Effects of irrigation on geochemical processes in a paddy soil and in ground waters in Camargue (France)

In waterlogged soils, dynamics of water influence the redox conditions and thus the mobility of elements. Irrigation of rice in Camargue (South eastern France) induces yearly dynamics of water. In order to determine the impact of irrigation on the geochemical properties of ground waters, a continuously in situ record of physico-chemical parameters (pH, Eh, temperature and electric conductivity) is performed during 1 year in an irrigated rice field. Seasonal dynamics show large Eh and pH variations. An annual irrigation cycle generates fast precipitations of Ca–Mg carbonates and Fe oxides between 50 and 110 cm depth when the soil is waterlogged. The dissolution of these minerals is initiated during a year without irrigation.     

四川盆地南部中-上寒武统储层成岩作用

四川盆地南部中—上寒武统(洗象池群)储层为一套碳酸盐岩局限台地沉积,其岩性为粗粉晶—细晶白云岩、砾屑白云岩、砂屑白云岩、鲕粒白云岩等。成岩作用主要有压实作用、胶结作用、白云石化作用、岩溶作用、破裂作用等,白云石化作用和岩溶作用是形成优质储层的关键。白云石化的机理为混合水白云石化。岩溶作用具有多期性,包括沉积期岩溶、风化期岩溶、埋藏期古岩溶和褶皱期古岩溶等,以风化期岩溶为主。压实作用和胶结作用破坏了大量的原生孔隙和次生孔隙。压实作用主要发生在浅埋藏期,它与埋藏期胶结一同作用使孔隙度由原来的15%左右骤降至2%～3%左右。随着后来的岩溶作用和破裂作用等,部分储层的孔隙度又扩大到4%～5%左右,以晶间孔和晶间溶孔为主要储集空间类型。     

Retention of cosmogenic 3He in calcite

Cosmogenic ³He can be used to date a wide range of mineral phases because it is produced from all target elements and can be readily measured above atmospheric contamination. Calcite is a particularly attractive target mineral due to its natural abundance, large crystal size (>1 mm), and low He closure temperature (<70 °C), which limit non-cosmogenic ³He components (Copeland et al., 2007). However, several recent studies have shown that some calcite may not be retentive to helium, even under surface temperatures (Cros et al., 2014; Copeland et al., 2007). This study thus explores ³He retention and production in natural calcite samples at four different sites. Samples from two high elevation sites appear retentive to ³He over 10 kyr timescales, whereas two additional sites clearly suffer from diffusive loss of ³He. Step-degassing experiments suggest that diffusion in calcite is controlled by multiple diffusion domains, with an apparent activation energy of 25–27 kcal mol⁻¹. Although minor ³He loss is expected from the smallest diffusion domains, the observed kinetics cannot explain the poor retention at all sites. We thus propose that opaque (non-transparent) calcite may be more retentive due to the presence of imperfections in the crystal lattice. We conclude that ³He dating of calcite shows promise in some settings. However, because retention depends on crystallographic variability it must be evaluated on a case-by-case basis until robust criteria for retention can be identified.     

Impact of early dolomitization on multi-scale petrophysical heterogeneities and fracture intensity of low-porosity platform carbonates (Albian-Cenomanian,southern Apennines,Italy)

Petrographic, petrophysical and fracture analyses were carried out on middle Cretaceous platform carbonates of the southern Apennines (Italy) that represent an outcrop analogue of the Val d’Agri and Tempa Rossa reservoirs of the Basilicata region. The studied outcrops, which are made of interlayered limestones and dolomites of inner platform environment, were selected to study the impact of dolomitization on reservoir properties and the control of dolomite texture on fracture development. Two types of dolomites – both formed during very early diagenesis – were found interlayered, at a metre scale, with micrite-rich limestones (mainly mudstones and wackestones). Dolomite A is fine-to medium crystalline and makes non-planar mosaics. Dolomite B is coarse-crystalline and makes planar-s and planar-e mosaics. The intercrystalline space of the planar-e subtype of dolomite B is either open or filled by un-replaced micrite or by late calcite or saddle dolomite cement. Dolomite A and dolomite B have similar average porosities of 3.7 and 3.1% respectively, which are significantly higher than the average porosity of limestones (1.4%). Their poro-perm relationships are similar, with the notable exception of planar-e type B dolomites, which generally display higher permeability values.The intensity of top bounded fractures is distinctly lower in coarse-crystalline dolomites than in fine-crystalline dolomites and limestones, both at the macro- and the micro-scale. On the other hand neither lithology (i.e. limestone vs. dolomite) nor dolomite crystal size control the intensity of perfect bed-bounded fractures, which is strictly controlled by the fracture layer thickness.Our results provide information that could be used as guidance for the characterization and modelling of fractured carbonate reservoirs made of interlayered limestones and dolomites.     

Genesis of fragmental carbonate rocks in the Mesozoic and Tertiary of Mallorca,Spain

Fragmental carbonate rocks are common in the Mesozoic and Tertiary succession of Mallorca, in the western Mediterranean. On the Formentor peninsula at the northeastern end of the Sierra Norte, two phases of fragmentation post-date Liassic platform carbonate and its subsequent reworking, and predate deposition of marine Burdigalian sediments. Phase 1 fragmentation resulted in brecciated rocks with angular fragments often little displaced, cemented by coarse calcite. Brecciated rock passes into veined or unbrecciated rock over short distances. These breccias are interpreted as the products of collapse during solution of an evaporite after uplift during the early Tertiary. Phase 2 fragmentation is related to the unconformity with Miocene sediments and is interpreted as a product of karstic processes operating prior to subsidence and deposition of Miocene marine conglomerates. Multiple brecciation is common, yielding complex fragmental rocks, but permitting a relative dating of the two phases and other depositional and structural events.     

Cold seep deposits of Beauvoisin (Oxfordian; southeastern France) and Marmorito (Miocene; northern Italy): microbially induced authigenic carbonates

The relation of two well-known ancient carbonate deposits to hydrocarbon seepage was confirmed by this study. Archaea are found to be associated with the formation of Oxfordian seep carbonates from Beauvoisin and with a Miocene limestone from Marmorito ("tube-worm limestone"). Carbonates formed due to a mediation by archaea exhibit extremely positive or extremely negative δ¹³C_carbonate values, respectively. Highly positive values (+15‰) reflect the use of ¹³C-enriched CO₂ produced by methanogenesis. Low δ¹³C values of the Marmorito carbonates (–30‰) indicate the oxidation of seepage-derived hydrocarbons. Likewise, the δ¹³C content of specific tail-to-tail linked isoprenoids, biomarkers for archaea, was found to be strikingly depleted in these samples (as low as –115‰). The isotopic signatures corroborate that archaea were involved in the cycling of seepage-derived organic carbon at the ancient localities. Another Miocene limestone ("Marmorito limestone") shows a strong imprint of methanotrophic bacteria as indicated by δ¹³C values of carbonate as low as –40‰ and biomarker evidence. Epifluorescence microscopy and field-emission scanning electron microscopy revealed that bacterial biofilms were involved in carbonate aggregation. In addition to lucinid bivalves previously reported from both localities, we infer that sponges from Beauvoisin and tube worms from Marmorito depended on chemosynthesis as well. Low δ¹³C values of nodules related to sponge taphonomy (–27‰) indicate that sponges might have been linked to an enhanced hydrocarbon oxidation. Tube worm fossils from Marmorito closely resemble chemosynthetic pogonophoran tube worms from Recent cold seeps and are embedded in isotopically light carbonate (δ¹³C –30‰). Received: 13 October 1998 / Accepted: 5 February 1999     

Influence of carbonate facies on fault zone architecture

Normal faults on Malta were studied to analyse fault propagation and evolution in different carbonate facies. Deformation of carbonate facies is controlled by strength, particle size and pore structure. Different deformation styles influence the damage characteristics surrounding faults, and therefore the fault zone architecture. The carbonates were divided into grain- and micrite-dominated carbonate lithofacies. Stronger grain-dominated carbonates show localised deformation, whereas weaker micrite-dominated carbonates show distributed deformation. The weaker micrite-dominated carbonates overlie stronger grain-dominated carbonates, creating a mechanical stratigraphy. A different architecture of damage, the ‘Fracture Splay Zone’ (FSZ), is produced within micrite-dominated carbonates due to this mechanical stratigraphy. Strain accumulates at the point of juxtaposition between the stronger grain-dominated carbonates in the footwall block and the weaker micrite-dominated carbonates in the hanging wall block. New slip surfaces nucleate and grow from these points, developing an asymmetric fault damage zone segment. The development of more slip surfaces within a single fault zone forms a zone of intense deformation, bound between two slip surfaces within the micrite-dominated carbonate lithofacies (i.e., the FSZ). Rather than localisation onto a single slip surface, allowing formation of a continuous fault core, the deformation will be dispersed along several slip surfaces. The dispersed deformation can create a highly permeable zone, rather than a baffle/seal, in the micrite-dominated carbonate lithofacies. The formation of a Fracture Splay Zone will therefore affect the sealing potential of the fault zone. The FSZ, by contrast, is not observed in the majority of the grain-dominated carbonates.     

Nucleation and crystallization of otavite, witherite, calcite, strontianite, hydrozincite, and hydrocerussite by CO2 membrane diffusion technique

Otavite, witherite, calcite, strontianite, hydrozincite and hydrocerussite nucleation was induced by CO₂ diffusion through a polyethylene membrane into a metal bearing solution. Nucleation and ongoing precipitation was followed at 25 ± 1 °C by the chemical evolution of the solution and the consumption of sodium hydroxide (pH-stat conditions). X-ray diffraction patterns as well as FT-infrared and Raman spectra confirmed the formation of well crystallized solids, except for less crystalline hydrozincite. In several experiments simonkolleite and laurionite precipitated concurrently with hydrozincite and hydrocerussite. The carbonate end-member minerals, smithsonite and cerussite, however were not formed. Carbonate minerals crystallized as spherical aggregates of thin layered otavite, spherical orientated witherite needles, rhombohedral calcite, pseudo-hexagonal strontianite laths, fibrous lumps of hydrozincite and planar hexagonal hydrocerussite crystals. Crystal and aggregate sizes range between 1 and 100 μm. Nucleation occurred at well defined reaction times and distinct critical supersaturation indices (SI_crit). The time for nucleation at constant pH decreased as the initial metal concentration increased for a given solid. The SI_crit values decreased in the order of hydrocerussite (3.2), otavite (2.5), strontianite (1.6), witherite (0.9) and calcite (0.7).     

Geochemistry of carbonate precipitation from the groundwater in a coastal region

Groundwater samples were collected from a coastal region of Andhra Pradesh to assess the possible conditions of the formation of carbonates. The area experiences a semi-arid climate and is underlain by khondalites, over which the Quaternary sediments occur. The study of the geochemistry of groundwater indicates that groundwater is mostly of fresh, with alkaline nature. The study further suggest that the breakdown of feldspars as kaolinite during rock-water interaction, releases Ca²⁺. Soils/weathered products contribute high CO₂ under the open system. The Ca²⁺ and CO₂ are added to the groundwater through the infiltrating recharge water. They subsequently precipitate as fine-grained carbonates in the weathering profile due to evapotranspiration under a freshwater environment.     

Authigenic albite in carbonate rocks – a tracer for deep-burial brine migration?

Euhedral, post-depositional albite from the Eastern and Western Alps, the western Carpathians and some Greek islands was examined petrographically and geochemically to gain insights into the nature of feldspar reactions in carbonate rocks. This study focuses on coarsely crystalline, homogeneously nucleated albite in order to avoid problems related to the presence of inseparable detrital material in fine-grained albite varieties. All albite samples show a very restricted compositional variability and are typically ≥ 99 mol% Ab component. Unit-cell parameters determined by Rietveld analysis are slightly more variable than previously accepted, but confirm high Al–Si ordering characteristic of low albite. The oxygen isotopic composition of albite ranges from + 19·4‰ to + 28·3‰ VSMOW. There is no direct relationship between the δ¹⁸O value and the inferred temperature of albite formation, nor is there one with stoichiometry. The coarse crystal size (up to several millimetres in diameter), petrographic evidence showing albite cross-cutting stylolites, greater abundance of albite in carbonate rocks subject to high-grade diagenetic or weak metamorphic overprinting and available fluid inclusion data suggest that albite precipitation is favoured at higher temperatures in carbonates than in sandstones. Pore fluids were invariably brines, as suggested by the inferred high positive δ¹⁸O_fluid values, the common association of albite-bearing carbonates and evaporites and reports of saline fluid inclusions in albite. The presence of authigenic albite may thus be a useful tracer of palaeobrine–carbonate reactions, particularly in deep-burial and incipient metamorphic settings.