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Acid sulfate soils: Identification, formation and implications for aquaculture

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ACID SULFATE SOILS: IDENTIFICATION, FORMATION
AND IMPLICATIONS FOR AQUACULTURE

JUAN IGNACIO GAVIRIA M.

Deparlamento de Acuacultura Marina, Escuela de Ciencias Apicadas Del Mar,
Universidad de Oriente, Apartado Postal 147, Polimar, Isla Margarita, Venezuela

H.R. SCHMITTOU and JOHN H. GROVER

Departmmt of Fisheries and Allied Aquacultures,
Auburn Uníversily, AL 36849

INTRODUCTION

Soil composition and quality are extremely important factors in pond aquaculture.
Soil is usually the main source of dike building materials, and soil quality determines
to a large extent the productivity of a pond. A pond soil, having the ability to absorb
and release nutrients, has been described by Hickling (1974) as "the chemical labora-
tory of the pond," and it will influence natural productivity, water quality and, hence,
fish survival and growth.
There are many reports on poor yields, slow growth and even acute fish kills
which are attributable at least in part to soil condition (see: IFP, 1914, 1976a &
1976b; Potter, 1976a1' Singh, 1981b). This situation seems to be very common in
brackish-water aquaculture, and a factor very often found to be the direct cause of
such problems in the presence of acid sulfate soils (Singh, 198la; IFP, 1914).
Pons (1973), defines acid sulfate soils, in the widest sense of the expression, as all
the materials and soils in which sulfuric acids will be, are being or have been pro-
duced in amounts that have a lasting effect on main soil characteristics. He also
classifies these soils into two categories: "potential acid soils" or "sulfidic muds" and
"actual" or "developed acid sulfate soils."
This paper reviews some of the work dealing with acid sulfate soils, their identifi-
cation, processes that take place in them and the way they affect aquaculture. For the
purposes of this paper, acid sulfate soils will be defined as soils developed from
reduced pyritic soils by air oxidation of pyrite (FeSz) to sulfuric acid. These soils have
free and absorbed sulfate, almost invariably contain pale yellow mottles of jarosite
and usually have a pH below 4 in water (Bloomfield and Coulter, 1973;van Breemen
and Harmsen, 1975).

J. Aqua Trop., | (1986) 99 109

@ Oxford & IBH Publishins Co. Pvt. Ltd.
 100

Acid sulfate soils occurin allclimatic zones (Pons, 1973), butthe majority occur
in coastal plains in the tropics, being less common under temperate climates
(Kawalec, 1973). The total extent of such soils is large, although estimates differ:
Ponnamperuma et al. (1973) give a figure of more than l5 x 106 ha, covering an area
equal to or greater than 170 of all the intensively farmed land in the world; while,
according to van Breemen (1980), actual and potential acid sulfate soils cover about
x 10" ha in Southeast and South Asia, abouf 3.77 x 106 ha in Africa and
5 about 2 x 106
in Venezuela.
- There seems to be a correlation between occurrence of acid sulfate soils and
presence of mangrove swamps all over the world. It is not surprising then that ponds
for brackish-water aquaculture are affected by acid sulfate soil conditions, since the
alluvial and deltaic environments have been traditionally considered as suitable for
fishpond construction (Macintosh, 1982) and are also a preferred habitat for man-
grove forests (Chapman, l9l6).
organic matter often builds up rapidly in the sediments of the mangrove zone
(Potter, 1976b). Anaerobic decomposition of organic matter, mainly mangrove
debris, in the soil by sulfur reducing bacteria can result in accumulation of sulfides
and reducing conditions (Rickard, 1973).
Sulfides may combine with iron in the soil to form iron sulfide and subsequently
pyrite (Glazovskaya, 1983). This produces a potentially acid sulfate condition where-
by drying of the soil may lead to a rapid drop in pH through oxidation of the pyrite
to sulfuric acid (Macintosh, 1982). This is the case during construction of fishponds,
when soils are drained and exposed to oxidation. Furthermore, the pond dikes are
usually constructed using soils from the same pond site, and in the event of heavy
rain, acid materials will reach the water and organisms in the pond.
Brinkman and Pons (1973) and Rorison (1973) indicate that a number of difficul-
ties in land agriculture, including rice agriculture, are the result of acidic sulfate
conditions. Aquaculture has been suggested as a more reasonable long-term produc-
tive use of pyrite-bearing coastal soils (Moormann, 1963). However, many of the
factors affecting highland agricultural productivity are also major problems for
aquaculture: low pH (IFP, 1976b): phosphate deficiency and poor fertilizer response
(Potter, 1976a); toxicity of soluble iron and aluminum (Simpson et al., 1983).
Aquaculture is a widespread activity in coastal areas, especially in Southeast
Asia. It is becoming important in Latin America, but as stated by Simpson et al.
(1983), despite high yields reported at a few aquaculture research facilities which have
instituted intensive management programs to reduce the impact of pyrite oxidation,
the general prognosis for aquaculture as currently practiced is not good.

ACID SULFATE SOILS FORMATION

Formation of Sulfides (Pyrite Accumulation)

SULFUR AND IRON

The source of iron for sulfidation is mainly the ferric oxides, oxyhydroxides and
 101

oxides, which are commonly supplied to the pyritisation environment absorbed on

organic and inorganic particulate matter (as in runoff waters) and living organisms
(Rickard, 1973). Ferrous iron in soils may occur in several forms. In air-dry soil most
of the little ferrous iron is present in inactive forms, but upon submergence, all forms
of iron, especially water-soluble, exchangeable and active forms, show an increase
(Harmsen and van Breemen, 1975).
Sulfur and sulfates come from seawater (Buringh, 1970). Sulfur is present in the
oceans mainly as sulfate (the second most common anion of the sea), which is
virtually inert towards inorganic reduction, the reaction being carried out through
the activities of biologic mediators (Rickard, 1973). Othei' sources of sulfur such as
soil minerals, atmosphere and even organic bound sulfur (Buckman and Brady,
1969), though important in biogeochemical cycles, do not seem to be relevant to acid
soils formation.

ORGANIC MATTER

High soil organic levels are typical of mangrove forests, being particularly associated
with Rhizophora mangroves because of their dense root systems (Macintosh, 1982).
However, in some higher areas influenced by spring tides, conditions can be favora-
ble to sulfide accumulation if Avicenniais a secondary forest following Rhizophora
(van der Kevie, 1973).

CHEMICAL REACTIONS

Oxidation of organic matter (represented by oxidation of glucose to pyruvic acid):

2CeHnOs* 2CH¡COCOOH + 8H-+ 8e. (l)
Reduction of sulfate:
SOo2- + 10H* 8e- HzS + 4HzO. (2)

Net reaction (production of hydrogen sulfide):

2CsHnOs+ SO¿2-+2H*- 2CH:COCOOH + HzS +2HzO. (3)

Anaerobic bacteria of the Desulfovibrio and Desulfomaculum genera are able to

use sulfates as electron acceptors during the (energy supplying) oxidation of organic
substances and/or hydrogen gas (Mohr et al., 1972). It is evident that pH will
increase during the reduction process.
Bloomfield and Coulter (1973) represent the process as:
2CH¡CHOHCOOH+SO¿2--*2CH¡COOH +2COz2HzO+S2-. (4)

They also explain that if adequate sulfate is available, as in marine or estuarine

environments, such hydrogen sulfide is formed at the expense of relatively little
organic matter.
Hydrogen sulfide can be also formed as a product of putrefaction (Bloomfield,
 102

1969), but as much sulfide would be formed from I mole of lactic acid as would be
provided by several kilograms of putrefying protein.
Anaerobic sulfate reducers are especially active in neutral media. However, Mohr
et al. (1972) and Bloomfield and coulter (1973) give different pH ranges for micro-
bial activity (pH = 4-9 and pH = 5-9, respectively). As the pH of seawater is approxi-
mately 8.2 and that of sea bottom sediments is about 7.5, sulfate reduction will
readily take place if enough organic material is present.
Reactions (l) to (a) can be generalized (Rickard, 1973) as;
2CHzO + SO¿2-* HCO:-+ HS-+ COz + HzO. (5)
The right hand part of reaction (5) could also be written as:

2HCOs-+HzS (Andriesse et al., 1973).

The decrease in the concentration of SO¿2- in the intersticial water during sulfate
reduction and formation of sulfides is balanced by an equivalent increase is dissolved
HCo:-. However, the carbonate alkalinity is not conserved in the sediments, but
carried away to the sea (van Breemen, 1973).
If sufficient iron is present in the soil, S'- are converted into black ferrous sulfide.
FeS (Kalpage, 1974). Pyrite is formed as follows:
3HzS + Fe(OH)¡ * 2FeS + So + 6HzO: (6)
FCS + SOI FESZ. Q)
Reactions (6) and (7) are purely chemical (van Dam and Pons, 1973).
Accumulation of pyrite in water-logged soils, under reducing conditions (as is the
case with many coastal areas) will produce a potentially acid sulfate condition (Brink-
man and Pons, 1973, Macintosh, 1982).

Oxidation of Pyrites

Upon drainage the soil comes in contact with air and the sulfides are oxidized. Pyrite
oxidizes to form ferric hydroxide and sulfuric acid. This oxidation phase may be
summed up as follows (van Dam and Pons, 1973):
FeSz+ 15l4oz+7l2HzO - Fe(OH)r+2SO¿2-+4H*. (8)
Because of the extreme insolubility of ferric iron, resulting in nearly quantitative
precipitation of ferric hydroxide phases, up to 4 equivalents of acid are produced for
each mole of pyrite oxidized (Simpson et al., 1983).
The first step in the series of reactions involved (Beye, 1973; Stumm and Morgan,
l98l) is the chemical oxidation of pyrite to sulfate:
FeSz + HzO + 7 l2 Oz - FeSO¿ + HzSO¿. (9)
This reaction is relatively slow, but within a month or so the soil pH drops to less
than 4 (Bloomfield and Coulter, 1973).
Ferrous iron is then oxidized to ferric iron:
2FeSO¿ + | I 2 Oz+ HzSO¿ - Fez(SO¿)¡ + HzO. (10)
 103

This reaction is catalysed by the microorganism Thibacillus ferrooxidanü a fer-

rous iron-oxidizing bacterium that grows best at pH 2.0-3.5. once the soil becomes
acid enough for this species to multiply, the rate of oxidation is greatly accelerated
(Bloomfield, 1972; Bloomfield and coulter, 1973). Half an equivalent of acidity for
each mole of iron is consumed.

Ferric iron then enters into two competing reactions, (ll) and (15);
Fez(SO¿)¡ + 6HzO* 2Fe(OH)¡ + 3HzSO¿. (11)
Ferric hydroxide is nearly insoluble in water if pH)3.5. The precipitation of this
compound removes hydroxide from the water. Three equivalents of acidity for each
mole of iron are produced. This is a purely chemical reaction. A closely related
reaction could also occur:
Fez(SOe): + 2HzO * 2Fe(OH)(SO¿) + HzSO¿. (12)
This produces one equivalent of acidity for each mole of iron. Reaction (8) is
promoted if only small amounts of Ca carbonates and/ or adsorbed bases are present
(van Dam and Pons, 1973), and if this is the case then jarosite (a basic iron sulfate) is
formed (van Dam and Pons, 1973):

3Fe(OH)r+2SO¿2-+K*+3H* * KFe:(SO¿)z(OH)u 2HzO+HzO. (13)

A substitution K- Na- H:O' can also occur, yielding natrojarosite
- -
(NaFe3(SO4)z(OH)r. 2HzO), or hydronium jarosite ((H:O)Fer(SO¿)z(OH)o), but only
after depletion of essentially all available K*, as demonstrated experimentally by van
Breemen (1973). However, according to Alibrook (1973), the presence of sodium
rather than potassium in the basic ferric sulfate is not suprising, in view ofthe closeness
to the sea of many acid sulfate soils.
In older acid sulfate soils in which H'and SO¿2- are lacking or neutralized, the
iarosite tends to hvdrolize:
KFe:(SO+)z(OH)o+3HuO * 3Fe(OH)3 +K*2SO42-+3H* (14)
In addition to jarosites, sulfates of sodium, magnesium, calcium and aluminum
are also formed in a similar way (Bloomfield and Coulter, 1973).
The reaction competing with (ll) is also fast:
Fez(SO¿): +FeSz * 3FeSO¿+25. (15)
In (15), free sulfur is produced and pyrite is consumed.
Next, free sulfur is oxidized by microorganisms:
S+3l2Oz+HzO - HzSO¿. (16)
Another bacterium, Thiobacillus thiooxídans, oxidizes the free sulfur and more
acidity is yielded. Bloomfield (1972) points out that T. thiooxidans also thrives in low
pH conditions (pH 2.0-3.5) and it does not have direct action on pyrite. one equival-
ent of acid is produced for each mole of sulfur.
 104

IDENTIFICATION OF ACID SULFATE SOILS

The detection of actual acid sulfate soils is not difficult. Several features are indica-
tive of their presence: low pH, presence of yellow jarosite mottles on exposed or
disturbed soil surfaces, ferruginous deposits in ditches, lack of vegetation on dikes,
and smell.
The recognition of potential acid sulfate soils is more difficult, as many a fish
farmer has found after experiencing a fish kill or a poor yield. According to Potter
(1976a), in drained fishponds a visual characteristic of developing acid sulfate condi-
tions is a red coloration of the pond bottoms. We have observed this as a reddish-
orange crust covering the entire pond bottom.

Field Identification

Surveying potential acid sulfate areas may be difficult and work is often incomplete.
These areas are swampy, difficult to access and often covered in healy vegetation or
extremely tough tall grasses (Bloomfield and Coulter, 1973). There are no completely
positive ways of identifying these soils or at least of determining how acid they will
become on drainage, but several features of potential acid sulfate soils that could be
helpful in their field identification have been described (Bloomfield and Coulter,
1973; Brinkman and Pons, 1973; Potter, 1976a) and will be listed here alons with our
own experience:
a. Acidification of soil samples upon drying.
b. Soft muds with buried organic matter, particularly if the remnants can be
identified as haloph¡ic.
c. Occurrence of mangrove trees, in particular Rhizophora.
d. Soil color from dark gray to black (not greenish).
e. Sulfurous smell of free hydrogen sulfide when the soil is disturbed by digging or
augering.
f. Located on the inland side of a slight rise with poorer drain than the rest of the
area.
g. Strong sulfur odor of smoke from burning driftwood or roots from the area.
h. Jarosite and sulfur mottles on exposed soil.
i. Fish kills after rains in new ponds in the area.
Absence or presence of any individual features or even of combinations of several
features will not always be a satisfactory identification method. There are exceptions
to consider for any of them, as discussed elsewhere in this report.

Analysis of Pyrite

If a soil contains pyrite considerably in excess of any neutralizing amounts of calcium

carbonate present, it can be considered a potential acid sulfate soil. Brinkman and
Pons (1973) discuss several methods for recognition and prediction of acid sulfate
soils. They include chemical methods for sulfide estimation and pyrite extraction,
 105

X-ray diffraction and fluorescent methods, a microscopic method for identification

of pyrite and slow and rapid oxidation methods.
Boyd ( I 98 1) describes a rapid oxidation method to determine potential acidity of
muds which contain sulfides. The method is simple and the reagents needed are easily
ar,ailable. Soil samples are air dried and ground, then weighed, oxidized using hydro-
gen peroxide, and finally, titrated. Brinkman and Pons (1973) consider rapid oxida-
don using HzOz an attractive method to simulate the development of acid suHate
soils.
Slow oxidation methods consist of either incubating for about two months soil
samples dried in the shade, with occasional remoistening, or storing moist soil mate-
rial for some weeks in a thin polyethylene bag (Bloomfield and Coulter, 1973).
.\ccording to Potter (1976a) the latter is an effective method, and it is recommended
as rhe best technique for general use by fish farmers and soil survey teams who must
process large numbers of samples (IFP, 1976b).

MANAGEMENT OF AQUACULTURE PONDS ON

ACID SULFATE SOILS

Brief Description of Selected Pond Culture Practices

Ponds for fish or prawn culture are often located on mangrove deltas. Swamplands
bordering the bend of an estuary, or situated in the angle between two watercourses
are ideal because a throughflow water exchange system can be operated (Bardach el
al.. 1972). The most desirable pond sites for fish culture have an average elevation
around high-water level of neap tides, allowing the ponds to be flushed l5 to 20 days
per month (Macintosh, 1982). Excavation is usually necessary, although it is not
unusual for 207o or more of the pond area to consist of unproductive high ground.
In building the pond, soil excavated while preparing the pond bed is used for
dike-building, and a puddle-trench and berm are usually constructed in conjunction
uith a dike, Construction of a perimeter dike, preferably rising 20-50 cm above the
high-water level is the initial step (Bardach et al., 1972).If healy machinery is used,
the pond must be dry (Pretto, 1983).
Growth of natural food organisms is encouraged by preparing the ponds before
stocking. "Lab-lab", a benthic association dominated by blue-green algae and di-
atoms, but including detritus, fungi, bacteria and meiofauna, is preferred for nursery
ponds and most types of prawn culture. "Lumut", filamentous green algae, is a
suitable food for several fish species (Ling, 1977).
Ponds are prepared for algal production by hrst draining and letting the bottom
dri' until cracks appear. Drying for 7-10 days is normal for ponds prepared for
-lablab" production. Drying causes organic matter in the soil to mineralise (Macin-
:osh. 1982). This preparation is repeated with each production cycle.
The production techniques described above have something in common. They all
disturb the soil and organic matter. The process is scratching, drying and aerating
(bringing the reduced soil horizons to the surface, incorporating more organic matter
and oxidizing) so it is not surprising thal. potential acid sulfate soils change rapidly to
¿crual acid sulfate soils.
 106

The practice of constructing the pond dikes with material excavated from the
pond site can prove to be dangerous. We have observed, farmers have claimed
and
Potter (1976a) and Simpson et al. (1973) report fish kills after hear,y rain when
sulfuric (acidic) materials are washed off the dikes. Also, erosion of pond dikes is
increased because of poor development of vegetative cover. Application offertilizers
(organic or inorganic) is a common practice in aquaculture; response to fertilizers
in
ponds on acid sulfate soils is poor.

Recommendations for Proper Management

Potter (1976a,1976b), Brinkman and Singh (l9gl), Singh (l9gla, lgglb) and Simp-
son et al.' (197 3) suggest management practices that can be used to mitigate the effect
of acid sulfate on fish production. A üst of their recommendations follows.

SITE SELECTION AND POND DESIGN AND CONSTRUCTION

If an area has been identified as having acid sulfate soil conditions, a decision
whether to develop it or not must be made. Detrimental effects of acid soils are
known. The effects of a costly improvement are not well known, but development of
fishponds in mangrove areas should be done with caution. A detailed soil survey is
adüsed prior to any development work. Design of dike pystems should minimize soils
exposed to the atmosphere. Construction methods that disturb the soil as little as
possible are advised (bottom left unlevel, network of drains should not be dug in the
pond bottom). Shallow ponds are recommended over deep ponds. In some areas,
taking into account the price of the expected crop, dikes could be built with non-
mangrove soil brought to the site, or fabricated walls made from other materials
could be used. Another remedy that would be too costly in most circumstances is
bringing non-toxic soils and spreading them over the bottom of the ponds.

PRODUCTION PRACTICES

To oxidize the soils by drying to lower the amount of pyrite and then repeated
flushing with seawater is one of the most promising methods for improving acid
sulfate soils. However, because of the location or design of many ponds, water
cannot always be renovated by tidal exchange as frequently as required so pumps
might be needed. This is a long term paliative. periods of l0 and more years have
been estimated as necessary to gradually remove acids formed from pyrite oxidation
in ponds. Ifpossible, the top ofthe internal dikes should be flooded. Iffor any reason
the ponds have to be drained and dried, only the soil surface should be dried. The
pond bottom should be thoroughly flushed before a new production cycle is started.
Ponds should be kept inundated for as long as possible. Maintaining equal water
levels in adjacent ponds and keeping this level higher than water levels in the canal
system would limit the transfer of acids, iron and alumrnum into ponds by seepage
through dikes,
 r07

Liming can be used to control soil and water acidity. It was believed that lime
requirements would be in excess of 20 metric tons per hectare, but lower and more
frequent applications, enough to keep pH at about 5.5, would be adequate. Low rates
of liming in combination with tilling and flushin-g of the pond bottom will raise fish
lields. Ábout I kg of agricultural lime per l0 m2 of dike slope and I kg/m2 of dike
iop applied while the pond is drying and the dikes are wet, will promote weeds or
grass growth (even pineapples could be planted) that will protect against erosion.
As soon as a heavy rain starts the pH of the pond water along the dikes should be
checked. Checking should be continued for several hours. If the pH drops below 5,
agricultural lime I kg/ l0 m of dike should be immediately broadcast. If no algal
_rrowth is observed within a week of pond preparation (draining, flushing, liming an{
fertilizing and filling to pool level), the water should be inoculated with algae col-
-ected from normal fishponds. In fishponds with acid sulfate soils, fertilizers (espe-
crally phosphates) should be divided into portions broadcast every two days, or
u eekly portions should be placed in jute bags just submerged below the surface plat-
forms. The first application of inorganic fertilizer should be applied after the pond
bottom has been sealed by swelling after inundation (about one week). Pond water
should not be drained for at least 4-5 days after fertilizer or lime applications.
Stocking should be done after the development of a solid mat of algae, not after a
stated standard number of days. Older and heavier fingerlings than usual for non-
acid ponds should be used for stocking.

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