Heavy metal solubility in podzolic soils exposed to the alkalizing effect of air pollutants

The heavy metal content of pine forest soil was studied near the boundary between Russia and Estonia, an area characterized by large amounts of acidic and basic air pollutants, mainly sulfur dioxide and calcium. Alkalization dominates the processes in soil, since sulfur is adsorbed only in small quantities, and calcium is much better adsorbed. In addition to Ca, great amounts of Al, Fe, K, and Mg are accumulated in the humus layer due to air pollution. The heavy metal content has increased. The exchangeable content of heavy metals was in many cases much higher in polluted alkaline soils than in non-polluted acidic soils, even the ratio of exchangeable to total metal content being higher in alkaline plots. To avoid a dangerous increase in soluble heavy metal content, it is important to decrease not only the large sulfur emissions of local pollutant sources, but also the alkaline pollutants. A similar concern must be taken into account when liming of acidic forest soils is planned.     

Effects of heavy metal contamination on macronutrient availability and acidification parameters in forest soil in the vicinity of the Harjavalta Cu-Ni smelter, SW Finland

Four experiments were established (1992) in Scots pine stands at distances of 0.5, 2, 4 and 8 km along a line running to the SE of the Cu-Ni smelter at Harjavalta, SW Finland, in order to investigate the effects of Cu and Ni emissions on macronutrient availability and estimates of cation exchange capacity (CEC) and base saturation (BS). The accumulation of Cu and Ni (total, exchangeable) in forest soil close to the smelter has resulted in a deficit of base cations (exchangeable Ca, Mg, K and BS) in the organic layer caused by inhibition of mineralisation and the displacement of base cations from cation exchange sites by Cu and Ni cations. No signs of soil acidification were found in the topmost layers of the soil measured as a change in pH, exchangeable acidity and Al. The determination of CEC by the summation method in heavy-metal polluted forest soils is not recommended unless heavy metal cations are also included in the calculations.     

Sulphur status in some Swedish podzols as influenced by acidic deposition and extractable organic carbon

To evaluate the changes in sulphur pools in response to acidic deposition, two studies were made-one in southwest Sweden where podzolic B horizons originally sampled in 1951 were resampled in 1989. At the Norrliden site, northern Sweden, sulphur pools in control plots were compared to plots that had been subjected to H(2)SO(4) application between 1971 and 1976. The results show that in southwest Sweden neither organic S nor extractable SO(4)(2-) increased significantly over the 38-year period, despite a decreasing pH and a high S deposition. At Norrliden, about 37% of the applied S was still remaining in the upper and central parts of the Bs horizon, most of which was inorganic sulphate. These contrasting results are explained by intrinsic differences in the soil organic carbon status between the sites-in southwest Sweden, organic carbon concentrations were high which inhibited SO(4)(2-) adsorption. Low organic carbon concentrations and high extractable Fe/Al concentrations promoted SO(4)(2-) adsorption and caused a low subsequent SO(4)(2-) desorption rate at the Norrliden site. The results suggest that sulphate adsorption may be an important mechanism which delays the response in soil chemistry to H(2)SO(4) deposition, provided that soil organic carbon concentrations are low. Organic S retention was not shown to be an important S retention mechanism in any of the sites studied.     

Monitoring the impact of sulphur with the Austrian Bioindicator Grid

In Austria, the impact of sulphur has been assessed since 1985 with the help of the Austrian Bioindicator Grid on 760 sample plots with Picea abies as the main tree species (90%). The annual sampling allows a precise evaluation of the temporal and regional development of the impact of sulphur on the basis of legal standards. Despite the reduction of SO2 emissions in Austria, the legal standard is still exceeded on 8% of the plots. These plots are mainly located near large Austrian emittors, but also in areas affected by transboundary sulphur emissions from neighbouring countries. The present paper describes how the Bioindicator Grid can be applied for the control of legal requirements to enact effective clean air measures in Austria and take supportive measures that reduce the impact of sulphur from emittors in neighbouring countries.     

Persistent episodic acidification of streams linked to acid rain effects on soil

Episodic acidification of streams, identified in the late 1980s as one of the most significant environmental problems caused by acidic deposition, had not been evaluated since the early 1990s despite decreasing levels of acidic deposition over the past decade. This analysis indicates that episodic acidification of streams in upland regions in the northeastern United States persists, and is likely to be much more widespread than chronic acidification. Depletion of exchangeable Ca in the mineral soil has decreased the neutralization capacity of soils and increased the role of the surface organic horizon in the neutralization of acidic soil water during episodes. Increased accumulation of N and S in the forest floor from decades of acidic deposition will delay the recovery of soil base status, and therefore, the elimination of acidic episodes, which is anticipated from decreasing emissions.     

Accumulating pollutants in conifer needles on an Atlantic island - a case study with Pinus canariensis on Tenerife, Canary Islands

Concentrations of potential pollutant elements Na, Cl, and S were investigated in needles of Pinus canariensis grown at 55 field plots in Tenerife. Microelement concentrations (including heavy metals) were measured at a subset of 18 plots. Na and Cl concentrations were high at low elevations (up to 8 mg g(-1) Cl and 5.5 mg g(-1) Na). Na/Cl ratio close to standard seawater indicated sea spray influence up to 1200 m a.s.l. Only at few plots, sulphur concentrations indicated possible pollutant impact. Cluster and correlation analyses identified a related group of V, As, Cr, Fe, Mo, Ni, Cu, Pb, and Al, possibly related to traffic exhaust aggregated with soil particles. Mainly north-eastern, lower elevated plots were exposed to those immissions, but metal concentrations were generally low compared to data from other studies. In conclusion, seawater and soil particles explained most of the element distribution pattern in pine needles in Tenerife, but strong indications for some effect of local sources of air pollutants were detected.     

Pyrolysis temperature influences ameliorating effects of biochars on acidic soil

The biochars were prepared from straws of canola, corn, soybean, and peanut at different temperatures of 300, 500, and 700 °C by means of oxygen-limited pyrolysis. Amelioration effects of these biochars on an acidic Ultisol were investigated with incubation experiments, and application rate of biochars was 10 g/kg. The incorporation of these biochars induced the increase in soil pH, soil exchangeable base cations, base saturation, and cation exchange capacity and the decrease in soil exchangeable acidity and exchangeable Al. The ameliorating effects of biochars on acidic soil increased with increase in their pyrolysis temperature. The contribution of oxygen-containing functional groups on the biochars to their ameliorating effects on the acidic soil decreased with the rise in pyrolysis temperature, while the contribution from carbonates in the biochars changed oppositely. The incorporation of the biochars led to the decrease in soil reactive Al extracted by 0.5 mol/L CuCl₂, and the content of reactive Al was decreased with the increase in pyrolysis temperature of incorporated biochars. The biochars generated at 300 °C increased soil organically complexed Al due to ample quantity of oxygen-containing functional groups such as carboxylic and phenolic groups on the biochars, while the biochars generated at 500 and 700 °C accelerated the transformation of soil exchangeable Al to hydroxyl-Al polymers due to hydrolysis of Al at higher pH. Therefore, the crop straw-derived biochars can be used as amendments for acidic soils and the biochars generated at relatively high temperature have great ameliorating effects on the soils.     

Norway spruce needles as bioindicator of air pollution in the area of influence of the Sostanj Thermal Power Plant, Slovenia

This paper reports the results of total sulphur content, photosynthetic pigments, ascorbic acid (vitamin C) and alpha-tocopherol (vitamin E) analysed in current-year needles of Norway spruce (Picea abies (L.) Karst.) in the area influenced by sulphur emissions from the Sostanj Thermal Power Plant (STPP), Slovenia, in the period 1991-2004. Ten differently polluted sampling sites in the emission area of STPP were selected. After desulphurization of emission gases from STPP total sulphur content in needles decreased and vitality parameters of needles increased. Moreover, a strong correlation between the average annual emissions of SO(2) from STPP and average annual sulphur content (increase) or average annual chlorophyll content (decrease) in current-year needles was found. The results showed that spruce needles may be an useful bioindicator for detecting changes in the emission rates of SO(2).     

Effects of organic fertilizers on soil physicochemistry and on the yield and botanical composition of forage over 3 years

Organic wastes have been reported to reduce saturation of the exchange complex by Al in Al-rich acid soils. For 3 years, the main soil fertility properties were studied in plots sown with mixed pasture species. These plots were fertilized with cattle slurry, dairy sludge (DS), or granulated broiler litter (BL) in comparison with mineral fertilizer. Al saturation levels were low after the initial inorganic liming treatment (19.00-33.71%) but tended to rise under all treatments (21.09-61.37%) except BL (8.45-30.98%), which was also associated with the highest average soil pH and the highest average levels of exchangeable Ca2+, Mg2+, and K+. Treatment DS performed similarly to mineral fertilizer in most respects, but it led to greater available P levels. Under the dry conditions of the second and third years of the study, BL and DS treatments were associated with significantly greater forage yields than the other treatments. Under DS treatment, available P levels were too low to allow the maintenance of mixed pasture, clover being eliminated by the less P-dependent species.     

Air pollution and health studies in China--policy implications

During the rapid economic development in China, ambient air pollutants in major cities, including PM10 (particulate matter with aerodynamic diameter < or =10 microm) and SO2 have been reduced due to various measures taken to reduce or control sources of emissions, whereas NO2 is stable or slightly increased. However, air pollution levels in China are still at the higher end of the world level. Less information is available regarding changes in national levels of other pollutants such as PM2.5 and ozone. The Chinese Ministry of Environmental Protection (MOEP) set an index for "controlling/reducing total SO2 emissions" to evaluate the efficacy of air pollution control strategy in the country. Total SO2 emissions declined for the first time in 2007. Chinese epidemiologic studies evidenced adverse health effects of ambient air pollution similar to those reported from developed countries, though risk estimates on mortality/morbidity per unit increase of air pollutant are somewhat smaller than those reported in developed countries. Disease burden on health attributable to air pollution is relatively greater in China because of higher pollution levels. Improving ambient air quality has substantial and measurable public health benefits in China. It is recommended that the current Chinese air quality standards be updated/revised and the target for "controlling/reducing total SO2 emissions" be maintained and another target for "reducing total NO2 emissions" be added in view of rapid increase in motor vehicles. Continuous and persistent efforts should be taken to improve ambient air quality.     

Sulphur dioxide adsorption in Scots pine canopies exposed to high ammonia emissions near a Cu-Ni smelter in SW Finland

Since 1994 the nickel-processing plant at the Cu-Ni smelter at Harjavalta, south-west Finland, has emitted considerable amounts of NH(3) into the atmosphere. The effects of NH(3) emissions on nitrogen and sulphur deposition in throughfall and the foliar nutrient status were investigated in a Scots pine stand at 0.5 km distance. Bulk deposition, stand throughfall and percolation water (20 cm depth) samples were collected at 4-week intervals during 1992-1998. pH and the Ca, Mg, K, NH(4) and SO(4) concentrations were determined on the samples. NH(3) emissions have strongly increased the scavenging of SO(2) from the air in the pine stand, and the increased levels of N and S deposition were clearly evident as increased foliar N and S concentrations and larger needle size. The increased input of SO(4) into the forest floor was not associated with an increase in the leaching of Ca and Mg from the surface soil layers.     

The change in O3, SO2 and NO2 concentrations in Lithuania

Due to the dynamic nature of the atmosphere, substantial amounts of gaseous and particulate pollutants are transported to the areas distant from their sources. In order to determine the regional concentration levels of atmospheric pollutants in Lithuania, concentrations of gaseous O₃, SO₂, NO₂ and other pollutants have been measured at the Preila background station (55°20′ N and 21°00′ E, 5 m a.s.l.) since 1981. The long-term concentration data set enabled us to get temporal trends, both on a seasonal and longer time scale, to identify source areas of pollutants and to relate them to the emission data. Based on the data obtained, the different tendencies in the pollutant concentration changes were revealed. Positive trends for ozone (of 2.9% per year during 1983–2000) and a distinct negative trend for both sulphur dioxide (of 3.8% per year during 1981–2000) and nitrogen dioxide (of 3.8% per year during 1983–2000) were found. The air mass back-trajectory analysis was used to assess the source region of air pollutants transported to Lithuania. The pollutant concentration levels were compared with their emission changes in Europe and Lithuania. The general trends in SO₂ as well as in NO₂ concentrations observed are consistent with changes in SO₂ and NO₂ emissions in Europe and Lithuania.     

Mineral content in the soil and tree foliage

Seedlings of fir (Abies alba Mill.) and spruce (Picea abies L. Karst.) were fumigated with SO(2), O(3) and SO(2) + O(3) in open-top chambers (OTCs) for almost 5 vegetation periods. As background stress, simulated rain of pH 4.0 was applied. Nutrient content of soil, soil solutions, and trees was investigated and balanced. In the upper partition of the soil high concentrations of exchangeable Ca(2+) were found in all chambers. The SO(2) and SO(2) + O(3) treatments led to increased Ca(2+), Mg(2+) and Mn(2+) concentrations in soil solution and the pool of exchangeable protons increased. This response was most evident in the SO(2) and SO(2) + O(3) chambers and less clear in the filtered pH 5.0 control chamber. In the SO(2) treatment increased Mn and S levels were found in the needles. Ca content in the needles showed a decreasing trend. O(3) alone had no consistent effect on needle nutrient content.     

Simulated Effects of Acidic Solutions on Element Dynamics in Monsoon Evergreen Broad-leaved Forest at Dinghushan,China - Part 1: Dynamics of K,Na, Ca,Mg and P (7 pp)

Background, Aim and Scope Acid deposition has become a concern in south China in recent years. This phenomenon has increased to a dramatic extent with the large use of cars and coal- fueled power plants. As a consequence, soils are becoming acidified and their element dynamics will change. A decrease in the nutrient availability will lead to slower plant growth and maybe to a change in the forest type with current species being replaced by new ones with less nutrient requirements. Because of these reasons, it is important to understand how the dynamics of elements will change and what mechanism is part of the process. This knowledge is important for modeling the acidification process and either finding ways to counter it or to predict its consequences. The primary purpose of this study was to provide information about how the dynamics of K, Na, Ca, Mg and P are affected by acid deposition in a typical forest in southern China. Materials and Methods: Experimental soils and saplings were collected directly from the monsoon evergreen broad-leaved forest in Dinghushan. All saplings were transplanted individually into ceramic pots in August 2000 and placed in an open area near their origin site. Pot soils were treated weekly from October, 2000 to July, 2002 with an acidic solution at pH 3.05, pH 3.52, pH 4.00 or pH 4.40, or with tap water as a control. The concentrations of SO42-, NO3-, K+, Na+, Ca2+, Mg2+ and available P and the pH were measured in soil and leachate samples taken at different times. The sapling leaves were collected and their element concentrations were measured at the end of the experiment. Results: Concentrations of soil exchangeable Ca and Mg decreased quickly over time, although only Ca showed changes with the acidic solution treatment and soil exchangeable K was stable because of soil weathering. Leaching of K, Mg and Ca was dependent upon the treatment acidity. Soil available P decreased slowly without any correlation with the acidity of the treatment. All the NO3- added by the treatment was taken up by the plants, but the SO42- added accumulated in the soil. Discussion: Amongst the plant species, Schima superba was little affected by the treatment, the leaf P content was affected in Acmena acuminatissima plants and Cryptocarya concinna was the most susceptible species to soil acidification, with a marked decrease of the leaf K, Ca and Mg concentrations when the treatment acidity increased. Conclusions: Simulated acid deposition affected the dynamics of K, Ca and Mg in the monsoon evergreen broad-leaved forest. The dynamics of Ca in the soil and of K, Mg and Ca in the soil leachates were affected by the acidic solution treatment. If such a soil acidification occurs, Cryptocarya concinna will be amongst the first affected species, but Schima superba will be able to sustain a good growth and mineral nutrition. Recommendations and Perspectives: Acid deposition will lead to imbalance the nutrient elements in the evergreen broad-leaved forest because of accelerated leaching losses of soil exchangeable Ca and Mg. Measures should be developed to slow down soil acidification or nutrient decrease.     

Effect of vegetation type on throughfall deposition and seepage flux

This paper compares different vegetation types (coniferous and deciduous forest, grassed and pure heathland) in terms of input (throughfall deposition) and output (seepage flux) in a region with intermediate nitrogen load (+/-20kg Nha(-1)y(-1) via bulk precipitation) in comparable conditions in north Belgium. Coniferous forest (two plots Pinus sylvestris and two plots Pinus nigra) received significantly higher nitrogen and sulphur throughfall deposition than deciduous forest and heathland. Grassed and pure heathland had significantly highest throughfall quantities of Ca(2+) and Mg(2+), respectively. The observed differences in throughfall deposition between the different vegetation types were not univocally reflected in the ion seepage flux. Considerable seepage fluxes of NO(3)(-), SO(4)(2-), Ca(2+) and Al(III) were only found under the P. nigra plots. We discuss our hypothesis that the P. nigra forests already evolved to a situation of N saturation, while the other vegetation types did not.     

Throughfall chemistry in a spruce chronosequence in southern Poland

The chemical composition of throughfall and canopy leaching, as well as the acid neutralizing capacity and alkalinity depended on the age of Norway spruce (Picea abies Karst) stands and season of the year. A higher amount of sulphur and strong acids was deposited to the soil in the older age classes. Concentrations of SO(4)(2)(-), K(+), H(+), Mn(2+), Fe(2+) and Zn(2+) in throughfall were higher than in bulk precipitation in any season. This suggests that these ions were washed out or washed from the surface of needles and/or barks. The other ions NO(3)(-), NH(4)(+), Ca(2+) and Mg(2+) were retained by the canopy, in particular Ca(2+) and Mg(2+) during the growing season in young stands. Principal component analysis identified five factors responsible for the data structure and suggested the major anthropogenic emission sources were acidic emission (SO(4)(2)(-)+NO(3)(-)), heavy metals-dust particles (Fe(2+)+Mn(2+)+Zn(2+)), ammonium (NH(4)(+)) and H(+), while the natural-origin emission was mineral dust (Na(+)+K(+)+Ca(2+)+Mg(2+)).     

Is tree growth reduction related to direct foliar injuries or soil chemistry modifications?

In the context of intense emissions causing atmospheric pollution, tree growth reductions could be related to soil chemistry modifications or direct foliar injuries. To verify these hypotheses, mineral soils were sampled in an area (Murdochville, Canada) where previous studies had demonstrated that tree growth was impacted by smelter emissions and that forest floor lead concentrations could be used as a proxy for atmospheric pollutant depositions. Samples were analysed for Al, Pb (concentrations and isotope ratios), basic cations (Ca, K, P, and Mg) and Zr. Mass balance calculations were performed on soil profiles to assess vertical migration of elements. Pb concentrations in litter diminished gradually with distance from the smelter. The Pb isotope ratios in these organic soil layers were close to those measured in the Murdochville ores. These patterns were not encountered in mineral soil layers. Pb isotope ratios in these layers were close to those measured in uncontaminated geological materials, and Pb concentrations and basic cation depletions were not related to the proximity of the smelter. Growth reduction was closely associated with litter Pb concentrations, which were used as a proxy for atmospheric deposition, but was not correlated with any elemental concentration or cation depletion measured in mineral soil layers. Our overall results suggest that trees responded mainly to direct atmospheric emissions, which caused foliar damage, rather than to soil chemistry modifications.     

Acid rain: chemistry and transport

This review describes the more important features of the emission, chemistry, transport and deposition of pollutants involved in acid deposition. Global emissions, both natural and man-made, of sulphur and nitrogen oxides are discussed and examples of spatial distributions and trends over the last century presented. The more significant chemical and physical processes involved in the transformation of the primary emissions into their acidic end products are described, including a summary of the approximate timescales of the processes involved. Measurements and modelled calculations of spatial and temporal patterns in the deposition of acidic pollutants by both wet and dry pathways are presented.     

Decreased acid deposition and the chemical recovery of Killarney,Ontario, lakes

Lakes in Killarney Park near Sudbury, Ontario, Canada, have shown dramatic water quality changes including general increases in pH and alkalinity, and decreases in SO4(2-), base cations and metals. While some lakes have recovered to pH > 6.0, many are still highly acidic despite decades of improvement. Very high historical S deposition related to emissions from the Sudbury metal smelters dominated the acidification process in this region. However, since the implementation of substantial S emission controls (90%) at the smelters, the Sudbury emissions are no longer the major source of S deposition in the Sudbury area. Wet deposition of SO4(2-) and SO4(2-) concentrations in lakewaters at Killarney now approach values in the Dorset, Ontario, area, about 200 km from Sudbury. This suggests that the S deposition to the Killarney area is now primarily from long-range transport, not from local sources. Studies of Killarney lakes are revealing the complex nature of the chemical recovery process. As lake acidity decreases, other changes including decreased Ca2+ concentrations, increased transparency, and altered thermal regimes may potentially affect some of these ecosystems. It is clear that continuing assessments of the recovery of Killarney lakes, within a multiple-stressor framework, are needed.     

Sulphur in the Arctic environment (3): environmental impact

Long term, high level airborne emissions of pollutants from nickel industries on the Kola Peninsula (NW Russia) have resulted in widespread ecosystem injury up to almost complete vegetation eradication within nearest surroundings of the smelters. Although SO2 is the prevailing component of the emissions, it is only part of a much more complex chemical emission spectrum in the region. In addition to acidic gases, industry also emits potentially toxic elements (e.g. metals) which being less volatile than SO2, are deposited within the immediate region in significant concentrations. Additionally, it appears that sources of base cations (co-emission by smelters, sea aerosols, other industries) are adequate to prevent environmental acidification on the regional scale. Acidification of soils and waters appeared only as single cases in the immediate vicinity of the smelters and is not believed to be a major mechanism of environmental deterioration. Proposed critical concentrations (5 microg/m(3)) of SO2 for the northern ecosystems are exceeded over a large area and direct exposure to SO2 is believed to be the possible mechanism of vegetation damage.