Subsurface absorption of anthropogenic warming of the land surface: the case of the world's largest brickworks (Stewartby, Bedfordshire, UK).

Stewartby works, for a time the world's largest brickworks, began operation around the start of the twentieth century and closed in 2008. Subsurface temperature measurements are available in its vicinity, obtained as part of monitoring of an adjacent landfill in one of the former quarries for the Oxford Clay, which was the raw material for brick manufacture. A striking subsurface temperature anomaly, an increment of ~12°C, was first measured in 2004, and has subsequently decayed over time. The anomaly is centred beneath one of the former brick kilns, which operated between 1935 and 1991. To investigate processes of heat absorption by the shallow subsurface, this anomaly has been modelled as a consequence of conductive heat flow into the ground due to the operation of the ~3000 m(2) kiln. This modelling indicates that a very large amount of heat energy was transported into the subsurface; we estimate the typical downward surface heat flow during operation of the kiln as ~1 W m(-2) and the energy stored in the subsurface beneath it at its time of shutdown as ~6 TJ, or ~0.03% of that released by the fuel for heating the kiln, such that the total heat energy stored beneath this multi-kiln site peaked at ~200TJ. The proportion of heat energy transported into the subsurface was relatively low due to the nature of the Oxford Clay, which has a low thermal conductivity (~0.8 W m(-1)°C(-1)) and diffusivity (~0.3mm(2)s(-1)); in a more conductive lithology it might well have been three times greater. After kiln shutdown this subsurface thermal anomaly began to dissipate by upward heat conduction and release of heat into the atmosphere; at present about half of the peak energy stored remains, decreasing at ~1% per year, the maximum temperature anomaly being currently ~7°C at a depth of ~30 m and the typical upward heat flow during this span of time having exceeded the regional ~40 mW m(-2) background by roughly an order of magnitude. We believe this to be the first documented case whereby a subsurface thermal anomaly associated with operation of industrial plant has been related in detail to the history of site operations. This case study thus bears upon the controversial topic of the development of subsurface heat islands in general, and the associated perturbation of the thermal state of the subsurface as a result of anthropogenic warming of the atmosphere. It has previously been suggested that the worldwide heat gain in the subsurface over recent decades has exceeded that in the atmosphere by a factor of three. We show that this result is subject to some uncertainty, for example because it does not factor in lateral variations in thermal properties. Nonetheless, our case study demonstrates dissipation of a subsurface thermal anomaly by heat transport into the atmosphere. This indicates that warming of the atmosphere will be sustained in the future by dissipation of the large amount of energy stored in pre-existing subsurface thermal anomalies on a global scale, an issue of major societal implications that demands more detailed investigation.

Synergistic wetland treatment of sewage and mine water: pollutant removal performance of the first full-scale system.

Wetland systems are now well-established unit processes in the treatment of diverse wastewater streams. However, the development of wetland technology for sewage treatment followed an entirely separate trajectory from that for polluted mine waters. In recent years, increased networking has led to recognition of possible synergies which might be obtained by hybridising approaches to achieve co-treatment of otherwise distinct sewage and mine-derived wastewaters. As polluted discharges from abandoned mines often occur in or near the large conurbations to which the former mining activities gave rise, there is ample scope for such co-treatment in many places worldwide. The first full-scale co-treatment wetland anywhere in the world receiving large inflows of both partially-treated sewage (∼100 L s(-)(1)) and mine water (∼300 L s(-1)) was commissioned in Gateshead, England in 2005, and a performance evaluation has now been made. The evaluation is based entirely on routinely-collected water quality data, which the operators gather in fulfillment of their regulatory obligations. The principal parameters of concern in the sewage effluent are suspended solids, BOD5, ammoniacal nitrogen (NH4-N) and phosphate (P); in the mine water the only parameter of particular concern is total iron (Fe). Aerobic treatment processes are appropriate for removal of BOD5, NH4-N and Fe; for the removal of P, reaction with iron to form ferric phosphate solids is a likely pathway. With these considerations in mind, the treatment wetland was designed as a surface-flow aerobic system. Sample concentration level and daily flow rate date from April 2007 until March 2011 have been analyzed using nonparametric statistical methods. This has revealed sustained, high rates of absolute removal of all pollutants from the combined wastewater flow, quantified in terms of differences between influent and effluent loadings (i.e. mass per unit time). In terms of annual mass retention rates, for instance, the wetland system sequesters the following percentages of the key pollutants: BOD5: 41%; Fe 89%; NH4-N: 66%; dissolved P: 59%; total P: 46%; suspended solids: 66%. For similar wastewater chemistries, application of this type of co-treatment elsewhere could reasonably be based on the observed areally-normalized mass removal rates for the various pollutants found in this investigation.

Detection of mixing dynamics during pumping of a flooded coal mine.

In complex hydrogeological environments the effective management of groundwater quality problems by pump-and-treat operations can be most confidently achieved if the mixing dynamics induced within the aquifer by pumping are well understood. The utility of isotopic environmental tracers (C-, H-, O-, S-stable isotopic analyses and age indicators-(14) C, (3) H) for this purpose is illustrated by the analysis of a pumping test in an abstraction borehole drilled into flooded, abandoned coal mineworkings at Deerplay (Lancashire, UK). Interpretation of the isotope data was undertaken conjunctively with that of major ion hydrochemistry, and interpreted in the context of the particular hydraulic setting of flooded mineworkings to identify the sources and mixing of water qualities in the groundwater system. Initial pumping showed breakdown of initial water quality stratification in the borehole, and gave evidence for distinctive isotopic signatures (δ(34) S(SO4) ≅ -1.6‰, δ(18) O(SO4 ) ≅ +15‰) associated with primary oxidation of pyrite in the zone of water table fluctuation-the first time this phenomenon has been successfully characterized by these isotopes in a flooded mine system. The overall aim of the test pumping-to replace an uncontrolled outflow from a mine entrance in an inconvenient location with a pumped discharge on a site where treatment could be provided-was swiftly achieved. Environmental tracing data illustrated the benefits of pumping as little as possible to attain this aim, as higher rates of pumping induced in-mixing of poorer quality waters from more distant old workings, and/or renewed pyrite oxidation in the shallow subsurface.

Phosphorus removal from waste waters using basic oxygen steel slag.

Few studies have characterized reactive media for phosphorus (P) removal in passive treatment systems in terms of both batch and continuous flow experiments. This study uses basic oxygen steel slag (BOS) from a U.K. feedstock. Batch experiments demonstrated the effective removal of phosphorus with varying initial pH, initial P concentration, clast size, and ionic strength to represent environmental conditions. Continuous flow column experiments, operated for 406 days, with an influent P concentration of 1-50 mg/L (typical of domestic and dairy parlour waste) achieved removal of up to 62%; a second set of column experiments running for 306 days with an influent P concentration of 100-300 mg/L achieved a maximum effective removal of 8.39 mg/g. This figure is higher than that for other slags reviewed in this study (e.g., EAF Slag 3.93 mg/g and NZ melter slag 1.23 mg/g). XRD, E-SEM, and EDX data provide evidence for a sequential series of increasingly less soluble P mineral phases forming on the BOS surface (octa-calcium phosphate, brushite, and hydroxylapatite),which suggests that BOS may be a suitable substrate in passive treatment systems, providing a long-term P removal mechanism.

The effect of pH on plant litter decomposition and metal cycling in wetland mesocosms supplied with mine drainage.

The long term effectiveness of compost-based wetland systems treating net-acidic mine waters is reliant upon a continuing supply of decomposed organic matter which provides the basic foodstock for sulphate reducing bacteria. The annual turnover of wetland vegetation within these systems has been suggested to be the primary source for this material once the original substrate has been consumed. This study aimed to determine whether plant litter (of Common Reed, Phragmites australis) decomposition rates and release of metals and nutrients were affected by pH using controlled experiments under laboratory conditions. Loss of plant biomass was found to be unaffected by pH (3.0-6.5) suggesting that plant litter could be an important source of organic molecules for bacterial populations even under acidic conditions. The decomposing plant litter also acted as a focus for the precipitation of Fe oxides and sorption of Zn thereby acting as a short-term sink for these contaminants. This has important implications for geochemical cycling within the wetland system and potential transport out of the system. The essential nutrients (K and Mg) released from plant litter were affected by pH which could be important in nutrient availability for re-use by vegetation and other organisms within the system.

Buffering of alkaline steel slag leachate across a natural wetland.

Buffering of high-pH (>12) steel slag leachate is documented across a small, natural calcareous wetland. The alkaline leachate is supersaturated with respect to calcite upstream of the wetland (Sl(calcite) values +2.3) and becomes less saturated with progress across the wetland, to Sl(calcite) values of +0.27 at the wetland outlet. Reduction in pH across the wetland (to around pH 8 at the wetland outlet) was observed to be more pronounced over summer months, possibly due to increased microbial activity, possibly further assisted by greater flow baffling by emergent vegetation. Calculated calcite precipitation rates downstream of the leachate source, estimated from hydrochemical data, flow, and surface area, were on the order of 0.4-15 g m(-2) day(-1), while direct measurements (using immersed limestone blocks) showed calcite precipitation values in the range 3-10 g m(-2) day(-1). Precipitation rate was highest in the pH range where the carbonate ion is a dominant constituent of sample alkalinity (pH 9.5-11) and at the locations where wetland biota became established downstream of the leachate emergence. These data provide valuable insights into the potential for using constructed wetlands for the passive treatment of high pH steel slag leachates.

Rapid manganese removal from mine waters using an aerated packed-bed bioreactor.

In the UK, the Environmental Quality Standard for manganese has recently been lowered to 30 microg/L (annual average), which is less than the UK Drinking Water Inspectorate's Maximum Permitted Concentration Value (50 microg/L). Current passive treatment systems for manganese removal operate as open-air gravel-bed filters, designed to maximize either influent light and/or dissolved oxygen. This requires large areas of land. A novel enhanced bioremediation treatment system for manganese removal has been developed that consists of a passively aerated subsurface gravel bed. The provision of air at depth and the use of catalytic substrates help overcome the slow kinetics usually associated with manganese oxidation. With a residence time of only 8 h and an influent manganese concentration of approximately 20 mg/L, >95% of the manganese was removed. The treatment system also operates successfully at temperatures as low as 4 degrees C and in total darkness. These observations have positive implications for manganese treatment using this technique in both colder climates and where large areas of land are unavailable. Furthermore, as the operation of this passive treatment system continually generates fresh manganese oxyhydroxide, which is a powerful sorbent for most pollutant metals, it potentially has major ancillary benefits as a removal process for other metals, such as zinc.

The contribution of science to risk-based decision-making: lessons from the development of full-scale treatment measures for acidic mine waters at Wheal Jane, UK.

The use of risk-based decision-making in environmental management is often assumed to rely primarily on the availability of robust scientific data and insights, while in practice socio-economic criteria are often of considerable importance. However, the relative contributions to decision-making made by scientific and socio-economic inputs are rarely assessed, and even less commonly reported. Such an assessment has been made for a major remediation project in southwest England, in which some 300 l/s of highly acidic, metalliferous mine waters are now being treated using oxidation and chemical neutralisation. In the process of reaching the decision to commission the treatment plant, a wide range of scientific studies were undertaken, including: biological impact assessments, hydrogeological investigations of the effect of pumping on the flooded mine system, and hydrological and geochemical characterisation, together with integrated catchment modelling, of pollutant sources and pathways. These investigations revealed that, despite the spectacular nature of the original mine water outburst in 1992, the ecology of the Fal estuary remains remarkably robust. No scientific evidence emerged of any grounds for concern over the estuarine ecology, even if mine water were left to flow untreated. However, a rare ecological resource known as "maerl" (a form of calcified seaweed) is harvested annually in the estuary, providing significant revenue to the local economy and underpinning the 'clean' image of local sea water. Social and environmental benefit surveys revealed strong public perceptions that any visible discoloration in the estuary must indicate a diminution in quality of the maerl, to the detriment of both the public image and economy of the area. This factor proved sufficient to justify the continued pump-and-treat operations at the mine site. Although the decisive factor in the end was socio-economic in nature, robust assessment of this factor could not have been made without robust scientific evidence. It is concluded that investment in investigating and contributing to the formation of public perceptions is just as important as investing in scientific investigations per se.

Growth of Phragmites australis (Cav.) Trin ex. Steudel in mine water treatment wetlands: effects of metal and nutrient uptake.

The abandoned mine of Shilbottle Colliery, Northumberland, UK is an example of acidic spoil heap discharge that contains elevated levels of many metals. Aerobic wetlands planted with the common reed, Phragmites australis, were constructed at the site to treat surface runoff from the spoil heap. The presence of a perched water table within the spoil heap resulted in the lower wetlands receiving acidic metal contaminated water from within the spoil heap while the upper wetland receives alkaline, uncontaminated surface runoff from the revegetated spoil. This unique situation enabled the comparison of metal uptake and growth of plants used in treatment schemes in two cognate wetlands. Results indicated a significant difference in plant growth between the two wetlands in terms of shoot height and seed production. Analyses of metal and nutrient concentrations within plant tissues provided the basis for three hypotheses to explain these differences: (i) the toxic effects of high levels of metals in shoot tissues, (ii) the inhibition of Ca (an essential nutrient) uptake by the presence of metals and H+ ions, and (iii) low concentrations of bioavailable nitrogen sources resulting in nitrogen deficiency. This has important implications for the engineering of constructed wetlands in terms of the potential success of plant establishment and vegetation development.

Hydrochemical stratification in flooded underground mines: an overlooked pitfall.

The fact that flooded underground mines are commonly hydrochemically stratified is often not appreciated. Water samples taken from the water surface in partly flooded shafts are often wrongly assumed to represent the water quality existing throughout the entire water column. In some cases, treatment systems have been designed on the basis of these often misleading water surface samples. Stratification can build up within a slowly recovering system where there are few lateral inflows and outflows to the system. Less mineralised, shallow-sourced water enters at the top of the water column and more heavily mineralised water tends to remain at the base of the water column. This water has a high dissolved solids content due to dissolution of increasing amounts of pyrite oxidation salts and other minerals as the water level rises through the old workings. However, such stratification can easily be lost following hydraulic disturbance of the system (either by pumping or by natural decant when the water level reaches an outflow pathway from the mine system, such as an old adit or shaft collar) and often results in surface discharges of poor water quality. Test pumping of one such stratified system (Frances Colliery, Scotland) has provided useful information about how stratified systems develop, and how they can behave when disturbed. The water quality observed after stratification was disturbed by pumping was worse than would have been anticipated on the basis of water samples taken from the surface of the water column prior to pumping (with concentrations of contaminants such as iron and zinc being around two orders of magnitude greater than in water surface samples). Taken together with other information from the literature, the experience at Frances Colliery supports the proposal of criteria for recognising when stratification of mine water quality might be anticipated, thus facilitating the timely deployment of measures required for its detection at an early stage.

Substrate characterisation for a subsurface reactive barrier to treat colliery spoil leachate.

Subsurface permeable reactive barriers (PRB) have been used to successfully treat acidic mine drainage in Canada and offer great potential for doing the same in the United Kingdom. A PRB for the treatment of colliery spoil leachate from a site near Newcastle upon Tyne, UK, has been designed. The selection of the reactive media to be used is of paramount importance, with particular reference to permeability and reactivity. A number of reactive media mixtures containing varying proportions of cattle slurry screenings, green waste compost, calcite limestone chips and pea gravel were prepared and their respective permeabilities and reactivities were investigated. Media mixtures containing 50% 10 mm grade calcite limestone chips showed better alkalinity addition and metals removal than a blank containing 50% pea gravel. A media mixture containing 50% limestone chips and 50% green waste compost showed a 24 h period to achieve maximum addition of alkalinity and maximum removal of acidity and metals. Mixtures containing 25% green waste compost and 25% slurry screenings achieved maximum addition/removal in 4 h. The likely presence of iron sulphide in samples drawn from test vessels during both test runs indicates that bacterial sulphate reduction is occurring in this composite.

Critical role of macrophytes in achieving low iron concentrations in mine water treatment wetlands.

Aerobic wetlands are increasingly being included in mine water treatment systems which need to achieve low residual iron concentrations (<0.5 mg L(-1)) in final discharges. Traditionally the macrophyte components of such systems have been thought to be insignificant sinks for major contaminants such as iron. However, we report high rates of plant uptake of iron where the latter is present at relatively low concentrations, suggesting that macrophytes may well be critical to achieving low residual iron concentrations in final effluents from such systems. The wetland macrophyte Phragmites australis was grown in waters with a range of iron concentrations (0-50 mg L(-1)). At an Fe supply of 1 mg L(-1) almost 100% of the Fe was taken up into plant tissues. The majority of iron was stored in and around the roots of the plants, which helps allay fears of possible release of contaminants during seasonal die-back of emergent shoots and leaves. The 1 mg L(-1) threshold also proved to be important in terms of plant growth, with significant inhibition (evident in root length and in dry weights of shoots and roots) in plants grown in waters with Fe above this concentration. No direct causal relationship between iron content in aerial tissues and growth inhibition was found, which strongly suggests that iron toxicity cannot explain these results. These results have implications for the design of mine water treatment wetlands, particularly with regard to initial establishment of vegetation and achieving sufficient Fe removal in "polishing" applications (i.e. where it is intended to remove the last few mg L(-1) of Fe).