Surface water acidification in the South Pennines I. Current status and spatial variability

The South Pennines, an area of acid-sensitive geology at the centre of a major industrial region, have undergone perhaps the most severe historic exposure to sulphur and nitrogen deposition in the UK. This study addresses a lack of existing research on the region by presenting the findings of a survey of 62 surface waters sampled during a 1-week period in April 1998. Results indicate that acidification in the region is acute; 27 of the sampled surface waters had a negative acid neutralising capacity (ANC) and 28 had a pH below 5.0. Minimum recorded pH values were below 4.0. Non-marine sulphate levels were extremely high (median 222 microeq/1), and widespread high nitrate concentrations (median 41 microeq/1) suggest that soils in the region as a whole may be at an advanced stage of nitrogen saturation. A consistent relationship was identified between site acidity and the balance between the major weathering-derived cations, calcium and magnesium, and sulphate. This could in turn be linked to catchment soil type and land use, with the most acidic conditions occurring in peat-dominated catchments, where weathering is minimal and the influence of atmospheric deposition most pronounced. Percentage of peat in each catchment was the single best predictor of surface water acidity. Nitrate concentrations, although not a dominant control on acidity, varied significantly according to land use. Elevated concentrations were observed in catchments containing forestry, due to enhanced deposition inputs, and in catchments containing improved land, linked to fertiliser use. Ammonium concentrations, although low at most catchments, were a significant component of the inorganic nitrogen total in a number of surface waters draining waterlogged peat catchments.     

Manipulation of precipitation in small headwater catchments at Storgama, Norway: effects on leaching of organic carbon and nitrogen species

Projected changes in climate in Southern Norway include increases in summer and autumn precipitation. This may affect leaching of dissolved organic matter (DOM) from soils. Effects of experimentally added extra precipitation (10 mm week) during the growing season of 3 years (2004-2006) to small headwater catchments at Storgama (59 degrees 0'N, 550-600 m a.s.l.) on leaching of total organic carbon (TOC) and total organic nitrogen (TON) were assessed. Extra precipitation did not have a significant effect on average TOC and TON concentrations in runoff. Thus, fluxes of TOC and TON increased nearly proportionally with water fluxes. This suggests that a store of adsorbed and potentially mobile TOC and TON in catchment soils buffers the concentration of DOM in runoff. The size and dynamics of the pool of TOC and TON depends on the balance between production and leaching rates. Infrequent short droughts had only small effects on TOC and TON fluxes in runoff from the reference catchments.     

Scale-dependence of land use effects on water quality of streams in agricultural catchments

The influence of land use on water quality in streams is scale-dependent and varies in time and space. In this study, land cover patterns and stocking rates were used as measures of agricultural development in two pasture and one native grassland catchment in New Zealand and were related to water quality in streams of various orders. The amount of pasture per subcatchment correlated well to total nitrogen and nitrate in one catchment and turbidity and total phosphorous in the other catchment. Stocking rates were only correlated to total phosphorous in one pasture catchment but showed stronger correlations to ammonium, total phosphorous and total nitrogen in the other pasture catchment. Winter and spring floods were significant sources of nutrients and faecal coliforms from one of the pasture catchments into a wetland complex. Nutrient and faecal coliform concentrations were better predicted by pastural land cover in fourth-order than in second-order streams. This suggests that upstream land use is more influential in larger streams, while local land use and other factors may be more important in smaller streams. These temporal and spatial scale effects indicate that water-monitoring schemes need to be scale-sensitive.     

A classification of acidified catchments in Britain

To compare catchments of possible acidified waters in Britain an extensive database was compiled for nearly 600 catchments of lakes and streams for which chemical data were available. Information on the database included map-derived data, pollutant deposition estimates and hydrological characteristics. To stratify the catchment database a randomly selected subset of 328 catchments was used to derive eight classes of catchments using the classification program TWINSPAN. Several classifications were generated by this method using an increasing number of catchment parameters. TWINSPAN classes were defined on the basis of some catchment parameters (indicators) but were shown to be associated with other variables. A general linear model (GLM) analysis of the available chemical data was used to test the different classifications. A TWINSPAN classification which excluded soil and geology characteristics gave the best GLM model because soil and geology types were poorly correlated with other catchment parameters. However, because of the recognized importance of soils and geology in acidification processes, these parameters were introduced into the GLM model as separate GLM classes. The resulting three-class model (TWINSPAN class, soil type, geology type) proved superior to both the one-class model and to two-class models which included either soil or geology. It was demonstrated that the TWINSPAN classes were associated with particular geographical areas and particular monitoring programmes. The TWINSPAN classification was used to evaluate a set of catchments selected as long-term monitoring sites for Britain. In general, the set covered a wide range of catchment types as defined by the classification. It was possible to identify minor shortfalls in classes of catchment selected and suggest possible additions to the sampling programme. Whilst the classification procedure has been applied to possible acidified waters, the method is of general relevance to all catchments and waters of more diverse nature.     

Dissolved phosphorus transport from soil to surface water in catchments with different land use

Diffuse phosphorus (P) export from agricultural land to surface waters is a significant environmental problem. It is critical to determine the natural background P losses from diffuse sources, but their identification and quantification is difficult. In this study, three headwater catchments with differing land use (arable, pasture and forest) were monitored for 3 years to quantify exports of dissolved (<0.45 µm) reactive P and total dissolved P. Mean total P exports from the arable catchment ranged between 0.08 and 0.28 kg ha^?1 year^?1. Compared with the reference condition (forest), arable land and pasture exported up to 11-fold more dissolved P. The contribution of dissolved (<0.45 µm) unreactive P was low to negligible in every catchment. Agricultural practices can exert large pressures on surface waters that are controlled by hydrological factors. Adapting policy to cope with these factors is needed for lowering these pressures in the future.     

Manipulation of snow in small headwater catchments at Storgama, Norway: effects on leaching of total organic carbon and total organic nitrogen

Projected increases in winter temperature due to future climate change may cause decreased snow accumulation at lower and intermediate altitudes in northern temperate regions. The resulting changes in soil temperature and water regime may affect the leaching of total organic carbon (TOC) and total organic nitrogen (TON). We manipulated the snow cover of small headwater catchments in a montane heathland area of southern Norway to quantify its effect on concentrations and fluxes of TOC and TON in runoff. Manipulations included snow removal, to promote soil frost, and insulation, to prevent soil frost. Snow removal resulted in increased TOC and TON concentrations, but decreased fluxes. Insulation caused a slight decrease in concentrations and fluxes of TOC. Our experiments show that a change in snow depth, and thus soil temperature, is not likely to have serious effects on TOC and TON leaching in the montane heathland area studied.     

Natural variability in soil and runoff from small headwater catchments at Storgama, Norway

To provide baseline data for climate manipulation experiments in 11 small (30-268 m2) headwater catchments at Storgama, Telemark County, Southern Norway, we assessed the natural variability in site characteristics and runoff quality. Annual average concentrations in runoff at the sites have coefficients of variation between 26-61%, with the smallest values for total organic carbon (TOC) and carbon to nitrogen (C/N) ratios and the largest for inorganic nitrogen (N). The catchments have between two and five times higher concentrations of inorganic N, TOC, and total phosphorus than the larger (0.6 km2) Storgama watershed nearby. Concentrations of TOC and TON in runoff tend to increase with soil C and N content and with the volume of soil in the catchment. For nitrate (NO3) and ammonium in runoff, the reverse is true. In wet years the proportion of bare rock is a major predictor for the annual average NO3 concentration in runoff.     

Land use influences macroinvertebrate community composition in boreal headwaters through altered stream conditions

Land use is known to alter the nature of land–water interactions, but the potential effects of widespread forest management on headwaters in boreal regions remain poorly understood. We evaluated the importance of catchment land use, land cover, and local stream variables for macroinvertebrate community and functional trait diversity in 18 boreal headwater streams. Variation in macroinvertebrate metrics was often best explained by in-stream variables, primarily water chemistry (e.g. pH). However, variation in stream variables was, in turn, significantly associated with catchment-scale forestry land use. More specifically, streams running through catchments that were dominated by young (11–50 years) forests had higher pH, greater organic matter standing stock, higher abundance of aquatic moss, and the highest macroinvertebrate diversity, compared to streams running through recently clear-cut and old forests. This indicates that catchment-scale forest management can modify in-stream habitat conditions with effects on stream macroinvertebrate communities and that characteristics of younger forests may promote conditions that benefit headwater biodiversity.     

Climate change impact on water quality: model results from southern Sweden

Starting from six regional climate change scenarios, nitrogen leaching from arable-soil, water discharge, and nitrogen retention was modeled in the R?nne? catchment. Additionally, biological response was modeled in the eutrophic Lake Ringsj?n. The results are compared with similar studies on other catchments. All scenarios gave similar impact on water quality but varied in quantities. However, one scenario resulted in a different transport pattern due to less-pronounced seasonal variations in the hydrology. On average, the study shows that, in a future climate, we might expect: i) increased concentrations of nitrogen in the arable root zone (+50%) and in the river (+13%); ii) increased annual load of nitrogen from land to sea (+22%) due to more pronounced winter high flow; moreover, remote areas in the catchment may start to contribute to the outlet load; iii) radical changes in lake biochemistry with increased concentrations of total phosphorus (+50%), total nitrogen (+20%), and planktonic algae such as cyanobacteria (+80%).     

Adsorption of natural organic matter from waters by iron coated pumice

Natural pumice particles were used as granular support media and coated with iron oxides to investigate their adsorptive natural organic matter (NOM) removal from waters. The impacts of natural pumice source, particle size fraction, pumice dose, pumice surface chemistry and specific surface area, and NOM source on the ultimate extent and rate of NOM removal were studied. All adsorption isotherm experiments were conducted employing the variable-dose completely mixed batch reactor bottle-point method. Iron oxide coating overwhelmed the surface electrical properties of the underlying pumice particles. Surface areas as high as 20.6m(2)g(-1) were achieved after iron coating of pumice samples, which are above than those of iron coated sand samples reported in the literature. For all particle size fractions, iron coating of natural pumices significantly increased their NOM uptakes both on an adsorbent mass- and surface area-basis. The smallest size fractions (<63 microm) of coated pumices generally exhibited the highest NOM uptakes. A strong linear correlation between the iron contents of coated pumices and their Freundlich affinity parameters (K(F)) indicated that the enhanced NOM uptake is due to iron oxides bound on pumice surfaces. Iron oxide coated pumice surfaces preferentially removed high UV-absorbing fractions of NOM, with UV absorbance reductions up to 90%. Control experiments indicated that iron oxide species bound on pumice surfaces are stable, and potential iron release to the solution is not a concern at pH values of typical natural waters. Based on high NOM adsorption capacities, iron oxide coated pumice may be a promising novel adsorbent in removing NOM from waters. Furthermore, due to preferential removal of high UV-absorbing NOM fractions, iron oxide coated pumice may also be effective in controlling the formation of disinfection by-products in drinking water treatment.     

Sources of phenolic compounds in two catchments of southern Portugal - effect of season, land use and soil type

Water quality monitoring in reservoirs used for human water consumption, carried out by the Alentejo Regional Authorities of the Environment (south Portugal), revealed seasonal peaks of phenolic compounds above the water-quality legislation. The main objectives of this work were to identify the main phenolic compounds present in water and soil leachates, and to determine the sources of the seasonal concentrations of phenolic compounds in two catchments with different land use patterns: Roxo and Santa Clara catchments. The main phenolic compound detected was 2,4-dinitrophenol (2,4-DNP), both in stream water and soil leachates, with concentrations higher in Roxo catchment. Roxo catchment represents a larger agricultural area than Santa Clara, and it is likely that the origin of the 2,4-DNP is associated with the use of pesticides. A peak of 2,4-DNP concentrations was observed in stream water of both catchments during February, when farmers plough their fields and apply pesticides. The 2,4-DNP peak was probably caused by a precipitation event shortly after the application of pesticides, increasing their transfer from land surfaces to adjacent streams. The leaching behaviour of 2,4-DNP was strongly dependent on the type of soil and pH. In soils with high clay content and low pH, 2,4-DNP was easily adsorbed, and its runoff from the soil to adjacent streams was reduced. Ribeira de Santa Vitória, from Roxo catchment, was the only stream showing a high abundance of vegetation, and the lowest concentrations of 2,4-DNP in water. Plants may play a role in removing contaminants from stream water.     

Total and methyl mercury concentrations and fluxes from small boreal forest catchments in Finland

Total mercury (TotHg) and methyl mercury (MeHg) concentrations were studied in runoff from eight small (0.02-1.3 km2) boreal forest catchments (mineral soil and peatland) during 1990-1995. Runoff waters were extremely humic (TOC 7-70 mg l-1). TotHg concentrations varied between 0.84 and 24 ng l-1 and MeHg between 0.03 and 3.8 ng l-1. TotHg fluxes from catchments ranged from 0.92 to 1.8 g km-2 a-1, and MeHg fluxes from 0.03 to 0.33 g km-2 a-1. TotHg concentrations and output fluxes measured in runoff water from small forest catchments in Finland were comparable with those measured in other boreal regions. By contrast, MeHg concentrations were generally higher. Estimates for MeHg output fluxes in this study were comparable at sites with forests and wetlands in Sweden and North America, but clearly higher than those measured at upland or agricultural sites in other studies. Peatland catchments released more MeHg than pure mineral soil or mineral soil catchments with minor area of peatland.     

土地利用/土地覆被变化对区域生态环境的影响

土地利用／ 土地覆被变化对区域生态环境的影响是土地利用／ 土地覆被变化研究的重要内容。本文分析了土地利用／ 土地覆被变化对区域气候、土壤、水量和水质的影响。土地利用／ 土地覆被变化通过改变地表发射率、温室气体和痕量气体的含量影响区域气候;土地利用／土地覆被变化影响着能量交换、水交换、侵蚀与堆积、生物循环和作物生产等土壤主要生态过程,不同土地利用方式和土地覆被类型的空间组合影响着土壤养分的迁移规律;土地利用／ 土地覆被变化对水质的影响主要是通过非点源污染途径,许多非点源污染来源都同土地利用／土地覆被变化紧密联系。文中还探讨了由于人类不合理的土地利用造成的土壤侵蚀、土地退化、水资源短缺、海水入侵等生态环境问题。     

Predicting stream-water quality using catchment and soil chemical characteristics

The distribution and chemistry of soils in 10 upland catchments in NE Scotland have been used to develop a means of predicting minimum, maximum and mean concentrations of calcium and hydrogen ions in streams. The approach is based on the control of stream-water chemistry by soil chemical properties. Stream-water chemistry was monitored over a two-year period. Each catchment was surveyed and soils sampled to characterize the chemistry of the main soil units. Stream-water chemical parameters are related to the chemical characteristics of the upper and lower soil horizons in the catchments. The contribution of each soil unit is assessed using randomly generated flow paths. Soil chemistry is weighted according to the distribution of soils in the immediate vicinity of the stream. In this paper the approach is largely confined to the prediction of minimum, maximum and mean concentrations of calcium ions in stream waters. In the longer term, the approach may have the potential to predict what effects changes in soil chemistry and management practice (drainage, ploughing) will have on water quality in upland catchments.     

Distributed,high-resolution modelling of critical source areas for erosion and phosphorus losses

Phosphorus losses from arable land need to be reduced to prevent eutrophication of surrounding waters. Owing to the high spatial variability of P losses, cost-effective countermeasures need to target parts of the catchment that are most susceptible to P losses. Field surveys identified critical source areas for overland flow and erosion amounting to only 0.4–2.6 % of total arable land in four different catchments in southern Sweden. Distributed modelling using high-resolution digital elevation data identified 72–96 % of these observed erosion and overland flow features. The modelling results were also successfully used to predict occurrence of overland flow and rill and gully erosion in a catchment in central Sweden. Such exact high-resolution modelling allows for accurate placement of planned countermeasures. However, current legislative and environmental subsidy programmes need to change their approach from income-loss compensation to rewarding high cost effectiveness of implemented countermeasures.     

Riparian Zone Influence on Stream Water Dissolved Organic Carbon Concentrations at the Swedish Integrated Monitoring Sites

Short-term variability in stream water dissolved organic carbon (DOC) concentrations is controlled by hydrology, climate and atmospheric deposition. Using the Riparian flow-concentration Integration Model (RIM), we evaluated factors controlling stream water DOC in the Swedish Integrated Monitoring (IM) catchments by separating out hydrological effects on stream DOC dynamics. Model residuals were correlated with climate and deposition-related drivers. DOC was most strongly correlated to water flow in the northern catchment (Gammtratten). The southern Aneboda and Kindla catchments had pronounced seasonal DOC signals, which correlated weakly to flow. DOC concentrations at Gårdsjön increased, potentially in response to declining acid deposition. Soil temperature correlated strongly with model residuals at all sites. Incorporating soil temperature in RIM improved model performance substantially (20–62% lower median absolute error). According to the simulations, the RIM conceptualization of riparian processes explains between 36% (Kindla) and 61% (Aneboda) of the DOC dynamics at the IM sites.     

A screening model-based study of transport fluxes and fate of airborne mercury deposited onto catchment areas.

Dynamics of airborne mercury deposited onto catchment areas is investigated within the framework of a simulation model. Model results show that, for a particular atmospheric deposition rate, significant interannual variability in mercury transport flux in catchments is caused by climatology and corresponding differences in catchment soil loss rates; in comparison to the normal year, runoff flux increased by a factor of 2-3 for the wet year (rainfall 35% above normal) while for the dry year (rainfall 18% below normal) runoff flux decreased by factors of 5-7. The interaction of parameters describing soil type, topography and vegetation cover causes variability in both transport and emission fluxes among catchments; as soil loss rate increases by a factor of 5 due to variations in these parameters among the examined catchments, annual average transport flux increases by a factor of 3; and annual average emission flux of mercury (as Hg0) from soil to the atmosphere decreases by a factor of 2 due to the decreased levels of soil mercury associated with catchment soil loss increases. Seasonal variability of transport flux is associated with seasonal changes in precipitation and soil loss rates while seasonal changes of emission flux are primarily due to changes in soil moisture regime and temperature. Although modeled results are consistent with observational data from previous studies, they must be interpreted in a relative sense due to the screening-level character of this study.     

Exceptional weather in the midlands, UK, during 1988-1990 results in the rapid acidification of an upland stream

Numerous catchment studies have identified the control exerted by hydrological processes on short-term (within a year) fluctuations in surface water acidity. Because discharge is, in turn, a function of broad climate parameters, there has been growing interest in the potential impact of changing precipitation and temperature regimes on water chemistry. The exceptionally warm and arid period 1988-1990 provided an opportunity to investigate the response of an acidic catchment in the East Midlands to an extreme climate scenario. The results obtained from three years of intensive monitoring indicated that between 1988 and 1990 there was a fourfold increase of the surface-water acidity at several observation sites within the Beacon catchment, Charnwood Forest, Leicestershire. As well as providing an indication of currently extreme hydrochemical conditions which in the near future may become the norm, these observations also have a bearing on the validity of long-term predictions derived from process-orientated models.     

Herbicides: A new threat to the Great Barrier Reef

The runoff of pesticides (insecticides, herbicides and fungicides) from agricultural lands is a key concern for the health of the iconic Great Barrier Reef, Australia. Relatively low levels of herbicide residues can reduce the productivity of marine plants and corals. However, the risk of these residues to Great Barrier Reef ecosystems has been poorly quantified due to a lack of large-scale datasets. Here we present results of a study tracing pesticide residues from rivers and creeks in three catchment regions to the adjacent marine environment. Several pesticides (mainly herbicides) were detected in both freshwater and coastal marine waters and were attributed to specific land uses in the catchment. Elevated herbicide concentrations were particularly associated with sugar cane cultivation in the adjacent catchment. We demonstrate that herbicides reach the Great Barrier Reef lagoon and may disturb sensitive marine ecosystems already affected by other pressures such as climate change.     

Influence of soil hydrological pathways on stream aluminium chemistry at Llyn Brianne, mid-wales

Storm runoff in afforested catchments at Llyn Brianne is acidic and Al-bearing. At baseflows, stream water is well-buffered with low Al levels. This paper presents the results of a study into how hydrological pathways account for these variations in stream-water chemistry. The investigation was carried out in the LI1 catchment; a 0.4-ha subcatchment covered by stagnohumic gley soils was monitored between October 1988 and September 1989. An instrumented hill-slope was established to identify the hydrological pathways that control the hydrochemistry of storm runoff draining from the subcatchment. Perched watertables developed in the surface horizons of the soil during storm episodes and produced lateral flow above the impeding subsoil. This near-surface flow path was responsible for generating acid, Al-rich storm runoff. Some water drained vertically through the soil profile into the underlying slope drift; seepage from groundwater in the drift sustained baseflows. Buffering reactions in the groundwater zone reduced the acidity and Al levels of baseflows. These hydrochemical characteristics are likely to be representative of other areas of stagnohumic gley soils, which cover 19% of the LI1 catchment: these soils may therefore provide a substantial source of acid, Al-bearing storm runoff in LI1 and similar afforested catchments.