The production and degradation of trichloroacetic acid in soil: results from in situ soil column experiments.

Previous work has indicated that the soil is important to understanding biogeochemical fluxes of trichloroacetic acid (TCA) in the rural environment, in forests in particular. Here, the hydrological and TCA fluxes through 22 in situ soil columns in a forest and moorland-covered catchment and an agricultural grassland field in Scotland were monitored every 2 weeks for several months either as controls or in TCA manipulation (artificial dosing) experiments. This was supplemented by laboratory experiments with radioactively-labelled TCA and with irradiated (sterilised) soil columns. Control in situ forest soil columns showed evidence of net export (i.e. in situ production) of TCA, consistent with a net soil TCA production inferred from forest-scale mass balance estimations. At the same time, there was also clear evidence of substantial in situ degradation within the soil ( approximately 70% on average) of applied TCA. The laboratory experiments showed that both the formation and degradation processes operate on time scales of up to a few days and appeared related more with biological rather than abiotic processes. Soil TCA activity was greater in more organic-rich soils, particularly within forests, and there was strong correlation between TCA and soil biomass carbon content. Overall it appears that TCA soil processes exemplify the substantial natural biogeochemical cycling of chlorine within soils, independent of any anthropogenic chlorine flux.

Comparison of different critical load approaches for assessing streamwater acid-sensitivity to broadleaf woodland expansion.

Due to its potential adverse effects on freshwater acidification, risk assessments of the impacts of forest expansion on surface waters are required. The critical load methodology is the standard way of assessing these risks and the two most widely used models are the Steady-State Water Chemistry (SSWC) and First-order Acidity Balance (FAB) models. In the UK the recommended risk assessment procedure for assessing the impact of forest expansion on freshwater acidification uses the SSWC model, whilst the FAB model is used for guiding emission policy. This study compared the two models for assessing the sensitivity of streamwater to acidification in 14 catchments with different proportions of broadleaf woodland cover in acid-sensitive areas in the UK. Both models predicted the exceedance of streamwater critical loads in the same catchments, but the magnitudes of exceedance varied due to the different treatment of nitrogen processes. The FAB model failed to account for high nitrogen leaching to streamwater, attributed to nitrogen deposition and/or fixation of nitrogen by alder trees in some study catchments, while both models underestimated the influence of high seasalt deposition. Critical load exceedance in most catchments was not sensitive to the use of different acid neutralising capacity thresholds or runoff estimates, probably due to the large difference between critical load values and acidic deposition loadings. However, the assessments were more sensitive to differences in calculation procedure in catchments where nitrogen deposition was similar to the availability of base cations from weathering and/or where critical load exceedance values were <1keqH(+)ha(-1)yr(-1). Critical load exceedance values from both models agreed with assessments of acid-sensitivity based on indicator macroinvertebrates sampled from the study catchments. Thus the methodology currently used in the UK appears to be robust for assessing the risk of broadleaf woodland expansion on surface water acidification and ecological status.

Evidence of traffic-related pollutant control in soil-based sustainable urban drainage systems (SUDS).

SUDS are being increasingly employed to control highway runoff and have the potential to protect groundwater and surface water quality by minimising the risks of both point and diffuse sources of pollution. While these systems are effective at retaining polluted solids by filtration and sedimentation processes, less is known of the detail of pollutant behaviour within SUDS structures. This paper reports on investigations carried out as part of a co-ordinated programme of controlled studies and field measurements at soft-engineered SUDS undertaken in the UK, observing the accumulation and behaviour of traffic-related heavy metals, oil and PAHs. The field data presented were collected from two extended detention basins serving the M74 motorway in the south-west of Scotland. Additional data were supplied from an experimental lysimeter soil core leaching study. Results show that basin design influences pollutant accumulation and behaviour in the basins. Management and/or control strategies are discussed for reducing the impact of traffic-related pollutants on the aqueous environment.

Medium-term performance and maintenance of SUDS: a case-study of Hopwood Park Motorway Service Area, UK.

One of the main barriers to implementing SUDS is concern about performance and maintenance costs since there are few well-documented case-studies. This paper summarizes studies conducted between 2000 and 2008 of the performance and maintenance of four SUDS management trains constructed in 1999 at the Hopwood Park Motorway Service Area, central England. Assessments were made of the wildlife value and sedimentation in the SUDS ponds, the hydraulic performance of the coach park management train, water quality in all management trains, and soil/sediment composition in the grass filter strip, interceptor and ponds. Maintenance procedures and costs were also reviewed. Results demonstrate the benefits of a management train approach over individual SUDS units for flow attenuation, water treatment, spillage containment and maintenance. Peak flows, pond sediment depth and contaminant concentrations in sediment and water decreased through the coach park management train. Of the 2007 annual landscape budget of pounds 15,000 for the whole site, the maintenance costs for SUDS only accounted for pounds 2,500 compared to pounds 4,000 for conventional drainage structures. Furthermore, since sediment has been attenuated in the management trains, the cost of sediment removal after the recommended period of three years was only pounds 554 and, if the design is not compromised, less frequent removal will be required in future.

Evaluation of iron ochre from mine drainage treatment for removal of phosphorus from wastewater.

Treatment of polluting discharges from abandoned coal mines in the UK currently produces ca 30,000 t y(-1) of hydrous iron oxides ("ochre"), for which there is no major end-use, but which has previously been shown to have potential for removing P from wastewater and agricultural runoff. The efficiency of ochre for P removal from wastewater was investigated in experiments at two sites in the UK: Leitholm in Scotland and Windlestone in England. The three-year experiment at Leitholm involved diverting secondary-treated wastewater effluent through a trough which contained granular and pelletized ochre at different times. In the nine-month experiment at Windlestone, beds of ochre pellets in horizontal and vertical flow configurations were tested. The ochre treatment systems at Leitholm reduced influent concentrations of total P (TP) and TP mass by ca 80% and 50%, respectively, during optimal flow conditions, and achieved a removal rate of up to 65+/-48 mg TP kg(-1) ochre d(-1). There was no detectable release of potentially toxic metals from the ochre during the experiments. P removal rates by concentration were inversely related to flow and declined during the different phases of the experiments, probably due to clogging. At Windlestone, higher removal rates up to 195 mg TP kg(-1) ochre d(-1) were achieved for short periods of time following cleaning of the experimental system. Ochre has considerable potential to remove P from wastewater in a multi-stage treatment system and has a lifetime estimated to be 10 times longer than other substrates tested for P removal.

Effects of broadleaf woodland cover on streamwater chemistry and risk assessments of streamwater acidification in acid-sensitive catchments in the UK.

Streamwater was sampled at high flows from 14 catchments with different (0-78%) percentages of broadleaf woodland cover in acid-sensitive areas in the UK to investigate whether woodland cover affects streamwater acidification. Significant positive correlations were found between broadleaf woodland cover and streamwater NO3 and Al concentrations. Streamwater NO3 concentrations exceeded non-marine SO4 in three catchments with broadleaf woodland cover>or=50% indicating that NO3 was the principal excess acidifying ion in the catchments dominated by woodland. Comparison of calculated streamwater critical loads with acid deposition totals showed that 11 of the study catchments were not subject to acidification by acidic deposition. Critical loads were exceeded in three catchments, two of which were due to high NO3 concentrations in drainage from areas with large proportions of broadleaved woodland. The results suggest that the current risk assessment methodology should protect acid-sensitive catchments from potential acidification associated with broadleaf woodland expansion.

Riparian wetlands for enhancing the self-purification capacity of streams.

Best Management Practices (BMPs) are increasingly used to restore river water quality but design guidance is limited. An alternative approach to remediating diffuse pollution loads is to identify the most polluting high flows from pollutographs and hydrographs and spill these flows into riparian treatment wetlands for treatment before drainage back into the watercourse. The approach is demonstrated for two contrasting catchments in Scotland impacted by diffuse pollution. The Caw Burn receives industrial estate drainage with high suspended solids, hydrocarbons, BOD and ammoniacal-nitrogen concentrations. Applying the proposed design criteria demonstrated that the existing retrofit BMP system at the site is undersized (4950 m2) compared to the required wetland area (11,800 m2), but accommodating the additional area is likely to be expensive. The second case-study is Brighouse Bay where bathing waters are impacted by faecal indicator organisms derived primarily from livestock runoff. In this catchment the riparian wetland area required to retain runoff so that E. coli bacteria would die-off to concentrations below bathing water standards was estimated to be 3-6ha (0.5-1% of catchment area). Further refinement and testing of the design approach is required, including consideration of other factors such as vegetation type, ownership and maintenance, to develop a more holistic approach to river restoration.

Sediment management in sustainable urban drainage system ponds.

Since removal and disposal of sustainable urban drainage system (SUDS) sediment can incur high maintenance costs, assessments of sediment volumes, quality and frequency of removal are required. Sediment depth and quality were surveyed annually from 1999-2003 in three ponds and one wetland in Dunfermline, Scotland, UK. Highest sediment accumulation occurred in Halbeath Pond, in the most developed watershed and with no surface water management train. From comparison of measured potentially toxic metal concentrations (Cd, Cr, Cu, Fe, Ni, Pb, Zn) with standards, the average sediment quality should not impair aquatic ecosystems. 72-84% of the metal flux into the SUDS was estimated to be associated with coarse sediment (> 500 microm diameter) suggesting that management of coarse sediment is particularly important at this site. The timing of sediment removal for these SUDS is expected to be determined by loss of storage volume, rather than by accumulation of contaminants. If sediment removal occurs when 25% of the SUDS storage volume has infilled, it would be required after 17 years in Halbeath Pond, but only after 98 years in Linburn Pond (which has upstream detention basins). From the quality measurements, sediment disposal should be acceptable on adjacent land within the boundaries of the SUDS studied.

Using mathematical modelling to inform on the ability of stormwater ponds to improve the water quality of urban runoff.

This paper concerns the mathematical modelling of flow and solute transport through stormwater ponds. The model is based on appropriate lumped system conservation equations that are solved using standard numerical techniques. The model was used to route a first flush pollution scenario through a cylindrical pond for 16 combinations of elevation and diameter of a submerged pipe outlet, in conjunction with a high level weir. Higher pipe elevations and smaller pipe diameters created larger pond volumes and hence led to greater dilution of the pollutant. In contrast, lower pipe elevations created larger storage volumes, leading to better flow attenuation. Interestingly, larger pipe diameters improved peak flow attenuation, even though the storage used decreased.

Enhancing phosphorus removal in constructed wetlands with ochre from mine drainage treatment.

No single end-use has yet been identified that is capable of consuming the projected production of ochre (mainly iron (III) oxides) from mine drainage treatment. However, the high sorption capacity of ochre for phosphorus (up to 26 mg kg(-1)) means that it could be used in constructed wetlands to enhance phosphorus removal. Laboratory batch experiments showed that coarse-grained ochre removes 90% of all phosphorus forms from sewage effluent after 15 minutes of shaking. From a larger-scale experiment, it is estimated that constructed wetlands with an ochre substrate should remove phosphorus from sewage effluent for up to 200-300 years. The suitability of ochre for phosphorus removal is being investigated at the field scale in a wastewater constructed wetland (175 m2 area) in Berwickshire, UK. The hydraulic and treatment performance of the wetland were monitored for 15 months prior to installation at the inlet in November 2003 of a tank containing approximately 1200 kg ochre. Results so far show that improved hydraulic design is required for ochre to increase the mean phosphorus removal efficiency of the system (27 +/- 28%), but potentially toxic metals (Al, Cd, Cr, Cu, Fe, Ni, Pb, Zn) have not been released from the ochre into the wetland outflow.

Persistent pollutants urban rivers sediment survey: implications for pollution control.

The impacts of diffuse urban sources of pollution on watercourses are quantified. A survey of nine urban streams in Scotland for persistent pollutants in stream sediments is described, together with sediments from SUDS ponds. Determinands reported are: PAHs, total hydrocarbons, and toxic metals (As, Zn, Ni, Pb, Cu, Cr, Cd). Results highlight hydrocarbons as a major urban pollutant, and show significant sediment contamination by toxic metals. The metals that occurred in the highest concentrations varied across the nine streams, but Pb, Cr, Ni, Zn and Cu most frequently present exceeded sediment quality standards. The pattern of contamination by PAHs suggested that pyrolytic sources were more ubiquitous and present in greater quantities than oil spill sources in these urban catchments. Exceptions were the sites below industrial estates. The findings indicate that four levels of activity will be needed to control urban diffuse sources of pollution: reductions in quantities of toxic pollutants used by manufacturers in the motor and construction industries; housekeeping measures to minimise storage and handling risks for oil and chemicals; public engagement to minimise polluting activities such as dumping oil and chemicals, and private car use; use of SUDS technology, including retro-fits in the worst affected urban areas.

Fluxes of trichloroacetic acid through a conifer forest canopy.

Controlled-dosing experiments with conifer seedlings have demonstrated an above-ground route of uptake for trichloroacetic acid (TCA) from aqueous solution into the canopy, in addition to uptake from the soil. The aim of this work was to investigate the loss of TCA to the canopy in a mature conifer forest exposed only to environmental concentrations of TCA by analysing above- and below-canopy fluxes of TCA and within-canopy instantaneous reservoir of TCA. Concentrations and fluxes of TCA were quantified for one year in dry deposition, rainwater, cloudwater, throughfall, stemflow and litterfall in a 37-year-old Sitka spruce and larch plantation in SW Scotland. Above-canopy TCA deposition was dominated by rainfall (86%), compared with cloudwater (13%) and dry deposition (1%). On average only 66% of the TCA deposition passed through the canopy in throughfall and stemflow (95% and 5%, respectively), compared with 47% of the wet precipitation depth. Consequently, throughfall concentration of TCA was, on average, approximately 1.4 x rainwater concentration. There was no significant difference in below-canopy fluxes between Sitka spruce and larch, or at a forest-edge site. Annual TCA deposited from the canopy in litterfall was only approximately 1-2% of above-canopy deposition. On average, approximately 800 microg m(-2) of deposited TCA was lost to the canopy per year, compared with estimates of above-ground TCA storage of approximately 400 and approximately 300 microg m(-2) for Sitka spruce and larch, respectively. Taking into account likely uncertainties in these values ( approximately +/- 50%), these data yield an estimate for the half-life of within-canopy elimination of TCA in the range 50-200 days, assuming steady-state conditions and that all TCA lost to the canopy is transferred into the canopy material, rather than degraded externally. The observations provide strong indication that an above-ground route is important for uptake of TCA specifically of atmospheric origin into mature forest canopies, as has been shown for seedlings (in addition to uptake from soil via transpiration), and that annualized within-canopy elimination is similar to that in controlled-dosing experiments.

Trichloroacetic acid cycling in Sitka spruce saplings and effects on sapling health following long term exposure.

Trichloroacetic acid (TCA, CCl(3)COOH) has been associated with forest damage but the source of TCA to trees is poorly characterised. To investigate the routes and effects of TCA uptake in conifers, 120 Sitka spruce (Picea sitchensis (Bong.) Carr) saplings were exposed to control, 10 or 100 microg l(-1) solutions of TCA applied twice weekly to foliage only or soil only over two consecutive 5-month growing seasons. At the end of each growing season similar elevated TCA concentrations (approximate range 200-300 ng g(-1) dwt) were detected in both foliage and soil-dosed saplings exposed to 100 microg l(-1) TCA solutions showing that TCA uptake can occur from both exposure routes. Higher TCA concentrations in branchwood of foliage-dosed saplings suggest that atmospheric TCA in solution is taken up indirectly into conifer needles via branch and stemwood. TCA concentrations in needles declined slowly by only 25-30% over 6 months of winter without dosing. No effect of TCA exposure on sapling growth was measured during the experiment. However at the end of the first growing season needles of saplings exposed to 10 or 100 microg l(-1) foliage-applied TCA showed significantly more visible damage, higher activities of some detoxifying enzymes, lower protein contents and poorer water control than needles of saplings dosed with the same TCA concentrations to the soil. At the end of each growing season the combined TCA storage in needles, stemwood, branchwood and soil of each sapling was <6% of TCA applied. Even with an estimated half-life of tens of days for within-sapling elimination of TCA during the growing season, this indicates that TCA is eliminated rapidly before uptake or accumulates in another compartment. Although TCA stored in sapling needles accounted for only a small proportion of TCA stored in the sapling/soil system it appears to significantly affect some measures of sapling health.

Fluxes and reservoirs of trichloroacetic acid at a forest and moorland catchment.

The concentrations and input/output fluxes of trichloroacetic acid (TCA) were measured in all relevant media for one year at a 0.86 km2 upland conifer plantation and moorland catchment in SW Scotland (n > 380 separate samples analyzed). Annual wet precipitation to the catchment was 2.5 and 0.4 m for rain and cloud, respectively. TCA input to the catchment for the year was 2100 g, predominantly in rainwater (86%), with additional input via cloudwater (13%) and gas plus particle dry deposition (1%). There were no seasonal trends in TCA deposition, and cloudwater concentration was not enhanced over rainwater. TCA in precipitation exceeded concentrations estimated using currently accepted routes of gas-phase oxidation from anthropogenic chlorinated hydrocarbon precursors, in agreement with previous studies. Export of TCA from the catchment in streamwater totalled 1970 g for the year of study. The TCA concentration in streamwater at outflow (median 1.2 microg L(-1)) was significantly greater than that before the stream had passed through the conifer plantation. To well-within measurement uncertainties, the catchment is currently at steady-state with respect to TCA input/output. The catchment reservoir of TCA was dominated by soils (approximately 90%), with the remainder distributed in forest litter (approximately 9%), forest branchwood and stemwood (approximately 0.7%), forest foliage (approximately 0.5%), and moorland foliage (approximately 0.1%). Although TCA is clearly taken up into foliage, which consequently may be important for the vegetation, this was a relatively minor process for TCA at the catchment scale. If it is assumed, on the basis of laboratory extraction experiments, that only approximately 20% of "whole soil" TCA measured in this work was water extractable, then total mass of TCA in the catchment is reduced from approximately 13 to approximately 3.5 kg. Comparing the latter value with the annual flux yields an average steady-state residence time for TCA in the catchment of approximately 1-2 y, if all TCA is involved in catchment turnover. Considering that other evidence indicates the lifetime of TCA in soil and biota is considerably shorter than this (weeks rather than years), the magnitude of the TCA reservoir is suggested to be strong evidence for net natural TCA production in soils and/or that the majority of TCA in the reservoir is not involved with external fluxes.

Hydrology and the ecological quality of Scottish river ecosystems.

Hydrology is a primary control on the ecological quality of river systems, through its influence on flow, channel geomorphology, water quality and habitat availability. Scottish rivers are widely perceived to be of high ecological quality, with abundant flow volumes and high water quality. However, historical and current river flow regulations, and land use change have altered the physical and chemical characteristics of Scottish rivers, with adverse consequences for aquatic biota. Baseline hydrological, geomorphological and water quality conditions in Scottish rivers are thus summarised. The impacts of river regulation and land use change on the hydrology, geomorphology and water quality of Scottish rivers are then discussed. Consequences of these changes for aquatic habitat are examined, with particular reference to the economically significant salmonid species (Salmo salar and Salmo trutta). Policy and management issues relating to the future ecological quality of Scottish rivers are reviewed. These include the impacts of climate change on ecological quality, the calculation and implementation of ecologically acceptable flows, and river restoration and best management practices within integrated catchment planning.

Manganese and land-use in upland catchments in Scotland.

Manganese (Mn) in surface waters is a micronutrient, but elevated concentrations are toxic to fish and impair drinking water quality. In Scotland, undesirable Mn concentrations (> 0.05 mg l(-1)) occur predominantly in upland freshwaters because the acidic pH and organic nature of catchment soils favour Mn mobilisation. The relationship between upland land-use in Scotland and Mn concentrations in surface waters is reviewed. Conifer afforestation is associated with enhanced Mn in runoff. Mn is leached from conifer foliage and litter, and mature conifers enhance acid deposition and loss of Mn from acidified catchment soils. After harvesting, increased soil pools of water-soluble Mn and elevated Mn concentrations in runoff have been observed. Liming, fertiliser addition, drainage ditch construction and ploughing to improve upland pastures, and muirburn on grouse moors may also increase Mn concentrations in runoff, but the evidence is less clear-cut. The extent to which land-use influences Mn concentrations in upland catchments in Scotland is modified by catchment hydrology and soil type. Catchment geology, instream processes and standing water stratification are probably lesser influences on Mn concentrations in surface waters of upland catchments in Scotland. The location of land-use in upland catchments, especially in the riparian zone, is critical in determining its effect on Mn in runoff. Climate change is expected to increase Mn concentrations in runoff from upland catchments in Scotland because of predicted changes in soil hydrology.