Soilaluminum, Iron, and Phosphorus Dynamics in Response to Long-Term Experimental Nitrogen and Sulfur Additions at the Bear Brook Watershed in Maine, USA

Atmospheric deposition of nitrogen (N) and sulfur (S) containing compounds affects soil chemistry in forested ecosystems through (1) acidification and the depletion of base cations, (2) metal mobilization, particularly aluminum (Al), and iron (Fe), (3) phosphorus (P) mobilization, and (4) N accumulation. The Bear Brook Watershed in Maine (BBWM) is a long-term paired whole-watershed experimental acidification study demonstrating evidence of each of these acidification characteristics in a northeastern U.S. forested ecosystem. In 2003, BBWM soils were studied using the Hedley fractionation procedure to better understand mechanisms of response in soil Al, Fe, and P chemistry. Soil P fractionation showed that recalcitrant P was the dominant fraction in these watersheds (49%), followed by Al and Fe associated P (24%), indicating that a majority of the soil P was biologically unavailable. Acidification induced mobilization of Al and Fe in these soils holds the potential for significant P mobilization. Forest type appears to exert important influences on metal and P dynamics. Soils supporting softwoods showed evidence of lower Al and Fe in the treated watershed, accompanied by lower soil P. Hardwood soils had higher P concentrations in surface soils as a result of increased biocycling in response to N additions in treatments. Accelerated P uptake and return in litterfall overshadowed acidification induced P mobilization and depletion mechanisms in hardwoods.     

Effect of application of phosphate and organic manure-based fertilizers on arsenic transformation in soil columns

The mobility of arsenic in Cambisol under the influence of added barnyard manure and application of a phosphate solution to the soil was described on the basis of column experiments. A soil sample containing 126 mg/kg total As and 3.72 mg/kg specifically-sorbed As was extracted using demineralized water (DIW) or a 28 μmol/l phosphate solution in a column containing untreated soil and in a column with added barnyard fertilizer. The pH, Eh, alkalinity, main components, including DOC, and selected trace elements (Al, Mn, Pb, Cu, Zn, Cd, Cr, Co, Ni, Ba and As) were determined in the extracts. Hydrodynamic tests of the flow and transport of the substances in the columns were carried out. The addition of barnyard manure was manifested in elevated concentrations of the main inorganic components, DOC and Al and a decrease in the Eh value and Mn concentration. Application of a phosphate solution was manifested in a decrease in the NO₃ and SO₄ concentrations, probably as a result of the effect of increased biological fixation. The As concentration in extracts varied from 8.8 to 15.5 μg/l and was not dependent on the composition of the extracting solution or the addition of barnyard fertilizer.     

Landscape Controls on Mercury in Streamwater at Acadia National Park, USA

Fall and spring streamwater samples were analyzed for total mercury (Hg) and major ions from 47 locations on Mount Desert Island in Maine. Samples were collected in zones that were burned in a major wildfire in 1947 and in zones that were not burned. We hypothesized that Hg concentrations in streamwater would be higher from unburned sites than burned watersheds, because fire would volatilize stored Hg. The Hg concentrations, based on burn history, were not statistically distinct. However, significant statistical associations were noted between Hg and the amount of wetlands in the drainage systems and with streamwater dissolved organic carbon (DOC). An unexpected result was that wetlands mobilized more Hg by generating more DOC in total, but upland DOC was more efficient at transporting Hg because it transports more Hg per unit DOC. Mercury concentrations were higher in samples collected at lower elevations. Mercury was positively correlated with relative discharge, although this effect was not distinguished from the DOC association. In this research, sample site elevation and the presence of upstream wetlands and their associated DOC affected Hg concentrations more strongly than burn history.     

Bacterial contamination in drinking water: a case study in rural areas of northern Rajasthan, India

Acid deposition has caused detrimental effects on tree growth near industrial areas of the world. Preliminary work has indicated that concentrations of NO(3-), SO(4)(2-), F( - ) and Al in soil solutions were 2 to 33 times higher in industrial areas compared to non-industrial areas in Korea. This study evaluated soil nutrient bioavailability and nutrient contents of red pine (Pinus thunbergii) needles in forest soils of industrial and non-industrial areas of Korea. Results confirm that forest soils of industrial areas have been acidified mainly by deposition of sulfate, resulting in increases of Al, Fe and Mn and decreases of Ca, Mg and K concentrations in soils and soil solutions. In soils of industrial areas, the molar ratios of Ca/Al and Mg/Al in forest soils were <2, which can lead to lower levels and availability of nutrients for tree growth. The Ca/Al molar ratio of Pinus thunbergii needles on non-industrial sites was 15, while that of industrial areas was 10. Magnesium concentrations in needles of Pinus thunbergii were lower in soils of industrial areas and the high levels of acid cations such as Al and Mn in these soils may have antagonized the uptake of base cations like Mg. Continued acidification can further reduce uptake of base cations by trees. Results show that Mg deficiency and high concentrations of Al and Mn in soil solution can be limiting factors for Pinus thunbergii growth in industrial areas of Korea.     

Assessing the removal potential of soil-aquifer treatment system (soil column) for endotoxin

Soil-aquifer treatment (SAT) of wastewater is an increasingly valued practice for replenishing aquifers due to ease of operation and low maintenance needs and therefore low cost. In this study, we investigated the fate of endotoxins through laboratory-scale SAT soil columns over a four month period. The effluent of rapid sand filtration was run through the columns under gravity flow conditions. Four SAT columns were packed with four different filter materials (fine sand, medium sand, coarse sand and very coarse sand). The effluent of rapid sand filtration (average dissolved organic carbon (DOC) = 4 mg l(-1) and average endotoxin concentration = 4 EU ml(-1)) was collected from a domestic wastewater treatment plant in Sapporo, Japan. DOC removal ranged from 12.5% to greater than 22.5% during the study, with DOC levels averaging 3.1 and 3.5 mg l(-1) for the SAT columns packed with different soils. Endotoxin transformation exhibited different profiles, depending on the time and soil type. Reduction in endotoxin concentration averaged 64.3% and was as high as 86.7% across the soil columns 1, 2, 3 and 4, respectively. While DOC removal was gradual, the reductions in endotoxin levels were rather rapid and most of the removal was achieved in the top layers. Soil with a larger grain size had lower efficiency in removing endotoxin. Tests were performed to evaluate the transformation of organic matter showing endotoxicity and to determine the mechanisms responsible for changes in the structural and size properties of dissolved organic matter (OM) during SAT. Dissolved OM was fractionated using Sep-Pack C18 Cartridges into hydrophobic and hydrophilic fractions. Dialysis tubes with different molecular weight cut-offs were used to perform size fractions of OM showing endotoxicity. Evaluation of the transformation of organic matter showing endotoxicity during SAT indicated that both hydrophobic and large molecules were reduced. Moreover, experimental findings showed that adsorption test data fit to the Freundlich isotherm and were affected by the particle grain size with higher adsorption capacity for fine and medium sand.     

Redistribution of zinc, cadmium, and lead among soil fractions in a sandy calcareous soil due to application of poultry litter

This study was conducted to evaluate, using soil columns, the mobilization and redistribution of heavy metals (Zn, Cd, and Pb) among different soil fractions by soluble organic ligands within poultry litter. Uncontaminated soil was amended with Zn, Cd, and Pb to achieve concentration levels of 400, 8, and 200 mg kg⁻¹ soil, respectively. Columns repacked with this amended soil were leached with distilled water, 0.01 M EDTA, 0.01 M CaCl₂, or poultry litter extract (PLE) solutions. After leaching, the soil samples in the columns were sequentially extracted for exchangeable (EXC), carbonate (CARB) organic matter (OM), Mn oxide (MNO), Fe oxide (FEO), and residual (RES) fractions. Considerable mobilization of Zn, Cd, and Pb occurred in soil during EDTA leaching. Leaching with PLE and CaCl₂ solutions significantly decreased Zn and Cd concentrations in the EXC, CARB, and OM fractions. These solutions significantly decreased Pb concentration in the EXC fraction, while PLE solubilized more Pb from EXC fraction than CaCl₂. Thus, the applied poultry litter may change Zn, Cd, and Pb fractions in metal-amended soil and possibly enhance metal mobility.     

An assessment of the nutrient status of sugar maple in Ontario: indications of phosphorus limitation

Soil acidification, caused by elevated anthropogenic deposition, has led to concerns over nutrient imbalances in Ontario's sugar maple (Acer saccharum Marsh.) forests. In this study, soil chemistry, foliar chemistry, crown condition, and tree growth were measured at 36 sugar maple stands that included acidic (pH?相似文献   

Background levels of some major,trace, and rare earth elements in indigenous plant species growing in Norway and the influence of soil acidification,soil parent material,and seasonal variation on these levels

Baseline levels of 43 elements, including major, trace, and rare earth elements (REEs) in several native plant species growing in boreal and alpine areas, are presented. Focus is placed on species metal levels at different soil conditions, temporal variations in plant tissue metal concentrations, and interspecies variation in metal concentrations. Vegetation samples were collected at Sogndal, a pristine site in western Norway, and at Risdalsheia, an acidified site in southernmost Norway. Metal concentrations in the different species sampled in western Norway are compared with relevant literature data from Norway, Finland, and northwest Russia, assumed to represent natural conditions. Except for aluminium (Al) and macronutrients, the levels of metals were generally lower in western Norway than in southern Norway and may be considered close to natural background levels. In southern Norway, the levels of cadmium (Cd) and lead (Pb) in particular appear to be affected by air pollution, either by direct atmospheric supply or through soil acidification. Levels of some elements show considerable variability between as well as within plant species. Calcium (Ca), magnesium (Mg), and potassium (K) are higher in most species at Sogndal compared to Risdalsheia, despite increased extractable concentrations in surface soil in the south, probably attributed to different buffer mechanisms in surface soil. Antagonism on plant uptake is suggested between Ca, Mg, and K on one hand and Al on the other. Tolerance among calcifuges to acid conditions and a particular ability to detoxify or avoid uptake of Al ions are noticeable for Vaccinium vitis-idaea.     

A study on chemical properties of groundwater and soil in ophiolitic rocks in Firuzabad, east of Shahrood, Iran: with emphasis to heavy metal contamination

In order to assess the chemical properties of groundwater and soil in ophiolitic zone of Firuzabad, in east of Shahrood, Iran, 10 soil samples with regard to sensitive points (vicinity to mine, ophiolitic rocks, and villages) and 10 groundwater samples including nine samples from springs, and also one sample from a well in a village of the study area were taken. These samples were analyzed in laboratories using inductively coupled plasma method. The soil samples were also evaluated for grain size. The obtained results show that most of heavy and major elements were exceeding the permissible levels in soil and water samples in the study area. On the subject of soil quality, concentrations of elements Cr, Mn, Fe, Ca, Mg, Ca, Ni, and Zn are above permissible levels. Enrichment factor and index of geoaccumulation have been calculated for heavy and major elements of all soil samples. According to the obtained results, it may be argued that soil samples are contaminated in relation to the above-mentioned indices. Comparing the concentrations of elements with results of grain size analysis illustrates that the concentrations of Cr, Ni, Fe, Mg, and Co are positively correlated with sand fraction and the concentrations of Al, P, Mn, and Pb are directly proportional with clay fraction in soil samples. The study on water contamination suggests that concentrations of elements Cr, Ni, and Mg in groundwater samples of the study area are above the permissible levels. Some indices like metal index and heavy metal pollution index show that most of the water samples include heavy metal contamination.     

Impacts of Ammonium Sulfate Treatment on the Foliar Chemistry of Forest Trees at the Bear Brook Watershed in Maine

Foliar chemistry was examined in mature sugar maple (Acer saccharum Marsh), red maple (Acer rubrum L.), American beech (Fagus grandifolia Ehrh.), and red spruce (Picea rubens Sarg.) in response to chronic, watershed-level additions of ammonium sulfate [(NH4)2SO4]. Following four years of treatment, N concentrations were significantly higher in foliage from the treated watershed for all four species, with increases ranging from 6% in American beech to 33% in sugar maple. Sugar maple foliage from the treated watershed had significantly lower Ca concentrations (18%). Concentrations of K were significantly lower in beech (13%) and red spruce (9%) from the treated watershed. Foliar Mg was not different between watersheds. Aluminum concentrations were significantly higher in the foliage from the treated watershed for beech (18%), red maple (33%), and sugar maple (65%), but no differences in Al concentration occurred in current year red spruce foliage. Red spruce foliage resampled following a fifth year of treatment contained higher concentrations of N and Al and lower concentrations of Ca and Mg in the treated watershed. Despite these differences in red spruce foliar chemistry, wood production and density did not appear to be affected by the treatment.Differences in the foliar chemistry between the treated and untreated watershed may reflect the temporal and spatial integration of changes taking place in the soil of the treated watershed. Increased N is likely directly due to the N contained in the (NH4)2SO4 treatment. Labile Ca and other cations in the treated watershed would be expected to initially increase and then decrease in response to the treatment, with these changes beginning at the top of the forest floor. Thus, lower cation concentrations in foliage from the treated watershed may reflect the fact that cations in the uppermost portions of the soil were rapidly depleted, even though deeper soil layers were experiencing increased Ca release due to cation exchange effect of the acidification. The generally higher Al in foliage from the treated watershed is likely due to the mobilization of inorganic Al in the soil as has been reported previously for the treated watershed. Collectively these results suggest that the long-term deposition of acidifying substances containing N and S not only influence the cycling of N within these systems, but may also alter the cycling of other important nutrients and Al.     

Spatial and temporal trace metal distribution of a Peruvian basin: recognizing trace metal sources and assessing the potential risk

Recent efforts have been made to determine the environmental impact of mining over the past 11 years in the Jequetepeque River basin, in northern Peru. We have now analyzed data from two studies to elucidate the spatial and temporal trace metal distributions and to assess the sources of contamination. These two studies were carried out from 2003 to 2008 by a Peruvian government administration and from 2008 to 2010 by us. We analyzed 249 samples by principal component analysis, measuring: pH, electrical conductivity, total dissolved solids, total suspended solids, chloride, weak-acid-dissociable cyanide, total cyanide, nitrite and nitrate, ammonium, sulfate, and trace metals and metalloids (Al, As, Ca, Cd, Cu, Cr, Fe, Mg, Mn, Ni, Pb, and Zn). Within the spatial distribution of the basin, the highest Al, As, Cu, Fe, Ni, and Pb concentrations were found at the closest point to the mine sites for both periods of time, with the higher peaks measured during the first years of the sampling data. Temporal trends showed higher concentrations of Cu and Fe in samples taken before 2005, at which point the two mines were closed. Risk assessment was quantified by the hazard quotient as related to water ingestion. The risk for human health posed by the concentrations of several trace metals and metalloids was found to be highly adverse (As and Cr), significant (Al, Cd, Cu, Fe, and Pb), or minimal (Ni and Zn).     

Effects of decaying wood on eluviation,podzolization, acidification,and nutrition in soils with different moisture regimes

One possible impact of large accumulations of decaying wood on forest sites is an increase in (1) eluviation, podzolization and acidification of, and (2) leaching and loss of nutrients from, the soil directly under decaying wood. As an exploratory investigation, we sampled soils beneath forest floors with and without large accumulations of decaying wood (lignic and algnic forest floors respectively) on three soil moisture regimes. Nine sites were located, three in each of central British Columbia, east Vancouver Island, and east of Vancouver. Among the moist sites, there were no differences in Ae horizon thickness between the alignic and lignic forest floors. However, the Ae horizon was thicker beneath the lignic forest floors (mean 4.2 cm) compared to the alignic forest floors (mean 0.7 cm) in slightly dry and fresh sites. Lignic and alignic forest floors differed (p<0.01) in pH, total C, total N, mineralizable N, available S, available P, extractable Mg, K and Ca, lipids, C in fraction B (soluble polysaccharide fraction), C in humic acid, C in fulvic acid, and polyphenol C in fulvic acid for all soil moisture regimes. There were no significant differences in the measures of nutrients or indicators of podzolization as measured by organically complexed Fe and Al, the total non-crystalline Fe and Al, and the poorly crystalline Fe and Al, in the underlying 10 cm of the Bf horizon between the two substrates regardless of the soil moisture regime. Further investigations are needed to establish the relationships between soil productivity and the observed soil chemical measures.     

抚顺市PM10中元素分布特征及来源分析

为了确定抚顺市PM10中元素的浓度特征及其来源,于2006—2007年的采暖季、风沙季和非采暖季在抚顺市的6个采样点采集PM10样品,并用等离子体原子发射光谱法(ICP-AES)测定样品中Ti、Al、Mn、Mg、Ca、Na、K、Cu、Zn、As、Pb、Cr、Ni、Co、Cd、Fe、V等17种元素的含量。结果表明,Al、Mg、Ca、Na、K、Mn、Fe等地壳元素在17种元素中占有较大比重,全年平均达到97.0%。富集因子分析结果表明,Cu、Zn、Pb、Cr、Co、Cd等元素在各季和各采样点明显受到人为活动影响,是典型的污染元素。主因子分析结果显示,土壤风沙尘、建筑尘、燃煤尘、道路扬尘、机动车尾气排放、金属冶炼、锰、铜、钛工业源是抚顺市PM10中元素的主要来源。     

抚顺市大气颗粒物主要排放源的成分谱研究

抚顺市的5种大气颗粒物主要排放源中土壤风沙尘的特征元素为K,钢铁尘的特征元素为Fe,建筑水泥尘的特征元素为Ca,煤烟尘的特征元素为Ti。土壤风沙尘和扬尘中含量最高的元素为Al,煤烟尘中含量最高的元素为EC,钢铁尘中含量最高的元素为Fe,建筑水泥尘中含量最高的元素为Ca。     

Soil response to a 3-year increase in temperature and nitrogen deposition measured in a mature boreal forest using ion-exchange membranes

The projected increase in atmospheric N deposition and air/soil temperature will likely affect soil nutrient dynamics in boreal ecosystems. The potential effects of these changes on soil ion fluxes were studied in a mature balsam fir stand (Abies balsamea [L.] Mill) in Quebec, Canada that was subjected to 3 years of experimentally increased soil temperature (+4 °C) and increased inorganic N concentration in artificial precipitation (three times the current N concentrations using NH₄NO₃). Soil element fluxes (NO₃, NH₄, PO₄, K, Ca, Mg, SO₄, Al, and Fe) in the organic and upper mineral horizons were monitored using buried ion-exchange membranes (PRS? probes). While N additions did not affect soil element fluxes, 3 years of soil warming increased the cumulative fluxes of K, Mg, and SO₄ in the forest floor by 43, 44, and 79 %, respectively, and Mg, SO₄, and Al in the mineral horizon by 29, 66, and 23 %, respectively. We attribute these changes to increased rates of soil organic matter decomposition. Significant interactions of the heating treatment with time were observed for most elements although no clear seasonal patterns emerged. The increase in soil K and Mg in heated plots resulted in a significant but small K increase in balsam fir foliage while no change was observed for Mg. A 6–15 % decrease in foliar Ca content with soil warming could be related to the increase in soil-available Al in heated plots, as Al can interfere with the root uptake of Ca.     

Long-term changes in acidity and DOC in throughfall and soil water in Finnish forests

The main objective of this study was to examine if any detectable trends in dissolved organic carbon (DOC), sulphate (SO₄-S) concentrations and acid neutralizing capacity (ANC) in throughfall (TF) and soil water (SW) could be found during 1990–2010 and to relate them to recent changes in decreased acid deposition. The study was conducted in seven boreal coniferous forest sites: four of which are managed and three unmanaged forests sites. Generally, temporal trend showed a significant decrease in SO₄-S concentrations in bulk precipitation (BP), TF and SW. At some of the sites, there was an increasing tendency in BP and TF in the DOC concentrations. This feature coincides with decreasing SO₄-S concentration, indicating that SO₄-S may be an important driver of DOC release from the canopy. However, a slightly increased temperature, larger senescing needle mass and consequently increased decaying activity in the canopy may partly explain the increasing trend in DOC. In SW, no consistent DOC trend was seen. At some sites, the decreased base cation concentrations mostly account for the decrease in the ANC values in SW and TF.     

Soil solution extraction techniques for microbial ecotoxicity testing: a comparative evaluation

The suitability of two different techniques (centrifugation and Rhizon sampler) for obtaining the interstitial pore water of soil (soil solution), integral to the ecotoxicity assessment of metal contaminated soil, were investigated by combining chemical analyses and a luminescence-based microbial biosensor. Two different techniques, centrifugation and Rhizon sampler, were used to extract the soil solution from Insch (a loamy sand) and Boyndie (a sandy loam) soils, which had been amended with different concentrations of Zn and Cd. The concentrations of dissolved organic carbon (DOC), major anions (F- , CI-, NO3, SO4(2-)) and major cations (K+, Mg2+, Ca2+) in the soil solutions varied depending on the extraction technique used. Overall, the concentrations of Zn and Cd were significantly higher in the soil solution extracted using the centrifugation technique compared with that extracted using the Rhizon sampler technique. Furthermore, the differences observed between the two extraction techniques depended on the type of soil from which the solution was being extracted. The luminescence-based biosensor Escherichia coli HB101 pUCD607 was shown to respond to the free metal concentrations in the soil solutions and showed that different toxicities were associated with each soil, depending on the technique used to extract the soil solution. This study highlights the need to characterise the type of extraction technique used to obtain the soil solution for ecotoxicity testing in order that a representative ecotoxicity assessment can be carried out.     

Inter-annual and spatial variability in hillslope runoff and mercury flux during spring snowmelt

Spring snowmelt is an important period of mercury (Hg) export from watersheds. Limited research has investigated the potential effects of climate variability on hydrologic and Hg fluxes during spring snowmelt. The purpose of this research was to assess the potential impacts of inter-annual climate variability on Hg mobility in forested uplands, as well as spatial variability in hillslope hydrology and Hg fluxes. We compared hydrological flows, Hg and solute mobility from three adjacent hillslopes in the S7 watershed of the Marcell Experimental Forest, Minnesota during two very different spring snowmelt periods: one following a winter (2009-2010) with severely diminished snow accumulation (snow water equivalent (SWE) = 48 mm) with an early melt, and a second (2010-2011) with significantly greater winter snow accumulation (SWE = 98 mm) with average to late melt timing. Observed inter-annual differences in total Hg (THg) and dissolved organic carbon (DOC) yields were predominantly flow-driven, as the proportion by which solute yields increased was the same as the increase in runoff. Accounting for inter-annual differences in flow, there was no significant difference in THg and DOC export between the two snowmelt periods. The spring 2010 snowmelt highlighted the important contribution of melting soil frost in the timing of a considerable portion of THg exported from the hillslope, accounting for nearly 30% of the THg mobilized. Differences in slope morphology and soil depths to the confining till layer were important in controlling the large observed spatial variability in hydrological flowpaths, transmissivity feedback responses, and Hg flux trends across the adjacent hillslopes.     

Variation of heavy metal and micro and macro element concentrations of bread and durum wheats and their relationship in grain of Turkish wheat cultivars

The 64 varieties displayed a large variation for all mineral elements, investigated Fe, Mn and Zn, ranging from 24.2 to 43.1 mg/kg, 27.6 to 64.8 mg/kg and 10.4 to 38.2 mg/kg, respectively. The mean Ca, K, Mg, Na, P and S concentrations in wheat rain varieties amounted to 378, 4,266, 1,183, 317, 3,513 and 1,542 mg/kg, respectively. Ca, K, Mg, Na, P and S contents of wheat varieties changed at the levels between 266 and 531 mg/kg, 3,029 and 5,566 mg/kg, 972 and 1,525 mg/kg, 277 and 368 mg/kg, 2,422 and 4,610 mg/kg and 1,241 to 2,052 mg/kg, respectively. The concentrations of Al, Cu, Fe, Mn and Zn of durum wheat samples were found at high levels. The mean Al, Cr, Mo, Ni, Cu, Fe, Mn and Zn concentrations in durum wheat varieties amounted to 10.93, 0.47, 0.72, 0.72, 5.37, 34.9, 37.28 and 20.88 mg/kg, respectively.     

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.