Distribution character of localized iron microniche in lake sediment microzone revealed by chemical image

  • Zhihao Wu
  • Shengrui WangEmail author
  • Ningning Ji
Research Article


DGT (diffusive gradients in thin films) technique and LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry) for heterogeneous distribution of the soluble labile iron (Fe) at submillimeter resolution in lake sediment porewater are reported. The soluble labile Fe species include ion and labile organic complexes. The chemical images in two dimensions (2D) for DGT concentration of Fe (CDGT(Fe)) are investigated for Fe remobilization character. There are 902 CDGT(Fe) values between 1000 and 2000 μg L−1, 463 values between 2000 and 3000 μg L−1, and 112 values over 3000 μg L−1 in all chemical maps. Based on the linear correlation relationships between CDGT (Fe) and total Fe (TFe), total organic carbon (TOC), acid-volatile sulfide (AVS), Eh, concentrations of the soluble reactive phosphorus (P) (SRP), and soluble labile trace metals (Zn, Cu, Pb, and Zn) in a vertical 1D profile of sediment or porewater, Fe release mechanisms are mainly due to the reductive Fe release from iron oxyhydroxides and the decomposition of organic matter in algae biomass and deep sediment layer. It can be used to explain the formation mechanisms of Fe microniches in chemical maps with heterogeneous character to a great extent. CDGT(Fe) peak flux in the center of Fe microniche and the low CDGT (Fe) at the edge of a microniche are due to the formation of the insoluble iron sulfide and the abundant acid-volatile sulfide (AVS) in sediment. The verified co-remobilization of the soluble labile Fe and trace metals or SRP in sediment porewater can be used to predict their simultaneous release from Fe microniches with the large CDGT (Fe) peaks. The different kinds of Fe microniche zones and hot spots from sediment/water interface (SWI) to deep sediment correspond to the formation mechanisms of microniches mentioned above. Moreover, some narrow Fe microniche zones with the large CDGT (Fe) across chemical maps are due to the desorption of Fe(II) from the freshly formed oxide on Myriophyllum verticiilatur roots, which are located at sites of microniche zones.


Microniche Chemical image Diffusive gradients in thin films Laser ablation inductively coupled plasma mass spectrometry 



The authors thank Mingyue Hu, Linghao Zhao, and Dongyang Sun in the “Institute of National Research Center for Geoanalysis of China” for LA-ICP-MS analysis.

Funding information

This research was financially supported by the National Major Science and Technology Program for Water Pollution Control and Treatment (2012ZX07102-004); the Open fund project of Yunnan Key Laboratory of Pollution Process and Management of Plateau Lake-Watershed (No. 230200069), and the talent project of Beijing Normal University (No. 312232102).

Supplementary material

11356_2019_6219_MOESM1_ESM.docx (4.3 mb)
ESM 1 (DOCX 4454 kb)


  1. Asaeda T, Siong K (2008) Dynamics of growth, carbon and nutrient translocation in Zizania latifolia. Ecol Eng 32:156–165CrossRefGoogle Scholar
  2. Bender M, Martin W, Hess J, Sayles F, Ball L, Lambert C (1987) A whole core squeezer for interfacial pore-water sampling. Limnol Oceanogr 32:1214–1225CrossRefGoogle Scholar
  3. Böstrom B, Pettersson K (1982) Different patterns of phosphorus release from lake-sediments in laboratory experiments. Hydrobiologia 91-2:415–429CrossRefGoogle Scholar
  4. Chen WT, Zhou MF, Li XC, Gao JF, Hou K (2015) In-situ LA-ICP-MS trace elemental analyses of magnetite: Cu-(Au, Fe) deposits in the Khetri copper belt in Rajasthan Province. NW India Ore Geol Rev 65:929–939CrossRefGoogle Scholar
  5. Christophoridis C, Fytianos K (2006) Conditions affecting the release of phosphorus from surface lake sediments. J Environ Qual 35(4):1181–1192CrossRefGoogle Scholar
  6. Davison W, Fones GR, Grime GW (1997) Dissolved metals in surface sediment and a microbial mat at 100 um resolution. Nature 387:885–888CrossRefGoogle Scholar
  7. Ding SM, Wang Y, Wang D, Li YY, Gong MD, Zhang CS (2016) In situ, high-resolution evidence for iron-coupled mobilization of phosphorus in sediments. Sci Rep 6:24341–24351CrossRefGoogle Scholar
  8. Fones GR, Davison W, Hamilton-Taylor J (2004) The fine-scale remobilization of metals in the surface sediment of the North-East Atlantic. Cont Shelf Res 24:1485–1504CrossRefGoogle Scholar
  9. Gao Y, van de Velde S, Williams PN, Baeyens W, Zhang H (2015) Two-dimensional images of dissolved sulfide and metals in anoxic sediments by a novel diffusive gradients in thin film probe and optical scanning techniques. Trends Anal Chem 66:63–71CrossRefGoogle Scholar
  10. Glud RN (2008) Oxygen dynamics of marine sediments. Mar Biol Res 4:243–289CrossRefGoogle Scholar
  11. Graméli W, Solander D (1988) Influence of aquatic macrophytes on phosphorus cycling in lakes. Hydrobiologia 170:245–266CrossRefGoogle Scholar
  12. Guan DX, Williams PN, Luo J, Zheng JL, Xu HC, Cai C, Ma LQ (2015) Novel precipitated zirconia-based DGT technique for high-resolution imaging of oxyanions in waters and sediments. Environ Sci Technol 49:3653–3661CrossRefGoogle Scholar
  13. Hamilton-Taylor J, Morris EB (1985) The dynamics of iron and manganese in surface sediments of a seasonally anoxic lake. Archiv Hydrobiol Suppl 72:135–165Google Scholar
  14. Hesslein RH (1976) An in situ sampler for close interval pore water studies. Limnol Oceanogr 21:912–914CrossRefGoogle Scholar
  15. Huerta-Diaz MA, Tesssier A, Carignan R (1998) Geochemical of trace metals associated with reduced sulfur in freshwater sediments. Appl Geochem 13:213–233CrossRefGoogle Scholar
  16. Hyacinthe C, Anschultz P, Carbonel P, Jouanneau JM, Jorissen FJ (2001) Early diagenetic processes in the muddy sediments of the Bay of Biscay. Mar Geol 177:111–128CrossRefGoogle Scholar
  17. Johnson RG (1974) Particulate matter at the sediment-water interface in coastal environments. J Mar Res 32:313–330Google Scholar
  18. Jørgensen BB (1977) Bacterial sulfate reduction within reduced microniches of oxidized marine-sediments. Mar Biodivers 41:7–17Google Scholar
  19. Krom MD, Mortimer RJG, Hayes SWP, Davies IM, Davison W, Zhang H (2002) In-situ determination of dissolved iron production in recent marine sediments. Aquat Sci 64:282–291CrossRefGoogle Scholar
  20. Kühl M, Revsbech NP (2001) Biogeochemical microsensors for boundary layer studies. In: Boudreau BP, Jørgensen BB (eds) The Benthic Boundary Layer. Oxford University Press, OxfordGoogle Scholar
  21. Laskov C, Horn O, Hupfer M (2006) Environmental factors regulating the radial oxygen loss from roots of Myriophyllum spicatum and Potamogeton crispus. Aquat Bot 84(4):330–340CrossRefGoogle Scholar
  22. Liu YS, Hu ZC, Gao S, Günther D, Xu J, Gao CG, Chen HH (2008) In situ analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without applying an internal standard. Chem Geol 257:34–43CrossRefGoogle Scholar
  23. Liu CY, Chen CL, Gong XF, Zhou WB, Yang JY (2014) Progress in research of iron plaque on root surface of wetland plants. Acta Ecol Sin 34(10):2470–2480 (in Chinese)Google Scholar
  24. Morse JW, Luther GW III (1999) Chemical influences on trace metal-sulfide interactions in anoxic sediments. Geochim Cosmochim Acta 63:3373–3378CrossRefGoogle Scholar
  25. Morse JW, Millero FJ, Cornwell J, Rickard D (1987) The chemistry of the hydrogen sulfide and iron sulfide systems in natural waters. Earth-Sci Rev 24:1–42CrossRefGoogle Scholar
  26. Motelica-Heino M, Naylor C, Zhang H, Davison W (2003) Simultaneous release of metals and sulfide in lacustrine sediment. Environ Sci Technol 37:4374–4381CrossRefGoogle Scholar
  27. Palmer-Felgate EJ, Mortimer RJG, Krom MD, Jarvie HPR, Williams JR, Spraggs E, Stratford CJ (2011) Internal loading of phosphorus in a sedimentation pond of a treatment wetland: Effect of a phytoplankton crash. Sci Total Environ 409:2222–2232CrossRefGoogle Scholar
  28. Rickard D, Schoonen MAA, Luther GWIII (1995) Chemistry of iron sulfides in sedimentary environments. In: Vairavamurthy MA, Schoonen MAA (eds) Geochemical Transformations of Sedimentary Sulfur ACS Symposium Series, 612. ACS Washington, D.C, USA., pp 168–193CrossRefGoogle Scholar
  29. Saleque MA, Kirk GJD (1995) Root-induced solubilization of phosphate in the rhizosphere of lowland rice. New Phytol 129:325–336CrossRefGoogle Scholar
  30. Santner J, Prohaska T, Luo J, Zhang H (2010) Ferrihydrite containing gel for chemical imaging of labile phosphate species in sediments and soils using diffusive gradients in thin films. Anal Chem 82:7668–7674CrossRefGoogle Scholar
  31. Santner J, Larsen M, Kreuzeder A, Glud RN (2015) Two decades of chemical imaging of solutes in sediments and soils – a review. Anal Chim Acta 878:9–42CrossRefGoogle Scholar
  32. Scally S, Davison W, Zhang H (2003) In situ measurements of dissociation kinetics and labilities of metal complexes in solution using DGT. Environ Sci Technol 37:1379–1384CrossRefGoogle Scholar
  33. Scally S, Davison W, Zhang H (2006) Diffusion coefficients of metals and metal complexes in hydrogels used in diffusive gradients in thin films. Anal Chem Acta 558:222–229CrossRefGoogle Scholar
  34. Scarpelli R, De Francesco AM, Gaeta M, Cottica D, Toniolo L (2015) The provenance of the Pompeii cooking wares: Insights from LA–ICP-MS trace element analyses. Microchem J 119:93–101CrossRefGoogle Scholar
  35. Seltzer MD, Berry KH (2005) Laser ablation ICP-MS profiling and semiquantitative determination of trace element concentrations in desert tortoise shells: documenting the uptake of elemental toxicants. Sci Total Environ 339:253–265CrossRefGoogle Scholar
  36. Stockdale A, Davison W, Zhang H (2009) Micro-scale biogeochemical heterogeneity in sediments: A review of available technology and observed evidence. Earth-Sci Rev 92:81–97CrossRefGoogle Scholar
  37. Stockdale A, Davison W, Zhang H (2010) Formation of iron sulfide at faecal pellets and other microniches within suboxic surface sediment. Geochim Cosmochim AC 74:2665–2676CrossRefGoogle Scholar
  38. Taillefert M, Luther GW III, Nuzzio DB (2000) The application of electrochemical tools for in situ measurements in aquatic systems. Electroanalysis 12:401–412CrossRefGoogle Scholar
  39. Warnken KW, Zhang H, Davison W (2004a) Analysis of polyacrylamide gels for trace metals using diffusive gradients in thin films and laser ablation inductively coupled plasma mass spectrometry. Anal Chem 76:6077–6084CrossRefGoogle Scholar
  40. Warnken KW, Zhang H, Davison W (2004b) Performance characteristics of suspended particulate reagent-iminodiacetate as a binding agent for diffusive gradients in thin films. Anal Chim Acta 508:41–51CrossRefGoogle Scholar
  41. Warnken KW, Zhang H, Davison W (2006) Accuracy of the diffusive gradients in thin-films technique: diffusive boundary layer and effective sampling area considerations. Anal Chem 78(11):3780–3787CrossRefGoogle Scholar
  42. Widerlund A, Davison W (2007) Size and density distribution of sulfide-producing microniches in lake sediments. Environ Sci Technol 41:8044–8049CrossRefGoogle Scholar
  43. Williams PN, Santner J, Larsen M, Lehto NJ, Oburger E, Wenzel W, Glud RN, Davison W, Zhang H (2014) Localized flux maxima of Arsenic, Lead, and Iron around root apices in flooded lowland rice. Environ Sci Technol 48:8498–8506CrossRefGoogle Scholar
  44. Wu ZH, Wang SR (2017) Release mechanism and kinetic exchange for phosphorus (P) in lake sediment characterized by diffusive gradients in thin films (DGT). J Hazard Mater 331:36–44CrossRefGoogle Scholar
  45. Wu B, Zoriy M, Chen YX, Becker JS (2009) Imaging of nutrient elements in the leaves of Elsholtzia splendens by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Talanta 78:132–137CrossRefGoogle Scholar
  46. Wu ZH, Wang SR, He MC, Zhang L, Jiao LX (2015a) Element remobilization, “internal P-loading” and sediment-P reactivity researched by DGT (diffusive gradients in thin films) technique. Environ Sci Pollut Res 22:16173–16183CrossRefGoogle Scholar
  47. Wu ZH, Wang SR, Jiao LX (2015b) Geochemical behavior of metals-sulfide-phosphorus at SWI (sediment/water interface) assessed by DGT (Diffusive gradients in thin films) probes. J Geochem Explor 156:145–152CrossRefGoogle Scholar
  48. Zeng XZ, Lv SH, Liu WJ, Zhang XK, Zhang FS (2001) Effects of root surface iron and manganese oxide plaque on iron, manganese and phosphorus, zinc nutrition of rice. Southw China J Agric Sci 14(4):34–38 (in Chinese)Google Scholar
  49. Zhang H, Davison W, Miller S, Tych W, (1995) In situ high-resolution measurements of fluxes of Ni, Cu, Fe, and Mn and concentrations of Zn and Cd in porewaters by DGT. Geochim.Cosmochim. Acta 59, 4181–4192CrossRefGoogle Scholar
  50. Zhang H, Davison W, Mortimer RJG, Krom MD, Hayes PJ, Davies IM (2002) Localised remobilization of metals in a marine sediment. Sci Total Environ 296:175–187CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.National Engineering Laboratory for Lake Pollution Control and Ecological Restoration, Chinese Research Academy of Environmental Sciences (CRAES)BeijingChina
  2. 2.Yunnan Key Laboratory of Pollution Process and Management of Plateau Lake-WatershedKunmingChina
  3. 3.College of Water SciencesBeijing Normal UniversityBeijingChina

Personalised recommendations