Chemistry of Soil Nutrient Cycle 89 Conservation District personnel as well as many commercial crop consultants are trained in the development of nutrient management plans. Software programs to develop your own nutrient management plan may be available from Cooperative Extension Service educators or Agronomy and Soil Science specialists at land grant universities. Figure 6, P Added in Manure/Removed by Crop Grazing Intensity Grazing intensity refers to the impact animals have on forage growth and reproduction and on soil and water quality. It is influenced by animal foraging habits, stocking rates, the length of time animals are allowed to graze within a given paddock, and the relation these factors have on soil characteristics and climatic conditions. Continuous high- intensity grazing depletes soil nutrients, decreases the diversity of forage species, inhibits the ability of some forage plants to regrow and reproduce, and increases the potential for nutrient runoff and erosion. Conversely, short-term high-intensity grazing combined with a resting period (as in rotational grazing practices) causes an increase int the diversity of forage species, enhances the dispersal of forage seeds, and helps conserve nutrient resources within the soil-plant system. Grazing behavior Grazing habits of different animal species have different impacts on forage species composition in pastures. For example, horses graze more closely to the ground than cattle; sheep graze at soil level and can take away the base of grass plants below the area of tiller emergence; while cattle tend to graze taller grasses that sheep may reject. Animal grazing behavior, the location of a plant’s growing point, and the amount of leaf area remaining when animals are rotated to another pasture affects the ability of plants to90 Soil Chemistry regrow. If grazing animals remove the growing point and substantial leaf area of grasses, new leaf growth must come from buds that have been dormant and the energy for this growth must come from stored carbohydrates rather than from photosynthesis. Early in the growing season, all grasses have their growing points at or near the ground level. Ryegrass, tall fescue, Kentucky bluegrass and many other species of cool- season grasses have growing, points that remain at or below ground level throughout most of the growing season. Other species of predominantly native grasses, including smooth broomgrass, timothy, reed canarygrass, switchgrass, and gamagrass have stems that elongate below the growing point above the soil level. As long as the growing point remains intact, the plant is capable of producing new leaves. Grasses with low growing points are able to recover from grazing relatively quickly because the growing point is not disturbed. If the growing point is removed, growth results from the emergence of new tillers, Under continuous, intensive grazing practices, warm-season grasses recover more slowly than cool-season grasses, especially during the spring. As a result, continuous grazing practices or grazing too early in the season tends to favor the growth of non-native grasses and decrease the diversity of forages in pastures. For areas with moderate rainfall, leaf area remaining after grazing is more critical for forage recovery than the location of a forage plant’s growing point. Most forbs and legumes, such as alfalfa and red clover, have aerial growing points relatively high up on the plant, which are easily removed by grazing animals. This is not detrimental to plant growth unless a majority of the leaf area or the basal portion of the plant is removed: For optimal recovery, at least 3-4 inches of residual leaf area should remain on cool- season grasses while 4-8 inches of leaf area should remain for warm-season grasses following grazing. Other factors that affect plant regrowth include treading impact on leaf and root growth, forage composition impact on the ability of plants to intercept sunlight for photosynthesis, and soil conditions. Nutrient uptake Forage plants that are cut or regrazed frequently during the growing season take up more nutrients than forages that are not cut or grazed, Research conducted in Kansas indicated that cutting pasture forage six times during the growing season resulted in 4.3 times greater nitrogen content and 5.2 times greater phosphorus content in cut forages compared to uncut ots. Cutting pastures in the spring when seed heads are forming can also increase the productivity and nutrient uptake of pasture forages. Other studies demonstrated that iricreased grazing intensity resulted in younger, more succulent plants with a higher nitrozen content compared to plants growing in ungrazed areas. The higher nitrogen conient was attributed to return of nitrogen to the system through urine and to the availabilii, of nitrogen fixed by legumes. In these studies legumes remained prevalent in the more ‘atensely grazed plots while their populations decreased in the more lightly grazed paddocks.Chemistry of Soil Nutrient Cycle a Yield During the first year of intensive grazing, increasing the intensity of cutting or grazing increases the amount of forage produced. Following grazing, photosynthesis is stimulated and plants take up more nutrients. This permits leaf regrowth in broadleaf plants. and increased tillering.in grasses. Increased leaf area then allows for greater photosynthesis. As photosynthesis and the formation of carbohydrates increases, nutrient uptake by roots and subsequent movement of nutrients from roots to leaves also increases, However, as more energy and nutrients are allocated to leaf production and increased photosynthesis, less energy and nutrients are provided for root growth. While frequently mowed or grazed plots exhibit high biomass production and nutrient uptake during the initial grazing season, if the intensity of grazing is too high, forage production will decrease in following years. This production decline is due to decreased plant ability to take up nutrients from the soil due to decreased root growth, as well as to a depletion of soil nutrients. Severe grazing will also affect plant diversity since grazing during flowering removes seed heads and flowers, limiting the reseeding of forage plants. Root growth is critical for water and nutrient uptake. Plants can also store food reserves in roots to allow for regrowth during periods of stress, Plants grazed too frequently or cut too short have difficulty producing, more leaves because of limited growth and food reserve storage by roots. In one study, plants that were not'cut until they reached 8 inches tall produced more growth than did plants cut every time they reached 2 inches tall. Similarly, grasses subjected to continuous intensive grazing by sheep produced less vegetation than lightly grazed pastures. In both cases, a longer resting period resulted in better plant growth, since the resting period allowed plants to regrow and produce adequate leaf area for photosynthesis. Grass tiller population and pasture production markedly increased in an extensively grazed pasture that was fallowed for one year. This resting period allowed plants and soil organisms to reduce soil compaction and increase the availability of nutrients through mineralisation. Cutting grasses short not only depresses plant regrowth, it also increases soil temperature. As soil temperature increases so does nutrient mineralisation by soil organisms. While mineralisation is necessary to release nutrients from plant and animal residues, if mineralisation is too rapid, it can cause a loss of organic matter. Grazing or cutting pastures too short can also expose bare soil to the impact of rainfall, increasing, the potential for soil compaction and the loss of topsoil and nutrients through erosion. Nutrient cycling and effective nutrient use by plants depend on pasture management practices that minimise soil compaction, conserve organic matter, and do not hinder plant regrowth following grazing. ‘The nutrient content of forage plants affects animal feeding habits, the amount of nutrition animals obtain, and the type of manure they produce. Succulent, nutritionally92 Soil Chemistry balanced pastures provide good animal productivity and cause animals to deposit moist manure piles, Animals feeding on dry, older, or overgrazed forages will obtain limited nutrient value. Manure piles produced from these forages will be stiff because of their high fiber content. Dry, stiff manure piles are difficult for soil organisms to decompose since there is little air within the pile. Conversely, animals often deposit very liquid manure as they begin feeding on pastures in the spring after a winter of eating hay. The high moisture content of the pasture forages results in a very wet manure pile that disperses across the soil. Soil organisms are able to decompose manure that has relatively high nitrogen and moisture content more readily than manure that is drier and more carbon-rich. Diversity of Pasture Plants Diverse forage mixtures of both broad-leaved plants and grasses use solar energy efficiently. The shape and orientation of plant leaves affects how and when the plant can best conduct photosynthesis. Tall plants and upright grasses capture light at the extreme angles of sunrise and sunset while horizontal leaves of broad-leaf plants use sunlight better at midday. A combination of tall, sun-loving plants with shorter shade-tolerant plants allows for the capture of both direct and filtered sunlight. A combination of warm- and cool-season grasses allows for effective photosynthesis throughout the growing season. Warm-season grasses like big bluestem are better able to grow and use solar energy at temperatures between 90 and 100 degrees F, while cool season grasses like tall. fescue grow best between 75 and 90 degrees F. Persistence of pasture legumes Maintaining legumes as part of the forage mix is necessary if nitrogen fixation is to provide most 6f the nitrogen input into the pasture system. Legumes with a deep taproot and a woody crown, such as alfalfa, red clover, and birdsfoot trefoil, are able to persist ina well-drained pasture because they are able to obtain water and nutrients from deep below the soil surface. They also tolerate drought and cold, and are able to regrow unless their growing points are elevated and exposed to defoliation. Rotational grazing has been shown to increase the proportion of red clover and alfalfa in mixed pastures. White clover has rhizomes rather than a taproot. This growth habit allows it to colonise bare soils by forming additional plants through the growth of stolons. White clover is competitive with grass at low production densities while legumes with taproots are more competitive at high production densities. The diversity of forage species also affects the persistence of legumes within a pasture. When six to eight forage species were planted together in a Missouri pasture, pasture plant diversity remained after three years of grazing. Pastures with a diversity of forage species also maintained a higher percentage of forage cover during this timeChemistry of Soil Nutrient Cycle 93 than did pastures planted to monocultures or simple mixtures of forages. Productivity within pastures is more stable when forages represent a diversity of function and structure, such as height, root growth habit, life cycle, and habitat requirements. Nitrogen fixation is directly related to the ability of legumes to accumulate energy through photosynthesis. Thus, leaf removal decreases nitrogen fixation and leaf regrowth increases the potential for nitrogen fixation. Legumes not only fix nitrogen for their own needs, but are also able to supply nitrogen to non-nitrogen-fixing forage crops. They primarily supply nitrogen to forage plants following decomposition. Pastures dominated by clover produce around 200 pounds nitrogen per acre per year through nitrogen fixation. Legumes can also provide nitrogen to companion grass species during the growing season. In New Zealand, perennial ryegrass obtained 6-12% of its nitrogen from associated white clover. Alfalfa and birdsfoot trefoil provided up to 75% of the nitrogen used by reed canarygrass in Minnesota. This nitrogen transfer occurs when roots die, nodules detach, or neighboring grasses and legumes become interconnected by their roots or through mycorrhizae. Nitrogen transfer between grasses and legumes is greatest when there is a close population balance between these species and they are growing, close together. In the first year of legume establishment, nitrogen transfer is relatively low and is derived predominantly from nodule decomposition; it increases in the second year as direct transfer mechanisms through mycorrhizae become established. ‘Nutrient use efficiency A diverse plant community uses soil nutrients more effectively than a monoculture or simple plant mixtures. Native grasses have a lower requirement for nitrogen and subsequently a lower concentration of nitrogen in their leaf tissue compared to non- native cool season grasses. Asa resullt, these grasses thrive under low nutrient conditions but they provide lower-quality feed and recycle nutrients more slowly back to the soil system. The low nitrogen content of the plant litter results in slow decomposition, immobilisation of nitrogen by organisms involved in decomposition, and a decrease in the nitrogen available for plant uptake. Broadleaf plants require higher nitrogen inputs for productive growth and have higher nitrogen content in their plant tissues than grasses. Due to their high nitrogen content, decomposition of residues from these plants stimulates the mineralisation or release of nutrients into the soil solution. Cool-season and warm-season forages grow and take up nutrients at different times of the year. A combination of cool- and warm- season forages ensures a relatively even uptake of nutrients throughout the growing season. Just as a diverse plant canopy covers the entire soil surface, a diversity of root systems occupies the entire soil profile from the soil surface to as far as 15 feet deep. Grasses4 Soil Chemistry generally have fine, bushy roots. Legumes such as alfalfa or red clover have taproots. Some plants have longer or deeper root systems while other plants have a root system that grows primarily in the surface soil. Pastures that contain plants with a diversity of root systems will be better able to harvest and use nutrients from the soil than a less- diverse community. Plants with more shallow roots are effective in recycling nutrients released through the decomposition of thatch and manure on the soil surface, while deep- rooted plants are able to scavenge nutrients that have been leached down through the soil profile. SOIL FOOD WEB Soil organisms play a critical role in nutrient cycling, Not only are they responsible for decomposing organic matter, formation of soil aggregates, solubilising mineral nutrients, and adjusting soil pH; they are also responsible for nitrogen fixation, nitrification, phosphorus uptake through mychorrizae, degradation of soil minerals, and formation of plant hormones. A healthy soil contains millions of organisms, ranging from visible insects and earthworms to microscopic bacteria and fungi. An acre of living soil may contain 900 pounds of earthworms, 2,400 pounds of fungi, 1,500 pounds of bacteria, 133 pounds of protozoa, and 890 pounds of arthropods and algae, as well as small mammals. The term soil food web-refers to the network of dynamic interactions among these organisms as they decompose organic materials and transform nutrients. While some of the organisms in this diverse community are plant pests, many more serve as antagonists of plant pests and diseases. Other soil organisms,” particularly bacteria, are able to use toxic chemicals, such as pesticides, as a source of food. As they consume these toxic chemicals, they break them down into substances, such as carbon dioxide, water, and atmospheric nitrogen, that are either not toxic or are less-toxic to plants, animals, and humans. * Predatory mites Myo EF s Soil ‘ungus-feeding® nat > FS sro renee residues” ay gtlagellates TH cots Bacteria-feeding: nematodes Figure 7. Foodweb of Grassland SoilChemistry of Soil Nutrient Cycle 95 Organic Matter Decomposition Soil organisms Many soil organisms are involved in the decomposition of organic matter. Larger soil organisms, including small mammals, insects, and earthworms, are primary decomposers, involved in the initial decomposition and cycling of nutrients. Primary decomposers make greater use of carbon than of nitrogen, in their growth and respiration processes. As a result, the feces and casts deposited by them have a lower carbon content and a lower ratio of carbon to nitrogen than the original organic matter. By transforming, organic matter into a simpler chemical form as well as physically breaking it down into smaller pieces, primary decomposers make these materials more available to microorganisms or secondary decomposers for further breakdown. In addition, the dead bodies of earthworms and insects are high in nitrogen and easily decomposed by soil microorganisms. Fungi and bacteria are predominant secondary decomposers, however algae, protozoa, amoebae, actinomycetes, and nematodes also play important roles in transforming soil nutrients. The chemistry of organic materials and environmental conditions determines how rapidly organic matter is broken down, which soil organisms are involved in the decomposition process, and whether organic matter decomposition will cause an initial decrease or increase in available nutrients. The soil environment determines which soil organisms are dominant and which soil organisms are less active. Some bacterial species thrive under flooded, anaerobic conditions but most soil organisms require access to oxygen. Earthworms and some soil insects require soil that is aggregated and relatively uncompacted so they can burrow through it. Environments with limited nitrogen availability are dominated by organisms that are able to fix nitrogen from the atmosphere, such as algae, lichens, and rhizobia associated with legumes. Many soil organisms are killed by non-specific insecticides as well as by highly concentrated fertilisers such as anhydrous ammonia, Organic materials that are old or woody, such as tree branches, old roots, or dried grass, contain a large amount of carbon compared to nitrogen. To decompose these materials, soil organisms may need to extract nitrogen from the soil solution in order to balance their carbon-rich diet, thus temporarily reducing the amount of nitrogen available for plant use. Young, succulent, “first-growth” plant materials, fresh manure, and materials that have gone through primary decomposition processes by larger soil organisms contain a higher concentration of nitrogen in relation to carbon. Soil organisms more readily decompose these materials and make nutrients in them available for plant uptake. The type of organic matter being decomposed will also affect the type of soil organisms involved in the decomposition process. As each decomposer feeds, it uses96 Soil Chemistry some nutrients for its own growth and reproduction and releases other nutrients into the soil solution where they are available for plant growth and production. Decomposer organisms may also excrete organic materials that can either be further broken down by other soil organisms or become part of the soil humus. In general, bacteria require more nitrogen in order to break down organic matter than do most fungi. Fungi are the dominant decomposer in forest environments since they require less nitrogen in their diet and are able to feed on woody, older, or more fibrous materials. They are also able to survive and replicate in environments that are less moist than those required by bacteria. Bacteria are more prevalent in garden and pasture environments because they require higher amounts of nitrogen, more moisture, and feed readily on fresh manure, young grasses, legumes and other easy-to-decompose materials. Primary Decomposers Earthworms are primary decomposers of leaf litter and manure piles. Research conducted in Denmark showed that earthworms were responsible for 50% of the breakdown and disappearance of cow manure, while dung beetle larvae accounted for between 14 and 20%. These organisms also consume fresh organic materials, then deposit their feces in the soil. When they burrow, they move manure and other organic materials into the soil, where it is more accessible to other organisms involved in decomposition. Burrowing organisms also aerate the soil. Good aeration promotes the growth of the majority of organisms involved in organic matter decomposition. For this reason, earthworms and dung beetles are visible indicators of soil health: their presence shows that nutrient decomposition processes are occurring and the soil food web is effectively operating. Earthworms According to research studies, the weight of earthworms in the soil is directly related to pasture productivity. In healthy soils with abundant earthworms, these organisms consume between 65-80 tons of manure per acre per year. Earthworms also break down pasture thatch and incorporate organic matter from the thatch into the soil. Where few orno earthworms are present, pastures develop a thick thatch layer, slow rates of organic matter decomposition, and a poor crumb structure. Decomposition of organic matter by earthworms speeds up the breakdown and release of plant nutrients, particularly nitrogen and phosphorus. Earthworms consume low-nitrogen plant materials as well as high-nitrogen manure. Under pasture conditions, earthworms have been shown to mineralise 10 pounds/acre/year of phosphorus in their casts. Earthworms also facilitate the transformation of straw and leaf litter into soil humus. The earthworm gut combines decomposed organic matter with particles of mineral soil and microorganisms, forming soil aggregates and humus-coated soil minerals.Chemistry of Soil Nutrient Cycle 7 Through their feeding and burrowing activities, earthworms move organic matter through the soil, enhancing soil aeration, water infiltration, and soil structure. They also improve root growth by creating channels lined with nutrients and help till the soil. They can completely mix the top six inches of a humid grassland soil in 10 to 20 years. Factors that contribute to an abundant population of earthworms include inputs of fresh organic matter, a medium-textured-soil, thick topsoil, a near-neutral pH, moist but well-aerated soils, and moderate’ temperatures. Tillage, acid-producing fertilisers, insecticides, and poorly-drained soils inhibit earthworm survival. Dung beetles Dung beetles improve nutrient cycling, enhance soil aeration, and improve forage growth while feeding on manure and using it to provide housing and food for their young. Adult dung beetles are drawn to manure by odor. They use the liquid contents for nourishment and the roughage to form a brood ball in which the female lays a single egg. This brood ball is buried in the soil where the larva grows, eating about 40 to 50% of the interior contents of the ball while depositing its own excrement. After the larva emerges, secondary decomposers readily break down the remaining dung ball. An adequate population and mix of dung beetle species can remove a complete dung, pile from the soil surface within 24 hours. This process decreases the potential for ammonia volatilisation and nutrient runoff while making manure nutrients available to secondary decomposers within the soil profile. While moving dung into the soil, dung beetles create tunnels that enhance soil aeration and water infiltration. Dung removal also increases forage availability, since it minimises the amount of forages that animals would avoid if dung were present. Environmental conditions that enhance activities of dung beetles include adequate soil moisture levels and warm temperatures. Dung beetle larvae are susceptible to some insecticides used for fly and internal parasite control for cattle. Both injectable and pour- on formulations of Ivermectin, applied to cattle at the recommended dosages, reduced survival of the larvae for 1-3 weeks. However, when administered as a bolus, effects on dung beetle populations lasted up to 20 weeks. Secondary Decomposers Soil organisms are responsible not only for the mineralisation and release of nutrients from organic material; they are also important for retaining nutrients in the soil, improving soil structure through the formation of aggregates and humus, degrading toxic substances, and suppressing diseases. Nutrients held in the bodies of soil organisms gradually become available for plant uptake and meanwhile they are protected against being lost through leaching, runoff, or other processes. Soil organisms involved in98 Soil Chemistry nutrient cycling release nutrients as they defecate and die. While they are still alive, these organisms conserve nutrients within their bodies. Bacteria and fungi Bacteria and fungi are the most prevalent soil organisms. Bacterial decomposers feed on root exudates as well as on plant litter and manure. Maintaining actively growing soil roots provides a nutrient rich habitat for the growth of many bacterial species. Some species of bacteria are able to detoxify pollutants while other species, particularly rhizobia and bluegreen algae, are able to fix nitrogen. Bacterial gels are an important component of soil aggregates. Fungi decompose complex or more carbon-rich forms of organic matter. They also form soil aggregates by binding them with fungal threads or hyphae. Mycorrhizal fungi enhance nutrient and water uptake by plants by extending the length and surface area of root uptake. In dry rangelands, crusts composed of green algae, bluegreen algae, lichens, fungi, and bacteria form over the soil surface. These crusts provide surface cover, erosion control, and soil aggregation. They are also involved in nitrogen fixation and nutrient decomposition. Crust organisms are most active during the cooler, moister part of the year when plant cover is minimal. Amoebas, nematodes, and protozoa Amoebas, nematodes, and protozoa feed on bacteria and fungi. Protozoa feeding on bacteria stimulate their growth and aggregate forming activities. Nematodes may consume up to 25% of the bacteria in the soil. According to one study, nematodes feeding on bacteria accelerated litter decomposition by 23%. Both protozoa and nematodes release nutrients to the soil system, making them available to plants and other soil organisms. Mutualistic relationships In undisturbed ecosystems, plants and soil organisms have co-evolved to form mutualistic relationships. Plants provide carbohydrates and other nutrient-rich substances through their root system, providing an excellent source of food for soil organisms. As a result, populations of soil organisms involved in nutrient decomposition are greatest next to plant roots. These organisms provide plants with nutrients necessary for their growth, produce hormones and other chemicals that improve plant vigor, and protect the plant against diseases. When the need of plants for nutrients is low, soil organisms will hold nutrients in their bodies rather than release them into the soil solution. This mutualistic relationship is disturbed during plowing, cultivation, and harvesting. When plant roots are removed, populations of soil organisms decrease since they no longer have'a source of nourishment and habitat.Chemistry of Soil Nutrient Cycle 9 Soil Organisms and Soil Health Soil health refers to the ability of soils to function as a productive environment for plant growth, an effective filter, and an efficient regulator of water flow. Soil mineralogy and chemistry form the basis for soil composition and soil health. However, much of soil health and function depends on an active community of diverse soil organisms. Nutrient cycling, aggregate formation, degradation of toxins, creation of soil pores, and absorption of water and nutrients are all functions of soil organisms. The activities of soil organisms serve as effective indicators of current land productivity and its ability to withstand degradation. By monitoring these indicators, farmers, soil conservationists, and other land managers can implement appropriate practices to minimise soil or nutrient losses, enhance nutrient cycling, and increase plant productivity. The Soil Quality Institute has taken the lead in developing and promoting, the use of soil health indicators. Qualitative, “farm-based” and “farmer friendly” indicators are incorporated into soil health cards specific to location and farming practice. These cards can be used to monitor the relative health and productivity of soils, identify areas of concern, and enhance awareness of the relationships between soil health and crop production. Below is a soil health card for pastures based on a compilation of indicators from soil health cards developed in various locations. Soil Organisms Bacteria—the most numerous microorganism in the soil. Every gram of soil contains/at least a million of these tiny one-celled organisms. Decompose simple or nitrogen-rich organic matter. Require moist environments. Also responsible for nitrogen fixation, soil aggregate formation, and detoxification of pollutants. Actinomycetes —thread-like bacteria, which look like fungi. They are decomposers and responsible for that sweet, earthy smell of biologically active soil. Fungi—multicelluar microorganisms that usually have a thread-like structure. Mycorrhizae form extensions on roots, increasing their ability to take up nutrients and water. They also transport nitrogen from legumes to grasses. Yeasts, slime molds, and mushrooms are other species of fungi. ~ Algae—microorganisms that are able to make their own food through photosynthesis. They often appear as a greenish film on the soil surface following a rainfall. Protozoa— free-living animals that craw! or swim in the water between soil particles. Many soil protozoa species are predatory and eat other microorganisms. By feeding on bacteria they stimulate growth and multiplication of bacteria and the formation of gels that produce soil aggregates. Nematodes—small, wormlike organisms that are abundant in most soils. Most nematodes help decompose organic matter. Some nematodes are predators on plant-100 Soil Chemistry disease-causing fungi. A few species of nematodes form parasitic galls on plant roots or stems, causing plant diseases. Earthworms—multi-cellular organisms that decompose and move organic matter through the soil. Earthworms thrive where there is little or no tillage, especially in the spring and fall, which are their most active periods. They prefer a near-neutral pH, moist soil conditions, an abundance of plant residues, and low light conditions. Other species of soil organisms—Many other organisms, including dung beetles, sowbugs, millipedes, centipedes, mites, slugs, snails, springtails, ants, and birds, facilitate nutrient cycling. They make residues more available to smaller organisms by breaking them down physically and chemically and by burying them in the soil. PASTURE MANAGEMENT AND WATER QUALITY Effective nutrient cycling and judicious applications of fertilisers and manure enhance plant growth. However, if nutrients are applied at the wrong time or in excess of what plants can use, they increase the potential contamination of nearby rivers and lakes. Similarly, grazing practices can degrade water quality if grazing intensity is too great, if paddocks are used when the soil is too wet, or if the duration of rest periods is too short. Long-term intensive grazing practices can negatively affect water quality, especially when combined with heavy fertilisation with either mineral or manure nutrients. Likely impacts include contamination of groundwater with nitrates and contamination of surface water with phosphate, sediments, and pathogens. Risk Factors for Nutrient Losses Nutrient loss pathways If more manure or fertiliser nutrients are applied to pastures than are used in the growth of forage crops, excess nutrients will either accumulate in the soil or be lost through leaching, runoff, or erosion. Nutrient accumulation occurs when minerals in the soil have the ability to bind or hold particular nutrients. Sandy or silty soils or soils with a near- neutral pH do not bind phosphorus well. When more phosphorus is applied to these soils than is used for plant growth, the excess phosphorus can be easily dissolved and carried away by runoff water to lakes and streams. Both acid clay soils and soils with a high calcium carbonate content have a strong ability to bind large amounts of phosphorus. If only moderate excesses of phosphorus are applied to these soils or if excess phosphorus is applied to the soil only occasionally, these soils will be able to bind the excess phosphorus and hold it against leaching. However, if phosphorus fertilisers or manure are continuously applied at high rates, phosphorus levels will eventually build up in the soil to the extent that soils will no longer be able to hold onto the additional phosphorus and these excesses will be susceptible to loss through runoff. High levelsChemistry of Soil Nutrient Cycle 101 of phosphorus in surface water cause eutrophication or algae blooms. When sources of drinking water have significant algae growth, chlorine in the water treatment process reacts with compounds in the algae to produce substances that can increase cancer risks. Unlike phosphorus, nitrogen does not readily bind to soil minerals or organic matter. Asa result, it easily leaches through the soil, especially if high rainfall follows manure or nitrogen fertiliser applications and the soil is sandy or gravelly. High levels of nitrate in ground water used for drinking can cause health problems for human babies and immature animals. Management practices that minimise the potential for nitrogen leaching include not applying excess levels of nitrogen and avoiding manure or nitrogen fertiliser applications during times when plants are not actively growing, Erosion occurs when water or wind moves soil particles, resulting in the loss of topsoil and of the nutrients, toxins, nd pathogens attached to these particles. Erosion by water can also transport surface-apptied manure into lakes, rivers, and streams. Water quality concerns associated with evosiv: include siltation, fish kills, eutrophication, and degraded quality for recreational and drinking water uses. Nutrient balances Water contamination problems associated with farming are becoming, an increasing societal and political concern. The Federal Clean Water Act mandates states to minimise non-point source pollution or pollution associated with runoff and erosion, much of this originating from agricultural lands. Currently, water quality regulations ate primarily focused on larger farms that have a high concentration of animals and use high inputs of purchased feeds. Societal concerns about farming operations are increasing, as increasing numbers of non-farm families move into rural areas and urban growth decreases the distance between farm and non-farm community members. On farms that have a high numbers of animals, a limited land area, and high use of feeds that are not grown on the farm, nutrient imbalances exist. This is because the amount of nutrients that accumulate in the animal manure is greater than the needs of all crops being grown on the farm. Maintaining a balance between the amount of nutrients added to the soil as manure and fertiliser and the amount of nutrients removed as forages, hay, crops, or livestock is critical for productive crop growth and water quality protection. If more nutrients are removed than are returned to the system, crop production will decline. If more nutrients are added than can be used for productive crop growth, nutrients will build up in the soil, creating, a high risk for leaching, runoff, and water contamination. While large farms are primarily being targeted by environmental regulations, these farms are not the only livestock operations at risk for contaminating water quality. Often, smaller livestock farms pose more risk than larger operations. For instance, on smaller dairy farms the barn is commonly located near a stream because it was built prior to102 Soil Chemistry rural electrification and the ability to pump water from wells or streams to watering troughs. On various small livestock operations. animals have access to paddocks located near a well head or over highly permeabie soils because land area is limited. Riparian areas are less likely to be protected by fencing or buffer areas. On farms without adequate manure storage facilities, manure is often applied to poorly drained or frozen fields during the winter, resulting in a high potential for surface water contamination. In addition, on smaller farms, necessary equipment or labor is often not available to properly apply manure according to a nutrient management plan. Careful management of animal grazing and manure handling practices are critical on all farms in order to protect water resources. Pathogens Pathogens in manure Although not directly related to nutrient cycling, pathogens are a critical water quality concern associated with manure management. Animal grazing or manure applications can contaminate water bodies not only with excess nutrients but also through parasites in feces. Parasites of greatest concern are E. coli, Giardia, and Cryptosporidium. E. coli is of most concern to rural residents dependent on well water and of limited concern to public water users since this parasite is killed by municipal water purification and treatment processes. Typically, this parasite causes mild to moderate gastrointestinal problems. However, new strains of E. coli have killed people who are very young, very old, or have weakened immune systems. Giardia and Cryptospordium are pathogens with a dormant stage that is very resistant to purification treatment. Almost all municipal water treatment facilities are required to use secondary filtration processes that remove these resistant forms from the water supply. Most private wells, however, do not the capability of filtering, out these pathogens. Like the virulent strain of E. coli, Giardia and Cryptospordium cause gastrointestinal problems that can be fatal for people with weak or undeveloped immune systems. Minimising the risk of pathogen movement into water bodies involves ensuring that animals, especially young calves, are not exposed to or kept in conditions that make them susceptible to these diseases. Any manure that potentially contains pathogens should either be completely composted before being land applied or applied to land far from streams and at low risk of erosion or runoff. Pasture management practices to reduce risks of pathogen contamination Manure or fertilisers should be applied when the nutrients in these materials can be most effectively used for plant growth and production, and never to ground that is snow- covered, frozen, or saturated. Under such wet or frozen conditions, manure or fertiliserChemistry of Soil Nutrient Cycle 103 nutrients are not bound by soil particles. Instead, these nutrients are lying, unbound on the soil surface where they have a high potential to be carried away by runoff into lakes or streams, Pathogens in manure applied to frozen or snow-covered soil will not be in contact with other soil organisms. In addition, most predatory soil organisms will be in a dormant state and unable to decrease pathogen numbers before snowmelts or heavy rainfalls cause runoff. Areas that need to be protected from contamination by nutrients and parasites in animal feces include well heads, depressions at the base of hills, drainage ways, rivers, streams, and lakes. Well heads and water bodies need protection because they serve as drinking and recreational water sources, while foot slopes and drainage ways have a high potential for nutrient runoff and transport of contaminants to water bodies. Nitrate Contamination Nitrate is not held by soil particles and is easily leached, especially through porous soils, such as sandy soils or soils with cracks or fissures that allow for rapid movement of excess nitrogen through the soil profile. Where excess nitrogen is not applied, nitrate leaching in pastures is minimal. High nitrate leaching losses were observed, however, when orchard grass pastures in Pennsylvania were fertilised with 200 pounds/acre of nitrogen as ammonium nitrate. These researchers also calculated that a stocking rate for Holstein dairy cows of 200 animal days would result in nitrate‘leaching from urine in excess of drinking water standards. In pastures where nitrogen was provided by nitrogen-fixing legumes, nitrate leaching was minimal when environmental conditions were normal. But high nitrate leaching was observed when a severe drought followed good growing conditions, causing legume nodules to die and release nitrogen into the soil. Nitrate concentrations greater than 10 ppm in well water may cause nitrate toxicity or methemoglobinemia. This ailment which affects infant children as well as young chickens and pigs, and both infant and adult sheep, cattle, and horses, increases nitrate concentration in the bloodstream and prevents the uptake and use of oxygen, thus causing suffocation. Pregnant animals that are affected may recover then abort within a few days. Personnel associated with local health departments can test wells to determine nitrate concentrations. Phosphorus Contamination ‘ Phosphorus can be transported from fields or pastures into lakes or streams either as a component of erosion or within runoff water. Phosphorus that is dissolved in runoff water has a greater effect on water quality than phosphorus that is attached to soil particles transported to water bodies by erosion. This is because the dissolved phosphorus is more available for use by algae and other aquatic organisms that cause eutrophication, noxious greening of water bodies, and fish kills. Phosphorus associatedane Soil Chemistry with soil particles tends to settle to the lake or river bottom where it remains biologically stable or only slowly available for use by aquatic organisms. Dissolved phosphorus In pastures, sources of dissolved phosphorus include manure or phosphorus fertilisers lying on the soil surface, and wet soils that have a high phosphorus concentration. Runoff water can readily dissolve soluble phosphorus in manure or phosphorus fertilisers. When the amount of phosphorus in soil exceeds the ability of soil particles to bind onto it, the excess phosphorus can readily be dissolved and transported by runoff water, especially when soils are saturated. Dissolved phosphorus has the greatest potential for being transported from pastures into waterbodies when rainfall is heavy, when high levels of phosphorus are present either on the surface of the soil or within the soil, and when pastures are located within 350 feet of waterbodies. Increasing forage diversity generally decreases runoff potential. Care should be taken to combine species, such as bunchgrasses, that enhance water infiltration but expose the soil surface between clumps, with closer-growing species such as tall fescue or prostrate species such as white clover. A combination of native forages and low-growing, shade- tolerant plants could allow for both enhanced water infiltration and cattle production. Setting up paddocks on the contour can also allow downslope paddocks that are regenerating following grazing to serve as buffer strips for upslope paddocks that are currently being grazed. Potential runoff from manure can also be reduced by applying it to alternate paddocks set up as contour strips. Phosphorus associated with erosion Soil-attached phosphorus can be transported to water bodies by erosion. Low-level sheet erosion contributes more phosphorus than higher-impact rill or gully erosion. This is because sheet erosion primarily transports nutrient-enriched topsoil, manure, and plant residues while gully erosion transports more nutrient-poor subsoil. As with runoff, the amount of phosphorus transported by erosion is greatest during intense rainfalls or snowmelts. Pasture soils that are completely covered by vegetation are protected against the forces of erosion. Erosion occurs primarily when soils are bare and land is sloping. Impact of phosphorus contamination on water quality The impact of phosphorus runoff on stream or lake water quality is greatest during summer and fall. While spring rains or snowmelts may transport a greater total amount of phosphorus, the large amount of water in the runoff dilutes the phosphorus so that it is in a relatively low concentration when it reaches water bodies. In contrast, intense rains falling on soils and pastures during the summer are likely to run off rather than soaking into dry, hard soils. When intense rains fall on pastures with surface-appliedChemistry of Soil Nutrient Cycle 105 manure or phosphorus fertilisers, runoff water will carry a high concentration of dissolved phosphorus into streams. If these streams have relatively low water flows, the runoff water will create a high concentration of phosphorus in streams, which then causes algae and other nuisance plants to grow. The type of phosphorus fertiliser used influences the potential risk of water contamination. Highly soluble fertilisers such as superphosphate present a greater short-term potential for phosphorus loss since it is easily dissolved and transported. In the long term, however, less- soluble fertilisers, such as dicalcium phosphate, may pose a greater risk. This is because less- soluble fertiliser remains on the soil surface and available for dissolution and runoff for a longer time. Impacts on water quality from sediment-attached phosphorus fertiliser have been observed to persist for up to six months. Runoff risks can be substantially decreased if fertilisers are incorporated into soil and applied according to a nutrient management plan. Phosphorus index The phosphorus index was developed to address federal and state water quality guidelines while recognising that phosphorus movement is influenced by local environmental conditions and land management practices. Each state is developing its ‘own phosphorus index to ensure that it is appropriate to local conditions. Each phosphorus index contains a component related to phosphorus sources, soil test phosphorus, manure phosphorus, and fertiliser phosphorus. Soil test. phosphorus accounts for the plant available or soluble phosphorus in the soil, derived either from the mineral base of the soil or from decomposing organic matter. The potential for manure or fertiliser phosphorus to be lost through runoff depends on the amount applied, how it was applied, and when it was applied. Manure and fertiliser that is incorporated into the soil at rates required for crop growth during or just prior to the time of crop production poses minimal risk to water quality. Conversely, surfa applying excess amounts of manure or fertiliser when crops are not actively growing or when the soil is saturated, frozen, or snow-covered will pose high risks for phosphorus run off. However, a high concentration of phosphorus in the soil or applied to the soil will not pose a risk to water quality unless there is a means of transporting this phosphorus to water bodies. Methods for transporting phosphorus from farm fields to water bodies include erosion, runoff, and flooding. Locations that have a high source of phosphorus and a high risk of transport are critical source areas or locations where management practices need to carefully consider risks of phosphorus losses. ‘Subsurface Drainage Artificial subsurface drainage makes normally wet soils drier, and decreases the wet period for seasonally wet soils, by allowing more water to seep into the soil profile. Subsurface drainage has been shown to decrease water runoff by 72% and total phosphorus losses due to runoff by 50%.106 Soil Chemistry Contaminant transport through drains Unfortunately, the advantage that subsurface drainage provides in decreasing runoff potential may be overshadowed by the ability of drainage systems to directly transport nutrients from fields to waterways. Most subsurface drainage systems were installed primarily for production reasons: to allow farmers to work their fields earlier in the year and to minimise plant stunting and disease problems associated with saturated soils. Since many of these systems were installed before agricultural impacts on water quality became a societal concern, agricultural drains often empty directly into streams and rivers.Because artificial drainage makes fields drier, farmers can drive tractors or other equipment onto these fields earlier in the year. Farmers who have a full manure-storage system to empty, or who have time constraints for spreading manure in advance of planting, may be tempted to apply manure and fertilisers to these fields during times when the soil would be wet if it was not drained. Farmers with a limited land base may want to graze these fields when the weather is wet. However, to protect water quality, these fields should be managed as though artificial drainage had not been installed. Nutrients in fertilisers or manure can leach through the soil to drainage pipes. If artificially drained fields are used for nutrient applications or grazing while water is flowing out of drainage outlets, drainage water can carry these leached nutrients directly to streams or rivers. To minimise the potential for water contamination, land that is artificially drained should not be grazed or have fertiliser or manure applied during times when drainage water is flowing from the field or just prior to a rainstorm. Alternatively, contaminated water flowing out of tile drains should not be allowed to empty directly into rivers or streams. Instead, it should be directed to a grassed filter or buffer area or treated in a wetlands area where biological and chemical processes lower contaminant levels through sedimentation and absorption. REFERENCES Alexander, 1977, Soil Microbiology, 2nd Ed., Wiley Interscience. Bohn, McNeal, and O'Connor, 1985, Soil Chemisiry, 2nd Ed, Wiley Interscience. Bolt and Bruggenwert, 1976, Soil Chemistry. A. Basic Elements, Elsevier. Cresser, Killham, and Edwards, 1993, Soil Chemistry and its applications, Cambridge.4 Soil pH Soil pH is a measure of the soil acidity or Soil alkalinity. An acid solution has a pH value less than 7. While a basic solution always has a pH larger than 7, an alkaline solution does not necessarily have a pH larger than 7. For details on the relation between pH and ANC, see acid neutralising capacity. Soil pH is an important consideration for farmers and gardeners for several reasons: — Many plants and soil life forms prefer either alkaline or acidic conditions — Some diseases tend to thrive when the soil is alkaline or acidic — The pH can affect the availability of nutrients in the soil. The majority of food crops prefer a neutral or slightly acidic soil (pH 7). Some plants however prefer more acidic or alkaline conditions. Once the cation exchange surface has become depleted of these ions, however, the concentration in soil solution can be quite low and is largely determined by the weathering rate. The weathering rate in turn is dependent on such things as mineralogy, surface area, soil moisture, pH, concentration of base cations such as Ca, Mg and K as well as concentration of aluminium. The amount of plant available nutrients is a much more difficult issue than soil solution concentrations. Itis thus important to realise that there exists no simple relation between soil solution concentration of Ca, Mg and K and reasonable pH-values. The reason for this is that Ca, Mg and K are base cations, i.e. cations of strong bases, and strong bases are fully dissociated at the pH-ranges occurring in most natural waters. However, as the soil solution pH is dependent on mineral weathering, and mineral weathering increases pH by releasing Ca, Mg and K, a soil which is rich in easily weatherable minerals tends to have both a higher pH and higher soil solution concentration of Ca, Mg and K. On the other hand deposition of sulfate, nitrate and to some extent ammonia decrease pH of soil solution essentially without affecting Ca, Mg and K concentrations whereas108 Soil Chemistry deposition of sea salt increases Ca, Mg and K concentrations without having much of an effect on soil solution pH. When interpreting soil solution pH values it is essential to take into account the method by which pH has been measured. Depending on whether or not the water has been equilibrated with ambient CO, pressure or not the pH reported from the same site may be either high or low. This is simply because the carbon dioxide pressure deep down in the soil might be 10-20 times higher than the ambient pressure due to decomposition of organic material. The higher carbon dioxide pressure result in more carbonic acid and hence a lower pH. Furthermore, soil solution can be extracted from the soil in many ways, e.g. by lysimeters, zero-tension lysimeters, centrifugation, extraction with CaCl, overhead shaking of soil sample with added water, etc. The CaCl, extraction method do not give the actual soil solution pH but rather a mix between soil solution pH and what is easily available e.g. through cation exchange. Also when mixing soil samples with water and using overhead shakers the result is a mix between actual soil solution and cation exchange, although the hope is that the extracted water will be similar to the actual soil solution in most respects. If centrifugation or pressurised lysimeters are used, care must be taken that the extracted water do not include water that is not readily available. Naturally, taking a sample introduces a disturbance of the system, which can e.g. result in a change in nutrient uptake and decomposition rates. Many nutrient cations such as zinc (Zn*"), aluminium (AF*), iron (Fe), copper (Cu), cobalt (Co), and manganese (Mn*) are soluble and available for uptake by plants below pH 5.0, although their availability can be excessive and thus toxic in more, acidic conditions. In more alkaline conditions they are less available, and symptoms of nutrient deficiency may result, including thin plant stems, yellowing (chlorosis) or mottling of eaves, and slow or stunted growth. pH levels also affect the complex interactions among soil chemicals. Phosphorus (P) for example requires a pH between 6.0 and 7.5 and becomes chemically immobile outside this range, forming insoluble compounds with iron (Fe) and aluminium (Al) in acid soils and with calcium (Ca) in calcareous soils. ACIDIC SOIL To understand how acid soils are formed, take a simple walk through a woodland. Rainfall filters through trees and into the ground, where it dissolves limestone sediment and other alkaline minerals that help neutralise soil acidity. The woodland floor is carpeted in needles of conifers, leaves of hardwood trees, and other dead plant matter, most of which increase soil acidity as they decompose. Unless this woodland is on top of a huge deposit of alkaline material such as limestone or serpentine, the soil will tend to be acidic.Soil pH 109 Soils and Acidity Under conditions in which rainfall exceeds evapotranspiration (leaching) during most of the year, the basic soil cations (Ca, Mg, K) are gradually depleted and replaced wi cations held in colloidal soil reserves, leading to soil acidity. Clay soils often contain iron and aluminium hydroxides, which affect the retention and availability of fertiliser cations and anions in acidic soils. Soil acidification may also occur by addition of hydrogen, due to decomposition of organic matter, acid-forming fertilisers, and exchange of basic cations for H’ by the roots. Soil acidity is reduced by volatilisation and denitrification of nitrogen. Under flooded conditions, the soil pH value increases. In addition, the following nitrate fertilisers — calcium nitrate, magnesium nitrate, potassium nitrate and sodium nitrate — also increase the soil pH value. Some alkaline soils have calcium in the form of limestone that is not chemically available to plants. In this case sulfuric acid Factors affecting soil pH The pH value of a soil is influenced by the kinds of parent materials from which the soil was formed. Soils developed from basic rocks generally have higher pH values than those formed from acid rocks. Rainfall also affects soil pH. Water passing through the soil leaches basic nutrients such as calcium and magnesium from the soil. They are replaced by acidic elements such as aluminium and iron. For this reason, soils formed under high rainfall conditions are more acidic than those formed under arid (dry) conditions. Soil Life and pH A pH level of around 6.3-68 is also the optimum range preferred by most soil bacteria, although fungi, molds, and anaerobic bacteria have a broader tolerance and tend to multiply at lower pH values. Therefore, more acidic soils tend to be susceptible to souring and putrefaction, rather than undergoing the sweet decay processes associated with the decay of organic matter, which immeasurably benefit the soil. These processes also prefer near-neutral conditions. pH and Plant Diseases Many plant diseases are caused or exacerbated by extremes of pH, sometimes because this makes essential nutrients unavailable to crops or because the soil itself is unhealthy. For example, chlorosis of leaf vegetables and potato scab occur in overly alkaline conditions, and acidic soils can cause clubroot in brassicas.10 Soil Chemistry Determining pH ‘A map of the pH level is a mosaic, varying according to soil crumb structure, on the surface of colloids, and at microsites. The pH also exhibits vertical gradients, tending to be more acidic in surface mulches and alkaline where evaporation, wormeasts, and capillary action draw bases up to the soil surface. It also varies on a macro level depending on factors such as slope, rocks, and vegetation type. Therefore the pH should be measured regularly and at various points within the land in question.dd c Methods of determining pH include: — Observation of soil profile. Strongly acidic soils often have poor incorporation of the organic surface layer with the underlying mineral layer. The mineral horizons are distinctively layered in many cases, with a pale eluvial (E) horizon beneath the organic surface; this E is underlain by a darker B horizon in a classic podzol horizon sequence. This is a very rough gauge of acidity as there is no correlation between thickne’ss of the E and soil pH. E horizons a few feet thick in Florida usually have pH just above 5 while E horizons a few inches thick in New England are “extremely acid” with pH readings of 4.5 or below. In the southern Blue Ridge Mountains there are “ultra acid” soils, pH below 3.5, which have no E horizon. — Observation of predominant flora. Calcifuge plants include Erica, Rhododendron and nearly all other Ericaceae species, many Betula (birch), Digitalis (foxgloves), gorse, and Scots Pine. Calcicole (lime loving) plants include Fraxinus (Ash), Honeysuckle (Lonicera), Buddleia, Cornus spp (dogwoods), Lilac(Syringa) and Clematis spp. — Observation of symptoms that might indicate acidic or alkaline conditions, such as occurrence of the plant diseases mentioned above or salinisation of alkaline soils. The house hydrangea (Hydrangea macrophylla) produces pink flowers at pH values of 6.8 or higher, and blue flowers at pH 6.0 or below. —_ Use of an inexpensive pH testing kit based on barium sulfate in powdered form, where in a small sample of soil is mixed with water which changes colour according, to the acidity/alkalinity. —_ Use of litmus paper. A small sample of soil is mixed with distilled water, into which a strip of litmus paper is inserted. If the soil is acidic the paper turns red, if alkaline, blue. — Use of a commercially available electronic pH meter, in which a rod is inserted into moistened soil and measures the concentration of hydrogen ions. Increasing soil pH The aim when attempting to adjust soil acidity is not so much to neutralise the pH as to replace lost cation nutrients, particularly calcium. This can be achieved by adding limestone to the soil, which is available in various forms:Soil pH m — Agricultural lime (ground limestone or chalk) is used for soil liming. These natural forms of calcium carbonate are probably the cheapest form of lime for gardening and agricultural use and can be applied at any time of the year. These forms are slow reacting, thus their effect on soil fertility and plant growth is steady and long lasting. Ground lime should be applied to clay and heavy soils at a rate of about 500 to 1,000 g/m? (1 to 2 Ib/yd? or 4,500 to 9,000 Ib/ac). The concept of “corrected lime potential” to define the degree of base saturation in soils became the basis for procedures now used in soil testing laboratories to determine the “lime requirement” of soils. — Quicktime and slaked lime: The former is produced by burning rock limestone in kilns. It is highly caustic and cannot be applied directly to the soil. Quicklime reacts with water to produce slaked, or hydrated, lime, thus quicklime is spread around agricultural land in heaps to absorb rain and atmospheric moisture and form slaked lime, which is then spread on the soil. Quicklime should be applied to heavy clays at a rate of about 400 to 500 g/m? (0.75 to 1 Ib/yd? or 3,600 to 4,500 Ib/ac), hydrated lime at 250 to 500 g/m? (0.5 to 1 Ib/yd2). However, quicklime and hydrated lime are very fast acting and are not suitable for inclusion in an organic system. Their use is prohibited under the standards of both The Soil Association and the Henry Doubleday Research Association. — Calcium sulfate (gypsum) cannot be used to amend soil acidity. It is a common myth that gypsum affects soil acidity. However, gypsum does reduce aluminium toxicity. Because gypsum is more soluble than alkaline earth carbonates, it is recommended for the treatment of acidic subsoils. Reducing soil pH — The pH of an alkaline soil is lowered by adding sulfur, iron sulfates or aluminium sulfate, although these tend_to be expensive, and the effects short term. — Urea, urea phosphate, ammonium nitrate, ammonium phosphates, ammonium sulfate and monopotassium phosphate also lower soil pH. — Fertilisers often also effect a slightly more acidic soil since this increases uptake of nutrients. — Decayed vegetable matter, compost, stable manure, urea, ete. ALKALI SOILS Alkali, or alkaline, soils are clay soils with high pH (> 9), a poor soil structure and a low infiltration capacity. Often they have a hard calcareous layer at 0.5 to 1 m. depth (in India this layer is called 'kankar’). Alkali soils owe their unfavorable physico-chemical properties mainly to the dominating presence of sodium carbonate. They derive their name from the alkali metal group of elements to which the sodium belongs and that can induce basicity. Sometimes these soils are also referred to as (alkaline) sodic soils.2 Soil Chemistry Causes The causes of soil alkalinity are natural or they can be man-made. — The natural cause is the presence soil minerals producing sodium carbonate (Na,CO,) upon weathering. — The man-made cause is the application of irrigation water (surface or ground water) containing, a relatively high proportion of sodium bicarbonates. The extent of alkaline soils is not precisely known. Alkaline soils are difficult to take into agricultural production. Due to the low infiltration capacity, rain water stagnates on the soil easily and, in dry periods, irrigation is hardly possible. Agriculture is limited to crops tolerant to surface waterlogging (e.g, ice, grasses) and the productivity is low. Soil alkalinity is associated with the presence of sodium carbonates or (soda) (Na,CO,) in the soil, either as a result of natu-ral weathering of the soil particles or brought in by irrigation and/or flood water. The sodium carbonate, when dissolved in water, dissociates into 2Na* (two sodium cations, ie. ions with a positive electric charge) and CO,= (a carbonate anion, i.e. an ion with a double negative electric charge). The sodium-carbonate can react with water to produce carbon dioxide (CO,), escaping as a gas, and sodium hydroxide (NatOH), which is alkaline (or rather basic) and gives high pH values (pH>9). Water (H,O) is partly dissociated into H’ (hydrogen) and OH: (hydroxyl) ions. In pure, neutral water, the concentration of H’ and OH ions equals 10-0.7 eq/l each (respectively 10-7 g/l and 17x10-7 g/l), a very small concentration. The pH, being the negative log value of the H*concen-tration in eq/|, is 7. Similarly, the pOH is also 7. Each unit decrease in pH indicates a tenfold increase of the H' concentration. Similarly, each unit increase in pH indicates a tenfold increase of the OH‘ concentration.In water with dissolved salts, the concentrations of the H* and OH: ions may change, but the sum of pH and pOH remains equal to 14. Water with excess H’ ions is called acid (pH < 6), and water with excess OH ions is called alkaline or rather basic (pH > 8). Soil moisture with pH < 4 is called very acid and with pH > 10 very alkaline (basic). The reaction between Na,CO, and H+O can represented as follows: 2Na‘ + CO, - + 2H*+ 20H -» 2Na’+ 20H «+ HCO, The acid H,CO, is unstable and produces H,O (water) and CO, (carbon dioxide gas,Soil pH 3 escaping into the atmosphere). This explains the remaining alkalinity (or rather basicity) in the form of soluble sodium hydroxide and the high pH or low pOH. Not all sodium carbonate follows the above chemical reac-tion. The remaining, sodium carbonate, and hence the presence of CO.= ions, causes CaCO, (which is only slightly soluble) to precipitate as solid calcium carbonate (lime-stone). Hence, the calcium ions Ca** are immobilized: 2Na*+ CO, = + Ca > 2Na’ + CaCO, (solid) soil moisture ==] Ma"* ma" --[ ca ca”? a] ee nat fo cet PS sees aay etsttees tect | ees panicle c 2 particle =| Nae Nat cots rae me ae difuse adsorption zone Exchange of adsorbed Ca and dissolved Na* ‘The ESP increases Figure 1. Sodium exchange process ‘The presence of abundant Na’ ions in the soil solution and the precipitation of Ca**ions as a solid mineral causes the clay particles, which have negative elec-tric charges along their surfaces, to adsorb more Na‘ in the diffuse adsorption zone and, in exchange, release Ca’*, by which their exchangeable sodium percentage (ESP) is increased. Natis more mobile and has a smaller electric charge than Ca** so that the thickness of the DAZ increases as more sodium is present. The thickness is also influenced by the total concentration of ions in the soil moisture in the sense that higher concentrations cause the DAZ zone to shrink. Clay particles with considerable ESP (> 16), in contact with non-saline soil moisture have an expanded DAZ zone and the soil swells (dispersion). The phenomenon results in deteriora-tion of the soil structure, and especial-ly crust formation and compaction of the top layer. Hence the infiltration capacity of the soil and the water availa-bility in the soil is reduced, whereas the sur-face-water-logging or runoff is increased. Seedling emergence and crop production are badly affected.4 Soil Chemistry Under saline conditions, the many ions in the soil solution counteract the swelling of the soil, so that saline soils usually do not have unfavorable physical properties. Alkaline soils, in principle, are not not saline since the alkalin-ity problem is worse as the salinity is less. Alkalin-ity problems are more pronounced in clay soils than in loamy, silty or sandy soils. The clay soils containing montmorillonite or smectite (swelling clays) are more subject to alkalinity problems than illite or kaolinite clay soils. The reason is that the former types of clay have lar-ger specific surface areas (i.e. the surface area of the soil particles divided by their volume) and higher cation exchange capacity (CEC). Certain clay minerals with 100% ESP (i.e. fully sodium saturated) are called bentonite, which is used in civil engi-neer-ing to place impermeable curtains in the soil, e.g. below dams, to prevent seepage of water. Solutions Alkaline soils with solid CaCO, can be reclaimed with grass cul-tures, ensuring the incorporation of much acidifying organic material into the soil, and leaching of the excess sodium. Deep plowing and incorporating the calcareous subsoil into the top soil also helps.It is also possible to reclaim alkaline soils by adding acidifying minerals like pyrite. Alternatively, gypsum (calcium sulfate, CaSO, 2,0) can also be applied as a source of Ca**ions to replace the sodium at the exchange complex. There must be enough natural drainage to the underground, or else an artificial subsurface drainage system must be present, to permit leaching of the excess sodium by percolation of rain and/or irrigation water through the soil profile. To reclaim the soils completely one needs prohibitively high doses of amendments. Most efforts are therefore directed to improving the top layer only (say the first 10 cm of the soils), as the top layer is most sensitive to deterioration of the soil structure. The treatments, however, need to be repeated in a few (say 5) years time.[t will be important to refrain from irrigation with poor quality water. Saline soils are mostly also sodic (the predominant salt is sodium chloride), but they do not have a very high pH nor a poor infiltration rate. Upon leaching they are usually not converted into a (sodic) alkali soil as the Na’ ions are easily removed. Therefore, saline (sodic) soils mostly do not need gypsum applications for their reclamation. MEASURING ACIDITY AND ALKALINITY The term pH stands for the potential (p) of the hydrogen ion (H+) in water. It is actually a way of reporting the concentration of H+ in solution using, an electrical “potential” to measure H+. The pH of any solution is one of the easiest laboratory measurements to make using a pH meter and an electrode specifically designed to measure hydrogen (pHSoil pH us electrode). Color indicators and litmus paper are a quick alternative for less precise measurements. By mixing a quantity of soil with demineralized or distilled water (usually a 1:1 mixture), we can measure the pH of the water solution in equilibrium with the soil The pH measurement is based on a scale from 1 to 14 (pH is reported as the negative logarithm of the hydrogen ion activity), At a pH of 7.0, there is an equal balance of hydrogen (H+) ions and hydoxyl (OH-) ions, and the soil (actually the soil-water suspension) is said to be neutral. Because the pH measurement is logarithmic, each unit change in pH represents a ten-fold increase in the amount of acidity or basicity. That is, a soil solution with a pH of 6.0 has 10 times as much active H+ as one with a pH of 70. pH of solution Hydrogen ion activity (g/liter) 9.0 (very alkaline). 10-9 (0.000000001) 8.0 (alkaline oF basic) 108 (0.000001) 7.0 (neutral, pure water) 10-7 (0.000001) 6.0 (slightly acid) 10-6 (0.000001) 5.0 (very acid) 10-5 (0.00001) 4.0 (extremely acid) 10-4 (0.0001) ‘Most Southeastern soils have a pH ranging from 4 to 8. With the exception of some native vegetation (e.g. pine trees) and a few acid-loving plants such as azaleas, blueberries, gardenias, and centipede grass, most plants do best in a slightly acid soil with a pH between 6.0 and 7.0. —_— > ot dt tt toes camelin cobacc, pine trees sudbértieiyidibveas. caraentas. nyarangeas ACID SOIL INFERTILITY When the pH falls below 6.0, the availability of nutrients such as phosphorus, potassium, calcium, and magnesium decreases. The availability of the metallic micronutrients, however, like zinc, manganese, copper, and iron increases as the pH decreases.116 Soil Chemistry Plants don’t need aluminum to grow. It's not an essential plant nutrient. Aluminum, however, is one of the prominent mineral components of silt and clay. Therefore, the earth’s crust is naturally high in aluminum. Like zinc, manganese , copper and iron, the more acid the soil, the more aluminum will be dissolved into the soil solution. If the pH is allowed to drop much below 5.5, the availability of manganese and alurhinum is increased to the point that they could become toxic to plants. Aluminum toxicity to plants is the main concern we have with acid soils in our region. Table 1. Problems in acid and alkaline soils Problems in very acid soils Problems in alkaline soils “Aluminum toxicity to plant roots “Iron deficiency "Manganese toxicity to plants “Manganese deficiency *Calcium & magnesium deficiency “Zine deficiencies “Molybdenum deficiency in legumes “excess salts (in some soils) *P tied up by Fe and Al °P tied up by Ca and Mg poor bacterial growth “bacterial diseases in potatoes ‘reduced nitrogen transformations Some plants such as alfalfa, spinach, and lettuce require high levels of calcium and potassium and can tolerate high salt levels that may occur in near neutral to alkaline soils. White potatoes will do well in near neutral to slightly acid soils but are usually grown in more acid soils (pH less than 6.0) because of “scab”, a bacterial disease. As already noted, bacteria don’t thrive in very acid soils. FACTORS AFFECTING SOIL PH Soils are not homogenous and the pH can vary considerably from one spot in the field to another. It also varies with depth. Soils in different geographic regions, as already mentioned, may have different pH’s because of the five soil forming factors: (1) parent material, (2) climate, (3) living organisms, (4) topography, and (5) time. Parent material. Soils of the Piedmont and Sandstone Plateau regions of Alabama are very acid because of the acid nature of the rocks (granites and sandstones, respectively) which formed these soils. Limestone valley soils were formed from basic rocks (limestones) but may be acid on the surface because of time and weathering, Some Black Belt Prairie soils may be alkaline because the Selma chalk (soft limestone) which formed the soils is alkaline. Rainfall/leaching. Rainfall also affects soil pH. Water passing through the soil leaches basic cations such as calcium (Ca”), magnesium (Mg), and potassium (K’) into drainage water. These basic cations are replaced by acidic cations such as aluminum (AP*) andSoil pH 7 hydrogen (H'). For this reason, soils formed under high rainfall conditions are more acid than those formed under arid conditions. Fertilizers. Both chemical and organic fertilizers may eventually make the soil more acid. Hydrogen is added in the form of ammonia-based fertilizers (NH,;) , urea-based fertilizers [CO(NH,),], and as proteins (amino acids) in organic fertilizers. Transformations of these sources of N into nitrate (NO, releases H+ to create soil acidity. Therefore, fertilization with fertilizers containing ammonium or even adding large quantities of organic matter to a soil will ultimately increase the soil acidity and lower the pH. NH,’ + 20, — bacteria » NO*+ 2H* + H,O Plant uptake. Plants take up basic cations such as K*, Ca++, and Mg++. When these are removed from the soil, they are replaced with H+ in order to maintain electrical neutrality. RAISING SOIL PH (LIMING ACID SOILS) Soils are limed to reduce the harmful effects of low pH (aluminum or manganese toxicity) and to add calcium and magnesium to the soil. The amount of lime needed to achieve a certain pH depends on (1) the pH of the soil and (2) the buffering, capacity of the soil. The buffering capacity is related to the cation exchange capacity (CEC). The higher the CEC, the more exchangeable acidity (hydrogen and aluminum) is held by the soil colloids. As with CEC, buffering capacity increases with the amounts of clay and organic matter in the soil. Soils with a high buffering capacity require larger amounts of lime to increase the pH than soils with a lower buffering, capacity. Most soil testing laboratories use a special buffered solution to measure the exchangeable acidity. This is the form of soil acidity that must be neutralized for a change in soil pH. By calibrating pH changes in the buffered solution with known amounts of acid, the amount of lime required to bring the soil to a particular pH can be determined. Lime reduces soil acidity (increases pH) by changing some of the hydrogen ions into water and carbon dioxide (CO,). A Ca" ion from the lime replaces two H+ ions on the cation exchange complex. The carbonate (CO,) reacts with water to form bicarbonate (HCO,). These react with H+ to form H,O and CO,, The pH increases because the H+ concentration has been reduced. H+ Soil Colloid + CaCO, -> Soil Colloid-Ca"* + H,O + CO, Ht Remember, the reverse of the above process can also occur. An acid soil can become more18 Soil Chemistry acid as basic cations such as Ca, Mg", and K° are removed, usually by crop uptake or leaching, and replaced by H’. LIMING OF SOIL Liming is the application of calcium and magnesium rich materials to soil in various forms, including marl, chalk, limestone, or hydrated lime. This neutralises soil acidity and increases activity of soil bacteria. However, oversupply may result in harm to plant life. Lime is a basic chemical, the effect of it makes the soil more basic thus making acidic soils neutral. The degree to which a given amount of lime per unit of soil volume will increase soil pH depends on the cation exchange capacity (CEC). Soils with low CEC will show a more marked pH increase than soils with high CEC. But the low-CEC soils will witness more rapid leaching of the added bases, and so will see a quicker return to original acidity unless additional liming is done. Over-liming is most likely to occur on soil which has low CEC, such as sand which deficient in buffering agents such as organic matter and clay.Most acid soils are saturated with aluminium rather than hydrogen ions. The acidity of the soil is therefore a result of hydrolysis of aluminium. This concept of “corrected lime potential” to define the degree of base saturation in soils became the basis for procedures now used in soil testing laboratories to determine the “lime requirement” of soils. An agricultural study at the Faculty of Forestry in Freising, Germany that compared tree stocks 2 and 20 years after liming found that liming promotes nitrate leaching and decreases the phosphorus content of some leaves. Liming Materials The most common liming materials are calcitic or dolomitic agricultural limestone. These are natural products made by finely grinding natural limestone. Since natural limestone is relatively insoluble in water, agricultural limestone must be very finely ground so it can be thoroughly mixed with the soil and allowed to react with the soil’s acidity. Calcitic limestone is mostly calcium carbonate (CaCO,). Dolomitic limestone, according to most state laws, must have at least 6 percent magnesium, and is made from rocks containing a mixture of calcium and magnesium carbonates. Either will neutralize soil acidity. Because high quality, finely ground limestone is very dusty and difficult to spread, some companies market a “prilled” or “granular” limestone for home use. A small amount of clay or a polymer is added to the ground limestone so small prills are formed instead of dust. This makes it easier to spread by hand or with a garden fertilizer spreader. Once applied, soil moisture will cause the “prills” or “granules” to dissociate and disperse the limestone particles. The limestone can then react with exchangeable acidity in the following, manner.Soil pH 9 nt ca** + (time) water) (Carbon CY Dioxige » Application and Placement of Lime Time of year. Lime may be applied at any time during the year. For the farmer or gardener, winter or early spring just prior to soil preparation is usually most convenient. Don’t apply caustic liming materials such as burned lime, hydrated lime, or wood ashes to actively growing plants. Ground limestone will not harm plants. Lime placement. The most important consideration is lime placement. Ground agricultural limestone is relatively insoluble in water so maximum contact with the soil is necessary to neutralize the soil acidity. Lime will not move into the soil like water- soluble fertilizers. Thoroughly mix the recommended amount of lime with the top 6 to 8 inches of soil. As soon as moisture is present, the lime will begin to react. Coarse lime particles react more slowly than very fine particles. Therefore, using very finely ground limestone and thoroughly mixing it are necessary to achieve the desired soil pH change within a few months. If the soil will be turned with a bottom plow, turn it first and then apply the lime and mix. Effectiveness of Surface Liming In 1985 a study was initiated at Penn State to look at the effects of surface application of lime ona very acid, long-term no-till soil. Since 1977 this field had been in no-till corn production with no limestone applied. The initial pH of “plow layer” was 5.1 and the surface 2 inch pH was 4.5. The limestone recommendation, based on the SMP buffer pH and a target pH of 6.5, was 6000 Ib calcium carbonate equivalent (CCE) per acre. The study included four limestone rates (0, 3000, 6000, 9000 Ib CCE/A) and liming programs ranging from applying lime every year to once every five years. Each year the soil was sampled in the spring in 2 inch increments to a depth of 6 inches. No-till corn was grown from 1985 to 1991, no-till soybeans were grown in 1992 and 1993, oats was grown in 1994 and wheat in 1995 and corn in 1996, 1997 and 1998. Soil pH results from soil samples taken in the spring of each year from 1985 through 1994 for selected liming programs are given in Figures 2 and 3. The soil pH results for the 6000 Ib/A, every third year liming program are shown in Figure 2. This treatment was chosen for illustration because this would be the recommended limestone rate based ona plow depth soil sample and this frequency of liming is fairly common in many areas. The pH results in Figure 3 are from the every year, 3000 Ib/A liming program. The every120 Soil Chemistry year program is of interest because there has been speculation that more frequent smaller applications of limestone may be necessary in no-till. Several observations can be made based on these results. First, it is clear that the recommended limestone application changed the soil pH in the surface 2 inches within the first year after application. Soil pH measurements taken within the first year indicated that most of the pH change in the surface layer occurred within the first two months after spring liming. This rapid increase at the surface was expected since this was a high quality finely ground limestone with 90% passing a 100 mesh sieve. Although the 0 to 2 inch layer was not subdivided for routine pH determination, spot checks of pH in this layer indicated that most of the pH change was in the surface 1/2 inch, However, there was little change in the soil pH below the surface 2 inches until about the fourth year of the study following subsequent limestone applications. Even after 9 years the soil pH in the 2 to 6 inch layers has not yet reached the target pH of 6.5 that was achieved rather quickly in the surface layer. There is little apparent difference between the standard, every third year liming program, and the more frequent every year liming program. 33 Bos }--0-2") 2 5. 0 |s—2-4"| fe a pauline io sTerretce cer ‘Tune (months) Figure 2, Soil pH vs time for a no-till soil limed at 6000 Ib/A every third year Lamentone pie very yer @ 2000 1h 0 12 24 36 48 60 72 84 96 108 ‘Tune (months) Figure 3. Soil pH vs time for a no-till soil limed at 6000 Ib/A initially and then every year since 1987 at 3000 Ib/A.