Weathering of marbles and granites in marine environment: petrophysical properties and special role of atmospheric salts

 The aim of this paper was to study the weathering mechanism of marbles and granites exposed to the marine environment at the Delos archaeological site. Alterations, as granular disintegration, contour scaling and alveolus formations, can be observed either at the base of blocks and columns, or at the median-high zones of monuments. A white marble, which originated from Naxos Island, had a weak porosity (0.2%). Its porous network was organized into two subnetworks of rectilinear and sinuous cracks, which limited capillary transfer to ∼10 cm. The granite, which originated from Delos Island, had a relatively high porosity (2.15%), and had a well-connected system of cracks and microporous zones of weathered minerals. This homogeneous network allowed good capillary transfer for long distances (1–2 m). For the marble, as for the granite, evaporation occurred mainly at depth in the stone, and encouraged its deterioration. This damage depends on the dissolution and crystallization of salts, which occur in cycles. First, by the capillary transfer of water and salt from the ground, when the stones are located near the sea. This processes can explain the deterioration of the marble and the granite bases, and the decay of granite on all its surfaces. Second, by fixation of water vapor by sea salt deposited on the stone by wind. This phenomenon can explain the degradations observed on the median-high parts of monuments in marble and granite, even though, for the granite, the first mechanism was more active.     

Environmental impact on the Roman monuments of Tarragona,Spain

The extant remains of the Roman monuments of Tarragona, Spain are made of different types of Miocenic rocks from the quarries surrounding the city, which vary from calcarenite to bioclastic limestones, showing different degrees of dolomitization, depending on their diagenetic evolution. The decay of these monuments is highly dependent on the mineralogy and the fabric of the stone as well as on the environmental conditions to which the monument subjected. As a consequence, different forms of decay are observed on these monuments, namely, granular disintegration, differential erosion between sparitic and micritic areas of the rock, and development of black crust and orange patinas, some of them attributed to a sulfation process. A number of processes have been established as being responsible for the decay forms observed: sulfation on sheltered areas of the building in the urban environment; differential dilatation because of the NaCl of the marine spray that crystallizes inside the porosity; hydric and thermal expansion of the stone, both related to the amount and crystallinity of the clay minerals forming the rock matrix; and biocolonization on the stone surface. An empirical model is proposed to explain the decay forms studied in relation to these factors (rock and environment).     

Chemical composition of landfill leachate in a karst area with a Mediterranean climate (Marbella, southern Spain)

 Between March 1994 and April 1997, the physical and chemical parameters and chemical composition of the urban solid waste leachate of the Marbella landfill (southern Spain) were determined. The data obtained show an ammonium and sodium chloride and bicarbonate type, a pH>7 and high mineralization, effectively described by the following parameters: Na⁺, K⁺, NH₄ ⁺, Cl^– and alkalinity. The chemical composition depends on the rainfall: in dry years, the mineralization and component concentrations have values as much as double those found in normal rainfall years. After storm events, a major and rapid dilution (within several hours) is seen in the leachate. Received: 28 January 1998 · Accepted: 2 June 1998     

Effect of impurities on grain growth in synthetic calcite aggregates

 We investigated grain growth of calcite aggregates fabricated from crushed natural single crystals with different impurity content. The total trace-element concentration of the starting powders varied from about 170 ppm to more than 930 ppm with Mn as the major component. Samples were produced by hot-isostatic pressing of the different powders at 300 MPa confining pressure at 600 °C for 2 h. The starting material for the anneals was dry and had a uniform microstructure with an average grain size of about 5 μm and a porosity of <2.1%. Three disks with Mn concentrations of 10, 350, and 670 ppm, respectively, were annealed in the same run at a confining pressure of 300 MPa, and temperatures between 700 and 900 °C for up to 20 h. Grain growth was fastest in samples with the highest Mn concentrations. A multivariable fit to the data yields grain-growth exponents of 2.0 ± 0.3 for samples with 10 ppm Mn and 2.3 ± 0.2 for those with 670 ppm Mn. The activation energies for grain growth vary from 99 ± 12 kJ mol⁻¹ to 147 ± 14 kJ mol⁻¹ for the respective calcite compositions. Received: 22 August 2000 / Accepted: 12 March 2001     

Effects of quarry mining and of other environmental impacts in the mountainous Chicam-Toctina drainage basin (Córdoba, Argentina)

 The environmental conditions prevailing in the Chicam-Toctina drainage system (approx. 138 km² in Córdoba, Argentina) are considered representative of a number of catchments in Argentina's Sierras Pampeanas Range. Two groups of ions reflect the sources of dissolved species in the catchment: a) a group (Cl^–, SO^2– ₄, and Na⁺) which recognizes natural and anthropogenic sources, and which exhibits significant correlations with N^– ₃ and NO^– ₂, and b) another group of components (Ca²⁺, Mg²⁺, and HCO^– ₃) which is clearly controlled by carbonate rocks and their waste rock products. In the headwaters, stockpiled marble quarry mining wastes provide a more open system to CO₂ gaseous exchange than the outcropping rocks, thus promoting the increase of carbonate dissolution (up to 4.88 g km^–2 s^–1 during the rainy season). This specific yield was 20% higher than the amount estimated for an area with fewer extended mining activities. The dissolved load delivered by the upper reaches is subjected in the lower drainage area to various processes, mainly controlled by the presence of the city of Alta Gracia (approx. 40,000 inhabitants). In the dry season, due to nutrient inputs supplied by the city, photosynthetic activity plays a major role controlling stream pH. Hence, the high values of calcite saturation indexes and the increase of CaCO₃ concentration in bed sediments can be explained by calcite precipitation. Such a process could be accompanied by the coprecipitation on calcium carbonate of low solubility heavy metal carbonates. Received : 17 January 1997 · Accepted : 31 March 1997     

The impact of incorrectly estimating factor productivity in agriculture on the environment and human health

 This paper explores the implications of a misspecification of the production function on the use of factor inputs in the context of the adoption of an alternative production practice (a technological innovation) designed to mitigate the impact of agricultural production on human health and the environment. It is demonstrated that if the level of the use of some inputs is considered rather than their consumptive use (i.e., the actual amount used by a plant), the productivity of the input is inaccurately measured. It is also demonstrated that an aggregate production function approach can lead to overestimation of the value of the marginal product of an input due to the frequently implicit assumptions that the output supply, output demand, and fertilizer demand are infinitely price elastic. The implications of the results are important for determining the optimal use of inputs such as fertilizer and pesticides which have known adverse impacts on the environment and human health. Received: 22 November 1996 · Accepted: 4 May 1998     

Sea level rise and impacts on nearshore sedimentation: an overview

 Impacts on nearshore sedimentation arising from potential sea level change of the magnitude predicted in Intergovernmental Panel on Climatic Change scenarios associated with global warming are reviewed. For sandy duned coasts, the obvious sedimentation impacts include potential erosion of coastal dunes with implied deposition of the eroded material in the nearshore, possible deepening of embayments, and flooding of wetlands. For the sandy coasts a number of two-dimensional models are available for predicting shoreline change, but there are significant difficulties in applying Bruun-type models for dune erosion and assessment of sediment redistribution over the inner shelf, and for predicting the amount of shoreline retreat for a given rate of sea level rise. If the beach profile contains excessive sand relative to its equilibrium profile, sensu Dean (1991), then shoreline retreat may not occur upon sea level rise. From the evidence of Kiel Bay, at least in these semi-enclosed basin types, it is during major transgressions that maximum deposition in adjacent basins occurs, due to the sea eroding weakly consolidated and weathered surface regolith. But at the same time climatic patterns were re-adjusting and probably contributed to maximum deposition in adjacent shelf and basins below wave base. Received: 16 June 1995 / Accepted: 29 January 1996     

Assessment of morphometric parameters of Greek Rhone-type deltas. Hydrogeologic and environmental aspects

 The morphometric characteristics and some features concerning the local conditions of three Rhone-type Greek deltas are considered, summarized and correlated. They both express the deltaic internal lithologic structure and the configuration of the coast lines and subaqueous profiles. Despite the existing differences, concerning the lithologic structure, the coastline shape and the subaqueous profile, the Rhone type deltas maintain their principal characters and their basic configuration of the deltaic prominence. The above-mentioned differences are mainly due to local conditions which, as epigenetic factors, affect the distribution of transported material and complete the classification and deposit action of marine mechanisms, mainly the wave action and sea currents. The totality of these factors determined the continental and subaqueous structure of the deltas, which is related to the environmental and hydrogeological aspects presented in this paper. Received: 19 May 1998 · Accepted: 15 September 1998     

The impact of atmospheric sodium on erodibility of clay in a coastal Mediterranean region

 Heavy rainfalls, between 25 and 100 mm·h–1, were simulated on Pliocene/Quaternary sediments. To reproduce the heterogeneity of natural environments, 231 small plots of various sizes (between 2.5 and 3.5 m²; mean: about 3 m²) were used. The duration of all simulations was 1 h. We used water that had been collected during natural rainfall. The concentration of clay particles in the sheet wash depended upon the concentration of dissolved sodium in the wash (for about 42%) and of the sheet wash quantity (for about 37%). Under natural water conditions colloidal matter, like clay minerals, is charged negatively and therefore is destabilized by metal cations such as in the case of Na⁺. Results suggest that relatively higher concentrations of montmorrillonite were related to higher concentrations of sodium as opposed to illite and kaolinite. Microflakes of up to 25 μ were observed to vary between face-to-edge and face-to-face modes (competition between protons and other cations). The concentration of dissolved sodium (Na⁺) in the runoff water depends on water and sodium balances such as atmospheric input, infiltration, evaporation and surface water runoff. The reduction of vegetation cover increases the amount of salt and amorphous matter in/on the topsoil between heavy rainfall generations. The best predictor to explain montmorillonite, illite and kaolinite in % of mineral clay-sized matter in the surface water runoff (sheet wash) is the percentage of each clay mineral in the topsoil. As opposed to illite and kaolinite, more sheet wash indicate for montmorillonite relatively higher concentrations in the wash. The results of model simulations were confirmed on different field plots of about 1 ha and small catchments during natural heavy rainfall events. Models can also be used to understand and to better simulate sheet, rill and gully erosion, micropedimentation; and pedimentation.     

Radiocarbon-dated ferricrete provides a record of natural acid rock drainage and paleoclimatic changes

 Ancient deposits of ferricrete (stratified iron oxyhydroxide or clastic sediment cemented by stratified iron oxyhydroxide) are present in headwater streams draining an historic mining district in the Rocky Mountains, USA. These deposits, which form under conditions of low pH and high metal concentrations, are present in streams draining many other mineralized areas. Radiocarbon dating of wood fragments entombed within the ferricrete indicates dates of deposition as old as 8840±50 years before present (b.p.). The ferricrete deposits provide evidence that natural, metal-rich acid rock drainage has been occurring in this mineralized region for thousands of years, due to the weathering and oxidation of exposed or near-surface massive sulfide ore deposits. The dating and chemical composition of the ferricrete deposits have applications to the environmental remediation of historic mining sites and to environmental issues related to natural background chemistry. In addition, the radiocarbon dates of the ferricrete deposits correlate closely with warm–wet periods in the Holocene record, showing that ferricrete deposits may represent a previously untapped source of paleoclimatic information. Received: 6 October 1997 · Accepted: 23 March 1998     

Atmospheric oxidation of the pyritic waste rock in Maardu, Estonia, 2: an assessment of aluminosilicate buffering potential

 The assessment of the aluminosilicate buffering potential during acid weathering of the Estonian alum shale is provided. It is found that the stoichiometric interaction between dissolved pyrite oxidation products and illite of the shale best describe the buffering process and are consistent with earlier field studies. The scheme includes incongruent dissolution of illite with smectite and K-jarosite precipitating. This complex mechanism involves buffering of 8% of the acidity by K⁺ and temporary precipitation of 25% of the acidity as K-jarosite. Dissolution proceeds at a low pH (1.5–3) until all pyrite in the shale particle is oxidised. Hence, if the total amount of illite present is larger than needed for stoichiometric interactions, only part of it is involved in a buffering process, neutralising a certain percentage of acidity. The next stage in shale weathering is the incongruent dissolution of K-jarosite with the release of the precipitated acidity and the formation of ferric oxyhydroxide. Received: 3 August 1998 · Revised paper: 26 January 1999 · Accepted: 23 February 1999     

Access to the coast and erosion control: use of wastes on local engineering works in the coast of Gaza City

 Investment in the coastal resources of Gaza City is vital to various developmental issues and projects. Access to the coast and coastal erosion represent two major geo-environmental problems to the city. This paper describes local engineering works developed by the municipality and local people to overcome such problems. A cliff of calcareous sandstone – Kurkar as it is locally known – (up to 18 m high), is located at a distance of 20–50 m from the water–land contact. People who need to reach the beach must cross this Kurkar cliff. The engineering works used to facilitate access to the beach are: old automobile tires, white waste skeletons (refrigerators) and construction waste, where long stairs were designed using these materials. Meanwhile the engineering works which were used as erosion control measures include: rock gabions, concrete wastes, construction waste, concrete walls and shallow excavations. Such practices are commonly used in third world countries and are characterized by inexpensive transportation and implementation costs. The performance of these methods was evaluated from an economic, environmental and safety point of view. Suggestions were made to improve the performance of these practices in the future. Received: 18 November 1998 · Accepted: 15 February 1999     

Potential application of oxygen-18 and deuterium in mining effluent and acid rock drainage studies

 Oxygen-18 (¹⁸O) and deuterium (D, or ²H) are routinely used in hydrologic, climatologic and geothermal studies. In hydrology, stable isotopes provide information on the type and topology (altitude and latitude) of the recharge waters and the historical effects on water, related to such physical processes as evaporation (in ponds), melting (of snow or ice), condensation, evapotranspiration and mixing. In geothermal studies, stable isotopes provide key information related to recharge and the various temperature-dependent water/rock isotope exchange reactions. The latter is assessed through the oxygen shift in the ¹⁸O/D correlation. At acid rock drainage (ARD) sites, water/rock interactions are primarily controlled by pH and oxidation potential. Using the isotopic characteristics of the rocks and the recharge waters as a basis, the relative oxygen shift of the ARD effluent can provide information on: (1) the residence time, (2) the rate of water/rock reactions, and (3) the actual pH at the rock/water interface. This paper offers a methodology for conducting oxygen and hydrogen isotope studies related to ARD and other mineral effluent problems. The methodology is based on: (1) comprehensive sampling of regional waters, ARD effluent and major contributing minerals and rocks, (2) isotopic and elemental analysis, and (3) data interpretation on the basis of a zero-dimensional (mass balance), multi-component mixing model. Received: 15 January 1999 · Accepted: 3 May 1999     

Atmospheric oxidation of the pyritic waste rock in Maardu, Estonia. 1 field study and modelling

 A field survey and modelling of the oxidation and carbonate buffering reactions inside the alum-shale-containing waste rock dumps located in Maardu, Estonia, was accomplished. In the slope areas, the shale has been altered at high temperatures due to the spontaneous combustion and the pyritic acidity has been eliminated through migration of SO_x gases out from the dump. In the central parts of the waste rock plateaus, low temperature pyrite oxidation fronts develop towards the dump depth and towards the centres of individual shale lumps. The main secondary phases precipitating in the weathering profile are gypsum, ferric oxyhydroxide, K-jarosite and smectite. The respective field data made it possible to calibrate the two-stage oxygen diffusion model and the characteristic pyrite oxidation rate 0.06–0.08 mol of pyrite reacted per kg of available water (pyrox/H₂O value) was estimated to describe the first tens of years of dump performance. The model is capable to compare different shale disposal strategies that are illustrated with two case scenarios. The buffering of sulphuric acid by Mg-calcite appears to be an incongruent reaction with gypsum precipitating that leads to the build-up of the high Mg/Ca ratio in the leachate. Application of the Mg/Ca method estimates the pyrox/H₂O value in the range of 0.05–0.14 mol/kg. Received: 26 January 1999 · Accepted: 23. February 1999     

Correlation between rock fabrics and physical properties of carbonate reservoir rocks

 Three carbonate core samples from an oil and gas reservoir of the NW German basin were chosen to study the correlation between rock fabrics and physical properties of reservoir rocks. Detailed fabric analyses and texture investigations were carried out as well as laboratory measurements of different physical properties, e.g. density, porosity, permeability, electrical conductivity, seismic compressional and shear wave velocities. Although the three core samples come from a similar depositional facies, they show great differences in the occurrence and three-dimensional distribution of the rock fabric elements. These heterogeneities are the result of various diagenetic and tectonic processes. For the correlation between the rock fabrics and the physical properties four main rock fabric types have to be considered: (a) major constituents, e.g. fossils, ooides, peloides and crystals; (b) pore space with different pore types; (c) fractures; and (d) stylolites. The results of the correlation clearly show that the values and anisotropies of the petrophysical properties are fairly related to the observed fabric elements, with their different arrangements, spatial distributions and preferred orientations. These results also provide a fundamental understanding of the petrophysical responses, such as seismics, to the different geological features (e.g. fractures) and their dynamic changes with pressure, which can be converted to different depths. The knowledge gained from such correlations may lead to an improved interpretation of geophysical data for hydrocarbon exploration and production and therefore to an advanced reservoir characterization. Received: 28 January 1999 / Accepted: 21 June 1999     

Microclimatic characterization of a karstic cave: human impact on microenvironmental parameters of a prehistoric rock art cave (Candamo Cave, northern Spain)

The Candamo Cave contains an important group of paleolithic paintings which have been seriously deteriorated due to mass tourism. In this work, an analysis was carried out of different climatic parameters (CO₂, temperature, humidity, ²²²Rn) during annual cycles with the cave closed to the public and during an experimental period of controlled visits. The effect of visits on the geochemical characteristics of karstic water was also analyzed together with the cave ventilation. The natural variations in the cave air CO₂ were above 3000 ppm, the increase produced through visits was only 100–110 ppm and since the humidity is almost permanently at saturation point, the critical parameter which limits the visitor capacity becomes air temperature. The temperature changes during the annual cycle are of the order of 1  °C in the external part and less than 0.5  °C in the internal part of the cave and a maximum increase of 0.13  °C was observed during the period of the visits. The ²²²Rn and CO₂ concentration minimums in the summer period (July–October) show that this is the most propitious time for visits, since the greatest ventilation is produced in the cave at this time and, therefore, the greatest capacity for recovery. The geochemistry of the water, on the other hand, indicated that this is the period of the year in which processes of wall corrosion can be most easily introduced, although this would be of limited magnitude. The visitor capacity calculated was 29 visitors/day. Received: 29 August 1996 · Accepted: 23 June 1997     

Distribution of calcareous dinoflagellates from the Maastrichtian to early Miocene of DSDP Site 357 (Rio Grande Rise, western South Atlantic Ocean)

 The evolution of calcareous dinoflagellate communities has been investigated for the latest Cretaceous to earliest Neogene interval of the mid-latitude South Atlantic. In doing so, the response of calcareous dinoflagellates to Cenozoic climatic change has been addressed for the first time. Trends in species composition and distribution patterns of wall types indicate significant changes which correlate with major palaeoenvironmental modifications. A first major shift concerning the relative abundance of species and wall types occurred across the Cretaceous–Tertiary boundary. The associations remained stable during the entire Paleocene and Eocene. Only in the late Eocene did a dramatic decrease in temperature cause a slight diversification. A second major shift in the abundance patterns occurred across the Eocene–Oligocene boundary. The early Miocene warming is possibly reflected in the distinct increase in relative abundance of one species. The assemblages of calcareous dinoflagellates evidently react to major climatic changes during the Cenozoic. These poorly investigated organisms may thus provide an important contribution to the understanding of earth's palaeoclimatic evolution. Received: 9 November 1998 / Accepted: 4 April 1999     

Thermomineral waters of Ca-chloride composition: review of diagnostics and of brine evolution

 Ca-chloride waters are defined as those in which Q=rCa/r(SO₄+HCO₃)>1, rNa/rCl<0.80, rMg/rCa<0.5 and wCl/wBr<286 (r=meq l^–1 and w=mg l^–1). Throughout the last 50 years, different models for the formation of such waters have been suggested. These models include: (1) filtration through semipermeable membranes under conditions of highly compacted argillaceous sediments, (2) deaquation of seawater by evaporation and/or by freezing followed by dolomitization, (3) hydrolysis of plagioclase and biotites in igneous metamorphic rock masses, (4) radiolytic modification of residual metamorphic fluids, and (5) dissolution of chalks followed by ion exchange on smectites. The better understanding of processes and of natural environments leading to the evolution and natural occurrence of such brines, is imperative for the prospection and further sustained exploitation of such waters. Received: 11 October 1996 · Accepted: 24 February 1997     

Drillability prediction: geological influences in hard rock drill and blast tunnelling

 Usually the main subject in preliminary site investigations prior to tunnelling projects is the prediction of tunnel stability. During the past years in conventional drill and blast tunnelling, problems have occurred also connected to the accurate prediction of drillability in hard rock. The drillability is not only decisive for the wear of tools and equipment but is – along with the drilling velocity – a standard factor for the progress of excavation works. The estimation of drillability in predicted rock conditions might bear an extensive risk of costs. Therefore, an improved prediction of drilling velocity and bit wear would be desireable. The drillability of a rock mass is determined by various geological and mechanical parameters. In this report some major correlations of specific rock properties and especially geological factors with measured bit wear and drilling velocity are shown. Drilling velocity is dependent on a lot of geological parameters: Those principal parameters include jointing of rock mass, orientation of schistosity (rock anisotropy), degree of interlocking of microstructures, porosity and quality of cementation of clastic rock, degree of hydrothermal decomposition and weathering of a rock mass. Drilling bit wear increases with the equivalent quartz content. The equivalent quartz content builds the main property for the content of wear-relevant minerals. For various groups of rock types different connections with the equivalent quartz content could be detected. In sandstone bit wear is also dependent on porosity or the quality of the cementation. Finally, an investigation program is submitted, which helps to improve the estimation of rock drillability in planning future tunnel projects. Received: 14 June 1996/Accepted: 10 January 1997