that waterquality risk is low. On the basis of the Water Safety Plan approach of the World Health Organization, DWI requires mapping of available data on raw-water sources in England and Wales to provide an evaluation of spatial distributions of the listed chemical parameters and their concentration ranges as evidence of risk for drinking water. An evaluation of temporal variability was also required to assess evidence for any trends to aid with decision making on future drinkingwater monitoring requirements. Data for an agreed list of 27 chemical parameters were collated, screened, evaluated and mapped, with surface water and groundwater being treated separately. This report details the data sources and steps taken to collate, evaluate, process and map them. Risk maps produced for individual parameters include expected values and 95th percentiles of measured values relative to the prescribed concentration or value (PCV) at any given location. The methodology employed required prediction of the entire statistical distribution of each parameter at each prediction location so that both expected value and percentile values for each parameter could be determined. This required the use of a statistical model to represent the variation of the data. The produced risk maps are produced for water-quality data analysed over the last three years, in line with the requirements of the 2015/1787 Directive. The correspondence between the two layers i

This report describes the results of activities carried out as part of the Environmental Monitoring Project (EMP) led by the British Geological Survey (BGS) in areas around two shale gas sites in England – Kirby Misperton (Vale of Pickering, North Yorkshire) and Preston New Road (Fylde, Lancashire). It focuses on the monitoring undertaken during the period April 2018–March 2019 but also considers this in the context of earlier monitoring results that have been covered in reports for earlier phases of the project (Phases I–IV) 2 . The EMP project is a multi-partner project involving BGS together with Public Health England (PHE), University of Birmingham, University of Bristol, University of Manchester, Royal Holloway University of London (RHUL) and University of York. The work has been enabled by funding from a combination of the BGS National Capability programme, a grant awarded by the UK Government’s Department for Business Energy & Industrial Strategy (BEIS) and additional benefit-in-kind contributions from all partners. The project comprises the comprehensive monitoring of different environment compartments and properties at and around the two shale-gas sites. The component parts of the EMP are all of significance when considering environmental and human health risks associated with shale gas development. Included are seismicity, ground motion, water (groundwater and surface water), soil gas, greenhouse gases, air quality, and radon. The monitoring started before hydraulic fracturing had taken place at the two locations, and so the results obtained before the initiation of operations at the shale-gas sites represent baseline conditions. It is important to characterise adequately the baseline conditions so that any future changes caused by shale gas operations, including hydraulic fracturing, can be identified. This is also the case for any other new activities that may impact those compartments of the environment being monitored as part of the project. In the per

This report details a reconnaissance investigation carried out between 2016 and 2018 from a British Geological Survey (BGS)–Environment Agency (EA) collaboration on the impacts of abandoned hydrocarbon (HC) wells on groundwater quality in England. The investigation involved collation of a database of HC wells that were identified from records provided by DECC (Department of Energy & Climate Change; now BEIS: Business, Energy & Industrial Strategy) as being abandoned (as opposed to operational or unspecified), categorising according to factors such as oil or gas designation, depth of HC resource, time since abandonment, productive life, absence of active wells nearby, and occurrence and type of overlying aquifer(s). From this categorisation, a subset of 27 sites were shortlisted for further investigation and fact sheets were produced for each outlining regional geology, hydrogeology and potential groundwater monitoring points in the area. Using these factsheets, four study areas were assessed as being most suitable for further field investigation. These comprised two gas fields: Nooks Farm (Staffordshire), and Ashdown (Sussex), and two oil fields: Hemswell (Lincolnshire) and Lomer (Hampshire). Groundwater sampling campaigns were conducted in 2016–2017 in the four study areas, with potential sampling points identified within a 5 km buffer zone around (downstream of) the HC well or HC field. In several areas, the number of sampling points was very limited as locations of HC wells do not necessarily have any relationship with locations of overlying aquifers. In others, large numbers of sites were deemed unsuitable for sampling, for reasons including disuse, decommissioning, safety or lack of access. This made representative sampling of groundwater a severe challenge. Suitable sites from the four study areas were sampled twice during the project, with a total of 48 groundwater samples being collected over the two campaigns. Results from both sampling rounds have shown th

This report presents the collated preliminary results from the British Geological Survey (BGS) led project Science-based environmental baseline monitoring associated with shale gas development in the Fylde, Lancashire. The project has been funded by a combination of BGS National Capability funding, in-kind contributions from project partners and a grant awarded by the Department of Business Energy and Investment Strategy (BEIS). It complements an on-going project, in which similar activities are being carried out, in the Vale of Pickering, North Yorkshire. Further information on the projects can be found on the BGS website: www.bgs.ac.uk. The project has initiated a wide-ranging environmental baseline monitoring programme that includes water quality (groundwater and surface water), seismicity, ground motion, atmospheric composition (greenhouse gases and air quality), soil gas and radon in air (indoors and outdoors). The motivation behind the project(s) was to establish independent monitoring in the area around the proposed shale gas hydraulic fracturing sites in the Fylde, Lancashire (Cuadrilla Resources Ltd) before any shale gas operations take place. As part of the project, instrumentation has been deployed to measure, in real-time or near real-time, a range of environmental variables (water quality, seismicity, atmospheric composition). These data are being displayed on the project’s web site (www.bgs.ac.uk/lancashire). Additional survey, sampling and monitoring has also been carried out through a co-ordinated programme of fieldwork and laboratory analysis, which has included installation of new monitoring infrastructure, to allow compilation of one of the most comprehensive environmental datasets in the UK. The monitoring programme is continuing. However, there are already some very important findings emerging from the limited datasets which should be taken into account when developing future monitoring strategy, policy and regulation. The information is not onl

Traditionally, potash mineral deposits have been characterized using downhole geophysical logging in tandem with geochemical analysis of core samples to establish the critical potassium (% K2O) content. These techniques have been employed in a recent exploration study of the Permian evaporite succession of North Yorkshire, United Kingdom, but the characterization of these complex deposits has been led by mineralogical analysis, using quantitative X-ray diffraction (QXRD). The novel QXRD approach provides data on K content with the level of confidence needed for reliable reporting of resources and also identifies and quantifies more precisely the nature of the K-bearing minerals. Errors have also been identified when employing traditional geochemical approaches for this deposit, which would have resulted in underestimated potash grades. QXRD analysis has consistently identified polyhalite (K2Ca2Mg(SO4)4·2(H2O) in the Fordon (Evaporite) Formation and sylvite (KCl) in the Boulby Potash and Sneaton Potash members as the principal K-bearing host minerals in North Yorkshire. However, other K hosts, including kalistrontite (K2Sr(SO4)2) a first recorded occurrence in the UK, and a range of boron-bearing minerals have also been detected. Application of the QXRD-led characterization program across the evaporitic basin has helped to produce a descriptive, empirical model for the deposits, including the polyhalite-bearing Shelf and Basin seams and two, newly discovered sylvite-bearing bittern salt horizons, the Pasture Beck and Gough seams. The characterization program has enabled a polyhalite mineral inventory in excess of 2.5 billion metric tons (Bt) to be identified, suggesting that this region possesses the world’s largest known resource of polyhalite. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution and reproduction in any medium

This report describes the regional geochemistry of the groundwater from the Corallian aquifer in the Vale of Pickering, North Yorkshire. The study aims to assess the likely natural baseline chemistry of the groundwater. Data have been collected from strategic sampling of 24 groundwater sources, in conjunction with collation of existing groundwater, rainfall, and mineralogical data. The Corallian aquifer comprise Upper Jurassic shallow shelf marine sediments, with a variety of facies including muds to micritic limestone and oolites, to bioclastic limestones with interbeds of silts and sands. These strata represent an important groundwater source in north-east England. The main chemical properties of the groundwater are determined by the interaction of rainwater recharge reacting with the aquifer minerals. Within the Corallian aquifer, groundwater major ion composition is dominantly influenced by reaction with calcite, and little variation is seen within the major ion proportions. Human impacts on the water quality are clearly evident, mainly through the presence of NO3-N as an indicator contaminant. The widespread presence, commonly in excess of the drinking water limit and the increases over time suggest that the aquifer is heavily influenced by agricultural practices. Agricultural land dominates the area underlain by the unconfined aquifer. With the exception of NO3-N, the available data for groundwater within the Corallian aquifer of the Vale of Pickering indicate they are of good quality for the analytes tested, with few elevated concentrations of potentially harmful trace elements. For many analytes the 95th percentile serves as a first approximation of the upper limit of the baseline range of concentrations, as this serves to eliminate the most extreme outlier concentrations.

Data for Mo in British surface water and groundwater collated from a number of databases show that concentrations are in most cases low, of the order of 2 μg/L or less. However, variability is large and sporadic high values are found in both streamwaters and groundwaters. Data for some 11,600 British streamwater samples indicate a 10–90th percentile range of 0.08–2.44 μg/L with a median of 0.57 μg/L and maximum observation of 230 μg/L. High values tend to be from streams on clay-rich formations and sulphide-mineralised bedrock and streams affected by localised urban and industrial contamination. Monitored lowland river waters also typically have median concentrations <1 μg/L although higher values are present in a number of urban/industrialised English rivers. Highest observed concentrations (median 20 μg/L), occur under low-flow conditions in a river system from an urban, industrial area of NE England and are likely the products of industrial contamination and mine drainage. Concentrations in 96 upland lakewater samples from NW England are universally 0.1 μg/L or less. Data for 1735 groundwater samples from across Britain have a 10–90th percentile range for Mo of 0.035–1.80 μg/L with a median of 0.20 μg/L and maximum observation of 89 μg/L. Relatively high values derive from some Lower Cretaceous greensand, Carboniferous limestone and mudstone (Coal Measures) aquifers, particularly under anaerobic conditions. Release from Fe oxides and possibly Mn oxides by reductive dissolution is a likely mechanism for the concentrations. Under more rarely observed sulphate-reducing conditions in British aquifers, concentrations of Mo diminish, likely due to sequestration by precipitating sulphide minerals. The observed ranges in aqueous samples indicate that most water sources in Britain have Mo concentrations more than an order of magnitude below the WHO health-based value for Mo in drinking water (70 μg/L). Such sources are unlikely to pose a risk to drinking water from the cu

The most popular and perhaps universal estimator of location and scale in robust estimation, where one accepts that ideally we have a normal population, but wish to guard against possible small departures from such, is Huber’s Proposal-2 M-estimator. We outline the first order small sample bias correction for the scale estimator, which has been verified both through theory and simulation. While there may be other ways of reducing small sample bias, say as in jackknifing or bootstrapping, these can be computationally intensive, and would not be routinely used with this iteratively derived estimator. It is suggested that bias reduced estimates of scale are most useful when forming confidence intervals for location and or scale based on the asymptotic distribution. In this paper we expand on the results of an earlier work by the authors to include Hampel’s three part re-descending psi function (with a three part re-descender for scale).

The intrinsic geochemical characteristics of geological for-mations have a considerable influence in controlling solute and pollutant transport behaviour during groundwater flow through the shallow geosphere. The interactions between solute or pollutants and the surface geochemistry of the rock matrix will often determine both the extent and speed of solute transport in the saturated and unsaturated zones. Consequently, understanding these processes is of critical importance for a range of environmental management re-quirements, such as landfill leachate monitoring or contam-inated land evaluation, including requirements related to statutory obligations for ensuring good groundwater status under the EU Water Framework Directive. Risk assessment and management approaches frequent-ly make use of numerical geochemical modelling to predict contaminant transport. These models necessarily require parameterization of the geochemical properties of the geo-logical formations involved and the predictions which can be obtained are inevitably only as good as the quality of the data which are used. However, the natural variation in li-thologies and extensive spatial heterogeneities of the UK rock formations result in considerable variability of the most important geochemical properties. Identifying or ob-taining good relevant data for calculations can be difficult; new laboratory measurements can be expensive and time-consuming, published data are relatively sparse and existing data from previous site investigations are often held com-mercially and are difficult to get hold of. This study, supported by the British Geological Survey and the Environment Agency, presents the first comprehen-sive national compilation of geochemical properties data of relevance to geochemical modelling. An assessment has been made of existing available primary data. Relatively few data are available, but those which are have been col-lated. To underpin this the project has undertaken an exten-sive pr

The most popular and perhaps universal estimator of location and scale in robust estimation, where the population is normal with possible small departures, is Huber's Proposal-2 M-estimator. This paper gives the first-order small sample bias correction for the scale estimator, verifying the calculation through theory and simulation. Other ways of reducing small sample bias, say by jackknifing or bootstrapping, can be computationally intensive, and would not be routinely used with this iteratively derived estimator. It is suggested that bias-reduced estimates of scale are most useful when forming confidence intervals for location and/or scale based on the asymptotic distribution.

The kinetics of As reduction for analysis using hydride-generation are presented. As III, As V and Organic arsenic species are all hydride forming depending on conditions used. For total As analysis all As species are reduced to +III oxidation state using KI and then reacted with NaBH4 to produce a hydride. Difference methods are employed by labs for calculation of As species. Acetic acid and citric acid buffers have been reportedly used for the selective reduction of As III by NaBH4 (assuming that only fully protonated species form hydrides), however As V can still be reduced to As III by NaBH4.Selectivity using acetic acid was investigated at pH ~6. HG-ICP-OES is a good method for total As. As V reduction by KI is highly dependant on acidity. As hydride formation is dependant on acidity and is not selective for As III, therefore calculating As V by difference is not an option. HG-OES gives a DL for total As comparable with that of MS, ~ 0.5ug/L, with good reproducibility at concentrations close to the detection limit. Speciation could be done using IC-HG-OES if time-resolved integration was possible in the Winlab software

Objective: To create a model which relates the number of people requiring the doctors’ time in a set period to the amount of people requiring the doctor‟s time in previous periods. Design: Observational study using the doctor’s accounts from January 1995 to December 1999. Participant: Western Australian Medical practice, with multiple doctors and after hours consulting times. Main Outcome Measures: Total number of people that are billed by the doctors at the medical centre for the thirteen 4-week periods each year. Results: The number of people requiring the doctors’ time from 65 observed 4-week periods leads to a seasonal time series model. This is successfully fitted for all but one observation that is deemed to be an outlier. Conclusions: Statistical time series models offer a useful predictor of number of peoples’ requests for future time periods, which can be helpful in managing modern general practices.

This final report summarizes work carried out by a partnership consisting of scientists from UK, Estonia, Denmark, The Netherlands, Belgium, France, Spain, Portugal and Switzerland under the Fourth Framework Programme, contract ENV4-CT94-0156, of the European Union. The format of the report reflects the country contributions as required by the Commission, but also draws together the main results at the European scale. Chapter 1 provides an introduction to the aims and approach of the project. Chapters 2 to 10 report the detailed regional case studies carried out by the individual partners. Chapters 11 to 17 build on the regional studies to develop key aspects and themes of the study and to take a wider view of the subject at a continental scale. Finally, Chapters 18 and 19 draw out the overall conclusions of the project and discuss the implications for effective long-term management of coastal palaeowater aquifers. Not all of the large amount of data collected during the project are recorded here. Should clarification be sought the reader is asked in the first instance to contact BGS as co-ordinators of the project. The results of the project are destined to be published in the open scientific literature and popular channels. However, a major part of the material reported here will, following appropriate peer review, be published in early 2000 as a Special Publication of the Geological Society of London.

Detailed potentiometric titration data were collected for a purified peat humic acid (PPHA) over a range of pH (pH 3.5–10.5) and KNO3 background electrolyte concentrations (0.001–0.3 M). The data were analyzed following the master curve approach which includes both an electrostatic double layer model and a model for the intrinsic heterogeneity of the PPHA. Spherical and cylindrical double layer models gave equally good fits to the data. A salt dependence observed around pH 5 could not be completely removed by taking into account the electrostatic interactions. Hysteresis was observed to a much greater extent in the first titration cycle compared with the second cycle. This suggested that some slow and only partly reversible aggregation was occurring possibly as a result of the aggregation created during the purification of the humic acid. Titration curves for fully redispersed samples fitted the master curve approach (surface charge vs. surface pH) reasonably well but still displayed an ionic strength dependence at a pH of less than 5 which could not be accounted for using the simple electrostatic model. Heterogeneity analysis of the master curve showed that the affinity distribution had two peaks centred at log KHint 4 and log KHint 8 to 9. The total number of weak acid sites titrated between pH 3.5 and 10.5 was approximately 3.5 eq kg−1 but the total number of sites estimated from the isotherm analysis was 5.3–5.8 eq kg t . Double Tóth and double Langmuir-Freundlich isotherms fitted the data almost equally well but the implied distribution of sites between the more acidic “carboxylic” sites and the weakly acidic “phenolic” sites varied with the isotherm chosen. An important source of uncertainty in the analysis was in estimating the charge on the humic acid at its initial pH of about pH 3.

Traditionally, potash mineral deposits have been characterised using downhole geophysical logging in tandem with geochemical analysis of core samples to establish the critical potassium (% K2O) content. These techniques have been employed in a recent exploration study of the Permian evaporite succession of North Yorkshire but the characterisation of these complex deposits has been led by mineralogical analysis. Quantitative X-ray diffraction (QXRD) analysis has consistently identified polyhalite (K2Ca2Mg(SO4)4·2(H2O) in the Fordon (Evaporite) Formation and sylvite (KCl) in the Boulby Potash and Sneaton Potash members as the principal K-bearing host minerals. However, other K hosts, including kalistrontite (K2Sr(SO4)2) a first recorded occurrence in the UK, and a range of boron-bearing minerals have also been detected. Application of the QXRD-led characterisation programme across the evaporitic basin has helped to produce a descriptive, empirical model for the deposits, including the polyhalite-bearing Shelf and Basin seams and two, newly discovered sylvite-bearing bittern salt horizons, the Pasture Beck and Gough seams. The characterisation programme has enabled a polyhalite mineral inventory in excess of 2.5 billion metric tons (Bt) to be identified, suggesting that this region possesses the world's largest known resource of polyhalite., Traditionally, potash mineral deposits have been characterised using downhole geophysical logging in tandem with geochemical analysis of core samples to establish the critical potassium (% K2O) content. These techniques have been employed in a recent exploration study of the Permian evaporite succession of North Yorkshire but the characterisation of these complex deposits has been led by mineralogical analysis. Quantitative X-ray diffraction (QXRD) analysis has consistently identified polyhalite (K2Ca2Mg(SO4)4·2(H2O) in the Fordon (Evaporite) Formation and sylvite (KCl) in the Boulby Potash and Sneaton Potash members as the principal K-bearing host minerals. However, other K hosts, including kalistrontite (K2Sr(SO4)2) a first recorded occurrence in the UK, and a range of boron-bearing minerals have also been detected. Application of the QXRD-led characterisation programme across the evaporitic basin has helped to produce a descriptive, empirical model for the deposits, including the polyhalite-bearing Shelf and Basin seams and two, newly discovered sylvite-bearing bittern salt horizons, the Pasture Beck and Gough seams. The characterisation programme has enabled a polyhalite mineral inventory in excess of 2.5 billion metric tons (Bt) to be identified, suggesting that this region possesses the world's largest known resource of polyhalite.