Abstract
A field and laboratory study of the accuracy of a method commonly used to determine free sulphide concentrations in the porewater of marine sediments is presented. The method uses an ion-selective electrode (ISE), sensitive to the sulphide ion (S2−), in sediments buffered to high pH (>12) and is commonly used in regulatory monitoring programs to assess the impacts of open net-pen finfish aquaculture on local marine habitats. Here we report that on the timescale of field measurements, the accepted protocol can lead to significant bias of free sulphide measurements, with orders of magnitude higher concentration detected in the buffered sediment–porewater slurry than in porewater samples isolated and analysed separately. Laboratory experiments with model marine sediments and analysis of sediment composition indicate that this bias is likely introduced by the dissolution of particulate sulphides and/or sulphur present in the sediments under the intense alkaline conditions of the protocol. Recommendations for the modification and continued use of this commonly applied field methodology are discussed.
Similar content being viewed by others
References
Allam AI, Pitts G, Hollis JP (1972) Sulfide determination in submerged soils with an ion selective electrode. Soil Sci 114(6):456–467
Auditor General (2004) Report 5, Salmon Forever: An assessment of the provincial role in sustaining wild salmon, Report of the auditor general of British Columbia, October 2004. ISBN 0—7726—5216—0. p 18
Bagarinao T (1992) Sulfide as an environmental factor and toxicant: tolerance and adaptations in aquatic organisms. Aquatic Toxicology 24:21–62
BCMOE (2002a) Environmental management act: Finfish aquaculture waste control regulation B.C Reg. 256/2002 O.C.836/2002. Queen’s Printer, Victoria
BCMOE (2002b) Protocols for Marine Environmental Monitoring B.C Reg. 256/2002 O.C.836/2002 Schedule B. Queen’s Printer, Victoria
BCMOE (2003) Environmental management act, SBC 2003, Chapter 53. Queen’s Printer, Victoria, British Columbia, Canada
Berner RA (1963) Electrode studies of hydrogen sulfide in marine sediments. Geochim Cosmo Act 27:563–575
Billon G, Ouddane B, Laureyns J, Boughriet A (2001) Chemistry of metal sulphide in anoxic sediments. Phys Chem Chem Phys 3:3586–3592
Brooks KM (2001a) An evaluation of the relationship between salmon farm biomass, organic inputs to sediments, physiochemical changes associated with those inputs and the infaunal response—with emphasis on total sediment sulphides, total volatile solids, and oxidation-reduction potential as surrogate endpoints for biological monitoring, Final Report. p 172. Aquatic Environmental Sciences, 644 Old Eaglemont Road, Port Townsend, Washington, USA
Brooks KM (2001b) Recommendations to the British Columbia farmed salmon waste management technical advisory group for biological and physicochemical performance standards applicable to marine Netpens. For: the technical advisory group, BC MoE. pp 24
Brooks KM, Mahnken CVW (2003) Interactions of Atlantic salmon in the Pacific northwest environment II. Organic wastes. Fish Res 62:255–293
Brooks KM, Stierns AR, Backman C (2004) Seven year remediation study at the Carrie Bay Atlantic salmon (Salmo salar) farm in the Broughton Archipelago, British Columbia, Canada. Aquaculture 239:81–123
Cassella RJ, De Oliveira LG, Santelli RE (1999) On line dissolution of ZnS for sulfide determination in stabilized water samples with zinc acetate, using spectrophotometry by methylene blue Spec. Letters 32(2):469–484
Clesceri LS, Greenberg AE, Eaton AD, Clesceri LS, Greenberg AE, Eaton AD (eds) (1998) Standard methods for the examination of water and wastewater. United book press (Maryland) pp 4–167
Cline JD (1969) Spectrophotometric determination of Hydrogen sulphide in natural waters. Limnol Oceaogr 14(3):454–458
Fonselius SH (1983) Determination of hydrogen sulphide. In: Grasshoff K, Ehrhardt M, Kremling K (eds) Methods of seawater analysis, 2nd edn. Verlag Chemie, Berlin, pp 73–80
Glaister MG, Moody GJ, Thomas JDR (1985) Studies on flow injection analysis with sulpihde ion-selective electrodes. Analyst 110:113–119
Hargrave BT, Phillipps GA, Doucette LI, White MJ, Milligan TG, Wildish DJ, Cranston RE (1997) Assessing benthic impacts of organic enrichment from marine aquaculture. Water Air and Soil Poll 99:641–650
Hargrave BT, Holmer M, Newcombe CP (2008) Towards a classification of organic enrichment in marine sediments based on biogeochemical indicators. Mar Poll Bull 56:810–824
Holland HD (1978) The chemistry of the atmosphere and oceans. Wiley, New York
Hseu TM, Rechnitz GA (1968) Analytical study of a sulfide ion-selective membrane electrode in alkaline solution. Anal Chem 40(7):1054–1060
Johnson KM, Grimm KA (2001) Opal and organic carbon in laminated diatomaceous sediments: Saanich Inlet, santa barbara basin and the miocene monterey formation. Marine Geo 174:159–175
Latimer WM (1952) Oxidation potentials (2nd edn). Prentice-Hall, Englewood Cliffs, pp 1–392
Luther GW III, Glazer BT, Hohmann L, Popp JI, Taillefert M, Rozan TF, Brendel PJ, Theberge SM, Nuzzio DB (2001a) Sulfur speciation monitored in situ with solid state gold amalgam voltammetric microelectrodes: polysulfides as a special case in sediments, microbial mats and hydrothermal vent waters. J Environ Monitoring 3(1):61–66
Luther GW III, Rozan TF, Taillefert M, Nuzzio DB, Di Meo C, Shank TM, Lutz RA, Cary SC (2001b) Chemical speciation drives hydrothermal vent ecology. Nature 410:813–816
Meyer B, Ward K, Koshlap K, Peter L (1983) Second dissociation constant of hydrogen sulfide. Inorg Chem 22(16):2345–2346
Migdisov AA, Williams-Jones AE, Lakshtanov LZ, Alekhin YV (2002) Estimates of the second dissociation constant of H2S from the surface sulfidation of crystalline sulfur. Geochem Cosmochim Acta 66(10):1713–1725
Morel FMM, Hering JG (1993) Principles and applications of aquatic chemistry. Wiley, New York. pp 264–272, 398–404
Mosher DC, Moran K (2001) Post-glacial evolution of Saanich Inlet, British Columbia: results of physical property and seismic reflection stratigraphic analysis. Marine Geo 174:59–77
Nash CE (2001) The net-pen salmon farming Industry in the Pacific Northwest. US Dept Commer, NOAA Tech. Memo. NMFS-NWFSC-49 pp 125
Nicholls P (1975) The effect of sulfide on cytochrome aa3 isoteric and allosteric shifts of reduced alpha-peak. Biochim Hiophyr Am 396:24–35
Parsons TR, Maita Y, Lalli CM (1984) A manual of biological and chemical methods for seawater analysis. Publ Pergamon Press, Oxford, p 173
Rickard D, Luther GW (2007) Chemistry of iron sulfides. Chem Rev 107(2):514–562
Rickard D, Morse JW (2005) Acid volatile sulphide (AVS). Mar Chem 97(3–4):141–197
Sarradin PM, LeBris N, Birot D, Caprais JC (1999) Laboratory adaptation of the methylene blue method to flow injection analysis: towards in situ sulfide analysis in hydrothermal seawater. Anal Commun 36:157–160
Statistics Canada (2007) Statistics Canada, Agriculture Division, Livestock Section: Aquaculture Statistics - Catalogue no. 23–222-×. Minister of Industry, Ottawa
Sutherland TF, Petersen SA, Levings CD, Martin AJ (2007) Distinguishing between natural and aquaculture-derived sediment concentrations of heavy metals in the Broughton Archipelago, British Columbia. Mar Poll Bull 54:1451–1460
Thamdrup B, Finster K, Fossing H, Wurgler-Hansen J, Barker-Jorgensen B (1994) Thiosulfate and sulfite distributions in porewater of marine sediments related to manganese, iron, and sulfur geochemistry. Geochim Cosmo Acta 58:67–73
Wang F, Chapman PM (1999) Biological implications of sulphide in sediment—a review focusing on sediment toxicity. Env Toxi Chem 18(11):2526–2532
Whitfield M (1969) Eh as an operational parameter in estuarine studies. Limnol & Oceanogr 14(4):547–558
Whitfield M (1974) The ion-association model and the buffer capacity of the carbon dioxide system in seawater at 25 C and 1 atmosphere total pressure. Limnol & Oceanogr 19(2):235–248
Wildish DJ, Akagi HM, Hamilton N, Hargrave BT (1999) A recommended method for monitoring sediments to detect organic enrichment from mariculture in the Bay of Fundy. Canadian Technical Report of Fisheries and Aquatic Sciences 2286, St. Andrews, NB
Acknowledgments
The authors would like to thank the following people for their much-appreciated assistance throughout the duration of this project: Kirsten White, the Ministry of Environment, Nanaimo BC; field work assistance from Conservation Officers Dan Dwyer and Gord Gudbranson, Marine Technician Conrad Cooper, Captain Ken Brown and the crew of the RV John Strickland; Sharon Blackmore (UVIC) for preparation of SEM samples; and the SEM laboratory (Brent Gowen) at the University of Victoria. This research was funded by a grant from the BC MOE and NSERC to JTC.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Brown, K.A., McGreer, E.R., Taekema, B. et al. Determination of Total Free Sulphides in Sediment Porewater and Artefacts Related to the Mobility of Mineral Sulphides. Aquat Geochem 17, 821–839 (2011). https://doi.org/10.1007/s10498-011-9137-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10498-011-9137-0