Sulphur deposition and changes in Swedish lake chemistry 1988–1993

Acidification of surface waters in northern Europe due to anthropogenic sulphur (S) deposition has led to new emission restrictions based on Critical Loads (CL). There is likely to be considerable interest in documenting the effect resulting S deposition changes have on surface water quality. This paper will focus on how the chemistry of 134 reference lakes in Sweden has changed between 1988 and 1993 in response to a decline in S deposition. Only 10% of the reference lakes had significant declines in sulphate during the 5 year study period. A similar number of lakes had an increase in the acid neutralizing capacity (ANC), but few of those with an increase in ANC were also lakes with significant sulphate decreases. Since there is good evidence that S deposition decreases will eventually result in ANC increases, a five year period is probably too short for evaluating the S protocol in terms of changes in lake chemistry. It takes a number of years to equilibriate to new deposition levels, and weather patterns may also obscure longer term trends.     

Acid deposition in the German solling area: Effects on soil solution chemistry and Al mobilization

The Al chemistry of soil solutions was evaluated in two forest ecosystems in the North-German Solling area which is heavily impacted by acidic deposition. The principal H⁺ buffering process in these soils is the release of Al ions. Within the stand of Norway spruce, Al concentrations increase with soil depth up to 370 umol/L. Ca/Al ratios of the soil solution decrease with depth and suggest high risk of Al toxicity to tree roots and potential antagonistic effects for ion uptake. The Al concentrations of the soil solution in the upper horizons do not appear to be in equilibrium with mineral phases of Gibbsite, Alunite and Jurbanite as suggested by the depth gradients and temporal patterns in ion activity products. Depletion of extractable soil Al in the upper horizons is occuring. The release of Al to the soil solution under these conditions seems to be restricted by kinetic constraints.     

Sulphate deposition by precipitation into lake Ontario

Measurements of sulphate concentration in precipitation from individual snow storms of several hours duration in the Western Lake Ontario region indicate that approximately 9–66 mg M^?2 of SO is being deposited into the Lake per storm. This amount is up to several times more than daily average values over long periods found by other workers. Using a mean sulphate concentration of 4 mg l^?1 and an annual accumulation of precipitation of 760 mm, the yearly sulphate deposition by precipitation is about 0.1 % of the total mass of sulphate in the Lake; however, more significantly, it is of the same order of magnitude as that discharged directly into the Lake by industry.     

Environmental chemistry of copper in torch lake,Michigan

A study of Keweenaw Peninsula and adjacent Lake Superior waters was undertaken to evaluate the significance of Cu tailings deposits as a potential source of Cu and the controlling Cu concentrations in these waters. Metal concentrations were determined by atomic absorption techniques. Copper concentrations, especially in areas affected by discharge of large quantities of Cu mine tailings for over 100 yr, were relatively high. Concentrations of apparently dissolved Cu of up to 100 μg 1^?1 were found in Torch Lake in the summer of 1972. These high Cu levels may be partially explained by industrial spills of copper wastes that occurred around that time. However, relatively high concentrations appeared to persist in Torch Lake waters throughout the annual cycle. The vast quantities of crushed Cu-bearing ore that comprise the bottom sediments and line the shores show a Cu content ranging from 1300 to 3800 mg 1^?1. These materials act as a reservoir of Cu providing a continual supply of Cu to these waters. Laboratory leaching studies of these materials demonstrate that they can release potentially significant amounts of Cu when suspended in lake water. Although the Cu levels found in Torch Lake exceed US EPA-recommended maximum allowable levels for these waters, there are reports of substantial fish and algal populations. Equilibrium calculations indicate the predominance of various soluble Cu species in the following order of abundance: Cu(OH)⁺ > Cu⁺⁺ > CuCO₃. However, Cu in these waters may not be controlled by solubility relationships of Cu compounds but rather by sorption onto surfaces of Fe and Mg hydrous oxides resulting in the occurrence of Cu in relatively non-toxic forms. Any additional mining or reclamation operations pose a potential hazard to aquatic ecosystems because of the wide-spread Cu contamination that already exists in the waters of this area.     

Adirondack headwater lake chemistry relationships with watershed characteristics

The Adirondack Region of New York State has been identified as having surface waters sensitive to acidic deposition and as receiving large annual inputs of acidic deposition. The large amount of data available for this region makes a quantitative study of the region possible. Compiled from a variety of sources, the Adirondack Watershed Data Base (AWDB) contains information on lake chemistry; lake elevation, area, and volume; and associated watershed data, such as size, slope, aspect, elevation, vegetation and wetland types, beaver activity, fire and logging history, and soils data. Bivariate and multivariate procedures were used to examine relationships between watershed attributes and lake chemistry. Because the variables in the data base are being refined and modified, the current relationships should be considered preliminary. Preliminary results indicate that wet deposition, lake elevation, and forest cover are the principal variables that are associated with variance in the data for lake pH and acid neutralizing capacity (ANC) in the Adirondacks. For headwater lakes in the Adirondacks, we estimate approximately 50% have a total ANC ≤ 40 μeq L^?1 and 40% have a pH ≤ 5.5.     

Headwater lake chemistry during the spring freshet in North-Central Ontario

From data on 30 headwater lakes in north-central Ontario we found that, during the spring snow melt of 1981, all lakes underwent serious declines in alkalinity. Generally, SO₄ ^2?, alkalinity, Ca⁺ and Mg²⁺ concentrations were reduced by runoff and rain then recovered to intermediate levels after the major inputs declined. As expected, a range in responses was evident with lower alkalinity systems showing the greatest changes. The observed changes, however, were consistent with acid loading having depleted alkalinity. In calculating an input-output budget for each lake, we found that changes in Cl^?, Na⁺, and K⁺ were consistent with atmospheric inputs being the major source as the difference between the expected input and the actual contribution from rain and snow had a mean near zero. There appears to be a significant, ? 45%, watershed source of sulphate that we hypothesize is from dry deposition occurring prior to snowfall and is eluted with the melting process. With refinements to a mass balance approach explaining the watershed source of SO₄ ^2? and Al, we feel it is possible to predict springtime lake changes given a few chemical and simple morphometric variables.     

Acid deposition: Perspectives in time and space

Most acid-deposition investigations have been concerned with the impact of nitrogen oxides (NO_x) and sulfur dioxide (SO₂) emissions on Europe and North America. This paper examines three issues beyond this central focus. Major conclusions are 1) ammonia (NH₃) emissions and subsequent nitrogen (N) accumulation in terrestrial ecosystems have the potential to generate significant acidification in terrestrial and aquatic ecosystems; 2) sulfur (S) and N accumulation in environmental reservoirs will not only result in significant and extensive acidification but will also impact the earth's radiation balance, tropospheric oxidizing capacity, ecosystem nutrient balance and groundwater quality; and 3) future emissions will substantially increase in the developing world, especially in Asia. By 2020, Asian emissions of SO₂, NO_x and NH₃ will be equal to or greater than the combined emissions from Europe and North America.     

Seasonal,annual and long-term variability in the water chemistry of a remote high mountain lake: Acid rain versus natural changes

Seasonal fluctuations as well as long-term trends in water chemistry were studied in Schwarzsee ob Sölden (Tyrol, Austria), an oligotrophic softwater lake situated at 2796 m a.s.l. The catchement is composed of granite, plagioclase and micaschists containing considerable amounts of sulphur, with little soil cover. The lake is ice covered for about nine months, during this time the deepest layers (>16m) become anoxic. During summer overturn, alkalinity (ALK) is lowest (?8 μeq l^?1) in the whole water column, whereas pH reaches its minimum (4.88) at the surface during snowmelt. A decrease of pH from 5.8 to 5.4 during winter is caused by CO₂ oversaturation, but deep water ALK increases to up to 130 μeq l^?1 due to in-lake ALK generation by reductive processes and base cation (BC) release. The seasonal pattern of ALK in SOS is driven by in-lake processes in winter, the snowmelting in spring and watershed processes and precipitation during summer. Since 1989 summer sulfate concentrations in SOS, originating mainly from the catchment, show a tendency to increase presumably caused by enhanced weathering. In contrast, SO₄ ^2? concentrations in other high mountain lakes which are dominated by atmospheric depositions show a decreasing trend. SOS is a good example for the complexity of interactions between catchment and in-lake processes which act at different time scales and depend on climate changes and atmospheric inputs.     

中国西南地区坡地钾素平衡及管理措施探讨

坡地钾素平衡及管理研究于2000年开始在贵州南部开展。试验分别设条带种植1、条带种植2、工程梯化、横坡种植四个水土保持农艺措施和农民习惯种植(对照)5个处理,探讨坡地钾素的平衡及其管理措施。试验结果表明,坡地的钾素平衡除了与施肥和植物吸收有关,还与降水、地表径流和土壤侵蚀有着密切的联系。在简化了的坡地钾素循环中(不包括地下渗漏的钾素部分),肥料提供给土壤的钾素达89.66.kg/hm2～176.83.kg/hm2,对土壤钾素输入总量的贡献达96%以上。而9.80%～26.26%来源于无机肥的钾素是通过作物吸收而带离土壤。地表径流和侵蚀泥砂中具有较高的有效钾含量,地表径流所含的有效钾是降水的4.28～6.67倍;侵蚀泥砂所含的有效钾是侵蚀前土壤耕层的1.51～1.92倍。它们不但带走降水中有效钾,而且还带走土壤中的有效钾,流失量每年分别达到14.82～23.10.kg/hm2和4.46～9.35.kg/hm2。每年通过作物吸收而造成土壤钾素损失为28.46～90.10kg/hm2。坡地农业活动造成土壤缓效钾水平急剧下降,缓效钾亏缺每年达175.34～306.04.kg/hm2。因此,在坡地钾素平衡中,应重视水土保持、秸秆还田及肥料的有效利用。条带种植措施可减少地表径流40.31%～43.77%、泥砂53.60%～65.63%、提高土壤有效钾12.62%～33.69%,使得无机肥的利用率达到26%,是坡地钾素管理的有效措施。     

Gårdsjön Project: lake acidification,chemistry in catchment runoff,lake liming and microcatchment manipulations

The Gårdsjön Project is an ecosystem approach in studying acid deposition and its effects on terrestrial parts and lakes within a catchment. The study is an attempt to quantify the processes causing the acidification as well as an analyses of the chemical and biological conditions before liming of the lake and manipulations in microcatchments. This paper gives a brief overview of some studies already performed and recently started experiments within the project, such as lake liming, lime application on land, forest fertilization, clearcutting and applications of acid and neutral sulphate on land.     

Modeling of throughfall chemistry and indirect measurement of dry deposition

Precipitation over a forested watershed is altered by interaction with plant surfaces which act as a filter for airborne gases and particles. This results in a major transfer to the forest floor of materials captured, washed, and leached from the forest canopy. Sequential samples of wetfall and sequential samples of throughfall under deciduous and coniferous trees were collected and chemically analyzed for major anions and cations. A simple washoff, mixing model based on leaf area index was used to simulate throughfall chemistry and to decouple foliar exudation from dry deposition. Model results gave excellent predictions of the measured sequential throughfall using estimated values of dry deposition. The model can also be used to calculate dry deposition, if the sequential throughfall data and wetfall data are used as input variables.     

Peatland water chemistry in Central Ontario in relation to acid deposition

Thirty-one peatlands from two areas of central Ontario were sampled to assess the influence of acid deposition on peatland water chemistry. Factor analysis differentiated peatland water chemistry along three major axes of chemical variation, interpreted as axes of organic concentration, mineral concentration, and deposition influence. Water from the surface mats had a higher organic concentration than water from open pools. Mineral influence in peatland waters was reflected by higher concentrations of Ca, Mg, Na, and silica in fen pools compared to bog pools. The influence of high acid deposition in the Wanapitei study area was indicated by high concentrations of sulphate, Ni, Mn, and Cu, and lower pH compared to an area that has received less acidic deposition (Ranger). Regression analyses indicated that H⁺ variation in bogs could be largely explained by organic C concentration, but that sulphate concentration was also positively associated with acidity, while Ca was negatively associated with acidity.     

Role of precipitation chemistry versus other watershed properties in Wisconsin lake acidification

Data for over 100 watershed properties, including aspects of topography, hydrology, geology, soils, vegetation, lake morphometry and input precipitation chemistry, have been developed since 1980 for 316 watersheds in northern Wisconsin. The hypothesis being evaluated for this lake population is that the observed water chemistry, can be accounted for as a function of antecedent water and chemical inputs, after considering exchange processes in the lake and watershed and the lake/groundwater interactions. The variables found by regression analysis to explain observed variability in color, sulfate, and acid neutralizing capacity (ANC) levels in Wisconsin lakes are: for color, vegetative characteristics, mean depth, and water renewal times; for sulfate, precipitation concentration of sulfur, evaporative concentration, and lake water renewal time; ANC appears to be controlled by the size of the watershed, lake depth or water renewal time, and the intensity of anthropogenic inputs and cultural developments in the watershed. These results differ from previous studies in Wisconsin and nearby areas of Michigan and Minnesota by indicating that in some lakes acidity may not be in equilibrium with current precipitation chemistry.     

Polluted precipitation and the geochronology of mercury deposition in lake sediment of northern Minnesota

Elevated Hg levels in game fish from wilderness lakes in northern Minnesota led to the present study of sediment cores from two lakes to ascertain the source and history of Hg deposition. Natural background levels of Hg were found to range from 0.03 to 0.06 μg g^?1, with cultural levels as high as 0.16 μg g^?1. Reconstructed geochronologies reveal a dramatic two-fold increase in Hg flux, from 0.008 to 0.017 μg cm^?2 yr^?1, occuring after the year 1880, suggesting an anthropogenic influence. No industrial or geologic source of Hg is found in the study watersheds. The entire historical increase in Hg flux can be accounted for by atmospheric loading provided that 1/5 of all the Hg presently supplied to the watershed via precipitation is ultimately deposited in lake sediment. Hg levels in fish are not correlated with Hg levels in lake sediment, although there is a link to acid-sensitivity of lake water, amount of acid-neutralizing geologic material exposed in the watershed, and watershed area/lake volume ratio. Thermal stratification of lake water and a complexation-adsorption mechanism are proposed to account for variations in Hg levels observed in sediment collected from different sites.     

Relations between lake acidification and sulfate deposition in Northern Minnesota,Wisconsin, and Michigan

From a level of 1 kg ha^?1yr^?1 in north central Minnesota, emission-related wet SO₄ deposition increases across northern Wisconsin and northern Michigan to about 18 kg ha^?1yr^?1 in south central Michigan. Samples taken from 82 clearwater (low color) lakes across this region in the summer of 1984 showed a pattern of acidification in proportion to deposition. We found a linear increase in the difference between alkalinity and Ca+Mg and in lake SO₄ concentration with increasing deposition. We developed a simple equation to predict the emission-related SO₄ deposition levels that will cause the alkalinity of sensitive clear-water lakes to go to zero.     

Acid rain deposition patterns in the continental United States

Acid rain has become a major environmental concern, the current extent of which is illustrated in this paper. Maps of both pH and H⁺ deposition in precipitation have been developed for the continental United States by analyzing laboratory pH data from nine precipitation chemistry networks and two single stations spread across the continental United States and southern Canada during the late 1970's. Average laboratory pH values were obtained or calculated for approximately 100 stations, and isopleths of weighted mean pH and mean annual H+ deposition in precipitation were drawn. Results of this analysis show that in spite of a wide variety of collection methods and sampling intervals, there is remarkable uniformity in the average pH among the various stations. The northeastern United States continues to exhibit the most acidic precipitation, with remaining portions of the eastern United States, states along the western coastline and a pocket in central Colorado also experiencing acid precipitation.     

Acidic deposition and its effects in southwestern China

The emissions of SO₂ in China correspond at present to 8–10 TgSyr^?1. The rapid industrialization has caused a dramatic increase in the emissions in recent years and this increase is likely to continue. This paper describes studies of concentrations and effects of acidifying substances in parts of the Guizhou and the Sichuan provinces where the S-emissions are large. A small catchment about 10 km from Guiyang centre was equipped with instruments for studies of soils, soil water and streamwater chemistry. The molar ratio Al/(Ca+Mg) is > 0.8 in soil water in some places. Two small streams have median pH-values about 4.6 and 5.1. Laboratory studies with selected Chinese soils showed that the anion adsorption was low. These studies gave also important information on soil sensitivity. The studies confirm that acid deposition may affect soils in parts of south-western China, but the sensitivity varies dramatically and there is a strong need for more information.     

Atmospheric deposition effects on the chemistry of a stream in Northeastern Georgia

A modeling study of the Allt a Mharcaidh catchment in the Cairngorm region of Scotland has been undertaken to investigate long term trends in acidification and model sensitivity to soil physical and chemical characteristics. The MAGIC model (Model of Acidification of Groundwater In Catchments) is used to demonstrate that the sulphate adsorption ability of the soil and quality and quantity of rainfall inputs have significant effects on model output. Optimal weathering rates and predicted present day ion concentrations in streamwater compare well with measured and observed values. The analysis shows that the catchment has become progressively acidified since pre-industrial times but major changes in stream acidity have yet to occur.     

西南地区玉米养分管理现状分析与评价

为了解西南地区玉米施肥现状与养分管理存在的问题,对西南地区4个省10个县的202份玉米养分调查数据进行了分析和评价。结果表明:(1)西南地区玉米生产中基肥以复合(混)肥为主,追肥以尿素和复合(混)肥为主;有机肥、玉米专用肥、缓(控)释肥等新型肥料使用率低。(2)化肥N、P_2O_5和K_2O平均投入量分别为323.52、80.93和56.55 kg·hm~(-2),总体表现为氮肥过量和钾肥不足,氮肥超量施用比例为62.38%,钾肥施用不足比例为60.89%,且区域之间差异较大。(3)玉米基肥以穴施覆土为主,但追肥养分管理粗放,第1次和第2次追肥中采用穴施不覆土的农户比例分别为63.22%和59.76%,表土撒施的比例分别为10.34%和25.61%。建议分区域明确玉米氮肥投入限量标准,引导农户降低氮肥用量;增施有机肥,发挥养分替代效应,同时推行秸秆还田,补充土壤钾素,提高土壤持续生产能力;推进玉米机械化生产,实现种、肥同播和化肥深施,降低农田养分流失。     

Soil geochemistry in relation to water chemistry and sensitivity to acid deposition in Finnish Lapland

Ecosystems in Finnish Lapland are threatened by heavy metal pollution and acid deposition derived from emissions of Cu-Ni smelters in Kola Peninsula and to varying extent to pollution from southern Fennoscandian and Central European sources. Extensive chemical analyses of small lake waters collected in Finnish Lapland have demonstrated that a significant number of lakes are acidified (ANC < 0μcq/l) or their buffering capacity is critical (ANC = 0–50μe/l). The relative abundance of mafic, ultramafic and carbonate rock components in the catchment were the chief factors controlling ANC and the main base cation (Ca²⁺, Mg²⁺) concentrations of lake waters. Both humic and clearwater lakes with low buffering capacity (ANC < 50μeq/l) were mainly located in the catchment areas identified as sensitive to acidification on the basis of low content of base cations (Ca²⁺ +Mg²⁺ +K⁺ < 500 meq/kg) in till. The ratio of the catchment area to the lake area was distinctly smaller for acidic lakes than for the well-buffered lakes, indicating the importance of catchment processes in determining the ANC and main base cations. The high sulphur concentrations (median 60μeq/1) of acidic lakes in northeastern Lapland, near the Finnish-Norwegian border, were strongly correlated with the highest deposition of sulphur derived from smelters of Kola Peninsula. The anomalously high concentrations of sulphur of well-buffered lakes in the western part of Lapland were due to sulphide minerals of soil and bedrock. The acidity of humic lakes in southern Lapland was in large part due to the organic acidity derived from peatlands.