Charge density of total organic carbon in Finnish lakes

Ion balance calculations were used to estimate the charge density of total organic carbon (TOC) and for calibrating the model of Oliver et al. (1983) for Finnish lakes. The database consisted of samples collected in the autumn of 1987 from 955 randomly selected lakes covering the whole country. Organic anion concentrations were estimated as the difference between Sigma cations and Sigma inorganic anions. The charge density of TOC was estimated by dividing the organic anion concentration by TOC. The median charge density was 7.5 microeq (mg TOC)(-1). In lakes with pH values lower than 4.5 the average charge density was 5.2 microeq (mg TOC)(-1) and it increased to 10.3 microeq (mg TOC)(-1) in lakes with pH higher than or equal to 7.0. The calibrated model explained 79% of the observed variability in organic anion concentration. The value for the total amount of acidic functional groups per mol organic carbon in the model of Oliver et al. (1983) was slightly higher compared to the Finnish calibration. At pH values higher than 4.4 the Finnish calibration gives lower organic anion concentrations compared to the model of Oliver et al. (1983).     

中国主要湖泊营养氮沉降临界负荷的研究

水体营养氮沉降临界负荷是不致使水体产生富营养化的最高氮沉降量。文中探讨了一种依据湖泊氮质量平衡原理计算营养氮沉降临界负荷的方法。用该方法计算表明 ,我国主要湖泊的营养氮沉降临界负荷比较低 ,大部分小于 1keq· hm- 1 · a- 1 ,部分已为目前的氮沉降量或者两者相当接近 ,意味着只接受氮沉降也能导致这些湖泊产生富营养化。但实际统计结果表明 ,氮沉降在导致受工农业生产和生活影响很大的城市和郊区湖泊的水质富营养化的所有氮污染源中所占比例较低 ,而其它来源的氮输入如河道入湖、工业生活废水和农田径流等才是导致富营养化的最主要因素 ,它们的量已远远超过了这些水体可随最高允许氮负荷。因此 ,对控制这些湖泊的水质富营养化而言 ,控制氮沉降并不是目前最紧迫的任务 ,而其它人为污染源的控制才是最急需的。但氮沉降临界负荷在湖泊富营养化的中长远控制中仍具有十分重要的意义。     

A survey of lakes in the Republic of Ireland: hydrochemical characteristics and acid sensitivity

In 1997, as part of a national program to determine and map critical loads, a lake survey was carried out in the Republic of Ireland. In total 200 lakes were sampled, which represents approximately 3.3% of the total lake population. The majority of lakes were situated in remote, high-altitude, acid-sensitive areas along the coastal margins of the country. Lake chemistry was dominated by marine inputs. Approximately 50% of the lakes had DOC > 5 mg L-1 due to the presence of organic soils in a large proportion of the catchments. Nonmarine sulfate concentrations were at background levels (< 20 mu eq L-1) in 50% of the lakes. Exceedance of critical load was observed in 7% of the sampled lakes (13 lakes). However, there are uncertainties in the critical load calculations due to the interference of sea salts and organic acids; accurate estimation under such conditions requires long-term lake and deposition chemistry.     

Source apportionment of fine particles at urban background and rural sites in the UK atmosphere

Airborne fine particulate matter (PM_2.5) has been collected at two sites in the West Midlands conurbation, UK, representing urban background and rural locations. Chemical analyses have been carried out for major anions, trace metals, total OC and EC, and for individual organic marker species including n-alkanes, hopanes, PAHs, organic acids and sterols. Source apportionment has been conducted using both a pragmatic mass closure model and the US EPA chemical mass balance (CMB) model. The pragmatic mass closure model is well able to account for the measured PM_2.5 mass in terms of chemical/source components, and the chemical mass balance model has been used to apportion the carbonaceous component of the aerosol. The dominant components of PM_2.5 at both sites are secondary inorganic (sulphate and nitrate) and carbonaceous particles. The CMB model shows the latter to arise mainly from road traffic sources, with smaller contributions from vegetative detritus, wood smoke, natural gas, coal, and dust/soil. The CMB model also identifies an important component of the organic aerosol not associated with these primary sources, which correlates very strongly with secondary organic aerosol estimated from the OC/EC ratio. The split between different automotive source types does not relate well to UK emission inventories, and may indicate that CMB source profiles from North American studies and different carbon analysis protocols may lead to erroneous conclusions.     

Sources of acidity in lakes and streams of the United States

Acidic (acid neutralizing capacity [ANC] < or = 0) surface waters in the United States sampled in the National Surface Water Survey (NSWS) were classified into three groups according to their probable sources of acidity: (1) organic-dominated waters (organic anions > SO4*; (2) watershed sulphate-dominated waters (watershed sulphate sources > deposition sulphate sources); and (3) deposition-dominated waters (anion chemistry dominated by inputs of sulphate and nitrate derived from deposition). The classification approach is highly robust; therefore, it is a useful tool in segregating surface waters into chemical categories. An estimated 75% (881) of acidic lakes and 47% (2190) of acidic streams are dominated by acid anions from deposition and are probably acidic due to acidic deposition. In about a quarter of the acidic lakes and streams, organic acids were the dominant source of acidity. In the remaining 26% of the acidic streams, watershed sources of sulphate, mainly from acid mine drainage, were the dominant source of acidity.     

Considerations of uncertainty in setting critical loads of acidity of soils: the role of weathering rate determination

The concept of critical loads has been generally accepted throughout Europe, and increasingly in Asian countries and the rest of the world, as providing the data which forms the basis for international negotiations on abatement strategies for emissions of acidifying pollutants. Central to the determination of quantitative critical loads of acidity for forests (and other ecosystems) is the rate at which the minerals in the soil weather or dissolve. Seven methods for determining these rates on a regional basis for the production of critical load maps have been suggested by the official bodies which are responsible for co-ordinating the European critical load mapping efforts. These methods are largely correlations which require a knowledge of the soil parent material and/or the soil mineralogy. The purpose of this paper is to review these weathering rate calculation methods and to assess whether it is currently possible to calculate numerically accurate critical loads for the production of regional critical load maps. A consideration of the data used to generate these methods and comparisons of the weathering rates calculated using various methods leads to the conclusion that at present it is not. Further work is needed to develop and maintain the initial credibility of critical loads both scientifically and as an aid to policy decisions.     

Metal bioavailability and toxicity to fish in low-alkalinity lakes: A critical review

Fish in low-alkalinity lakes having pH of 6.0-6.5 or less often have higher body or tissue burdens of mercury, cadmium, and lead than do fish in nearby lakes with higher pH. The greater bioaccumulation of these metals in such waters seems to result partly from the greater aqueous abundances of biologically available forms (CH(3) Hg(+), Cd(2+), and Pb(2+)) at low pH. In addition, the low concentrations of aqueous calcium in low-alkalinity lakes increase the permeability of biological membranes to these metals, which in fish may cause greater uptake from both water and food. Fish exposed to aqueous inorganic aluminum in the laboratory and field accumulate the metal in and on the epithelial cells of the gills; however, there is little accumulation of aluminum in the blood or internal organs. In low-pH water, both sublethal and lethal toxicity of aluminum has been clearly demonstrated in both laboratory and field studies at environmental concentrations. In contrast, recently measured aqueous concentrations of total mercury, methylmercury, cadmium, and lead in low-alkalinity lakes are much lower than the aqueous concentrations known to cause acute or chronic toxicity in fish, although the vast majority of toxicological research has involved waters with much higher ionic strength than that in low-alkalinity lakes. Additional work with fish is needed to better assess (1) the toxicity of aqueous metals in low-alkalinity waters, and (2) the toxicological significance of dietary methylmercury and cadmium.     

Trace Metals in Upland Headwater Lakes in Ireland

Trace elements (n = 23) in Irish headwater lakes (n = 126) were investigated to determine their ambient concentrations, fractionation (total, dissolved, and non-labile), and geochemical controls. Lakes were generally located in remote upland, acid-sensitive regions along the coastal margins of the country. Total trace metal concentrations were low, within the range of natural pristine surface waters; however, some lakes (~20 %) had inorganic labile aluminum and manganese at levels potentially harmful to aquatic organisms. Redundancy analysis indicated that geochemical weathering was the dominant controlling factor for total metals, compared with acidity for dissolved metals. In addition, many metals were positively correlated with dissolved organic carbon indicating their affinity (or complexation) with humic substances (e.g., aluminum, iron, mercury, lead). However, a number of trace metals (e.g., aluminum, mercury, zinc) were correlated with anthropogenic acidic deposition (i.e., non-marine sulfate), suggesting atmospheric sources or elevated leaching owing to acidic deposition. As transboundary air pollution continues to decline, significant changes in the cycling of trace metals is anticipated.     

Use of historical assessment for evaluation of process-based model projections of future environmental change: Lake acidification in the Adirondack mountains, New York, USA

Because of the considerable uncertainties associated with modeling complex ecosystem processes, it is essential that every effort be made to test model performance prior to relying on model projections for assessment of future surface water chemical response to environmental perturbation. Unfortunately, long-term chemical data with which to validate model performance are seldom available. The authors present here an evaluation of historical acidification of lake waters in the northeastern United States, and compare historical changes in a set of lakes to hindcasts from the same watershed model (MAGIC) used to estimate future changes in response to acidic deposition. The historical analyses and comparisons with MAGIC model hindcasts and forecasts of acid-base response demonstrate that the acidic and low-ANC lakes in this region are responsive to strong acid inputs. However, the model estimates suggest lakewater chemistry is more responsive to atmospheric inputs of sulfur than do the estimates based on paleolimnological historical analyses. A 'weight-of-evidence approach' that incorporates all available sources of information regarding acid-base response provides a more reasonable estimate of future change than an approach based on model projections alone. The results of these analyses have important implications for predicting future surface water chemical change in response to acidic deposition, establishing critical loads of atmospheric pollutants, and other environmental assessment activities where natural variation often exceeds the trends under investigation (high noise-to-signal ratio). Under these conditions, it is particularly important to evaluate future model projections in light of historical trends data.     

Supramolecular interactions of humic acids with organic and inorganic xenobiotics studied by capillary electrophoresis

Methodology based on capillary electrophoresis (CE) to study humic acids (HAs)-xenobiotics interactions is proposed. The interactions of HAs with organic and inorganic xenobiotics like paraquat, diquat, p,p(')-DDE, p,p(')-DDT, potassium ferrocyanide, potassium ferricyanide, chloride, 4-nitrocatechol and other organic compounds were studied. They were found to be of different kind depending on the structure of the xenobiotic molecule and on its charge (neutral, positive or negative). Ion binding, hydrogen bonding, van der Waals forces, ligand exchange, hydrophobic and hydrophilic adsorption, charge-transfer complexes and sequestration are some of the different mechanisms proposed to bind inorganic and organic compounds to HAs.It was also observed that some of the pollutants are strongly complexed (bound) only with some of the HA fractions forming quite stable entities of supramolecular kind, which can migrate independently. In addition, the stability constant of HA-Cl (negatively charged species) was estimated to be logk=3.1+/-0.95. In order to explain the interaction between negatively charged HAs and inorganic anions (like Cl(-), [Fe(CN)(6)](3-) and [Fe(CN)(6)](4-)), it is proposed that macropolycyclic polyamine structures are present in HA supramolecules, and that they are responsible for such strong binding.     

Polycyclic aromatic hydrocarbons in lake sediments from the High Tatras

European alpine lake systems are used as indicators of air quality over the continent. Preliminary data showed high polycyclic aromatic hydrocarbons (PAH) loads in the High Tatras (Eastern Europe) in comparison to other mountain regions. Here, insight on the spatial distribution of PAH is provided from analysis of top-core sediments of 27 alpine lakes distributed along the High Tatras.Top-core sediment concentrations were higher than those in deep-cores, and they were higher than those observed in other European high mountain regions. The PAH profiles were uniform and comparable to those observed in aerosols and snow, indicating that atmospheric deposition was the predominant PAH input pathway to the lakes. Good agreement between estimated atmospheric deposition and sedimentation fluxes was observed. However, in several lakes in the western range higher sediment fluxes may correspond to higher PAH depositions levels. The higher concentrations may also reflect inputs from potential emission source areas.     

Long-term trends in water chemistry of acid-sensitive Swedish lakes show slow recovery from historic acidification

Long-term (1987–2012) water quality monitoring in 36 acid-sensitive Swedish lakes shows slow recovery from historic acidification. Overall, strong acid anion concentrations declined, primarily as a result of declines in sulfate. Chloride is now the dominant anion in many acid-sensitive lakes. Base cation concentrations have declined less rapidly than strong acid anion concentrations, leading to an increase in charge balance acid neutralizing capacity. In many lakes, modeled organic acidity is now approximately equal to inorganic acidity. The observed trends in water chemistry suggest lakes may not return to reference conditions. Despite declines in acid deposition, many of these lakes are still acidified. Base cation concentrations continue to decline and alkalinity shows only small increases. A changing climate may further delay recovery by increasing dissolved organic carbon concentrations and sea-salt episodes. More intensive forest harvesting may also hamper recovery by reducing the supply of soil base cations.     

Dynamic modelling of recovery from acidification of lakes in Killarney Park,Ontario, Canada

During much of the 1900s, the lakes in Killarney Provincial Park have been exposed to high levels of acid deposition due to sulfur emissions from the nearby metal smelters in Sudbury. The sulfur emissions from this large point source have decreased to about 10% of what they were in the 1960s. Lake water quality in Killarney Park has greatly changed in response to reduced emissions, with noticeable declines in sulfate, aluminum and calcium concentrations. Here we apply the dynamic acidification model MAGIC to 3 lakes in Killarney Park. The lakes, which have different buffering capacities and response times, were selected to represent fast, intermediate and slow recovery from acidification. The model was calibrated to match observed data for the lakes and 4 different forecast scenarios for future sulfur deposition reductions were applied. The results indicate that there is still a large potential for improvement in the water quality in Killarney. The recovery time for the different lakes varies greatly. For the lake having the slowest response time several decades are needed for the chemistry to stabilize after implementation of deposition reductions.     

A dynamic modelling approach for estimating critical loads of nitrogen based on plant community changes under a changing climate

A dynamic model of forest ecosystems was used to investigate the effects of climate change, atmospheric deposition and harvest intensity on 48 forest sites in Sweden (n = 16) and Switzerland (n = 32). The model was used to investigate the feasibility of deriving critical loads for nitrogen (N) deposition based on changes in plant community composition. The simulations show that climate and atmospheric deposition have comparably important effects on N mobilization in the soil, as climate triggers the release of organically bound nitrogen stored in the soil during the elevated deposition period. Climate has the most important effect on plant community composition, underlining the fact that this cannot be ignored in future simulations of vegetation dynamics. Harvest intensity has comparatively little effect on the plant community in the long term, while it may be detrimental in the short term following cutting. This study shows: that critical loads of N deposition can be estimated using the plant community as an indicator; that future climatic changes must be taken into account; and that the definition of the reference deposition is critical for the outcome of this estimate.     

Nutrient dynamics and the eutrophication of shallow lakes Kasumigaura (Japan), Donghu (PR China), and Okeechobee (USA)

We compared the nutrient dynamics of three lakes that have been heavily influenced by point and non-point source pollution and other human activities. The lakes, located in Japan (Lake Kasumigaura), People's Republic of China (Lake Donghu), and the USA (Lake Okeechobee), all are relatively large (> 30 km2), very shallow (< 4 m mean depth), and eutrophic. In all three lakes we found strong interactions among the sediments, water column, and human activities. Important processes affecting nutrient dynamics included nitrogen fixation, light limitation due to resuspended sediments, and intense grazing on algae by cultured fish. As a result of these complex interactions, simple empirical models developed to predict in-lake responses of total phosphorus and algal biomass to external nutrient loads must be used with caution. While published models may provide 'good' results, in terms of model output matching actual data, this may not be due to accurate representation of lake processes in the models. The variable nutrient dynamics that we observed among the three study lakes appears to be typical for shallow lake systems. This indicates that a greater reliance on lake-specific research may be required for effective management, and a lesser role of inter-lake generalization than is possible for deeper, dimictic lake systems. Furthermore, accurate predictions of management impacts in shallow eutrophic lakes may require the use of relatively complex deterministic modeling tools.     

Evaluation of the OECD activated sludge,respiration inhibition test

The OECD Activated Sludge, Respiration Inhibition Test was evaluated as a method for assessing the potential impact of chemicals on wastewater treatment systems. Reproducibility of the test method was examined with respect to variation in oxygen consumption rates measured for a series of reactions set under identical conditions, and the variability in IC50 values estimated for three reference compounds. Several statistical procedures were also evaluated for analyzing activated sludge inhibition data. The test method was subsequently used to examine the effects of a wide variety of inorganic and organic chemicals on activated sludge respiration rates.     

Acidification in developing countries: ecosystem sensitivity and the critical load approach on a global scale

Acidification represents a growing threat to certain developing country ecosystems in tropical and subtropical climates. A methodology investigating the extent of acidification risks from sulfur emissions on a global scale is presented. Atmospheric transfer models have been used to calculate transfer and deposition of sulfur (using emissions for 1990 and a projection for 2050) and alkaline soil dust. A method to derive the relative sensitivity of terrestrial ecosystems is explained and preliminary critical load values are assigned. A range of values for critical loads and base cation deposition have been used to investigate uncertainty in maps depicting the excess of deposition above critical loads. These show an increasing risk of acidification in 2050 in extended regions of southern and eastern Asia, as well as parts of southern Africa, in comparison to 1990. Certain areas, especially in Asia, are shown at risk even when high values of critical load and base cation deposition are used.     

Importance of natural soil processes relative to atmospheric deposition in the mobility of aluminium in forested watersheds of the Black Forest

The dynamics of aqueous aluminium in the ARINUS experimental watersheds at Schluchsee (granite) and Villingen (quartz sandstone), Black Forest (South-west Germany), were studied in order to detect the processes and factors controlling its mobility. Aluminium speciation was performed in the seepage of typical soils (podsol, acidic brown earth, stagnogley) at 3 depths (organic layer, 30 cm and 80 cm of the mineral soil) as well as in streamwater. The studies concentrated on the variability in time and space of inorganic monomeric Al (Ali), and organic monomeric Al (Alo). Furthermore, the equilibrium speciation model WATEQF was used to calculate the distribution of inorganic Al species. Natural soil properties and processes, such as DOC mobilization and excess mineralization of NO3(2-) and SO4(2-), appeared to have great influence and outweigh the deposition effects upon Al mobilization in these systems which receive only low to moderate loads of acidic deposition.     

Estimation of the rate of VOC emissions from solvent-based indoor coating materials based on product formulation

Two computational methods are proposed for estimation of the emission rate of volatile organic compounds (VOCs) from solvent-based indoor coating materials based on the knowledge of product formulation. The first method utilizes two previously developed mass transfer models with two key parameters – the total vapor pressure and the average molecular weight for total volatile organic compounds (TVOCs) – being estimated based on the VOC contents in the product. The second method is based on a simple, first-order decay model with its parameters being estimated from the properties of both the source and the environment. All the model parameters can be readily obtained. Detailed procedures for computing the key parameters are described by using examples. The predictive errors were evaluated with small chamber data, and the results were satisfactory. Thus, the proposed methods provide a way to predict the VOC emissions in the indoor environment without having to conduct costly chamber testing. The two proposed methods work for both TVOCs and individual VOCs. Pros and cons for each method are discussed.     

铁和铝氧化物涂层砂的过滤与吸附性能评价

总结性地对3种不同氧化物涂层砂和未涂层砂的表面特性、过滤和吸附性能进行了比较与分析,明确了适用范围。改性滤料的高温加热和碱性沉积两种制备方法中,涂铁宜选前者,涂铝宜用后者。涂层砂的比表面积增大,吸附容量增加,使石英砂表面电荷的带电性质改变,有利于水中杂质的去除。涂铁砂适合于除氟和除砷及除有机物;涂铝砂适合于除浊、除有机物和除锌。