Sensitivity to acidification of subalpine ponds and lakes in north‐western Colorado

Although acidifying deposition in western North America is lower than in many parts of the world, many high‐elevation ecosystems there are extremely sensitive to acidification. Previous studies determined that the Mount Zirkel Wilderness Area (MZWA) has the most acidic snowpack and aquatic ecosystems that are among the most sensitive in the region. In this study, spatial and temporal variability of ponds and lakes in and near the MZWA were examined to determine their sensitivity to acidification and the effects of acidic deposition during and after snowmelt. Within the areas identified as sensitive to acidification based on bedrock types, there was substantial variability in acid‐neutralizing capacity (ANC), which was related to differences in hydrological flowpaths that control delivery of weathering products to surface waters. Geological and topographic maps were of limited use in predicting acid sensitivity because their spatial resolution was not fine enough to capture the variability of these attributes for lakes and ponds with small catchment areas. Many of the lakes are sensitive to acidification (summer and autumn ANC < 100 µeq L^?1), but none of them appeared to be threatened immediately by episodic or chronic acidification. In contrast, 22 ponds had minimum ANC < 30 µeq L^?1, indicating that they are extremely sensitive to acidic deposition and could be damaged by episodic acidification, although net acidity (ANC < 0) was not measured in any of the ponds during the study. The lowest measured pH value was 5·4, and pH generally remained less than 6·0 throughout early summer in the most sensitive ponds, indicating that biological effects of acidification are possible at levels of atmospheric deposition that occurred during the study. The aquatic chemistry of lakes was dominated by atmospheric deposition and biogeochemical processes in soils and shallow ground water, whereas the aquatic chemistry of ponds was also affected by organic acids and biogeochemical processes in the water column and at the sediment–water interface. These results indicate that conceptual and mechanistic acidification models that have been developed for lakes and streams may be inadequate for predicting acidification in less‐understood systems such as ponds. Copyright © 2004 John Wiley & Sons, Ltd.     

Chronic and episodic acidification of streams along the Appalachian Trail corridor,eastern United States

Acidic atmospheric deposition has adversely affected aquatic ecosystems globally. As emissions and deposition of sulfur (S) and nitrogen (N) have declined in recent decades across North America and Europe, ecosystem recovery is evident in many surface waters. However, persistent chronic and episodic acidification remain important concerns in vulnerable regions. We evaluated acidification in 269 headwater streams during 2010–2012 along the Appalachian Trail (AT) that transits several ecoregions and is located downwind of high levels of S and N emission sources. Discharge was estimated by matching sampled streams to those of a nearby gaged stream and assuming equivalent daily mean flow percentiles. Charge balance acid-neutralizing capacity (ANC) values were adjusted to the 15th (Q15) and 85th flow percentiles (Q85) by applying the ANC/discharge slope among sample pairs collected at each stream. A site-based approach was applied to streams sampled twice or more and a second regression-based approach to streams sampled once to estimate episodic acidification magnitudes as the ANC difference from Q15 to Q85. Streams with ANC <0 μeq/L doubled from 16% to 32% as discharge increased from Q15 to Q85 according to the site-based approach. The proportion of streams with ANC <0 μeq/L at low flow and high flow decreased from north to south. Base cation dilution explained the greatest amount of episodic acidification among streams and variation in sulfate (SO₄²⁻) concentrations was a secondary explanatory variable. Episodic SO₄²⁻ patterns varied geographically with dilution dominant in northern streams underlain by soils developed in glacial sediment and increased concentrations dominant in southern streams with older, highly weathered soils. Episodic acidification increased as low-flow ANC increased, exceeding 90 μeq/L in 25% of streams. Episodic increases in ANC were the dominant pattern in streams with low-flow ANC values <30 μeq/L. Chronic and episodic acidification remain an ecological concern among AT streams. The approach developed here could be applied to estimate the magnitude and extent of chronic and episodic acidification in other regions recovering from decreasing levels of atmospheric S and N deposition.     

Stream geochemical response to reductions in acid deposition in headwater streams: Chronic versus episodic acidification recovery

In the decades since dramatic reductions in acid emissions and subsequent deposition in North America and Europe, the vast majority of research on aquatic chemical recovery has focused on trends in acid–base concentrations during baseflow conditions. Missing from such assessments is consideration of higher flow periods, when flow paths and chemical concentrations change and episodic acidification may occur. Stream samples collected weekly and bi‐hourly during high‐flow storm events from 1992 to 2015 at three watersheds representing a gradient in response to acid deposition in the south‐eastern United States were used to evaluate temporal trends in acid anions, base cations, acid neutralizing capacity (ANC), and pH for each of five distinct flow exceedance regimes, as well as trends in concentration–discharge (C–Q) relationships. For the most well‐buffered watershed (mean ANC = 220 μeq L^?1), ANC and pH increased at a similar rate for baseflow and storm flow conditions. Decreases in sulfate controlled ANC trends at higher flows, whereas smaller sulfate decreases in combination with base cation increases resulted in similar ANC improvements for low‐flow periods. For the most acid sensitive watershed (mean ANC = 10 μeq L^?1), no trends in ANC or pH were observed for the lowest flows (>90% flow exceedance), whereas reductions in sulfate resulted in significant increases in ANC during higher flow conditions. At all sites, greater rates of sulfate decline during high‐flow, as compared with low‐flow, conditions are likely a result of a reduced capacity of near surface soils to adsorb and retain sulfur in these non‐glaciated watersheds. Overall, consistent increases in pH (~0.01–0.02 pH units year^?1) during higher flow conditions (<10% flow exceedance) in contrast to the variable trends observed during lower flows (>50% flow exceedance) illustrate that episodic acidification is recovering at an equal or greater rate than chronic acidification in these watersheds.     

Factors affecting water chemistry of alpine lakes

During a four-year study (1988–1991), 413 lakes in the Central Alps (Italy, Switzerland and Austria) were investigated to quantify their acidification. The ionic content of the lakes was generally low: 68% of them had alkalinity values of less than 200 µeq 1^–1 and were regarded as sensitive to acidification. Moreover, 36% of the lakes showed alkalinity values of less than 50 µeq 1^–1. Redundancy Analysis was used to relate the hydrochemistry of 187 lakes to their catchment characteristics. Calcite weathering was the main factor influencing lake chemistry. The same analysis, applied to a subset of 101 lakes lying in watersheds exclusively composed of silicic rocks, showed that lake chemistry was influenced by silicate weathering and nitrogen uptake. These processes were found to be mainly related to lake altitude and the fraction of the watershed not covered by vegetation, i.e. controlled by temperature. The importance of these relations to explain the pH shift produced by climatic variation is also discussed.     

Factors controlling the acid‐neutralizing capacity of Japanese cedar forest watersheds in stands of various ages and topographic characteristics

Acid‐neutralizing capacity (ANC) is an important index for streamwater acidification caused by external factors (i.e. chronic acid deposition) and internal factors such as soil acidification due to nitrification. In this study, the influence of forest clear‐cutting and subsequent regrowth on internal acidification was investigated in central Japan, where stream pH (near 7·0) and ANC (above 0·1 meq L^?1) are high. pH, the concentrations of major cations (Na⁺, K⁺, Mg²⁺ and Ca²⁺), major anions (NO₃^?, Cl^? and SO₄^2?) and dissolved silica (Si), and ANC were measured in 33 watersheds of various stand ages, during 2002 to 2004. Only NO₃^? concentration decreased with stand age, whereas pH, ANC, and concentrations of the sum of base cations (BC) and Si were negatively correlated with the minimum elevation of the watershed. The correlation between the BC/Si ratio and minimum elevation suggested that factors contributing to acid neutralization changed at 1100 m above sea level. In watersheds at lower elevations (?1100 m), the relatively high contribution of soil water with longer soil contact times should result in higher ANC, and cation exchange reactions should be the dominant process for acid neutralization due to deposition of colluvial soils on the lower slope. In contrast, in higher‐elevation watersheds (≥1100 m), weathered residual soils are thin and the small contribution of deeper groundwater results in lower ANC. These results suggest that the local acid sensitivity is determined by the hydrological and geomorphologic factors generated by steep topography. Copyright © 2008 John Wiley & Sons, Ltd.     

Impact of elevated levels of CO2 on animal mediated ecosystem function: The modification of sediment nutrient fluxes by burrowing urchins

A mesocosm experiment was conducted to quantify the relationships between the presence and body size of two burrowing heart urchins (Brissopsis lyrifera and Echinocardium cordatum) and rates of sediment nutrient flux. Furthermore, the impact of seawater acidification on these relationships was determined during this 40-day exposure experiment. Using carbon dioxide (CO₂) gas, seawater was acidified to pH_NBS 7.6, 7.2 or 6.8. Control treatments were maintained in natural seawater (pH ≈ 8.0). Under normocapnic conditions, burrowing urchins were seen to reduce the sediment uptake of nitrite or nitrate whilst enhancing the release of silicate and phosphate. In acidified (hypercapnic) treatments, the biological control of biogeochemical cycles by urchins was significantly affected, probably through the combined impacts of high CO₂ on nitrifying bacteria, benthic algae and urchin behaviour. This study highlights the importance of considering biological interactions when predicting the consequences of seawater acidification on ecosystem function.     

Influence of basin characteristics on baseflow and stormflow chemistry in the Great Smoky Mountains National Park,USA

Relationships between stream chemistry and elevation, area, Anakeesta geology, soil properties, and dominant vegetation were evaluated to identify the influence of basin characteristics on baseflow and stormflow chemistry in eight streams of the Great Smoky Mountains National Park. Statistical analyses were employed to determine differences between baseflow and stormflow chemistry, and relate basin‐scale factors governing local chemical processes to stream chemistry. Following precipitation events, stream pH was reduced and aluminium concentrations increased, while the response of acid neutralizing capacity (ANC), nitrate, sulfate, and base cations varied. Several basin characteristics were highly correlated with each other, demonstrating the interrelatedness of topographical, geological, soil, and vegetative parameters. These interrelated basin factors uniquely influenced acidification response in these streams. Streams in higher‐elevation basins (>975 m) had significantly lower pH, ANC, sodium, and silicon and higher nitrate concentrations (p < 0.05). Streams in smaller basins (<10 km²) had significantly lower nitrate, sodium, magnesium, silicon, and base cation concentrations. In stormflow, streams in basins with Anakeesta geology (>10%) had significantly lower pH and sodium concentrations, and higher aluminium concentrations. Chemical and physical soil characteristics and dominant overstory vegetation in basins were more strongly correlated with baseflow and stormflow chemical constituents than topographical and geological basin factors. Saturated hydraulic conductivity, of all the soil parameters, was most related to concentrations of stormflow constituents. Basins with higher average hydraulic conductivities were associated with lower stream pH, ANC, and base cation concentrations, and higher nitrate and sulfate concentrations. These results emphasize the importance of soil and geological properties influencing stream chemistry and promote the prioritization of management strategies for aquatic resources. Copyright © 2012 John Wiley & Sons, Ltd.     

Geochemical survey of Levante Bay,Vulcano Island (Italy), a natural laboratory for the study of ocean acidification

Shallow submarine gas vents in Levante Bay, Vulcano Island (Italy), emit around 3.6t CO₂ per day providing a natural laboratory for the study of biogeochemical processes related to seabed CO₂ leaks and ocean acidification. The main physico-chemical parameters (T, pH and Eh) were measured at more than 70 stations with 40 seawater samples were collected for chemical analyses. The main gas vent area had high concentrations of dissolved hydrothermal gases, low pH and negative redox values all of which returned to normal seawater values at distances of about 400 m from the main vents. Much of the bay around the vents is corrosive to calcium carbonate; the north shore has a gradient in seawater carbonate chemistry that is well suited to studies of the effects of long-term increases in CO₂ levels. This shoreline lacks toxic compounds (such as H₂S) and has a gradient in carbonate saturation states.     

柴达本盆地沙下盐湖的卤水化学及矿物沉积特征——以察尔汗盐湖区北部外围地带为例

对柴达木盆地察尔汗盐湖区外围沙下盐湖的卤水及沉积进行了综合研究。沙下盐湖卤水化学组成与地表径流和开放性盐湖卤水之间存在明显的差异性,具有高Na⁺+Cl^-、低Mg²⁺+Ca²⁺+SO₄^2-、贫K⁺+CO₃^2-+HCO₃^-等特征。沙下盐湖析盐层位含有新生矿物并夹带碎屑矿物,其盐类矿物组合为:石盐+羟氯镁铝石+光卤石。25℃等温蒸发相图表明,其卤水演化方向往光卤石析出区迁移,在穿越上覆盖层通道中卤水发生的物理化学反应与独特的沉积特征,可以作为继续寻找沙下盐湖的指导。     

Acidification recovery in a changing climate: Observations from thirty-five years of stream chemistry monitoring in forested headwater catchments at the Turkey Lakes watershed,Ontario

Long-term ecosystem studies are valuable for understanding integrated ecosystem response to global changes in atmospheric deposition and climate. We examined trends for a 35-year period (1982/83–2017/18) in concentrations of a range of solutes in precipitation and stream water from nine headwater catchments spanning elevation and surficial geology gradients at the Turkey Lakes watershed (TLW) in northeastern Ontario, Canada. Average annual water year (WY, October to September) concentrations in precipitation significantly declined over the period for sulphate (SO₄²⁻), nitrate (NO₃⁻) and chloride (Cl⁻), while calcium (Ca²⁺) and potassium (K⁺) concentrations increased, resulting in a significant pH increase from 4.2 to 5.7. Trends in stream chemistry through time are generally consistent with expectations associated with acidification recovery. Concentration of many stream water solutes (SO₄²⁻, Cl⁻, calcium [Ca²⁺], magnesium [Mg²⁺] and NH₄⁺ generally decreased, while others (silica [SiO₂] and dissolved organic carbon [DOC]) generally increased. Increases were also observed for alkalinity (six of nine catchments), acid neutralizing capacity ([ANC]; six of nine catchments) and pH (eight of nine catchments), while conductivity declined (six of nine catchments). Variability in trends among catchments are associated with differences in surficial geology and wetland cover. While absolute solute concentrations were generally lower at bedrock dominated high-elevation catchments compared to till dominated lower elevation catchments, the rate of change of concentration was often greater for high elevation catchments. This study confirms continued, but non-linear stream chemistry recovery from acidification, particularly at the less buffered high and moderate elevation sites. The heterogeneity of responses among catchments highlights our incomplete understanding of the relative importance of different mechanisms influencing stream chemistry and the consequences for downstream ecosystems.     

Prediction of episodic acidification in North‐eastern USA: an empirical/mechanistic approach

Observations from the US Environmental Protection Agency's Episodic Response Project (ERP) in the North‐eastern United States are used to develop an empirical/mechanistic scheme for prediction of the minimum values of acid neutralizing capacity (ANC) during episodes. An acidification episode is defined as a hydrological event during which ANC decreases. The pre‐episode ANC is used to index the antecedent condition, and the stream flow increase reflects how much the relative contributions of sources of waters change during the episode. As much as 92% of the total variation in the minimum ANC in individual catchments can be explained (with levels of explanation >70% for nine of the 13 streams) by a multiple linear regression model that includes pre‐episode ANC and change in discharge as independent variables. The predictive scheme is demonstrated to be regionally robust, with the regional variance explained ranging from 77 to 83%. The scheme is not successful for each ERP stream, and reasons are suggested for the individual failures. The potential for applying the predictive scheme to other watersheds is demonstrated by testing the model with data from the Panola Mountain Research Watershed in the South‐eastern United States, where the variance explained by the model was 74%. The model can also be utilized to assess ‘chemically new’ and ‘chemically old’ water sources during acidification episodes. Copyright © 1999 John Wiley & Sons, Ltd.     

Assessment of episodic acidification in Sierra Nevada,California

Monte-Carlo simulations were used to assess the extent of shortterm alkalinity depressions occuring in Sierra Nevada lakes due to acidic deposition events. The Episodic Event Model (EEM) was used to simulate spring snowmelt events. Snow course data, precipitation data and lake acidification surveys were used to derive values for the EEM parameters. Spring snowmelt events were shown to have great impacts on the water quality of Sierran lakes. Lakes are likely to be most affected by the early-spring snowmelt event because the epilimnion depth is at a minimum, which indicates minimum dilution. Under annual average loading conditions, no Sierran lake has been reported as acidic although 29% of the lakes have alkalinities less than 40 µeq/L indicating a sensitivity to acidification. In simulations of early-spring snowmelt events, using present-day acidic loading conditions, it was estimated 79% ± 9% of the lakes would experience shortterm lake alkalinity depressions to levels less than 40 µeq/L. The results provided by the model simulations are valuable in establishing upper and lower limits on the extent of possible episodic acidification to lake-resources-at-risk. The most critical parameters controlling the magnitude of lake alkalinity depressions during snowmelt episodic events are a) the lake area to watershed area ratio — a measure of input loading, and b) the epilimnion volume — a measure of dilution and mixing.     

The toxicological interaction between ocean acidity and metals in coastal meiobenthic copepods

Increased atmospheric CO₂ concentrations are causing greater dissolution of CO₂ into seawater, and are ultimately responsible for today’s ongoing ocean acidification. We manipulated seawater acidity by addition of HCl and by increasing CO₂ concentration and observed that two coastal harpacticoid copepods, Amphiascoides atopus and Schizopera knabeni were both more sensitive to increased acidity when generated by CO₂. The present study indicates that copepods living in environments more prone to hypercapnia, such as mudflats where S. knabeni lives, may be less sensitive to future acidification. Ocean acidification is also expected to alter the toxicity of waterborne metals by influencing their speciation in seawater. CO₂ enrichment did not affect the free-ion concentration of Cd but did increase the free-ion concentration of Cu. Antagonistic toxicities were observed between CO₂ with Cd, Cu and Cu free-ion in A. atopus. This interaction could be due to a competition for H⁺ and metals for binding sites.     

Prediction of dissolved inorganic nitrogen (DIN) concentrations in deep,seasonally stratified lakes based on rates of DIN input and N removal processes

Mean dissolved inorganic nitrogen concentrations ([DIN]) in deep, seasonally stratified lakes with comparable DIN inputs can differ by up to a factor of 3 depending on hydraulic and morphometric properties and/or different trophic states of the lakes. In such lakes, net N sedimentation rates were estimated with two independent methods (sediment core analysis and input-output mass balances). They were higher in eutrophic lakes (Mean: 5.1; SD: ± 1.6 g m^–2 yr^–1; n = 13) than in oligotrophic lakes (1.6 ± 1.0 g m^–2 yr^–1; n = 3), but independent of [DIN]. Gaseous N loss rates to the atmosphere, as calculated from combined N- and P-mass balances from selected lakes, ranged from 0.9 to 37.4 g m^–2 yr^–1 (n = 10) and were positively correlated with [DIN]. Reduction of NO ₃ ^- to N₂ is assumed to be the main cause for gaseous N losses. A simple one-box mass balance model for [DIN], based on DIN input and rates and kinetics of N removal processes (net sedimentation and gaseous N loss) is proposed, and validated with a data base on [DIN] and DIN input in 19 deep, seasonally stratified lakes of central Europe. The model illustrated that the amount of water loading per unit surface area of a lake (called water discharge height q) is the critical parameter determining mean lake [DIN] relative to mean input [DIN]. Lakes with a q > 50 m yr^–1 have average [DIN] similar to the [DIN] of the inflows regardless of their trophic states, because input and outflow exceed lake-internal N removal processes. A high primary production favors DIN removal in lakes with q < 50 m yr^–1. It is concluded that measures to decrease primary production, e.g. by means of P removal programs, lead to an increase of [DIN] in lakes.     

湖光岩玛珥湖水体中营养盐的时空分布特征及其影响因素

湖光岩玛珥湖是世界上最大的玛珥湖,它几乎是封闭的,受外界的干扰小.目前有关玛珥湖的研究主要集中在古气候及生态环境研究方面,而有关玛珥湖营养盐在一年中的生物地球化学循环的研究较少,因此研究湖光岩玛珥湖营养盐的生物地球化学过程具有重要意义.于2015年10月-2016年9月对湖光岩玛珥湖全水柱的营养盐及其他相关参数进行逐月调查,分析营养盐的结构特征、垂直分布特征和时间变化情况,并讨论营养盐时空变化的影响因素.结果表明,湖光岩玛珥湖水中的无机氮（DIN）以铵态氮（NH₄⁺-N）为主（>60%）,其次是硝态氧（NO₃^--N）,亚硝态氮（NO₂^--N）所占比利最低.湖光岩玛珥湖水中的硅酸盐（SiO₃^2--Si）浓度较高,水体浮游植物生长受磷限制.冬季风期间,水体垂直混合较均匀,导致营养盐的垂直分布比较均匀;夏季风期间,水体层化,营养盐浓度在浅层水体较低,在深层水体较高.湖光岩玛珥湖表层水中的NO₃^--N、NH₄⁺-N和SiO₃^2--Si具有明显的时间变化规律：NO₃^--N浓度从10月-次年3月升高,从3-9月降低;NH₄⁺-N浓度从10月-次年5月降低;SiO₃^2--Si浓度从11月-次年5月降低,从5-9月持续升高.营养盐浓度的时间变化受有机质的矿化分解、水体的季节性混合、浮游植物的吸收、降雨的输入等多种因素的综合影响.     

Effusive natrocarbonatite activity of Oldoinyo Lengai,June 1988

Oldoinyo Lengai in the Tanzanian rift valley is the only active carbonatite volcano in the world and its natrocarbonatitic lavas are unique in composition. The characteristics of effusive natrocarbonatite activity in June 1988 were studied and fresh samples were directly collected from active carbonatitic lava lakes and flows. Analyses of these samples provide the first information on natrocarbonatites since these unusual volcanic rock type was first described from the 1960–1961 eruptions. The analytical results constrain the original chemistry of fresh natrocarbonatite. Temperatures in lava lakes and of carbonatite lava flows range 491–544°C. The natrocarbonatite lava is extremely fluid at these temperatures and reaches incandescence. The most common variety of natrocarbonatite is porphyritic with abundant phenocrysts of nyerereite (Na_0.82K_0.19)₂(Ca, Sr, Ba)_0.975(CO₃)₂ and gregoryite Na_1.74K_0.1(Ca, Sr, Ba)_0.16CO₃, with complex substitution of (CO₃)^2- by (SO₄)^2-, (PO₄)^3-, F^-, and Cl^-. A phenocryst-poor to aphyric natrocarbonatite variety reflects residual liquids separating from the crystal-rich porphyritic flows. Sylvite, fluorite, and Fe-alabandite (Mn_0.7Fe_0.3S) have been identified as additional primary magmatic phases. Rare phases in the matrix are witherite (BaCO₃) and sellaite (MgF₂). Sylvite and gregoryite, and to a lesser extent nyerereite, are water-soluble and are responsible for the immediate decomposition and chemical alteration of natrocarbonatites under atmospheric conditions. A peralkaline combeite-bearing nephelinite lava is closely related to the natrocarbonatite activity, and is isotopically indistinguishable. It is likely that these two magma compositions are related by liquid immiscibility. The unusual hyperalkaline composition of both magma types makes Oldoinyo Lengai an exotic volcano, and its carbonatites have extreme compositions, and are not representative of carbonatites in general.     

Effect of Acidification on Zooplankton Communities of Small Lakes in Mountain Tundra

Small lakes in mountain tundra are studied. The typical features of their water are low pH and acid-neutralizing capacity, the predominance of sulfates over hydrocarbonates, organic matter content <2 mg/l, the rate of sulfur precipitation >1 g S/(m² year). The lakes zooplankton is found to have poor species composition and low quantitative characteristics. The dominating organism complex consists of acid-tolerant species Bosmina obtusirostris and Holopedium gibberium. The water acid neutralizing capacity ANC, Ni, and N_tot are shown to have negative effect (stronger than that of pH) on the quantitative characteristics of coarse filter-feeders of the Calanoida group.     

Hydrochemistry of Three Dystrophic Lakes in Northeastern Poland

A hydrochemical investigation was carried out in spring, summer, and autumn, in the years 1991–1994, in three dystrophic lakes of the Wigry National Park (NE Poland). In spite of the fertile catchment basin, the developing ombrofile peat bogs of lake environment results in the acidification of lakes, the presence of small concentrations of dissolved mineral substances (below 50 mg L^–1), and exceptionally high DOC concentrations, exceeding 10 mg L^–1 C. During summer, a strong thermic stratification develops in the lakes, with constant conditions of oxygen deficiency prevailing below 3 m. In the course of the spring and autumn mixing of dystrophic lakes, the deterioration of oxygen conditions occurs in the epilimnion. In spite of high TP and NH₄⁺ concentrations, which increase from spring to autumn, the conditions developing in the lakes are unfavourable, for the functioning of aquatic organisms, on account of the strong shading. The increased direct irradiation of water bodies caused by deforestation or favourable atmospheric conditions results in an increased trophy of lakes.