Critical loads and steady-state chemistry for streams in the state of Maryland

The critical loads to streams, steady-state stream chemistry and catchment chemical weathering rate in 73 catchments has been determined in the state of Maryland, USA. It was calculated with the PROFILE model from chemical limits for biological indicators, soil mineralogy, soil texture, annual average temperature, average soil moisture, net long-term uptake of base cations and nitrogen to the vegetation, annual precipitation and runoff and deposition of sulphur and nitrogen precursors of acid deposition. The results show a full range of critical loads from very low values in the sensitive catchments of western Maryland and the Coastal Plain on the Chesapeake Bay, to insensitive catchments in the Fredrick Valley and Ridge and the Piedmont plain. The critical loads will be used as an input to an integrated regional assessment of the quantitative sensitivity of streams to acid rain, and the assessment of regional stream alkalinity response to different abatement strategies. The mapping of steady-state stream chemistry indicates that streams in Maryland are still acidfying under the present deposition load. Land-use seems to play an important role in maintaining neutral pH in many of the streams of Maryland.     

Investigation into atmospheric deposition through precipitation studies at New Delhi (India)

Rain water samples were collected during the monsoon of 1994, using automatic wet-only and manual bulk collectors at a height of 30 m above the ground at the National Physical Laboratory, New Delhi. The average pH of the rain water was 5.7 and its chemical composition was dominated by NH₄ and SO₄. The free acidity of the rain water was found to be due to S04 rather than N03 and it was mainly neutralized by NH₄ and Ca. Calculation of sea salt fraction and enrichment factor revealed that this site is free for marine influence. On an average the bulk samples had 13% higher concentration than that of wet-only samples which may be due to the deposition of soil-derived particles during the 24 h period of exposure. The higher neutralization factors of Ca and Mg in bulk samples and highest dry deposition rates for Ca in comparison to other components, indicated the positive interference of dust particles in neutralization.     

Biochemical responses of the mycorrhizae in Pinus massoniana to combined effects of Al, Ca and low pH

Biochemical responses of Pinus massoniana, with and without the inoculation mycorrhizal fungus Pisolithus tinctorius at the root, to artificial acid rain (pH 2.0) and various Ca/Al ratios were investigated. Some enzymes associated with the nutritive metabolism, such as acid phosphatase, alkaline phosphatase, nitrate reductase, mannitol dehydrogenase and trehalase, in the roots, stems and leaves of plant were obviously inhibited by the artificial acid rain and Al. After treatment with pH 2.0 + Ca/Al (0/1 or 1/10) artificial acid rain, the protein content in the organs was decreased. However, the activities of superoxide dismutase (SOD) and peroxidase (POD) and glutathione (GSH) concentrations were induced. It demonstrated that acid rain and Al could induce oxygen radicals in plant. Compared with the treatments with lower pH or Al, respectively, the combination of lower pH and Al concentration was more toxic to P. massoniana. Al toxicity could be ameliorated by the addition of Ca and the amelioration was the most when the ratio was 1/1 among the various Ca/Al ratio. Infection with mycorrhizal fungus P. tinctorius at the root of P. massoniana increased the ability of the plant to resist the toxicity of artificial acid rain and Al stress.     

Artificial acidification of a non-acidic and an acidic headwater stream in Maine, USA

Two headwater streams with low DOC and different pHs (4.5-4.8 and 5-6.5) were acidified with H2SO4 to pH 4.1 and 4.5, respectively, for 24-h periods. Neutralization of the added acid occurred by protonation of ANC (HCO3-dominated in the higher pH stream), desorption of Ca (< 15 microeq litre(-1)) and Mg (<6 microeq litre(-1)), and desorption and dissolution of AL (<250 microg litre(-1)) from the stream bed. The concentrations of dissolved organic carbon (DOC) remained constant within the experimental reaches. The concentrations of Na, K an H4SiO4 also remained constant, indicating no detectable increase in the rate of chemical weathering in the stream bed. After acid addition was stopped, concentrations of Ca, Mg and Al decreased to below background, indicating reversible ion exchange as the principal mechanism for the mobility of Ca and Mg and to a lesser extent for Al. Repeated acidifications indicated that significant regeneration of cations on the exchange surfaces of the stream substrate occurs rapidly.     

On the relationship between acid rain and cloud type

Spanish European Monitoring and Evaluation Programme (EMEP) stations were selected to relate acid rain episodes with the meteorological structure that caused the rainfall during a 5-year period. A principal component analysis (PCA) was used to determine the origin of major ions (SO4(2-), NO3-, Cl-, Ca2+, K+, Mg2+, and Na+) in the rainwater. In addition, the meteorological origin of the rain was identified. Previous works suggested a relationship between acid rain and storm convective clouds. However, statistical analyses of pH values show that only the short-lived convective phenomena may cause acid rain in Spain. In fact, rain generated by fronts and that related to long-lived convective systems is neutral or even slightly basic. Results suggest that the acid rain might be related to the meteorological time scale instead of to the cloud type.     

Modelling acidification at Beacon Hill-a low rainfall, high pollutant deposition site in Central England

The model MAGIC (Model of Acidification of Groundwater In Catchments) has been applied to the Beacon Hill site, near Loughborough in Central England. This site is heavily impacted by wet and dry deposition of oxides of sulphur and nitrogen. The high acid inputs have caused soil acidification and acid stream waters. Long term simulations suggest that there has been a major decline in alkalinity and pH over the past 50 years. Despite recent reductions in deposition levels, soils and streams are predicted to continue to acidify in the future. For this heavily impacted site, deposition must be reduced by 80-90% to reverse the acidification trend and allow recovery of soil and stream waters.     

Base cation depletion, eutrophication and acidification of species-rich grasslands in response to long-term simulated nitrogen deposition

Pollutant nitrogen deposition effects on soil and foliar element concentrations were investigated in acidic and limestone grasslands, located in one of the most nitrogen and acid rain polluted regions of the UK, using plots treated for 8-10years with 35-140kg Nha(-2)y(-1) as NH(4)NO(3). Historic data suggests both grasslands have acidified over the past 50years. Nitrogen deposition treatments caused the grassland soils to lose 23-35% of their total available bases (Ca, Mg, K, and Na) and they became acidified by 0.2-0.4 pH units. Aluminium, iron and manganese were mobilised and taken up by limestone grassland forbs and were translocated down the acid grassland soil. Mineral nitrogen availability increased in both grasslands and many species showed foliar N enrichment. This study provides the first definitive evidence that nitrogen deposition depletes base cations from grassland soils. The resulting acidification, metal mobilisation and eutrophication are implicated in driving floristic changes.     

Power-law distribution of acid deposition

The scaling behaviour in acid deposition dynamics of 184 monitoring sites under the National Atmospheric Deposition Program (NADP) is analysed for the 1978–2001 period. The results show that: the distribution of weekly hydrogen deposition (WHD) is consistent with a power law in two different regimes separated by a crossover WHD (CWHD), and both the CWHD and its probability density increase as the power law commensurate with the mean of WHD series; the distribution of pH values shows a series behaviour similar to that of WHD and can be depicted as a log–linear model with the same form of Gutenberg–Richter model of earthquake occurrence; and the successive time-duration (weeks) of both acid and non-acid rain also obeys a power law, with the average duration of acid rain scaling as a positive power law and that of non-acid rain as a negative power law of average WHD. The power laws in the acid deposition dynamics are considered to be indicators of self-organisation of the atmosphere under environmental pollution stress.     

Acid rain and pollen germination in corn

The properties of an acid rain episode that could influence the germination of pollen in corn, Zea mays L., were evaluated by treating silks with a simulated acid rain and measuring the subsequent germination of pollen on the silks. The data indicated that acid rain creates an inhospitable environment for pollen germination on the silk surface. Reduced germination appeared directly related to the acidity of the rain, but not the sulphate concentration. Rinsing silks with a pH 5.6 rain after treatment with a pH 2.6 rain did not increase pollen germination above that on silks treated only with a pH 2.6 rain, suggesting the reduced germination was due to physical and/or chemical modifications of the silk surface and not to residual acid on the tissue. Pollen germination on silks was inhibited even when silk tissue was exposed to a simulated rain of pH 2.6 for <1.5min.     

Composition of wet and bulk deposition in Erzurum, Turkey

Seasonal variations in the chemical characteristics of wet and bulk deposition samples collected in Erzurum were investigated for the period March 2002-January 2003. Major cations (Ca2+, K+, Mg2+) and major anions (SO4(2-),NO3-) were determined in bulk and wet deposition samples; pH was also measured in wet deposition. The average pH of the wet deposition at Erzurum was 6.6 due to extensive neutralization of the acidity. A strong relationship between pH and SO4(2-) concentrations was observed in all seasons; however, only a weak relationship was found between pH and NO3-. On a seasonal basis, the correlation between Ca2+ and SO4(2-) concentrations was stronger in winter than in summer. Seasonal variations of ions were examined in both wet and bulk deposition samples. Although maximum concentrations of anions generally occurred during winter and spring, cation concentrations peaked in summer for both wet and bulk deposition. Results indicated that Ca2+ was the dominant cation and SO4(2-) the dominant anion in all deposition samples at Erzurum. Even though correlations among the crustal ions (calcium, magnesium and potassium) were high, the relationship between anthropogenic ions (sulfate and nitrate) was less clear in bulk deposition.     

Accumulation of Al, Mn, Fe, Cu, Zn, Cd and Pb by the bryophyte Scapania undulata in three upland waters of different pH.

Measurements were made of the contents of Al, Mn, Fe, Cu, Zn, Cd and Pb in Scapania undulata in three streams (D2, D5, D11) in the English Lake District. The stream waters had average pH values of 5.35 (D2), 5.81 (D5) and 7.26 (D11), the main differences in other major chemical components being in Mg, Al, Ca and alkalinity. There was generally more metal accumulation in the older parts of the plants, but this was not significant in all cases. Extents of accumulation varied with stream pH and dissolved metal concentration. For Al, accumulation was greatest in streams D2 and D5. Mn accumulated most in D5 and Fe was without preference. Cu, Zn and Cd accumulated mostly in the plants in stream D11 and Pb accumulated more in D5 and D11. In terms of enrichment factors (amount of metal in the plants divided by stream water concentration) the sequence was Zn < Cd < Cu < Mn < Pb < Al < Fe. Laboratory experiments supported the findings of the field data, providing evidence that uptake increases with pH at constant total metal concentration. The results are interpreted qualitatively in terms of the chemical speciation of the metals in the stream water and competition between metal ions and protons at the plant-water interface. It is suggested that Al, Cu, Zn, Cd and Pb behave according to chemical complexation, whereas redox processes and/or colloidal interactions may be significant for Mn and Fe.     

Effects of acid rain on growth and nutrient concentrations in Scots pine and Norway spruce seedlings grown in a nutrient-rich soil

The effects of artificially applied acid precipitation on growth and nutrient concentrations of Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies [L.] Karst.) seedlings were investigated in a long-term acid irrigation experiment in field conditions. Seedlings of northern and southern origin were planted in boxes containing peat and composted soil rich in nutrients, and sprinkler irrigated with water acidified with nitric and sulphuric acids to pH 3 or pH 4 for periods varying from two to three and a half growing seasons during 1986-1989. Water irrigated (pH 5.4-7.6) and non-irrigated groups of seedlings were also included in the experiment. At the end of the experiment needles, main and lateral shoots and roots were collected from the seedlings for the determination of height growth and biomass partitioning, and for the analysis of S, N, Mg, P, K, Ca, Mn and Fe concentrations. The treatment effects compared to the irrigated control were studied using multivariate analyses of variance and covariance. In the pine seedlings the total dry matter production increased by 25-70% compared with the irrigated controls when the total wet deposition to the seedlings exceeded 67 kg S ha(-1) and 36 kg N ha(-1) (e.g. after two growing seasons' exposure of the pH 3 treatment). The increase was mainly due to an increase in needle dry weight (54-72% greater at pH 3) and root weight (20-65% greater at pH 3), whereas the height growth or shoot weight growth were less affected. The northern provenance pine seedlings responded more clearly to the pH 3 irrigation than the southern ones. The treatments had no consistent effects on any of the growth variables studied in the spruce seedlings, however. The pines had higher root and foliage Ca concentrations as a result of the acid irrigation, whereas in spruce, acid rain decreased the Ca concentration in needles and shoots. Root Mn and Fe concentrations were higher in both species as a result of the pH 3 treatment. A higher soil conductivity and Ca concentration resulted from the prolonged pH 3 treatment. The results strongly support the hypothesis that the long-term growth and nutrient allocation response of conifers to acid precipitation is dependent both on the tree species and on the nutritional status of the soil.     

Effects of rhizobium, arbuscular mycorrhizal fungi and anion content of simulated rain on subterranean clover

An experiment was conducted to determine the extent to which rhizobia, mycorrhizal fungi, and anions in simulated rain affect plant growth response to acid deposition. Germinating subterranean clover seeds were planted in steam-pasteurized soil in pots and inoculated with Rhizobium leguminosarum, Glomus intraradices, Glomus etunicatum, R. leguminosarum + G. intraradices, R. leguminosarum + G. etunicatum, or no microbial symbionts. Beginning 3 weeks later, plants and the soil surface were exposed to simulated rain in a greenhouse on 3 days week(-1) for 12 weeks. Rain solutions were deionized water amended with background ions only (pH 5.0) or also adjusted to pH 3.0 with HNO3 only, H2SO4 only, or a 50/50 mixture of the two acids. Glomus intraradices colonized plant roots poorly, and G. intraradices-inoculated plants responded like nonmycorrhizal plants to rhizobia and rain treatments. Variation in plant biomass attributable to different rain formulations was strongest for G. etunicatum-inoculated plants, and the effect of rain formulation differed with respect to nodulation by rhizobia. The smallest plants at the end of the experiment were noninoculated plants exposed to rains (0.38 g mean dry weight total for 3 plants pot(-1)). Among nonnodulated plants infected by G. etunicatum, those exposed to HNO3 rain were largest, followed by plants exposed to HNO3 + H2SO4, pH 5.0, and H2SO4 rain, in that order. Among plants inoculated with both R. leguminosarum + G. etunicatum, however, the greatest biomass occurred with pH 5.0 rains, resulting in the largest plants in the study (1.00 g/3 plants). Treatment-related variation among root and shoot biomass data reflected those for whole-plant biomass. Based on quantification of biomass and N concentrations in shoot and root tissues, total N content of plants inoculated with G. etunicatum alone and exposed to the HNO3 + H2SO4 rains was approximately the same as plants inoculated with R. leguminosarum + G. entunicatum and exposed to pH 5 rains. Thus, the acid-mixture rains and rhizobia under no acid deposition provided approximately equal amounts of N in biomass. The significant interactions among rain formulation and the symbiotic status of the plants suggest that conclusions concerning the impact of acid deposition on plants in the environment cannot be considered reliable because most experiments on which such assessments are based have not tested confounding influences of microorganisms and precipitation characteristics.     

The influence of organic acids in relation to acid deposition in controlling the acidity of soil and stream waters on a seasonal basis

Much uncertainty still exists regarding the relative importance of organic acids in relation to acid deposition in controlling the acidity of soil and surface waters. This paper contributes to this debate by presenting analysis of seasonal variations in atmospheric deposition, soil solution and stream water chemistry for two UK headwater catchments with contrasting soils. Acid neutralising capacity (ANC), dissolved organic carbon (DOC) concentrations and the Na:Cl ratio of soil and stream waters displayed strong seasonal patterns with little seasonal variation observed in soil water pH. These patterns, plus the strong relationships between ANC, Cl and DOC, suggest that cation exchange and seasonal changes in the production of DOC and seasalt deposition are driving a shift in the proportion of acidity attributable to strong acid anions, from atmospheric deposition, during winter to predominantly organic acids in summer.     

Effects of simulated rain acidity on ectomycorrhizae of red spruce seedlings potted in natural soil

Formation of ectomycorrhizae of red spruce (Picea rubens) grown in natural soil was measured after seedlings were exposed to 25 or 50 applications of simulated rain of pH 5.5, 3.5 or 2.5. Ectomycorrhizae were quantified as the total number of ectomycorrhizal tips per centimeter, and as the number of ectomycorrhizal tips for each morphotype and for Cenococcum geophilum. Rain solutions were applied to the soil alone, to foliage and stem alone, or to entire potted seedlings. Final soil pH was linearly related to rain solution acidity. Lower base saturation, calcium and zinc content, and higher exchangeable acidity were observed after pH 2.5 treatments if the soil was exposed. Rain solutions and the subsequent changes in soil characteristics did not affect the total numbers of ectomycorrhizal tips. Four morphotypes of ectomycorrhizae observed for these seedlings were unaffected by simulated rain. However, the numbers of ectomycorrhizal tips formed by C. geophilum tended to increase with rain solution acidity after 50 applications. Method of rain deposition did not affect ectomycorrhizae, suggesting both plant and soil mediated responses may favor certain mycobionts. The results of this study indicate that short-term acidic deposition does not induce significant changes in the frequency of ectomycorrhizae, but higher numbers of C. geophilum tips suggest there may be changes in the relative occurrence of specific morphotypes of fungus species.     

Direct damage to vegetation caused by acid rain and polluted cloud: definition of critical levels for forest trees

The concept of critical levels was developed in order to define short-term and long-term average concentrations of gaseous pollutants above which plants may be damaged. Although the usual way in which pollutants in precipitation (wet deposition) influence vegetation is by affecting soil processes, plant foliage exposed to fog and cloud, which often contain much greater concentrations of pollutant ions than rain, may be damaged directly. The idea of a critical level has been extended to define concentrations of pollutants in wet deposition above which direct damage to plants is likely. Concentrations of acidity and sulphate measured in mountain and coastal cloud are summarised. Vegetation at risk of injury is identified as montane forest growing close to the cloud base, where ion concentrations are highest. The direct effects of acidic precipitation on trees are reviewed, based on experimental exposure of plants to simulated acidic rain, fog or mist. Although most experiments have reported results in terms of pH (H(+) concentration), the accompanying anion is important, with sulphate being more damaging than nitrate. Both conifers and broadleaved tree seedlings showing subtle changes in the structural characteristics of leaf surfaces after exposure to mist or rain at or about pH 3.5, or sulphate concentration of 150 micromol litre(-1). Visible lesions on leaf surfaces occur at around pH 3 (500 micromol litre(-1) sulphate), broadleaved species tending to be more sensitive than conifers. Effects on photosynthesis and water relations, and interactions with other stresses (e.g. frost), have usually been observed only for treatments which have also caused visible injury to the leaf surface. Few experiments on the direct effects of polluted cloud have been conducted under field conditions with mature trees, which unlike seedlings in controlled conditions, may suffer a growth reduction in the absence of visible injury. Although leaching of cations (Ca(2+), Mg(2+), K(+)) is stimulated by acidic precipitation, amounts leached are small compared with root uptake, unless soils have been impoverished. This aspect of the potential effects of acidic precipitation is best considered in terms of the long-term critical-load of pollutants to the soil. Given the practical difficulties in monitoring cloud water composition, a method for defining critical levels is proposed, which uses climatological average data to identify the duration and frequency of hill cloud, and combines this information with measured or modelled concentrations of particulate sulphate in the atmosphere, to derive cloud water concentrations as a function of cloud liquid water content. For forests within 100 m of the cloud base the critical levels of particulate sulphate, corresponding to solution concentrations in the range 150-500 micromol litre(-1), are in the range 1-3.3 microg S m(-3). These concentrations are observed over much of central Europe, suggesting that many montane forests are at risk of direct effects of fossil-fuel-derived pollutants in cloud.     

Recovery from acidification in Swedish forest streams

Sulphur deposition in Sweden has decreased to less than half of the levels recorded in 1970 and now signs of recovery from acidification of surface waters are beginning to appear. We investigated time trends of water chemistry between 1985 and 1998 in 13 streams draining small forested catchments with generally shallow acid sensitive soils. At nine of the catchments, bulk deposition was monitored as well. Sulphate concentrations decreased in both stream water and deposition, although with somewhat smaller trends in stream water compared with deposition. The magnitude of the trends in sulphate increased from north to south, following a gradient of increasing industrial influence. Five sites in the southern half of the country showed weak signs of recovery from acidification in terms of increasing concentrations of acid neutralising capacity and decreasing concentrations of hydrogen ions, corresponding to annual increases of 0.01 pH units. Changes in stream discharge and concentrations of marine salts and organic acids could not explain the observed decrease in acidity and the results were interpreted as recovery from anthropogenic acidification. For the northern half of Sweden, any changes in water chemistry could be attributed to natural variation in climate and marine influence, and the effect of anthropogenic acidification was negligible.     

Effects of simulated acid rain and ozone on foliar chemistry of field-grown Pinus ponderosa seedlings and mature trees

We investigated the additive and interactive effects of simulated acid rain and elevated ozone on C and N contents, and the C:N ratio of one-year-old and current-year foliage of field-grown mature trees and their half-sib seedlings of a stress tolerant genotype of ponderosa pine. Acid rain levels (pH 5.1 and 3.0) were applied weekly to foliage only (no soil acidification or N addition), from January to April, 1992. Plants were exposed to two ozone levels (ambient and twice-ambient) during the day from September 1991 to November 1992. The sequential application of acid rain and elevated ozone mimicked the natural conditions. Twice-ambient ozone significantly decreased foliar N content (by 12-14%) and increased the C:N ratio of both one-year-old and current-year foliage of seedlings. Although similar ozone effects were also observed on one-year-old foliage of mature trees, the only statistically significant effect was an increased C:N ratio when twice-ambient ozone combined with pH 3.0 rain (acid rain by ozone interaction). Enhancing the effect of twice-ambient ozone in increasing the C:N ratio of one-year-old foliage of mature trees in June was the only significant effect of acid rain.     

Responses of microbial populations in the rhizosphere to deposition of simulated acidic rain onto foliage and/or soil

Air pollutants or some chemicals applied to plant foliage can alter the ecology of the rhizosphere. Experiments were conducted to distinguish among possible foliage-mediated versus soil- or root-mediated effects of acid deposition on microorganism in the rhizosphere. Seedlings of a sorghum x sudangrass hybrid in pots of non-sterile soil-sand mix in a greenhouse were exposed to simulated rain solution adjusted with H2SO4 + HNO3 to pH 4.9, 4.2, 3.5 or 2.8. Solutions were applied as simulated rain to foliage and soil, foliage only (soil covered by plastic, and deionized water applied directly to the soil), or soil only (solution applied directly to the soil). Solutions were applied on 16 days during a 6-week period (1.5 cm deposition in 1 h per application). Plant shoot and root dry weights and population densities of selected types of bacteria, filamentous actinomycetes and fungi in the rhizosphere were quantified after exposures were completed. Deposition of simulated acidic rain onto foliage alone had no effect on plant biomass or microbial population densities in the rhizosphere (colony-forming units per gram of rhizosphere soil). However, plant growth was stimulated and all microbial populations in the rhizosphere increased 3- to 8-fold with increased solution acidity (relative to pH 4.9 solution) when solution penetrated the soil. Statistical analyses indicated that the acid dose-population response relationships for soil-only and foliage-and-soil applications were not different. Thus, no foliage-mediated effect of simulated acidic rain on rhizosphere ecology was detected.     

Field evaluation of an acid rain-drought stress interaction

Various methods have been proposed to simulate natural field conditions for growing agricultural crops while controlling conditions to study specific environmental effects. This report briefly describes the use of moveable rain exclusion shelters (10.4 x 40.9 m) to study the results of the interaction of acid rain and drought stress on corn and soybean yields. The rain exclusion shelters are constructed of galvanized pipe framing and covered with polyethylene film. Movement is automated by a rain switch to protect crops from ambient rainfall and to treat them with simulated acid rain The facility simulates a real environment with respect to variables such as solar exposure, wind movement, dew formation, and insect exposure, while allowing careful control of moisture regimes. Soybeans and corn were treated with average rainfall amounts, and with one-half and one-quarter of these rainfall amounts (drought stress) at two levels of rainfall acidity, pH 5.6 and 3.0. While drought stress resulted in considerable yield reduction for Amsoy and Williams soybeans, no additional reduction in yield was observed with rainfall of pH 3.0, as compared to rainfall of approximately pH 5.6. Similar results were observed for one corn cultivar, Pioneer 3377. For one year of the study however, yield of B73 x Mo17 (corn) was reduced 3139 kg ha(-1) by the most severe drought, and an additional 1883 kg ha(-1) by acid rain of pH 3.0, as compared to the control (pH 5.6). Yield reduction from acidic rain was considerably less at full water rates, resulting in a significant pH by drought stress interaction. However, during the second year of the experiment, no pH effect or drought by pH interaction was observed for this cultivar. The reason for the difference in the two years was not identified.