sulfur - university of florida · 2 learning objectives identify the forms of s in wetlands sulfur...

1

Biogeochemistry of WetlandsS i d A li tiS i d A li ti

Institute of Food and Agricultural Sciences (IFAS)

Science and ApplicationsScience and Applications

Wetland Biogeochemistry LaboratorySoil and Water Science Department

SULFUR

6/22/2008 P.W. Inglett 16/22/2008 WBL 16/22/2008 16/22/2008 WBL 1

Instructor :Patrick [email protected]

Soil and Water Science DepartmentUniversity of Florida

Sulfur

IntroductionS Forms, Distribution, Importance

Basic processes of S CyclesExamples of current researchExamples of applications

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Key points learned

2

Learning ObjectivesIdentify the forms of S in wetlands

Sulfur

yUnderstand the importance of S in

wetlands/global processesDefine the major S processes/transformationsUnderstand the importance of microbial activity

in S transformations Understand the potential regulators of S

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processesSee the application of S cycle principles to

understanding natural and man-made ecosystems

Sources of SulfurSources of Sulfur

• Sulfur is a ubiquitous elementSulfur is a ubiquitous element.• Various sulfur compounds are present in:

– The atmosphere– Minerals– Soils– Plant tissue

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– Animal tissue– Microbial biomass– Sediment

3

Reservoirs of Sulfur Reservoirs of Sulfur

•Atmosphere 4.8 x 109 kg•Lithosphere 24.3 x 1018 kg•Hydrosphere

– Sea 1.3 x 1018 kg– Freshwater 3.0 x 1012 kg

•PedosphereS il 2 6 1014 k

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– Soil 2.6 x 1014 kg– Soil Organic matter 0.1 x 1014 kg

•Biosphere 8.0 x 1012 kg

General Forms of Sulfur in the Environment


• Organic S in plant, animal, and microbial tissue (as i l f i id d i )essential components of amino acids and proteins)

CysteineH3C-S-CH2-CH2-

Methionine

HS-CH2-

OR1-C~S-R2

Thioester

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– Organic sulfur primarily in soil and sediments as humic material (naturally occurring soil and sediment organic matter)

4



• Gaseous S compounds (SO2, H2S, DMSO, DMS)

• Oxidized Inorganic S (sulfate, SO42-, is the primary

compound). Seawater contains about 2,700 mg/L (ppm) of sulfate

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• Reduced Inorganic S (elemental sulfur, So, and sulfide, S2-)



• MineralsGalena (PbS2) Gypsum (CaSO4)

Jarosite(Fe2S) Barite (BaSO4)

Pyrite (FeS2)

F il F l

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• Fossil Fuels– Petroleum (0.1-10%)

– Coal (1-20%)

5

Oxidation states of selected sulfur compounds

Oxidation states of selected sulfur compounds

• Organic S (R-SH) -2• Sulfide (S2-) -2• Elemental S (S0) 0• Sulfur dioxide (SO2) +4• Sulfite (SO3

-2) +4

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Sulfite (SO3 ) +4• Sulfate (SO4

2-) +6

Global Sulfur CycleGlobal Sulfur Cycle

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6

1. Dissimilatory sulfate reduction

Sulfur Cycling ProcessesSulfur Cycling Processes

2. Assimilatory sulfate reduction

3. Desulfurylation

4. Sulfide oxidation

5. Sulfur oxidation

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6. Dissimilatory So reduction

So

Sulfur CycleSulfur Cycle

45

SO42- S2-

SH groupsof protein

SH groups

AerobicAerobic

Anaerobic1

2 3

2 3

5

AerobicAerobic

Anaerobic

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So

SH groupsof protein 45

6

Anaerobic

7

Distribution of sulfur in soilsDistribution of sulfur in soils

Organic sulfur [93%]Organic sulfur [93%]– Carbon-bonded sulfur (cysteine and methionine) 41%

– Non-carbon-bonded sulfur (ester sulfates) 52%

Inorganic sulfur [7%]– Adsorbed + soluble sulfates 6%

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Adsorbed + soluble sulfates 6%

– Inorganic compounds less oxidized than sulfates and reduced sulfur compounds (e.g. sulfides) 1%

20Freshwater

Organic Sulfur FormsOrganic Sulfur Forms

15

10

5Sulfu

r, g/

kg

Freshwater

Brackish

Salt

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0

S

Ester C-S Total

Organic Geochemistry vol. 18, no. 4, pp. 489-500, 1992

8

Freshwater400 4

Inorganic Sulfur FormsInorganic Sulfur Forms

Freshwater

Brackish

Salt

300

200

100

3

2

1ulfu

r, m

g/kg

Sulfu

r, g/

kgSu

lfur,

g/kg

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0 0FeS So FeS2 HCl

Su

SS

Krairapanond et al. 1992. Organic Geochemistry 18: 489-500.

Organic S HydrolysisOrganic S Hydrolysis

R - S-H2 + H2O R-OH + H2S

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SulfohydrolaseR S H2 + H2O R OH + H2SThiol

9

Assimilatory Sulfate Reduction• Bacteria fungi algae and plants

Sulfur – Organism GroupsSulfur – Organism Groups

• Bacteria, fungi, algae, and plants

Dissimilatory Sulfate Reduction• Hetrerotrophs

Desulfovibrio, Desulfotomaculum, Desulfobacter, Desulfuromonas

Sulfide Oxidation

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Sulfide Oxidation• Phototrophs: Chlorobium, Chromatium

• Chemolithoautotrophs: Thiobacillus, Beggiatoa

Sulfate Reducing Bacteria: SRB(habitats)

Sulfate Reducing Bacteria: SRB(habitats)

Desulfovibrio - found in water-logged soils.

Desulfotomaculum - spoilage of canned foods.

Desulfomonas - found in intestines.

Archaeglobus - a thermophilic Archea whose optimal growth temperature is 83oC

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growth temperature is 83 C.

10

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Sulfate ReductionSulfate Reduction

DepositionSO4

2-

AEROBICAEROBIC

Adsorbed SO 2ReductionReduction

Tidal Exchange

SO42-

SO42-

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ANAEROBIC

SO42-

MicrobialBiomass-S

S2-ReductionReduction

SO42-So

11

Glucose OxidationGlucose Oxidation

Oxidation – Reduction ReactionkJ/mol

GlucoseGlucose

C6H12O6 + 6O2 = 6CO2 + 6H2O 2,880

5C6H12O6 + 24NO3- + 24H+ = 30CO2 + 12N2 +42H2O 2, 712

C6H12O6 + 12MnO2 + 24H+ = 6CO2 + 12Mn2+ + 18H2O 1,920

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C6H12O6 + 24Fe(OH)3 + 48H+ = 6CO2 + 24 Fe2+ +66H2O 432

C6H12O6 + 3SO42- = 6CO2 + 3S2- + 6H2O 381

120

Oxygen Equivalents-Energy Yield from Glucose

Oxygen Equivalents-Energy Yield from Glucose

40

60

80

100

erob

ic E

nerg

y Yi

eld

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0

20

O2 NO3- MnO2 Fe(OH)3 SO4

2-SO42-

% o

f Ae

Electron Acceptors

12

SO42- S2-SO42- S2- Mn4+ Mn2+ O2 H2O

Oxidation-ReductionOxidation-Reduction

CO2 CH4 Fe3+ Fe2+ NO3- N2

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-200 -100 0 +100 +200 +300 +400Redox Potential, mV (at pH 7)Redox Potential, mV (at pH 7)

Sequential Reduction of Sequential Reduction of Electron Acceptors Electron Acceptors

Sequential Reduction of Sequential Reduction of Electron Acceptors Electron Acceptors

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13

WATERWATER

SOILSOIL

Redox Zones With DepthRedox Zones With DepthRedox Zones With DepthRedox Zones With Depth

Oxygen Reduction Zone AerobicAerobicSOILSOIL Oxygen Reduction ZoneEh = > 300 mV

Nitrate Reduction ZoneMn4+ Reduction ZoneEh = 100 to 300 mVFe3+ Reduction ZoneEh = -100 to 100 mV

I

II

III

FacultativeFacultative

Dep

thD

epth

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Sulfate Reduction ZoneEh = -200 to -100 mV

MethanogenesisEh = < -200 mV

IV

V

AnaerobicAnaerobic

DD

1000

800

Redox Potential and pHRedox Potential and pHRedox Potential and pHRedox Potential and pH

600

400200

0

-200

E h[m

V]

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0 2 4 6 8 10 12

-200

-400

-600

pHBaas Becking et al.

14

Microbial Activity[Site: Water Conservation 2A]

Microbial Activity[Site: Water Conservation 2A]

50

60on

s on

s y = 0.33x + 1.3r2 = 0 88; n = 24

20

30

40

50

e re

duci

ng c

ondi

tie

redu

cing

con

diti

[mg

kg[m

g kg

--11ho

urho

ur--11

]]r 0.88; n 24

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0

10

10 20 30 40 50 60

Sul

fate

Sul

fate

AerobicAerobic [mg kg[mg kg--11 hourhour--11]]

0

Detrital MatterEnzymeHydrolysisComplex Polymers

Cellulose, Hemicellulose,Monomers

Sugars, Amino AcidsF tt A id

Sulfate RespirationSulfate Respiration

Glucose

PyruvateGlycolysis

Substrate level TCA Cycle

Oxidative phosphorylation

CO

Proteins, Lipids, Waxes, Lignin Fatty Acids

Uptake

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Products:CO2, H2O, S2-, Nutrients

phosphorylation AcetateCO2

ATP

SO42- + e- Organic Acids

[acetate, propionate, butyrate, lactate, alcohols, H2, and CO2]

LactateUptake

[Sulfate Reducing Bacterial Cell] [Fermenting Bacterial Cell]

Substrate level phosphorylation

15

Electron donors used during sulfate reduction


• SRB lack enzymes necessary for complex carbon assimilation

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16

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Decreasing energy

yield

Electron DonorsElectron Donors

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Capone and Kiene. 1988. Limnol Oceanogr, 33: 725-749.

17

Activity [nmol/g per day]

Sulfate Reduction RatesSulfate Reduction Rates

[ g p y]

Low carbon wetland 23

Peaty wetland 130

Oligotrophic lake 707

Eutrophic lake 1,224

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Marine and salt-marsh 744-24,000

Respiration [g C/m2 year] Sapelo Island Sippewissett Sapelo Island

[GA] [MA] (199 )

Salt MarshesSalt Marshes

[GA] [MA] (1997)

Aerobic respiration 390 390Denitrification 10 3Mn and Fe reduction ND NDSulfate reduction 850 1,800 2,000Methanogenesis 40 1-8

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Methanogenesis 40 1 8

~65%~65% ~82%~82% ~69-87%~69-87%S Respiration

18

Sulfate RespirationSulfate Respiration

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19

Seasonal EffectsSeasonal Effects

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Jorgensen, 1977. Marine Biology 41:7-17.

Seasonal EffectsSpartina alterniflora marshSeasonal EffectsSpartina alterniflora marsh

Great Sippewissett Marsh

0 50.5

0.4

0.3

0.2

Mol

es S

O42-

m-2

d-1

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J J JMF MA A S O N D

0.1

0.0

M

MonthsHowarth and Giblin, 1983. Limnol and Oceanogr, 28:70-82.

20

Seasonal EffectsSpartina alterniflora marshSeasonal EffectsSpartina alterniflora marsh

0 50.5

0.4

0.3

0.2

Mol

es S

O42-

m-2

d-1

Mol

es O

2m

-2d-

1

0.01

0.03

0.02

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0.1

0.0

M M-5 20 2550 1510 30

Temp (C)-5 20 2550 1510 30

Temp (C)

Howarth and Teal. 1979. Limnol and Oceanogr, 24: 999-1013.

Regulators of Sulfate ReductionRegulators of Sulfate Reduction

P f l t t ith hi h• Presence of electron acceptor with higher reduction potentials

• Oxygen is toxic to sulfate reducers• Sulfate concentration

– Freshwater (< 0.1 mM)– Marine (20-30 mM)

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• Substrate/Electron Donor• Temperature• Microbial populations

21

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Decreasing energy

yield

Sulfidogenic aggregate Sulfidogenic/Methanogenic aggregate

Anaerobic Sludge Reactor(FISH)

Anaerobic Sludge Reactor(FISH)

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Appl Environ Microbiol. 1999 October; 65(10): 4618–4629. SRB Probe Archeal Probe

22

Competition With MethanogensCompetition With Methanogens

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XXXX

Sulfate Reducers vs MethanogensSulfate Reducers vs Methanogens

Sulfate reducersVmax

V

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Methanogens

Vmax

Km Km

[Substrate]

V = [Vmax S]/Km + S

23

0.6CH

Sulfate ReductionTypical Lake Sediments


0.2

0.4

mM

CH

4

mM

SO

42-

20

10

CH4

SO42-

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1000 20 40 60 80

Daysfrom Jorgensen: in Microbial Geochemistry. Krumbein, ed: 1983 Blackwell.



12

8

mM SO42-

0.20.10

mM SO42-

2010

SO 28

4

0

8

cm

CH4

SO42-

4

0.5

1.0

1.5 CH4

SO42-

m

6/22/2008 P.W. Inglett 46from Jorgensen: in Microbial Geochemistry. Krumbein, ed: 1983 Blackwell.

12

1 2mM CH4

2.0

0.5 1.0mM CH4

FreshwaterFreshwater MarineMarine

24

Sulfate ReductionCattail Marsh – Sunnyhill Farm Wetland

Sulfate ReductionCattail Marsh – Sunnyhill Farm Wetland

0 5 10 1510

W t

CH4 (mg L-1)

0

-10

Dep

th (c

m)

Water

Soil

CH4

SO42-

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0 20 40 60 80 100-30

-20

SO42- (mg L-1)

Sulfate ReductionSulfate Reduction

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Iversen and Jorgensen. 1985. Limnol Oceanogr, 30: 944-955.

25

Sulfur EmissionsSulfur Emissions

H2S

AEROBICAEROBICOrg-SMineralization

SO 2

H2SDMS

O S S2

Mineralization ReductionReduction

2DMS

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ANAEROBIC

SO42-Org-S S2- So

Gaseous S EmissionsGaseous S Emissions

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26

SALT BRACKISH FRESH

Gaseous SpeciationGaseous SpeciationDeLaune et al. 2001

H2SH3C-S-CH3CO-S

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ug S m-2 hr-1

Sulfide FormationSulfide Formation

H2S

AEROBICAEROBICOrg-SMineralization

SO 2

H2SDMS

O S S2

Mineralization ReductionReduction

2DMS

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ANAEROBIC

SO42-Org-S S2- So

27

Sulfide SpeciationSulfide Speciation

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Problems With Hydrogen SulfideProblems With Hydrogen Sulfide

• Malodorous (rotten egg smell)

• Acidic (corrosion/fouling)

• Toxic (reactive with metalloenzyme systems)

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metalloenzyme systems)

28

Sulfide ToxicityTall vs. Short Spartina alterniflora


Tall FormTall Form

Short FormShort Form

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29

Sapelo Island MarshTall vs. Short Spartina alternifloraTall vs. Short Spartina alterniflora

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CreekCreek TallTall ShortShortKostka et al., 2002. Biogeochemistry 60:49-76.



Lower VmaxHigher Vmax

NH4+ UptakeNH4+ Uptake

MHT

Higher KmLower Km

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MLT

Inc. Flood Frequency, Pore Water Turnover

Inc. NH4+, S2-, and Salt Concentrations

30

Sulfide PrecipitationSulfide Precipitation

AEROBICAEROBIC

SO 2S2ReductionReduction

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ANAEROBIC

SO42-S2- So

FeS2

Me+-S

Iron and Sulfide InteractionsIron and Sulfide Interactions

2F OOH H S S 2F 2+ 4OH2FeOOH + H2S = So + 2Fe2+ + 4OH-

Fe2+ + H2S = FeS + 2H+

FeS + So = FeS2

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Acid Volatile S (AVS)

Chromium Reducible S (CRS)

31

Pyrite FramboidsPyrite Framboids

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Pyrite FormationPyrite Formation

Fe Oxides

Monosulfides (AVS)

FeS

ΣH2SS0

Intermediate

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FeS2Pyrite (CRS)

Redox S

Sulfate Reduction

32

SolidSolid--FeFe AVSAVS CRSCRS

Pyrite FormationSapelo Island Marsh

Pyrite FormationSapelo Island Marsh

CreekTallShort

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Kostka et al., 2002. Biogeochemistry 60:49-76.

ZnSZnS

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33

Metal Sulfide Solubility-Uptake by Rice Plant

Metal Sulfide Solubility-Uptake by Rice Plant

5

4d 35

S Na2S

4

3

2

1

% U

ptak

e of

add

e

MnSFeS ZnS C S H S

6/22/2008 P.W. Inglett 65Engler and Patrick, 1981

0

%

100 10-10 10-20 10-30 10-40 10-50

FeS ZnS CuS HgS

Solubility Product (Ksp)

Metal Sulfide SolubilityMetal Sulfide Solubility

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Yu et al. 2001. Wat Res. 35:4086-4094.

34

Sulfur OxidationSulfur Oxidation

AEROBICAEROBICSO42-So

H2SDMS

S2

Oxidation Oxidation

Reduction

Tidal Exchange

SO42-

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ANAEROBIC

S2- So

Sulfide OxidationSulfide Oxidation

2H2S + O2 = 2So + 2H2O204 kJ/ ti-204 kJ/reaction

2So + 3O2 + 2H2O = 2SO42- + 4H+

-583 kJ/reaction

H2S + 2O2 = SO42- + 2H+

-786 kJ/reaction

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86 J/ eact o

H2S So SO32- SO4

2-

35

Sulfur Cycling Cyanobacterial Mat Sediments


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Aphanothece Diatoms

Phormidium, Lyngbya

Chromatium salexigens Thiocapsa halophila.

SurfaceSurface Green LayerGreen Layer Red LayerRed Layer

36

Oxidation-ReductionOxidation-ReductionSoil-floodwater InterfaceSoil-floodwater Interface

O2

SO42- H2S + O2

Floodwater

Aerobic soil

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H2SAnaerobic soil

SO42-

Sulfur Cycling Salt Marsh Surface Sediments

Sulfur Cycling Salt Marsh Surface Sediments

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37

Oxidation-ReductionOxidation-Reduction

Root- Soil InterfaceRoot- Soil Interface

AEROBICAEROBIC

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ANAEROBIC

Oxidation-ReductionInfaunal Burrows


Uca spp.

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38



ca. 12” Deepca. 12” Deep

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39

Sulfur CycleSulfur Cycle

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from Jorgensen: in Microbial Geochemistry. Krumbein, ed: 1983 Blackwell.

Rates = mmol/m2 day

FeS2 + 3.5O2 + H2O = Fe2+ + 2SO42- + 2H+

Fe2+ + 0.25O2 + H+ = Fe3+ + 0.5H2O

Pyrite OxidationPyrite Oxidation

(1) FeS2 + 3.75O2 + 0.5H2O = Fe3+ + 2SO42- + H+

(2) FeS2 + 14Fe3++ 8H2O = 15Fe2+ + 2SO42- + 16H+

Fe2+ SO42- + H+

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Fe2+

Fe3+ FeS2

O2Slow (at low pH)

Biological[Thiobacillus ferrooxidans]

FastChemical/Biological

SO4 H

40

Drainage Effects on Acid Sulfate SoilsDrainage Effects on Acid Sulfate Soils

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Acid Sulfate SoilsAcid Sulfate Soils

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41

Acid Mine DrainageAcid Mine Drainage

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Sulfur Cycling in WetlandsSulfur Cycling in WetlandsPlant Biomass-S

DepositionSO4

2-

AEROBICAEROBICOrg-S

Adsorbed SO4

2-

Litterfall

Mineralization .

SO 2

SO42-So

H2SDMS

S2

Mineralization

Oxidation Oxidation

ReductionReduction

Tidal ExchangeH2SDMS

SO42-

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ANAEROBIC

4SO42-

MicrobialBiomass-S

Org-S S2- So

SO42-

FeS2

Me+-S

S2-

42

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Hg MethylationHg Methylation

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Gilmore et al., 1992. Env Sci Tech. 26:2281-2287.

43


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Gilmore et al., 1992


Desulfobacteriaceae

Lactate

Acetate

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King et al., 2000. Applied and Environmental Microbiology, June 2000, p. 2430-2437.

Control

44


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Methylmercury in Floating Periphyton

All Cycles 1995-1996

Periphyton Delta 32S

September 1996

ug/kg

>6

4

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2

0

Kendall et al., http://sofia.usgs.gov/publications/posters/

45

S2-


S0

HgS0HgS0

HgHg H3C-HgH3C-Hg

SRBSRB??

S0

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SO42-

HgS2HgS2

Importance of Sulfur in WetlandsImportance of Sulfur in Wetlands

• Source of nutrient

• Source of energy

• Role in decomposition of organic matter

• Adverse effects of sulfide on plant growth

• Immobilization of toxic metals

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• Contribution to acid development (oxidation)

• Role in methylation of Hg

sulfur - university of florida · 2 learning objectives identify the forms of s in wetlands sulfur...

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