Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: A flow field-flow fractionation study

The interaction of Cs(I), Eu(III), Th(IV) and U(VI) with montmorillonite colloids was investigated in natural Grimsel Test Site groundwater over a 3 years period. The asymmetric flow field-flow fractionation combined with various detectors was applied to study size variations of colloids and to monitor colloid association of trace metals. The colloids suspended directly in the low ionic strength (I), slightly alkaline granitic groundwater (I = 10⁻³ mol/L, pH 9.6) showed a gradual agglomeration with a size distribution shift from initially 10-200 nm to 50-400 nm within over 3 years. The Ca²⁺ concentration of 2.1 × 10⁻⁴ mol/L in the ground water is believed to be responsible for the slow agglomeration due to Ca²⁺ ion exchange against Li⁺ and Na⁺ at the permanently charged basal clay planes. Furthermore, the Ca²⁺ concentration lies close to the critical coagulation concentration (CCC) of 10⁻³ mol L⁻¹ for clay colloids. Slow destabilization may delimit clay colloid migration in this specific groundwater over long time scales. Eu(III) and Th(IV) are found predominantly bound to clay colloids, while U(VI) prevails as the UO₂(OH)₃⁻ complex and Cs(I) remains mainly as aquo ion under our experimental conditions. Speciation calculations qualitatively represent the experimental data. A focus was set on the reversibility of metal ion-colloid binding. Addition of humic acid as a competing ligand induces rapid metal ion dissociation from clay colloids in the case of Eu(III) even after previous aging for about 3 years. Interestingly only partial dissociation occurs in the case of Th(IV). Experiments and calculations prove that the humate complexes dominate the speciation of all metal ions under given conditions. The partial irreversibility of clay bound Th(IV) is presently not understood but might play an important role for the colloid-mediated transport of polyvalent actinides over wide distances in natural groundwater.     

Comparison of gas with liquid chromatography for the determination of benzenepolycarboxylic acids as molecular tracers of black carbon

Existing methods for black carbon (BC) quantification measure different parts of the BC continuum, which complicates the calculation of a global BC budget. Benzenepolycarboxylic acids (BPCA) are used as molecular markers to quantify and characterize BC in soils and sediments using gas chromatography for BPCA separation (GC-BPCA). Recently, this method was refined for BC analysis in seawater using high performance liquid chromatography (LC-BPCA), which omits the cleaning steps and derivatization necessary in GC analysis. As yet it is not clear whether the two analytical methods yield similar results. Here we apply both methods to a suite of laboratory produced charcoals derived from wood and grass. We found systematically lower total BPCA-C contents and larger analytical variability for all tested charcoals when using GC-BPCA compared to LC-BPCA, the latter giving 1.5 ± 0.3 times higher yields for the charcoal samples formed at 275-700 °C. At lower and higher pyrolysis temperatures the differences between the two analytical methods were larger. The main reason for the differences between the two methods is the loss of BPCA during sample preparation for GC analysis. We propose a correction factor of 1.5 to account for at least part of these losses. No qualitative biases, i.e. towards more or less functionalized BPCAs, were observed between the two methods. The relative contribution of mellitic acid C to total BPCA-C, a measure for the degree of condensation of BC, was the same in the two analytical techniques. Qualitative differences between wood and grass charcoals as detected by both methods were small.     

Cultivable bacteria from bulk water,aggregates, and surface sediments of a tidal flat ecosystem

Most-probable-number (MPN) dilution series were used to enumerate and isolate bacteria from bulk water, suspended aggregates, the oxic layer, and the oxic–anoxic transition zone of the sediment of a tidal flat ecosystem in the southern North Sea. The heterotrophic aerobic bacteria were able to grow on agar-agar, alginate, cellulose, chitin, dried and ground Fucus vesiculosus, Marine Broth 2216, palmitate, and starch. MPN counts of bulk water and aggregate samples ranged between 0.18?×?10¹ and 1.1?×?10⁶ cells per milliliter and those of the sediment surface and the transition zone between 0.8?×?10¹ and 5.1?×?10⁷ cells per gram dry weight. Marine Broth and F. vesiculosus yielded the highest values of all substrates tested and corresponded to 2.3–32% of 4,6-diamidinophenyl indole cell counts. Strains of seven phylogenetic classes were obtained: Actinobacteria, Bacilli, α- and γ-Proteobacteria, Sphingobacteria, Flavobacteria, and Planctomycetacia. Only with agar-agar as substrate could organisms of all seven classes be isolated.     

Surface selection,adhesion, and retention behavior of marine bacteria on synthetic organic surfaces using self-assembled monolayers and atomic force microscopy

Adhesion of two marine bacteria Shewanella sp. strain T1 and Pseudoalteromonas sp. strain T8, on differently terminated alkanethiolate self-assembled monolayers on gold was investigated. The selected model surfaces—terminated by CH₃, OH, NH₂, COOH, OH-terminated oligo(ethylene glycol), and methyl-terminated oligo(ethylene glycol)—are characterized by contact angle measurement using water, methylene iodide, 1-bromonaphthalene, and formamide. Surface free energies were calculated. Cell counting of the two bacterial strains on the model surfaces after different times revealed differences between the two strains by at least one order of magnitude. For the different surfaces, the bacteria showed comparably small selectivity. Atomic force microscopy images of adhered bacteria showed very different fingerprints on the different surfaces. Electronic supplementary material  Supplementary material is available in the online version of this article at and is accessible to authorized users.     

Electrical resistivity and 57Fe Mössbauer spectra of Fe-bearing calcic amphiboles

Electrical resistivity and ⁵⁷Fe Mössbauer spectra are reported for three calcic amphiboles with different Fe concentrations. AC measurements (20?Hz–1?MHz) were performed, applying impedance spectroscopy between 100 and 785?°C in an N₂ gas atmosphere. It was found that up to three semiconducting charge transport processes can be distinguished, which in part changed slightly when several runs were carried out to higher temperatures. The extrapolated DC resistivity is much smaller for an amphibole with high Fe content than for the two with lower Fe concentrations. The derived activation energies are between ～0.48 and ～1.06?eV. For temperatures ≤600?°C the results are compatible with a charge transport mechanism due to electron hopping between Fe²⁺ and Fe³⁺. Above 600?°C, dehydrogenation and/or beginning amphibole decomposition obviously alter the conduction mechanism. From Mössbauer spectra it was established that in all amphibole samples Fe²⁺ and Fe³⁺ are simultaneously present. Mössbauer parameters were derived by fitting the observed spectra to models taking the occupation of various M sites into account.     

Biomass-Cover Relationship for Eelgrass Meadows

Eelgrass meadows play key roles in coastal ecosystems, and the extent of the standing biomass is focal to address ecosystem functioning. Eelgrass cover is commonly assessed in marine monitoring programs while biomass sampling is destructive and expensive. Therefore, we have proposed a functional relationship that translates eelgrass cover into aboveground biomass using site-specific information on Secchi depth or light attenuation. The relationship was estimated by non-linear regression on 791 combined observations of eelgrass cover and biomass from eight different coastal sites in Denmark. Eelgrass biomass initially increased with cover and flattened out as cover exceeded 40–50 % due to increased self-shading. Decreasing light energy with depth reduced the eelgrass biomass potential (assessed at 100 % cover), and this reduction was stronger for coastal sites with lower water transparency. Moreover, the biomass potential varied seasonally from around 110–140 g DW m^?2 in spring months to a peak of 241 g DW m^?2 in August, consistent with other seasonal studies. The model explained 56 % of the variation in log-transformed biomasses, but significant variation between coastal sites still remained, deviating between ?23 and 39 % from the mean relationship. These site-specific deviations could be due to differences in losses related to grazing, drifting algae and epiphytes, better light capture by dense canopies, as well as differences in how well light conditions within eelgrass meadows are represented by actual measurements of Secchi depth and light attenuation. The relationship can be employed to estimate eelgrass biomass of entire coastal ecosystems from observations of eelgrass cover and depth.     

Tracing terrigenous dissolved organic matter and its photochemical decay in the ocean by using liquid chromatography/mass spectrometry

Reversed-phase liquid chromatography/mass spectrometry (LC/MS) is introduced as a new molecular fingerprinting technique for tracing terrigenous dissolved organic matter (DOM) and its photochemical decay in the ocean. DOM along a transect from the mangrove-fringed coast in Northern Brazil to the shelf edge was compared with mangrove-derived porewater DOM exposed to natural sunlight for 2–10 days in a photodegradation experiment. DOM was isolated from all samples via solid-phase extraction (C18) for LC/MS analysis. DOM in the estuary and ocean showed a bimodal mass distribution with two distinct maxima in the lower m/z range from 400 to 1000 Da (intensity-weighted average of 895 Da). Terrigenous porewater DOM from the mangroves was characterized by a broad molecular mass distribution over the detected range from 150 to 2000 Da (intensity-weighted average of 1130 Da). Polar compounds, i.e., those that eluted early in the reversed-phase chromatography, absorbed more UV light and had on average smaller molecular masses than the more apolar compounds.     

Thermogenic organic matter dissolved in the abyssal ocean

Formation and decay of thermogenic organic matter are important processes in the geological carbon cycle, but little is known about the fate of combustion-derived and petrogenic compounds in the ocean. We explored the molecular structure of marine dissolved organic matter (DOM) for thermogenic signatures in different water masses of the Southern Ocean. Ultrahigh-resolution mass spectrometry via the Fourier transform-ion cyclotron resonance technique (FT-ICR-MS) revealed the presence of polyaromatic hydrocarbons (PAHs) dissolved in the abyssal ocean. More than 200 different PAHs were discerned, most of them consisting of seven condensed rings with varying numbers of carboxyl, hydroxyl, and aliphatic functional groups. These unambiguously thermogenic compounds were homogenously distributed in the deep sea, but depleted at the sea surface. Based on the structural information alone, petrogenic and pyrogenic compounds cannot be distinguished. Surface depletion of the PAHs and first estimates for their turnover rate (> 1.2 · 10¹² mol C per year) point toward a primarily petrogenic source, possibly deep-sea hydrothermal vents, which is thus far speculative because the fluxes of combustion-derived and petrogenic matter to the ocean are not well constrained. We estimate that > 2.4% of DOM are thermogenic compounds, and their global inventory in the oceans is > 1.4 · 10¹⁵ mol C, significantly impacting global biogeochemical cycles.     

Tracing suspended organic nitrogen from the Yangtze River catchment into the East China Sea

Total suspended matter was collected along the Yangtze River (Changjiang) and in the East China Sea in April to May and in September 2003, respectively, to study origin and fate of particulate organic nitrogen. Concentrations of particulate organic carbon (POC), nitrogen (PN) and hydrolyzable particulate amino acids (PAA; d- and l-enantiomers) were higher in the Yangtze Estuary than in the river and decreased offshore towards the shelf edge. In the coastal area, higher values of PAA were observed in the surface layer than in the bottom water. Stable carbon isotope ratios (δ¹³C) of POC increased from − 24.4‰ in the river to values around − 21‰ on the East China Sea Shelf. Dominant amino acids were aspartic acid + aspartine (Asx), glutamic acid + glutamine (Glx), glycine, alanine and serine. The proportions of Asx, Glx and isoleucine were higher in the marine than in the riverine samples contrary to the distributions of glycine, alanine, threonine and arginine. The proportions of d-amino acids were highest in the riverine suspended organic matter (6% of PAA) decreasing towards the shelf edge (1.5% of PAA). d-arginine, not reported in natural aquatic samples so far, was the most abundant d-amino acid in the river. The amino acid composition of the particulate organic matter (POM) in the Yangtze River indicates an advanced stage of degradation of POM. Highly degraded organic matter from soils is probably a main source of POM in the Yangtze River, but the relatively high δ¹³C values and low C/N ratios (7.7 ± 1.6) also indicate contribution from anthropogenic sources. The degraded riverine material was a dominant organic matter source in the estuary, where aquatic primary production had only a small overall contribution. In the East China Sea, gradual settling of riverine organic matter and the addition of fresher phytoplankton impacted the amino acid composition and δ¹³C values, and on the outer shelf relatively fresh phytoplankton-derived organic matter dominated.