Controls on uranium distribution in lake sediments     

Anthony Chappaz  André Tessier 《Geochimica et cosmochimica acta》2010,74(1):203-88

Uranium geochemistry has been investigated in three acid lakes located on the Canadian Shield and one circumneutral lake in the Appalachian Region of Eastern Canada. In all Shield lakes, dissolved U concentrations were higher in the porewater than in the overlying water. In one of them, whose hypolimnion is perennially oxic, U released to porewater at depths of Fe remobilization was removed from the porewater at depths of Fe oxyhydroxides precipitation; these similarities in the U and Fe profiles indicate that part of the U becomes associated to Fe oxyhydroxides. The dissolved U and Fe profiles in the other two Shield lakes, whose hypolimnions were anoxic when sampled, did not show any significant recycling of these elements in the vicinity of the sediment-water interface and both elements diffused from the sediment to the overlying water. In contrast, in the Appalachian Lake, dissolved U concentrations were higher in the overlying water than in porewater, strongly decreased at the vicinity of the sediment-water interface and then remained relatively constant with sediment depth. Diagenetic modeling of the porewater U profiles, assuming steady-state, reveals that authigenic U always represented ?3% of the total U concentration in the sediments of all lakes. This observation indicates that diagenetic reactions involving U are not quantitatively important and that most of the U was delivered to the sediments at our study sites as particulate U and not through diffusion across the sediment-water interface, as is seen in continental margin sediments. Comparison of the U:C_org and U:Fe molar ratios in diagenetic material collected across the sediment-water interface with Teflon sheets and in surface sediments (0-0.5 cm) of the lake having a perennially oxic hypolimnion suggest that solid phase U was mainly bound to organic matter originating from the watershed; a strong statistical correlation between sediment non-lithogenic U and C_org in the Appalachian Lake supports this contention. Thermodynamic calculations of saturation states suggest that dissolved U was not removed from porewater through precipitation of UO_2(s), U₃O_7(s) and U₃O_8(s) as previously proposed in the literature.  相似文献   

The nature of Cu bonding to natural organic matter     

Alain Manceau  Anthony Matynia 《Geochimica et cosmochimica acta》2010,74(9):2556-2587

Copper biogeochemistry is largely controlled by its bonding to natural organic matter (NOM) for reasons not well understood. Using XANES and EXAFS spectroscopy, along with supporting thermodynamic equilibrium calculations and structural and steric considerations, we show evidence at pH 4.5 and 5.5 for a five-membered Cu(malate)₂-like ring chelate at 100-300 ppm Cu concentration, and a six-membered Cu(malonate))_1-2-like ring chelate at higher concentration. A “structure fingerprint” is defined for the 5.0-7.0 Å⁻¹ EXAFS region which is indicative of the ring size and number (i.e., mono- vs. bis-chelate), and the distance and bonding of axial oxygens (O_ax) perpendicular to the chelate plane formed by the four equatorial oxygens (O_eq) at 1.94 Å. The stronger malate-type chelate is a C₄ dicarboxylate, and the weaker malonate-type chelate a C₃ dicarboxylate. The malate-type chelate owes its superior binding strength to an -OH for -H substitution on the α carbon, thus offering additional binding possibilities. The two new model structures are consistent with the majority of carboxyl groups being clustered and α-OH substitutions common in NOM, as shown by recent infrared and NMR studies. The high affinity of NOM for Cu(II) is explained by the abundance and geometrical fit of the two types of structures to the size of the equatorial plane of Cu(II). The weaker binding abilities of functionalized aromatic rings also is explained, as malate-type and malonate-type structures are present only on aliphatic chains. For example, salicylate is a monocarboxylate which forms an unfavorable six-membered chelate, because the OH substitution is in the β position. Similarly, phthalate is a dicarboxylate forming a highly strained seven-membered chelate.Five-membered Cu(II) chelates can be anchored by a thiol α-SH substituent instead of an alcohol α-OH, as in thio-carboxylic acids. This type of chelate is seldom present in NOM, but forms rapidly when Cu(II) is photoreduced to Cu(I) at room temperature under the X-ray beam. When the sample is wet, exposure to the beam can reduce Cu(II) to Cu(0). Chelates with an α-amino substituent were not detected, suggesting that malate-like α-OH dicarboxylates are stronger ligands than amino acids at acidic pH, in agreement with the strong electronegativity of the COOH clusters. However, aminocarboxylate Cu(II) chelates may form after saturation of the strongest sites or at circumneutral pH, and could be observed in NOM fractions enriched in proteinaceous material. Overall, our results support the following propositions:

(1)

The most stable Cu-NOM chelates at acidic pH are formed with closely-spaced carboxyl groups and hydroxyl donors in the α-position; oxalate-type ring chelates are not observed.

(2)

Cu(II) bonds the four equatorial oxygens to the heuristic distance of 1.94 ± 0.01 Å, compared to 1.97 Å in water. This shortening increases the ligand field strength, and hence the covalency of the Cu-O_eq bond and stability of the chelate.

(3)

The chelate is further stabilized by the bonding of axial oxygens with intra- or inter-molecular carboxyl groups.

(4)

Steric hindrances in NOM are the main reason for the absence of Cu-Cu interactions, which otherwise are common in carboxylate coordination complexes.

  相似文献   

A New Fossil Termite(Isoptera,Stolotermitidae,Stolotermes)from the Early Miocene of Otago,New Zealand   总被引：1，自引：1，他引：0  

Uwe Kaulfuss  Anthony C. Harris  Daphne E. Lee 《《地质学报》英文版》2010,84(4):705-709

<正>The forewing of a termite from Early Miocene lake sediments in Otago,southern New Zealand is figured and described.It exhibits the generic characters of the damp-wood termite Stolotermes Hagen,but differs from forewings of the known species in size and venation pattern and is described as Stolotermes kupe sp.nov.S.kupe represents the first confident record of fossil Stolotermitidae and extends the fossil record of the family back to the Early Miocene.It also is the first direct evidence of fossil Isoptera from New Zealand,though silicified termite faecal pellets,referable to Kalotermes brauni,have been previously described.S.kupe indicates that Stolotermitidae has been present in the Australasian region since at least the Early Miocene.  相似文献   

A Fe K-edge XAS study of amethyst     

Francesco Di Benedetto  Francesco D’Acapito  Gabriele Fornaciai  Massimo Innocenti  Giordano Montegrossi  Luca A. Pardi  Silvia Tesi  Maurizio Romanelli 《Physics and Chemistry of Minerals》2010,37(5):283-289

An X-ray absorption spectroscopy (XAS) study of the Fe local environment in natural amethyst (a variety of α-quartz, SiO₂) has been carried out. Room temperature measurements were performed at the Fe K-edge (7,112 eV), at both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions. Experimental results were then compared with DFT calculations. XANES experimental spectra suggest Fe to occur mainly in the trivalent state, although a fraction of Fe²⁺ is identified. EXAFS spectra, on the other hand, reveal an unusual short distance for the first coordination shell:  = 1.78(2) Å, the coordination number being 2.7(5). These results allow to establish that Fe replaces Si in its tetrahedral site, and that numerous local distortions are occurring as a consequence of the presence of Fe³⁺ variably compensated by protons and/or alkaline ions, or uncompensated. The formal valence of Fe, on the basis of both experimental and DFT structural features, can be either 4+ or 3+. Taking into account the XANES evidences, we suggest that Fe mainly occurs in the trivalent state, compensated by protons, and that a minor fraction of Fe⁴⁺ is stabilised by the favourable local structural arrangement.  相似文献   

The crystal structure of waylandite from Wheal Remfry, Cornwall, United Kingdom     

Stuart J. Mills  Anthony R. Kampf  Mati Raudsepp  William D. Birch 《Mineralogy and Petrology》2010,100(3-4):249-253

Sr- and Ca-rich waylandite, $ {\left( {{\hbox{B}}{{\hbox{i}}_{0.{54}}}{\hbox{S}}{{\hbox{r}}_{0.{31}}}{\hbox{C}}{{\hbox{a}}_{0.{25}}}{{\hbox{K}}_{0.0{1}}}{\hbox{B}}{{\hbox{a}}_{0.0{1}}}} \right)_{\Sigma 1.12}}{{\hbox{H}}_{0.{18}}}{\left( {{\hbox{A}}{{\hbox{l}}_{{2}.{96}}}{\hbox{C}}{{\hbox{u}}_{0.0{2}}}} \right)_{\Sigma 2.98}}{\left[ {{{\left( {{{\hbox{P}}_{0.{97}}}{{\hbox{S}}_{0.0{3}}}{\hbox{S}}{{\hbox{i}}_{0.0{1}}}} \right)}_{\Sigma 1.00}}{{\hbox{O}}_4}} \right]_2}{\left( {\hbox{OH}} \right)_6} $ , from Wheal Remfry, Cornwall, United Kingdom has been investigated by single-crystal X-ray diffraction and electron microprobe analyses. Waylandite crystallises in space group R $ \overline 3 $ ? m, with the cell parameters: a?=?7.0059(7) Å, c?=?16.3431(12) Å and V?=?694.69(11) ų. The crystal structure has been refined to R ₁?=?3.76%. Waylandite has an alunite-type structure comprised of a rhombohedral stacking of (001) composite layers of corner-shared AlO₆ octahedra and PO₄ tetrahedra, with (Bi,Sr,Ca) atoms occupying icosahedrally coordinated sites between the layers.  相似文献   

Testing the credibility of historical newspaper reporting of extreme climate and weather events     

Duncan Munro  Anthony Fowler 《New Zealand geographer》2014,70(3):153-164

In recent years, newspaper research has been streamlined by digitisation and online hosting by PapersPast. This paper tests the reliability and credibility of reporting of extreme weather and climatic events through PapersPast to determine if newspaper research of past climate can be further streamlined. Searches were conducted through four early‐20th‐century Auckland newspapers, where counts of articles returned by key‐word searches for particular periods were compared against periods of known extremes. We find that blind searches have only limited potential in identifying extreme weather and climatic events and that they are no substitute for thorough analyses of documentary sources.  相似文献   

Public perceptions of rainfall change in India   总被引：1，自引：1，他引：0  

Peter D. Howe  Jagadish Thaker  Anthony Leiserowitz 《Climatic change》2014,127(2):211-225

People’s perceptions of changes in local weather patterns are an important precursor to proactive adaptation to climate change. In this paper, we consider public perceptions of changes in average rainfall in India, analyzing the relationship between perceptions and the instrumental record. Using data from a national sample survey, we find that local instrumental records of precipitation are a strong predictor of perceived declines in rainfall. Perceptions of decreasing rainfall were also associated with perceptions of changes in extreme weather events, such as decreasing frequency of floods and severe storms, increasing frequency of droughts, and decreasing predictability of the monsoon. Higher social vulnerability—including low perceived adaptive capacity and greater food and livelihood dependence on local weather—was also associated with perceptions of decreasing rainfall. While both urban and rural respondents were likely to perceive local changes in precipitation, we show that rural respondents in general were more sensitive to actual changes in precipitation. Individual perceptions of changes in local climate may play an important role in shaping vulnerability to global climate change, adaptive behavior, and support for adaptation and mitigation policies. Awareness of local climate change is therefore particularly important in regions where much of the population is highly exposed and sensitive to the impacts of climate change.  相似文献   

The Little Ice Age climate of New Zealand reconstructed from Southern Alps cirque glaciers: a synoptic type approach   总被引：2，自引：1，他引：1  

Andrew Lorrey  Nicolas Fauchereau  Craig Stanton  Petra Chappell  Steven Phipps  Andrew Mackintosh  James Renwick  Ian Goodwin  Anthony Fowler 《Climate Dynamics》2014,42(11-12):3039-3060

Little Ice Age (LIA) austral summer temperature anomalies were derived from palaeoequilibrium line altitudes at 22 cirque glacier sites across the Southern Alps of New Zealand. Modern analog seasons with temperature anomalies akin to the LIA reconstructions were selected, and then applied in a sampling of high-resolution gridded New Zealand climate data and global reanalysis data to generate LIA climate composites at local, regional and hemispheric scales. The composite anomaly patterns assist in improving our understanding of atmospheric circulation contributions to the LIA climate state, allow an interrogation of synoptic type frequency changes for the LIA relative to present, and provide a hemispheric context of the past conditions in New Zealand. An LIA summer temperature anomaly of ?0.56 °C (±0.29 °C) for the Southern Alps based on palaeo-equilibrium lines compares well with local tree-ring reconstructions of austral summer temperature. Reconstructed geopotential height at 1,000 hPa (z1000) suggests enhanced southwesterly flow across New Zealand occurred during the LIA to generate the terrestrial temperature anomalies. The mean atmospheric circulation pattern for summer resulted from a crucial reduction of the ‘HSE’-blocking synoptic type (highs over and to the west of NZ; largely settled conditions) and increases in both the ‘T’- and ‘SW’-trough synoptic types (lows passing over NZ; enhanced southerly and southwesterly flow) relative to normal. Associated land-based temperature and precipitation anomalies suggest both colder- and wetter-than-normal conditions were a pervasive component of the base climate state across New Zealand during the LIA, as were colder-than-normal Tasman Sea surface temperatures. Proxy temperature and circulation evidence were used to corroborate the spatially heterogeneous Southern Hemisphere composite z1000 and sea surface temperature patterns generated in this study. A comparison of the composites to climate mode archetypes suggests LIA summer climate and atmospheric circulation over New Zealand was driven by increased frequency of weak El Niño-Modoki in the tropical Pacific and negative Southern Annular Mode activity.  相似文献   

Groundwater flux as a determinant of coastal-zone upland loss: a case study from the Pennsylvania coast of Lake Erie,USA     

Anthony M. Foyle 《Environmental Earth Sciences》2014,71(10):4565-4578

Climate change in the Great Lakes Basin of North America over the next several decades is projected to lead to significant changes to coastal environments. Groundwater-driven coastal bluff recession should increase in areas where groundwater forcing is important and lead to increased loss of coastal uplands. The latter is an issue in NW Pennsylvania because of coastal development pressures, and because the state ranks within the top five US states in grape production, most of which occurs within 5 km of the Lake Erie coastline. In 2007, viticulture contributed almost $2.4 billion to the state economy. An analysis of a 20-km stretch of coast shows that bluff retreat is pervasive and variable under current climatic conditions. Over a 9-year time frame, bluff change rates ranged from ?4.2 to +0.98 m/year. In general, higher retreat rates (?0.2 to ?0.65 m/year) occurred along the sandy central beach–ridge sector which lacks significant surface drainage. Lower retreat rates (?0.10 to ?0.25 m/year) occurred along coastal sectors where surface drainage networks are well developed. Conservative estimates of groundwater discharge at the bluff correlate strongly (r = 0.74, p < 0.001) with bluff retreat rate. Groundwater is inferred to be the principal driving mechanism for both bluff retreat and spatial variability in retreat rates on this coast. Other common factors that may spatially influence bluff retreat elsewhere (bluff height, land use, beach width) do not correlate strongly with retreat rate.  相似文献   

Streamflow response to regional climate model output in the mountainous watershed: a case study from the Swiss Alps     

Kazi?RahmanEmail author  Christophe?Etienne  Ana?Gago-Silva  Chetan?Maringanti  Martin?Beniston  Anthony?Lehmann 《Environmental Earth Sciences》2014,72(11):4357-4369

Regional climate model (RCM) outputs are often used in hydrological modeling, in particular for streamflow forecasting. The heterogeneity of the meteorological variables such as precipitation, temperature, wind speed and solar radiation often limits the ability of the hydrological model performance. This paper assessed the sensitivity of RCM outputs from the PRUDENCE project and their performance in reproducing the streamflow. The soil and water assessment tool was used to simulate the streamflow of the Rhone River watershed located in the southwestern part of Switzerland, with the climate variables obtained from four RCMs. We analyzed the difference in magnitude of precipitation, maximum and minimum air temperature, and wind speed with respect to the observed values from the meteorological stations. In addition, we also focused on the impact of the grid resolution on model performance, by analyzing grids with resolutions of 50 × 50 and 25 × 25 km². The variability of the meteorological inputs from various RCMs is quite severe in the studied watershed. Among the four different RCMs, the Danish Meteorological Institute provided the best performance when simulating runoff. We found that temperature lapse rate is significantly important in the mountainous snow and glacier dominated watershed as compared to other variables like precipitation, and wind speed for hydrological performance. Therefore, emphasis should be given to minimum and maximum temperature in the bias correction studies for downscaling climatic data for impact modeling in the mountainous snow and glacier dominated complex watersheds.  相似文献