Effects of acid deposition on watershed ecosystems of national parks in the great lakes basin

Legally protected national parks provide an appropriate substrate for essential long-term study of ecosystem structure and function, and for detecting trends in natural and human-induced stress. The absence of unplanned site manipulation in such areas is especially valuable for such research. Our present research has two major components. The first is the long-term ecosystem-level study of the effects of atmospheric contaminants on ecosystem processes. The overall objective is to evaluate ecosystem aquatic/terrestrial linkages and their role in establishing aquatic ecosystem sensitivity to anthropic atmospheric inputs. Four watershed/lake ecosystems, representative of much of the region's diversity, are under study. Two mature boreal sites on Isle Royale are characterized by first-order perennial surface stream input and lake outflow. Two additional mainland northern hardwood sites, one with shallow soils and one with soils derived from glacial till, are characterized by sensitive aquatic systems. One site is in a private reserve and the other in Pictured Rocks National Lakeshore. Surface outflow is gaged by Parshall flume and stage height recorder. Meteorological stations record variables for estimating evapotranspiration. One-tenth ha plots have been established in all watersheds and three sites have had intensive study of precipitation modification by canopy and forest soil. Five-year mean maximum and minimum lake pH varies from 6.85 to 4.94, Ca²⁺ from 1070 to 54 eq l^-1, K⁺ from 5.42 to 8.35 eq l^-1, NH ₄ ⁺ from 10.12 to 3.23 eq l^-1, HCO ₃ ^sup- from 635 to 24 eq l^-1, NO ₃ ^sup- from 3.27 to 1.54 eq l^-1, and SO ₄ ^sup2- from 110 to 52.7 eq l^-1. The relatively high NO ₃ ^sup- values observed in one lake are the result of stream drainage from a watershed dominated by Alnus rugosa, and another has high seasonal NO ₃ ^sup- inputs during spring runoff. However, owing to periodic winter thaws, significant snowpack release of nutrients generally precedes maximum spring stream runoff. Water chemistry in both sensitive and non-sensitive lakes appears to be primarily reflecting how the conterminous terrestrial system is retaining atmospheric inputs more than the quality of direct lake atmospheric input. This is especially evident for H⁺, NO ₃ ^sup- and SO ₄ ^sup2- .The second component is the assessment of watershed acidification, SO ₄ ^sup2- output and soil retention across an input gradient. An anthropic deposition gradient provides the opportunity for intersite time-trend analyses as to the effects of inputs. Our study objective was to see if the decreasing west to east input/output values for SO ₄ ^sup2- , noted in small first-order watersheds in national parks from Minnesota to Ohio, might be related to present atmospheric inputs, potential and total soil SO ₄ ^sup2- adsorption, or soil SO ₄ ^sup2- desorption from earlier higher inputs. Precipitation pH ranged from 5.05 at Fernberg, Minnesota to 4.24 at Wooster, Ohio. Minimum and maximum concentrations of NH ₄ ⁺ , NO ₃ ^sup- , SO ₄ ^sup2- and Cl^- were also found at these stations. Stream water concentrations of NO ₃ ^sup- and SO ₄ ^sup2- increase in a similar but sharper gradient. Streams are well buffered. Cation, HCO ₃ ^sup- , NO ₃ ^sup- and especially SO ₄ ^sup2- output increase west to east, but H⁺ output decreases. At the eastern site stream SO ₄ ^sup2- concentration and output exceed HCO ₃ ^sup- . Potential soil SO ₄ ^sup2- adsorption capacity increases eastward, but this capacity is filled. Crystalline Fe hydrous oxides appear more effective than amorphous Fe hydrous oxides at adsorbing SO ₄ ^sup2- . High anthropic anion inputs, inability of forest soil to adsorb additional inputs and perhaps SO ₄ ^sup2- desorption appear responsible for the replacement of HCO ₃ ^sup- by SO ₄ ^sup2- in stream water. The major cation accompanying SO ₄ ^sup2- is Ca²⁺.Contribution from Fourth World Wilderness Congress—Acid Rain Symposium, Denver (Estes Park), Colorado, September 11–18, 1987.     

Factors affecting the leaching of lead from UPVC pipes

This paper summarizes the results of a series of studies on the various factors that affect the leaching of lead from unplasticized poly(vinyl chloride) (UPVC) pipes. Factors that were studied include temperature, pH and extractants. Results showed that, for a given UPVC pipe, the rate of leaching of lead depended primarily on temperature and the nature of extractants. While the rate of leaching of lead was quite low with distilled water, it was very much enhanced by the presence of low concentration of anions such as Cl^-, HPO _inf4 ^sup2- HCO _inf3 ^sup- , NO _inf3 ^sup- , SO _inf4 ^sup2- and EDTA. EDTA, being a strong complexing agent, was most effective. Rates of leaching were found to be higher at elevated temperature except in the cases of HPO _inf4 ^sup2- and EDTA. Effect of pH was not pronounced. The temperature at which the UPVC pipes were extruded was found to affect the rate of leaching of lead. Pipes extruded at 190°C were found to have lower rate of leaching than those extruded at 180°C and 170°C. Analysis of the pipes by Scanning Electron Microscopy showed that the distribution of lead in the pipes extruded at 190°C was more uniform than those extruded at 170°C.     

On density of precipitation chemistry networks

Using Scandinavian precipitation chemistry data the dependence of the accuracy of the interpolation and areal averaging of SO _inf4 ^sup2- , NO _inf3 ^sup- , NH _inf4 ^sup+ , and Ca²⁺ contents of precipitation water on the density of the network and on the size of the area considered is studied. On the basis of the results obtained the density of networks operating with a given accuracy can be determined as a function of the area. As an example the density of the networks determining the annual and monthly areal SO_f4/^p2- deposition as well as the point values of the monthly SO_f4/^p2- concentration with an accuracy of 10%, 25%, and 30%, respectively, is calculated. The accuracy provided by such networks for other components in precipitation water is also studied.     

The predicted effect of SO2 emission controls on the water quality of eastern Canadian lakes

Changes in SO _inf4 ^sup2- deposition predicted to occur in response to implementation of announced SO₂ emission control programs in Canada and the U.S.A. have been used as input to water chemistry models thereby giving an estimate of the changes in lake acid neutralizing capacity (ANC) and pH that can be expected from these programs. Eastern Canada has been divided into 22 subregions for the purpose of this analysis. Relative to the current level (1982–86) of SO _inf4 ^sup2- deposition (Scenario 1), the effect of the Canadian SO₂ emission control program alone (Scenario 2) is compared to that obtained when controls are implemented throughout North America (Scenarios 3 and 4). SO₂ emission reduction will effect a shrinkage of the high wet SO _inf4 ^sup2- deposition field in NE North America such that under Scenario 4 conditions, almost no area will remain in Canada that receives >20 kg ha^-1 yr^-1. The greatest decrease in deposition and resulting change in lake chemistry occurs in southern Ontario and southwestern Quebec. ANC distributions shift to higher concentrations and the percentage of lakes having pH<6 decreases in these areas. The Atlantic Provinces will obtain only a minor benefit from the control programs, i.e. experiencing only a small decrease in deposition and improvement in water quality. High sensitivity of the terrain in many parts of Atlantic Canada means that large numbers of lakes will remain acidic (i.e. ANC<0) and/or have pH<6 (an important biological threshold) even after full implementation of the current plans for SO₂ control in Canada and the U.S.     

Gastro-enteric methane versus sulphate and volatile fatty acid production

The breakdown of low digestible components present in food during passage through the human and animal gastro-intestinal (GI) tract is performed by the highly diverse microbial community present in this ecosystem. Fermentation of these substances yields, besides CO₂ and volatile fatty acids, H₂, which is used as a substrate by three different H₂-consuming bacteria. Sulphate-reducing bacteria (SRB) use H₂ to reduce SO _inf4 ^sup2- to H₂S, hydrogenotrophic methane-producing bacteria (MPB) use H₂ to reduce CO₂ to CH₄ and reductive acetogens (RAC) use H₂ to reduce CO₂ to CH₃COOH. A competition between these three bacterial groups exists for the common H₂ substrate. This results generally in the dominance of one group above the other two.     

Detection of sulphur dioxide in the air using Scotch pine needles

Air quality is especially important in surface layers, for it is this layer that provides the living components of environment with the needed oxygen and carbon dioxide. Various air polluting gases penetrate cells affecting and contaminating them. Chloroplast shell of some pine species, for instance, doubles under the impact of carbon dioxide which is followed by tillacoids swelling and reduction.Literature provides opinions of some authors, who consider Scotch pine needle to be a biological indicator of sulphur dioxide. Others object to it basing on the observations of physiological development.The property of a Scotch pine as that of biological indicator manifests in SO₂ absorption by its needles. The analysis of total content of SO₂ in the needles shows an increase of SO₂ concentration.Sulphur in the needles is found in the form of organically bound sulphur, aminoacids, hormones as well as in the form of sulphates.Basing on our previous analysis we have generalized the data on the correlation concentrations of sulphur dioxide in the air and general concentrations of sulphur in the needles. We have supplemented the observations with the analyses of organically bound sulphur and concentrations of nonorganic sulphur. According to research data, needles contain a characteristic and rather stable quantity of organically bound sulphur.So we may state that the SO _inf4 ^sup2– concentration and the amount of SO₂ absorbed from the air are interdependent.Some authors state that SO _inf4 ^sup2– content in the soil doesn't affect sulphur content in pine needles. That is why we studied the affect of SO _inf4 ^sup2– content in the soil on sulphur content in Scotch pine needles.We could prove this statement by means of various kinds of analyses only partially. The ion transport is affected by the presence of other ions, pH and a lot of other factors.What may be said for sure is that different qualities of soils gave only minor and insignificant deviations.Hence our assumption about the SO₂ contamination from air, proved by its effect on the soils, turns to suit approximate measurements.     

Evaluation of the effects of acid precipitation in eastern Canada using the raison system

Evaluations have been made of the key chemical factors in the aquatic effects upon surface waters due to acidic precipitation in eastern Canada. The region of Canada east of the Manitoba/Ontario border was divided into 22 aggregates and assessments of inorganic and organic ion chemistry appraised relative to sulphate deposition rates and distributions. Aquatic sensitivity is largely dominated by the concentration, distribution and magnitude of SO _inf4 ^sup2- (sulphate) deposition and by the prevalent geology and derived soils found in each aggregate. The RAISON system provided an adaptable and highly flexible platform to evaluate interactively, multiple data sets of divergent characteristics. Attributes usually associated with geographical information systems are significantly augmented by quantitative numerical and stochastic capabilities that were used extensively in this study.     

The characteristics of size distribution of suspended particulates in the air for sulphates and selected metals in different areas and seasons

The characteristics of the distribution of particles by size were investigated for sulphates and selected metals (Pb, Fe, Mn, and Cu) in the air in two urban and an industrial area during the winter and summer periods using an Andersen cascade impactor.In the case of metals, but not sulphates, the character of the area affected the value of mass median diameter. Lowest values were obtained in a sparsely populated urban area, whereas in a densely populated urban area and in the industrial area the values were higher.In the industrial area a high correlation coefficient was found between sulphate and manganese, and between sulphate and lead, as well as a high value of the equivalent Mn²⁺/SO _inf4 ^sup2- ratio for the total sample. It may therefore be assumed that in the industrial area manganese produces a catalytic effect on SO₂ conversion to sulphate. Among the investigated metals lead stands out as a dominant cation which binds to the sulphate ion in the industrial and densely populated areas.     

An overview of the acidification of lakes in Atlantic Canada

Analysis of water chemistry from a sample of lakes (1300) in Atlantic Canada has indicated that lakes in geologically sensitive portions of Nova Scotia and Newfoundland have been acidified due to the combined effects of natural organic acids and anthropogenically derived mineral acids. Principal component analysis of six measured variables (pH, Ca, Conductance, SO _inf4 ^sup* , Alkalinity, Colour) and one computed variable (Alk/Ca^*+Mg^*) for each province result in four components which retain at least 89% of the original variability. Cluster analysis of the four principal components resulted in 6 lake groups for New Brunswick and 8 groups for Nova Scotia and 7 groups for Newfoundland. Geographic ordination of these clusters indicates that there is good correspondence between cluster group and the underlying bedrock geology of the region.     

Inorganic Ion Levels of Soils and Streams in some Areas of Ogoniland, Nigeria as Affected by Crude Oil Spillage

The inorganic ion concentrations of soils and streams in the three locations (Yorla, Zaakpon and Goi) in Ogoniland,Nigeria affected by crude oil spillage were investigated. In general, inorganic ion concentrations of polluted soilsand streams varied significantly (p = 0.05) from those of unpolluted soils and streams. Anions such as nitrate (NO ₃ ^- ), sulphate (SO ₄ ^2- ) and chloride(Cl^-) showed significantly (p = 0.05) higher values inthe polluted soils and steams than in the unpolluted controls. The phosphate (PO ₄ ^3- ) values were lowerin the polluted soils and streams than in the unpolluted controls.PO ₄ ^3- , NO ₃ ^- , SO ₄ ^2- and Cl^- concentrations were generally significantly (p = 0.05) higher in soils and streams from Yorla, Zaakpon and their control than in Goi North, Goi South and Goi control.Exchangeable cations and trace metal concentrations weresignificantly (p = 0.05) higher in the polluted soils andstreams than in the unpolluted controls. Yorla and Zaakponpolluted soils and streams had higher concentrations of theexchangeable cations and trace metals compared to valuesfrom Goi, except for Na. Results also showed significantlyhigher values of heavy metals (Pb, Cd, Cr and Ni) in the polluted soils compared to their controls, and values werealso significantly (p = 0.05) higher in Yorla, Zaakpon andtheir control compared to Goi North, Goi South and Goicontrol. Values obtained in polluted streams were higherthan in the unpolluted though not significant at the 5%level (p = 0.05). The anionic and cationic concentrationsof Yorla and Zaakpon soils and streams were generally higherthan those of Goi, indicating that Yorla and Zaakpon areaswere more polluted than Goi.Although the concentrations of most of the anions andcations analysed in the polluted soils and streams werewithin the World Health Organisation's permissible valuesfor the protection of humans and environment, the streams ofYorla, Zaakpon and Goi are in general being polluted withinorganic ions. This may make these soils and streamsunacceptable for domestic and industrial uses if not treated,and soils (farmlands) may also become unsuitable for agricultural purposes.     

Mineral Soil and Solution Responses to Experimental N and S Enrichment at the Bear Brook Watershed in Maine (BBWM)

Buried mineral soil-bags and natural solutions were studied as indicators of forest ecosystem response to elevated N and S inputs at the Bear Brook Watershed in Maine (BBWM). The BBWM is the site of a paired watershed manipulation experiment in a northern New England forested ecosystem. The study includes two small (10 ha each) catchments dominated by northern hardwood forests with red spruce in the upper elevations. Treatments consist of (NH4)2SO4 applied to the West Bear watershed six times per year, increasing N and S deposition 3× and 2× above ambient values, respectively. Buried mineral soil-bag changes over time reflected both the native soil environment and the treatments. Most of the treatment effects on mineral soils were evident as higher inorganic S found in the treated watershed soils. Adsorbed SO4 in the buried mineral soil-bags increased by approximately 40% under softwood stands and 50% under hardwood stands over the study period. Hardwood soil solutions responded with significant increases in NO3 and SO4 concentrations that resulted in accelerated cation leaching, primarily Ca and Al. Few differences that could be attributed to treatments were evident in soil solutions under softwoods. No treatment effects were evident in throughfall and stemflow chemistry.     

Acid precipitation-related chemical trends in 18 rivers of atlantic Canada — 1983 to 1992

Using non-parametric techniques, we studied water chemistry changes from 1983 to 1992 in 18 rivers located at the extreme northeastern portion of North America. This period was marked by a decrease in sulfate (SO ₄ ^– ) production in eastern Canada from 1982 to 1986, followed by a levelling off from 1986 to 1992. Nitrate (NO ₃ ^– ) production and deposition generally increased over this whole period. We used two time windows, 1983 to 1989 and 1983 to 1992, to determine if changes in river acidification variables occurred over the ten year period. We found significant trends of increasing pH and acid neutralization capacity (ANC) concentrations at eight sites using both time windows, while SO ₄ ^–2 increased at five and seven sites during the same two time periods. Nitrate concentrations showed few consistent trends, while base cations showed increases in the earlier part of the data set and total organic carbon (TOC) showed long-term decreases. There were few significant trends in hydrogen (H⁺), and a slight decrease in SO ₄ ^–2 exports as opposed to increased concentrations over the same period. We attribute the discrepancy between SO ₄ ^–2 concentration and export trends to be due to evapotranspiration in the basins, causing a concentration of ions in water. Nitrate and calcium exports showed no trends, while TOC decreased at four or five sites, depending on the time window used. Longer data sets tended to produce more detectable trends. Overall, water chemistry in the region is showing the effects of reduced SO ₄ ^– loads and is not yet being affected by the increases in NO ₃ ^– deposition.     

上海青浦地区大气降水的化学特征

利用上海青浦地区2003—2014年观测的大气降水监测资料,分析该区域12 a以来大气降水的酸化程度、化学组成特征,探讨降水中化学成分的不同来源及相对贡献。结果表明:降水pH年均值为4.43~6.33,酸雨频率为2.6%~86.8%,降水酸化程度大致经历了明显恶化和波动变化2个阶段。降水电导率年均值为1.77~4.01 m S/m,呈下降趋势。降水中各离子雨量加权平均当量浓度顺序为SO_4~(2-)NH_4~+Ca~(2+)NO_3~-Cl~-Na~+Mg~(2+)F-K~+,SO_4~(2-)、NH+4、Ca~(2+)和NO_3~-是降水中的主要离子,占离子总量的83.0%;降水类型由硫酸型向硫酸和硝酸混合型转变。降水离子中的二次组分SO_4~(2-)、NO_3~-和NH_4~+绝大部分来源于人为源,Ca~(2+)、Mg~(2+)和K+主要来自于土壤源和人为源的贡献,Cl~-主要来自海洋源,同时人为源的影响也不可忽视。     

Biogeochemical indicators of elevated nitrogen deposition in semiarid Mediterranean ecosystems

Nitrogen (N) deposition has doubled the natural N inputs received by ecosystems through biological N fixation and is currently a global problem that is affecting the Mediterranean regions. We evaluated the existing relationships between increased atmospheric N deposition and biogeochemical indicators related to soil chemical factors and cryptogam species across semiarid central, southern, and eastern Spain. The cryptogam species studied were the biocrust-forming species Pleurochaete squarrosa (moss) and Cladonia foliacea (lichen). Sampling sites were chosen in Quercus coccifera (kermes oak) shrublands and Pinus halepensis (Aleppo pine) forests to cover a range of inorganic N deposition representative of the levels found in the Iberian Peninsula (between 4.4 and 8.1 kg N ha^?1 year^?1). We extended the ambient N deposition gradient by including experimental plots to which N had been added for 3 years at rates of 10, 20, and 50 kg N ha^?1 year^?1. Overall, N deposition (extant plus simulated) increased soil inorganic N availability and caused soil acidification. Nitrogen deposition increased phosphomonoesterase (PME) enzyme activity and PME/nitrate reductase (NR) ratio in both species, whereas the NR activity was reduced only in the moss. Responses of PME and NR activities were attributed to an induced N to phosphorus imbalance and to N saturation, respectively. When only considering the ambient N deposition, soil organic C and N contents were positively related to N deposition, a response driven by pine forests. The PME/NR ratios of the moss were better predictors of N deposition rates than PME or NR activities alone in shrublands, whereas no correlation between N deposition and the lichen physiology was observed. We conclude that integrative physiological measurements, such as PME/NR ratios, measured on sensitive species such as P. squarrosa, can provide useful data for national-scale biomonitoring programs, whereas soil acidification and soil C and N storage could be useful as additional corroborating ecosystem indicators of chronic N pollution.     

Twenty-year inter-annual trends and seasonal variations in precipitation and stream water chemistry at the Bear Brook Watershed in Maine, USA

Mean annual concentration of ${\textrm{SO}}_{4}^{2-}$ in wet-only deposition has decreased between 1988 and 2006 at the paired watershed study at Bear Brook Watershed in Maine, USA (BBWM) due to substantially decreased emissions of SO₂. Emissions of NO_x have not changed substantially, but deposition has declined slightly at BBWM. Base cations, ${\textrm{NH}}_{4}^{+}$ , and Cl^??? concentrations were largely unchanged, with small irregular changes of <1 μeq L^???1 per year from 1988 to 2006. Precipitation chemistry, hydrology, vegetation, and temperature drive seasonal stream chemistry. Low flow periods were typical in June–October, with relatively greater contributions of deeper flow solutions with higher pH; higher concentrations of acid-neutralizing capacity, Si, and non-marine Na; and low concentrations of inorganic Al. High flow periods during November–May were typically dominated by solutions following shallow flow paths, which were characterized by lower pH and higher Al and DOC concentrations. Biological activity strongly controlled ${\textrm{NO}}_{3}^{-}$ and K^?+?. They were depressed during the growing season and elevated in the fall. Since 1987, East Bear Brook (EB), the reference stream, has been slowly responding to reduced but still elevated acid deposition. Calcium and Mg have declined fairly steadily and faster than ${\textrm{SO}}_{4}^{2-}$ , with consequent acidification (lower pH and higher inorganic Al). Eighteen years of experimental treatment with (NH₄)₂SO₄ enhanced acidification of West Bear Brook’s (WB) watershed. Despite the manipulation, ${\textrm{NH}}_{4}^{+}$ concentration remained below detection limits at WB, while leaching of ${\textrm{NO}}_{3}^{-}$ increased. The seasonal pattern for ${\textrm{NO}}_{3}^{-}$ concentrations in WB, however, remained similar to EB. Mean monthly concentrations of ${\textrm{SO}}_{4}^{2-}$ have increased in WB since 1989, initially only during periods of high flow, but gradually also during base flow. Increases in mean monthly concentrations of Ca^2?+?, Mg^2?+?, and K^?+? due to the manipulation occurred from 1989 until about 1995, during the depletion of base cations in shallow flow paths in WB. Progressive depletion of Ca and Mg at greater soil depth occurred, causing stream concentrations to decline to pre-manipulation values. Mean monthly Si concentrations did not change in EB or WB, suggesting that the manipulation had no effect on mineral weathering rates. DOC concentrations in both streams did not exhibit inter- or intra-annual trends.     

Soil chemical and physical properties at the Bear Brook Watershed in Maine, USA

Acidic deposition leads to the acidification of waters and accelerated leaching and depletion of soil base cations. The Bear Brook Watershed in Maine has used whole-watershed chemical manipulations to study the effects of elevated N and S on forest ecosystem function on a decadal time scale. The objectives of this study were to define the chemical and physical characteristics of soils in both the reference and treated watersheds after 17 years of treatment and assess evidence of change in soil chemistry by comparing soil studies in 1998 and 2006. Results from 1998 confirmed depletion of soil base cation pools and decreased pH due to elevated N and S within the treated watershed. However, between 1998 and 2006, during a period of declining SO $_{4}^{\,\,2-}$ deposition and continued whole-watershed experimental acidification on the treated watershed, there was little evidence of continued soil exchangeable base cation concentration depletion or recovery. The addition of a pulse of litterfall and accelerating mineralization from a severe ice storm in 1998 may have had significant effects on forest floor nutrient pools and cycling between 1998 and 2006. Our findings suggest that mineralization of additional litter inputs from the ice storm may have obscured temporal trends in soil chemistry. The physical data presented also demonstrate the importance of coarse fragments in the architecture of these soils. This study underscores the importance of long-term, quantitative soil monitoring in determining the trajectories of change in forest soils and ecosystem processes over time.     

The Bear Brook Watershed, Maine (BBWM), USA

The Bear Brook Watershed Manipulation project in Maine is a paired calibrated watershed study funded by the U. S. EPA. The research program is evaluating whole ecosystem response to elevated inputs of acidifying chemicals. The project consists of a 2.5 year calibration period (1987-1989), nine years of chemical additions of (NH4)2SO4 (15N- and 34S-enriched for several years) to West Bear watershed (1989-1998), followed by a recovery period. The other watershed, East Bear, serves as a reference. Dosing is in six equal treatments/yr of 1800 eq SO4 and NH4/ha/yr, a 200% increase over 1988 loading (wet plus dry) for SO4 and 300% for N (wet NO3 + NH4). The experimental and reference watersheds are forested with mixed hard- and softwoods, and have thin acidic soils, areas of 10.2 and 10.7 ha, and relief of 210 m. Thin till of variable composition is underlain by metasedimentary pelitic rocks and calc-silicate gneiss intruded by granite dikes and sills. For the period 1987-1995, precipitation averaged 1.4 m/yr, had a mean pH of 4.5, with SO4, NO3, and NH4 concentrations of 26, 14, and 7 eq/L, respectively. The nearly perrenial streams draining each watershed have discharges ranging from 0 (East Bear stops flowing for one to two months per year) to 150 L/sec. Prior to manipulation, East Bear and West Bear had a volume weighted annual mean pH of approximately 5.4, alkalinity = 0 to 4 eq/L, total base cations = 184 eq/L (sea-salt corrected = 118 eq/L), and SO4 = 100 to 111 eq/L. Nitrate ranged from 0 to 30 eq/L with an annual mean of 6 to 25 eq/L; dissolved organic carbon (DOC) ranged from 1 to 7 mg/L but was typically less than 3. Episodic acidification occurred at high discharge and was caused by dilution of cations, slightly increased DOC, significantly higher NO3, and the sea-salt effect. Depressions in pH were accompanied by increases in inorganic Al. The West Bear catchment responded to the chemical additions with increased export of base cations, Al, SO4, NO3, and decreased pH, ANC, and DOC. Silica remained relatively constant. Neutralization of the acidifying chemicals occurred dominantly by cation desorption and mobilization of Al.     

Laboratory study of the emission of NO and N2O from some Belgian soils

The NO, NO₂ and N₂O emission was measured, upon application of nitrate, ammonium and both, to four Belgian soils with different characteristics. The addition of NH ₄ ⁺ caused higher NO and N₂O emissions than the addition of no nitrogen, or the addition of NO ₃ ^– . In contrast to the two soils with a pH of approximately 8 the two soils with a pH around 6 showed a considerable delay in production of both NO and N₂O upon the application of the ammonium, probably due to the lag-period of nitrification. The soils with a pH of 8 gave higher emissions on the application of NH ₄ ⁺ than the soils with a pH of 6. The emission of NO₂ was found to be considerably lower than the NO emission from the soils. The NO/NO₂ ratio varied between 5–25 at considerable NO emissions (>50 nmol kg^–1). In the controls of soil 1 and soil 2, which showed very low NO emissions ratios of <1 were observed. The N₂O/NO ratios varied between 5–20 when NO emissions were considerable (>50 nmol kg^–1). Soil 3 and 4 gave lower N₂O/NO ratios than soil 1 and 2. In the controls of soil 1 and soil 2, at low NO emissions, N₂O/NO ratios of >300 were observed. Soil 3 and 4 gave higher NO/NO₂ and lower N₂O/NO ratios than soil 1 and 2.     

Comparisons of Geochemical Signatures of Biotransformation of Fuel Hydrocarbons in Groundwater

Biotransformation processes play an active role in reducing the environmental impact of fuel hydrocarbon releases to groundwater. Because monitoring data at release locations are typically sparse, spatial variations in geochemical indicator parameters are often called upon as indirect evidence of biotransformation. These parameters include concentrations of electron acceptors (O₂, NO₃ ^-, SO> ₄ ^2- , reduced redox reaction by-products (Fe²⁺, Mn²⁺, CH₄), as well as bicarbonate alkalinity, pH and E_h. However, background variability in a number of these parameters complicates the task of data interpretation, particularly in the case of small data sets. In this study, correlation analyses are applied to geochemical indicator data at six hydrocarbon groundwater contamination sites in California to identify which parameters are the most reliable indicators. The results of the analyses suggest that the most direct indicators of the local redox environment – Fe²⁺, Mn²⁺, CH₄, E_h – yield the most consistent evidence of hydrocarbon biotransformation. Indicators which rely largely on mass balance – O₂, NO ₃ ^- , SO ₄ ^2- , alkalinity – appear to be less reliable. These findings may provide guidance in both the collection and interpretation of groundwater monitoring data at hydrocarbon contamination sites.     

Fluctuations of Climatic Conditions, Elemental Cycling and Forest Growth at the Watershed Scale

The relationships between fluctuations in climatic conditions,forest productivity and elemental cycling were studied from 1994 to 1997 in a headwater catchment of the southern Laurentians dominated by sugar maple (Acer saccharumMarsh.) growing on podzolic soils. Annual budgets show that H⁺, K, and NO₃ were retained in the watershed whileCa, Mg and Na were lost. The magnitude of the net annual budget for Ca, Mg and Na was correlated to annual variationsin precipitation with the absolute budget value decreasing during dry years. Stemwood (r² = 0.85) and total tree biomass production (r² = 0.99) were correlated with mean annual temperature but fine roots and leaf litter werenot. During the growing season, the pH of the organic horizons(FH) decreased as the volumetric water content of soildecreased. A positive association was also found between airtemperature and H₂O-soluble (r² = 0.88) and PO₄-extractable (r² = 0.99) SO₄ in the upper B horizon. On a multi-year scale, we suspect that the decreasein the storage of inorganic SO₄ in the soil results from the cumulative effects of annual variations in climatic conditions superimposed on the long-term decrease in SO₄deposition from the atmosphere. These soil changes were reflected by a decline in SO₄, Ca and Mg concentrationsin the stream. The generalisation of the observed short-term patterns to longer time scales must be approached with caution. Yet, our results indicate that the associations between climatic variations and the biogeochemistry of the ecosystem occur at different spatial and temporal scales and integrate abroad range of chemical components and ecosystem compartments. This reflects the inherent complexity of natural systems and offers a vast palette of indicators of the response of terrestrial ecosystems to variations in the intensity of environmental factors such as climatic conditions.