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IV. Mining and Corrosion Problems

IV. Mining and Corrosion Problems

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GENESIS AND MANAGEMENT OF ACID SULFATE SOILS



A.



29 1



POLLUTION



Mines and their spoil often contain large quantities of pyrites, which oxidize on exposure to the air and render the spoil almost sterile to plant

growth, thus adding to the danger and ugliness of the heaps; water draining

from spoil tips and mines may be so acid that whole watersheds are polluted. Temple and Koehler (1954) give a comprehensive account of the

problems in bituminous coal mining areas of the United States. Not all

areas are affected, but those that are produce sulfuric acid in such large

amounts that pumps, pipes, and concrete structures are corroded. Brayley

(1954) estimated that the bituminous coal fields of western Pennsylvania

produced about one million tons of sulfuric acid per annum, all of which

found its way into the Ohio River and its tributaries. Acid mine water

comes from the large tips of overburden or unsalable coal; in these oxidation may be stopped by suitable consolidation. A second source is the roofs

of disused mines, which gradually disintegrate, continuously exposing pyrite-bearing formations to oxidation; these can supply acid mine water for

at least 50 years after abandonment. Indeed where the mines drain by

gravity, crumbling mine roofs may provide acid drainage water almost indefinitely, and abandoned shaft and strip mines have been reported by

Martin and Hill (1968) to contribute over 60% of the acid pollution in

coal mining areas of the United States.

The problem may be less spectacular in other regions, but it exists in

many mining areas; Doubleday (1969) stated that the area of derelict land

in Great Britain exceeds 40,000 ha, much of it from coal mining. Such

areas have been increasing yearly and there is now strong pressure to reclaim these, mainly for recreational uses.

James (1966) describes similar problems in the slime tips of South

Africa’s goldfields. Much of this material is quartzitic, and very low pH

values (1.5) can be caused by quite small amounts of pyrite. Strip mining

in Denmark has covered several thousand hectares with sand, gravel, and

pyrite-bearing clay. According to Petersen et al. (1968), some of these

tippings have remained bare of vegetation for 50 years; in these the pH

of the soil is 2.3.

The problems of reclamation vary greatly, and several factors are involved. Thus Doubleday (1971 ) showed that the maximum acidity (pH

2.5) develops in some tips at a depth of about 20 cm; this is the maximum

depth of drying out, and depends on the rainfall and the exposure; southfacing slopes dry out more deeply. Wind and water erosion may expose

fresh material, and loose tipping allows aeration to considerable depths.

Deep aeration leads to formation of sulfates which appear in spring

lines on the sides or base of the tip, giving zones of high toxicity. Regrad-



292



C. BLOOMFIELD AND J. K. COULTER



ing to provide level or gentle slopes may also expose new zones of

pyrite.



B. CORROSION

Corrosion from acid sulfate waters is a common problem in mining;

the corrosion of concrete in acid sulfate soils has been described by van

Holst and Westerveld (1973); sulfate corroded the surface of concrete

piles, giving soft and porous surfaces. Similar conditions are likely to arise

with the engineering structures of irrigation projects in acid sulfate soils

in the tropics. The solution is probably the use of sulfate-resistant blastfurnace cement, or bituminous coatings on concrete.

V.



Classification and Mapping



A.



CLASSIFICATION



It has long been recognized that there are considerable variations in the

agricultural potential of acid sulfate soils, but until recently attempts at their

classification have been based largely on the amount of sulfide sulfur or

the acidity that develops on drying. Generally pH values of air-dry material

below 4.0, commonly about 3.5 have been taken as the values below which

soils may be regarded as acid sulfate soils.

Recently the importance of these soils have been recognized in classification studies (Soil Taxonomy, 1970), and a distinction has been made

between horizons that have already developed acidity i.e., acid sulfate soils,

and those that have the potential to do so, i.e., potential acid sulfate soils.

A sulfuric horizon is defined as “a mineral or organic horizon with a pH

lower than 3.5 (1 : 1 in water) and with yellow jarosite mottles with hues

2.5 or yellower and chromas 6 or more in the Munsell notation.” Sulfidic

materials are defined as waterlogged mineral or organic soil materials that

have 0.75% (on a dry weight basis) or more total sulfur, mostly in the

form of sulfides, and less than three times 2s much carbonates (CaC03

equivalent) as sulfur.

Another international definition is that in the legend of the Soil Map

of the World (Dudal, 1968) where a thionic unit is defined as one containing sufficient sulfur compounds to cause acidification of the soil, when oxidized, to a pH (in KCl) of less than 3.5,within 100 cm of the surface.

The term “pseudo-acid sulfate soil” occurs in the literature; although

no definitive terms have been given, it seems to refer to a soil containing

jarosite, but with a pH in water above 4.0, a good structure, and insufficient acidity in the form of exchangeable aluminum to prevent good crop

growth.



GENESIS AND MANAGEMENT OF ACID SULFATE SOILS



293



In the classification proposed in “Soil Taxonomy,” the great soil group

of sulfaquepts has been introduced. This comprises strongly acid soils with

a sulfuric horizon with yellow jarosite mottles and a pH (1 : 1 in water)

less than 3.5 in some part of the top 50 cm of the profile; where the acidic

horizon is between 50 and 150 cm in depth, sulfic subgroups of other

aquepts are distinguished. These would be regarded as buried cat clays.

Thus many of the acid sulfate soils of the tropics would be classified as

Typic Sulfuquepts or SuZfic Tropuquepts (van der Kevie, 1973). In the

temperate areas they would be mainly Typic Sulfaquepts and SuZfic

Haplaquepts.

Acid sulfate soils may be buried by layers of peat or muck, in which

case they may be Histic Sulfuquepts or Histic Sulfic Tropaquepts. Sulfohemists are organic soils with a sulfuric horizon within 50 cm of the surface. Potential acid sulfate soils, i.e., those with sulfidic horizons, are classified as Typic Sulfaquents if the pH (1 :1 water) of the dried soil is less

than 3.5 in the upper part of the profile. Potential acid sulfate soils that

are dominantly organic are classified as Sulfihemists. Very soft, unripened,

swamp soils that gave a pH upon drying below 4.5 in the upper 25 cm

or more may be classified as Sulfic Hydraquents. Sulfic Tropaquents and

Sulfic Fluvuquents are similar soils but with some profile development. Van

der Kevie (1973) drew attention to sulfidic soils that may be saline under

natural conditions and suggested hulk subgroups for these. Similarly some

of the sulfuquepts may also be saline where they occur in swamps, subject

to very infrequent flooding with saline water, but with a strong dry season

leading to oxidation of sulfides.

Table I, from van der Kevie (1973), summarizes the properties and

main classes as they are placed in the Soil Survey of the U.S.(Soil Taxonomy) and in the legend of the Soil Map of the World.



B. MAPPING

Potential acid sulfate areas are swampy and usually difficult of access

and often covered in heavy vegetation, either mangrove or other swamptolerant trees, or extremely tough tall grasses in the tropics, and reeds in

temperate areas. Apart from drying the samples and determining the acidity,

or other laboratory methods, including microscopic examination, there are

no completely positive ways of identifying these soils, or at least of determining how acid they will become on drainage. Several morphological features are indicative; soft muds with buried organic matter, particularly if

the remnants can be identified as halophytic, dark gray rather than greenish

gray colors, yellow mottles of jarosite in spoil from ditches, etc., are all

useful indicators. As discussed in Section 11, D, physiographic relationships



TABLE I

International Classifications of Acid Sulfate Soilsa

Climatic zone



World wide



Soil Taxonomy



Typic Sulfaquenta



Main characteristics=



Potmh'al acid sulfatc soils

pH (1: 1 water) of dried soil

<3.5 within 50 cm if n

1.0: within SO cm if



Worldwide



Sulfic Hydraquents



World Soil Map



Thionic fluvisols



>



n < 0.7

pH (1: 1 water) of dried soil Thionic fluvisols

<4.5 in upper 45 cm, or

more acid-between 50 and

100 cm; n > 0.7 between

80 and 50 cm

Gleyic solonchaka



Dystric fluvisols



Wet tropics and monsoon



Sulfic Tropaquents*



Temperate

Worldwide



Sulfic Fluvaquents

Typic Sulfihemists



Acidity requirements of

sulfic hydraquents, but

n < 0.7 between 80 and

50 cm

Same as Sulfic Tropaquents

Sulfidic materials within

100 cm; pH (1: 1 water)

of dried soil <5.5



Thionic fluvisols,

gleyic solonchaks,

dystric fluvisols



Thionic fluviSols



t

d



W



P



Main characteristics



pH (KCl) of dried soil <5.5

within 100 cm



Some t h a t are less acid than

sulfaquents but sufficiently

acid t o be included in

Sulfic Hydraquents;

nonsaline

Salic horizon and saline at

some time of the year; part

that meets acidity requirements for Sulfic Hydraquents but not for Thionic

Fluvisols

Not sufficiently acid for Thionic Fluvisols but meets

requirements for Sulfic

Hydraquents; nonsaline

As above



As above



hU

4

?



8

s



Worldwide



Typic Sulfihemists



Worldwide



Typic Sulfaquepts



Wet tropics and monsoon



Sulfic Tropaquepts



Acid sulfate soils

pH ( 1 : l water) <3.5 within

50 cm

pH (1:1 water) <3.5 within

50 cm

pH ( 1 : l water) <4.0 between 50 and 150 cm

and/or 3.5 to 4.0 within

50 cm



Thionic fluvisols



As above



Thionic fluvisols



As above



Thionic fluvisols

Humic gleysols

Dystric gleysols



As above

pH(KC1) 2 3.5; umbric or

0 horizon

pH(KC1) 2 3.5; ochric A



Wet tropics



Histic Sulfic Tropaquepts



Acidity as in Sulfic Tropaquepts; Histic epipedon



Thionic fluvisols

Humic gleysols



Monsoon and semiarid



Vertic Sulfic Tropaquepts



Acidity as in Sulfic Tropaquepts; cracks (1 cm)

a t 50 cm when dry



Thionic fluvisols

Humic gleysols

Dystric gleysols



Acidity as in Sulfic

Tropaquepts; Umbric or

Histic epipedon

Acidity as in Sulfic

Tropaquepts; Ochric

epipedon

Acidity as in Sulfic Tropaquepts; sodium saturation > 15 in half or more

of upper 50 cm; mostly

saline in some part of t h e

year



Thionic fluvisols

Humic gleysols



Humid temperate



Sulfic Humaqueptsb



Temperate



Sulfic Haplaquepts



Monsoon and semiarid



a



Sulfic Halaqueptsb



From van der Kevie (1973).



a Tentative subgroups suggested by van der Kevie (1973).

I value: an estimate of the degree of ripening (development).



Thionic fluvisols

Dystric gleysols

Thionic fluvisols

Gleyic solonchaks



horizon

As above

Umbric or 0 horizon

pH(KC1) 2 3.5; 0 horizon

As above

pH(KC1) 2 3.5; umbric or

0 horizon

pH(KC1) 2 3.5;ochric A

horizon

As above

pH(KC1) 2 3.5;umbric or



0 horizon

As above

pH(KC1) 2 3.5; ochric A

horizon

As above

pH(KC1) 2 3.5;salic horizon and/or saline at

some time of the year



n

m



5

*z

zm



U



5



z



Em

5

cU2



2

r

T

*4I

m

m



0,



rl

t3



W



v1



296



C. BLOOMFIELD AND J. K. COULTER



and vegetation type can have strong local correlations with sulfidic materials, and are useful in mapping on aerial photographs, on which the different mangrove species, sedges, gelam (Melaleuca) are easy to identify.

A complicating feature for soil mapping is the very strong macro- and

microvariation in levels of sulfur. Microvariation arises because of the nature of pyrite formation related to the uneven distribution of organic matter; sampling should be replicated unless large samples are taken. Macrovariation arises from the relationship between physiographic features and

pyrite formation. The degree of variation is illustrated by Westerveld and

van Holst (1973), who stated that delineation of acid sulfate areas requires

maps on a scale of 1:25,000 to 1 :10,000 in the more homogeneous areas

and a scale as large as 1 :500 in the most heterogeneous areas. Because

of the environment it is logistically impossible to map potential acid sulfate

soils at such scales in the tropics. However the decision on whether to

develop them for agriculture usually rests more on the percentage of the

total area which will be affected by severe acidity rather than the actual

location of the areas affected. The former can be decided by adequate sampling; because of difficulties of access random sampling is usually impossible, so that some form of grid sampling is necessary; a random grid,

i.e., one in which the spacing of the grid lines is determined but the direction of the lines is decided at random, is possibly the best solution. Having

obtained an estimate of the area likely to be affected by strong acidity,

it can be decided whether the development project can support a limited

area of very infertile soils that require expensive ameliorative measures,

or whether the area affected is large enough to have a serious detrimental

effect on the agricultural prospects of the whole project.

Mapping soils that have already developed acid sulfate characteristics

is less difficult, for jarosite mottles are usually evident, and pH values can

be measured by a portable meter; agricultural development may have

cleared the area, so that the state of crop growth can be ascertained, and

the physiographical features can be clearly seen on the ground, or on aerial

photographs. However, the problems presented are usually not so much

those of identification of acid sulfate soils, but rather of assessing the seriousness of acidity, the limitations on agriculture and the probability of improvement. None of the soil classifications so far proposed can be related

directly to a land capability classification of this sort.



VI.



Conditions for Plant Growth



We have seen that acid sulfate soils are characterized by low pH values,

whereas potential acid sulfate soils have pH values near neutrality but are



GENESIS AND MANAGEMENT OF ACID SULFATE SOILS



297



strongly reduced. Rorison (1973) has listed the factors detrimental to

plant growth under strong acid conditions. These include:

1 . Direct effect due to injury by H+ions

2. Direct effect due to low pH

( a ) Impaired absorption of calcium and nitrogen

(b) Increased solubility, and thus toxicity, of iron, aluminum and

manganese

(c) Decreased availability of phosphorus, caused by aluminumphosphorus interactions, and of molybdenum

3. Low base status, leading to deficiency of calcium, magnesium, and

potassium

4. Abnormal biotic factors, such as impairment of the nitrogen cycle

and mycorrhizal activity, and increased virulence of pathogens.



Most of these have been studied on acid soils, but a few on very acid soils.

In addition, the presence of aluminum salts could lead to salt injury.

Under strong reducing conditions the following factors may contribute

to poor plant growth: ( 1 ) production of hydrogen sulfide; ( 2 ) mobilization of ferrous and manganous ions; (3) production of organic acids.

In temperate areas cropping of acid sulfate soils takes place after the

soils have been drained, so that in these regions we are concerned only

with the effects of acidity. In the tropics, such soils may be drained for

annual or perennial crops or temporarily waterlogged for rice, and in these

regions we are concerned with toxic factors under both oxidizing and reducing conditions.

A.



TOXICITIES



I. Hydrogen Ion and p H

At the pH levels of acid sulfate soils some Htmay be present, and

whereas root injury as a direct result of Htions below pH 4 has been

suggested by work in solution culture, Rorison points out that plants may

tolerate relatively large concentrations of Htions, so long as the concentrations of other cations are large, and the concentration of toxic polyvalent

cations is small. Thus it is likely that the detrimental effects of aluminum

and manganese in the soil solution far outweigh those of H+ ions (Adams

and Pearson, 1967).

Low pH inhibits the conversion of ammonium to nitrate, so that NH,'

ions accumulate. Some plants take up both ammonium arid nitrate ions,

but calcicole species may give poor or no growth when supplied with

at this

NHN

,

at pH 4.2, whereas calcifuge plants flourish with NH,-N

pH (Rorison, 1973). Since conditions more acid than these are common



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