Experimental and numerical studies of the O exchange between CO2 and water in the atmosphere-soil invasion flux

The ¹⁸O/¹⁶O ratio of CO₂ is a potentially powerful tracer of carbon dioxide fluxes from the soil to the atmosphere, which is influenced by complex interactions involving both biotic and abiotic soil processes. We use a simplified experimental approach and numerical simulations to examine in isolation the ¹⁸O exchange between CO₂ and soil water associated with the abiotic invasion of atmospheric CO₂ into soil. This allowed us to verify, in particular, whether the ¹⁸O of the retro-diffusion flux of CO₂ from the soil reflects ¹⁸O equilibration with water at the soil surface, or at some depth. Sterile soil samples with known water isotopic composition were placed in a closed box attached to a specially designed flow chamber and the changes in δ¹⁸O of CO₂ between the chamber inlet and outlet, due only to invasion effects, were determined. Numerical simulations constrained by the laboratory gas exchange measurements indicated that between the two commonly used diffusion models [Penman, H.L. (1940). Gas and vapor movements in soil, 1: the diffusion of vapors through porous solids. Int. J. Agric. Sci.30, 437-462; Moldrup, P., Olesen, T., Yamaguchi, T., Schjonning, P., Rolston, D.E. (1999). Modeling diffusion and reaction in soils, IX, the Backingham-Burdine-Campbell equation for gas diffusivity in undisturbed soil. Soil Sci.164, 542-551], only the former provided good agreement with the measurements over a wide range of soil water contents. Based on the model calculations constrained by experimental data, and on comparison of characteristic diffusion/reaction times, we conclude that the depth required for full CO₂-water ¹⁸O equilibration ranges between 2 and 8.5 cm. The depth depends, in order of importance, on (1) soil moisture content; (2) temperature, which dominates the rate of hydration isotopic exchange; (3) CO₂ residence time, which is determined by the time of replacement of the column air above the soil; and (4) soil structure, including porosity, tortuosity and grain size, with the later probably influencing the water surface area exposed to CO₂ exchange. Using field data from a semi-arid forest site in Israel, numerical simulations indicated that the ¹⁸O full equilibrium depth varied at this site between 4 cm (January) and 8 cm (November), being sensitive mostly to temperature and soil water content. Deepening of the equilibration depth as the soil dries should limit the effects of ¹⁸O evaporative enrichment at the surface on the isotopic composition of the soil-atmosphere CO₂ flux.     

Disintegration of marl slopes in Israel

Disintegration of marl slopes in Israel is directly related to the climatic characteristics of the region even where water is not an obvious component of the environment. Seasonal contrasts between long, dry summers and short, wet winters are manifested by wide ranges in temperature (13–26°C) and water content (5−>42 percent) within the marl. These variations lead to both solution and aggregation of carbonate material in the marl. Chemical disintegration in summer followed by mechanical disintegration in winter causes progressive weakening of the marl. The repeated wetting and drying results in the formation of an open texture in the marl. Scanning electron microscope (SEM) observations made over several seasons on marl from freshly excavated slopes confirm the progressive disintegration from the slope's surface to a depth of at least 1.50 m. Solution holes, channels, and gaps between aggregates and matrix, formed during the summer, greatly increase the effective porosity and permeability of the marl. Water infiltration in the winter results in the mechanical washing out of fine material to the surface of the slope by throughflow and piping.     

Expériences sur la précipitation directe de l'apatite dans l'eau de mer: Implication dans la genèse des phosphorites

The direct precipitation of apatite in seawater is inhibited by Mg ions. The action of various factors on this precipitation is studied: addition of Ca, addition of F, reduction of pH and simultaneous effect of reduction of pH and addition either of F or of Ca. It is established that the reduction of the pH of seawater to 7 allows the precipitation of the apatite with a Ca/Mg ratio in the water of 1.2. The favourable environment for the settlement of natural apatite must then be either neutral or acid. This result is corroborated by the re-study of Gulbrandsen's equation. Such an acid environment with a high phosphorus content may be the result of oxidation of large quantities of organic matter due to previous intense biological activity. The acidity is probably brought about by bubbling of CO₂.     

A new approach to the problem of tektite genesis

Variations in the major cation ratios in the (micro-) tektites of each of the different strewn fields were studied with the help of Niggli parameters. There is a high degree of variability in almost each individual strewn field which, however, is not random. Invariably, as SiO₂ increases the proportion of alumina and the alkalies among the cations increases, that ofMgO + ΣFeO (total iron as FeO) and CaO decreases; simultaneouslyK₂O/Na₂O increases whileMgO/FeO decreases. This is entirely analogous to magmatic differentiations and is incompatible with an explanation by mechanical mixing of sedimentary parent rocks. The picture can best be explained by partial melting, in analogy to fulgurites and combustion ultrametamorphic glasses.In some strewn fields (e.g. javaites, georgiaites, bediasites), all tektites formed from the same set of parent rocks. In these fields each cation parameter, when plotted against silica, follow a linear slightly curved path with a very small scatter (simple type). In others (e.g. moldavites, philippinites, australites) some or all cation parameters show a strong scatter which sometimes almost obliterates the differentiation trends. These complex diagrams can be reduced to 2–5 diagrams (lineages) of the simple type, each reflecting a different combination of parent rocks. Most lineages again show the influence of partial melting differentiation.If the chemical variations of tektites are caused by partial melting, the silica-poor end of each variation diagram (case of total melting) and not the average composition corresponds to the parent rock combination involved. Thus, neglecting losses by evaporation (which are minor), the chemical compositions of 25 starting materials were established. All except one of these can very closely be matched by a combination, in appropriate proportions, of only two of the most common sedimentary rocks. The only group which cannot be duplicated by a combination of any two sedimentary rocks are the bottle-green microtektites.     

Diagenetic trends of fluorine concentration in Negev phosphorites, Israel: implications for carbonate fluorapatite composition during phosphogenesis

An electron probe and chemical study of bulk phosphorite samples and separated constituents from various Negev deposits was carried out together with XRD, FTIR spectroscopy and textural analysis. The results allow a better understanding of the distribution of fluorine in these Upper Cretaceous phosphorite sequences and shed light on variations in the composition of the carbonate fluorapatite (CFA) phase during phosphogenesis. Two facies are recognized: (1) a pristine, microbially generated phosphorite facies; (2) a recycled, peloidal and biodetrital facies. Fluorine distribution in the Negev phosphorites is facies controlled: F/P₂O₅ is much lower in the pristine facies (0·090–0·107) than in the recycled facies (0·107–0·120). In addition, F/P₂O₅ varies considerably between the various constituents of the phosphate fraction; F‐poor francolites (F/P₂O₅ as low as 0·080) co‐exist with F‐rich francolites (F/P₂O₅ as high as 0·135) in the same phosphorite bulk sample. A lower F/P₂O₅ in francolite is associated with higher Cd and Zn concentrations in the phosphorite, an increase in Fe‐rich smectites in the clay fraction and the presence of structural OH in the francolite. The lower F/P₂O₅ ratios in the pristine facies are attributed to high organic deposition rates during the formation of these matted sediments, leading to rapid burial of the in situ‐forming CFA. This is possibly coupled with diffusion of F from sea water into bottom sediments being hampered by microbial mat coatings. These conditions resulted in O₂‐depleted porefluids, inducing the precipitation of Cd‐rich Zn sulphides and the formation of Fe‐rich smectites. F‐enrichment probably takes place when the earlier formed F‐poor ‘primary’ CFA is relocated close to the sea floor and bathed with interstitial sea water solutions of higher F concentrations. Oxidation and removal of the sulphide‐bound Cd and Zn apparently occurred together with enrichment in F of the francolite. Combining chemical data with XRD and FTIR results suggests a multistage growth for the Negev phosphate constituents in shifting formational sites and porefluids of varying F concentrations. This multiphase growth is reflected in the patchy distribution of F in the Negev constituents and might explain the inverse correlation between mean CO₂/F and F/P₂O₅ ratios of the analysed phosphorites in the two facies. It also suggests that CFA (or an amorphous precursor) initially formed with some OH groups in the apatite structure, which were subsequently substituted by F ions in recycled francolite through re‐equilibration with porefluids of higher F concentrations.     

Geochemical, mineralogical and isotopic signatures of the Semikan, West Kasrık “Turkish” phosphorites from the Derik–Mazıdağı–Mardin area, SE Anatolia

The geochemistry and mineralogy of a condensed section, ~6 m thick of the West Kasrik member (Coniacian–Santonian) near the uplifted northern flank of the Mardin–Derik anticline (south-eastern Turkey) was studied. The only deposit exploited in Turkey is found in this area. The sediment textures as well as the mineralogical and the geochemical results collectively suggest that these recycled phosphorites accumulated in areas of intensive very early diagenesis of the sediments in highly oxic bottom waters, and almost no detrital apport. The total concentration of redox-sensitive trace metals is very low (<600 μg/g); in addition the structural CO₂ and F/P₂O₅ are unusually high (~5 wt % and 0.14, respectively). REE distribution shows a clear “seawater” pattern with a strongly negative Ce-anomaly (0.20 ± 0.02) and heavy REE enrichment (Lu_N/La_N = 1.50 ± 0.12), however their total concentration is very low. The low REE contents, quite unexpected in recycled phosphorites, are explained by the scarcity of terrigenous components which leads to minimal incorporation of REEs from detrital clastic phases in the CFA fraction. Weathering previously suggested as responsible for the high P enrichment of the Mazidagi phosphorites is rather improbable in the samples we studied, in view of their high structural CO₂, high F/P₂O₅, high (La/Nd)_N and (La/Sm)_N ratios, and high Sr/P and Ca/P of separated CFA fractions that all negate post-depositional weathering. More likely, the high P enrichment of some rocks (P₂O₅ content reaches 34%) was produced by sedimentary and early diagenetic processes acting in oxygenated areas of starved sedimentation on and around tectonic highs.     

Accelerated recession of a desert cliff due to sewage water disposal,Sede Boqer,Israel

Accelerated erosion of a desert cliff due to uncontrolled sewage water disposal was investigated at the Sede Boqer Campus in the Negev, Israel An erosional cirque formed by this water was studied as a model simulating natural processes. The cliffs consist of loess and conglomerate underlain by soft marl, clay, and chalk. The rate of erosion is of the order of 5%–8% of the volume of water discharged. The rate of incision ranges from 10 2 to 13.3 m/yr and is several orders higher than that expected under normal rainfall conditions The introduction of this new hydrological factor resulted in a severe disturbance of the morphological balance in the vicinity of the cliffs, accelerated erosion, and generated circular slides     

The city of Tyre,Lebanon and its semi-artificial tombolo

The sedimentological history of the peninsular city of Tyre, located on the southern coast of Lebanon, reflects the political events surrounding Alexander the Great's conquest of the East (332 B.C.E.). Like many other Phoenician settlements, the city was originally situated on a small, relict rocky islet, but was later connected to the mainland by an artificial causeway constructed by Alexander's troops. As a result of the causeway construction, a gigantic tombolo formed, composed of at least 10 million m³ of sediment, mostly sand. Calculations based on the present size of the land tombolo of Tyre show that the average regional yearly volume of sand drift from the south and the north for the past 2300 years was approximately 4000 m³. If the present composition of high carbonate tombolo sands is representative of the entire sand body of the tombolo, about two thirds of the mass originates from nearby beaches which formed as a result of the erosion of the Pleistocene carbonate sandstone known as “Hajar Ramli.” © 1996 John Wiley & Sons, Inc.