This article was downloaded by: [University of Delaware] On: 10 July 2009 Access details: Access Details: [subscription number 731847334] Publisher Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK Communications in Soil Science and Plant Analysis Publication details, including instructions for authors and subscription information: http://www.informaworld.com/smpp/title~content=t713597241 Effect of acid rain on the soil environment: A review J. E. Rechcigl a; D. L. Sparks a a Department of Plant Science, University of Delaware, Newark, Delaware Online Publication Date: 01 July 1985 To cite this Article Rechcigl, J. E. and Sparks, D. L.(1985)'Effect of acid rain on the soil environment: A review',Communications in Soil Science and Plant Analysis,16:7,653 — 680 To link to this Article: DOI: 10.1080/00103628509367636 URL: http://dx.doi.org/10.1080/00103628509367636 PLEASE SCROLL DOWN FOR ARTICLE Full terms and conditions of use: http://www.informaworld.com/terms-and-conditions-of-access.pdf This article may be used for research, teaching and private study purposes. Any substantial or systematic reproduction, re-distribution, re-selling, loan or sub-licensing, systematic supply or distribution in any form to anyone is expressly forbidden. The publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date. The accuracy of any instructions, formulae and drug doses should be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims, proceedings, demand or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or arising out of the use of this material. COMMUN. IN SOIL SCI. PLANT ANAL., 16(7), 653-680 (1985) EFFECT OF ACID RAIN ON THE SOIL ENVIRONMENT: A REVIEW Downloaded By: [University of Delaware] At: 18:09 10 July 2009 KEY WORDS: acid rain, aluminum, soil acidity J. E. Rechcigl and D. L. Sparks 2 Department of Plant Science University of Delaware Newark, Delaware, 19717-1303. ABSTRACT This paper reviews the literature on acid rain, with emphasis on soils and leaching of soil elements. Several questions still exist concerning the effects of atmospheric acid deposition on soils: 1) does acid rain enhance mobilization of harmful heavy metals in soils which could leach into the groundwater; 2) does acid rain accelerate the kinetics of weathering of primary minerals and of secondary clay minerals in soils which would release large quantities of Al, Fe, and Si into the groundwater making it unfit for human consumption; and 3) do the beneficial effects of acid deposition outweigh the negative effects or vice versa? Literature pertaining to these questions is addressed in this review. 653 Copyright © 1985 by Marcel Dekker, Inc. 0010-3624/85/1607-0653S3.50/O 654 RECHCIGL AND SPARKS INTRODUCTION Acid rain is one of the most significant environmental problems facing the world today 3 . becoming a significant obstacle to It is agricultural production as well as an impediment to the development of our forest and water resources 3 . It could seriously hinder the prospects of using coal as an energy source. According Downloaded By: [University of Delaware] At: 18:09 10 July 2009 Environmental to the estimates Protection Agency of the (EPA), annually discharges nearly 5.0 x 1O 10 U. the U. S. S. kg of S0 2 and N 2 0 into the atmosphere as a result of the combustion of large amounts converted of into fossil acids which components in rain or snow. may produce serious fuels. These return gases to are earth as The resulting "acid rain" ecological effects on the environment 3 . The seriousness and the widespread nature of the problem can be shown by simply listing the components of the ecosystem which can be affected by acid rain. It affects pathogens; soils, alters plants, lake and and the river spread biota; of plant accelerates material corrosion and deterioration of buildings; and finally, it affects human health 4 . While voluminous amounts of data have appeared on the effects of acid rain on plants and animals, few reports on acid effects on soils have appeared, yet there is increasing concern about the effect of acid rain on soils. The Acid Rain Phenomenon The first precipitation published apppeared in reports the on acid 1 5 mid-1950 s , and rain the ACID RAIN ON SOIL ENVIRONMENT 655 problem has been well documented for Scandinavia 6 7 eastern North America ) . 4 and The phenomenon is apparently not limited to northern climates, as there have been reports of acid rain in the southern and western parts of the United States 8 ) 9 ) 1 0 . In both Norway and Sweden, declines in rainfall pH of 0.02-0.05 units per year have been recorded over recent decades 1 1 ) 1 2 . In the northwestern U. S., 4% of Downloaded By: [University of Delaware] At: 18:09 10 July 2009 the mountain lakes had pHs below 5.0 in 1940, whereas 13 in the 1970's 51% were less than 5.0 , the average 12 decline being 0.05 units per year . According to EPA, hundreds of lakes in North America and Scandinavia have become so acidic that they can no longer support fish life 3 . in the Adirondack fishless because reproduction3. mountains acidic Other More than 90 lakes in New York conditions areas of State have the U. are inhibited S., such as 3 northern Minnesota may also be vulnerable . Data from New York State and New England indicate acid rain is 60-70% H 2 SO 4 14 and 30-40% HN0 3 . These strong acids are thought to stem primarily from gaseous man-made pollutants such as S and N 2 0 . Acid rain contains a variety of heavy metals, particularly in the vicinity of metal smelters 15 . In lake sediments in the northeastern U. S., Ag, Au, Cr, Ni, Pb, Sb, quantities Acid 16 and V have been may rain also contains be transferred a 1S increased from number including hydrocarbons, phthalic alkanes, acid of plant and possibly P land addition, it can also carry a wide molecules, in > . nutrients such as Ca, K, S, N These found a7 to water. . In range of organic polycyclic esters, 15 and aromatic fatty acid 656 ethyl esters, as well RECHCIGL AND SPAEKS as a variety of commonly used Downloaded By: [University of Delaware] At: 18:09 10 July 2009 industrial chemicals such as polychlorinated biphenyls Sensitivity of Soils to Acid Rain Acid rain may bring about variable effects on soil, depending on the type and properties of the soil involved. The sensitivity of soil to acid rain is determined by four key parameters 2 0 ' 2 4 : 1) the total buffering capacity or the cation exchange capacity (CEC) provided primarily by clay and soil organic matter contents; 2) the base saturation of that exchange capacity, which can be estimated by the pH of the soil; 3) the management system imposed on the soil, whether it is cultivated and fertilized or renewed by flooding or other additions; and, 4) the presence or absence of carbonates in the soil profile. A change in soil pH is most closely linked to its CEC. If the soil has a low CEC (<12 cmol (+)/kg), then the acid precipitation is likely to reduce the soil and the groundwater pH quickly 25 . However, a soil with a high CEC (>12 cmol (+)/kg) is strongly buffered against changes in pH or leachate composition 23 . The original pH of the soil also has a great bearing on the sensitivity of the • soil to acid precipitation. 23 According to McFee , acid soils with a pH near that of acid rain will not change in pH rapidly in response to acid inputs. Also, soils with a low CEC have a low reserve of plant nutrients (such as Ca, Mg, or K) and slight losses may be significant to their productivity. McFee 2 5 categorized soil areas into three major classes based on their sensitivity to acidity: ACID RAIN ON SOIL ENVIRONMENT 1) 657 Nonsensitive Areas (NS) include a) all soils that are calcareous (i.e., contain free carbonates) in the surface layer (within 0.25m ); b) all soils that are subject to frequent flooding (it is assumed that the renewal effects of fresh deposition would negate acid precipitation effects); and, c) all soils with an average CEC greater than 15.4 cmol ( + )/kg Downloaded By: [University of Delaware] At: 18:09 10 July 2009 in the top 0.25m. 2) Slightly Sensitive Areas (SS) include areas not in class la or lb that have average CEC in the range of 15.4 to 6.2 cmol(+)/kg in the top 0.25m. 3) Sensitive Areas (S) include those areas not in class la or lb that have average CEC less than 6.2 cmol(+)/kg in the top 0.25m. Using the above criteria, McFee constructed maps of soil sensitive regions for the eastern U. S., including New York, North Carolina, West Virginia, Pennsylvania and Indiana 23 . In similar fashion, Klopatek et al. 2 6 prepared computer maps of soil pH, CEC, base saturation, and base content for the eastern U. S., using county-level data. By overlaying these maps with computer maps of the H ion loading, maps of acid-sensitive and insensitive soils were made. Of 1572 counties in the eastern U. S., 117 were classified as being acidsensitive. Sensitivity of Soil Orders of the U. S. Soil 27 Classification System To Acid Rain (after Petersen ) 658 RECHCIGL AND SPARKS Petersen 27 has classified the major soil orders as to their sensitivity to acid rain. This classification is given below. Mollisols - are soils containing a high percentage of humus. and They have not been subject to much leaching often contain CaCO 3 . Their base saturation percentage and buffer capacity are usually fairly high, and thus they are not likely to be sensitive to acid Downloaded By: [University of Delaware] At: 18:09 10 July 2009 precipitation. Oxisols - are red soils usually containing a considerable percentage of clay which contains a large amount of Fe and Al oxides and kaolinite, and they have a low CEC. soil The humus content is also very low and the itself Therefore, is they capacity. highly have This weathered a low soil is pH and and leached. low buffering sensitive to acid precipitation. Vertisols - are black heavy clay soils having a high degree of base saturation. The clay mainly of smectite which has a high CEC. consists Thus, these soils most likely would not be affected by acid rain. Histosols - consist predominantly of matter and have a high buffering capacity. organic These soils are already very acid and any additional acidity would not change the pH very much. Alfisols and Ultisols - have a high clay content, and the percentage. Alfisols have Alfisols a are high not base likely saturation to be very sensitive to acidity, whereas Ultisols, with their low base saturation percentage, may be susceptible to acidity. Inceptisols - with a high clay content, they are rather insensitive to acid rain, whereas the Inceptisols are rather susceptible to acidity. sandy ACID RAIN ON SOIL ENVIRONMENT Entisols - have 659 a high degree of variation, and thus a generalization as to their sensitivity cannot be made. Downloaded By: [University of Delaware] At: 18:09 10 July 2009 Soil Acidification Process While acid rain may be a major source of soil acidity, it is not the only source. Acidification of soils is a natural process occurring 22 28 29 continuously > > . There" are several natural sources of soil acidity. One such source is H 2 C 0 3 . Water in equilibrium with the 0.03% C 0 2 in the atmosphere may have a pH of 5.6. When this water comes into contact with soil, the equilibrium with C 0 2 no longer exists. This is because topsoils may have a higher concentration of C 0 2 due to the respiration of soil flora and fauna. The C 0 2 concentration between air and soil will occasionally vary as much as 0.01% by lowering the pH from 5.6 to 4.9. A pH of 5 is thus quite common in subsurface soils where H 2 C 0 3 is the only source of a c i d i t y 2 2 ) 2 9 . Another source of soil acidity is nitrification. Plant residues and humus break down naturally in soils by heterotrophic microflora, producing NH 4 ions. Nitric acid is then formed when autotrophic bacteria oxidize NH 4 to N 0 3 . The reaction is as follows: N H 4 + + 2 0 2 + H 2 0 — > 2 H 3 0 + + N0 According to Bache 2 2 , the theoretical amount of acid rain produced by the nitrification of 100 kg N/ha added 660 RECHCIGL AND SPARKS as NH 4 salt is 13 kg. This would be equivalent to 286 kg Ca, requiring 714 kg of CaCO 3 for neutralization. Still another source of acidity could be organic acids formed from the decomposition of plant residues by microbes. These acids are particularly important in the formation of the podzolic soils 2 2 > 3 0 . Finally, the air the oxidation may cause F e 2 ( S 0 4 ) 3 which may produce acid SO 4 Downloaded By: [University of Delaware] At: 18:09 10 July 2009 of pyrite by exposure 22 and H 2 SO 4 to be to formed . Acidification of soils may cause the loss of the cations Ca, Mg, K, and Na. on the water soil 22 31 . type, pH A decrease These losses are dependent and the amount of in soil pH may percolating also cause a reduction in CEC because the charges on the weak acid exchange sites are pH dependent and the undissociated at a. low pH. 22 decreases 1 23 acids become Thus, CEC is reduced as pH 3 > * . Degradation of primary and secondary soil minerals may result following large inputs of mineral acids into acid soils 2 2 . organic matter sulfonation 32 acids" . of Where soil is extremely acidified, the in the soil carboxylated These may be benzene altered changed rings molecules due to of "humic will have strengthened capacities to bind metals and will prevent leaching into groundwater. This area has not yet been extensively investigated. One of the extreme effects of acidification is the process of podzolization. Podzol soils are found in cool, humid regions of North America, Europe and Asia. They are when there leaching. usually is confined enough to rainfall sandy to parent result materials in severe Podzol soils must have an acid reaction and usually have a low content of plant nutrients as well ACID RAIN ON SOIL ENVIRONMENT 661 as a low content of Al, Fe, and organic matter in the surface. This is the result of leaching. The Al, Fe, and organic matter are immobilized in the lower profile of the soil. The solubility of Al(0H) 3 is high enough to account for a significant equilibrium concentration of dissolved Al at pH 3.0-3.5. This range of pH is often found in the surface horizon of Podzols. The capacity of soils to adsorb and retain anions Downloaded By: [University of Delaware] At: 18:09 10 July 2009 increases with a decreasing pH and with the concentration of Fe- and Al-oxides and hydroxides. The polyvalent anions, such as P0 4 and S 0 4 , are bound by the hydrated Fe- and Al-oxides and hydroxides. anion effect increases with the ratio of hlz03 This + Fe203 to SiO 2 in the soil 3 0 . Effects of Acid Rain on Soil Exchange Properties Anion soils adsorption is a very in terms of regulating anions other than bicarbonate. important feature the leaching rates of of Bicarbonate leaching.is regulated by soil C 0 2 pressure and solution pH. In general, the anions to soil is: order of affinities of major P 0 4 3 ' > S 0 4 2 ' > Cl" = N 0 3 " . first two anions can be adsorbed non-specifically The or specifically, while the latter two can only be adsorbed non-specifically. Specific adsorption is penetration of the anion into the coordination of metal oxides, and nonspecific anion retention in the diffuse the sphere adsorption refers to double layer next to oxide surfaces. The anion adsorption capacity of a soil is related to the content the soil 33 » 34 > 35 of positively . charged sesquioxides Highly weathered, Al- and in Fe-rich 662 _ RECHCIGL AND SPARKS soils have higher adsorption capacities than younger Al- and Fe-poor adsorbed soils. anions mobilization of to The a addition of soil will non-specifically specifically result in adsorbed the anions. Phosphate is the most strongly adsorbed anion and will displace specifically adsorbed S0 4 as well as non36 specifically adsorbed anions, such as Cl and N 0 3 . Nitrate and Cl are considered indifferent anions, since Downloaded By: [University of Delaware] At: 18:09 10 July 2009 they do not specifically adsorb and can be completely desorbed by eliminating the positive charge on 34 sesquioxide surfaces . This problem was investigated by Wiklander 24 using the following soils: 1. Cambisols, cultivated, loamy clay, podzol, (bleached) (Fe, Al) 2 0 3 /Si0 2 , 2. Humo-orthic A2 and B2 (rusty) horizons, and (Fe, Al) 2 0 3 /Si0 2 medium, and 3. Latosol from Kenya, lateritic clay, (Fe, Al) 2 0 3 /Si0 2 high. Sodium, K, Mg, and Ca combined with Cl, N 0 3 / S0 4 , H 2 PO 3 , or salts were HPO 3 were added added to to the above solutions fertilization or higher levels. established, centrifugation the or solution membrane in soils. amounts The used in After equilibrium was was separated filtration and with analyzed. Without exception, the adsorption of N, K, Mg, and Ca varied with the type of salt anion and increased in the following order: el" NO3- < S 0 4 2 - < H 2 P0 4 - < HPO 4 = The solubility of the added salts was highest for Cl and N 0 3 , somewhat less for S0 4 and least for H 2 P0 4 . ACID RAIN ON SOIL ENVIRONMENT Wiklander 24 thus 663 showed that anions and soil type directly affect the adsorption of cations on the soil. The results were similar for single salts with Na and NH 4 as for combined salts with Ca, Mg, K and Na. The lateritic soil, the B horizon from the podsol and cultivated cambisol soils behaved similarly, with the anion effect varying quantitatively with soil type. Removal of hydrated oxides in the Latosol before Downloaded By: [University of Delaware] At: 18:09 10 July 2009 the salt addition strongly reduced the differences in retention of Ca, Mg, K, Na between the H 2 PO 4 , S0 4 and N0 3 systems caused by decreased adsorption of H 2 PO 4 and SO4 . It was found that the capacity of a soil to bind cations in exchangeable form depends not only on the soil properties but also on the anion of the salt used for saturation. The increased retention and reduced salt cations processes by of adsorbed great leaching of polyvalent significance in anions soil are formation, geochemical circulation of nutrients, fertilization in agronomic and horticultural systems and also in pollution of soils and waters. The mobility of S0 4 in soils is an important consideration in studying the possible effects of acid rain on nutrient mobilization from the soil. to experiments conducted by Johnson According Cole 3 7 , and it cannot be assumed that inputs of H 2 SO 4 will result in equivalent soil. a outputs of cation-S04 solutions To test this, Johnson and Cole gravelly significant Everett increases soil. 37 Results in leaching from the added H 2 SO 4 to showed occurred in that the A horizons, but no increase was noted in the B horizons. Through soil analysis, it was found that all applied S0 4 was retained' in the soil profile. Downloaded By: [University of Delaware] At: 18:09 10 July 2009 664 RECHCIGL AND SPARKS In another study, Johnson et a l . 3 8 compared atmospheric H 2 SO 4 inputs and leaching in a tropical and temperate forest soil. In both cases, H was mostly removed in the forest canopy. The tropical forest appeared to be accumulating S 0 4 , whereas the temperate forest was near steady state with respect to S. In both soils, the lower horizon adsorbed more S0 4 than did the upper horizon. The tropical soil had a high capacity permanently to retain S0 4 which was probably related to its high sesguioxide content, rendering it very resistant to leaching by atmospheric H 2 S0, inputs. Many researchers have noted higher soil S0 4 to be found in subsoil horizons than in surface horizons 36, 39-42_ Hesse 3 9 suggested that there was a S0 4 cycle operating somewhat independently of the biological S cycle in an East African forest. He suggests that the S0 4 leached from foliage or from input in precipitation can leach past the organic soil horizons and adsorb to sesguioxide surfaces in lower horizons. It may be that surface organic matter blocks S0 4 adsorption sites to some extent. This would explain why more S0 4 is found in the subsoil than in surface horizons of .many soils. The relationship between S0 4 adsorption and soil sesguioxide content has been demonstrated by several other investigators 3 8 » 4 2 > 4 5 . Soils that adsorb S0 4 tend to maintain an eguilibrium between S0 4 in solution and that sorbed into soil surface as shown below. SO 4 2 " (solution),, > S 0 1 2 ~ The Freudlich and Langmuir (sorbed) adsorption isotherms have been used to describe this eguilibrium 38 i 41 > 46 . ACID RAIN ON SOIL ENVIRONMENT Johnson study to 665 Henderson4 7 and determine whether adsorption in a Sesquioxide rich subsurface reservoir of undertook mixed NaH 2 PO 4 S a laboratory accumulates deciduous soils solution by forest which had were found SO 4 soil. a large to have adsorbed SO 4 -S at a level of 2700 kg/ha but would not permanently adsorb more. The surface soils had no detectable adsorbed SO 4 but had a substantial reserve Downloaded By: [University of Delaware] At: 18:09 10 July 2009 of H20-soluble-S04-S (110 kg/ha). This high proportion of H 2 O soluble solution SO4 appeared to have played an important role headwater streams. surface in determining It was SO 4 also concentrations found that in these soils were capable of adsorbing more SO4 in forms not extractable with water or PO 4 solution. Tyler 48 studied the leachability of some metal ions (Mn, Zn, Cd, Ni, V, Cr, Pb) in two purely organic spruce soils: one control soil and one similar soil heavily polluted with Cu and Zn from a brass foundry in southern Sweden. 4.2, 3.2 Artificial rain water acidified to pH and 2.8 was leachability of used in the heavy precipitation was metals experiments. through the found to vary greatly different elements. The leaching The action of between the rate of Ni in the control soil (similar to that of Mn) was considerably high. In the polluted soil, only V and Zn released more rapidly with the pH 4.2 acid rain. 4.2 the 10% residence time estimated from were At pH Tyler's experimental data varied from 3-yr (Mn) to 70 to 90-yr (Pb) in the control soil and from 2-yr (V) to 200-yr (Pb) in the polluted soil. Residence time for most elements in this study (except V and Cr) decreased with pH of the precipitation"16. Downloaded By: [University of Delaware] At: 18:09 10 July 2009 666 RECHCIGL AND SPARKS Reuss 4 6 came up with a simulation model that provides a quantitative system using established relationships from soil chemistry to predict the most likely effect of rainfall acidity on the leaching of cations from noncalcareous soils. The model utilizes: the relationships between lime potential (pH-Jjp Ca) and base saturation described by Clark and Hill 4 9 and by Turner and Clark 50 ; the equilibrium between C0 2 partial pressure and H and HC0 3 in solutions; the apparent solubility product of Al(0H) 3 ; the equilibrium of cations and anions in solution; the Langmuir isotherm description of S0 4 adsorption; and mass balance considerations to predict the distribution of ions between the solution and sorbed or exchangeable phases. The ionic composition of leachates in response to rainfall composition can thus be computed. The model predicts almost exact chemical equivalence between basic cations removed in the leachate and strong acid anions entering the system in the rainfall if pH-ijp Ca is above 3.0, at which point the base saturation will generally not exceed 20%. Soils with a significant capacity to adsorb S0 4 tend to dampen the effect of H 2 SO 4 induced leaching of basic cations. The leaching of bases will respond more slowly to acid inputs than on non-S0 4 adsorbing soils, but will reach a similar equilibrium rate of leaching as the S0 4 adsorption capacity reaches equilibrium with the rainfall S0 4 . Atmospheric inputs of H 2 SO 4 and HN0 3 to noncalcareous higher elevation watersheds in the Adirondack regions lead to comparatively higher concentrations of dissolved Al in the surface horizon and in the groundwater. This appears to result from Downloaded By: [University of Delaware] At: 18:09 10 July 2009 ACID RAIN ON SOIL ENVIRONMENT 667 increased soil Al leaching. Aluminum leaching is enhanced in well drained acid soils where there are significant inputs of organic acids from litter decay and canopy leaching. In the presence of organic ligands, the solubility of Al can be greatly enhanced by the formation of soluble organic-Al complexes. Aluminum and Fe are transported from upper to lower soil horizons by means of such soluble organometallic complexes. Such increased Al concentrations can lead to fish mortality. There may be indirect effects on P availability through increased inorganic precipitation of A1PO.,. Accelerated Al leaching may also have implications for soil forming processes, the health of plant communities, and alterations in the clay minerology of the soil 5 1 . On the positive side, Al has been found to neutralize strong acids from acid precipitation 52 . , Wiklander 21 has demonstrated that neutral salts in the precipitation reduce the acidification of soils by acid precipitation. The magnitude of the salt effect depends on the relative bonding energy of H 3 0 and of Ca, Mg, Na, K, NH 4 in the soil as well as concentrations of H 3 0 and the above cations in the precipitation. The salt effect may be considerable in very acid soils. It decreases with rising pH to become very small or negligible in neutral soils, chiefly due to the increasing bonding energy of H 3 0 in this direction. The adverse effect of acid precipitation, therefore, is likely to be less in very acid soils such as podzols than in slightly acid and neutral soils with low buffering capacity against pH change. 668 RECHCIGL AND SPARKS Effect of Acid Rain on Soil Microorgani sms In the past, enormous literature accumulated in soil microbiology on various changes which are brought about by the acidification of the use of fertilizers. soils, associated with Similar stresses induced by acid precipitation have renewed interest in this area. The subject has been recently reviewed by Alexander 53 . The studies in microbiological processes are Downloaded By: [University of Delaware] At: 18:09 10 July 2009 usually performed in a laboratory setting which makes it difficult to directly extrapolate the findings to the field. There are six major microbial groups residing in the soil fungi, ecosystem, algae, i.e., protozoa bacteria, and actinomycetes, viruses. The various species have been found in widely dissimilar soils, and only a few possess a distinct biogeographical characteristic. Microorganisms are involved in at least four key processes affecting the soil and plant productivity. First, they are essential for plant growth by affecting certain essential nutrients which would unavailable. otherwise be A case in point is N, P and S, which are normally found in combination with organic materials, a form of which Microorganisms is unavailable convert the to higher organic forms plants. to the inorganic state which is a vital step in maintaining plant growth. Microorganisms also play a key role in affecting the characteristic soil structure. This is, in part, due to the formation of humus and, in part, to the binding of soil particles as aggregates. The microfiora also perform a crucial role by preventing the excessive accumulation of organic matter ACID RAIN ON SOIL ENVIRONMENT with the likely 669 build-up of high concentrations of toxic chemicals. Finally, microflora are involved in the maintenance of environmental quality, particularly as it affects the soil ecosystem. Modernized society has introduced into soil a variety of toxic substances, be they synthetic chemicals or natural waste materials. The degradations of these materials is entirely Downloaded By: [University of Delaware] At: 18:09 10 July 2009 dependent on microbial action. It should be borne transformations population. in The soil in mind that most microbial may elimination involve more of one any than one population therefore does not necessarily have to be detrimental, since unaffected populations(s) may continue to carry out the chemical reactions in question. An example of this is the conversion of organic N to inorganic forms. However, there are a few processes which are known to be carried out only by a single microbial species. In a situation like that, elimination of the particular population would be detrimental. This is especially true about the nitrification process which converts NH 4 to N 0 3 , and the nodulation of bacteria are quite legumes specific, for which the depending on the leguminous host. As it autotrophic sensitive to turns out, nitrifying acidity. of the various microflora, are particularly bacteria Their activity falls rapidly with decreasing pH and is undetectable below pH 4.5 Limited nitrification that is observed may be the result of the action of in acid 54 . soils heterotrophic organisms. Soil acidification can also be expected to cause a general reduction in population of bacteria and 670 RECHCIGL AND SPARKS actinomycetes fungi. and an The increase decreased increase in the abundance of in fungi has been attributed to competition from other heterotrophic organisms at low p H 5 4 . Acidity is generally linked with decreased rates of humus decomposition, while liming will conversion of the humic compounds to CO 2 . promote However, in some instances, depending on the soil and the nature of Downloaded By: [University of Delaware] At: 18:09 10 July 2009 the organic materials, rapid degradation can be observed even at moderate or extreme acidities, such as pH 1.8 55 . Increasing acidity can also profoundly biological N fixation rates. the essential fixing prelude system to involving decrease The nodulation, which is the development legumes and of the In- Rhizobium, especially sensitive to acid conditions. is In the case of clover, nodulation is frequently absent at pH 5.2 or below 5 6 . The reduced numbers of root-nodule bacteria were also reported below pH 5.0 exists at present on the S7 . effect of No information acidity fixation in the roots of non-leguminous plants. case of free-living N fixers, a majority sensitive resistant to 58 low pH, although a few on N In the seem to be may be quite . Conversion of soil organic N to NH 4 , in contrast with nitrification, apparently does not show a marked pH sensitivity elevated NH« 54 . In fact, the acid soils may show levels in contrast to non-acid soils in which NO 3 is the dominant form of N. Denitrification, which converts NO 3 to N 2 and N 2 O, is also adversely affected by low pH. The number of bacteria which carry out this reaction was shown to be inversely correlated with acidity 59 . ACID RAIN ON SOIL ENVIRONMENT The decomposition important part ecosystems. of Many 671 of organic nutrient nutrients matter cycling taken up is in by an natural plants are returned to the soil through litter fall. The matter effect of artificial decomposition involved, has been rain process studied and by using the ecosystem approach. Downloaded By: [University of Delaware] At: 18:09 10 July 2009 litter were different isolated H ion and on on the the organic organisms Abrahamsen al.60, et Fungi from decomposing their growth concentrations. measured Soil animals at were extracted from soil samples taken from laboratory and field experiments, with applications of simulated acid rain and lime. In coniferous forests located on acid podzolic soils, the abundance of many soil invertebrate animals were found to increase under the more acidic conditions induced by the animals were simulated observed present reduced by liming. species of soil animals in availability available to animals species rain, whereas when soil a few acidity was The increased population of certain increase fungal acid may of due to have been fungus the outcompeting food more more due to an reserves acid-tolerant acid-sensitive bacteria for available food. Decomposition decomposition of studies plant showed remains influenced by acidification. that was the only initial slightly However, decomposition of raw humus material was pH dependent, and decreased with increased acidity. It should be noted that the effects observed were produced with much higher concentrations of H ions than normally found in precipitation, and as a consequence, cannot be applied directly to the acid rain problem. Long-term studies with more realistic 672 RECHCIGL AND SPARKS Downloaded By: [University of Delaware] At: 18:09 10 July 2009 inputs of H are necessary to assess acid rain effects under natural conditions. A case study of forest litter decomposition near the Ni smelter at Sudbury, Ontario was recently reported 51 . A series of field plots of various distance from the smelter were used to examine potential effects of heavy metal and S0 4 burdens. Decreasing inputs and accumulations of Cu, Ni, Fe and S were shown in organic soil horizons and vegetation along a 60 km SSE transect away from the smelter. There was; however, no effect on the pH of the precipitation or on the distance of the soil litter horizons from the smelter. Rates of litter-fall were determined to be unchanged as a function of distance from the smelter, but the litter standing crop was increased close to the source, implying an effect on litter decomposition. Lower rates of decomposition of leaves in litter bags occurred at contaminated sites, together with low rates of soil metabolic activity. These included soil C 0 2 flux and acid phosphatase acitivity. Lower populations of soil microfungi and microarthropods also occurred. In a laboratory experiment involving the addition of Cu and/or Ni to a litter homogenate, a depression of litter mineralization and C 0 2 flux was shown to occur at metal concentrations similar to those observed at contaminated sites in the field. Whereas the observed vegetation toxicity near the smelter was likely primarily an effect of S0 2 and of heavy metals in soils, and the effects on litter decomposition were primarily due to heavy metals, specifically Cu and Ni. Overall, the negative effects attributable to acid precipitation near the smelter appeared to be small, ACID RAIN ON SOIL ENVIRONMENT 673 Downloaded By: [University of Delaware] At: 18:09 10 July 2009 relative to the effects of S0 2 and heavy metal residue in soils. As was mentioned above, several nutrients in the soil are bound in organic form and thus unavailable to the plants. In the case of P, 15-85% is organic. An inhibition in the mineralization process would have serious repercussions on the plant productivity. 62 According to Halstead et a l . , there may be in fact a decrease in the microbial conversion of organic to inorganic forms of P in more acid environments; however, the data are too limited to make definite conclusions. There is also some evidence for slower conversion of organic S compounds in humus to products that can be assimilated by plants under comparable conditions 63 . SUMMARY Acid rain is a phenomenon of modern times. The first published reports on acid rain appeared in the mid-1950's. Since that time it has'become widespread occurring in all parts of the United States. While its effects on aquatic systems are fairly well documented, its effects on soils are still not fully understood. In this review we have discussed the sensitivity of soils to acid rain. Acid rain may bring about variable effects on soils, depending on the type and properties of the soil involved. These parameters include: the total buffering capacity or the total cation exchange capacity, the base saturation of the exchange complex, the management system imposed on the soil, viz., whether it is cultivated, fertilized, or renewed by flooding or other additions, and the 674 RECHCIGL AND SPARKS presence or absence of carbonates in the soil profile. Other topics discussed in our review include the soil acidification process, the effects of acid rain on soil exchange properties, and the effects of acid rain on soil microorganisms. 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