Major ion chemistry and weathering processes in the Midyan Basin, northwestern Saudi Arabia

Chemical characteristics of 72 groundwater samples collected from Midyan Basin have been studied to evaluate major ion chemistry together with the geochemical and weathering processes controlling the water composition. Water chemistry of the study area is mainly dominated by Na, Ca, SO₄, and Cl. The molar ratios of (Ca?+?Mg)/total cations, (Na?+?K)/total cations, (Ca?+?Mg)/(Na?+?K), (Ca?+?Mg)/(HCO₃?+?SO₄), (Ca?+?Mg)/HCO₃, and Na/Cl reveal that water chemistry of the Midyan Basin is controlled by evaporite dissolution (gypsum and/or anhydrite, and halite), silicate weathering, and minor contribution of carbonate weathering. The studied groundwater samples are largely undersaturated with respect to dolomite, gypsum, and anhydrite. These waters are capable of dissolving more of these minerals under suitable physicochemical conditions.     

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.     

Precipitation Chemistry and Occurrence of Acid Rain Over Dhanbad, Coal City of India

The present study investigated the chemical composition of wet atmospheric precipitation over Dhanbad, coal city of India. The precipitation samples were collected on event basis for three years (July 2003 to October 2005) at Central Mining Research Institute. The precipitation samples were analyzed for pH, conductivity, major anions (F, Cl, NO₃, SO₄) and cations (Ca, Mg, Na, K, NH₄). The pH value varied from 4.01 to 6.92 (avg. 5.37) indicating acidic to alkaline nature of rainwater. The pH of the rainwater was found well above the reference pH (5.6), showing alkalinity during the non-monsoon and early phase of monsoon, but during the late phase of monsoon, pH tendency was towards acidity (<5.6~pH) indicating the non-availability of proper neutralizer for acidic ions. The observed acidic events at this site were 91, (n = 162) accounting 56% for the entire monitoring months. The (NO₃ + Cl)/SO₄ ratio in majority of samples was found below 1.0, indicating that the acidity is greatly influenced by SO₄. The calculated ratio of (Ca + NH₄)/(NO₃ + SO₄) ranges between 0.42–5.13 (average 1.14), however in most of the samples, the ratio is greater than unity (>1.0) indicating that Ca and NH₄ play an important role in neutralization of acidic ions in rainwater. Ca and SO₄ dominate the bulk ionic deposition and these two ions along with NH₄ accounts 63% of the annual ionic deposition.     

Assessment of groundwater quality of the Tatlicay aquifer and relation to the adjacent evaporitic formations (Cankiri,Turkey)

One of the most important hydrogeologic problems in and adjacent areas of evaporitic formations is severe quality degradation of groundwaters. These kinds of groundwaters contain high content of dissolved solids and generally have some limitations for use. Tatlicay basin (north-central Turkey) is an example to effects of the evaporites on groundwater quality in the adjacent alluvium aquifer. Gypsum and anhydrites in the two evaporite formations (Bayindir and Bozkir) effect of the groundwater quality in the alluvium adversely, by dissolution of the evaporites by surface drainage and infiltration into the alluvium aquifer (widespread effect) and by infiltration of low quality gypsum springs (local effect) into the aquifer. Evaporitic formations significantly increased EC, TDS, Ca and SO₄ parameters in the alluvium aquifer in the central and downstream regions. EC has increased roughly from 500–800 to 1,700–2,000 μS/cm, Ca has roughly increased from 3–4 to 10 meq/l, SO₄ has increased 0.5–1 to 11–12 meq/l. Consequently, three clusters were distinguished in the basin; (1) nonevaporitic waters in low TDS, Na, Ca, Mg, Cl and SO₄, (2) diluted waters in high TDS and relatively high Cl, moderate-relatively high Na, Ca, Mg, SO₄, (3) gypsum springs in highest TDS, Ca, SO₄, but moderate Mg and low Na, Cl.     

Interactions of Atmospheric Deposition with Coniferous Canopies in Estonia

Throughfall and open field bulk precipitation were measured at three coniferous sites during 1995–2002 in the framework of ICP Integrated Monitoring and at five coniferous sites during 1996–2002 in the framework of ICP Forests (Level II). The coniferous canopies acted as a sink for nitrate and ammonium and as a source for base cations: Ca²⁺, Mg²⁺ and K⁺. The estimated share of SO₄–S dry deposition from total deposition was 1.5–4 times higher for dormant period compared to growing period. During the study period average annual throughfall and bulk deposition of SO₄–S decreased significantly, 2.8 and 2.3 times, respectively. Throughfall enrichment with base cations increased in the order Mg < Na < Ca < K. Using Na as a tracer ion, average dry deposition and canopy leaching were calculated. Leaching was the dominant process for TF enrichment by potassium. Leaching of base cations occurred during growing as well as dormant period. The calculated internal flux of Ca²⁺ and Mg²⁺ varied in the range of 0.6–2.0 and 0.6–1.2 kg ha⁻¹ per year in spruce and pine stands, respectively. The internal circulation of K⁺ was significantly higher (8.9–10.9 kg ha⁻¹ per year) in spruce stands than in pine stands (2.7–4.4 kg ha⁻¹ per year).     

Storm runoff quality and pollutant loading from commercial, residential, and industrial catchments in the tropic

Information on the pollution level and the influence of hydrologic regime on the stormwater pollutant loading in tropical urban areas are still scarce. More local data are still required because rainfall and runoff generation processes in tropical environment are very different from the temperate regions. This study investigated the extent of urban runoff pollution in residential, commercial, and industrial catchments in the south of Peninsular Malaysia. Stormwater samples and flow rate data were collected from 51 storm events. Samples were analyzed for total suspended solids, 5-day biochemical oxygen demand, chemical oxygen demand, oil and grease (O&G), nitrate nitrogen (NO₃-N), nitrite nitrogen, ammonia nitrogen, soluble reactive phosphorus, total phosphorus (TP), and zinc (Zn). It was found that the event mean concentrations (EMCs) of pollutants varied greatly between storm characteristics and land uses. The results revealed that site EMCs for residential catchment were lower than the published data but higher for the commercial and industrial catchments. All rainfall variables were negatively correlated with EMCs of most pollutants except for antecedent dry days (ADD). This study reinforced the earlier findings on the importance of ADD for causing greater EMC values with exceptions for O&G, NO₃-N, TP, and Zn. In contrast, the pollutant loadings are influenced primarily by rainfall depth, mean intensity, and max 5-min intensity in all the three catchments. Overall, ADD is an important variable in multiple linear regression models for predicting the EMC values in the tropical urban catchments.     

The temporal changes in road stormwater runoff quality and the implications to first flush control in Chongqing, China

This study investigates the quality of stormwater runoff from a driveway in the southwest mountainous urban area of Chongqing, China, from 2010 to 2011. The results showed that the mean concentrations of chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP) were 4.1, 2.4, and 2.2 times the grade V levels of the national surface water standard of China. The pollutant concentration peak preceded or synchronized with the rainfall intensity peak and occurred 10 min after the runoff started. The significant high pollutant concentration in the initial stage of the rainfall suggested that first flush control is necessary, especially for the most polluted constitutes, such as total suspended solids, COD, and TN. Three potential pollution sources were identified: the atmospheric dry and wet deposition (TN, NO₃ ^?-N, NH₄ ⁺-N, and DCu), the road sediment and materials (total suspended solids, COD, and TP), and the vehicle emissions (DPb and DZn). Therefore, this study indicates that reductions in road sediments and material pollution and dry and wet deposition should be the priority factors for pollution control of road stormwater runoff in mountainous urban areas.     

The Rengen Grassland experiment: bryophytes biomass and element concentrations after 65 years of fertilizer application

The Rengen Grassland Experiment in Germany, established in 1941, consists of the following fertilizer treatments applied under a two cut management: control, Ca, CaN, CaNP, CaNP-KCl, and CaNP-K₂SO₄. The aim of this study was (1) to identify effects of fertilizer application on biomass and species composition of bryophytes and (2) to investigate the impact of fertilizer application on macro- (N, P, K, Ca, Mg), micro- (Cu, Fe, Mn, Zn), and toxic (As, Cd, Cr, Pb, Ni) element concentrations in bryophyte biomass. In June 2006, Rhytidiadelphus squarrosus was the only bryophyte species recorded in the control. In treatment Ca, R. squarrosus was the dominant bryophyte species whereas Brachythecium rutabulum occurred sporadically only in a single plot of that treatment. The latter was the only bryophyte species collected in CaN, CaNP, CaNP-KCl, and CaNP-K₂SO₄ treatments. Dry matter accumulation of bryophytes was highest in the control (180 g m^???2) followed by Ca (46 g m^???2), CaNP (25 g m^???2), CaNP-KCl (15 g m^???2), CaNP-K₂SO₄ (9 g m^???2), and CaN (2 g m^???2) treatments. A negative correlation between biomass production of bryophytes and dry matter production of vascular plants was revealed up to a threshold value of 400 g m^???2. Above this limit, biomass production of bryophytes remained obviously unaffected by further increase in biomass production of vascular plants. A significant effect of treatment on As, Cd, Cr, Fe, Mn, Ni, Pb, P, Ca, Mg, K, and N concentrations was revealed. Concentrations of these elements were a function of amount of elements supplied with fertilizers. Bryophytes seem to be promising bio-indicators not only for airborne deposition of toxic element but also for fertilizer introduced as well.     

Applications of behavioral science to biodiversity management in agricultural landscapes: conceptual mapping and a California case study

Regime shifts of major salinity constituents (Ca, Mg, Na, K, SO₄, Cl, HCO₃, and NO₃) in the lower Salinas River, an agricultural ecosystem, can have major impacts on ecosystem services central to continued agricultural production in the region. Regime shifts are large, persistent, and often abrupt changes in the structure and dynamics of social-ecological systems that occur when there is a reorganization of the dominant feedbacks in the system. Monitoring information on changes in the system state, controlling variables, and feedbacks is a crucial contributor to applying sustainability and ecosystem resilience at an operational level. To better understand the factors driving salinization of the lower Salinas River on the central coast of California, we examined a 27-year record of concentrations of major salinity constituents in the river. Although limited in providing an understanding of solute flux behavior during storm events, long-term “grab sampling” datasets with accompanying stream discharges can be used to estimate the actual history of concentrations and fluxes. We developed new concentration–discharge relationships to evaluate the dynamics of chemical weathering, hydrological processes, and agricultural practices in the watershed. Examinations of long-term records of surface water and groundwater salinity are required to provide both understanding and perspective towards managing salinity in arid and semi-arid regions while also enabling determination of the influence of external climatic variability and internal drivers in the system. We found that rock weathering is the main source of Ca, Mg, Na, HCO₃, and SO₄ in the river that further enables ion exchange between Ca, Mg, and Na. River concentrations of K, NO₃, and Cl were associated with human activities while agricultural practices were the major source of K and NO₃. A more direct anthropogenic positive trend in NO₃ that has persisted since the mid-1990s is associated with the lag or memory effects of field cropping and use of flood irrigation. Event to inter-year scale patterns in the lower Salinas River salinity are further controlled by antecedent hydrologic conditions. This study underscores the importance of obtaining long-term monitoring records towards understanding watershed changes-of-state and time constants on the range of driving processes.

     

Chemical characterization of precipitation at a coastal site in Trombay, Mumbai, India

Precipitation is the best scavenger for the particulates and dissolved gaseous pollutants present in the atmosphere. The chemical composition of precipitation is dominated by a number of in-cloud and below-cloud scavenging processes. The present study is aimed at analyzing the chemical composition of rainwater in the relatively less industrialized part of Mumbai. The pH of rainwater in this region ranges from 4.8 to 6.4. The percentage contributions of ions were calculated and the major contributing ions were calcium (28%), chloride (23%), sodium (18%), sulfate (14%), magnesium (11%), ammonium (4%), potassium (1%), and nitrate (1%). The correlation coefficient is highest for Na and Cl (r ²?=?0.99), giving a clear indication of contribution from sea salt. Sulfate and nitrate ions also show a very good correlation (r ²?=?0.90), which may be due to their coemission from fossil fuel combustion. Acidification caused by these ions is neutralized by Ca, Mg, and NH₄ ions. The neutralization effect due to these ions is validated by calculating the neutralization factor (NF). The NF values are in the order Ca > Mg > NH₄. The major source contributors for the ions in precipitation are sea salt (Na, Cl, and K) and fossil fuel combustion (SO₄ and NO₃). These assumptions are supported by the values of wet-only ratio, enrichment factor, and percent sea salt fraction.     

The hydrochemistry of groundwater in the Densu River Basin, Ghana

Hydrochemical analyses of groundwater samples were used to establish the hydrochemistry of groundwater in the Densu River Basin. The groundwater was weakly acidic, moderately mineralized, fresh to brackish with conductivity ranging from of 96.6 μS cm^???1 in the North to 10,070 μS cm^???1 in the South. Densu River basin have special economic significance, representing the countries greatest hydrostructure with freshwater. Chemical constituents are generally low in the North and high in the South. The order of relative abundance of major cations in the groundwater is Na^?+??> Ca^2?+??> Mg^2?+??> K^?+? while that of anions is Cl^????> HCO $_{3}^{-} >$ SO $_{4}^{2-} >$ NO $_{3}^{-}$ . Four main chemical water types were delineated in the Basin. These include Ca–Mg–HCO₃, Mg–Ca–Cl, Na–Cl, and mixed waters in which neither a particular cation nor anion dominates. Silicate weathering and ion exchange are probably the main processes through which major ions enter the groundwater system. Anthropogenic activities were found to have greatly impacted negatively on the quality of the groundwater.     

Urban and suburban aerosol in Yokohama, Japan: a comprehensive chemical characterization

This article analyses elemental composition of suspended particulate matter (SPM) samples collected monthly from 1999 to 2005 at two locations in Yokohama, Japan. Microwave digestion and inductively coupled plasma mass spectroscopy was employed to measure Mg, Al, Ca, V, Cr, Mn, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Ag, Cd, Cs, Ba, Pb, and Bi. Water-soluble ions (Na^?+?, NH₄ ^?+?, K^?+?, Ca^2?+?, Cl^???, NO₃ ^???, and SO₄ ^2???) and carbonaceous mass (elemental and organic carbon) were detected using ion chromatograph and CHN analyzer, respectively. The results indicate that the composition of SPM on one of the sites is determined by automobile emissions and on the other by industrial combustions. The impact of the emission regulations for automobiles in large Japanese cities, which were enacted during 2002 and 2003, on the SPM composition of the samples is also studied.     

Evaluating Controlling Factors to Ali/(Ca + Mg) Molar Ratio in Acidic Soil Water, Southern and Southwestern China: Multivariate Approach

Al_i/(Ca + Mg) molar ratio in soil water has been used as an indicator to the effects of acid deposition on terrestrial ecosystems. However, the main factors controlling this ratio have not been well documented in southern and southwestern China. In this study, we presented the variation in inorganic aluminum (Al_i) and Al_i/(Ca + Mg) molar ratio in different sites and soil horizons based on two to three years monitoring data, and evaluated the main factors controlling Al_i/(Ca + Mg) molar ratio using principle component analysis (PCA) and partial least square (PLS) regression. Monitoring data showed although Al_i/(Ca + Mg) molar ratios in most soil water were lower than assumed critical 1.0, higher molar ratios were found in some soil water at TSP and LXH site. Besides acid loading, both soil properties and soil water chemistry affected the value of Al_i/(Ca + Mg) molar ratio in soil water. Partial least square (PLS) indicated that they had different relative importance in different soil horizons. In A-horizon, soil aluminum saturation (AlS) had higher influence on Al_i/(Ca + Mg) molar ratio than soil water chemistry did; higher soil aluminum saturation (AlS) led to higher Al_i/(Ca + Mg) molar ratio in soil water. In the deeper horizons (i.e., B₁-, B₂- and BC-horizon), inorganic aluminum (Al_i) in soil water had more and more important role in regulating Al_i/(Ca + Mg) molar ratio. On regional scale, soil aluminum saturation (AlS) as well as cation exchange capacity (CEC) was the dominant factor controlling Al_i/(Ca + Mg) molar ratio. This should be paid enough attention on when making regional acid rain control policy in China.     

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.     

Atmospheric deposition of major and trace elements in Amman, Jordan

Wet and dry deposition samples were collected in the capital of Jordan, Amman. Concentrations of Al, Ba, Bi, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, V, Zn, Fe, Sr, Mg²⁺, Ca²⁺, Na⁺, K⁺, Cl⁻, NO₃ ⁻ and SO₄ ²⁻, along with pH were determined in collected samples. Mean trace metal concentrations were similar or less than those reported for other urban regions worldwide, while concentrations of Ca²⁺ and SO₄ ²⁻ were among the highest. High Ca²⁺ concentrations were attributed to the calcareous nature of the local soil and to the influence of the Saharan dust. However, high SO₄ ²⁻ concentrations were attributed to the influence of both anthropogenic and natural sources. Except for Cl⁻, NO₃ ⁻, SO₄ ²⁻ and Cu, monthly dry deposition fluxes of all measured species were higher than wet deposition fluxes. The annual wet deposition fluxes of trace metals were much lower than those reported for other urban areas worldwide.     

Effects of chronic ammonium sulfate treatment on the forest at the Bear Brook Watershed in Maine

At the Bear Brook Watershed in Maine (BBWM), the forest tree composition was characterized and the effects of the chronic ammonium sulfate ((NH₄)₂SO₄) treatment on basal area growth, foliar chemistry, and gas exchange were investigated on forest species. The BBWM is a paired watershed forest ecosystem study with one watershed, West Bear (WB), treated since 1989 with 26.6 kg N ha^???1 year^???1 and 30 kg S ha^???1 year^???1applied bimonthly as (NH₄)₂SO₄, while the other watershed, East Bear (EB), serves as a reference. Tree species richness, density, and mortality were found to be similar between watersheds. Basal area increment was estimated from red spruce and sugar maple, showing that, for the first 7 years of treatment, it was significantly higher for sugar maple growing in WB compared to EB, but no differences were observed for red spruce between watersheds. However, the initial higher sugar maple basal area growth in WB subsequently decreased after 8 years of treatment. Foliar chemical analysis performed in trees, saplings, and ground flora showed higher N concentrations in the treated WB compared to the reference EB. But, foliar cation concentrations, especially Ca and Mg, were significantly lower for most of the species growing in WB compared with those growing in EB. For sugar maple, foliar N was higher on WB, but there were no differences in foliar Ca and Mg concentrations between treated and reference watersheds. In addition, only sugar maple trees in the treated WB showed significantly higher photosynthetic rates compared to reference EB trees.     

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.     

The hydrochemistry of groundwater in rural communities within the Tema District, Ghana

A detailed study has been carried out on groundwater in rural communities in the Tema District of the Greater Accra region of Ghana to establish the hydrochemistry and identify the various sources of contaminants as well assess the physical and chemical quality of the groundwater to ascertain their wholesomeness and the health impacts of the groundwater on the communities. The groundwater was found to vary considerably in terms of chemical and physical properties. Generally, the water was mildly acidic (pH 4.3–7.4), brackish to fresh, and undersaturated with respect to gypsum and halite. The majority of groundwater clustered toward Ca–Mg–SO₄ and Na–Cl facies. About 70% of boreholes sampled have elevated levels of NO₃ ^??–N, Cl^???, and SO₄ ^2? emanating from anthropogenic activities.     

Quantifying long-term changes in water quality and quantity of Euphrates and Tigris rivers, Turkey

The Euphrates and Tigris watersheds originating from Turkey and passing through Syria and Iraq are one of the most important transboundary watersheds in the Middle East. Long-term data (1971 to 2002) from 14 stations over the Euphrates river and seven stations over the Tigris river were analyzed and compared using the nonparametric Kruskal–Wallis and Mann–Kendall trend tests, and box-and-whisker plots. The upper Euphrates river had significantly lower values of flow rate (FR), water temperature (WT), electrical conductivity (EC), Cl, and SO₄ than did the lower Euphrates river. The middle Euphrates river had significantly higher Na, K, HCO₃, Cl, sodium adsorption ratio (SAR), and boron (B) and lower EC and SO₄ than the lower Euphrates river. The upper west Tigris river had higher EC, Ca + Mg, and SO₄ and lower FR, Na, and SAR than the lower Tigris river. The upper east Tigris river had higher HCO₃ and B and lower FR and WT than the lower Tigris river.     

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.