Advertisement

Biogeochemistry

, Volume 103, Issue 1–3, pp 263–279 | Cite as

Effects of hyper-enriched reactive Fe on sulfidisation in a tidally inundated acid sulfate soil wetland

  • Annabelle F. Keene
  • Scott G. Johnston
  • Richard T. Bush
  • Leigh A. Sullivan
  • Edward D. Burton
  • Angus E. McElnea
  • Colin R. Ahern
  • Bernard Powell
Article

Abstract

Solid phase Fe and S fractions were examined in an acid sulfate soil (ASS) wetland undergoing remediation via tidal inundation. Considerable diagenetic enrichment of reactive Fe(III) oxides (HCl- and dithionite-extractable) occurred near the soil surface (0–0.05 m depth), where extremely large concentrations up to 3534 μmol/g accounted for ~90% of the total Fe pool. This major source of reactive Fe exerts a substantial influence on S cycling and the formation, speciation and transformation of reduced inorganic S (RIS) in tidally inundated ASS. Under these geochemical conditions, acid volatile sulfide (AVS; up to 57 μmol/g) and elemental sulfur (S0; up to 41 μmol/g) were the dominant fractions of RIS in near surface soils. AVS–S to pyrite–S ratios exceeded 2.9 near the surface, indicating that abundant reactive Fe favoured the accumulation of AVS minerals and S0 over pyrite. This is supported by the significant correlation of poorly crystalline Fe with AVS–S and S0–S contents (r = 0.83 and r = 0.85, respectively, P < 0.01). XANES spectroscopy provided direct evidence for the presence of a greigite-like phase in AVS–S measured by chemical extraction. While the abundant reactive Fe may limit the transformation of AVS minerals and S0 to pyrite during early diagenesis (~5 years), continued sulfidisation over longer time scales is likely to eventually lead to enhanced sequestration of S within pyrite (with a predicted 8% pyrite by mass). These findings provide an important understanding of sulfidisation processes occurring in reactive Fe-enriched, tidally inundated ASS landscapes.

Keywords

Acid sulfate soil Reactive iron Reduced inorganic sulfur Sulfidisation Tidal inundation Wetland 

Abbreviations

ASS

Acid sulfate soil

AVS

Acid volatile sulfide

CRS

Chromium-reducible sulfur

DOP

Degree of pyritisation

DOS

Degree of sulfidisation

RIS

Reduced inorganic sulfur

XANES

X-ray absorption near-edge structure

Notes

Acknowledgements

We would like to thank the Queensland Department of Environment and Resource Management (DERM) who facilitated this research and the assistance of DERM staff at the East Trinity field site is gratefully acknowledged. Synchrotron access was funded by the Australian Synchrotron Research Program and the National Synchrotron Radiation Research Centre (NSRRC) in Taiwan, and we thank Dr Rosalie Hocking of Monash University, Australia and Dr L-Y Jang of NSRRC, Taiwan for their assistance with XANES data collection. This research was supported by the Cooperative Research Centre for Contamination Assessment and Remediation of the Environment (Project No. 6-6-01-06/07). We thank the Editor and reviewers for their constructive comments on this manuscript.

References

  1. APHA-AWWA-WEF (2005) Standard methods for the examination of water and wastewater. American Public Health Association, American Water Works Association and Water Environment Federation, BaltimoreGoogle Scholar
  2. Bartlett JK, Skoog DA (1954) Colorimetric determination of elemental sulfur in hydrocarbons. Anal Chem 26:1008–1011CrossRefGoogle Scholar
  3. Berner RA (1970) Sedimentary pyrite formation. Am J Sci 268:1–23CrossRefGoogle Scholar
  4. Boesen C, Postma D (1988) Pyrite formation in anoxic environments of the Baltic. Am J Sci 288:575–603CrossRefGoogle Scholar
  5. Boman A, Åström M, Fröjdö S (2008) Sulfur dynamics in boreal acid sulfate soils rich in metastable iron sulfide—the role of artificial drainage. Chem Geol 255:68–77CrossRefGoogle Scholar
  6. Boman A, Fröjdö S, Backlund K, Åström ME (2010) Impact of isostatic land uplift and artificial drainage on oxidation of brackish-water sediments rich in metastable iron sulfide. Geochim Cosmochim Acta 74:1268–1281CrossRefGoogle Scholar
  7. Bureau of Meteorology (2010) Monthly climate statistics for Cairns Aero. Commonwealth of Australia, Canberra. http://www.bom.gov.au/climate/averages. Accessed 29 Mar 2010
  8. Burton ED, Phillips IR, Hawker DW (2005) Reactive sulfide relationships with trace metal extractability in sediments from southern Moreton Bay, Australia. Mar Pollut Bull 50:589–595Google Scholar
  9. Burton ED, Bush RT, Sullivan LA (2006a) Fractionation and extractability of sulfur, iron and trace elements in sulfidic sediments. Chemosphere 64:1421–1428CrossRefGoogle Scholar
  10. Burton ED, Bush RT, Sullivan LA (2006b) Reduced inorganic sulfur speciation in drain sediments from acid sulfate soil landscapes. Environ Sci Technol 40:888–893CrossRefGoogle Scholar
  11. Burton ED, Bush RT, Sullivan LA, Mitchell DRG (2007) Reductive transformation of iron and sulfur in schwertmannite-rich accumulations associated with acidified coastal lowlands. Geochim Cosmochim Acta 71:4456–4473CrossRefGoogle Scholar
  12. Burton ED, Bush RT, Sullivan LA, Mitchell DRG (2008a) Schwertmannite transformation to goethite via the Fe(II) pathway: reaction rates and implications for iron-sulfide formation. Geochim Cosmochim Acta 72:4551–4564CrossRefGoogle Scholar
  13. Burton ED, Sullivan LA, Bush RT, Johnston SG, Keene AF (2008b) A simple and inexpensive chromium-reducible sulfur method for acid-sulfate soils. Appl Geochem 23:2759–2766CrossRefGoogle Scholar
  14. Burton ED, Bush RT, Sullivan LA, Hocking RK, Mitchell DRG, Johnston SG, Fitzpatrick RW, Raven M, McClure S, Jang LY (2009) Iron-monosulfide oxidation in natural sediments: resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions. Environ Sci Technol 43:3128–3134CrossRefGoogle Scholar
  15. Bush RT, Sullivan LA (1997) Morphology and behaviour of greigite from a Holocene sediment in eastern Australia. Aust J Soil Res 35:853–861CrossRefGoogle Scholar
  16. Bush RT, Fyfe D, Sullivan LA (2004) Occurrence and abundance of monosulfidic black ooze in coastal acid sulfate soil landscapes. Aust J Soil Res 42:609–616CrossRefGoogle Scholar
  17. Canfield DE (1989) Reactive iron in marine sediments. Geochim Cosmochim Acta 53:619–632CrossRefGoogle Scholar
  18. Canfield DE, Raiswell R, Westrich JT, Reaves CM, Berner RA (1986) The use of chromium reduction in the analysis of reduced inorganic sulfur in sediments and shales. Chem Geol 54:149–155CrossRefGoogle Scholar
  19. Canfield DE, Raiswell R, Bottrell S (1992) The reactivity of sedimentary iron minerals towards sulfide. Am J Sci 292:659–683CrossRefGoogle Scholar
  20. Cornwell JC, Morse JW (1987) The characterization of iron sulfide minerals in anoxic marine sediments. Mar Chem 22:193–206CrossRefGoogle Scholar
  21. Dent D (1986) Acid sulphate soils: a baseline for research and development. ILRI Publication 39. International Institute for Land Reclamation & Improvement, WageningenGoogle Scholar
  22. Fältmarsch RM, Åström ME, Vuori K-M (2008) Environmental risks of metals mobilised from acid sulphate soils in Finland: a literature review. Boreal Environ Res 13:444–456Google Scholar
  23. Gagnon C, Mucci A, Pelletier E (1995) Anomalous accumulation of acid-volatile sulphides (AVS) in a coastal marine sediment, Saguenay Fjord, Canada. Geochim Cosmochim Acta 59:2663–2675CrossRefGoogle Scholar
  24. Giblin AE, Howarth RW (1984) Porewater evidence for a dynamic sedimentary iron cycle in salt marshes. Limnol Oceanogr 29:47–63CrossRefGoogle Scholar
  25. Giblin AE, Wieder RK (1992) Sulfur cycling in marine and fresh wetlands. In: Howarth RW, Stewart JWB, Ivanov MV (eds) Sulfur cycling on the continents: wetlands, terrestrial ecosystems and associated water bodies. Wiley, Chichester, pp 85–117Google Scholar
  26. Hicks WS, Bowman GM, Fitzpatrick RW (1999) East Trinity acid sulfate soils. Part 1: Environmental hazards. Technical Report 14/99. CSIRO Land & Water, Adelaide, p 79Google Scholar
  27. Hicks W, Fitzpatrick RW, Bowman G (2003) Managing coastal acid sulfate soils: the East Trinity example. In: Roach IC (ed) Advances in regolith: Proceedings of the CRC LEME regional regolith symposia. CRC LEME, Bentley, pp 174–177Google Scholar
  28. Holmer M, Kristensen E, Banta G, Hansen K, Jensen M, Bussawarit N (1994) Biogeochemical cycling of sulfur and iron in sediments of a south-east Asian mangrove, Phuket Island, Thailand. Biogeochemistry 26:145–161CrossRefGoogle Scholar
  29. Howarth RW, Jørgensen BB (1984) Formation of 35S-labelled elemental sulfur and pyrite in coastal marine sediments (Limfjorden and Kysing Ford, Denmark) during short-term 35SO4 2− reduction measurements. Geochim Cosmochim Acta 48:1807–1818CrossRefGoogle Scholar
  30. Hsieh YP, Chung SW, Tsau YJ, Sue CT (2002) Analysis of sulfides in the presence of ferric minerals by diffusion methods. Chem Geol 182:195–201CrossRefGoogle Scholar
  31. Huerta-Díaz MA, Morse JW (1990) A quantitative method for determination of trace metal concentrations in sedimentary pyrite. Mar Chem 29:119–144CrossRefGoogle Scholar
  32. Johnston SG, Bush RT, Sullivan LA, Burton ED, Smith D, Martens MA, McElnea AE, Ahern CR, Powell B, Stephens LP, Wilbraham ST, van Heel S (2009a) Changes in water quality following tidal inundation of coastal lowland acid sulfate soil landscapes. Estuar Coast Shelf Sci 81:257–266CrossRefGoogle Scholar
  33. Johnston SG, Keene AF, Bush RT, Burton ED, Sullivan LA, Smith D, McElnea AE, Martens MA, Wilbraham S (2009b) Contemporary pedogenesis of severely degraded tropical acid sulfate soils after introduction of regular tidal inundation. Geoderma 149:335–346CrossRefGoogle Scholar
  34. Johnston SG, Burton ED, Bush RT, Keene AF, Sullivan LA, Smith D, McElnea AE, Ahern CR, Powell B (2010a) Abundance and fractionation of Al, Fe and trace metals following tidal inundation of a tropical acid sulfate soil. Appl Geochem 25:323–335CrossRefGoogle Scholar
  35. Johnston SG, Keene AF, Burton ED, Bush RT, Sullivan LA, McElnea AE, Ahern CR, Smith CD, Powell B, Hocking RK (2010b) Arsenic mobilization in a seawater inundated acid sulfate soil. Environ Sci Technol 44:1968–1973CrossRefGoogle Scholar
  36. Kostka JE, Luther GW (1994) Partitioning and speciation of solid phase iron in saltmarsh sediments. Geochim Cosmochim Acta 7:1701–1710CrossRefGoogle Scholar
  37. Kostka JE, Luther GW (1995) Seasonal cycling of Fe in saltmarsh sediments. Biogeochemistry 29:159–181CrossRefGoogle Scholar
  38. Lax K (2005) Stream plant chemistry as indicator of acid sulphate soils in Sweden. Agric Food Sci 14:83–97CrossRefGoogle Scholar
  39. Leventhal J, Taylor C (1990) Comparison of methods to determine degree of pyritization. Geochim Cosmochim Acta 54:2621–2625CrossRefGoogle Scholar
  40. Lord CJ, Church TM (1983) The geochemistry of salt marshes: sedimentary ion diffusion, sulfate reduction, and pyritization. Geochim Cosmochim Acta 47:1381–1391CrossRefGoogle Scholar
  41. Lovely DR, Phillips EJP (1987) Competitive mechanisms for inhibition of sulfate reduction and methane production in the zone of ferric iron reduction in sediments. Appl Environ Microbiol 53:2636–2641Google Scholar
  42. Luther GW, Ferdelman TG, Kostka JE, Tsamabis EJ, Church TM (1991) Temporal and spatial variability of reduced sulfur species (FeS2, S2O3 2−) and porewater parameters in salt marsh sediments. Biogeochemistry 14:57–88CrossRefGoogle Scholar
  43. Macdonald BCT, Smith J, Keene AF, Tunks M, Kinsela A, White I (2004) Impacts of runoff from sulfuric soils on sediment chemistry in an estuarine lake. Sci Total Environ 329:115–130CrossRefGoogle Scholar
  44. Middelburg JJ (1991) Organic carbon, sulphur, and iron in recent semi-euxinic sediments of Kau Bay, Indonesia. Geochim Cosmochim Acta 55:815–828CrossRefGoogle Scholar
  45. Morgan KE, Burton ED, Cook P, Raven MD, Fitzpatrick RW, Bush RT, Sullivan LA, Hocking RK (2009) Fe and S K-edge XAS determination of iron-sulfur species present in a range of acid sulfate soils: effects of particle size and concentration on quantitative XANES determinations. 14th international conference on x-ray absorption fine structure (XAFS14). J Phys Conf Ser 190:012144CrossRefGoogle Scholar
  46. Morse JW, Cornwell JC (1987) Analysis and distribution of iron sulfide minerals in recent anoxic marine sediments. Mar Chem 22:55–69CrossRefGoogle Scholar
  47. Morse JW, Rickard D (2004) Chemical dynamics of sedimentary acid volatile sulfide. Environ Sci Technol 38:131A–136ACrossRefGoogle Scholar
  48. Nickerson NH, Thibodeau FR (1985) Association between pore water sulfide concentrations and the distribution of mangroves. Biogeochemistry 1:183–192CrossRefGoogle Scholar
  49. Otero XL, Macías F (2002) Variation with depth and season in metal sulfides in salt marsh soils. Biogeochemistry 61:247–268CrossRefGoogle Scholar
  50. Otero XL, Ferreira TO, Huerta-Díaz MA, Partiti CSM, Souza V, Vidal-Torrado P, Macías F (2009) Geochemistry of iron and manganese in soils and sediments of a mangrove system, Island of Pai Matos (Cananeia, SP, Brazil). Geoderma 148:318–335CrossRefGoogle Scholar
  51. Portnoy JW, Giblin AE (1997) Effects of historic tidal restrictions on salt marsh sediment chemistry. Biogeochemistry 36:275–303CrossRefGoogle Scholar
  52. Postma D, Jacobsen R (1996) Redox zonation: equilibrium constraints on the Fe(III)/SO4-reduction interface. Geochim Cosmochim Acta 60:3169–3175CrossRefGoogle Scholar
  53. Poulton SW (2003) Sulfide oxidation and iron dissolution kinetics during the reaction of dissolved sulfide with ferrihydrite. Chem Geol 202:79–94CrossRefGoogle Scholar
  54. Powell B, Martens M (2005) A review of acid sulfate soil impacts, actions and policies that impact on water quality in Great Barrier Reef catchments, including a case study on remediation at East Trinity. Mar Pollut Bull 51:149–164CrossRefGoogle Scholar
  55. Pyzik AJ, Sommer SE (1981) Sedimentary iron monosulfides: kinetics and mechanism of formation. Geochim Cosmochim Acta 45:687–698CrossRefGoogle Scholar
  56. Raiswell R, Canfield DE, Berner RA (1994) A comparison of iron extraction methods for the determination of degree of pyritisation and the recognition of iron-limited pyrite formation. Chem Geol 111:101–110CrossRefGoogle Scholar
  57. Rayment GE, Higginson FR (1992) Australian laboratory handbook of soil and water chemical methods. Inkata Press, MelbourneGoogle Scholar
  58. Rickard DT (1974) Kinetics and mechanism of the sulfidation of goethite. Am J Sci 274:941–952CrossRefGoogle Scholar
  59. Rickard DT (1975) Kinetics and mechanism of pyrite formation at low temperatures. Am J Sci 275:636–652CrossRefGoogle Scholar
  60. Rickard D (1997) Kinetics of pyrite formation by the H2S oxidation of iron(II) monosulfide in aqueous solutions between 25 and 125°C: the rate equation. Geochim Cosmochim Acta 61:115–134CrossRefGoogle Scholar
  61. Rickard D, Morse JW (2005) Acid volatile sulfide (AVS). Mar Chem 97:141–197CrossRefGoogle Scholar
  62. Sammut J, White I, Melville MD (1996) Acidification of an estuarine tributary in eastern Australia due to drainage of acid sulphate soils. Mar Freshw Res 47:669–684CrossRefGoogle Scholar
  63. Smith CD, Martens MA, Ahern CR, Eldershaw VJ, Powell B, Hopgood GL, Barry EV, Watling KM (2003) Demonstration of management and rehabilitation of acid sulfate soils at East Trinity: Technical Report QNRM03059. Queensland Department of Natural Resources & Mines, IndooroopillyGoogle Scholar
  64. Soil Survey Staff (2006) Keys to soil taxonomy. US Department of Agriculture (USDA) & National Resources Conservation Service (NRCS), Washington, DCGoogle Scholar
  65. Solomon S, Qin D, Manning M, Chen Z, Marquis M, Avery KB, Tignor M, Miller HL (eds) (2007) Climate change 2007: the physical science basis. Contribution of working group I to the fourth assessment report of the intergovernmental panel on climate change. Cambridge University Press, New YorkGoogle Scholar
  66. Sullivan LA, Bush RT (2004) Iron precipitate accumulations associated with waterways in drained coastal acid sulfate landscapes of eastern Australia. Mar Freshw Res 55:1–10CrossRefGoogle Scholar
  67. Sundström R, Åström M, Österholm P (2002) Comparison of the metal content in acid sulfate soil runoff and industrial effluents in Finland. Environ Sci Technol 36:4269–4272CrossRefGoogle Scholar
  68. Tenderholt A, Hedman B, Hodgson KO (2006) PySpline: a modern, cross-platform program for the processing of raw averaged XAS edge and EXAFS data. SLAC-PUB-12219Google Scholar
  69. Thode-Andersen S, Jørgensen BB (1989) Sulfate reduction and the formation of 35S-labelled FeS, FeS2, and S0 in coastal marine sediments. Limnol Oceanogr 34:793–806CrossRefGoogle Scholar
  70. van Breemen N (1973) Soil forming processes in acid sulphate soils. In: Dost H (ed) Proceedings of the international symposium on acid sulphate soils. ILRI Publication 18, vol 1. International Institute for Land Reclamation & Improvement, Wageningen, pp 66–129Google Scholar
  71. Wallmann K, Hennies K, König I, Petersen W, Knauth HD (1993) New procedure for determining reactive Fe(III) and Fe(II) minerals in sediments. Limnol Oceanogr 38:1803–1812CrossRefGoogle Scholar
  72. Yao WS, Millero FJ (1996) Oxidation of hydrogen sulfide by hydrous Fe(III) oxides in seawater. Mar Chem 52:1–16CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2010

Authors and Affiliations

  • Annabelle F. Keene
    • 1
  • Scott G. Johnston
    • 1
  • Richard T. Bush
    • 1
  • Leigh A. Sullivan
    • 1
  • Edward D. Burton
    • 1
  • Angus E. McElnea
    • 2
  • Colin R. Ahern
    • 2
  • Bernard Powell
    • 2
  1. 1.Southern Cross GeoScienceSouthern Cross UniversityLismoreAustralia
  2. 2.Department of Environment and Resource ManagementIndooroopillyAustralia

Personalised recommendations