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.

Is water quality in British rivers "better than at any time since the end of the Industrial Revolution"?

We explore the oft-repeated claim that river water quality in Great Britain is "better now than at any time since the Industrial Revolution". We review available data and ancillary evidence for seven different categories of water pollutants: (i) biochemical oxygen demand (BOD) and ammonia; (ii) heavy metals; (iii) sewage-associated organic pollutants (including hormone-like substances, personal care product and pharmaceutical compounds); (iv) macronutrients (nitrogen and phosphorus); (v) pesticides; (vi) acid deposition and (vii) other variables, including natural organic matter and pathogenic micro-organisms. With a few exceptions, observed data are scarce before 1970. However, we can speculate about some of the major water quality pressures which have existed before that. Point-source pollutants are likely to have increased with population growth, increased connection rates to sewerage and industrialisation, although the increased provision of wastewater treatment during the 20th century will have mitigated this to some extent. From 1940 to the 1990s, pressures from nutrients and pesticides associated with agricultural intensification have increased in many areas. In parallel, there was an increase in synthetic organic compounds with a "down-the-drain" disposal pathway. The 1990s saw general reductions in mean concentrations of metals, BOD and ammonia (driven by the EU Urban Waste Water Treatment Directive), a levelling out of nitrate concentrations (driven by the EU Nitrate Directive), a decrease in phosphate loads from both point-and diffuse-sources and some recovery from catchment acidification. The current picture is mixed: water quality in many rivers downstream of urban centres has improved in sanitary terms but not with respect to emerging contaminants, while river quality in catchments with intensive agriculture is likely to remain worse now than before the 1960s. Water quality is still unacceptably poor in some water bodies. This is often a consequence of multiple stressors which need to be better-identified and prioritised to enable continued recovery.

Overriding water table control on managed peatland greenhouse gas emissions.

Global peatlands store more carbon than is naturally present in the atmosphere1,2. However, many peatlands are under pressure from drainage-based agriculture, plantation development and fire, with the equivalent of around 3 per cent of all anthropogenic greenhouse gases emitted from drained peatland3-5. Efforts to curb such emissions are intensifying through the conservation of undrained peatlands and re-wetting of drained systems6. Here we report eddy covariance data for carbon dioxide from 16 locations and static chamber measurements for methane from 41 locations in the UK and Ireland. We combine these with published data from sites across all major peatland biomes. We find that the mean annual effective water table depth (WTDe; that is, the average depth of the aerated peat layer) overrides all other ecosystem- and management-related controls on greenhouse gas fluxes. We estimate that every 10 centimetres of reduction in WTDe could reduce the net warming impact of CO2 and CH4 emissions (100-year global warming potentials) by the equivalent of at least 3 tonnes of CO2 per hectare per year, until WTDe is less than 30 centimetres. Raising water levels further would continue to have a net cooling effect until WTDe is within 10 centimetres of the surface. Our results suggest that greenhouse gas emissions from peatlands drained for agriculture could be greatly reduced without necessarily halting their productive use. Halving WTDe in all drained agricultural peatlands, for example, could reduce emissions by the equivalent of over 1 per cent of global anthropogenic emissions.

A dynamic baseline for dissolved methane in English groundwater.

Elevated dissolved methane (CH4) concentrations in groundwater are an environmental concern associated with hydraulic fracturing for shale gas. Therefore, determining dissolved CH4 baselines is important for detecting and understanding any potential environmental impacts. Such baselines should change in time and space to reflect ongoing environmental change and should be able to predict the probability that a change in dissolved CH4 concentration has occurred. We considered four dissolved CH4 concentration datasets of English groundwater using a Bayesian approach: two national datasets and two local datasets from shale gas exploration sites. The most sensitive national dataset (the previously published British Geological Survey CH4 baseline) was used as a strong prior for a larger (2153 measurements compared to 439) but less sensitive (detection limit 1000 times higher) Environment Agency dataset. The use of the strong prior over a weak prior improved the precision of the Environment Agency dataset by 75%. The expected mean dissolved CH4 concentration in English groundwater based on the Bayesian approach is 0.24 mg/l, with a 95% credible interval of 0.11 to 0.45 mg/l, and a Weibull distribution of W(0.35 ± 0.01, 0.34 ± 0.16). This result indicates the amount of CH4 degassing from English groundwater to the atmosphere equates to between 0.7 and 3.1 kt CH4/year, with an expected value of 1.65 kt CH4/year and a greenhouse gas warming potential of 40.3 kt CO2eq/year. The two local monitoring datasets from shale gas exploration sites, in combination with the national datasets, show that dissolved CH4 concentrations in English groundwater are generally low, but locations with concentrations greater than or equal to the widely used risk action level of 10.0 mg/l do exist. Statistical analyses of groundwater redox conditions at these locations suggest that it may be possible to identify other locations with dissolved CH4 concentrations ≥10.0 mg/l using redox parameters such as Fe concentration.

Aeolian abrasion of rocks as a mechanism to produce methane in the Martian atmosphere.

Seasonal changes in methane background levels and methane spikes have been detected in situ a metre above the Martian surface, and larger methane plumes detected via ground-based remote sensing, however their origin have not yet been adequately explained. Proposed methane sources include the UV irradiation of meteoritic-derived organic matter, hydrothermal reactions with olivine, organic breakdown via meteoroid impact, release from gas hydrates, biological production, or the release of methane from fluid inclusions in basalt during aeolian erosion. Here we quantify for the first time the potential importance of aeolian abrasion as a mechanism for releasing trapped methane from within rocks, by coupling estimates of present day surface wind abrasion with the methane contents of a variety of Martian meteorites, analogue terrestrial basalts and analogue terrestrial sedimentary rocks. We demonstrate that the abrasion of basalt under present day Martian rates of aeolian erosion is highly unlikely to produce detectable changes in methane concentrations in the atmosphere. We further show that, although there is a greater potential for methane production from the aeolian abrasion of certain sedimentary rocks, to produce the magnitude of methane concentrations analysed by the Curiosity rover they would have to contain methane in similar concentrations as economic reserved of biogenic/thermogenic deposits on Earth. Therefore we suggest that aeolian abrasion is an unlikely origin of the methane detected in the Martian atmosphere, and that other methane sources are required.

Identifying groundwater compartmentalisation for hydraulic fracturing risk assessments.

An environmental concern with hydraulic fracturing (fracking) is that injected fluids or formation fluids could migrate upwards along high-permeability faults and contaminate shallow groundwater resources. However, numerical modelling has suggested that compartmentalisation by low-permeability faults may be a greater risk factor to shallow aquifers than high-permeability faults because lateral groundwater flow is reduced and upward flow through strata may be encouraged. Therefore, it is important that compartmentalisation can be adequately identified prior to fracking. As a case study we used historical groundwater quality data and two-dimensional seismic reflection data from the Bowland Basin, northwest England, to investigate if compartmentalisation could be adequately identified in a prospective shale basin. Five groundwater properties were spatially autocorrelated and interpolation suggests a regional trend from recent (<10 000 years old) meteoric groundwater in the upland Forest of Bowland to more brackish groundwater across the Fylde plain. Principal components analysis suggests two end-member brackish groundwater types. These end-members along with seismic interpretation suggest that a fault may structurally compartmentalise the northwest Bowland Basin. Furthermore, the Woodsfold fault structurally compartmentalises the southern Fylde and the Blackpool area provides evidence for stratigraphic compartmentalisation in the superficial deposits. However, large areas of the Bowland Basin are not sampled and the influence of known faults on groundwater is therefore difficult to assess. Consequently, the adequate identification of compartmentalisation in prospective basins may require supplementing historic data with dedicated basin-wide groundwater monitoring programmes and the acquisition of new seismic reflection data in areas of poor coverage or quality.

The potential for spills and leaks of contaminated liquids from shale gas developments.

Rapid growth of hydraulic fracturing for shale gas within the USA and the possibility of shale developments within Europe has created public concern about the risks of spills and leaks associated with the industry. Reports from the Texas Railroad Commission (1999 to 2015) and the Colorado Oil and Gas Commission (2009 to 2015) were used to examine spill rates from oil and gas well pads. Pollution incident records for England and road transport incident data for the UK were examined as an analogue for potential offsite spills associated with transport for a developing shale industry. The Texas and Colorado spill data shows that the spill rate on the well pads has increased over the recorded time period. The most common spill cause was equipment failure. Within Colorado 33% of the spills recorded were found during well pad remediation and random site inspections. Based on data from the Texas Railroad Commission, a UK shale industry developing well pads with 10 lateral wells would likely experience a spill for every 16 well pads developed. The same well pad development scenario is estimated to require at least 2856 tanker movements over two years per well pad. Considering this tanker movement estimate with incident and spill frequency data from UK milk tankers, a UK shale industry would likely experience an incident on the road for every 12 well pads developed and a road spill for every 19 well pads developed. Consequently, should a UK shale industry be developed it is important that appropriate mitigation strategies are in place to minimise the risk of spills associated with well pad activities and fluid transportation movements.

An assessment of the footprint and carrying capacity of oil and gas well sites: The implications for limiting hydrocarbon reserves.

We estimate the likely physical footprint of well pads if shale gas or oil developments were to go forward in Europe and used these estimates to understand their impact upon existing infrastructure (e.g. roads, buildings), the carrying capacity of the environment, and how the proportion of extractable resources maybe limited. Using visual imagery, we calculate the average conventional well site footprints to be 10,800m2 in the UK, 44,600m2 in The Netherlands and 3000m2 in Poland. The average area per well is 541m2/well in the UK, 6370m2/well in The Netherlands, and 2870m2/well in Poland. Average access road lengths are 230m in the UK, 310m in The Netherlands and 250m in Poland. To assess the carrying capacity of the land surface, well pads of the average footprint, with recommended setbacks, were placed randomly into the licensed blocks covering the Bowland Shale, UK. The extent to which they interacted or disrupted existing infrastructure was then assessed. For the UK, the direct footprint would have a 33% probability of interacting with immovable infrastructure, but this would rise to 73% if a 152m setback was used, and 91% for a 609m setback. The minimum setbacks from a currently producing well in the UK were calculated to be 21m and 46m from a non-residential and residential property respectively, with mean setbacks of 329m and 447m, respectively. When the surface and sub-surface footprints were considered, the carrying capacity within the licensed blocks was between 5 and 42%, with a mean of 26%. Using previously predicted technically recoverable reserves of 8.5×1011m3 for the Bowland Basin and a recovery factor of 26%, the likely maximum accessible gas reserves would be limited by the surface carrying capacity to 2.21×1011m3.

Assessing the fugitive emission of CH4 via migration along fault zones - Comparing potential shale gas basins to non-shale basins in the UK.

This study considered whether faults bounding hydrocarbon-bearing basins could be conduits for methane release to the atmosphere. Five basin bounding faults in the UK were considered: two which bounded potential shale gas basins; two faults that bounded coal basins; and one that bounded a basin with no known hydrocarbon deposits. In each basin, two mobile methane surveys were conducted, one along the surface expression of the basin bounding fault and one along a line of similar length but not intersecting the fault. All survey data was corrected for wind direction, the ambient CH4 concentration and the distance to the possible source. The survey design allowed for Analysis of Variance and this showed that there was a significant difference between the fault and control survey lines though a significant flux from the fault was not found in all basins and there was no apparent link to the presence, or absence, of hydrocarbons. As such, shale basins did not have a significantly different CH4 flux to non-shale hydrocarbon basins and non-hydrocarbon basins. These results could have implications for CH4 emissions from faults both in the UK and globally. Including all the corrected fault data, we estimate faults have an emissions factor of 11.5±6.3tCH4/km/yr, while the most conservative estimate of the flux from faults is 0.7±0.3tCH4/km/yr. The use of isotopes meant that at least one site of thermogenic flux from a fault could be identified. However, the total length of faults that penetrate through-basins and go from the surface to hydrocarbon reservoirs at depth in the UK is not known; as such, the emissions factor could not be multiplied by an activity level to estimate a total UK CH4 flux.

Fugitive emissions of methane from abandoned, decommissioned oil and gas wells.

This study considered the fugitive emissions of methane (CH4) from former oil and gas exploration and production wells drilled to exploit conventional hydrocarbon reservoirs onshore in the UK. This study selected from the 66% of all onshore wells in the UK which appeared to be properly decommissioned (abandoned) that came from 4 different basins and were between 8 and 79 years old. The soil gas above each well was analysed and assessed relative to a nearby control site of similar land use and soil type. The results showed that of the 102 wells considered 30% had soil gas CH4 at the soil surface that was significantly greater than their respective control. Conversely, 39% of well sites had significant lower surface soil gas CH4 concentrations than their respective control. We interpret elevated soil gas CH4 concentrations to be the result of well integrity failure, but do not know the source of the gas nor the route to the surface. Where elevated CH4 was detected it appears to have occurred within a decade of it being drilled. The flux of CH4 from wells was 364 ± 677 kg CO2eq/well/year with a 27% chance that the well would have a negative flux to the atmosphere independent of well age. This flux is low relative to the activity commonly used on decommissioned well sites (e.g. sheep grazing), however, fluxes from wells that have not been appropriately decommissioned would be expected to be higher.

The flux of radionuclides in flowback fluid from shale gas exploitation.

This study considers the flux of radioactivity in flowback fluid from shale gas development in three areas: the Carboniferous, Bowland Shale, UK; the Silurian Shale, Poland; and the Carboniferous Barnett Shale, USA. The radioactive flux from these basins was estimated, given estimates of the number of wells developed or to be developed, the flowback volume per well and the concentration of K (potassium) and Ra (radium) in the flowback water. For comparative purposes, the range of concentration was itself considered within four scenarios for the concentration range of radioactive measured in each shale gas basin, the groundwater of the each shale gas basin, global groundwater and local surface water. The study found that (i) for the Barnett Shale and the Silurian Shale, Poland, the 1 % exceedance flux in flowback water was between seven and eight times that would be expected from local groundwater. However, for the Bowland Shale, UK, the 1 % exceedance flux (the flux that would only be expected to be exceeded 1 % of the time, i.e. a reasonable worst case scenario) in flowback water was 500 times that expected from local groundwater. (ii) In no scenario was the 1 % exceedance exposure greater than 1 mSv-the allowable annual exposure allowed for in the UK. (iii) The radioactive flux of per energy produced was lower for shale gas than for conventional oil and gas production, nuclear power production and electricity generated through burning coal.

Predicting soil respiration from peatlands.

This study considers the relative performance of six different models to predict soil respiration from upland peat. Predicting soil respiration is important for global carbon budgets and gap filling measured data from eddy covariance and closed chamber measurements. Further to models previously published new models are presented using two sub-soil zones and season. Models are tested using data from the Bleaklow plateau, southern Pennines, UK. Presented literature models include ANOVA using logged environmental data, the Arrhenius equation, modified versions of the Arrhenius equation to include soil respiration activation energy and water table depth. New models are proposed including the introduction of two soil zones in the peat profile, and season. The first new model proposes a zone of high CO(2) productivity related to increased soil microbial CO(2) production due to the supply of labile carbon from plant root exudates and root respiration. The second zone is a deeper zone where CO(2) production is lower with less labile carbon. A final model allows the zone of high CO(2) production to become dormant during winter months when plants will senesce and will vary depending upon vegetation type within a fixed location. The final model accounted for, on average, 31.9% of variance in net ecosystem respiration within 11 different restoration sites whilst, using the same data set, the best fitting literature equation only accounted for 18.7% of the total variance. Our results demonstrate that soil respiration models can be improved by explicitly accounting for seasonality and the vertically stratified nature of soil processes. These improved models provide an enhanced basis for calculating the peatland carbon budgets which are essential in understanding the role of peatlands in the global C cycle.

Charcoal addition to soils in NE England: a carbon sink with environmental co-benefits?

Interest in the application of biochar (charcoal produced during the pyrolysis of biomass) to agricultural land is increasing across the world, recognised as a potential way to capture and store atmospheric carbon. Its interest is heightened by its potential co-benefits for soil quality and fertility. The majority of research has however been undertaken in tropical rather than temperate regions. This study assessed the potential for lump-wood charcoal addition (as a substitute for biochar) to soil types which are typically under arable and forest land-use in North East England. The study was undertaken over a 28 week period and found: i) No significant difference in net ecosystem respiration (NER) between soils containing charcoal and those without, other than in week 1 of the trial. ii) A significantly higher dissolved organic carbon (DOC) flux from soils containing large amounts of charcoal than from those untreated, when planted with ryegrass. iii) That when increased respiration or DOC loss did occur, neither was sufficiently large to alter the carbon sink benefits of charcoal application. iv) That charcoal incorporation resulted in a significantly lower nitrate flux in soil leachate from mineral soils. v) That charcoal incorporation caused significant increases in soil pH, from 6.98 to 7.22 on bare arable soils when 87,500 kg charcoal/ha was applied. Consideration of both the carbon sink and environmental benefits observed here suggests that charcoal application to temperate soils typical of North East England should be considered as a method of carbon sequestration. Before large scale land application is encouraged, further large scale trials should be undertaken to confirm the positive results of this research.

Nitrate in United kingdom rivers: policy and its outcomes since 1970.

Modern conventional farming provides Western Europe and North America with reliable, high quality, and relatively cheap supplies of food and fiber, increasingly viewed as a potential source of fuel. One of the costs is continued widespread pollution of rivers and groundwater-predominantly by nutrients. In 1970, in both the United States and UK, farming was focused on maximizing yield and management practices were rapidly modernizing. Little attention was paid to the external impacts of farming. In 2010, diffuse pollution from agriculture is being seriously addressed by both voluntary and statutory means in an attempt to balance environmental costs with the continued benefits of agricultural production. In this paper we consider long-term changes in the concentration and flux of nitrate in five rural UK rivers to demonstrate the impact of agricultural intensification and subsequent policies to reduce diffuse pollution on river water quality between 1970 and 2010.

Assessing the probability of carbon and greenhouse gas benefit from the management of peat soils.

This study proposes a method for assessing the probability that land management interventions will lead to an improvement in the carbon sink represented by peat soils. The method is able to: combine studies of different carbon uptake and release pathways in order to assess changes on the overall carbon or greenhouse gas budget; calculate the probability of the management or restoration leading to an improvement in the budget; calculate the uncertainty in that probability estimate; estimate the equivalent number of complete budgets available from the combination of the literature; test the difference in the outcome of different land management interventions; and provide a method for updating the predicted probabilities as new studies become available. Using this methodology, this study considered the impact of: afforestation, managed burning, drainage, drain-blocking, grazing removal; and revegetation, on the carbon budget of peat soils in the UK. The study showed that afforestation, drain-blocking, revegetation, grazing removal and cessation of managed burning would bring a carbon benefit, whereas deforestation, managed burning and drainage would bring a disbenefit. The predicted probabilities of a benefit are often equivocal as each management type or restoration often leads to increase in uptake in one pathway while increasing losses in another.

Long-term monitoring of river water nitrate: how much data do we need?

Long records of river water quality are invaluable for helping to understand the biogeochemistry of hydrological systems. They allow relationships to be established between changes in water quality (including seasonal cycles, episodic responses and long-term trends) and potential drivers, such as climatic forcing or human activity; they can act as a stimulus for process-oriented experimental research; they can be used to help to make predictions about future temporal and spatial patterns; and they can help to guide management options to mitigate water pollution. In this paper we present the case in favour of maintaining some long records of river water nitrate concentration at "benchmark" sites, in terms of enhancing process understanding and identifying system lags. Many long-term time series of nitrate concentration data share similar features including a pronounced seasonality characterised by a clear winter maximum, an upward trend in the post-war period followed by a levelling off, or even a decline in the last 20 years, and unusually high concentrations following drought years. Concentrations in any one year are often dependent on conditions in previous years; relationships can be established between concentrations and hydrological drivers (such as rainfall) with different lag periods which can yield information about supply or transport limitations to nitrate transfers. The interpretation of any record is dependent on its length: short records have a high potential for misinterpretation. Often, the value of long records only becomes apparent when analysed in retrospect, perhaps yielding insight into processes and phenomena for which the data collection programme was not originally designed. We, therefore, urge monitoring agencies to devise a strategy for maintaining long records--at least for a few benchmark stations.

The multi-annual carbon budget of a peat-covered catchment.

This study estimates the complete carbon budget of an 11.4 km(2) peat-covered catchment in Northern England. The budget considers both fluvial and gaseous carbon fluxes and includes estimates of particulate organic carbon (POC); dissolved organic carbon (DOC); excess dissolved CO(2); release of methane (CH(4)); net ecosystem respiration of CO(2); and uptake of CO(2) by primary productivity. All components except CH(4) were measured directly in the catchment and annual carbon budgets were calculated for the catchment between 1993 and 2005 using both extrapolation and interpolation methods. The study shows that: Over the 13 year study period the total carbon balance varied between a net sink of -20 to -91 Mg C/km(2)/yr. The biggest component of this budget is the uptake of carbon by primary productivity (-178 Mg C/km(2)/yr) and in most years the second largest component is the loss of DOC from the peat profile (+39 Mg C/km(2)/yr). Direct exchanges of C with the atmosphere average -89 Mg C/km(2)/yr in the catchment. Extrapolating the general findings of the carbon budget across all UK peatlands results in an approximate carbon balance of -1.2 Tg C/yr (+/-0.4 Pg C/yr) which is larger than previously reported values. Carbon budgets should always be reported with a clear statement of the techniques used and errors involved as this is significant when comparing results across studies.

A molecular topology approach to predicting pesticide pollution of groundwater.

Various models have proposed methods for the discrimination of polluting and nonpolluting compounds on the basis of simple parameters, typically adsorption and degradation constants. However, such attempts are prone to site variability and measurement error to the extent that compounds cannot be reliably classified nor the chemistry of pollution extrapolated from them. Using observations of pesticide occurrence in U.S. groundwater it is possible to show that polluting from nonpolluting compounds can be distinguished purely on the basis of molecular topology. Topological parameters can be derived without measurement error or site-specific variability. A logistic regression model has been developed which explains 97% of the variation in the data, with 86% of the variation being explained by the rule that a compound will be found in groundwater if 6 chi Pv < 0.55. Where 6 chi p is the sixth-order molecular path connectivity. One group of compounds cannot be classified by this rule and prediction requires reference to higher order connectivity parameters. The use of molecular approaches for understanding pollution at the molecular level and their application to agrochemical development and risk assessment is discussed.

Limitations on the role of incorporated organic matter in reducing pesticide leaching.

The use of organic amendments has been suggested as a method of controlling pesticide leaching through soils. The enarenados soils of the intensive horticulture of the Almeria province of southern Spain contain buried organic matter horizons above a soil layer amended with clay. This region is ideal for understanding the potential for and limitations of organic amendments in preventing pesticide pollution. This study measured the sorption and degradation potential of carbofuran in this soil system and the hydrological behaviour of the soil horizons. The sorption of carbofuran was controlled by the organic carbon content, the degradation was strongly pH-dependent and the acidic organic layer protected the sorbed carbofuran against degradation. Hydrologically, the soil system is dominated by ponding above an amended clay layer and by the presence of macropores that can transport water through this clay. A simple model is proposed on this basis and shows that although high levels of dissolved organic carbon can be released by buried organic horizons, the major control on re-release of sorbed pesticide is the potential for sorption hysteresis in this organic layer. A comparison of sorption and degradation data for carbamate insecticides used in the region with groundwater observations for these compounds shows that no amount of incorporated organic would protect against pollution from highly water-soluble compounds.

A simple modelling approach for water quality: the example of an estuarine impoundment.

With the increasing development of water quality standards for all forms of water bodies and all forms of their uses, there is a greater need for models that can predict water quality in relation to these standards. This paper proposes an empirical method based on logistic regression techniques that deliver probabilities that given quality standards are met (i.e. water above or below the given standard). This technique is applied to data from a saline intrusion barrage (River Wansbeck, Northumberland, England) to predict low water quality events on the basis of UK water standards. The approach accurately classifies the overwhelming majority of pollution events that are caused by processes internal to the system. Misclassification can be ascribed to external processes, such as combined sewer outfalls. The general applicability of this method is compared to physically-based models.