Variation in Freshwater Critical Loads Across Two Upland Catchments in the UK: Implications for Catchment Scale Management

In the UK the "critical loads" approach has been used to derive maps based on the 10km × 10km national grid. However, this grid based approach is inappropriate for catchment scale management and these maps cannot be used for "stock at risk" assessments of the number of water bodies or lengths of streams in a given area that may be vulnerable to acidification. Critical loads are determined across two large river catchments in England (The Duddon) and Wales (The Glaslyn). High resolution, digital datasets are used to characterise the attributes of each subcatchment in terms of land cover, soil, geology, topography and topology. Empirical models used to examine the relationship between these attributes and critical loads indicate that the former can be used to account for significant variation in the latter. However, these relationships can vary from catchment to catchment. Thus, although this approach provides the potential for identifying sensitive surface waters on a catchment wide basis, it is likely that models will need to be parameterised on a catchment specific basis.     

Mapping the Potential Sensitivity of Surface Waters to Acidification Using Measured Freshwater Critical Loads as an Indicator of Acid Sensitive Areas

Environmental organisations in the UK have shown increasing interest in freshwater critical loads and acid sensitivity maps as a means of assessing pollution at the local and regional level. These maps can be used to identify sensitive areas when considering catchment management plans. The use of national data sets to map the sensitivity of freshwaters to acidification, highlighted the problems of relating national datasets to smaller, localised areas. The study described here investigated the use of detailed large-scale maps to predict the sensitivity of surface waters to acidification for two river catchments. Three large-scale acid sensitivity maps were produced and validated using measured freshwater critical loads. In addition, a score system relating to the buffering capacity for each soil and geology type was devised. The score value was found to have a better correlation with water chemistry and freshwater critical loads than the acid sensitivity maps. The study concluded that it was not necessary to use the largest scale data available in order to improve predictions of sensitive areas.     

Dynamic Modelling of Spatially Variable Catchment Hydrochemistry for Critical Loads Assessment

Concern about acidification in upland areas has brought about the need to model the stream hydrochemical response to deposition and land-use changes and calculate critical loads. Application of dynamic models such as MAGIC are preferable to steady-state methods, since they are able to produce an estimate of the time scale required to meet some water chemistry target given a reduction in acid deposition. These models typically consider annual changes in stream chemistry at one point. However, in order to protect biota from 'acid episodes', quantification of temporal variability needs to encompass event responses; in addition spatial variability across the catchment also needs to be considered. In this paper, modelling of both spatial and temporal variability is combined in a new framework which enables quantification of catchment hydrochemical variability in time and space. Both low and high flow hydro-chemical variability are quantified in terms of statistical distributions of ANC (Acid Neutralisation Capacity). These are then input as stochastic variables to an EMMA (End-Member Mixing Analysis) model which accounts for temporal variability and ANC is hence predicted as a function of time and space across the whole catchment using Monte-Carlo simulation. The method is linked to MAGIC to predict future scenarios and may be used by iteration to calculate critical loads. The model is applied to the headwaters of the River Severn at Plynlimon, Wales, to demonstrate its capabilities.     

Topographical Influences on the Spatial Distribution of Soil Mercury at the Catchment Scale

The catalytic effect of Cu(II) on the formation of disinfection by-products (DBPs) and chlorine degradation during chlorination of humic acid (HA) solutions was comparatively investigated under different experimental conditions. The experimental results showed that the total organic halogen (TOX) and trihalomethane (THM) formation increased with increasing Cu(II) concentration during chlorination, while haloacetic acids (HAAs) increased insignificantly. Accelerated chlorine decay and increased TOX and HAA formation were observed at high pH in the presence of 1.0 mg/L Cu(II) compared with that observed at low pH but THM formation decrease. Furthermore, the Cu(II) effect catalyzed the formation of brominated DBPs as it did for chlorine analogues in the presence of bromide ion. The microcalorimetry analysis demonstrated that more DBPs were formed in the Cu(II)-catalyzed chlorination, in which second-order rate constants obtained from reaction of HA with chlorine under given experimental conditions were 0.00256 M^?1?s^?1 (without Cu(II)) and 0.00865 M^?1?s^?1 (with Cu(II)), respectively. To discriminately examine the role of Cu(II) in greater detail, nine model compounds, which approximately represent the chemical structural units of HA, were individually oxidized by chlorine. It was demonstrated that carboxylic acids significantly enhanced the formation of TOX, THMs, and HAAs in the presence of Cu(II). Based on the previously published information and our experimental results, the possible pathway for Cu(II)-catalyzed TOX, THM, and HAA formation from chlorination of carboxylic acids were tentatively proposed.     

Predicting Reversibility of Acidification: The European Sulfur Story

Because of the deleterious effects of acid rain and the need to predict reversibility of acidification, various scientific tools such as modeling, stable isotopes and flux/budget calculations have been used in biogeochemical sulfur (S) research. The aim of this study was to evaluate consistencies and discrepancies between these different tools. While modeling has been seemingly successful in predicting S dynamics in soil solution and stream water by considering inorganic sulfate sorption and desorption only, stable S isotopes indicate that biological S turnover plays a crucial role for the sulfate released to soil solution and stream water. A comparison of budget calculations with soil S pools reveals that inorganic sulfate sorption and desorption are the controlling processes as long as deposition is high (> 15 kg S ha^?1yr^?1) and soils have a high sulfate sorption capacity. This explains the successful model predictions of the last two decades. However, for soils with low sulfate sorption capacity and under low sulfate deposition, organic S seems to be a significant source for stream water sulfate and has to be considered in future modeling.     

An Assessment of Long-term Risks of Metals in Sudbury: A Critical Loads Approach

Over a century of metal processing activity has resulted in widespread metal contamination of soils in Sudbury, ON, Canada. To assess the potential for recovery from the large reductions in metal deposition, critical loads were estimated for metals at 415 sites in Sudbury using an ??effects based?? approach that is based on exceedance of provincial soil guidelines using multiple independent estimates of metal partitioning (K_d) for each metal. Sudbury soils are heavily contaminated with copper (Cu) and nickel (Ni), with 74?% of samples currently exceeding the provincial soil guideline for Cu and 87?% of samples exceeding the guideline for Ni. Both metals are strongly correlated with other metals (zinc (Zn), cadmium (Cd), lead (Pb)), although they rarely exceed provincial guidelines Copper and Ni are also strongly correlated with organic matter but not soil pH. Based on the most recent Cu and Ni deposition estimates (mid-1990s), it is estimated that between 20?% and 51?% of the sites receive deposition in excess of the ??effects based?? critical load for Cu and between 5?% and 97?% of sites receive atmospheric deposition in excess of the ??effects based?? critical load for Ni. These results suggest that Cu and Ni concentrations in soil will generally decrease resulting in slightly fewer sites that exceed the provincial soil guideline, but that the timeframe of this response will be very slow, with relatively little change occurring over the next 100?years. Even assuming a best case deposition scenario whereby Cu and Ni deposition were to immediately fall to background levels, the percentage of sites with Cu and Ni levels in excess of the OMOE guideline would still be between 69?% and 72?%, and 56?% and 86?%, respectively, demonstrating that while recovery of the Sudbury soils is possible, greater reductions in metal deposition are needed and even so, it will be a process that takes several centuries.     

Acidification of Freshwater Wetlands: Combined Effects of Non-Airborne Sulfur Pollution and Desiccation

In recent decades, SO₄ ^2- concentrations have increased in groundwater and surface water of freshwater wetlands. For many minerotrophic peatlands, S originating from SO₄ ^2--polluted groundwater and surface water is a more significant source of SO₄ ^2- than the actual atmospheric deposition of S compounds. Lowered groundwater tables in wetlands, as a result of either natural or anthropogenic desiccation, may cause acidification because of concomitant geochemical oxidation processes. The impact of the enhanced availability of reduced S compounds, due to preceding SO₄ ^2- pollution, on these processes was tested in a mesocosm experiment, using soil cores including vegetation from a mesotrophic wet meadow. The soils had been maintained in waterlogged condition for seven months, using two environmentally relevant SO₄ ^2- concentrations (2 and 4 mmol L^-1). The groundwater table was reduced in two successive steps: 10 cm below soil surface, and complete desiccation. Control pretreated soils did not show a decrease in soil pH during desiccation, due to adequate buffering by bicarbonate. However, both SO₄ ^2--pretreated groups showed a significant drop in pH (from 6.5 to 4.5) caused by additional sulfide oxidation, leading to high SO₄ ^2- concentrations (10 and 16 mmol L^-1, respectively). Cation exchange and acidification-related solubilization processes induced the mobiliztation of base cations and potentially phytotoxic metals like Al. Nutrient concentrations in soil moisture were influenced strongly by SO₄ ^2- pretreatment, showing distinct patterns for P, N and K. Therefore, S polluted groundwater and surface water may severely increase the sensitivity of wetlands to desiccation. The results are discussed in relation to wetland management.     

An Empirical Model for Estimating Remediation Costs at Contaminated Sites

A model for estimating the remediation costs at contaminated sites is developed, in which the predictor variable is a composite of surface, subsurface, and contaminant risk factors. Calibration of the model is performed at 83 sites in an urbanized watershed with diverse surface geology in southeastern Michigan. These test sites exhibited different extents of contamination, including some where only soil was contaminated, and others where soil and groundwater were contaminated. The model was then applied to 79 sites with multiple contamination extents within different watersheds in North America, Europe, Australia, and Africa. The results indicate a very high correlation between the estimated and actual remediation costs at these sites. This model thus has the potential for providing reliable estimates of remediation costs across a broad array of soil and groundwater contamination scenarios, including dense nonaqueous phase liquid (DNAPL) contamination in sandy soil and lead in clay soil.     

Foliar Nitrogen as an Indicator of Nitrogen Deposition and Critical Loads Exceedance on a European Scale

The foliar N content of bryophytes and Calluna vulgaris (L.) has been shown to be an indicator of atmospheric N deposition in the UK at a regional scale (1000km) and more recently on a smaller scale in the vicinity of intensive livestock farms. This work extends the geographical scale of the relationship between foliar N concentration of Calluna vulgaris and other ericaceous shrubs and N deposition with 2 measurement transects, one extending from northern Finland to southern Norway (2000 km) and the other extending from central Sweden to Stockholm, south east Sweden (330 km). Included in the second transect is a region of complex terrain in the Transtrand uplands, where the variation in N deposition with altitude and canopy cover was quantified using ²¹⁰Pb inventories in organic soil. The relationship between foliar N (F_N) and N deposition was shown to increase linearly with N deposition (N_D) over the range 0.8% N to 1.4% N according to F_N = 0.040N_D + 0.793 (r² = 0.70). The data are entirely consistent with earlier studies which together provide a valuable indicator of critical loads exceedance, the threshold value being approximately 1.5% N, which is equivalent to a N deposition of 20 kg N ha^?1 y^?1.     

Calculating Critical Loads of Sulfur Deposition for 100 Surface Waters in China Using the Magic Model

Although decades of acid deposition have apparently not resulted in surface water acidification in China, some surface waters may have the potential trend of being acidified, especially those in southern China. In this paper, a dynamic acidification model–MAGIC was applied to 100 surface waters in southern and northeastern China to evaluate the impact of acid deposition to surface waters and to determine their critical loads of S deposition, both regions having distinguishing soil, geological and acid deposition characteristics. Results indicate that most surface waters included in this paper are not sensitive to acid deposition, with critical loads of S for these waters comparatively high. On the other hand, surface waters in southern China, especially those in Fujian, Jiangxi and Guangdong provinces, are more susceptible to acidification than those in northeastern China, which coincides with their different patterns of soil, geological and acid deposition conditions. Among all the waters, a few small ponds, such as those on top of the Jinyun mountain and Emei mountain, are the most sensitive to acid deposition with critical loads of 1.84 and 3.70 keq·ha^?1·yr^?1, respectively. For the considerable ANC remaining in most 100 surface waters, it is not likely that acidification will occur in the near future for these waters.     

Critical Loads of Trace Metals in Soils: a Method of Calculation

Critical load of trace metals in soils is a function of biological uptake, leaching by percolating water, input of the trace metals due to bedrock weathering, and the norms set to protect soils from metal pollution. The exceedance of the critical load is a difference between the calculated load and the measured input of the metals by atmospheric deposition and by application of agrochemicals. A critical time is the time when the concentration of a trace metal in soil, which is the result of all inputs and outputs of the metal in the soil, reaches the value of the norm. Data on biologically important trace metals in a small agricultural catchment in the Czech Republic indicate that the soil concentrations of As, Cd and Pb will reach the norms set for the soils after 4.5, 61, and 980 years, respectively. The present mass balances of Cu and Zn in the soils indicate that their steady-state concentrations will be below the norms so that the atmospheric and agricultural inputs will never overshoot the calculated critical load.     

Selection of Target Loads for Acidification in Emission Abatement Policy: The Use of Gap Closure Approaches

The Abatement Strategies AssessmentModel, ASAM, has been used to investigateEuropean emission abatement policies for ammoniaand oxides of sulphur and nitrogen. Thesepolicies are designed to reduce the depositionof acidifying substances towards critical loadsdefining the deposition which ecosystems cansustain. Since critical loads are not allattainable the model has been set up to reachvarious intermediate target loads. This paperuses the model to illustrate the sensitivity ofthe derived abatement strategies to the choiceof target load. Particular attention is paidto the various methods of `gap closure',designed to calculate target loads. Thesemethods have been discussed within the frameworkof the UN ECE Task Force on IntegratedAssessment Modelling in its preparations for thenew UN ECE `multi-pollutant multi-effectprotocol' and involve the reduction of the gapbetween the situation in 1990 and the criticalloads. The `gap' can be measured using variousmethods, `area', `ratio' and `accumulatedexceedance'. It is shown that the methods ofdefining target loads have an important bearingon the nature of abatement strategies forpollutants, in terms of the distribution acrosscountries of both costs and benefits. The`accumulated exceedance' approach reflects boththe differing sizes of ecosystem areas indifferent parts of Europe and the differentamounts by which their critical loads areexceeded. It probably reflects much morerealistically the relationship betweendeposition levels and damage to ecosystems.     

Runoff-Related Pesticide Input into the Lourens River,South Africa: Basic Data for Exposure Assessment and Risk Mitigation at the Catchment Scale

The characterization of runoff-related pesticide input and the identification of areas of concern in the field are essential for a comprehensive assessment of risk and the planning of mitigation measures. To this end, the agriculturally-derived aqueous and particle-associated pesticide contamination of the Lourens River and its tributaries was measured in a comprehensive design. Sampling was performed in the beginning of April prior to the first rainfall of the wet season and in the middle of April during high water conditions following the first rainfall of 9.6 mm d^-1. Pre-runoff samples indicated contamination with endosulfan at levels up to 0.06 μg L^-1, while no other pesticides were detectable. Rainfall-induced runoff resulted in an increase in the levels of the pesticides endosulfan, deltamethrin, azinphos-methyl, chlorpyrifos, and procymidone up to levels of 0.35, 1.4, 0.6, 0.19 and 9 μg L^-1, respectively in water samples. Endosulfan, azinphos-methyl, and chlorpyrifos were detected at maximum concentrations of 273, 152, and 245 μg kg^-1 in suspended sediments. No increased pesticide levels were detected at a control site upstream of the agricultural area. The Lourens River received its contamination via the tributaries discharging the surrounding farming area. Contamination of the six tributaries depended on landuse and slope characteristics and enabled the identification of target sites for risk reduction approaches. Transient pesticide levels exceeded the target water quality limit proposed by the South African Department of Water Affairs and Forestry (DWAF). The Lourens River site downstream of the farming area has been identified as a site where potential toxic conditions could arise.     

An Overview of Nitrogen Critical Loads for Policy Makers, Stakeholders, and Industries in the United States

Critical load values are calculated to determine ecosystem responses to deposition in a given area; these values may act as a tool to identify sensitive ecosystems in further need of protection. This overview provides an introduction to nitrogen critical loads for policy makers and parties involved in managing nitrogen deposition including electric utility generators, transportation managers and automobile manufacturers, and large-scale agricultural operators in the United States. It examines the use of the critical loads concept in European nations for establishing policy guidelines, current research on nitrogen critical loads in the U.S., and the development of nitrogen critical loads modeling and mapping.     

Prediction of Soil Acidification Using a Dymanic Model at a Bamboo Forest in Osaka Prefecture

This study is based on research of throughfall formation and soil chemistry processes. Through the experimental verification of the cation exchange part of the simulation model; making use of results of the flux of acid deposition on the forest and the chemical weathering of soil mineral, we predicted the future soil acidification. The result indicated that chemical weathering occupies the important portion of acid neutralization capacity of the soil and that significant soil acidification will not occur in this field within 40 years, even if the present acid load continues in the future.     

基于小流域划分的拉林河流域农业非点源污染物入河量估算

针对拉林河流域土地利用类型及气候特点,将输出系数模型和GIS技术相结合,以小流域为计算单元,对拉林河流域的非点源污染负荷进行了计算。计算结果表明:流域内COD负荷为16 454.83 t/a、TP负荷为668.80 t/a、TN负荷为1 319.08 t/a;灌区退水对流域内非点源污染负荷的贡献相对较大,由灌区退水导致的COD负荷占总量的69.37%、TP负荷占总量的85.33%;子流域2、5、7、15是流域内水土流失非点源污染整治的重点区域。     

Critical Loads of Acid Deposition for Wilderness Lakes in the Sierra Nevada (California) Estimated by the Steady-State Water Chemistry Model

Major ion chemistry (2000–2009) from 208 lakes (342 sample dates and 600 samples) in class I and II wilderness areas of the Sierra Nevada was used in the Steady-State Water Chemistry (SSWC) model to estimate critical loads for acid deposition and investigate the current vulnerability of high elevation lakes to acid deposition. The majority of the lakes were dilute (mean specific conductance?=?8.0 μS cm^?1) and characterized by low acid neutralizing capacity (ANC; mean?=?56.8 μeq L^?1). Two variants of the SSWC model were employed: (1) one model used the F-factor and (2) the alternate model used empirical estimates of atmospheric deposition and mineral weathering rates. A comparison between the results from both model variants resulted in a nearly 1:1 slope and an R ² value of 0.98, suggesting that the deposition and mineral weathering rates used were appropriate. Using an ANC_limit of 10 μeq L^?1, both models predicted a median critical load value of 149 eq ha^?1 year^?1 of H⁺ for granitic catchments. Median exceedances for the empirical approach and F-factor approach were ?81 and ?77 eq ha^?1 year^?1, respectively. Based on the F-factor and empirical models, 36 (17 %) and 34 (16 %) lakes exceeded their critical loads for acid deposition. Our analyses suggest that high elevation lakes in the Sierra Nevada have not fully recovered from the effects of acid deposition despite substantial improvement in air quality since the 1970s.     

Adapting the Profile Model to Calculate the Critical Loads for East Asian Soils by Including Volcanic Glass Weathering and Alternative Aluminum Solubility System

Adaptation of the steady-state soil chemistry model PROFILE was studied, on the following two parts, to calculate the critical loads for East Asian soils: (1) Dissolution rate coefficients of volcanic glass were derived from published experimental data, and calculated field weathering rate was compared with the rate estimated based on Sr isotope analysis. When BET surface area of sand fraction was regarded as mineral surface area, the calculated rates fairly agreed with the estimate, suggesting that sand fraction surface area is a reasonable estimate of weatherable mineral surface area of volcanic soils. (2) In repeated leaching experiments, Al solubility of a number of Japanese soils was explained by a model which assumed complexation of Al to soil organic matters. Such an Al solubility model is more appropriate for predicting soil chemistry than apparent gibbsite dissolution equilibrium.     

Implications of Uncertainty in a Pre-treatment Dataset when Estimating Treatment Effects in Paired Catchment Studies: Phosphorus Loads from Forest Clear-cuts

Water, Air, & Soil Pollution - Estimates of increased nutrient export caused by forest clear-cuttings are mostly based on long-term paired catchment studies, where the treatment effect is...     

Critical Nitrogen Deposition Loads in High-elevation Lakes of the Western US Inferred from Paleolimnological Records

Critical loads of nitrogen (N) from atmospheric deposition were determined for alpine lake ecosystems in the western US using fossil diatom assemblages in lake sediment cores. Changes in diatom species over the last century were indicative of N enrichment in two areas, the eastern Sierra Nevada, starting between 1960 and 1965, and the Greater Yellowstone Ecosystem, starting in 1980. In contrast, no changes in diatom community structure were apparent in lakes of Glacier National Park. To determine critical N loads that elicited these community changes, we modeled wet nitrogen deposition rates for the period in which diatom shifts first occurred in each area using deposition data spanning from 1980 to 2007. We determined a critical load of 1.4 kg N ha^?1 year^?1 wet N deposition to elicit key nutrient enrichment effects on diatom communities in both the eastern Sierra Nevada and the Greater Yellowstone Ecosystem.