Moisture sorption behaviour of salt mixtures in porous stone     

Christoph Franzen  Peter W. Mirwald 《Chemie der Erde / Geochemistry》2009,69(1):91-98

Moisture in stone material is the key factor for all stone deterioration processes and also in weathering of cultural heritage. With additional presence of salts in the material the situation gets even more critical. While the properties of pure salts with moisture are well known, knowledge about the interaction of salt mixtures with moisture is still poor. In different approaches the reactions of salt-contaminated stone material on changing moisture were tested in the laboratory. Experiments with different solutions in the Na-Mg-SO₄-NO₃-H₂O system revealed interesting new results on the moisture behaviour of salt-contaminated samples. Theoretical considerations and computer simulations are helpful to interpret the data obtained, but are not yet sufficient to explain the real processes acting on site at the monuments. More encouraging to this fact are complementary studies on visible efflorescences in the same salt system. It is shown how by experimental approaches the understanding on salt-induced stone deterioration is strongly complemented.  相似文献   

Limiting hydrochemical factors for sustainability of water resources: The Cisjordanian experience     

Eliahu Rosenthal  Joseph Guttman  Peter Möller 《Chemie der Erde / Geochemistry》2009,69(3):191-222

In Cisjordan, surface- and groundwater flow are either towards the Jordan Valley-Dead Sea-Arava Valley (the Rift) or the Mediterranean Sea. Due to upstream exploitation by riparians to the Jordan River, the historical annual flow, which fluctuated between 250 and 1100 Mm³, has declined to a mere 100-200 Mm³. The remaining flow south of Lake Kinneret is highly polluted and heavily loaded with salts. Lake Kinneret (Sea of Galilee) is one of the major water resources in the area. Annually, between 200 and 700 Mm³ reach the Lake as surface and groundwater flow. The relatively high salinity of the Lake is caused by thermomineral water discharging from springs and seepages located onshore and on the bottom of the Lake. The main factors causing deterioration of the groundwater quality in the Rift are of geogenic character. These are different types of brines, whose outflow and penetration into freshwater aquifers was triggered by overpumpage. Contemporary encroachment of seawater caused by intensive water exploitation in the Coastal Plain is manageable and reversible. However, due to lack of hydrogeological evidence, no such statement can be made about the circulation of seawater beneath the Coastal Plain and into the deep-seated Yarkon-Taninim aquifer or the upflow of brines in the Rift.The flow regimes of the different brine bodies could not be elucidated. Whether each such brine-body flows by its particular hydrological regime or whether the movement of the different bodies is intradependent or interdependent with the regional movement of fresh groundwater, remain open questions. Therefore, sustainable development of groundwater resources is clearly dependent on the elucidation of the relationship between changes in the pressure of the brine with depth and its relationship to the overlying freshwater.The average total annual recharge of all water sources in Cisjordan is 1820 Mm³, which means that the total production of water must be managed within the limits of this annual volume. During drought years, total groundwater extraction exceeds the safe yield, causing drastic lowering of water levels and upflow of saline waters from greater depths.Because of the structural complexity of aquifers and hydrochemical variability of the numerous groundwater bodies, new hydrochemical methods have been developed for the identification of groundwater bodies and for the elucidation of their origins. These methods combine macrochemical, microchemical, and isotopic evidences. By combining distribution patterns of rare earths, yttrium and stable isotopes, a complete picture of catchment lithology and the altitude and latitude of precipitation could be obtained.The area west of the Jordan River is characterized by the occurrence of transboundary surface- and groundwater basins in which fresh and saline water and brines flow across political borders between Israel and the Palestinian Authority. It is very difficult to assess separately the annual safe yield of water resources for each of the two national entities. Neither country may dispose independently of its waters and is usually at the mercy of the other riparian. There is as yet no general multilateral international treaty in force allocating the water resources of international watercourses. At present there are two rules for the management of the waters of an international drainage basin—the rule of Equitable Distribution, and the obligation Not to Cause Significant Harm. The rules of equitable distribution have tended to focus on the issue of quantities of water rather than on quality of water, which is really relevant to the issue of equitable distribution. Future negotiations on the uses of the basin will need to deal with issues of characteristic salinities and geochemical features and on their impact on equitable sharing of water resources.  相似文献   

Analysis of small-scale heterogeneity in clastic rocks by using computerized X-ray tomography (CT)     

Janos Geiger  Zoltan Hunyadfalvi  Peter Bogner   《Engineering Geology》2009,103(3-4):112-118

The aim of this study is to recognize the basic clastic rock types on the basis of Hounsfield Units (HUs) by using statistical methods (hypothesis tests, distribution fitting, and confidence intervals). How does this recognition depend on depositional history of samples tested? Does the numerical pattern of HUs obtained from small-scale analyzing of some particular sedimentary structures coincide to the textural expectations of those sedimentary structures? Are the HU values provided by the CT measurements capable of evidencing micro-cycles belonging to a particular depositional history?For testing the numerical recognition, we analyze macroscopically homogeneous argillaceous marl, siltstone and fine sandstone samples with similar depositional background, age, and degree of diagenesis. The preliminary research shows that the Hounsfield Units can identify different sedimentary rocks considerably well. There are significant differences among the confidence intervals belonging to the different rock types. However, there also have been some slight overlaps among them.For analyzing the effects of the depositional processes in case of a particular rock type, samples from channel sandstone, distributary mouth-bar, massive (structureless) sandstone from a delta-fed turbidity fan, and channel sandstone with traction carpet origin from a delta-fed turbidity fan (all coming from Pannonian basin filling series) are used. The results prove again the significant differences in the terms of both confidence intervals and distribution-types; however, some overlapping also occurs.  相似文献   

The contribution of agricultural and urban activities to inorganic carbon fluxes within temperate watersheds   总被引：8，自引：0，他引：8  

Rebecca T. Barnes  Peter A. Raymond 《Chemical Geology》2009,266(3-4):327-336

The lateral transport of bicarbonate as dissolved inorganic carbon (DIC) to the oceans is an integral component of the global carbon budget and can represent the sequestration of CO₂ from the atmosphere. Recently studies have implicated land use change, in particular agricultural development, as an accelerator of bicarbonate export. However, due to the co-variation of land use, bedrock and surficial geologies, and the relationship between bicarbonate export and climate, the impact of anthropogenic activities on DIC export remains an important research question. In order to examine the land use controls on DIC export from small temperate watersheds we sampled 19 streams draining catchments of varying land uses with similar bedrock and surficial geologies. In addition to an agricultural effect, there was a strong correlation between the percent of watershed in urban development and DIC concentrations and DIC yields. Urban watersheds exported 7.8 times more DIC than their nearby forested counterparts and 2.0 times more DIC than nearby agricultural catchments. Isotopic data suggest that excess DIC export from altered systems results from increased chemical weathering, enhanced CO₂ production within urban green spaces, and as a result of organic matter loading from septic systems and leaky sewer lines. Furthermore, we found that nitrogen additions (e.g. fertilizers and manure) are aiding in the dissolution of lime, increasing the total export of DIC from agricultural watersheds. Calculated anthropogenic loading rates ranged from 0.43 to 0.86 mol C m^− 2 yr^− 1. These loading rates suggest that a significant portion of global DIC export might be attributable to human activities, although the impacts on CO₂ sequestration are difficult to determine.  相似文献   

Influence of anthropogenic combustion emissions on the deposition of soluble aerosol iron to the ocean: Empirical estimates for island sites in the North Atlantic     

Edward R. Sholkovitz  Peter N. Sedwick 《Geochimica et cosmochimica acta》2009,73(14):3981-3081

The results of several recent studies challenge the reigning paradigm that continental soil dust provides the only significant atmospheric source of dissolved iron to the surface ocean. This evidence includes correlations between the operational solubility of aerosol iron and atmospheric loadings of black carbon and aluminum-normalized vanadium and nickel, each of which are associated with emissions from the combustion of fossil fuel oil. These observations suggest that the relative solubility of aerosol iron, hence the eolian flux of soluble iron to the surface ocean, may be significantly impacted by anthropogenic oil combustion products. Using recent field data from the Bermuda region, we have developed an empirical method to estimate the solubility of aerosol iron using bulk aerosol concentrations of Fe, V and Al. We apply this method to a large body of published data from the AEROCE program for North Atlantic island sites on Tenerife, Barbados, Bermuda and Ireland, where the relative proportions of anthropogenic aerosols range from minor to major, respectively. Our aerosol iron solubility estimates suggest that anthropogenic emissions contribute approximately 70% and 85% of the annual dry deposition of soluble iron to the surface ocean near Bermuda and Ireland, respectively, implying that human activities have profoundly affected the iron budget of the North Atlantic region. The annual mean dry deposition of soluble iron at Barbados and Izana is dominated by soil dust. The anthropogenic contribution at these two sites ranges from 12% to 30% and is highly dependent on the soil dust solubility of Fe employed in the model. The low end (∼12%) estimate appears to be more representative of these high-dust sites.  相似文献   

Oxygen and hydrogen isotope fractionation in serpentine-water and talc-water systems from 250 to 450 °C, 50 MPa     

Peter J. Saccocia  Jeffrey S. Seewald 《Geochimica et cosmochimica acta》2009,73(22):6789-18

Oxygen and hydrogen isotope fractionation factors in the talc-water and serpentine-water systems have been determined by laboratory experiment from 250 to 450 °C at 50 MPa using the partial exchange technique. Talc was synthesized from brucite + quartz, resulting in nearly 100% exchange during reaction at 350 and 450 °C. For serpentine, D-H exchange was much more rapid than ¹⁸O-¹⁶O exchange when natural chrysotile fibers were employed in the initial charge. In experiments with lizardite as the starting charge, recrystallization to chrysotile enhanced the rate of ¹⁸O-¹⁶O exchange with the coexisting aqueous phase. Oxygen isotope fractionation factors in both the talc-water and serpentine-water systems decrease with increasing temperature and can be described from 250 to 450 °C by the relationships: 1000 ln  = 11.70 × 10⁶/T² − 25.49 × 10³/T + 12.48 and 1000 ln  = 3.49 × 10⁶/T² − 9.48 where T is temperature in Kelvin. Over the same temperature interval at 50 MPa, talc-water D-H fractionation is only weakly dependent on temperature, similar to brucite and chlorite, and can be described by the equation: 1000 ln = 10.88 × 10⁶/T² − 41.52 × 10³/T + 5.61 where T is temperature in Kelvin. Our D-H serpentine-water fractionation factors calibrated by experiment decrease with temperature and form a consistent trend with fractionation factors derived from lower temperature field calibrations. By regression of these data, we have refined and extended the D-H fractionation curve from 25 to 450 °C, 50 MPa as follows: 1000 ln  = 3.436 × 10⁶/T² − 34.736 × 10³/T + 21.67 where T is temperature in Kelvin. These new data should improve the application of D-H and ¹⁸O-¹⁶O isotopes to constrain the temperature and origin of hydrothermal fluids responsible for serpentine formation in a variety of geologic settings.  相似文献   

Experimental determination of carbon isotope fractionation between CaCO₃ and graphite     

Peter Deines 《Geochimica et cosmochimica acta》2009,73(24):7256-348

Carbon isotopic exchange between graphite and three polymorphs of CaCO₃ was investigated at temperatures of 600-1400 °C and at pressures from 1.4 to 2.3 GPa. Fractionation factors at all temperatures were determined by the partial exchange treatment of Northrop and Clayton (1966).Graphite starting material for the majority of the experiments was milled in water for 20-25 h, producing aggregates of nanosheets. The sheets range in width from 50 to 1000 nm and in thickness from 20 to 30 nm, and they retain hexagonal symmetry.Isotopic exchange appears to be the sum of surface exchange and interior exchange. At 1100-1400 °C, interior exchange exceeded surface exchange, probably by a combination of grain growth, as determined by increase in crystallite size, recrystallization, as observed in FESEM images, and diffusion. In some runs at 1200 and 1400 °C with an isotopic contrast between the initial graphite and calcite of close to 50‰, equilibrium fractionation was actually overstepped due to a kinetic effect. A weighted regression of fractionation factors from the high-temperature runs yields the line of equilibrium interior exchange: