How to overcome inter-electrode variability and instability to quantify dissolved oxygen, Fe(II), mn(II), and S(?II) in undisturbed soils and sediments using voltammetry

Background

Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach??the pilot ion method??has not been documented in detail.

Results

A detailed procedure for testing electrode quality is provided, and the application and limitations of the pilot ion method have been documented. To quantify Fe(II) and Mn(II), subtraction of non-linear baseline functions from voltammetric signals produced better calibration curves than did linear baselines, enabled lower detection limits and reliable deconvolution of overlapping signals, and was successfully applied to sediment pore water signals. We observed that electrode sensitivities often vary by tens of percent, and that the sensitivity declines over time. The ratio of calibration slopes of Mn(II) to Fe(II) varied by no more than 11% from one Hg/Au electrode to another and Fe(II) concentrations predicted by the Mn(II) pilot ion were, on average, 13% different from their actual values. However, concentration predictions by the pilot ion method were worse for less than 15???M Fe(II) (46% different on average). The ratio of calibration slopes of Mn(II) to S(?II) varied by almost 20% from one Hg/Au electrode to another, and S(?II) predicted concentrations were as much as 58% different from their actual values. These predictions of Fe(II) and S(?II) concentrations indicate that the accuracy of the pilot ion method depends on how independent calibration slope ratios are from the electrode used. At medium-to-high concentration for the ocean, naturally derived dissolved organic carbon did not significantly affect the baseline-corrected electrode response of Mn(II) and Fe(II), but did significantly affect the response of S(?II).

Conclusions

Despite their intrinsic variability, Hg/Au electrodes fabricated by hand can be used to quantify O₂, S(?II), Fe(II), and Mn(II) without calibrating every electrode for every constituent of interest. The pilot ion method can achieve accuracies to within 20% or less, provided that the underlying principle??the independence of slope ratios??is demonstrated for all voltammetric techniques used, and effects of the physicochemical properties of the system on voltammetric signals are addressed through baseline subtraction.     

Submarine outcrop and acoustic expression of lithified sediment layers in northwest Providence Channel, Bahamas

 Visual observations of the wall of Great Bahama Canyon indicate that ledges produced by differential submarine erosion occur at depths like reflectors on high-resolution seismic profiles, suggesting lithologic changes produce acoustic impedance contrasts and therefore reflectors. Quaternary-aged sediments in a core from Little Bahama Bank exhibit changes in lithology (and presumably acoustic impedance) associated with glacial-to-interglacial transitions, which also correspond in depth to seismic reflectors. This supports the concept that reflectors on high-resolution seismic profiles of Bahamian periplatform ooze correspond directly to changes in lithology and may be associated with climate/sea level fluctuations. Received: 30 June 1998 / Revision received: 20 January 1999     

Acoustic backscatter and sediment textural properties of inner shelf sands,northeastern Gulf of Mexico

The relationship between spatial variations of the properties of sea-floor sediments and acoustic backscatter from the surface of the sea floor on the continental shelf off of Panama City, Florida, USA, is investigated using surficial sediment grab samples and digital side-scan sonar data. Acoustic backscatter strength has a high, direct correlation with the mean grain size of the sediments. Acoustic backscatter strength also correlates directly with the carbonate content of the sediments, particularly in medium-and coarse-sand facies, because large, irregularly shaped, carbonate particles affect both the mean grain size of the sediments and the roughness of the surface of the sea floor.     

Comparison of high-resolution seismic profiles and the geoacoustic properties of Eckernförde Bay sediments

High-resolution seismic profiles of Eckernförde Bay and the adjacent Baltic Sea were collected, and the geoacoustic properties of sediments there were measured. Bulk densities averaged ~ 1.35 g cm^–3 and ranged from ~ 1.2 to ~ 1.7 g cm^–3. Compressional wave velocities in gas-free sediments averaged ~ 1460 m s^–1 and ranged from ~ 1425 to ~ 1555 m s^–1. In nongassy sediments, bulk density variations typically controlled changes of acoustic impedance. Impedance changes were usually too small and closely spaced to be resolved seismically, although, at certain sites, significant impedance changes are far apart enough that they correlate one-to-one with seismic reflectors. Where free gas is present, velocity decreases and wave energy is scattered, causing a prominent seismic reflector.     

Radiocarbon Ages Constraints on the Origin and Shedding of Bank-Top Sediment in the Bahamas during the Holocene

Great quantities of fine-sized aragonite needles are produced in the shallow waters that cover the tops of the Bahama Banks and then exported to the bank margins where they accumulate with shells of pelagic organisms. To better understand these processes, we investigated Holocene-aged sediments in a core from the southwestern margin of Little Bahama Bank. The aragonite content of the sediments, ??¹⁸O of planktonic foraminifera shells, and radiocarbon ages of aragonite-rich <63 ??m sediments and coexisting planktonic foraminifera shells were determined. Sediment deposition was rapid overall, and a significant increase in deposition rate occurred 3,500?C4,000 years ago, shortly after rising sea level flooded the bank top with seawater and caused a dramatic increase in the shallow water area where aragonite production occurred. During the latest Holocene when high deposition rates minimize effects of bioturbation, aragonite-rich <63 ??m sediments are 400?C600 years older than coexisting foraminifera. This difference indicates the net age of aragonite when it was exported from the bank top. It is consistent with expectations of the ??hip-hop??n?? model (Morse et al. in Geochimica et Cosmochimica Acta 67: 2819?C2826, 2003) whereby aragonite needles on the bank top, formed initially by biologic or other processes, continue to grow for hundreds of years via precipitation of epitaxial carbonate cement from seawater. Earlier in the Holocene, when sea level was lower and the top of Little Bahama Bank was subaerially exposed, the deposition rate and aragonite content of the sediments were less, and the aragonite-rich <63 ??m sediments are about 1,000 years younger than coexisting foraminifera. This age difference can be explained by downward mixing of latest-Holocene <63 ??m material into older early-Holocene sediments.     

Mud‐rich delta‐scale compound clinoforms in the Triassic shelf of northern Pangea (Havert Formation,south‐western Barents Sea)

In recent years it has become clear that many shallow‐marine heterolithic and mudstone‐dominated successions are deposited as mud belts forming part of subaqueous deltas that are related to major fluvial sources either upstream or along shore. Here the Havert Formation is presented as an ancient example of this kind of system. The Havert Formation in the south‐western Barents Sea represents shelf margin clinoforms consisting predominantly of heterolithic deposits. Sediments were mainly derived from the east (Ural Mountains), but a smaller system prograded northward from Fennoscandia. The Havert Formation holds a lot of interest due to: (i) its stratigraphic position, directly above the Permo–Triassic boundary and contemporaneous to the emplacement of the Siberian Traps; (ii) the fact that it represents the first siliciclastic input in the south‐western Barents Sea and it shows interaction between Uralian‐derived and Fennoscandian‐derived sediments; and (iii) its hydrocarbon potential. This study is focused on a detailed sedimentological analysis of cored intervals of the (Ural‐derived) Havert Formation, in combination with seismic interpretation, well‐log correlations and palynological analysis of the Havert and overlying Klappmyss formations. The cored intervals belong to the shelf environment of the Havert shelf‐margin clinoforms (300 to 500 m thick). This sedimentological analysis distinguishes six facies associations, spanning from tidally‐influenced channels at the shoreline to mud‐rich subaqueous platform and foresets of the subaqueous delta. Seismic lines and well‐log correlations show the larger‐scale evolution of the Ural‐derived Havert Formation, characterized by episodes of low‐accommodation and high‐accommodation. The palynological analyses provide the first detailed study of the Havert Formation in the Nordkapp Basin, revising its depositional age in the region as Induan to early Olenekian (Smithian). Furthermore, they strengthen the environmental interpretation; palynofacies present on the shelf record flora of tidally‐influenced coastal plains, whereas the palynofacies in the deep‐water slope contain only amorphous organic matter.