Watershed vs in-lake alkalinity generation: A comparison of rates using input-output studies

As a means of assessing the relative contributions of watershed (terrestrial) and in-lake processes to overall lake/watershed alkalinity budgets, alkalinity production rates for watersheds and low alkalinity lakes were compiled from the literature and compared. Based on net alkalinity production data, derived using wet or bulk deposition data, mean and median alkalinity production for 20 watersheds in North America and Europe were 89 and 69 meq m^?2 yr^?1 (range 20 to 235 meq m^?2 yr^?1). For a subset of 10 watersheds with dry deposition data, terrestrial alkalinity production neutralized an additional 35 meq m^?2 yr^?1 of acidic deposition. For 11 lakes, mean and median in-lake alkalinity generation were 99 and 88 meq m^?2 yr^?1 (range 22 to 240 meq m^?2 yr^?1). Analysis of data indicates that for the low alkalinity systems described here, areal alkalinity production rates for watersheds and lakes are approximately equal. This relationship suggests that watershed area to lake area ratio can be used as a convenient estimator of the relative importance of watershed and in-lake sources of alkalinity for drainage lake systems. For precipitation-dominated seepage lakes and other systems where hydrology limits soil-water contact, hydrologic flow paths and residence times can be of overriding importance in determining alkalinity sources. For regions dominated by drainage lakes with high watershed area to lake area ratios (such as the Northeastern U.S.), however, alkalinity budgets are dominated by watershed processes. Omission of in-lake alkalinity consideration for most lakes in such regions would have little impact on computed alkalinity budgets or on predicted response to changes in acidic deposition loadings.     

Acidification of Nova Scotia Lakes

Although water chemistry of precipitation and lakes in Nova Scotia is dominated by C1 from sea salt, correction for marine influence reveals that the dominant anion in acidified lakes is SO₄. Atmospheric deposition of non-marine SO₄ (SO₄) and NO₃- for the period 1977–1980 at 4 stations in southwest Nova Scotia averaged 47 meq SO₄ ^* m^?2 yr^?1 and 21 meq NI₃-m^?2 yr^?1 compared with 38 and 13 meq, respectively, for the average of 3 stations in the northeastern third of the province. Precipitation pH increased from 4.5 to 4.8 along the same axis. Almost 50% of the SO₄ deposition occurred when storms came from the southwest, indicating low pressure tracks which pass south of major Canadian sources of S. SO₄ ^* deposition in metropolitan Halifax (1982 bulk data) was 87 meq m^?2 yr^?1, due to local emissions of ca. 28 300 tonne S in the area, as well as LRTAP. Concurrent deposition of NO₃-N was 15 meq m^?2 yr^?1 (2.1 kg ha^?1 yr ^?1). Loadings from SO₄ deposition in the Halifax area amount to 42 kg ha^?1 yr^?1 and clearly exceed the federal guideline (M.O.I., 1983) of 20 kg ha^?1 yr^?1. Water chemistry of southwest, northeast, and Halifax area lakes show the same general SOI trends as observed for atmospheric deposition. In addition we find a positive relationship between SOI concentrations in the urban lakes and proximity to the center of the urban area.     

Historical deposition rates of mercury in scandinavia estimated by dating and measurement of mercury in cores of peat bogs

Historical deposition rates of Hg were determined in 7 ombrotrophic bogs located far from direct sources in Sweden and Norway. The peat bog cores were dated using ²¹⁰Pb. Based on the dating result 10 to 12 slices from each core were analyzed for Hg. In Southwestern Scandinavia (Rörvik) the deposition rate has increased from about 10 to about 30 μg Hg m^?2 yr^?1 since the beginning of this century. In Northwestern Norway (Överbygd) the deposition rate has increased from about 10 to about 35 μg Hg m^?2 yr^?1 since the 1960's. In Southeast Sweden (Aspvreten) the deposition rate decreased since the beginning of this century. There are no significant trends in the historical deposition rates at the two other stations in middle Scandinavia. A comparison between recent Hg deposition rates measured by peat bog analysis, wet precipitation and mosses shows good agreement at all stations except those in Northern Norway were local dry deposition of Hg may be an important source of Hg.     

Concentrations of Nitrogen and Sulfur Species in Gas and Rainwater from Six Sites in Indonesia

Gas mixing ratios of SO₂, NO₂ and HNO₃ and nitrate and sulfate concentrations in rainwater have beenmeasured at six sites in Indonesia. The sites, Jakarta, Serang,Cilegon, Merak and Bogor, in Java, and Bukit Koto Tabang inSumatra, provide a range of pollution regimes in Indonesia.Jakarta and Bogor are heavily polluted sites in Java, whereasBukit Koto Tabang is a clean air station in a relativelyunpopulated area on the west coast of equatorial Sumatra. At thesesites rainwater was collected daily and gas samples weeklyduring 1996. The other three sites Serang, Cilegon and Merakrepresent smaller regional towns in west Java. At these sitesrainwater samples were collected weekly from June 1991 untilJune 1992.The results show that Jakarta has the highest volume-weightedmean sulfate concentrations in rainwater while the lowest weremeasured at Bukit Koto Tabang. Volume-weighted mean nitrateconcentration was about 24 μeq L^-1 at Jakarta and Bogor,significantly higher than the 0.8 μeq L^-1 measured atBukit Koto Tabang.Sulfur dioxide mixing ratios ranged from 4–7 ppbv in Jakarta toan average of 1.3 ppbv at Bukit Koto Tabang. Nitrogen dioxidemixing ratio was highest in Jakarta averaging 28 ppbv comparedwith the background mixing ratio of 1.2 ppbv at Bukit KotoTabang. Using dry deposition velocities estimated during aseparate study in the similar conditions of Malaysia enabled drydeposition estimates of SO₂, HNO₃ and NO₂.Results of estimated total acidic S and N deposition (wet anddry) were greater than 250 meq m^-2 yr^-1 at the Jakartaand Bogor sites compared with about 23 meq m^-2 yr^-1 atBukit Koto Tabang. At Jakarta and Bogor dry deposition accountedfor more than 50% of the total deposition estimates compared with about 20% at Bukit Koto Tabang. Such deposition rates arehigh when compared to critical loads estimated for Indonesia bythe RAINS-Asia model. In this model, critical loads in western Java and equatorial western Sumatra fall into one of twoclasses: 50–100 and 20–50 meq m^-2 yr^-1. Thus acidic deposition flux at Jakarta and Bogor wasfound to be above the predicted critical loads even for the moreacid insensitive soils.     

The cation denudation rate as a quantitative index of sensitivity of eastern Canadian rivers to acidic atmospheric precipitation

A model has been developed that relates the cation denudation rate (CDR) of a watershed (the rate that cations derived from chemical weathering are carried off by runoff), the atmospheric load of excess SO₄, and the pH of the river. Chemical and discharge data for rivers in Nova Scotia and Newfoundland were used to develop and test the model, which is based upon the common major ion chemistry of soft surface waters, and may be expressed by three statements: (1) CDR (meq m^?2 yr^?1) ? Excess SO₄ ^?? load (meq m^?2 yr^?1) = HCO₃ ^? (meq m^?2 yr^?1), (2) HCO₃ ^? (meq m^?2 yr^?1)/Runoff (m³ m^?2 yr^?1) = HCO₃ ^? (meq m^?3), (3) pH = pK + \(pP_{CO_2 } \) ? pHCO₃ ^?. The model in concentration form applies well to lakes. A detailed analysis of the data for the Isle aux Morts River, Newfoundland, is presented, showing that the CDR varies throughout the year, affected by both discharge and seasonal pattern.     

Atmospheric sulfur and nitrogen in West Java

Wet-only rainwater composition on a weekly basis was determined at four sites in West Java, Indonesia, from June 1991 to June 1992. Three sites were near the extreme western end of Java, surrounding a coal-fired power station at Suralaya. The fourth site was ～100 km to the east in the Indonesian capital, Jakarta. Over the 12 months study period wet deposition of sulfate at the three western sites varied between 32–46 meq m^?2 while nitrate varied between 10–14 meq m^?2. Wet deposition at the Jakarta site was systematically higher, at 56 meq m^?2 for sulfate and 20 meq m^?2 for nitrate. Since sulfate and nitrate wet deposition fluxes in the nearby and relatively unpopulated regions of tropical Australia are both only ～5 meq m^?2 anthropogenic emissions of S and N apparently cause significant atmospheric acidification in Java. It is possible that total acid deposition fluxes (of S and N) in parts of Java are comparable with those responsible for environmental degradation in acid-sensitive parts of Europe and North America.     

Effects of nitrogen deposition on the acidification of terrestrial and aquatic ecosystems

The concentration of ammonium and nitrate in precipitation has increased during this century. The deposition of N compounds (wet + dry) is reaching 30 to 40 kg ha^?1yr^?1 in many areas in Central Europe and above 20 kg in the southern parts of Scandinavia. In extreme situations throughfall data indicate depositions above 60 kg ha^?1yr^?1 in Central Europe and above 40 kg ha^?1yr^?1 in south Sweden. Very high depositions are observed on slopes at forest edges and adjacent to areas with animal farms and manure spreading. In areas with low N deposition almost all deposited N (>95%) will be absorbed in the tree canopies or in the soil. In areas with high deposition an increased outflow is observed which in some cases reach 10 to 15 kg ha-lyr-1. The increased output is an indication of N saturation of the ecosystem and it leads to acidification effects in soils, soilwater, groundwater and surface waters.     

Critical loads for nitrogen deposition on forest ecosystems

Critical loads for N deposition are derived from an ecosystem's anion and cation balance assuming that the processes determining ecosystem stability are soil acidification and nitrate leaching. Depending on the deposition of S, the parent soil material, and the site quality critical N deposition rates will range between 20 to 200 mmol m^?2 yr^?1 (3 to 14 kg ha^?1 yr^?1) on silicate soils and reach 20 to 390 mmol m^?2 yr^?1 (3 to 48 kg ha^?1) on calcareous soils.     

Seasalt and pollution inputs over the continental United States

The average deposition rate of sea salt chloride over the world continents is about 10 meq m^?2 yr^?1. Only about 14 ± 1% of chloride in the pollution-corrected world average river is contributed by seasalt aerosols and the rest from the dissolution of evaporites. The significant increase of the ion concentrations in the Mississippi river from the year 1905 to 1987 was caused by anthropogenic inputs such as fossil fuel burning, common salt consumption, and dissolution of carbonate and silicate rocks by acids derived from acid precipitation.     

Biogeochemistry of a forested watershed in the central Adirondack Mountains: Temporal changes and mass balances

Information on atmospheric inputs, water chemistry and hydrology were combined to evaluate elemental mass balances and assess temporal changes in elemental transport from 1983 through 1992 for the Arbutus Lake watershed. This watershed is located within a northern hardwood ecosystem at the Huntington Forest within the central Adirondack Mountains of New York (USA). Changes in water chemistry, including increasing NO₃ ^? concentrations (1.1 μmol _c , L^?1 yr-1), have been detected during this study period. Starting in 1991 hydrological flow has been measured from Arbutus Lake and these measurements were compared with predicted flow using the BROOK2 hydrological simulation model. The model adequately (r²=0.79) simulated flow from this catchment and was used to estimate drainage for earlier periods when direct hydrological measurements were not available. Modeled drainage water losses coupled with estimates of wet and dry atmospheric deposition were used to calculate solute budgets. Export of SO₄ ^2? (831 mol _c ha^?1 yr^?1) from the greater Arbutus Lake watershed exceeded estimates of atmospheric deposition in an adjacent hardwood stand suggesting an additional source of S. These large drainage losses of SO₄ ^2? also contributed to the drainage fluxes of basic cations (Ca²⁺, Mg²⁺, K⁺ and Na⁺). Most of the atmospheric inputs of inorganic N were retained (average of 74% of wet precipitation and 85% total deposition) in the watershed. There were differences among years (56 to 228 mol ha^?1 yr^?1) in drainage water losses of N with greatest losses occurring during a warm, wet period (1989–1991).     

Chemistry of soft-water seepage lakes in the upper midwest: Lacustrine alkalinity production in summer

A total of 26 soft-water, seepage lakes in the Northern Highlands (NH) of Wisconsin (N =16) and the Upper Peninsula (UP) of Michigan (N=10) were sampled four times between early May and mid October 1984 as part of the ‘PIRLA’ Project (Paleolimnological Investigations of Recent Lake Acidification). Because of low antecedent recharge of the local water-table, this ‘summer’ interval likely featured minimal groundwater inputs (<2 cm over lake surface) to most of these seepage lakes. Based on this hydrogeologic relationship, and on regional deposition data, I evaluated short-term net epilimnetic (June–August) and whole-lake (May–October) sediment-water exchange of ANC, base cations, acid oxy-anions, Al, DOC and silicic acid in these lakes using a simplified mass balance algorithm. Silica, nitrate and ammonium were all efficiently retained in these seepage lakes. The assimilation of NO₃ ^? (19±4 meq m^?2) slightly exceeded assimilation of NH₄ ⁺ (16±4), resulting in a net internal ANC production of only +3 meq m^?2 over 161 d between early May and mid October 1984. Over this same interval ANC production resulting from lacustrine S retention averaged +35±8 meq m^?2 in the NH, but was too variable to be statistically significant (+21±21 meq m^?2) in the UP. Epilimnetic S retentions in mid summer were more comparable (21±4 in NH; 14±5 meq m^?2 in UP). McNearney Lake (UP) illustrates how high sulfate, linked to low alkalinity, high Al, low P, and low productivity, can become a negative correlate of lacustrine S retention. Temporal changes in base cations in the 26 lakes were generally small and erratic compared with uncertainties in deposition inputs and analytical errors, rendering estimates of related ANC production inconclusive. Even small analytical biases can be critical when designing and interpreting lake monitoring studies.     

Calculation and Mapping of Sulfur Critical Loads for Terrestrial Ecosystems of Thailand

The essential parameters needed for the calculation of critical load of sulfur, CL(S), are base cation weathering rate, base cation uptake, acid neutralizing capacity leaching and base cation deposition. These parameters are estimated and mapped for the most area of terrestrial ecosystems of Thailand using data of national data soil survey. The values of CL(S) range from <200 to 2,225 eq.ha^?1yr^?1 and about 70% of terrestrial ecosystems are characterized by low values (<200 eq.ha^?yr^?1). These CL values reflect the sensitivity of Thai ecosystems to sulfur deposition.     

Carbon sequestration in Norway spruce in south Sweden as influenced by air pollution,water availability,and fertilization

Carbon sequestration in 30 yr old Norway spruce in south Sweden following manipulation of nutrient and water availability is presented. The site has an annual precipitation of 1100 mm and a deposition of about 20 kg N and 25 kg S per ha^?1 yr^?1. The soil type is a poorly developed podzol. Treatment include irrigation; artificial drought; ammonium sulphate addition; nitrogen-free-fertilization and irrigation with liquid fertilizers including a complete set of nutrients. The experiment has a randomized block design with four replicates per treatment. A comprehensive investigation of the above ground C storage on an areal basis was made at the start of the experiment and after 3 yr of treatment. After 3 yr of treatment with simulated N-S deposition using ammonium sulphate (100 kg N, 114 kg S ha^?1 yr^?1), C accumulation rates in the above ground compartments had increased by 37%. Similarly, irrigation caused increased C accumulation rates by 25%, whereas simulated drought during the vegetation period during 2 yr followed by 1 yr of recovery caused a 15% reduction of the C accumulation rates. Irrigation combined with liquid fertilization (100 kg N ha^?1 yr^?1), including all important nutrient elements, led to 65% increase in C accumulation rates compared to the control. The C sequestration of the latter treatment gradually increased and, during yr 5 of treatment, 8.6 Mg C ha^?1 accumulated in stems and branches, compared to 3.6 Mg ha^?1 for the control. It is concluded that there is a strong interaction between N-deposition and C accumulation rates in Norway spruce in south Sweden. The C accumulation rates are also sensitive to water availability. The study indicates a great potential to cultivate Norway spruce in south Sweden as a renewable energy source. A shift in energy source from fossil fuels to renewable energy sources will directly reduce the net emissions of CO₂ to the atmosphere.     

Assessment of soil acidification effects on forest growth in Sweden

The results of mapping critical loads, areas where they have been exceeded and steady state (Ca+Mg+K)/Al ratios of soils in Sweden, has been used to assess the order of magnitude of the ecological and economic risks involved with acid deposition for Swedish forests. The results of the calculations indicate that 81% of the Swedish forested area receive acid deposition in excess of the critical load at present. Under continued deposition at 1990 level, forest die-back is predicted to occur on approximately 1% of the forested area, and significant growth rate reductions are predicted for 80% of the Swedish forested area. For Sweden, growth losses in the order of 17.5 million m^?3 yr^?1 is predicted, equivalent to approximately 19% of current growth. Comparable losses can be predicted for other Nordic countries. The soil acidification situation is predicted to deteriorate significantly during the next 5–15 years, unless rapid emission reductions can be achieved. A minimum deposition reduction over Sweden of 85% on sulphur deposition and 30% on the N deposition in relation to 1990 level is required in order to protect 95% of the Swedish forest ecosystems from adverse effects of acidification. A minimum reduction of 60% on sulphur deposition and 30% on the N deposition is required to keep forest harvest at planned levels.     

Pattern and cause of acidic deposition in the Chongqing region,Sichuan Province,China

The Chongqing region located in Sichuan Province of China, comprises a large city, many small towns and rural areas. The region relies heavily on high-sulfur coal for energy production. Atmospheric pollution by sulfur oxides and other compounds from coal burning has become a major issue. Acid rain is observed throughout the region; volume weighted average pH is about 4.30. Average total S deposition for the region is estimated to be about 8 g S m^?2 yr^?1. In this paper we report concentrations of major ions in rain, fog, dew and clouds, of SO₂ in air and of airborne particles as well as dustfall. The emissions and interactions between important chemical species in air and water droplets are discussed.     

Atmospheric monitoring network operations and results in Canada

Atmospheric monitoring activities in Canada relevant to the long-range transport of atmospheric pollutants and the ‘acid rain’ problem are reviewed. Particular aspects examined are network objectives, station density and location, sampling protocol, and quality assurance. Results from a number of these networks are presented for the purpose of outlining the nature and extent of air and precipitation contamination by pollution released in eastern North America. Examples discussed include: the spatial distribution of acidic wet deposition, the temporal variation of acid-related substances in both air and precipitation, an episode of long-range transport, and the impact of acidic emissions on the Arctic atmosphere. Acidic wet deposition is greatest in Canada east of the Manitoba-Ontario border. In 1978, it ranged from 18 to 46 mmol H⁺ m^?2 yr^?1 in the southern half of eastern Canada, with maxima in southern Ontario (44 mmol H⁺ m^?2 yr^?1) and southwestern Quebec (46 mmol H⁺ m^?2 yr^?1). Western Canada receives less acidity in precipitation, but areas of some concern are the Pacific Coast (10 mmol H⁺ m^?2 yr^?1) and to a lesser extent northern Alberta and Saskatchewan (3 to 5 mmol H⁺ m^?2 yr^?1). Acidic emissions from mid-latitude sources which reach the Arctic in winter cause an increase in the acidity of snow from a pH of approximately 5.6 in the summer to values of 4.9 to 5.1 in January through March.     

Deposition of acidic species at a rural location in New South Wales,Australia

Wet-only rainwater composition on a daily basis, and atmospheric SO₂ and NO₂ concentrations on a monthly basis have been measured over a two year period at four sites ～100 km to the west of Sydney. Bulk aerosol composition on a monthly basis was also measured at one site. The study region is predominantly rural in character, but contains two coal-fired thermal power stations with a total installed capacity of 2320 MW, as well as several min or population centres, including a small city, with a total population of about 21,000. The measurement sites were located roughly on the perimeter of a circle of about 20 km radius having the power stations at its centre. Three of the sites were situated in rural settings, while the fourth was located on the outskirts of the small city of Lithgow. Atmospheric acid loadings at all sites were low by the standards usually associated with industrialised regions of Europe and North America, with about one third of rainwater total acidity provided by organic acids (formic, acetic and oxalic). At the three rural sites, total inorganic acid deposition, comprising measured wet deposition plus inferred dry deposition of acidic S and N species, averaged about 30 meq m^?2 y^?1, a low figure by most standards. At the site located near the city of Lithgow total deposition of acidic S and N species averaged about 80 meq m^?2 y^?1.     

Biogenic hydrogen sulfide emissions from selected Florida wetlands

Biogenic H₂S emissions from Florida wetland surfaces enclosed by transparent polycarbonate cylinders were collected on silver nitrate impregnated filters and analyzed fluorometrically. The areal emission rates ranged from 0.024 to 0.272 g S M-2 yr^?1 for a mangrove and from 0.001 to 0.110 g S m^?2 yr^?1 for two freshwater wetlands (cypress swamp and riverine marsh) and a saltwater marsh. The total quantity of biogenic S emitted from these wetlands was estimated to range from 1.8 x 10⁹ to 3.0 × 10⁹ g yr^?1. While biogenic emissions from wetlands may be a factor in local patterns of acid deposition, they are probably insignificant contributors to Florida's atmospheric S burden and acidity of precipitation compared to anthropogenic S sources.     

Total sulfur content in the humus layer of urban polluted forest soils

Total S content of the humus layer was determined from Scots pine forests in the surroundings of Oulu, an industrialized city in northern Finland. The S content nearest the city center and emission sources (zone IV; bar x=3870 μg g^?1 on an organic matter basis) was about twice as high as in three background areas (80 to 170 km from the city) and about 40% higher than at the sites which were ca 20 km from the main emission sources (zone I). The estimated accumulation of S in humus layer was, on average, 0.4 to 0.6 g m^?2 yr^?1 in the most polluted study sites and 0.1 to 0.2, 0.2 to 0.3 and 0.4 to 0.5 g m^?2 yr^?1 in zones I, II, and III, respectively.