Effect of citrate on the local Fe coordination in ferrihydrite, arsenate binding, and ternary arsenate complex formation     

Christian Mikutta  Jakob Frommer  Ralf Kaegi 《Geochimica et cosmochimica acta》2010,74(19):5574-6504

In oxic environments contaminated with arsenate (As(V)), small polyhydroxycarboxylates such as citrate may impact the structure of precipitating ferrihydrite (Fh) and thus the surface speciation of As(V). In this study, ‘2-line’ Fh was precipitated from ferric nitrate solutions that were neutralized to pH 6.5 in the presence of increasing citrate concentrations and in the absence or presence of As(V). The initial citrate/Fe and As/Fe ratios were 0-50 mol% and 5 mol%, respectively. The reaction products, enriched with up to 0.32 mol citrate per mole Fe, were characterized by X-ray diffraction, transmission electron microscopy, and Fe and As K-edge X-ray absorption spectroscopy. Citrate decreased the particle size of Fh by impairing the polymerization of Fe(O,OH)₆ octahedra via edge and corner linkages. In the presence of citrate and As(V), coordination numbers of Fe decreased by up to 28% relative to pure Fh. Citrate significantly reduced the static disorder of Fe-O bonds, implying a decreased octahedral distortion in Fh. Mean bond distances in Fh were not affected by citrate and remained constant within error at 1.98 Å for Fe-O, 3.03 Å for Fe-Fe1, and 3.45 Å for Fe-Fe2. Likewise, citrate had no effect on the As-Fe (3.31 Å) bond distance in As(V) coprecipitated with Fh. The As K-edge EXAFS data comply with the formation of (i) only monodentate binuclear (²C) As(V) surface complexes and (ii) combinations of ²C, monodentate mononuclear (¹V), and outersphere As(V) surface complexes. Our results suggest that increasing citrate concentrations led to a decreasing ¹V/²C ratio and/or that citrate increasingly impaired the formation of outersphere As(V) complexes. Moreover, citrate stabilized colloidal suspensions of Fh (pH 4.3-6.6, I ∼0.45 M) and reduced Fh formation at the expense of soluble Fe(III)-citrate complexes. At initial citrate/Fe ratios ?25 mol%, between 8% and 41% of total Fe was bound in Fe(III)-citrate complexes after Fh formation. Polynuclear Fe(III)-citrate species were found to bind As(V) via surface complexes indistinguishable by EXAFS from those of As(V) adsorbed to or coprecipitated with Fh. Our study implies that low molecular weight polyhydroxycarboxylates may enhance the mobility of As(V) in aqueous systems of high ionic strength (e.g., neutralizing acid mine drainage) by colloidal stabilization of suspended Fh particles and the formation of ternary As(V) complexes.  相似文献   

Mercury flux to estuarine sediments, derived from Pb-210 and Cs-137 geochronologies (Guaratuba Bay, Brazil)   总被引：1，自引：0，他引：1  

Sanders CJ  Santos IR  Silva-Filho EV  Patchineelam SR 《Marine pollution bulletin》2006,52(9):1085-1089

A sediment core from Guaratuba Bay was used to indicate possible Hg modifications to this coastal environment brought about by growing agricultural activity. Sedimentation rates were estimated to be 6.1 mm/year and 5.2 mm/year through 210Pb and 137Cs geochronologies, respectively. Mercury concentrations and organic matter ratios in the surface layers are greater than in the older sediments, supporting the hypothesis of anthropogenic enrichment. Results show that the Hg flux has raised more than twofold during the second half of the 20th century. These results point to the need for further studies to substantiate the hypothesis of anthropogenic enrichment and to quantify point sources of Hg to this estuary.  相似文献   

Pumping test in a confined aquifer under tidal influence   总被引：2，自引：0，他引：2  

Chapuis RP  Bélanger C  Chenaf D 《Ground water》2006,44(2):300-305

In a coastal environment, tide-induced head fluctuations can complicate the interpretation of drawdown data from pumping tests. For confined aquifers and sinusoidal tides, the superposition principle can be used to obtain a closed-form solution. After subtracting the net tidal effects, the drawdown data become amenable to the standard analyses. Numerical simulations have shown that the method is reliable when the distance of the monitoring well to the well does not exceed 10% of the distance between the well and the tidal boundary.  相似文献   

Cubic law with aperture-length correlation: implications for network scale fluid flow   总被引：2，自引：2，他引：0  

Christian Klimczak  Richard A. Schultz  Rishi Parashar  Donald M. Reeves 《Hydrogeology Journal》2010,18(4):851-862

Previous studies have computed and modeled fluid flow through fractured rock with the parallel plate approach where the volumetric flow per unit width normal to the direction of flow is proportional to the cubed aperture between the plates, referred to as the traditional cubic law. When combined with the square root relationship of displacement to length scaling of opening-mode fractures, total flow rates through natural opening-mode fractures are found to be proportional to apertures to the fifth power. This new relationship was explored by examining a suite of flow simulations through fracture networks using the discrete fracture network model (DFN). Flow was modeled through fracture networks with the same spatial distribution of fractures for both correlated and uncorrelated fracture length-to-aperture relationships. Results indicate that flow rates are significantly higher for correlated DFNs. Furthermore, the length-to-aperture relations lead to power-law distributions of network hydraulic conductivity which greatly influence equivalent permeability tensor values. These results confirm the importance of the correlated square root relationship of displacement to length scaling for total flow through natural opening-mode fractures and, hence, emphasize the role of these correlations for flow modeling.  相似文献   

Deep alpine valleys: examples of geophysical explorations in Austria     

Ewald Brückl  Johanna Brückl  Werner Chwatal  Christian Ullrich 《Swiss Journal of Geoscience》2010,103(3):329-344

Results from geophysical explorations of three deep valleys, selected from different tectonic regimes in the Eastern Alps (Ötz-, Oichten-, and Drau Valley), are presented and discussed. Ongoing tectonic deformation may use tectonic structures related to these valleys. However, seismic activity is low there. During the Würm ice age, the thickness of the ice cover ranged between 300 and 1,500 m above present ground elevation. The geophysical investigations comprised reflection seismology, gravity- and resistivity surveys. The maximum depth down to the erosional base of the valleys varies from ~340 to 700 m. Distinct layer packages of the valley-infill at depths greater than 250 m were termed “old valley-fill”. Geophysical parameters and a comparison with the reflection seismic image of an intermediate layer at the recent Pasterze glacier suggest that the top of the “old valley-fill” represents the glacier bed during the decay of the Würm glaciation. Deep erosion is not related to high basal shear stress. The confluence of tributary glaciers is apparently not a significant factor for deep erosion in our examples of deep alpine valleys. We conclude that deep erosion may be related to high water pressure at the glacier bed, supported by specific processes of tectonic weakening.  相似文献   

Bosumtwi impact structure,Ghana: Geochemistry of impactites and target rocks,and search for a meteoritic component     

Xiongxin Dai  Daniel Boamah  Christian Koeberl  Wolf Uwe Reimold  Gordon Irvine  Iain McDonald 《Meteoritics & planetary science》2005,40(9-10):1493-1511

Abstract— Major and trace element data, including platinum group element abundances, of representative impactites and target rocks from the crater rim and environs of the Bosumtwi impact structure, Ghana, have been investigated for the possible presence of a meteoritic component in impact‐related rocks. A comparison of chemical data for Bosumtwi target rocks and impactites with those for Ivory Coast tektites and microtektites supports the interpretation that the Bosumtwi structure and Ivory Coast tektites formed during the same impact event. High siderophile element contents (compared to average upper crustal abundances) were determined for target rocks as well as for impactites. Chondrite‐normalized (and iron meteorite‐normalized) abundances for target rocks and impactites are similar. They do not, however, allow the unambiguous detection of the presence, or identification of the type, of a meteoritic component in the impactites. The indigenous siderophile element contents are high and possibly related to regional gold mineralization, although mineralized samples from the general region show somewhat different platinum‐group element abundance patterns compared to the rocks at Bosumtwi. The present data underline the necessity of extensive target rock analyses at Bosumtwi, and at impact structures in general, before making any conclusions regarding the presence of a meteoritic component in impactites.  相似文献   

The record of Miocene impacts in the Argentine Pampas     

Peter H. SCHULTZ  Marcelo ZRATE  Willis E. HAMES  R. Scott HARRIS  T. E. BUNCH  Christian KOEBERL  Paul RENNE  James WITTKE 《Meteoritics & planetary science》2006,41(5):749-771

Abstract— Argentine Pampean sediments represent a nearly continuous record of deposition since the late Miocene (～10 Ma). Previous studies described five localized concentrations of vesicular impact glasses from the Holocene to late Pliocene. Two more occurrences from the late Miocene are reported here: one near Chasicó (CH) with an ⁴⁰Ar/³⁹Ar age of 9.24 ± 0.09 Ma, and the other near Bahía Blanca (BB) with an age of 5.28 ± 0.04 Ma. In contrast with andesitic and dacitic impact glasses from other localities in the Pampas, the CH and BB glasses are more mafic. They also exhibit higher degrees of melting with relatively few xenoycrysts but extensive quench crystals. In addition to evidence for extreme heating (>1700 °C), shock features are observed (e.g., planar deformation features [PDFs] and diaplectic quartz and feldspar) in impact glasses from both deposits. Geochemical analyses reveal unusually high levels of Ba (～7700 ppm) in some samples, which is consistent with an interpretation that these impacts excavated marine sequences known to be at depth. These two new impact glass occurrences raise to seven the number of late Cenozoic impacts for which there is evidence preserved in the Pampean sediments. This seemingly high number of significant impacts over a 10⁶ km² area in a time span of 10 Myr is consistent with the number of bolides larger than 100 m expected to enter the atmosphere but is contrary to calculated survival rates following atmospheric disruption. The Pampean record suggests, therefore, that either atmospheric entry models need to be reconsidered or that the Earth has received an enhanced flux of impactors during portions of the late Cenozoic. Evidence for the resulting collisions may be best preserved and revealed in rare dissected regions of continuous, low‐energy deposition such as the Pampas. Additionally, the rare earth element (REE) concentrations of the target sediments and impact melts associated with the Chasicó event resemble the HNa/K australites of similar age. This suggests the possibility that those enigmatic tektites could have originated as high‐angle, distal ejecta from an impact in Argentina, thereby accounting for their rarity and notable chemical and physical differences from other Australasian impact glasses.  相似文献   

The recovery of microalgal production and biomass in a South African temporarily open/closed estuary, following mouth breaching     

Akash Anandraj  Renzo Perissinotto  Christian Nozais  Derek Stretch 《Estuarine, Coastal and Shelf Science》2008,79(4):599-606

Mouth breaching is a recurrent event in temporarily open/closed estuaries (TOCEs). Such disturbances result in flushing and sediment scouring, reducing the microalgal biomass stock. The depletion of these microalgae may have negative repercussions in the form of depleted stocks of commercial fish, game fish, crustaceans and mollusks. The aim of this investigation was therefore: (1) to monitor the recovery of microalgal biomass and production following a breaching event; and (2) to determine the key environmental parameters influencing primary production during the open and recovery phases. Phytoplankton and benthic microalgal production was measured (¹⁴C-uptake method) successively during the closed, open and recovery phases of the Mdloti TOCE (South Africa). Upon breaching, 94–99% of microalgal biomass was washed out to sea through flushing and sediment scouring. A temporary recovery of phytoplankton and benthic microalgal biomass was observed during the open phase, but this was not sustained because of continual flushing and scouring of the sediment. During the re-closure (recovery phase), microalgal biomass immediately increased, reaching pre-breaching levels 35–40 days following the breaching event. In contrast to biomass, autochthonous pelagic primary production reached a maximum level (341 mg C m⁻² h⁻¹) during the open phase. Pelagic primary production normalized to biomass (P^B) significantly increased during the open phase. This is attributed to a favorable combination of optimum light conditions, high influx of macronutrients and high water temperatures (33 °C). Similarly, benthic primary production normalized to biomass (P^B) peaked during the open phase (35 mg C mg chl-a⁻¹ h⁻¹). Multivariate analysis showed that major variations in primary production were mainly controlled by temperature, dissolved inorganic nitrogen (DIN) to phosphorus (DIP) molar ratios (water-column and pore-water) and light extinction (K_d), all of which were regulated by the state of the mouth.  相似文献   

Chemical variation within fragments of Australasian tektites     

Trinh Hai SON  Christian KOEBERL 《Meteoritics & planetary science》2005,40(6):805-815

Abstract— In previous studies, intersample variation between compositions of different tektites from one particular group were studied and, in a few cases, major element variations within single tektites. No data for intra‐sample trace element variations existed. Thus, we sectioned a Muong Nong‐type tektite fragment from Vietnam and a splash‐form tektite fragment from the Philippines into eleven and six pieces, respectively, and analyzed the individual fragments for major and trace element contents. The compositions obtained agree well with those found in previous studies, supporting argument that tektites have been derived from terrestrial upper crustal sediments. Chemical variations within the tektite fragments are present, but do not show any systematic trends, probably reflecting incomplete mixing of parent rocks. The intra‐sample heterogeneity of the Muong Nong‐type tektite is more pronounced than that in the philippinite. For the Muong Nong‐type tektite, the intra‐sample variation in the trace element contents is higher than that for the major elements, again reflecting target rock properties. For the philippinite the intra‐sample variations mostly do not exceed the limits imposed by the precision of the analytical data, confirming that the splash form tektites are indeed well homogenized.  相似文献   

Experimental evidence of fast groundwater responses in a hillslope/floodplain area in the Black Forest Mountains,Germany     

Jochen Wenninger  Stefan Uhlenbrook  Nils Tilch  Christian Leibundgut 《水文研究》2004,18(17):3305-3322

Analysis of water flow pathways from hillslopes to streams is essential for the optimal protection of water resources as well as for ecohydrological studies. This study addresses runoff generation processes at a hillslope and near‐stream shallow groundwater system in the Black Forest Mountains, southwestern Germany. The changing spatial and temporal flow patterns during differing hydrological situations were examined using a combined hydraulic and hydrochemical approach. Groundwater levels at 10 wells, discharge at a near‐stream saturated area, and several natural tracers (deuterium, dissolved silica, and major anions and cations) were observed at different locations during high and low flows. The importance of the groundwater component during flood formation was clearly demonstrated: its contribution was about 80% during a double peak flood event at the saturated area. In addition, a rapid change of the shallow groundwater levels was observed along two transects of groundwater wells in the floodplain. This led to an enhanced groundwater discharge into the saturated area located at the end of one study transect. The amount of groundwater additionally activated during the event was about 30% of total discharge recorded at the outlet of the saturated area. Two alternative hypotheses are discussed to explain this phenomenon: the establishment of locally confined conditions and the development of a pressure wave (hypothesis A), or the significant change of the three‐dimensional groundwater flow lines that caused a large increase of the groundwater catchment at the saturated area during the investigated event (hypothesis B). Even if the exact flow paths and mechanisms could not be clearly identified, the importance of rapid responding hillslope groundwater was undoubtedly demonstrated by a combination of tracer and hydrometric methods. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献