Comparing in situ colorimetric DET and DGT techniques with ex situ core slicing and centrifugation for measuring ferrous iron and dissolved sulfide in coastal sediment pore waters

In productive coastal sediments the separation between different biogeochemical zones (e.g. oxic, iron(III)-reducing and sulfate-reducing) may be on the scale of millimetres. Conventional measurement techniques simply cannot resolve changes in pore water solute concentrations over such small distances. The diffusive equilibration in thin films (DET) and the diffusive gradients in thin films (DGT) techniques allow in situ determination of pore water solute concentration profiles with one-dimensional profiles and/or two-dimensional distributions on the millimetre scale. Here we compare measurements of pore water iron(II) and sulfide using conventional core sampling (slicing and centrifugation) and colorimetric DET-DGT techniques. DET-DGT samplers were deployed within replicate sediment cores from three different sites, which were processed by slicing and centrifugation following retrieval of the samplers, so that the measurements were approximately co-located. Iron(II) concentrations were determined by DET at all three sites (0.3–262 μmol L⁻¹), while dissolved sulfide was consistently measured by DGT at one site only (0.003–112 μmol L⁻¹). Pore water concentrations of iron(II) and sulfide determined conventionally following pore water extraction (iron(II); 0.4–88 μmol L⁻¹ and sulfide; 0.05–36 μmol L⁻¹), were systematically lower than the colorimetric DET and DGT measurements in the same sample. This underestimation was most likely due to the mixing of sediment from different biogeochemical zones during pore water extraction, which resulted in the precipitation of iron(II) and sulfide. This study shows that conventional pore water extraction methods can be unreliable for the determination of redox-active solutes due to artefacts associated with pore water mixing.