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91.
92.
The objective of this study was to determine the local coordination of Zn in hydroxy-interlayered smectite (HIS) as a function of Zn loading and synthesis conditions and to assess the importance of hydroxy-interlayered minerals (HIM) for Zn retention in contaminated soils. Published and newly collected extended X-ray absorption fine structure (EXAFS) spectra of HIS reacted with Zn at molar Zn/hydroxy-Al ratios from 0.013 to 0.087 (corresponding to final Zn contents of 1615-8600 mg/kg Zn) were evaluated by shell fitting. In Zn-HIS, Zn was octahedrally coordinated to oxygen at 2.06-2.08 Å and surrounded by Al atoms at 3.03-3.06 Å in the second-shell. With increasing molar Zn/hydroxy-Al ratio, the coordination number of second-shell Al decreased from 6.6 to 2.1. These results were interpreted as a progressive shift from Zn incorporation in the vacancies of gibbsitic Al-polymers to Zn adsorption to incomplete Al-polymers and finally uptake by cation exchange in the polymer-free interlayer space of HIS with increasing Zn loadings. In a second part, we determined the speciation of Zn in eight contaminated soils (251-1039 mg/kg Zn) with acidic to neutral pH (pH 4.1-6.9) using EXAFS spectroscopy. All soils contained hydroxy-Al interlayered vermiculite (HIV). The analysis of EXAFS spectra by linear combination fitting (LCF) showed that a substantial fraction of total Zn (29-84%) was contained in HIM with high Zn loading. The remaining Zn was adsorbed to organic and inorganic soil components and incorporated into phyllosilicates. In sequential extractions of Zn-HIS spiked into quartz powder and the Zn contaminated soils, Zn was mainly released in the two most resistant fractions, in qualitative agreement with the findings from LCF. Our results suggest that formation of Zn-HIM may strongly retain Zn in pristine and moderately contaminated acidic to neutral soils. Due to their limited sorption capacity, however, HIM do not allow for the accumulation of high levels of Zn in response to continued Zn input into soils.  相似文献   
93.
We determined the speciation of Zn in 49 field soils differing widely in pH (4.1–7.7) and total Zn content (251–30,090 mg/kg) by using extended X-ray absorption fine structure (EXAFS) spectroscopy. All soils had been contaminated since several decades by inputs of aqueous Zn with runoff-water from galvanized power line towers. Pedogenic Zn species identified by EXAFS spectroscopy included Zn in hydroxy-interlayered minerals (Zn-HIM), Zn-rich phyllosilicates, Zn-layered double hydroxide (Zn-LDH), hydrozincite, and octahedrally and tetrahedrally coordinated sorbed or complexed Zn. Zn-HIM was only observed in (mostly acidic) soils containing less than 2000 mg/kg of Zn, reflecting the high affinity but limited sorption capacity of HIM. Zn-bearing precipitates, such as Zn-LDH and Zn-rich trioctahedral phyllosilicates, became more dominant with increasing pH and increasing total Zn content relative to available adsorption sites. Zn-LDH was the most abundant Zn-precipitate and was detected in soils with pH > 5.2. Zn-rich phyllosilicates were detected even at lower soil pH, but were generally less abundant than Zn-LDH. Hydrozincite was only identified in two calcareous soils with extremely high Zn contents. In addition to Zn-LDH, large amounts of Zn in highly contaminated soils were mainly accumulated as sorbed/complexed Zn in tetrahedral coordination. Soils grouped according to their Zn speciation inferred from EXAFS spectroscopy mainly differed with respect to soil pH and total Zn content. Clear differences were observed with respect to Zn fractionation by sequential extraction: From Zn-HIM containing soils, most of the total Zn was recovered in the exchangeable and the most recalcitrant fractions. In contrast, from soils containing the highest percentage of Zn-precipitates, Zn was mainly extracted in intermediate extraction steps. The results of this study demonstrate that soil pH and Zn contamination level relative to available adsorption sites are the most important factors controlling the formation of pedogenic Zn-species in aerobic soils and, consequently, Zn fractionation by sequential extraction.  相似文献   
94.
95.
This study addresses sources and diagenetic state of early-season dissolved organic matter (DOM) in the Northeast Water Polynya (NEWP) area northeast of Greenland from distributions of humic substance fluorescence (HSfl), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) in the water column inside and outside the NEWP area. The water masses of the polynya area had acquired their spring/summer temperature–salinity characteristics at the time of sampling, and also had individual, different DOM signatures. DOC concentrations were variable within and among water masses in the polynya area, indicating patchy local sources and sinks of DOC. PySW and polynya intermediate water (PyIW) had higher average DON concentrations and average lower C:N ratios than polynya bottom water (PyBW), indicating a larger fraction of fresh DOM in PySW and PyIW than in PyBW. Ice-covered, polynya area surface waters (PySW) had higher DOC concentrations (113±14 μM, n=68) than surface water (SW) outside the polynya area (96±18 μM, n=6). The DOM C:N ratios in a low-salinity, ice-melt subgroup of PySW samples indicate labile material, and these low-salinity surface waters appeared to have a local DOC and DON source. In contrast, HSfl was significantly lower inside than outside the NEWP area. Despite the lower HSfl values within the NEWP area, the PySW values were high when compared to open-ocean water. There were no local terrestrial sources for HSfl to the NEWP area and the East Greenland Current is therefore proposed as a likely source of allochtonous HSfl. When HSfl was used as a conservative tracer, up to 70% of the water in PySW and PyIW was found to be derived from SW, which contains a high fraction of water from the East Greenland Current. Similarly, a mixing model based on HSfl indicated that 80% of early-season DOC and 90–100% of early-season DON in PySW and PyIW were derived from SW, indicating a potentially high fraction of terrestrially-derived, relatively refractory DOM in the early-season NEWP area.  相似文献   
96.
Various studies have revealed high concentrations of contaminants such as organochlorines (OCs) and heavy metals in Mediterranean cetaceans. A geographical trend of contamination (PCBs and DDTs) has been found for striped dolphin (Stenella coeruleoalba). In this study we used a non-lethal approach (skin biopsy) to investigate bioaccumulation of OCs, including polychlorobiphenyls (PCBs), DDTs, polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), trace elements (Hg, Cd, Pb) and CYP1A activity (BPMO) in nine striped dolphins sampled in the Aeolian area (Sicily - Italy) in summer 2002. The arithmetic mean value of BPMO activity in this group was 43.46 AUF/g tissue/h. This value is approximately 3 times and 5 times lower, respectively, than the value found in the Ionian and in the Ligurian groups. Skin biopsies of striped dolphins emerged as a suitable material for assessing the toxicological status of the various Mediterranean groups.  相似文献   
97.
Dissolved organic matter (DOM) from the Opalinus Clay, a potential host rock for the disposal of radioactive waste, was isolated under strictly anoxic conditions from ground rock material and compared with DOM of in situ pore water samples. For the extractions, deionized water, synthetic pore water (SPW, water containing all major ions at pore water concentrations but no organic matter) and 0.1 M NaOH were used. The influence of the solid-to-liquid ratio, extraction time, acid-pretreatment and O2 exposure of the rock material on the isolated DOM were investigated. Liquid chromatography coupled with a total organic C detector (LC-OCD) and reverse-phase ion chromatography were used to characterize the DOM size distributions and to determine the low molecular weight organic acid (LMWOA) contents in the pore water samples and the rock extracts.The results revealed that only a small portion of the total organic C of the rock material (<0.38%) was extractable, even after removal of carbonates by acid-pretreatment. The concentrations of dissolved organic C (DOC) were found to range from 3.9 ± 0.4 to 8.0 ± 0.8 mg/L in the anoxic extracts. The pore waters exhibited similar DOC concentrations ranging from 1.2 to 15.8 ± 0.5 mg/L. The analysis by LC-OCD showed that the DOM extracted under anoxic conditions and the pore water DOM mainly consisted of hydrophilic compounds of less than 500 Da. The DOM extracted with SPW was most similar in size to the pore water DOM. Grinding the rock under oxic conditions increased the DOC yields and shifted the size distribution toward higher molecular weight compounds compared to the strictly anoxic treatment. Acetate, lactate and formate were identified in all extracts and in the pore water. In total, LMWOA accounted for 36% of the total DOC in both pore water and SPW extracts. The results imply that controlled anoxic conditions and the use of SPW as an extractant are required to isolate DOM from Opalinus Clay rocks which most resembles the in situ pore water DOM with respect to its size distribution and the LMWOA contents.  相似文献   
98.
Two nanociliates of the order Prostomatida,Pseudobalanion planctonicum (12–18 µm) andUrotricha furcata (12–21 µm), were found to be the most abundant ciliates in the epilimnion of Piburger See, a small mesotrophic lake. Temperature and food availability were the main factors controlling the sudden increase in abundance, which reached a maximum of 101 cell ml–1 at the beginning of summer. During their exponential development in numbers and biomass, a strong decrease in chlorophylla and in the abundance of phytoplankton, especiallyRhodomonas, was observed. We assume, therefore, thatPseudobalanion planctonicum andUrotricha furcata together with rotifers, mainlyPolyarthra dolichoptera, are able to reduce the phytoplankton biomass in the upper epilimnion to the same level as found during the clearwater phase. Preliminary results of grazing on bacteria suggest that these nanociliates are omnivorous, although their impact on bacterial assemblages was low (3.1% of the standing stock grazed per day). Feeding on the base of the food web combined with their high abudance at certain times makes them an important link for higher trophic levels. This study constitutes the second report onPseudobalanion as an important component of the microbial food web in lakes.  相似文献   
99.
100.
The formation of loess deposits strongly depends on the availability of deflatable dust‐sized material. Identification of source areas and mechanisms of dust production is essential for an appropriate characterization of related palaeoenvironmental conditions. So far, little research has been done on loess deposits in the Mediterranean region and information about mechanisms of dust production is very rare. In this context, it is not clear from where the loess deposits from the upper Tagus Basin in central Spain originated. The main objective of this study was to find out whether these loess deposits were formed primarily by mountain processes and fluvial comminution, or whether they have their origin in the weathering of Tertiary marls in the centre of the Madrid Basin. A further concern was to link the determined source areas with loess formation mechanisms and concomitant environmental contexts. Following a comprehensive approach using heavy minerals and grain‐size data, together with information on stratigraphic features and geomorphic positions, different local loess sources could be identified. This study shows that during the last 35 kyr a major proportion of the Tagus loess deposits was deflated from river floodplains, while the mountain region of the Iberian Range was identified as a significant source of respective floodplain sediments. Based on heavy mineral compositions and dating results, it was found that during Heinrich Stadial 3, sediment supply from the Iberian Range strongly increased, suggesting an environmental shift from initially warmer towards colder temperatures in late Marine Isotope Stage 3. Furthermore, it was found that grain‐size patterns clearly indicate maximum wind strengths during Heinrich Stadial 3, followed by Heinrich Stadial 2 and Heinrich Stadial 1. These results demonstrate that the formation of dust‐sized particles in this part of the Mediterranean operated similar to many other places in temperate and continental regions, and that weathering processes linked to hot and dry environments were only of minor importance.  相似文献   
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