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The effectiveness of liquid carbon additions to enhance zinc removal in laboratory-scale short hydraulic residence time (19 h) compost bioreactors receiving synthetic mine water with a high influent zinc concentration (45 mg/L) was investigated. Effective removal of such elevated zinc concentrations could not be sustained by sulfate reduction and/or other attenuation processes without carbon supplementation. Propionic acid addition resulted in improved and sustained performance by promoting the activities of sulfate reducing bacteria, leading to efficient zinc removal (mean 99%) via bacterial sulfate reduction. In contrast, cessation of propionic acid addition led to carbon limitation and the growth of sulfur oxidising bacteria, compromising zinc removal by bacterial sulfate reduction. These research findings demonstrate the potential for modest liquid carbon additions to compost-based passive treatment systems to engineer microbial responses which enhance rates of zinc attenuation in a short hydraulic residence time, enabling remediation of highly polluting mine drainage at sites with limited land availability.

Geochemical and hydrological data from abandoned mine watersheds demonstrated that (1) point sources of pollution fail to account for total receiving watercourse metal load at higher flows and (2) an inverse relationship exists between river flow and pH due to peatland runoff. Quantifying the varying importance of point and diffuse pollution sources enabled prediction of treatment benefits for a major point source of pollution in one watershed. Instream zinc load increases with river flow (∼3 to 14 kg Zn/d) due to diffuse groundwater and surface runoff pollution sources at higher flows. Lab tests demonstrated that metal release from the streambed, driven by pH decreases at higher flows, also contribute to increased downstream metal loads. Predicting point source treatment benefits demonstrates major instream improvements at low flow (zinc decreases from >800 to 120 μg Zn/L). At higher flows treatment benefits diminish (Zn decreases from 240 to only 200 μg Zn/L) due to the greater influence of diffuse sources. A quantitative understanding of the variable importance of point and diffuse sources of pollution, and instream processes of metal attenuation and release, is crucial to evaluating the benefits of treatment to downstream water quality.

The performance of an innovative pilot-scale subsurface flow compost wetland for the attenuation of zinc in mine drainage was investigated. The particular novelty of the system, which operated under ambient environmental conditions, was the short hydraulic residence time (HRT) of 7.5–14.5 h. Short HRT is crucial because it reduces absolute wetland size and construction cost, which can be major impediments to use of wetlands. Over a 2 year period mean treatment efficiency was 67.5% (total Zn) and 84.4% (0.45 μm filtered Zn). Mean volume-adjusted removal rates for total and filtered Zn were 0.92 g/m3/day and 1.05 g/m3/day respectively. Both water and compost analyses showed bacterial sulfate reduction to be the most important Zn removal process within the subsurface flow wetland: water analyses showed consistent decreases in sulfate concentration through the system, whilst Acid Volatile Sulfide − Simultaneously Extracted Metals (AVS-SEM) analysis of the compost revealed concentrations of Zn up to 12,227 mg/kg and AVS up to 9066 mg/kg. Geochemical modelling using PHREEQC also showed that biogeochemical conditions within the wetland favored Zn attenuation as its sulfide: ZnS was the only solid Zn phase that was super-saturated in the wetland effluent water (mean Saturation Index of +9.52). Preliminary investigation of the use of liquid waste carbon sources to further enhance performance were ambiguous, but the results of the research nevertheless show the potential of short hydraulic residence time subsurface flow compost wetlands as a low cost treatment option for metal-polluted abandoned mine drainage.

Paul was born in north-east England, in Hebburn, on the south bank of the River Tyne. He moved over the river to attend the University of Newcastle, receiving a first class honours B.Sc. Geology in 1984. He then crossed the Atlantic, to Oklahoma State University, USA, where he completed his M.S. Geology as a Harkness Fellow, specialising in hydrogeology.

Quantitatively evaluating progress toward energy neutral, or even energy positive, wastewater treatment necessitates reliable data on the intrinsic energy content of the wastewater. It has long been assumed that the amount of energy in wastewater is directly related to its chemical oxygen demand (COD), but the convoluted method for measuring the wastewater energy content has meant that a reliable, statistically robust relationship between COD and energy has never been drawn. In this research, we used a new drying method and analyzed a set of 107 municipal wastewater samples, with a range of COD values from 16.4 to 1151 mg/L. The results revealed a strong correlation between COD and energy content of 16.1 kJ/g of COD (p < 0.001). Reliable predictions of a wastewater’s energy content can now be made on the basis of the COD measurement alone.

Extreme rainfall events are predicted to become more frequent with climate change and can have a major bearing on instream solute and pollutant transport in mineralised catchments. The Coledale Beck catchment in north-west England was subject to an extreme rainfall event in December 2015 that equated to a 1 in 200-year event. The catchment contains the UK's first passive metal mine water treatment system, and as such had been subject to intense monitoring of solute dynamics before and after commissioning. Due to this monitoring record, the site provides a unique opportunity to assess the effects of a major storm event on (1) catchment-scale solute transport, and (2) the resilience of the new and novel passive treatment system to extreme events. Monitoring suggests a modest decline in treatment efficiency over time that is not synchronous with the storm event and explained instead by changes in system hydraulic efficiency. There was no apparent flushing of the mine system during the event that could potentially have compromised treatment system performance. Analysis of metal transport in the catchment downstream of the mine suggests relatively subtle changes in instream chemistry with modest but statistically-significant reductions in zinc in the lower catchment irrespective of flow condition after the extreme event, but most parameters of interest show no significant change. Increased export of colloidal iron and aluminium is associated with major landslips in the mid-catchment after the storm and provide fresh sorption sites to attenuate dissolved zinc more rapidly in these locations, corroborated by laboratory experiments utilising site materials to investigate the attenuation/release of metals from stream and terrestrial sediments. The data are important as they show both the resilience of passive mine water treatment systems to extreme events and the importance of catchment-scale monitoring to ensure continued effectiveness of treatment initiatives after major perturbation.

The iron and steel industry has a long tradition of bulk reuse of slags for a range of construction applications. Growing interest in recent years has seen slag resource recovery options extend to critical raw material recovery and atmospheric carbon capture. Full scale deployment of such technologies is currently limited in part by absent or partial inventories of slag deposit locations, data on composition, and volume estimates in many jurisdictions. This paper integrates a range of spatial information to compile a database of iron and steel slag deposits in mainland United Kingdom (UK) for the first time and evaluate the associated resource potential. Over 190 million tonnes of legacy iron and steel slag are present across current and former iron and steel working regions of the UK, with particular concentrations in the north west and north east of England, and central Scotland. While significant potential stockpiles of blast furnace and basic oxygen furnace slag could provide up to 0.9 million tonnes of vanadium and a cumulative carbon dioxide capture potential of 57–138 million tonnes, major management challenges for resource recovery are apparent. Over one third are located in close proximity to designated conservation areas which may limit resource recovery. Furthermore, land use analyses show that many of the sites have already been redeveloped for housing (nearly 30% urban cover). Deposits from recent decades in current or recently closed steel-working areas may have the greatest potential for resource recovery where such ambitions could be coupled with site restoration and regeneration efforts.

Treatment of pollution from abandoned coal mines often requires significant inputs of electrical power, particularly at sites where long-term pumping of mine water is required. Given the large fossil fuel generation element of the UK electricity supply network, this has a direct impact on carbon emissions. The potential for recovery of low enthalpy heat at mine water treatment sites in Great Britain, such that they could become net sources of energy during operation, rather than consumers, was explored using data from April 2014 to March 2015. To do this, an inventory of coal mine water treatment systems across England, Scotland and Wales was first collated, including key variables for each site. The heat energy which could potentially be recovered was then assessed against the energy consumption of each site and reviewed at a national scale. It was found that 47.5 MW of thermal energy was available for recovery from mine waters, compared to 2.3 MW of electrical power already committed for pumping and treatment of these waters. Recovery of thermal energy might be achievable by the use of heat pumps for space heating of nearby properties. Yet, because of the high carbon cost of UK grid electricity required to power heat pumps, this approach would offer only very modest CO2 savings over domestic gas central heating. Calculations made in this paper suggests that just 0.33 kt CO2 savings are achievable using this approach, compared to existing emissions of 10.8 kt CO2 entailed by the pumping and treatment sites themselves.

A study of hydraulic residence time has been conducted for several UK Coal Authority mine water treatment systems to evaluate the impact of residence time on the overall hydraulic performance and iron removal within the systems. A series of tracer tests were conducted within the Coal Authority mine water treatment wetlands and lagoons to measure actual hydraulic residence time. The tracer residence time distributions (RTDs) were analysed based on a tanks-in-series (TIS) model to yield the mean residence time and corresponding hydraulic characteristics of the systems. The relationship between iron retention and residence time was tested against a first-order removal model. The mean hydraulic efficiency is 69 % for the wetlands compared to 24 % for the lagoons, mainly attributable to comparatively greater volumetric efficiency within the wetland systems. The mean number of TIS, n, is 3.9 for the wetlands and 2.1 for the lagoons, illustrating considerably different flow patterns between wetlands and lagoons. There is also a notable difference of treatment efficiency for iron; mean of 81 % and 47 % for wetlands and lagoons, respectively. Generally, it appears that system hydraulic efficiency (derived from the principle of TIS model) corresponds with iron retention in the treatment systems.

The failure of the Ajka red mud depository in October 2010 led to the largest single release of red mud into the surface water environment. This study provides a comparative assessment of stream sediment quality in the Torna-Marcal-Rába catchment between post-disaster surveys (2010) and follow up surveys at an identical suite of 21 locations in 2013. The signature of red mud apparent in initial surveys with high Al, As, Cr, Na, V was only apparent at a small number of sample stations in recent surveys. These constitute1 km of stream, compared to the20 km reach of affected sediments in the immediate aftermath of the spill. Concentrations of red mud-derived contaminants are predominately associated with fine fractions of the red mud (8 μm). This enhances transport out of the system of red mud-derived contaminants and, along with extensive remedial efforts, has substantially limited the within-channel inventory of potentially ecotoxic metals and metalloids.

Hydraulic performance assessment of passive treatment systems has been conducted for UK's Coal Authority mine water treatment systems. The study aims to improve the understanding of the hydraulic factors that govern contaminant behaviour, such that future design of treatment systems is able to optimise treatment efficiency and make performance more predictable, and improve performance over the long-term. Assessment of the hydraulic behaviour (i.e. residence time and flow pattern) of the treatment systems was accomplished by means of tracer tests. The tracer tests were undertaken at eight UK Coal Authority mine water treatment systems (lagoons and wetlands) within Northern England (main study areas) and part of southern Scotland. A modelling approach using a tanks-in-series (TIS) model was adopted to precisely analyse and characterise the residence time distributions (RTDs), in an effort to account for the different flow patterns across the treatment systems. Generally, lagoon RTDs are characterised by a greater flow dispersion compared to wetlands (i.e. higher dispersion number, D and lower number of TIS, n). Consequently, the hydraulic efficiency, eλ for lagoons is much lower than wetlands (mean of 0.20 for lagoons compared to 0.66 for wetlands). Implications for design and maintenance of mine water treatment systems are discussed.

A number of emergency pollution management measures were enacted after the accidental release of caustic bauxite processing residue that occurred in Ajka, western Hungary in October, 2010. These centred on acid and gypsum dosing to reduce pH and minimise mobility of oxyanion contaminants mobile at high pH. This study assessed the effectiveness of gypsum dosing on contaminant mobility and carbon sequestration through assessment of red mud and gypsum-affected fluvial sediments via elemental analysis and stable isotope analysis. There was a modest uptake of contaminants (notably As, Cr, and Mn) on secondary carbonate-dominated deposits in reaches subjected to gypsum dosing. C and O stable isotope ratios of carbonate precipitates formed as a result of gypsum dosing were used to quantify the importance of the neutralisation process in sequestering atmospheric carbon dioxide. This process was particularly pronounced at sites most affected by gypsum addition, where up to 36% of carbonate-C appears to be derived from atmospheric in-gassing of CO(2). The site is discussed as a large scale analogue for potential remedial approaches and carbon sequestration technologies that could be applied to red mud slurries and other hyperalkaline wastes. The results of this work have substantial implications for the aluminium production industry in which 3-4% of the direct CO(2) emissions may be offset by carbonate precipitation. Furthermore, carbonation by gypsum addition may be important for contaminant remediation, also providing a physical stabilisation strategy for the numerous historic stockpiles of red mud.

Results are presented from X-ray absorption spectroscopy based analysis of As, Cr, and V speciation within samples of bauxite ore processing residue (red mud) collected from the spill site at Ajka, Western Hungary. Cr K-edge XANES analysis found that Cr is present as Cr(3+) substituted into hematite, consistent with TEM analysis. V K-edge XANES spectra have E(1/2) position and pre-edge features consistent with the presence of V(5+) species, possibly associated with Ca-aluminosilicate phases. As K-edge XANES spectra identified As present as As(5+). EXAFS analysis reveals arsenate phases in red mud samples. When alkaline leachate from the spill site is neutralized with HCl, 94% As and 71% V are removed from solution during the formation of amorphous Al-oxyhydroxide. EXAFS analysis of As in this precipitate reveals the presence of arsenate Al-oxyhydroxide surface complexes. These results suggest that in the circumneutral pH, oxic conditions found in the Torna and Upper Marcal catchments, incorporation and sorption, respectively, will restrict the environmental mobility of Cr and As. V is inefficiently removed from solution by neutralization, therefore, the red mud may act as a source of mobile V(5+) where the red mud deposits are not removed from affected land.

Diurnal fluctuations of metals have been observed in the South Tyne river catchment, UK, in both upland tributaries and major river reaches. Zinc exhibits the most pronounced cyclicity, with concentrations increasing during the night to a maximum near 05:00 before decreasing during the day. This trend is the inverse of pH and temperature observations, which are thought to be the predominant drivers behind the cyclicity. Photosynthetic reactions of biomass and algae alter the pH within the river systems, therefore promoting hydrous metal oxide precipitation during the daylight which consequently allows divalent cations including zinc to sorb onto them. This mechanism may be supported by direct uptake of zinc by algae and other biogeochemical reactions which combine to create large differences in zinc concentrations; during base flow zinc concentrations increased by 326% from the minima over 48 hours. Maximum concentrations are not being captured during routine water quality analysis resulting in inaccurate and misleading EQS results and total flux estimations, for example the annual total zinc flux in a small tributary increases from 17 to 76 tonnes/year when routine grab sample data are supplemented with 24-hour sampling results.

Bioreactors utilising bacterially mediated sulphate reduction (BSR) have been widely tested for treating metal-rich waters, but sustained treatment of mobile metals (e.g. Zn) can be difficult to achieve in short residence time systems. Data are presented providing an assessment of alkalinity generating media (shells or limestone) and modes of metal removal in bioreactors receiving a synthetic acidic metal mine discharge (pH 2.7, Zn 15 mg/L, SO(4)(2-) 200mg/L, net acidity 103 mg/L as CaCO(3)) subject to methanol dosing. In addition to alkalinity generating media (50%, v.v.), the columns comprised an organic matrix of softwood chippings (30%), manure (10%) and anaerobic digested sludge (10%). The column tests showed sustained alkalinity generation, which was significantly better in shell treatments. The first column in each treatment was effective throughout the 422 days in removing >99% of the dissolved Pb and Cu, and effective for four months in removing 99% of the dissolved Zn (residence time: 12-14 h). Methanol was added to the feedstock after Zn breakthrough and prompted almost complete removal of dissolved Zn alongside improved alkalinity generation and sulphate attenuation. While there was geochemical evidence for BSR, sequential extraction of substrates suggests that the bulk (67-80%) of removed Zn was associated with Fe-Mn oxide fractions.

Quantifying diffuse sources of pollution is becoming increasingly important when characterising river catchments in entirety – a prerequisite for environmental management. This study examines both low and high flow events, as well as spatial variability, in order to assess point and diffuse components of zinc pollution within the River West Allen catchment, which lies within the northern England lead–zinc Orefield. Zinc levels in the river are elevated under all flow regimes, and are of environmental concern. Diffuse components are of little importance at low flow, with point source mine water discharges dominating instream zinc concentration and load. During higher river flows 90% of the instream zinc load is attributed to diffuse sources, where inputs from resuspension of metal-rich sediments, and groundwater influx are likely to be more dominant. Remediating point mine water discharges should significantly improve water quality at lower flows, but contribution from diffuse sources will continue to elevate zinc flux at higher flows.

Mineralogical characterization of the precipitates developed in passive systems treating mine-polluted waters is an essential tool to fully understand and control the removal processes taking place in these systems. In 2008, after five years of operation, a section of the permeable reactive barrier (PRB) at Shilbottle, Northumberland, was subjected to a low intrusive/non-destructive solid sampling. These solid samples were mineralogically characterized by XRD, ESEM-EDS, and sequential extractions. In addition to the solid sampling, 44 water samples obtained in the PRB from January 2004 to August 2009 were used to study the mineral stability of some selected phases in these waters. It was observed that the main iron phases in the PRB were those associated with mineral phases typically developed in non-reducing environments (schwertmannite and goethite), while the presence of a significant amount of pyrite was also observed. The low residence time of the water within the PRB (from 10 to 40 h) appears to be the reason for the absence of a more reducing and less acidic environment in the reactive substrate. An increase of residence time in the PRB, by increasing reactive mixture porosity and resizing the PRB, changes in the reactive material employed (smaller limestone grain size and inclusion of zerovalent iron) and changes in the PRB design (isolating top layer and forced homogeneous flow upward through all the reactive material) are proposed for future reconditioning of the system.

A full-scale passive treatment system (PTS) was commissioned in 2003 to treat two net-acidic coal mine water discharges in the Durham coalfield, UK. The principal aim of the PTS was to decrease concentrations of iron (177 mg L(-1)) and aluminium (85 mg L(-1)) and to increase pH (3.2) and alkalinity (or =0 mg L(-1) CaCO(3) eq). Secondary objectives were to decrease zinc (2.8 mg L(-1)), manganese (20.5 mg L(-1)) and sulfate (2120 mg L(-1)). Upon treatment, water qualities were improved by 84% in the case of Fe, 87% Al, 83% acidity, 51% Zn, 23% Mn and 29% SO(4)(2)(-). Alkalinity (74%) and pH (95% as H(+)) were increased. Area adjusted removal rates (Fe=1.49+/-0.66 g d(-1) m(-2); acidity=6.7+/-4.9 g d(-1) m(-2)) were low compared to design criteria, mainly due to load limitation. Disregarding seasonality effects, acidity removal and effluent pH were stable over time. A substantial temporal decrease in calcium and alkalinity generation suggests that limestone is increasingly armoured. Once pH is no longer buffered by the carbonate system, metals could be remobilized, putting treatment efficiency at risk.

Analysis of residence time distribution (RTD) has been conducted for the UK Coal Authority's mine water treatment wetland at Lambley, Northumberland, to determine the hydraulic performance of the wetland over a period of approximately 4 years since site commissioning. The wetland RTD was evaluated in accordance with moment analysis and modelled based on a tanks-in-series (TIS) model to yield the hydraulic characteristics of system performance. Greater hydraulic performance was seen during the second site monitoring after 21 months of site operation i.e. longer hydraulic residence time to reflect overall system hydraulic efficiency, compared to wetland performance during its early operation. Further monitoring of residence time during the third year of wetland operation indicated a slight reduction in hydraulic residence time, thus a lower system hydraulic efficiency. In contrast, performance during the fourth year of wetland operation exhibited an improved overall system hydraulic efficiency, suggesting the influence of reed growth over the lifetime of such systems on hydraulic performance. Interestingly, the same pattern was found for iron (which is the primary pollutant of concern in ferruginous mine waters) removal efficiency of the wetland system from the second to fourth year of wetland operation. This may therefore, reflect the maturity of reeds for maintaining efficient flow distribution across the wetland to retain a longer residence time and significant fractions of water involved to enhance the extent of treatment received for iron attenuation. Further monitoring will be conducted to establish whether such performance is maintained, or whether efficiency decreases over time due to accumulation of dead plant material within the wetland cells.

In regions affected by historic non-coal (principally metal) mining activity, government agencies are often faced with the challenge of deploying limited remedial resources at abandoned mine sites to achieve maximum improvements in the chemical and ecological quality of impacted ground and surface waters. As such, strategies for the defensible allocation of public funds require comprehensive and systematic frameworks by which to identify and prioritise polluting sites for remediation. This paper describes the development and initial findings of such a national initiative in England and Wales which allies catchment-scale environmental impact assessments using existing public archive data, with recognition of the uncertainty in impact appraisals arising from disparities in data availability between sites and regions. The methodology identifies polluting sites and takes account not only of the chemical and ecological impacts of mine water discharges on receiving watercourses, but also of socio-economic factors such as conservation and heritage concerns, which can both impede or complement efforts to remediate mine sites. Using a Geographic Information System database and a suite of spatial analyses employing Boolean operators, both the extent of the pollution problem from abandoned non-coal mines in England and Wales (6% of 7815 surface water bodies are affected nationally) and the insight that can be gleaned from systematic analyses of existing archive data are highlighted. The results of the nationwide survey can be used as a dynamic database to inform future remedial planning, in terms of prioritising impacted river basins and abandoned non-coal mine sites themselves for either remediation or future monitoring efforts. As the assessment framework is built upon existing water quality and ecological data and mine site/geological data, there is considerable scope for the approach to be applied elsewhere where the legacy of historic mining persists through the widespread pollution of the aquatic environment.

High pH (>12) leachates are an environmental problem associated with drainage from lime (CaO)-rich industrial residues such as steel slags, lime spoil and coal combustion residues. Recent research has highlighted the potential for natural (‘volunteer’) wetlands to buffer extremely alkaline influent waters. This appears ascribable to high CO2 partial pressures in the wetland waters from microbial respiration, which accelerates precipitation of calcium carbonate (CaCO3), and the high specific surface area for mineral precipitation offered by macrophytes. The research presented here builds on this and provides preliminary evaluation of a constructed wetland built in March 2008 to buffer drainage from steel slag heaps in north-east England. The drainage water from the slag mounds is characterised by a mean pH of 11.9, high concentrations of Ca (up to 700 mg/L), total alkalinity (up to 800 mg/L as CaCO3) and are slightly brackish (Na = 300 mg/L; Cl = 400 mg/L) reflecting native groundwaters at this coastal setting. Documented calcite precipitation rates (mean of 5 g CaCO3/m2/day) from nearby volunteer sites receiving steel slag drainage were used to scale the constructed wetland planted with Phragmites australis; a species found to spontaneously grow in the vicinity of the discharge. Improved performance of the wetland during summer months may at least in part be due to biological activity which enhances rates of calcite precipitation and thus lowering of pH. Secondary Ca-rich precipitates also serve as a sink for some trace elements present at low concentrations in the slag leachate such as Ni and V. The implications for scaling and applying constructed wetlands for highly alkaline drainage are discussed.

Constructed wetlands are an established treatment technology for a diverse range of polluted effluents. There is a long history of using wetlands as a unit process in treating acid mine drainage, while recent research has highlighted the potential for wetlands to buffer highly alkaline (pH>12) drainage. This paper reviews recent evidence on this topic, looking at wetlands treating acidic mine drainage, and highly alkaline leachates associated with drainage from lime-rich industrial by-products or where such residues are used as filter media in constructed wetlands for wastewater treatment. The limiting factors to the success of wetlands treating highly acidic waters are discussed with regard to design practice for the emerging application of wetlands to treat highly alkaline industrial discharges. While empirically derived guidelines (with area-adjusted contaminant removal rates typically quoted at 10 g Fe m(2)/day for influent waters pH>5.5; and 3.5-7 g acidity/m(2)/day for pH>4 to

In the UK, the Coal Authority has more than 40 mine water treatment systems, most of which are wetland systems with settlement lagoon pretreatment. The purpose of treatment in wetlands is the oxidation of ferrous to ferric iron and the subsequent hydrolysis and precipitation of ferric hydroxide within the wetland. It is generally accepted (Hedin et al., Passive treatment of coal mine drainage, 1994, p 35; Skousen and Ziemkiewicz, Acid mine drainage control and treatment, 1996, p 362; Younger et al., Mine water: hydrology, pollution, remediation, 2002, p 442) that this process proceeds by a first-order rate law, although most systems are designed based on an areal removal rate (10 g/m2/day) developed by the U.S. Bureau of Mines (Hedin et al., Passive treatment of coal mine drainage, 1994, p 35); this design guideline inherently assumes a constant removal rate. Given the actual kinetics of iron removal in wetlands, it follows that residence time will control iron removal; given the wide range of system geometries and aspects, it is logical to ascertain the actual hydraulic residence time of wetlands and settlement lagoons and determine the effect this has on iron removal. To make a preliminary assessment of this link, hydraulic residence time of two Coal Authority wetlands (Lambley and Whittle) and two Coal Authority settlement lagoons (Acomb East, Acomb West and Whittle) were measured using bromide tracer tests. Water samples for iron analysis and flow measurements were taken during each tracer test. The Lambley wetland performs well in terms of residence time, and, as reeds become established and adsorptive processes increase, its iron removal performance (currently 58% removal) may improve, but the low influent iron concentration appears to be a significant impediment to meeting the original performance target. In contrast, the hydraulic performance of the Whittle wetland system is poor, which appears to be due to accumulation of dead plant material coupled with a high length to width ratio. However, performance in terms of iron removal is good (92% removal), which appears to be due to the higher influent iron concentration, and especially the fact that the iron enters the wetland largely in particulate form. The longer residence time of water within the Acomb lagoons (≈12 h) resulted in far more effective iron removal (72% in the east lagoon and 85% in the west lagoon) than the shorter residence time at Whittle (24% iron removal, ≈5 h residence time). Performance (in terms of iron removal) of the settlement lagoon systems appears to be far more closely related to the hydraulic residence time (albeit this conclusion must be tentative, given that only three systems have been investigated, and the Acomb system receives chemical addition). Based on this study, treatment system sizing using 100 m2 lagoon area per 1 L/s flow appears to be a more appropriate basis for design rather than an areal iron removal rate.

Data are presented which evaluate the performance of a pilot-scale treatment system using pelletised hydrous ferric oxide (HFO; a waste stream from coal mine water treatment) as a high surface area sorbent for removing zinc (Zn) from a metal mine water discharge in the North Pennines Orefield, UK. Over a 10-month period the system removed Zn at mean area- and volume-adjusted removal rates of 3.7 and 8.1 g m−3 day−1, respectively, with a mean treatment efficiency of 32% at a low mean residence time of 49 min. There were seasonal effects in Zn removal owing to establishment and dieback of algae in the treatment tank. This led to increased Zn uptake in early summer months followed by slight Zn release upon algae senescence. In addition to these biosorptive processes, the principal sinks for Zn appear to be (1) sorption onto the HFO surface, and (2) precipitation with calcite-dominated secondary minerals. The latter were formed as a product of dissolution of portlandite in the cement binder and calcium recarbonation. Further optimisation of the HFO pelletisation process holds the possibility for providing a low-cost, low footprint treatment option for metal rich mine waters, in addition to a valuable after-use for recovered HFO from coal mine water treatment facilities.

Mine water pollution is a major cause of surface- and groundwater pollution in former mining districts throughout Europe. It is a potential barrier to achieving good status water bodies, which is a requirement of the EU Water Framework Directive. In the UK, a concerted effort has been made over the last decade or so to address the scientific and practical challenges relating to the remediation of mine water pollution. However, most of this work has focused on remediation of point sources of pollution (typically arising from abandoned mines and shafts), while the behaviour of mine water at the groundwater-surface water interface (the "hyporheic zone") has received far less attention in relevant scientific and engineering literature. The extent of mine water pollution and capacity for its attenuation at the hyporheic zone has not been well quantified while, furthermore, the complex chemical and microbial processes occurring there (specifically with reference to mining-derived pollutants) have not been investigated in any depth. The absence of such data may relate, in a large part, to the difficulty in physically measuring volumes and concentrations associated with these river inputs/exports. A far greater body of literature addresses biogeochemical processes at the hyporheic zone (especially relating to manganese), albeit many such articles relate to aqueous metal dynamics in general, rather than mine water specifically. This paper presents a review of the natural attenuation processes that may limit the movement and availability of mining-derived pollutants at the groundwater-surface water (GW-SW) interface, and specifically within the hyporheic zone. A substantial part focuses on precipitation and adsorption processes at the hyporheic zone, as well as discussing the role of microbial processes in governing metal ion mobility.

Field and laboratory measurements of mine waters emerging from abandoned deep coal mines in the UK have shown that CO2 partial pressures (pCO2) may be more than 100 times greater than atmospheric levels. Measured values of acidity vary significantly with time due to degassing of CO2 from such samples. The evolution (i.e. decrease) of pCO2 with time is described. The significance of these findings for mine water treatment process selection is discussed, and plans for future research in this area are outlined.

Recent implementation of the EU Water Framework Directive necessitates addressing water quality issues at the catchment scale. In this study, contaminant loading of all point discharges have been measured, establishing the overall impact of mine waters within the catchments, and allowing the derivation of contributions of diffuse mine water pollution to these totals. The results of two ongoing case studies of mine-impacted river catchments in the north-east of England are presented. The Allen catchment, Northumberland, is impacted by discharges from abandoned Pb/Zn mines with up to 6 mg/l Zn and 0.2 mg/l Pb, which significantly exceed European ecotoxicological standards by up to a factor of 75 and 20 respectively. The Gaunless catchment, County Durham, receives uncontrolled discharges of coal mine waters with up to 8 mg/l Fe. Preliminary findings show that during both low and high flow conditions diffuse iron pollution contributes significantly to in-stream iron loadings. Probable pathways include direct groundwater input and remobilisation due to scouring of streambed sediments.

The use of copper(I) Schiff base complex catalysed atom transfer polymerisation of methacrylates is described. The use of a range of functional and multi-functional initiators enables the synthesis of a range of functional and star polymers to be prepared under undemanding synthetic conditions. End capping with silyl enol ethers allows for ω-functional polymers. The combination of novel initiators, functional monomers and end capping allows an unprecedented array of macromolecular structures to be produced with limited need for protecting group chemistry.

Mine water pollution is one of the most severe forms of aquatic pollution in the UK, and it is a widespread problem internationally. The impacts of mine waters and current methodologies for quantifying these impacts are detailed. Current EIA methods take little account of the socioeconomic effects of these discharges, which can be severe. Local public interest and concern may constitute a major driving force towards remedial action. A number of benefits are associated with involving local communities in mine water EIA and remediation. Thus, some provision for incorporating these issues into mine water EIA is recommended. There is also a pressing need to develop predictive EIA strategies for future mine water discharges. While predictions of the pollution risks associated with a cessation of deep mining are now possible, the accuracy and precision of the latest techniques still falls short of what is needed to allow rational cost–benefit analysis of future environmental management options for redundant mine workings.

The synthesis and characterization, including crystallographic analysis, of the bifunctional boranes RCHC[B(C6F5)2]2 (R = t-C4H9, 1a; C6H5, 1b; C6F5, 1c) by regioselective hydroboration of the corr...

Mine water pollution is causing increasing concern in the UK as some of the world's largest and longest-worked coalfields are abandoned and flooded. Many of the resulting polluting discharges are typified by higher mineral acidity (low pH), and high concentrations of iron and sulphate. Two streams, receiving mine water discharges in the Durham coalfield in northern England, have been studied to identify the major chemical factors affecting the welfare of benthic invertebrates. One of the discharges is strongly acidic (pH 3.9), and the second is marginally acidic (pH 5.3). Simultaneous analyses of hydrochemistry and invertebrate diversity and abundance demonstrate serious faunal impoverishment downstream of minewater discharges. Pathway analysis has been applied to ascertain statistically the dominating chemical factors in this faunal impoverishment. in both cases, total acidity (acidity to pH 8.3 = 612 mg 1-1 as CaCO3; pH 3.9) and iron concentration (up to 112.5 mg 1-1) account for nearly all of ...

Passive treatment of net-acidic minewaters using compost wetlands was pioneered in the USA but, so far, has had limited application in Europe. At Quaking Houses (County Durham), strongly acidic ferruginous and aluminium-rich waters discharging from the spoil heap of the abandoned Morrison Busty colliery have been obliterating aquatic life in the Stanley Burn for almost a decade. A concerted investigation involving the National Rivers Authority, the local community and a nearby University, has established the origins of the polluting discharge and assessed its impact on the receiving water. An evaluation was carried out on the possible treatment methods for the discharge, drawing upon the literature and supported by laboratory microcosm tests. A compost wetland was the favoured option, and a pilot facility was constructed with the assistance of the local community. Plans for full-scale treatment are now well advanced, with long-term maintenance being undertaken by local volunteers at minimal cost.

The flux of metals at the tidal limits of major rivers are an important metric of freshwater contaminant transfer to marine habitats, reported in Northeast Atlantic bordering countries under the 1992 Oslo-Paris (OSPAR) Convention. This paper presents an assessment of long-term OSPAR data for four trace metals (Cd, Cu, Pb, and Zn) using a range of spatial datasets to assess the broad distribution of metal flux and yield across England and Wales. Mine site records and geological and land use data are used to classify river basins into six classes. The bulk of metal flux to seas around England and Wales occurs from catchments containing extensive mineralization and a legacy of metal mining (52 % of the total Zn flux, 47 % of Pb, 39 % of Cu, and 48 % of Cd were associated with mined catchments). Catchment area, metal flux from point mine discharges at source, and extent of mineralization typically accounted most for variation in catchment outlet metal flux in stepwise multiple linear regression (SMLR). There are a number of small mining-impacted rural catchments contributing significant fluxes of metals to coastal waters. Of particular prominence are Restronguet Creek (drainage area 87 km2) in southwest England that discharges 176 t Zn/year and 18 t Cu/year and the Afon Goch Dulas (27 km2) in north Wales, which releases 20 t Zn/year and 9 t Cu/year. Although such exercises cannot directly determine the provenance of metals, comparison with metal release data and a review of catchment-scale studies suggest a critical role of mining-related contaminants in contributing to catchment metal export.

An integrated assessment of biological activity and ecotoxicity of fluvial sediments in the Marcal river catchment (3078 km(2)), western Hungary, is presented following the accidental spill of bauxite processing residue (red mud) in Ajka. Red mud contaminated sediments are characterised by elevated pH, elevated trace element concentrations (e.g. As, Co, Cr, V), high exchangeable Na, and induce an adverse effect on test species across a range of trophic levels. While background contamination of the river system is highlighted by adverse effects on some test species at sites unaffected by red mud, the most pronounced toxic effects apparent in Vibrio fischeri bioluminescence inhibition, Lemna minor bioassay and Sinapis alba root and shoot growth occur at red mud depositional hotspots in the lower Torna Creek and upper Marcal. Heterocypris incongruens bioassays show no clear patterns, although the most red mud-rich sites do exert an adverse effect. Red mud does however appear to induce an increase in the density of aerobic and facultative anaerobic bacterial communities when compared with unaffected sediments and reference sites. Given the volume of material released in the spill, it is encouraging that the signal of the red mud on aquatic biota is visible at a relatively small number of sites. Gypsum-affected samples appear to induce an adverse effect in some bioassays (Sinapis alba and Heterocypris incongruens), which may be a feature of fine grain size, limited nutrient supply and greater availability of trace contaminants in the channel reaches that are subject to intense gypsum dosing. Implications for monitoring and management of the spill are discussed.

Reactions of tin(IV) chloride with selected thiacrown ligands in acetonitrile have been studied. With [9]aneS3(1,4,7-trithiacyclononane) the yellow compound 3SnCl4·2[9]aneS3 has been isolated and structurally characterised by X-ray diffraction: orthorhombic, space group Pbca, a= 11.245(5)A, b= 12.927(6)A. c= 23.779(10)A, Z= 4, at 230(2) K. The structure consists of six-co-ordinate [SnCl3([9]aneS3)]+ cations and [SnCl6]2– anions in the ratio 2 : 1. In the cation the thiacrown is chelated facially to a SnCl3 unit with Sn–Cl 2.369(4)(mean), Sn–S 2.637(4)A(mean). The [SnCl6]2– counter anions exhibit a regular octahedral geometry with Sn–Cl 2.448(4)(mean)A. The reaction with [18]aneS6(1,4,7,10,13,16-hexathiacyclooctadecane) provides yellow crystals of the adduct 2SnCl4·[18]aneS6·MeCN the structure of which has also been determined by X-ray diffraction; monoclinic, space group C2, a= 16.901 (5), b= 12.968(5), c= 7.284(3)A, β= 100.50(3)°, Z= 2, at 240(2) K. The structure consists of two SnCl4 units located at opposite ends of the ring cavity with one above and the other below the ring plane. Each tin atom is six-co-ordinate and is attached to the ring via cis chelation of two sulfur atoms.

This paper identifies the spatial extent of bauxite processing residue (red mud)-derived contaminants and modes of transport within the Marcal and Rába river systems after the dike failure at Ajka, western Hungary. The geochemical signature of the red mud is apparent throughout the 3076 km² Marcal system principally with elevated Al, V, As, and Mo. Elevated concentrations of Cr, Ga, and Ni are also observed within 2 km of the source areas in aqueous and particulate phases where hyperalkalinity (pH13.1) is apparent. Although the concentrations of some trace elements exceed aquatic life standards in waters (e.g., V, As) and fluvial sediments (As, Cr, Ni, V), the spatial extent of these is limited to the Torna Creek and part of the upper Marcal. Source samples show a bimodal particle size distribution (peaks at 0.7 and 1.3 μm) which lends the material to ready fluvial transport. Where elevated concentrations are found in fluvial sediments, sequential extraction suggests the bulk of the As, Cr, Ni, and V are associated with residual (aqua-regia/HF digest) phases and unlikely to be mobile in the environment. However, at some depositional hotspots, association of As, Cr, and V with weak acid-extractable phases is observed.

The impact of discharges from abandoned metal and ironstone mines has been a much studied form of aquatic pollution in recent decades. Few attempts however, have been made to accurately determine the overall contaminant mass flux arising from abandoned mine sites at scales above catchment level. Such assessments are critical to determine the significance of former mining to national, regional and ultimately global trace metal flux. This paper presents the most comprehensive national survey to date across England and Wales of the total pollution burden discharged at source from abandoned non-coal mine sites. 338 discharges have been identified (from 4923 known abandoned metal mines) and while concurrent flow and contaminant concentration records are only available for around 30% of these, significant quantities of metals (and As) have been quantified to be discharged. A minimum of 193 tonnes of Zn, 18.5 tonnes of Pb, 0.64 tonnes Cd, 19.1 tonnes of Cu, 551 tonnes Fe, 72 tonnes Mn and 5.1 tonnes As are released in water discharges from abandoned non-coal mines to the surface water environment of England and Wales each year. Precautionary extrapolation of mass fluxes based on the frequency distribution of measured concentration and flow data, for discharges with absent data, suggests that the actual total mass flux for these contaminants could be up to 41% higher. The mass flux of Pb released from mines exceeds that of all currently permitted discharges (e.g. active industrial sites and wastewater treatment works) to surface waters across England and Wales, while those of As, Cd and Zn are of a similar magnitude. These data put into context the enduring legacy of historic mining on the water environment, highlighting its significance relative to more highly regulated polluting sites. Comparison of the figures with estimates of global trace metal flux suggests that the national total identified here is significant on a global scale.

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.

There has been considerable progress in developing treatment systems for point sources of minewater pollution in recent years; however, there remains a knowledge gap in the characterisation and remediation of diffuse minewater sources. Data are presented from the River Gaunless catchment, a historically heavily coal mined catchment in the northeast of England. Instream iron (Fe) loadings were monitored alongside loadings arising from point minewater discharges over a 12-month period to assess the dynamic importance of diffuse sources of minewater pollution. In low flow, diffuse sources account for around 50% of instream loading, a proportion which increases to 98% in high flow conditions. The low flow sources appear to be dominated by direct discharge of contaminated groundwater to surface waters in lower reaches of the catchment. In high flow, resuspended Fe-rich sediments, which are both naturally occurring and derived from historic mining, become the dominant diffuse source of Fe in the water column.

A permeable reactive barrier (PRB) for remediation of coal spoil heap drainage in Northumberland, UK, is described. The drainage has typical chemical characteristics of pH4, [acidity]1400 mg/L as CaCO3, [Fe]300 mg/L, [Mn]165 mg/L, [Al]100mg/L and [SO4]6500 mg/L. During 2 years of operation the PRB has typically removed 50% of the iron and 40% of the sulphate from this subsurface spoil drainage. Bacterial sulphate reduction appears to be a key process of this remediation. Treatment of the effluent from the PRB results in further attenuation; overall reductions in iron and sulphate concentrations are 95% and 67% respectively, and acidity concentration is reduced by an order of magnitude. The mechanisms of attenuation of these, and other, contaminants in the drainage are discussed. Future research and operational objectives for this novel, low-cost, treatment system are also outlined.

A Reducing and Alkalinity Producing System (RAPS) has been constructed to treat the acidic tip leachate from a former coal mine at Deerplay, Lancashire, UK. The tip leachate has a mean pH of 3.5, and is strongly net-acidic (up to 380 mg/L as CaCO3). In addition it contains elevated concentrations of iron (≤ 60 mg/L) and aluminium (≤ 30 mg/L). The flow-rate varies with weather conditions, but has been as high as 6.5 L/second.

Rapid oxidation and accretion of iron onto high surface area media has been investigated as a potential passive treatment option for ferruginous. net-alkaline minewaters. Two pilot-scale reactors were installed at a site in County Durham, UK. Each 2.0 m high cylinder contained different high surface area plastic trickling filter media. Ferruginous minewater was fed downwards over the media at various flow-rates with the objective of establishing the efficiency of iron removal at different loading rates. Residence time of water within the reactors was between 70 and 360 s depending on the flow-rate (1 and 12 l/min, respectively). Average influent total iron concentration for the duration of these experiments was 1.43 mg/l (range 1.08-1.84 mg/l; n = 16), whilst effluent iron concentrations averaged 0.41 mg/l (range 0.20-1.04 mg/l; n = 15) for Reactor A and 0.38 mg/l (range 0.11-0.93 mg/l; n = 16) for Reactor B. There is a strong correlation between influent iron load and iron removal rate. Even at the highest loading rates (approximately 31.6 g/day) 43% and 49% of the total iron load was removed in Reactors A and B, respectively. At low manganese loading rates (approximately 0.50-0.90 g/day) over 50% of the manganese was removed in Reactor B. Iron removal rate (g/m3/d) increases linearly with loading rate (g/day) up to 14 g/d and the slope of the line indicates that a mean of 85% of the iron is removed. In conclusion. it appears that the oxidation and accretion of ochre on high surface area media may be a promising alternative passive technology to constructed wetlands at certain sites.

Erratum to: Mine Water and the Environment (2004)23:162–182DOI 10.1007/s10230-004-0060-0The names of some of the authors of this section wereinadvertently omitted in the original publication. We regretthis omission and provide all of the authors’ names here:Wolkersdorfer, Christian; Bowell, Rob; Amezaga, JaimeM.; Kroll, Adeline; Jarvis, Adam P.; Rees, Ben; Puura,Erik; Misere´, Wiel M. H.; Wings, Roy W. M. G.; Bajto,Peter; Weber, Leopold; Sa´rva´ryne´-Szentkatolnay, Blanka;Garzonio, Carlo Alberto; Younger, Paul L.

The reaction of [Ni(η4-C8H12)2] with the industrially important monomer methyl methacrylate, CH2C(Me)CO2Me, in the presence of 1 or 2 mol equivalents of tricyclohexylphosphine leads to the formation of [Ni{η2-CH2C(Me)CO2Me}{P(C6H11)3}2]1 and [Ni{η2-CH2C(Me)CO2Me}2{P(C6H11)3}]2, respectively. The crystal structures of 1 and 2 have been determined and reveal an η2-CC mode of co-ordination of the methyl methacrylate ligands, with the CO2Me groups pendant and outside the nickel co-ordination sphere. Complexes 1 and 2 represent the first structurally characterised methyl methacrylate complexes; 2 is formed as a mixture of meso and DL diastereomers in the ratio 2.34:1. Solution NMR studies indicate that the diastereomers interconvert rapidly, via an intramolecular mechanism, which is proposed to proceed via an O-co-ordinated intermediate. Reaction of 1 with an excess of tert-butyl acrylate CH2CHCO2But yields [Ni(η2-CH2CHCO2But)2{P(C6H11)3}]4, which may be prepared independently from [Ni(η4-C8H12)2], P(C6H11)3 and tert-butyl acrylate.