International Biodeterioration 23 (1987) 249-256

The SolubUization of Low-grade Rock Phosphate with

Anaerobic Digester Slurry

C. P. Singh,* D. S. Ruhal and M. Singh

Department of Soils, Haryana Agricultural University, Hisar 125004, India
(Received 17 June 1986; accepted 8 March 1987)

ABSTRACT

The effect of biogas slurry on the solubilization of low-grade rock phosphate

was studied by digestion in compost pits. Biogas slurry had solubilizing
power for up to 60 days while molasses addition prolonged it throughout a
digestion period of 120 days. In this case solubilization reached a maximum
of 42. 6% of added rock phosphate. Pyrite incorporation depressed drastically
the rate of solubilization in spite of decreasing the pH and increasing the
citrate-soluble P of the digesting biogas slurry.
The concentration of total P increased with increase in the loss of organic
matter during digestion. The maximum weight loss was recorded in rock
phosphate-containing treatment, where release of water-soluble P increased
continuously with time and organic P decreased after 30 days of incubation.
On the other hand, incorporation of molasses both in presence and absence of
pyrite, decreased the water-soluble P but increased the organic P content of the
digesting material.

INTRODUCTION

T h e total reserve o f k n o w n rock p h o s p h a t e in India is estimated to be

a r o u n d 220 million tonnes, o f w h i c h a b o u t 100 million t o n n e s are
r e p o r t e d to o c c u r in the U d a i p u r a n d J a i s a l m a r districts o f R a j a s t h a n
a n d 45 million t o n n e s are in M u s s o o r i e , Uttar Pradesh. T h e o t h e r k n o w n
deposits are l o c a t e d in J h a b u a ( M a d h y a Pradesh), Singh B h u m (Bihar),
*Present address: Krishi Gyan Kendra, Rohtak 124001, India.
249
International Biodeterioration 0265-3036/87/$03.50 Elsevier Applied Science Publishers
Ltd, England, 1987. Printed in Great Britain.
250 C P. Singh, D. S. Ruhal, M. Singh

Purulia (W. Bengal), Kasipatnam (Andhra Pradesh), Tiruchirapalli

(Tamil Nadu) and Mayur Bhanj (Orissa). In spite of large deposits, the
country has imported high-grade rock phosphate to meet its entire
demand because most of these deposits are of low-grade and unacceptable
to the phosphate fertilizer industries. Recently, it has been reported that
low-grade rock phosphate can be solubilized by composting with
lignocellulosic waste (Singh et al., 1983a, 1983b; Ruhal et al., 1983) and it
is utilized efficiently in place of water-soluble phosphatic fertilizers for
successful crop production (Singh, 1985). Biogas slurry, a partially
decomposed organic material, may also be used for the same purpose.
The availability ofbiogas slurry in India is increasing due to increased
number of biogas plants every year. The installation of biogas plants in
the country was started in 1962 by the Khadi and Village Industries
Commission. The Commission had constructed 457 100 gas plants by
1985. The Department of Non-conventional Energy Sources, Ministry of
Energy, has now fixed the target of 1.5 million plants for the seventh
five-year plan. The nutrient status of anaerobic digester slurry is higher
than that of farmyard manure and/or compost, but the problem comes in
its transportation and equal distribution in the field. Hard lumps are
formed upon uneven drying of slurry either in the pits or in the field; they
are not broken down even when mixed with soil and emerge on to the
surface at the time of irrigation. The physical condition and nutrient
status of slurry can be improved by further digestion after its enrichment
with low-grade rock phosphate. In view of the above, the present
investigation was planned to evaluate the capacity ofbiogas slurry for the
solubilization of indigenous low-grade rock phosphate.

MATERIALS AND METHODS

The biogas slurry was collected from a biogas plant installed at Kishan
Ashram of Haryana Agricultural University, Hisar, The slurry contained
25.26, 1.33 and 0.59% of carbon, nitrogen and phosphorus, respectively.
The organic matter in the slurry was determined by igniting it at 500 C in
a muffle furnace and then carbon values were calculated on dividing
organic matter values by 1.724 (Mitchell, 1932). Total nitrogen was
estimated by Kjeldahl's method (Bremner, 1965) and phosphorus was
determined by ashing the dried slurry with magnesium nitrate at 550 C
for 2 h. Ash was dissolved in 1 M-HzSO4 and blue colour was then
developed in sulphomolybdic acid by using stannous chloride as
reducing agent (Jackson, 1967). There were five treatment combinations
in all, containing biogas slurry, Mussoorie rock phosphate (9% total P),
 Solubilization of rock phosphate with biogas slurry 251

pyrite and molasses as shown in Table 1. Rock phosphate at the rate of

1 kg was added to 4 kg slurry, on a dry weight basis. Pyrite at the rate of
750 g per kg rock phosphate (RP) was added to study its effect on the
efficiency of RP solubilization. Molasses (500 ml in each case) was used
to enhance the microbial activity (Alexander, 1977) during the digestion
period.
The materials were weighed and moisture adjusted to 70%. The
mixture was then inoculated with 1 litre of natural inoculant containing
200 g each of soil, dung and well-decomposed compost. After thorough
mixing, the material was put in nylon bags and allowed to decompose in
the centre of compost pits of 1 m 1 m X 1 m size. One bag was kept for
each treatment and the treatments were replicated thrice in the separate
pits. The contents of the bags were mixed at intervals up to 90 days of
digestion and samples were taken on these days for moisture measure-
ment. On the basis of moisture percentage, the moisture content of the
slurry was adjusted to the original level.
The loss in organic material during decomposition was measured by
weighing the digestion slurry in each bag at intervals up to 120 days and
representative samples were taken for chemical analysis. A few drops of
chloroform were added to these samples to prevent microbial activity.
The samples were dried at room temperature, ground to pass through a
1 mm sieve and analyzed for 2% citric acid-soluble P (Hesse, 1971) and
water-soluble, organic and total P contents (Jackson, 1967). The pH was
also measured. The percentage solubilization of added rock phosphate
was calculated at different time intervals from the formula:
Organic'] \
Increased + Increased]_ EWater-soluble P + e in | ~ 100
water-soluble P organic PJ [}n control control J /
[Total P - Total P in control]

RESULTS AND DISCUSSION

The solubilization of rock phosphate (RP) is dependent on the

decomposition of organic matter which was measured by estimating the
loss of organic matter during the period of digestion (Table 1). The
enrichment of slurry with RP, pyrite and molasses significantly
increased the loss of organic matter. The greatest loss (40.3%) was found
in the presence of rock phosphate after 120 days of digestion. This was
probably achieved mainly due to increase in availability of phosphate
and other nutrients from the rock phosphate (Dash et al., 1981) which
252 C. P Singh, D. S. Ruhal, M. Singh

TABLE 1
Effect of RP, Molasses and Pyrite Enrichment on Organic Matter Loss and pH of Biogas
Slurry During Digestion

Treatment Digestion period (days) Mean

0 15 30 60 90 120

Organic matter loss (%)

Biogas slurry -- 17'7 25"0 28'6 29'8 30"4 26"3

+ RP -- 25"5 33-0 36"2 38"6 40"3 34"7
+ RP + molasses -- 19.0 32.0 34.7 35.2 37"7 31-7
+ R P + pyrite -- 16.1 31.7 34.6 35.7 37.0 31-0
+ R P + pyrite + molasses -- 13'0 29-8 33"4 35"0 35'9 29"0
Mean loss (%) -- 18'3 30"3 33"5 34.9 36"3 --
C . D 9 (5%): D a y s 0-44, T r e a t m e n t - 0-44, D a y s T r e a t m e n t - 0"98

pH

Biogas slurry 8"20 8"52 8-42 8' 10 8"05 8"05 8"22

+ RP 8"28 8'44 8'41 8"05 7"96 7-94 8-18
+ RP + molasses 7'65 8"62 8.60 8'30 8-14 7'43 8-12
+ R P + pyrite 6'75 8"41 7'00 6" 16 6" 14 6' 10 6"76
+ R P + pyrite + molasses 6.35 6.96 6.89 6-08 6.04 6.00 6'39
Mean p H 7-45 8.19 7.86 7.34 7.24 7' 10 --

C.D. ~ (5%): D a y s - 0"45, T r e a t m e n t - 0"41. D a y s T r e a t m e n t - 1-00

aCritical difference.

enhanced the activity of heterotrophic microorganisms (Singh et al.,

1980). Addition of pyrite suppressed the rate of decomposition throughout
the digestion period, compared with the RP and RP + molasses
treatments. This was most probably due to the toxic effect of excess iron
and/or production of sulphide (Ca-soluble complexes) under partially
anaerobic conditions. The pH of incubated slurry increased up to 15
days mainly because of release of bases from the decomposition of
organic matter and/or RP solubilization, and decreased thereafter
gradually in all treatments, being as low as pH 6-00 in the case of pyrite
incorporation,
The data presented in Table 2 show that total P in the digesting slurry
increased significantly in all the treatments due to the loss of organic
matter with time. The release of water-soluble P in biogas slurry
increased up to 15 days and then decreased gradually. The continuous
increase on the incorporation of RP showed that phosphorus was the
 Solubilization of rock phosphate with biogas slurry 253

limiting factor for organic matter decomposition in the former. The

growth ofmicroflora increased rapidly with the availability of phosphorus,
leading to very high decomposition as compared with slurry alone
(Table 1). The lower initial values of water-soluble P in RP-containing
treatment compared with later values suggested that the immobilization
and incorporation predominated over the mineralization up to 30 days
of incubation. The further reduction of water-soluble P was observed
when molasses was added along with rock phosphate indicating the
positive effect of molasses on the immobilization. These observations are
broadly supported by the data on organic P (Table 3) which show an
increase in organic P up to 30 days in treatments containing the RP and
120 days in RP + molasses respectively. In spite of the decreased pH in
pyrite-containing treatment, the water-soluble P did not increase. This
might have been due to the re-fixation of released P with free iron content

TABLE 2
Effect of RP. Molasses and Pyrite Enrichment on Total and Water-Soluble P Content of
Biogas Slurry D u r i n g Digestion

Treatment Digestion period (days) Mean

0 15 30 60 90 120

Total P (rag g-t )

Biogas slurry 11"00 13"75 14"88 15"60 16"23 16"75 14.70

+ RP 26"63 36"25 40"75 42"25 43"00 43"75 38"77
+ RP + molasses 26.63 33"75 37-50 39"25 40.75 41'50 36-56
+ RP +pyrite 23'88 27"25 31-50 33"00 33'75 34"50 32-31
+ R P + pyrite + molasses 23.25 26-63 30.00 31.50 32-25 33,00 29.44
Mean pH 22"28 27-53 30"93 32"32 33-20 33'90 --
C.D. a (5%): D a y s - 2"38, T r e a t m e n t - 2"17, D a y s X T r e a t m e n t - 5"32

Water-soluble P (ragg-l)

Biogas slurry 0"54 5"83 4'20 3"75 3"38 3.26 3"49

+ RP 0'50 2'44 3-54 6-78 6"93 7.09 4"55
+ RP + molasses 0"20 1-58 1'74 2'38 2-48 2.15 1.76
+ R P + pyrite 0"11 0'96 1"73 2"03 2"33 2"08 1"54
+ R P + pyrite + m o l a s s e s 0' l I 0'54 0-69 1.06 0.80 0.45 0.61
Mean 0"29 2"27 2.38 3.20 2"78 3.01 --
C . D # (5%): D a y s - 0'51, T r e a t m e n t - 0"46, T r e a t m e n t x D a y s - 1"14

UCritical difference.
254 C. P. Singh, D. S. Ruhal, M. Singh

of the pyrite (Chakravarti and Talibudeen, 1962). The comparatively

high amount of citric acid-soluble P in the same treatment further
supported these observations (Table 3) because citric acid mainly
extracts the iron phosphates.

TABLE 3
Effect of RP, Molasses and Pyrite Enrichment on Citric Acid-Soluble and Organic P
Content of Biogas Slurry During Digestion

Treatment Digestion period (days) Mean

0 15 30 60 90 120

Citric acid-soluble P (mg g -1)

Biogas slurry 6.6 9"2 10.3 11.5 11.8 12"0 10.2

+ RP 15.8 18"0 21'0 22-5 23.0 23.4 20"6
+ RP + molasses 14-5 17"5 20"0 22.0 22.6 22"3 19.8
+ RP + pyrite 16.5 20.0 22.3 23.6 24.3 25-0 21.9
+ RP + pyrite + molasses 15.0 19"5 22"8 23.9 23.7 24"6 21.6
Mean 13.7 16'8 19'3 20-7 21.1 21'5 --
C.D. a (5%): Days - 2'75, Treatment - 2.51, Days Treatment - 5"62

Organic P (mg g-l)

Biogas slurry 0'63 1'75 1"63 1.35 1.23 1-13 1"29

+ RP 0"50 9.00 9"63 7"00 6-50 4"75 6'23
+ RP + molasses 0.50 1 1 . 2 5 11'50 12.00 12.50 1 4 "5 0 10.38
+ RP + pyrite 0.40 7.63 5"50 5.00 4.50 4.50 4'59
+ RP + pyrite + molasses 0"40 8'63 9 " 0 0 9 " 7 5 9 " 7 5 10'75 8"05
Mean 0.49 7.65 7.45 7.02 6-90 7' 13 --
C.D. (5%): Days - 1"61, Treatment - 1"46, Days X Treatment - 3.59

~Critical difference.

The decrease in organic P after 15 days in the control and 60 days in

the RP-containing treatment indicated that the activity of the microflora
was reduced due to the exhaustion of energy sources and/or lack of P and
other nutrients which were required for their growth. On the incorporation
of molasses, organic P content continuously increased throughout the
digestion period due to the greater availability of substrate. Most
probably the consumption of P by microflora led to such a high increase
in the organic P (Grula et al., 1954; Tardioux, 1966). The addition of
molasses in the presence of pyrite also increased the organic P of the
digesting material regularly throughout the incubation period by
 Solubilization of rock phosphate with biogas slurry 255

eliminating the toxic effects of pyrite and/or making released P available

for immobilization. The concentration of citric acid-soluble P increased
with time in all other treatments also.
The solubilization of added rock phosphate increased up to 60 days
and then decreased gradually, but on addition of molasses it increased
continuously, reaching a maximum of 42-6% after 120 days (Table 4).
Pyrite slowed down the rate of solubilization. The deleterious effect of
pyrite was reduced to a great extent by the addition of molasses, an
energy source for the microflora.

TABLE 4
Percentage Solubilization of Added Rock Phosphate During Digestion of Biogas
Slurry

Treatment Digestion period (days)

15 30 60 90 120

Biogas slurry + RP 16"0 2 4 " 5 2 8 " 8 2 5 " 4 23'8

Biogas slurry + RP + molasses 22-2 2 9 " 6 3 6 " 2 39'4 42.6
Biogas slurry + RP + pyrite 3"8 5"3 8'1 9-8 9"4
Biogas slurry + RP + pyrite + molasses 8.4 22.1 29.8 3 3 " 9 38.7

Rock phosphate and molasses enrichment enhances the rate of

organic matter decomposition by providing easily available substrate
and mineral nutrients required for fast and prolific growth. A high rate of
organic matter decomposition encourages the production of carbonic
acid which initially dissolves the insoluble salts of the rock phosphate.
As a result of the by-product generating activity of microflora, some
organic acids, such as humic, fulvic, citric and oxalic acids, are also
produced during the decomposition of organic matter. They solubilize
the inorganic salts of rock phosphate prior to their being oxidatively
metabolized by the aerobic microflora in the system (Duff et al., 1963:
Singh et al., 1982). Subsequently, a large amount ofsolubilized P is taken
up by the microflora for their cell synthesis. On exhaustion of the
substrate, the cells decompose and release the bound P. However, in the
presence of pyrite a large amount of the solubilized P is preferentially
re-fixed with its Fe and A1 contents before utilization by the microbial
cells.
The results above demonstrate that indigenous low-grade rock
phosphate can be solubilized by digesting with anaerobic digester slurry.
The efficiency of utilization of phosphorus from this material by crops
256 c. P. Singh, D. S. Ruhal. M. Singh

would be m u c h greater because it has a very high content of organic P in

the form o f b i o m a s s . P h o s p h o r u s from microbial cells is released slowly,
but over a longer time, a n d is free from the risk of fixation with soil
constituents, unlike water-soluble p h o s p h a t i c fertilizers.

REFERENCES

Alexander, M. (1977). Introduction to Soil Microbiology, 2nd edn, New Delhi,

Wiley Eastern, pp. 241,345.
Bremner, J. M. (1965). Total nitrogen. In Methods of Soil Analysis, Vol. 2 (Black,
C. A. (ed.)), Madison, Wisconsin, American Society of Agronomy, p. 1171-5.
Chakravarti, S. N.; Talibudeen, O. (1962). Journal of Soil Science 13, 231-40.
Dash, R. N.; Mohanty, S. K.; Patnaik, S. (1981). Journal of the Indian Society of Soil
Science 29, 559-62.
Duff, R. B.; Webley, D. M.; Scott, R. O. (1963). Soil Science 95, 105-14.
Grula, E. A.; Weaver, 1L H.; Edwards, O. F. (1954).Journal of Bacteriology 68, 201-6.
Hesse, P. R. (1971). A Text Book of Soil Chemical Analysis, London, John Murray,
p. 255-300.
Jackson, M. L. (1967). Soil ChemicalAnalysis, New Delhi, Prentice Hall of India,
pp. 141,206.
Mitchell, J. (1932). Journal of the American Society of Agronomy 24, 256-75.
Ruhal, D. S.; Singh, C. P.; Singh, M. (1983). Soil andHealth 42, 36-7.
Singh, C. P. (1985). Biological Agriculture and Horticulture 2, 223-9.
Singh, C. P.; Mishra, M. M.; Yadav, K. S. (1980).Annales deMicrobiologie (Paris)
131B, 289-96.
Singh, C. P.; Mishra, M. M.; Kapoor, IC K. (1982). Revue d'Ecologie et de Biologie
du Sol 19, 17-25.
Singh, C. P.; Ruhal, D. S.; Singh, M. (1983a). Agricultural Wastes 8, 17-25.
Singh, C. P.; Ruhal, D. S.; Singh, M. (1983b). Indian Journal of Microbiology 23,
164-8.
Tardioux, R. A. (1966). Annales Agronomiques 17, 403-528.