Trace metal enrichments in Lake Tanganyika sediments: Controls on trace metal burial in lacustrine systems

We investigate the distributions of several key diagenetic reactants (C, S, Fe) and redox-sensitive trace metals (Mo, Cd, Re, U) in sediments from Lake Tanganyika, East Africa. This study includes modern sediments from a chemocline transect, which spans oxygenated shallow waters to sulfidic conditions at depth, as well as ancient sediments from a longer core (∼2 m) taken at ∼900 m water depth. Modern sediments from depths spanning ∼70-335 m are generally characterized by increasing enrichments of C, S, Mo, Cd, and U with increasing water depth but static Fe distributions. It appears that the sedimentary enrichments of these elements are, to varying degrees, influenced by a combination of organic carbon cycling and sulfur cycling. These modern lake characteristics contrast with a period of high total organic carbon (C_org), total sulfur (S_Tot), and trace metal concentrations observed in the 900 m core, a period which follows the most recent deglaciation (∼18-11 ky). This interval is followed abruptly by an interval (∼11-6 ky) that is characterized by lower C, S, U, and Mo. Consistent with other work we suspect that the low concentrations of S, Mo, and U may indicate a period of intense lake mixing, during which time the lake may have been less productive and less reducing as compared to the present. An alternative, but not mutually exclusive, hypothesis is that changes in the lake’s chemical inventory, driven by significant hydrological changes, could be influencing the distribution of sedimentary trace elements through time.     

Discrimination of TiO<Subscript>2</Subscript> polymorphs in sedimentary and metamorphic rocks

Investigation by Raman spectroscopy of samples from different geological settings shows that the occurrence of TiO₂ polymorphs other than rutile can hardly be predicted, and furthermore, the occurrence of anatase is more widespread than previously thought. Metamorphic pressure and temperature, together with whole rock chemistry, control the occurrence of anatase, whereas variation of mineral assemblage characteristics and/or fluid occurrence or composition takes influence on anatase trace element characteristics and re-equilibration of relict rutiles. Evaluation of trace element contents obtained by electron microprobe in anatase, brookite, and rutile shows that these vary significantly between the three TiO₂ phases. Therefore, on the one hand, an appropriation to source rock type according to Nb and Cr contents, but as well application of thermometry on the basis of Zr contents, would lead to erroneous results if no phase specification is done beforehand. For the elements Cr, V, Fe, and Nb, variation between the polymorphs is systematic and can be used for discrimination on the basis of a linear discriminant analysis. Using phase group means and coefficients of linear discriminants obtained from a compilation of analyses from samples with well-defined phase information together with prior probabilities of groupings from a natural sample compilation, one is able to calculate phase grouping probabilities of any TiO₂ analysis containing at least the critical elements Cr, V, Fe, and Nb. An application of this calculation shows that for the appropriation to the phase rutile, a correct-classification rate of 99.5% is obtained. Hence, phase specification by trace elements proves to be a valuable tool besides Raman spectroscopy.     

A neuro-fuzzy-based modelling approach for sediment transport computation

Abstract

The application of a data-driven adaptive neuro-fuzzy modelling technique for predicting bed load and total bed-material load for the River Rhine is summarized. Four main parameters affecting sediment transport are used to construct the model, using 560 and 510 measured bed load and total bed-material load data, respectively. Two-thirds of the available data sets are used for training and one third for testing. The initial fuzzy model is obtained by grid partitioning of the input variables. The optimization of the model is performed by data-driven tuning of the fuzzy model parameters using the adaptive neuro-fuzzy inference system, so that the model output is able to reproduce the measured value. A sensitivity analysis for the combination of input parameters, as well as the number and type of membership functions, is also performed. The model results show that the data-driven adaptive neuro-fuzzy modelling approach can be a powerful alternative technique for estimating both bed load and total bed-material load.

Editor D. Koutsoyiannis

Citation Wieprecht, S., Tolossa, H.G., and Yang, C.T., 2013. A neuro-fuzzy-based modelling approach for sediment transport computation. Hydrological Sciences Journal, 58 (3), 587–599.     

The continental shelf benthic iron flux and its isotope composition

Benthic iron fluxes from sites along the Oregon-California continental shelf determined using in situ benthic chambers, range from less than 10 μmol m⁻² d⁻¹ to values in excess of ∼300 μmol m⁻² d⁻¹. These fluxes are generally greater than previously published iron fluxes for continental shelves contiguous with the open ocean (as opposed to marginal seas, bays, or estuaries) with the highest fluxes measured in the regions around the high-sediment discharge Eel River and the Umpqua River. These benthic iron fluxes do not covary with organic carbon oxidation rates in any systematic fashion, but rather seem to respond to variations in bottom water oxygen and benthic oxygen demand. We hypothesize that the highest rates of benthic iron efflux are driven, in part, by the greater availability of reactive iron deposited along these river systems as compared to other more typical continental margin settings. Bioirrigation likely plays an important role in the benthic Fe flux in these systems as well. However, the influence of bottom water oxygen concentrations on the iron flux is significant, and there appears to be a threshold in dissolved oxygen (∼60-80 μM), below which sediment-ocean iron exchange is enhanced. The isotope composition of this shelf-derived benthic iron is enriched in the lighter isotopes, and appears to change by ∼3‰ (δ⁵⁶Fe) during the course of a benthic chamber experiment with a mean isotope composition of −2.7 ± 1.1‰ (2 SD, n = 9) by the end of the experiment. This average value is slightly heavier than those from two high benthic Fe flux restricted basins from the California Borderland region where δ⁵⁶Fe is −3.4 ± 0.4‰ (2 SD, n = 3). These light iron isotope compositions support previous ideas, based on sediment porewater analyses, suggesting that sedimentary iron reduction fractionates iron isotopes and produces an isotopically light iron pool that is transferred to the ocean water column. In sum, our data suggest that continental shelves may export a higher efflux of iron than previously hypothesized, with the likelihood that along river-dominated margins, the benthic iron flux could well be orders of magnitude larger than non-river dominated shelves. The close proximity of the continental shelf benthos to the productive surface ocean means that this flux is likely to be essential for maintaining ecosystem micronutrient supply.     

Microphysical and chemical characteristics of cloud droplet residuals and interstitial particles in continental stratocumulus clouds

During June and July 2003 the Sources and Origins of Atmospheric Cloud Droplets experiment (SOACED) was carried out on a mountain-top site in central Sweden. The main objective of the experiment was to characterise the microphysical and chemical properties of cloud droplet residuals and interstitial aerosol particles in continental clouds and to understand the processes controlling cloud properties at this location.Interstitial and residual aerosol size distributions, cloud liquid water content and species- and size-resolved aerosol mass concentrations are the main variables employed to address questions pertaining to the cloud droplet number concentration and scavenging efficiency during a stratocumulus cloud event observed on July 28, 2003. In this cloud event, about 56% of the aerosol mass was associated with organic species, whilst SO₄ accounted for 23% and NH₄ for 14%. NO₃ and Cl made up about 7% of the total mass.The partitioning of the aerosol particles between cloud droplets and interstitial air has been studied in terms of their microphysical properties. The scavenging efficiency, defined as the fraction of particles activated into cloud elements compared to the total amount of particles, was investigated as a function of size. The scavenging efficiency curves displayed different shapes during the cloud event, from an S-shaped curve, with low scavenging efficiency in the Aitken mode and larger scavenging efficiency in the accumulation mode, to more unusual shapes where Aitken-mode particles were either solely activated or activated in addition to accumulation-mode particles.This study suggests that alterations of the aerosol chemical composition occurred during the measurement period, changing the hygroscopic nature of the CCN and decreasing their activation diameter. It is also hypothesized that entrainment of drier air aloft may have introduced inhomogeneities in the supersaturation field and modified the S-shaped scavenging curves.     

The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments

Iron isotope compositions in marine pore fluids and sedimentary solid phases were measured at two sites along the California continental margin, where isotope compositions range from δ⁵⁶Fe = −3.0‰ to +0.4‰. At one site near Monterey Canyon off central California, organic matter oxidation likely proceeds through a number of diagenetic pathways that include significant dissimilatory iron reduction (DIR) and bacterial sulfate reduction, whereas at our other site in the Santa Barbara basin DIR appears to be comparatively small, and production of sulfides (FeS and pyrite) was extensive. The largest range in Fe isotope compositions is observed for Fe(II)_aq in porewaters, which generally have the lowest δ⁵⁶Fe values (minimum: −3.0‰) near the sediment surface, and increase with burial depth. δ⁵⁶Fe values for FeS inferred from HCl extractions vary between ∼−0.4‰ and +0.4‰, but pyrite is similar at both stations, where an average δ⁵⁶Fe value of −0.8 ± 0.2‰ was measured. We interpret variations in dissolved Fe isotope compositions to be best explained by open-system behavior that involves extensive recycling of Feflux. This study is the first to examine Fe isotope variations in modern marine sediments, and the results show that Fe isotopes in the various reactive Fe pools undergo isotopic fractionation during early diagenesis. Importantly, processes dominated by sulfide formation produce high-δ⁵⁶Fe values for porewaters, whereas the opposite occurs when Fe(III)-oxides are present and DIR is a major pathway of organic carbon respiration. Because shelf pore fluids may carry a negative δ⁵⁶Fe signature it is possible that the Fe isotope composition of ocean water reflects a significant contribution of shelf-derived iron to the open ocean. Such a signature would be an important means for tracing iron sources to the ocean and water mass circulation.