Sulphur biogeochemistry of agro-ecosystems

Ramesh Kumar SinghRoll no. 10260

Division of Agronomy, IARI

Contents

Biogeochemistry

Introduction to S biogeochemistry

Processes involved in S biogeochemistry

S Biogeochemistry of agro-ecosystems

Conclusion

Future work

Study of Biogeochemistry

Connected to the role of living organisms in the migration and distribution of chemical elements in the Earth’s crust

Recognizes the importance of the biology and the geology of a particular environment in controlling chemical transformations

Understanding the role each component in regulating elemental cycling

Sulphur biogeochemistry 5th most abundant (by weight) element in the

universe & the 13th most abundant element in

the Earth's crust

Valence states ranging from +6 to -2

Mostly found in sedimentary rocks

Aerobic environments, S weathered from

rocks is converted to its most highly oxidized

form – SO42−

SO42− : assimilated by plant and microbial

SO42− can accumulate, as gypsum in

illuviation zones of semiarid and arid soils

Likens, 2002

Imm

obili

zatio

n

SOM & biomassR-C-S & R-O-SO4

SO4 in solution

Elemental S

Sulphide (S2-)

Mineralization

Oxidation

Reducti

on

Oxidation

Reduction

Minera

lizati

on

Oxidation

Reduction

Sulphide soil mineral

Solution

Solid phase of soilLeaching

Des

orpt

ion

Ads

orpt

ion

Earth surface

Coal & Fuel burning

Sulphur gasesSO2, H2S, COS

Vol

atil

izat

ion

loss

SO2--->SO42-

Direct absorption

Fertilizer & pesticides

Wet & dry deposition

Animal &

Human

Residue

SO42- soil

mineral

Erosion& Runoff

S Bigeochemical Cycle in Agro-ecosystem

Processes involved in S biogeochemistry in agro-ecosystem

Mineralization

Immobilization

Oxidation-reduction

Adsorption-desorption

Mineral weathering

Leaching

Volatilization

S pools and fluxes in agro-ecosystemInput Range S pools Range Output Range

Forest

Atmospheric deposition

37-50 (kg S/ha/yr)

Mineral soil S 310-3070 (kg S/ha)

Seepage 37-41 (kg S/ha/yr)

AdsorbedSO42- -S 8-700 (kg S/ha)

Microbial biomass 12 (kg S/ha)

Literfall 4.8-6.3 (kg S/ha/yr)

Forest floor 20-60 (kg S/ha) Uptake 6.4-7.6 (kg S/ha/yr)

Forest stand 20-60 (kg S/ha) Run-off 21-34 (kg S/ha/yr)

Agricultural land

Atmospheric deposition

12-21 (kg S/ha/yr)

Total S in soil 224-1120 (kg S/ha)

Uptake 13-42 (kg S/ha/yr)

Ground water 0-295 (kg S/ha/yr)

Leaching 30-80 (kg S/ha/yr)

Mineralization 10-30 (kg S/ha/yr)

Gaseous losses 0.2-3.0 (kg S/ha/yr)

Wetland

Inflow 3.2 (kg S/ha/yr)

SO42- -S conc. in

water30-500 (µM SO4

2-)Discharge 10-70% (% of input)

Burial sediments 0.03-32 (kg S/ha/yr)

H2S 0.01-26 (kg S/ha/yr)

DMS 0.004-1.8(kg S/ha/yr)

Haneklaus et al., 2003

S deficiency in Indian soils

S deficiencies are a critical problem in 40-45% of districts of the country

S deficiency covers 57-64 mha of net sown area

The deficit to the tune of 1 mt/annum

http://www.sulphurindia.com/link3.html

Northern Region (15323)

Western Region (12474)

Eastern Region (10108)

Southern Region (11289)

All India (49194)0

10

20

30

40

50

60

70

Low Medium High

% d

efic

ien

t s

oil s

amp

les

Literature search

Key words: sulfur biogeochemistry, agroecosystem, India

Selected literatureS. No. Country Author (s) Name Journal

1. United Kingdom Hendrik Schafer, Natalia Myronova & Rich Boden

Journal of Experimental Botany

2. India Indranil Das, A. Datta, Koushik Ghosh, Sourov Chatterjee & A. Chakraborty

Archives of Agronomy and Soil Science

3. China Y. Jiang, Y. Zhang, W. Liang Agricultural Journal

4. Columbia Dawit Solomon, Johannes Lehmann, Katrin Knoth de Zarruk, Julia Dathe, James Kinyangi, Biqing Liang & Stephen Machado

Journal of Environmental Quality

5. Sweden K . Boyea , G. Almvist, S. I. Nilsson, J. Eriksen & I . Persson

European Journal of Soil Science

6. China Wei Zhou, Ping He, Shutian Li, Bao Lin Geoderma

7. Thailand N. Janjirawuttkul, M. Umitsu & S. Tawornpruek

Internation Journal of Soil Science

8. India K.N. Das, Anjali Basumatari & Bikram Borkotoki

Journal of the Indian Society of Soil Science

9. India Pradip Kumar Giri, Mintu Sahab, Murari Prasad Halder & Debatosh Mukherjee

International Journal of Plant, Animal and Environmental Sciences

10. India S.P. Singh , Room Singh , M.P. Singh & V.P. Singh

Journal of Plant Nutrition

11. Denmark Jorgen Eriksen Soil Biology & Biochemistry

12. Sweden K. Boye, J.Eriksen , S. I. Nilsson &L. Mattsson

Plant Soil

S biogeochemistry of agro-ecosystems

S biogeochemistry in upland soils Pedogenesis Land use/cropping Fertilization/residue management Pesticide application

S biogeochemistry in flooded soils S emission

Effect of pedogenesis on

sulphur biogeochemistry

Dobrovolsky (1994)

Reservoir 1018 g S

Atmosphere 0.0000028

Seawater 1280

Sedimentary rocks

Evaporites 2470

Shales 4970

Land plants 0.0085

Soil organic matter 0.0155

Total 8720

Reservoirs of S near the surface of the Earth

Pedogenesis of acid sulphate soil

Janjirawuttkul et al., 2011

Sampling site and distribution acid sulphate soil in Thailand

A model of 15 soil profiles

Janjirawuttkul et al., 2011

Profile A: Post-active acid sulphate soilProfile B: Deep potential acid sulphate soilProfile C: Non-acid sulphate soilProfile D: Shallow potential acid sulphate soil

Physical analysis by optical micrograph

Janjirawuttkul et al., 2011

2Cg in L3 profile

BCjg in L4 profile

Bjg2 in L3 profile

Janjirawuttkul et al., 2011

Chemical composition

Profiles

Pyri

te (

%)

X-ray diffraction study of acid sulphate soil

Bjg1 of L4

Bjg2 of L11

Bg3 of L12

ACg of L4

Janjirawuttkul et al., 2011

Hysteresis curves of sulphate sorption/desorption

Sulphate sorption/desorption behaviour of S deficient soils of WB

Das et al., 2009

S added to the soil (mg/l)

Quantity intensity parameters during sorption run

ToofanganjAeric Haplaquept

DebagramFluventic Ustochrept

KaliagangTypic Fluvaquent

PundibariTypic Ustorthent

SP EBC SP EBC SP EBC SP EBC

30 2.80 0.945 2.36 1.17 2.96 0.765 3.25 1.06

45 3.76 0.595 3.39 0.998 4.16 0.625 4.86 0.820

60 3.84 0.425 4.23 0.826 4.94 0.508 5.90 0.634

75 5.88 0.298 5.16 0.708 5.88 0.425 6.88 0.504

Quantity intensity parameters during desorption run

30 1.76 0.558 1.08 1.48 2.38 0.802 13.86 1.49

45 1.98 0.461 1.55 1.16 3.58 0.656 16.51 0.903

60 2.29 0.302 1.73 0.996 3.56 0.627 17.31 0.814

75 2.25 0.307 2.24 0.929 4.08 0.589 18.20 0.736

Sulphate sorption/desorption behaviour of S deficient soils of WB

Das et al., 2009

SP: Supply parameterEBC: Equilibrium buffering capacity

Effect of land use on sulphur biogeochemistry

Profile distribution of S under different land use Land use: Paddy field (>14 yrs), maize field (14 yrs), fallow field (9 yrs) &

woodland (Poplur, 14 yrs)

Soil total S content under different land uses (g/kg)

Jiang et al., 2007

0 to 5 5 to 10 10 to 20 20 to 30 30 to 40 40 to 60 0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

0.5

Paddy field Maize field Fallow field Woodland

Soi

l tot

al S

(g/

kg)

Soil depth (cm)

Relationships of Soil Total Sulphur (STS) with organic carbon (SOC)

Land use Regression model R square (p=<0.01)

Paddy field STS=1.077 × 10-3+2.239 × 10-2SOC 0.894

Maize field STS=5.301 × 10-2+1.709 × 10-2SOC 0.833

Fallow field STS=4.776 × 10-2+1.525 × 10-2SOC 0.974

Woodland STS=8.004 × 10-2+1.282 × 10-2SOC 0.953

Soil total S storage under different land use

Jiang et al., 2007Soil depth (cm)

S S

tora

ge (

t/ha

)

Soil available S content under different land use

Jiang et al., 2007

Soil

ava

ilab

le S

(m

g/kg

)

Soil depth (cm)Series1

0

10

20

30

40

50

60

70

Paddy field Maize field Fallow field Woodland

0 to 5 5 to 10 10 to 20 20 to 30 30 to 40 40 to 60

Sulphur fractions & S availability index (SAI)in some Rapeseed-growing soils of Assam

District Total S Organic S Non-SO4-S Adsorbed S Available S SAI

Golaghat 614 399.9 170 19.5 37.3 16.3

Jorhat 573 379.9 159 17.8 33.8 15.1

Sibsagar 444 310.0 100 12.0 27.7 10.8

Dibrugarh 552 441.7 80.6 5.10 29.8 12.9

Das et al., 2012

Effect of land use on organic S speciation result by XANES

Solomon et al., 2011

Undisturbed grassland since 1880

Undisturbed grassland since 1931 Cultivated since 1880

Tot

al o

rgan

ic S

(%

)

Sulphur biogeochemistry as affected

by fertilization & residue management

-S FYM -S CR +S FYM +S CR

Plant

-S FYM -S CR +S FYM +S CR

Soil

Specific 35S-activity (% of recovered 35S per mg S) in rye grass biomass and soil fraction

Shoots at 1st (dark grey) and 2nd (light grey) harvest, stubble (white), roots (black)

Sol-S (white with black dots), Org-non prot. S (light grey with black dots), Org-prot. S (dark grey with black dots) & residual S (black with white dots)

Boye et al., 2010

Fo: Silt loam, Or: Sandy loam

Net flow of soil S in soil-plant system (mg S/kg dry soil)

Soil Treatment Inorganic to plants S

Organic to plant S

Inorganic to Organic S

Silt loam (Fo) FYM 0.2 4.1 0.2

CR 0.1 3.0 0.1

Sandy loam (Or)

FYM 3.0 6.7 1.8

CR 1.3 4.8 0.6

Boye et al., 2010

CR- Crop residueFYM: Farm yard manure

S mineralisation and immobilisation over 5 days incorporation of plant materials

Eriksen et al., 2005

Relationship between C:S ratio & lignin on S transformation over 5 days of residue incorporation

Eriksen et al., 2005

Model spectra of S species under organic amended soil

FYM Crop residue

Soil (solid black) Unprotected S (light grey)Protected S (dark grey) Residual S (dashed black)

Boye et al., 2011

Agronomic efficiency (AE), apparent S recovery (ASR) & % response in wheat-soybean cropping sequence

Singh et al., 2014

AE

, AS

R &

% R

espo

nse

S levels

Vertical distribution of S after harvest of wheat & soybean

Wheat

Soybean

Singh et al., 2014

Effect f Pesticides on sulphur

biogeochemistry

Effect of pesticides on available sulphur content in soil

Effect of pesticides on the population of thiosulphate oxidizing bacteria

Giri et al., 2011

Ava

ilab

le S

(m

g/k

g)C

FU

x 1

03 /g

soil

TreatmentsDays after incubation

5th 10th 15th 30th 60th 90th

Control 2.34 2.52 2.81 3.07 3.46 3.16

Endosulfan 1.86 2.14 2.42 2.91 2.79 2.64

Diathane M-45

2.36 3.01 3.39 3.41 3.14 2.97

2, 4-D 2.51 3.12 3.21 3.68 3.94 3.86

Effect of pesticides on aryl sulphatase activity (n kat 100/g) in soil

Giri et al., 2011

Relationship between R2

Available sulphur vs aryl sulfatase activity 0.97

Available sulphur vs thiosulphate oxidizing bacteria 0.98

Aryl sulfatase activity vs thiosulphate oxidizing bacteria 0.98

Sulphur biogeochemistry ofFlooded agro-ecosystem

Mineralization of organic S in flooded paddy soilSite description:-

Place: China

Climate: Temperate

Soil No. Soil Texture pH Organic C(g/kg)

Total S (mg/kg)

1 Blacksoil

Loam 6.2 16.8 316.6

2 Black soil Clay 6.7 19.6 373.0

3 Red soil Loamy clay 5.8 9.1 164.2

4 Red soil Clay 5.5 10.4 195.0

Zhou et al., 2005

S mineralization in incubated paddy soil

Incubation period in week

Incubation period in week Incubation period in week

Cum

ulat

ive

min

eral

ized

S (

mg/

kg)

Cum

ulat

ive

min

eral

ized

S (

mg/

kg)

Sulphate-S OI-S

TI-S

Zhou et al., 2005

OI-S: other inorg.STI-S: total inorg. S

Cum

ulat

ive

min

eral

ized

S (

mg/

kg)

Changes in soil S pools in incubated flooded paddy soil

Zhou et al., 2005

C-O-S: ester sulphateNRO-S: non reducible org.-S

Changes in soil S pools under soil S exhaustion by rice

Zhou et al., 2005

C-O-S: ester sulphateNRO-S: non reducible org.-S

Effect of sulphur emissionon sulphur biogeochemistry

Microbial degradation of DMS & related C1-S compound

Importance:-• Dimethylsulphide (DMS) plays a major role in the global sulphur cycle• Important implications for atmospheric chemistry, climate regulation, and

sulphur transport from the marine to the atmospheric and terrestrial environments

Sources of DMS:-

1. Marine environment

Major pathways of DMS production and transformation in the marine environment

DMS emission into the atmosphere is a source of heat-reflecting aerosols that can serve as cloud condensation nuclei and thereby affect the radiative balance of the Earth, thus linking DMS production to climate regulation. Atmospheric transport of DMS and its oxidation products and deposition in the terrestrial environment provides an important link in the global sulphur cycle.

2. Terrestrial sources• Soils may also emit volatile organic sulphur compounds, including DMS, and fluxes can be enhanced by waterlogging• The decomposition of plant residues in soil, especially those of crucifer species with a high content of sulphur-containing glucosinolates, can generate a number of volatile sulphur compounds3. Production by plant4. Anthropogenic sources

Schafer et al., 2010

Sinks for DMS

Microbial metabolism of DMS

Three principle:-(i) Utilization of DMS as a carbon and energy source(ii) Oxidation to DMSO by phototrophic or heterotrophic organisms(iii) Utilization as a sulphur source

Schafer et al., 2010

Phylogenetic tree

Depicting the genetic diversity of bacterial isolates capable of assimilating carbon from DMS (overlaid in pink) or degrading DMS to DMSO (green). Schafer et al., 2010

Conclusion

Woodland have the potential to make a significant contribution to soil total

S storage as compared to cropping

The majority of mineralized S was derived from the C–O–S pool by rice

plant under flooded condition

Higher hystersis effect was more for S deficient soils, (i.e. Aeric

Haplaquept and Typic Ustorthent soil) adequate S fertilization is needed to

ensure optimum plant growth and yield

The AE and ASR by wheat-soybean system decreased with increase in S

application, while the percent response increased with increase in levels of

S

Conversion of undisturbed grassland towards cultivation leads to formation

of strongly oxidized S

Future work

Challenge of optimizing S availability & use efficiency in cropping systems in

synchrony with plant demand and in the required form and quantity

The emission of DMS from terrestrial and freshwater sources has not been

studied as intensively as that from the marine environment

Future research should include evaluation of all components of S cycle

collaborating with others to asses environmental impact and sustainability of

feedstock production.

Thank you