Calcareous Deposits Research Articles

Biotic agents of tufa formation in сarbon dioxide enriched hard-water springs of Mizhhirya basin and adjacent territories

The main groups of biote and their functional role in the calcareous tufa formation at the hard-water springs enriched by carbon dioxide of the Mizhhirya basin and adjacent territories were investigated. It has been studied that in the formation of calcareous tufa of all surveyed locations, representatives of micro-, bryo and phytobiota play an important role, and therefore, the studied sedimentary rock are mainly biogenic in their origin. Microbiota agents, mainly cyanobacteria of the order Oscillatoriales, play a leading role in the initial acts of calcareous tufa accumulation (stage I). These bacteriogenic initial forms, which can be defined as initial thromboids, are represented by small- or medium-grained, ocher-yellow aggregates of a spherical shape, with a diameter of 0.5-2 mm, which actively accumulate at the springs exits. These congestions (mesoclots) are growing and compacting over time and forming weakly cemented thrombolites, which are a cluster of separate aggregates together with particles of sand, silt, rocks, plant remains, etc. The next post-pioneer stage (II) is marked by the appearance of specialized amphibious Bryophytes vegetation of the Pellion endiviifoliae alliance and pioneer caliciophilic vegetation of the Grimmaldion fragrantis alliance. In the formation of calcareous tufa deposits of the next stage (III), the leading role is played by the Bryophytes vegetation of the Pellion endiviifoliae alliance. Their mineralized turfs are modeling light, fragile and porous bryolithes of an ocher-brown color. Bryolithes usually contain seasonal layers richly encrusted with leaves of trees, which growing near the spring. Base on the specificity and ecological value of the biotic (calcicolous Bryobiota) and abiotic, primarily geological (calcareous iron tufa) component, the hard-water tufagenic springs of Mizhhirya Verkhovyna can be considered significant natural monuments of Transcarpathia region. However, regardless of the nature protection status of most hard-water iron springs (they are hydrological monuments of nature of local importance), they often suffer from human’s improvement, illegal water extraction, high recreational load etc. Thus, they need applicating of conservation measures and nature protection management planning.

Unravelling the role of calcareous deposits on hydrogen uptake: The duality in the calcite behavior

The permeation of hydrogen in carbon steel immersed in deaerated NaCl and artificial seawater solutions under various cathodic polarization is investigated using the Devanathan and Stachurski method combined with in-situ electrochemical impedance spectroscopy (EIS). The results indicate calcite's dual role in hydrogen uptake: it promotes uptake for bare samples and lower cathodic currents, but inhibits it for preformed deposits and higher cathodic currents. Deposits are characterized through in-situ EIS and scanning electron microscopy, providing further insights into the specific morphology of calcite. These findings are correlated with hydrogen permeation results, elucidating a mechanism for the dual behavior of calcite.

What do Lateglacial and Holocene land snail communities tell us about the palaeoenvironments of Mediterranean France?

Southeastern France occupies a key biogeographical position on the lower Rhone corridor, at the interface between southern and northern Europe. It is also at the heart of long‐standing ecological debates about the respective roles of natural and human drivers in shaping the Mediterranean landscape. Molluscan analysis may represent a valuable contribution to this issue. In this paper, land snail assemblages from three calcareous tufa deposits in the Luberon mountain were used to reconstruct Lateglacial and Holocene palaeoenvironments. The Lateglacial communities only differ from the Pleniglacial ones by the development of hygrophilic snails. We note a high moisture budget at the end of the Lateglacial Interstadial (LGI). A patchy, steppe landscape is attested. A time lag in recolonization by woodland species during the LGI is conceivable. The postglacial woodland assemblages then trace a laborious reassembly of forest snail communities. It takes place mainly between c. 8000 and c. 6600 cal. a BP with spatial disparities and delayed recruitments. The French Mediterranean region has not benefitted from the macrorefugia that it would have sheltered or with which it would have been close. Woodlands, however, appear progressively more closed and complex c. 8000 cal. a BP. They reached their optimum c. 7500 to 7400 cal. a BP although their canopy seems to have stayed quite open. Anthropization remained weak during the Early Neolithic. A significant woodland opening is observed in the Early–Middle Neolithic. Human impact becomes clear from the Late Neolithic. Nevertheless, there are substantial differences compared with Basse‐Provence, where a more marked openness of the landscape from 7000 cal. a BP was accompanied by the development of Mediterranean synanthropic snails. The molluscan successions of the Luberon mountain should be a reference for the development of the Lateglacial and Holocene malacofauna in the SE of France, at the northern boundary of the western Mediterranean domain.

Effect of cathodic current density on hydrogen embrittlement susceptibility of X70 steel girth weld in different soil simulation solutions

PurposeIn this paper, the authors aim to study the relationship between hydrogen embrittlement (HE) susceptibility and cathodic current density applied on the X70 steel girth welds.Design/methodology/approachThe HE susceptibility of X70 steel girth welds were investigated through slow strain rate tensile test and observed and analyzed by optical microscope and scanning electron microscope methods.FindingsThe results show that HE susceptibility of X70 girth weld was basically unchanged with increasing of ion concentration while gradually increased and maintain at a specific value with the increase of cathodic current density. As for same ion content, a dense calcareous deposit layer generated on the sample surface in soil simulation solution with Ca2+ and Mg2+ resulted a decreased HE susceptibility while the porous calcareous deposit layer resulted a increased HE susceptibility.Originality/valueA logistic regression model was established to describe the correlation between HE index and the cathodic current density.

Influence of temperature on the cathodic polarization behavior and calcareous deposit properties of X65 steel in sea water

PurposeThis paper aims to investigate how cathodic polarization behavior significantly affects the selection of cathodic protection parameters and the effectiveness of protecting underwater metal structures. Factors such as water depth and operating conditions impact seawater temperature, making it crucial to understand the effects of temperature on cathodic protection parameters for underwater pipelines.Design/methodology/approachIn this paper, potentiostatic polarization was carried out by three-electrode method, and morphology, X-ray diffraction and electrochemical analysis.FindingsIt was determined that the stable current densities at the minimum negative potential (−0.8 VSSC) for pipeline steel varied at different temperatures: 7°C, room temperature and 60°C. The cathodic protection potential corresponding to the lowest stable current density was observed to be −1.0 VSSC at 7°C and −0.95 VSSC at room temperature and 60°C.Originality/valueThis study elucidates the mechanisms by which different temperatures affect the protective performance of calcareous deposits and current densities.

Investigation on localized corrosion behavior of pipeline steel under AC interference in alkaline earth metal environment using wire beam electrode

The localized corrosion behavior of X65 steel under AC interference in alkaline earth metal environment was investigated using the detachable wire beam electrode (WBE). The AC/DC current distribution, electrochemical properties, and elemental distribution were traced through the WBE to characterize the localized corrosion behavior and mechanism. The results show that hydrogen evolution under high cathodic protection (CP) conditions leads to an uneven distribution of calcareous deposits, and areas not covered by calcareous deposits have higher JAC and Cl− concentrations. The synergistic effect of Fe3O4 dissolution reprecipitation process, hydrogen evolution and Cl− leads to severe localized corrosion.

The Influence of Rust Layers on Calcareous Deposits’ Performance and Protection Current Density in the Cathodic Protection Process

Calcareous deposits are a consequential outcome of cathodic protection in marine environments, exerting significant influence on the cathodic protection process and current density prerequisites. This study investigates the process of calcium deposition and its impact on the cathodic protection current density of carbon steel under the influence of a rust layer in different corrosion periods. This was investigated using electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). The results demonstrate that the formation processes of calcareous deposits vary after exposure to the corrosive environment for 0, 7, and 30 days. While a longer corrosion period leads to thicker rust layers on the metal surface and a higher initial cathodic protection current, the presence of these rust layers facilitates the deposition of calcium and magnesium ions, resulting in a rapid decrease in cathodic protection current density after a certain period. Meanwhile, long-term cathodic protection facilitates the thickening and densification of the oxide layer, thereby enhancing its protective efficacy, effectively reducing the corrosion rate of the metal surface and stabilizing the cathodic protection current density at a lower level. This study provides theoretical data and experimental evidence to support the maintenance of corroded marine engineering equipment.

Combined effect of cathodic potential and calcareous deposits on hydrogen evolution and permeation in Q460 steel

Cathodic protection is widely employed to prevent the corrosion of steel in marine environments. However, an inappropriate cathodic potential may lead to the generation of hydrogen and consequently induce cracking. Therefore, this study investigates the relationships between cathodic deposition potential, calcareous deposits, hydrogen evolution, and hydrogen permeation. Combining scanning electron microscopy, Raman spectroscopy, coupled focused ion beam lithography, and energy dispersive X-ray spectroscopy, it is observed that all calcareous deposits formed in artificial seawater at the potential range of −1.0 to −1.3 VSCE have calcium-rich inner and magnesium-rich outer layers, respectively. The thickness and compactness of each layer of the double-layer deposits vary with the cathodic deposition potential. Combining potentiodynamic polarization, hydrogen permeation experiments, and the morphology of calcareous deposits, we can find that the deposits formed at the cathodic deposition potential of −1.1 VSCE exhibit a thin inner layer and a condensed outer layer, which is effective in balancing hydrogen recombination and absorption, thus, inhibiting hydrogen entry. This study provides guidelines for the cathodic protection of steel materials in marine environments.

Application of voltammetry as a technique to monitor cathodic protection performance of steel in simulated soil solution

Cathodic protection (CP) in combination with organic coating is applied as a secondary technique to mitigate corrosion of buried steel in an effort to prolong the lifespan of the buried steel pipeline. This study was aimed at developing and applying an adequate technique for monitoring the electrochemical behaviour of buried steel in the presence of CP. A modified voltammetry procedure was applied on carbon steel immersed in simulated soil solution for four days under open circuit potential (OCP) before applying CP for further ten days. Electrochemical impedance spectroscopy (EIS) was also applied at various time intervals to investigate the electrochemistry at the steel/solution interface. The voltammetry experiments revealed that the corrosion rate peaked at 680 µm/yr after three days of being subjected to OCP and then decreased to 411 µm/yr on day four as a result of a passive layer development on the steel surface. The corrosion rate was reduced from 411 µm/yr to 8 µm/yr as result of CP application before fluctuating between 21 and 40 µm/yr. The examination of steel surface via x-ray diffraction revealed the presence of calcareous deposit which resulted due to the application of cathodic protection.

Cu-mediated electron-rich Ru centers on metal carbides for highly efficient hydrogen production from seawater

Seawater splitting for hydrogen production provides a promising pathway for green energy systems. However, the sluggish kinetics, corrosive ions, and the calcareous deposit seriously impede the wide-scale application of seawater electrolysis. Here, we report a trace amount of Cu-mediated anchoring electron-rich Ru centers on metal carbides (Cu-Ru/WC@C) for efficient hydrogen evolution from corrosive seawater. Benefiting from the conductive, electron-loss, and protophilic capacities of Cu atoms, the created Cu-Ru/WC@C catalyst possesses an electron-rich, anti-corrosive, and low oxophilic microenvironments, which eventually delivers excellent hydrogen evolution activities and anti-corrosion properties in seawater electrolysis. It requires a low overpotential of 392 mV to reach 1 A cm−2 and good long-term stability in alkaline seawater. Notably, the membrane electrolyzer with Cu-Ru/WC@C cathode exhibits outstanding performances for continuous H2 production under 1.875 V with 250 mA cm−2. This approach provides essential insights into the seawater corrosion resistance for cathode materials that match the electrochemical hydrogen production industry.

Palaeoenvironmental reconstruction of Holocene calcareous tufas distributed over a manganese deposit in Mexico

The Holocene calcareous tufa deposits are located in the north-central sector of the state of Hidalgo, Mexico. These deposits outcrop on the Upper Jurassic Chipoco Formation in the Molango Manganese District. Calcareous tufa deposits correspond to carbonate formations of inactive tufas disconnected from the current hydrological network. To better understand the textural, geochemical, and biological characteristics and environmental conditions during their formation, a detailed study involving field analysis, X-ray diffraction analysis, X-ray fluorescence analysis, and morphometric analysis with light microscopy, and scanning electron microscopy was carried out. Similarly, 14C analysis was undertaken to determine the age of the deposit. On this basis, two biofacies were defined, one with stem structures and the other with Phyto clasts, bryophytes (Plagiomnium cuspidatum), and copepods, limited both at the base and the top by lenticular-shaped erosive surfaces and sigmoidal clinoforms. These bio facies formed in lacustrine and paludal environments, and barrier waterfalls. From a geomorphological point of view, the accumulations of these calcareous tufas originated on slopes and/or at the foot of karstic springs, where the accumulation of material originated from the height of the spring with respect to the bottom of the valley, giving rise to a set of stepped tuffaceous plains with a wedge-shaped profile, colonized by important masses of bryophyte mounds, copepods, and vascular plants. This suggests a swampy environment where sedimentation took place in shallow water accumulations, where there is clear evidence of exposure and pedogenetic modification, indicating wet and dry episodes that translate into seasonal fluctuations in the water table. Six mineral phases were observed including silicates, carbonates and arsenates. The 14C analysis indicates that the plant found in the charcoal sample within the calcareous tufa deposit is of Holocene age.

Effect of barnacle on the cathodic protection of high-strength steel and its potential risk related to hydrogen permeation

The cathodic protection efficiency and hydrogen permeation behaviour of high-strength steel with barnacle adhesion in the tidal zone were studied using field exposure and laboratory simulation tests for 2 years. Because of the shielding effect, barnacles can lead to an uneven calcareous deposition, a flatter morphology and a higher protection efficiency of steel. By contrast, because of the higher hydrogen permeation current at the edge of the barnacle adhesion area (caused by a higher hydrogen evolution rate), barnacle adhesion can promote hydrogen permeation. A mechanism was proposed to explain the observed phenomenon, and its effect on service safety was analysed.

Protective Properties of Calcareous Deposit Layer for Cathodically Polarized AH36 Steel in Natural Seawater

A calcareous deposit is a by-product of the cathodic polarization in seawater environments. This study presents the results of evaluating the anticorrosion and anti-macro-biofouling effectiveness of a calcareous deposit layer on the surface of the cathodically polarized AH36 structural steel in tropical seawater. The polarization is induced with initial current densities at which the calcareous deposit layer formed with both aragonite and brucite for 12 months continuously. The protective properties of the layer were compared with those of the passive layer from corrosion products under the same environmental conditions. The macro-biofouling in the tropical seawater is observed in the closed and open surfaces of the steel. The comparison of the anticorrosion property shows that, to some degree, the calcareous deposit layer contributes to surface passivation, as in the case of the corrosion product layer. In addition, the composition of the brucite and aragonite in the calcareous layer in the study plays a role as a macro-biofouling growth-limiting factor.

Influence of Calcareous Deposits on Hydrogen Embrittlement Susceptibility of Q460 Steel.

Cathodic protection is widely used to protect structural steel from corrosion in marine environments. However, an inappropriate cathodic potential may lead to hydrogen embrittlement (HE). Therefore, this study investigates the relationship between cathodic protection potential, structure and composition of calcareous deposits, and hydrogen embrittlement susceptibility of Q460 steel. The slow strain rate test results and fracture analysis reveal that Q460 steel had the smallest HE susceptibility when covered with the calcareous deposits formed under -1.1 VSCE. The deposits have a relatively thin calcium-rich inner layer and a condensed magnesium-rich outer layer, which can significantly inhibit hydrogen entry. A sustained deposition reaction during slow strain rate testing (SSRT) in artificial seawater can also decrease the HE susceptibility of Q460 steel.

Evolution of the Júcar-Cabriel fluvial system on the Mediterranean watershed of the Iberian Peninsula (Valencia, eastern Spain)

This study presents the characterization and chronology of the Quaternary terrace sequence developed in the confluence zone of the Júcar and Cabriel river valleys. The study area covers a radius of 10 km from the confluence of the two valleys near the locality of Cofrentes (Valencia). It is located in the northern zone of the Ayora-Cofrentes Graben in the northeastern sector of the External Prebetic Zone adjacent to southern Iberian Chain. This N-S graben is an inherited tectonic feature with an axial salt wall subject to different periods of fluvial dissection and refilling since at least the end of the Messinian Salinity Crisis (MSC). Regional isostatic uplift and local uplift and subsidence processes related to salt flow and dissolution during the Quaternary period, favored by fluvial entrenchment and terrace development. The terrace system and the previous pre-incision erosional and depositional surfaces are analyzed from a geomorphological point of view. The terrace system only develops within the soft Mio-Pliocene sedimentary fill of the graben, whilst upstream and downstream this zone the studied valleys develop important gorges (canyons) carved in the Cretaceous tablelands (Caroch Massif) and Mio-Pliocene deposits (Llanura Manchega). The geochronological control is established from 20 numerical ages obtained by different dating methods, such us Electron Spin Resonance (ESR), Optically Stimulated Luminescence (OSL) in detrital sequences and Th/U series in calcareous tufa deposits. Additionally, four K/Ar dates available for volcanic materials disrupting the upper and oldest terrace have been considered. A total of 14 terrace levels were identified between +130–135 m (T1) and +3–4 m (T14) of relative height above the river thalwegs. The T1 has an approximate age of c. 1.6–2.0 M.a. as indicate the age of the volcanic materials from the Agras Volcano intruded in the terrace, marking the onset of Quaternary fluvial dissection in the zone. The obtained geochronological data indicate that the Lower-Middle Pleistocene boundary is slightly above T6 (+60–65 m), which has an ESR age of 577 ± 43 ka. This terrace also documents the onset of the most important period of rise of the salt within the graben interfering drainage development. The geochronological data indicate the occurrence of a second eruptive event during the second half of the Middle Pleistocene related to the terraces T7 (+50 m) and T8 (+35–40 m), updating the volcanic activity in the zone. The beginning of the Upper Pleistocene is recorded by the top sequences of the T9 terrace (+25–30 m) where numerous OSL and Th/U data have been obtained with ages between ca. 105 and 81 ka (MIS 5). However, these young terraces (T8 to T13) are thickened (8–10 m) recording Middle Pleistocene sediments in their basal sequences with ages between ca. 193 and 137 ka (MIS 6). The study provides important data on valley evolution under the interference of volcanic activity, salt –related deformation (diapirism, solution subsidence) and fluvial incision fostered by the rise of the axial diapir (salt wall) protruding the graben since at least the Brunhes-Matuyama boundary. The analyzed fluvial evolution documents interesting cases of river capture, drainage antecedence and tectonic adaptation of the drainage throughout the Quaternary Period. The paper also poses interesting geochronological data on the long-term Quaternary evolution of Mediterranean valleys in the Iberian Peninsula, poorly explored to the date.

Short- to Medium-Term Corrosion of Mild Steel in Highly Calcareous Seawaters: Effects of Calcium Carbonate Concentration, Coupon Orientation, and Nutrient Addition

Mild steels exposed to marine immersion conditions in which carbonate solubilities are exceeded, leading to deposition of calcareous material, have been shown to exhibit much-reduced corrosion rates compared with corrosion under conditions in which there is no exceedance of solubility limits and therefore no calcareous deposition. However, the differences in corrosion including the potential effect of microbiologically influenced corrosion (MIC) in these conditions have not been examined systematically in the literature. The study reported herein involves short- to medium-term marine immersion exposures (up to 18 month) of mild steel coupons in natural seawater (control) and in environments using the same seawater source dosed with (1) CaCO3, acting as an inorganic particulate suspension representative of that encountered in seawater with elevated calcareous content; and (2) a nitrate salt, acting as an industrial pollutant and bacterial nutrient source. The results show the extent to which the deposition of particulate CaCO3 from suspension in seawater onto and into the rusts reduces the rate of corrosion of mild steel; a rate that was found to be dependent on the coupon orientation within the seawater. Coupons that were permanently buried beneath a cap of settled CaCO3 particles exhibited a 70% reduction in corrosion rate compared with the representative control coupons. The results also show that for these exposure durations and conditions, while iron-related bacteria and sulfate-reducing bacteria populations were identified in high concentrations (respectively ∼1 × 106 cfu/g and ∼1 × 102 to 4 × 106 cfu/g, depending on coupon orientation) within the rust products themselves after 18 month of exposure, there was no clear evidence of MIC. These findings indicate that short and medium-term (nonaccelerated) studies of MIC for mild steel are insufficient or even misleading for the prediction of long-term corrosion rates in these environments.

The effect of particle breakage on the dilatancy and shear behavior of marine calcareous and siliceous deposits

A large part of ocean surface is covered by calcareous deposits. The Low stiffness and weak particles of calcareous soils deposited by marine organisms showed significant particle breakage under applied loads, which resulted in different behavior compared to terrigenous soils. A series of compression drained triaxial tests were carried out to evaluate the monotonic shear behavior of crushable and non-crushable soils. Three different soils, including Firoozkuh siliceous sand (as a non-crushable soil) and Hormuz and Bushehr calcareous sands (as crushable soils) which were different in mineralogy compositions were obtained from northern and southern Iran. The specimens were prepared in different relative densities (i.e., loose, medium and dense conditions) and consolidated under confining pressures ranging from 100 to 600 kPa. The monotonic shear and dilatancy behaviors of the soils have been presented in detail and the effect of particle breakage has been discussed. The results showed that particle breakage has a significant effect on the mobilized friction and dilatancy angles of marine crushable soils. There is a linear relationship between the amount of particle breakage occurring during a triaxial test and breakage angle. In addition, the mineralogical difference influences the breakage properties of calcareous deposits.

Oblique tensile tests on model anchor piles in calcareous sand deposits

Offshore anchor piles are extensively used as moor-floating structures in harsh environments that experience oblique tensile loads and the mechanical response is complex. This study investigated the effect of oblique tensile loads on the response of anchor piles in calcareous sand through a series of model tests and the standard penetration tests (SPT) to obtained bearing capacity equations. Eight model piles were installed into the calcareous sand bed with relative densities (Dr) of 53%, 75% and were loaded with different load inclination angles (α). The test results showed that the load-displacement curves were nonlinear and that dense sand could effectively control deformation and improve the bearing capacity. The critical load inclination, corresponding to the maximum load capacity for a given pile under tension loading, was around 30° and was larger than that for the terrestrial sand (5°∼10°), which may have been caused by particle breakage. The bending stress of the anchor pile was 2∼8 times the axial stress. In dense sand (Dr = 75%), the bending moment reaches its maximum around the critical angle (30°), indicating a the strong interaction between the pile and calcareous sand. The ultimate tensile load of anchor piles is a function of load inclination angle and ultimate capacity of uplift and horizontal piles.

Long-term corrosion of abandoned offshore steel infrastructure

ABSTRACT A common practice in the offshore oil and gas (O&G) industry is to leave abandoned decommissioned pipelines and other steel infrastructure on the seafloor. Decisions about long-term environmental and other impacts and about the possibility of recovery require estimates of the likely long-term rate of deterioration, including corrosion loss and pit depth. These are considered as functions of time and environmental conditions including seawater temperature, dissolved oxygen concentration, salinity, seawater velocity, water pollution, microbiological activity, water depth, calcareous deposition and the effect of burial, all interpreted using established physico-chemical behaviour relevant for long-term exposures. Data for exposures up to some 600 years in seawaters are reviewed. Remaining research gaps and future perspectives of marine corrosion control are briefly discussed. Specific attention is given, by way of an example, to the influence on long-term durability of protective coatings and remnant cathodic protection, both areas in which further research is required.

Cathodic protection of carbon steel in thin layers of seawater

Purpose The purpose of this study is to investigate cathodic protection (CP) efficiency in the tidal zone and its associated processes. Design/methodology/approach Specific features of CP in the tidal zone, that is, persistence of a thin seawater film and insufficient cathodic potential due to ohmic drop, were addressed. In this preliminary study, carbon steel electrodes were polarized at two cathodic potentials (correct or insufficient protection) while immersed in 1 mm or 5 mm thick natural seawater layers. After CP interruption, the protective ability of the layers covering the steel electrodes was studied using various electrochemical methods, including electrochemical impedance spectroscopy. The layers were characterized by XRD. Findings The protective ability of calcareous deposits was increased in thin seawater films. Insufficient CP could promote protective aragonite/corrosion products layer. Originality/value The combined effects of thin seawater film and applied potential were never addressed, and the conclusions drawn from this preliminary study give new insight on the efficiency of CP in the tidal zone.