Dissolution Of Carbonate Rocks Research Articles

Development and Application of Carbonate Dissolution Test Equipment under Thermal-Hydraulic-Chemical Coupling Condition.

The latest continuous flow micro reaction technology was adopted to independently develop carbonate rock dissolution test equipment. Carbonate rock dissolution tests were conducted under different temperatures, flow rates, and dynamic water pressure conditions to study the dissolution process of carbonate rocks under the coupling of heat-water-chemistry. The dissolution effect and development law of carbonate rocks were explored by quantitatively studying carbonate rock dissolution rate and chemical composition of karst water. The results showed that the self-designed dissolution test equipment has obvious advantages. After dissolution, carbonate rock specimens were damaged to varying degrees. The dissolution rate was proportional to water velocity and hydrodynamic pressure, with the velocity effect being greater than the hydrodynamic pressure effect. The pH value, conductivity, and Ca2+ ion content of the reaction solution gradually increased after dissolution. The development and application of the equipment have proved that, at low dynamic water pressures (2 MPa), the water flow velocity effect on the dissolution velocity was 1.5 times that when the dynamic water pressure was high (6 MPa); at a low water flow velocity of 15 mL/min, the dynamic water pressure effect on the dissolution velocity was three times that when the water flow velocity was high (75 mL/min). The development process is gradually becoming strong and stable. Its research has important theoretical significance and engineering application value to provide technical means and guarantee for the early identification, karst development, and safety evaluation of karst geological disasters.

Hydro-geochemical Study of the Coastal Aquifer in Tripoli (Lebanon)

Groundwater geochemistry refers to the general chemical properties of water, particularly groundwater. Precipitation, volatilization, oxidation/reduction, sorption/partition, and complexation are processes involved in the distribution and fate of organic molecules in water. Determining hydrogeochemical facies is a great help for determining relationships and similarities among the chemistry of waters in an aquifer. This study focused on the coastal aquifer of Tripoli (Lebanon) with Mio-Quaternary age. It is considered as a confined aquifer and an important hydraulic reserve for domestic water use in the region. Recently, it underwent an urban development that leads to an increase in water demand causing a decrease in the piezometric level and a high-risk of deterioration to water quality through seawater intrusion and anthropic pollution. To understand the origin of mineralization and the mechanism of water hydro-chemistry variation and to provide a vision to underground water recharge, this study aims to analyze the hydrodynamic, piezometric, and geochemical characteristics of the coastal aquifer. The fluctuation of physicochemical parameters for cool and warm seasons has been studied and monitored for 16 coastal wells during April, May, and June 2020. Results were interpreted by using a statistical analysis called Principal Components Analysis (PCA). Cartographic of groundwater levels and concentrations for nitrate, chloride, sulphate ions, the ratio sulphate/chloride were determined by using SUFFER8 software. It can be noticed that the Mio-Quaternary formation at Tripoli consists of thick sedimentary sandstones and conglomerates with argillaceous roots, which provide significantly high permeability characteristics. It is mainly recharged from precipitations through karstic formations. Chemical analysis shows that bicarbonate ions (HCO3-), characterized by dissolution of carbonate rocks from geological upstream formations of Tripoli, means that the aquifer is subjected to intensive recharge of fresh water and snow melting making a hydrostatic equilibrium facing marine intrusion [1]. High contents of chloride and Sodium are due to anthropic contamination or seawater intrusion. However, Magnesium ion concentration assures this intrusion. Meanwhile, nitrates, sulfates and phosphorus high concentrations are related to wastewater leakage or agricultural activities [2].

Hydrochemical and Isotopic Characteristics in the Surface Water of the Fenhe River Basin and Influence Factors

The Fenhe River Basin is the mother river of Shanxi Province. Due to the over-exploitation of water resources and the impact of social and economic development, the ecological environment has deteriorated. After a series of treatment and protection measures, the water quality has since been improved. Mathematical statistics, Piper diagrams, Gibbs model, hydrogen and oxygen isotopes, and other methods were used to analyze the characteristics and sources of hydrochemistry in the surface water of the Fenhe River basin, which revealed the evolution process of surface water quality of the Fenhe River basin. The results showed that the content of the main hydrochemical components in the main stream surface water of Fenhe River basin increased gradually along the runoff path. The hydrochemical types of surface water of Fenhe River basin were mainly HCO3·SO4·Cl-Ca·Na·Mg and SO4·HCO3·Cl-Ca·Na·Mg. There were great differences in hydrochemical components of tributaries and karst water in the basin. There were also great differences in hydrochemical components of tributaries in the basin. The hydrochemical types of surface water of karst water were mainly SO4·HCO3-Ca·Mg. The hydrochemical composition of surface water in Fenhe River basin was mainly affected by rock weathering and evaporation crystallization, whereas rainfall had little effect. Na+ and K+ mainly came from the dissolution of evaporated salt rocks with Na in the surrounding loess. Ca2+, Mg2+, and HCO3- mainly came from the dissolution of carbonate rocks. SO42- may have also come from the dissolution of sulfide minerals in the loess layer around Fenhe River in addition to the dissolution of gypsum. The values of δD and δ18O of Fenhe River surface water were gradually enriched from upstream to downstream. The characteristics of hydrogen and oxygen isotopes further showed that the surface water was mainly affected by evaporation. The results of this study can provide evidence for ecological restoration and protection and ecological civilization construction in the Fenhe River basin.

Characteristics and Causes of Groundwater Salinization in the Plain Area of the Lower Kashgar River

This study revealed the distribution characteristics and formation mechanism of groundwater salinization in the plain area of the lower Kashgar River in Xinjiang, which can provide scientific basis for a local sustainable groundwater exploitation plan and practical significance for local water supply security and social stability. Fifteen phreatic water samples, 38 shallow confined groundwater samples, and 16 deep confined groundwater samples were collected in September 2018. Mathematical statistics, a Duorv diagram, PCA-APCS-MLR model, ion ratios, and hydrogeochemical simulations were comprehensively used for sample analysis. The results showed that groundwater was weakly alkaline in general (pH ranged between 6.48 and 8.60 with an average of 7.57), with total dissolved solids (TDS) ranging from 573.0 to 16700.0 mg·L-1. Groundwater was mainly composed of Cl-, SO42-, Na+, and Ca2+. The main groundwater hydrochemical types included were HCO3·SO4·Cl, SO4, and SO4·Cl. No brine was observed in the study area, phreatic water was mainly composed of brackish water and saline water, and confined groundwater was mainly composed of saline water. The salinization coefficient calculation results showed that the salinization degree gradually increased from phreatic water to deep confined groundwater. Evaporation concentration and lixiviation were the main factors leading to the salinization of groundwater. The dissolution and cation exchange of carbonate and silicate rocks gradually weakened from phreatic water to deep confined groundwater, whereas the dissolution of evaporite rock always dominated and was gradually strengthened, which was also the primary factor that caused the salinity of deep groundwater to be higher than that of shallow groundwater. Human activities such as agricultural fertilization, unreasonable use of surface water for irrigation, and improper treatment of domestic sewage had a certain impact on groundwater salinization. The leaking recharge of salt water from adjacent aquifers aggravated the groundwater salinization.

Evidencing the role of carbonic anhydrase in the formation of carbonate minerals by bacterial strains isolated from extreme environments in Qatar

Calcium carbonate, one of the most abundant minerals in the geological records is considered as primary source of the carbon reservoir. The role of microorganisms in the biotic precipitation of calcium carbonate has been extensively investigated, especially at extreme life conditions. In Qatar, Sabkhas which are microbial ecosystems housing biomineralizing bacteria, have been carefully studied as unique sites of microbial dolomite formation. Dolomite (CaMg(CO3)2 is an important carbonate mineral forming oil reservoir rocks; however, dolomite is rarely formed in modern environments. The enzyme carbonic anhydrase is present in many living organisms, performs interconversion between CO2 and the bicarbonate ion. Thus, carbonic anhydrase is expected to accelerate both carbonate rock dissolution and CO2 uptake at the same time, serving as carbonite source to carbonites-forming bacteria. This study gathered cross-linked data on the potential role of the carbonic anhydrase excreted by mineral-forming bacteria, isolated from two different extreme environments in Qatar. Dohat Faishakh Sabkha, is a hypersaline coastal Sabkha, from where various strains of the bacterium Virgibacillus were isolated. Virgibacillus can -not only-mediate carbonate mineral formation, but also contributes to magnesium incorporation into the carbonate minerals, leading to the formation of high magnesium calcite. The latter is considered as precursor for dolomite formation. In addition, bacterial strains isolated from marine sediments, surrounding coral reef in Qatar sea, would provide additional knowledge on the role of carbonic anhydrase in mineral formation. Here, the quantification of the two mostly described activities of carbonic anhydrase; esterase and hydration reactions were performed. Mineral-forming strains were shown to exhibit high activities as opposed to the non-forming minerals, which confirms the relation between the presence of active carbonic anhydrase combined with elevated metabolic activity and the biomineralizing potential of the bacterial strains. The highest specific intracellular carbonic anhydrase activity; as both esterase and hydration (i.e., 66 ± 3 and 583000 ± 39000 WAU/108 cells respectively), was evidenced in mineral-forming strains as opposed to non-mineral forming strains (i.e., 6 ±. 0.5 and 1223 ± 61 WAU/108cells) respectively. These findings would contribute to the understanding of the mechanism of microbially mediated carbonate precipitation. This role may be both in capturing CO2 as source of carbonate, and partial solubilization of the formed minerals allowing incorporation of Mg instead of calcium, before catalyzing again the formation of more deposition of carbonates.

The Increase in the Karstification–Photosynthesis Coupled Carbon Sink and Its Implication for Carbon Neutrality

Two of the most important CO2 sequestration processes on Earth are plant photosynthesis and rock chemical dissolution. Photosynthesis is undoubtedly the most important biochemical reaction and carbon sink processes on Earth. Karst geological action does not produce net carbon sinks. Photosynthesis and karstification in nature are coupled. Karstification–photosynthesis coupling can stabilize and increase the capacity of karstic and photosynthetic carbon sinks. Bidirectional isotope tracer culture technology can quantify the utilization of different inorganic carbon sources by plants. Bicarbonate utilization by plants is a driver of karstification–photosynthesis coupling, which depends on plant species and the environment. Carbonic anhydrase, as a pivot of karstification–photosynthesis coupling, can promote inorganic carbon assimilation in plants and the dissolution of carbonate rocks. Karst-adaptable plants can efficiently promote root-derived bicarbonate and atmospheric carbon dioxide use by plants, finally achieving the conjugate promotion of karstic carbon sinks and photosynthetic carbon sinks. Strengthening karstification–photosynthesis coupling and developing karst-adaptable plants will greatly improve the capacity of carbon sinks in karst ecosystems and better serve the “Carbon peak and Carbon neutralization” goals of China.

Genesis and mineralogical studies of zircons in the Alamas, Yurungkash and Karakash Rivers nephrite deposits, Western Kunlun, Xinjiang, China

Nephrite, an aggregate of fine-grained tremolite or actinolite, is mainly found in Mg-skarn at the contact zone between granitoids and dolomitic marble. The nephrite belt in the southern Western Kunlun Mountains in China is the largest in the world, and includes 11 major skarn deposits and >20 orebodies including the Alamas deposit. In addition, economic placer nephrite deposits occur along the Yurungkash & Karakash Rivers. The nephrite in these deposits contains numerous zircons and some grains have high δ18O values, but the genesis of these zircons is not clear. In this study, we investigated the formation mechanism of the nephrite and origin of zircons in nephrite based on the geochemical and δ18O characteristics of zircons in nephrite from the deposits at Alamas and along the Yurungkash & Karakash Rivers, as well as the CO isotopes of the dolomitic marble at Alamas. We found that zircons in nephrite often occur with tremolite and apatite and the major elements of these zircons are close to those of common magmatic zircon. Zircon grains in the Alamas nephrite are mainly subhedral, 80–130 μm long, 50–90 μm wide, and have clear oscillatory zoning. These zircons have similar REE patterns with Alamas granodiorite, including heavy REE (HREE) enrichment and large positive Ce anomalies (Ce/Ce* = 5.30–368). Such petrographic and geochemical characteristics suggest most zircons are magmatic zircons, with some experienced hydrothermal alteration. Zircon δ18O values in Alamas nephrite are 5.69 ‰–8.85 ‰ (n = 25; an exception of 13.35 ‰), close to those zircons in Alamas granodiorite (6.4 ‰–9.0 ‰) but higher than mantle magmatic zircon (5.3 ± 0.3 ‰). The δ13C (0.79 ‰–1.02 ‰) and δ18O (18.7 ‰–20.6 ‰) values of the Alamas dolomitic marble indicate formation by the partial dissolution of marine carbonate rocks. Zircons in nephrite from Yurungkash & Karakash Rivers deposits are mainly subhedral, 100–160 μm long, 80–30 μm wide, and show clear or obscure irregular zoning. They show HREE enrichment and relatively weak positive Ce anomalies (2.58–35.8), suggesting most zircons have magmatic origin, with some experienced hydrothermal alteration. Zircons from Yurungkash & Karakash Rivers have δ18O values range from 14.6 ‰ to 21.37 ‰ (n = 31; an exception of 9.03 ‰). Irregular baddeleyite grains occur in the nephrite, and fragmented or granular grains occur locally within the nephrite zircons or fissures of zircon. These baddeleyite may have formed via the following reaction between zircon and dolomite: 2Zr[SiO4] + CaMg[CO3]2 → 2ZrO2 + CaMg[SiO3]2 + 2CO2 at 660–710 ℃ and 3 kbar. In Yurungkash & Karakash Rivers nephrite deposits, considering these placer nephrite come from Mg-skarn, these high δ18O zircons probably have initially formed within endoskarn, close to the margin of the granitoid where marble with high δ18O was assimilated into the melt, and retain nice oscillatory and/or sector zoning.

Seasonal Differences in the Hydrochemical Characteristics of Karst Wetlands and the Associated Mechanisms in Huixian, China

The present study aimed to identify the seasonal changes in the hydrochemical characteristics of the Huixian karst wetland and the underlying mechanism. Conventional ions and isotopes of 130 groundwater samples collected during the wet and dry seasons were analyzed. The hydrochemical characteristics of groundwater in the Huixian karst wetland were clarified using mathematical statistics and hydrochemical methods, including Durov diagrams, ionic ratios, Gibbs diagrams, and H and O isotopes. The hydrochemical evolution and sources of major ions in the Huixian karst wetland were also investigated. The results showed that cations and anions in groundwater in the study area were dominated by Ca2+ and HCO3−, respectively, sourced mainly from calcite weathering. The ions of some groundwater samples were regulated by weathering of dolomite, dolomitic limestone, and pyrite, resulting in relatively high concentrations of Mg2+ and SO42−. K+, Na+, SO42−, NO3−, and Cl− in groundwater originated from precipitation, Na+ and Cl− originated from domestic sewage, K+ was related to the application of potassium fertilizer in agriculture, and NO3− mainly originated from chemical fertilizer. Groundwater ions were primarily controlled by rock weathering, followed by evaporative concentration. The sources of major ions were dependent on the dissolution and precipitation of carbonate rock, as well as the chemical weathering of silicate rock and evaporite. Samples from the various water sources were scattered on both sides of the local meteoric water line (δD = 3.13δ18O − 13.9), which indicated isotopic composition was affected by evaporation and precipitation.

Long-term denudation rate of karstic North Dalmatian Plain (Croatia) calculated from 36Cl cosmogenic nuclides

The development of a karst landscape results from complex interactions between lithology, climate, hydrology, soil, vegetation and tectonics. Weathering and erosion of carbonate rocks leads to denudation of karst landscapes. As dissolution of carbonate rocks is often considered to be the main process governing carbonate weathering, other processes are often overlooked. Here we present research done in the North Dalmatian Plain, a carbonate erosive surface located in the Dinaric karst region. Although the study site is composed of two different carbonate lithologies having different weathering style, there is no evident lithological impact on the topography of the erosive surface. Analyses of 36Cl concentration were performed in ten proximal bedrock samples from both lithologies and resulted in long-term denudation rates ranging from 14.7 to 22.8 m/Ma. Since no statistical significance was found between samples from different lithologies (all samples belong to a single normal population) and they have the same geomorphological context and climate features, variable denudation rates are attributed to local (sample specific) differences. In the study site there are no large outstanding rock residuals or patches with deep soil profiles. Thus, to maintain the levelled erosive surface, local differential denudation rates have to vary with time. We hypothesize that lichens and pedogenic carbonates have a significant role in modulating local differences in denudation rates. Our study shows that even at outcrop scale those differences can be significant, and the study of sample populations is preferred to single or limited number of analyses. Thus, the long-term denudation rate of the North Dalmatian Plain, including its local variability is 18.91 ± 0.81 m/Ma. Despite classical studies on karst terrains assume that dissolution is the main process responsible for development of these landscapes, our research highlights the importance of physical weathering in combination with dissolution of carbonates as main controls on the denudation of karst landscapes.

Valuasi Ekonomi Kawasan Karst Desa Jatijajar Kecamatan Ayah Kabupaten Kebumen

Jatijajar Village which is included in the Gombong karst area in accordance with the Minister of Energy and Mineral Resources Decree No. 3043 K / 40 / MEM / 2014 and confirmed by the Kebumen Regency Regional Regulation No. 23 of 2012 concerning RTRW of Kebumen Regency for 2011 - 2013. Karst is a landscape of the karstification process of carbonate rock (CaCO3) which is deposited after passing through the available geological space and time. Karst has a distinctive hydrological condition due to the dissolution of carbonate rock due to the physical properties of limestone which is easily soluble and has secondary porosity so that it cannot store water for a long time. Rainwater that flushes the karst area directly falls to the bottom of the water-saturated zone and then flows through cracks and large passageways (caves) such as canals to springs exit points or is directly dumped into the sea, only a small amount flows on the surface. Until now, it has the potential value of environmental services (environmental services) and ecological services both in the karst area itself and in the non-karst area which is used as a buffer zone. The underground river system that is formed in the karst area provides benefits to the environment around the karst area and even the community as a provider of clean water needs that are perennial / flowing throughout the season. Characteristics of natural resources in the Karst Gombong area of Jatijajar Village have resource characteristics in the form of direct use, namely from the existence of a water hydrological system from the karst area which consists of the value of water resource utilization which is used to meet household needs, the value of water resources for lowland rice farming, and Water Resources from underground rivers in the karst area are 15 springs. The total economic value of the potential use of existing resources in the Gombong Karst Gombong area of Jatijajar Village is IDR 87,616,789,519 in one year. The magnitude of this value is the value of natural and environmental resources from the direct use of the availability of natural resources to the community. These values will be lost if the karst area is damaged either from mining activities or changes in environmental functions. In fact, this value will be a value that must be spent by the community in order to compensate for the loss of potential natural resources in the karst area

A Comparison of the Geochemical Characteristics of Ultra-Deep Natural Gas in the Kuqa Foreland and Marine Craton Areas in the Tarim Basin, China

This research analyzed the composition and hydrocarbon isotope geochemical characteristics of ultra-deep natural gas (buried deeper than 6000 m) in more than 130 wells in the Tarim Basin. Characteristics of the ultra-deep natural gas components in the Tarim Basin are as follows: natural gas in the Kuqa sandstone reservoir is developed as dry gas, with a high methane content (an average of 95.53%) and a low ethane content (an average of only 1.39%). The ultra-deep gas of the marine craton carbonate reservoirs in the North Tarim-Central Tarim-East Tarim area is developed as wet gas. It is mainly composed of methane ranging from 56.1% to 98.8%, with an average content of 76.36% and also contains a small amount of ethane amounting to 6.74%. CO2 and H2S contents of ultra-deep condensate gas in the Central Tarim area are high, with maximum values of 24.2% and 23.1%, respectively. Isotopic characteristics are as follows: δ13C1 values of Kuqa natural gas are distributed between −36‰ and −25.3‰, with an average of −28.2‰, δ13C2 values are distributed between −26.2‰ and −13.8‰, with an average of −18.3‰. Most gas samples in Kuqa area are developed with the reversal of carbon isotopic series as δ13C2 > δ13C3, and the δ13CCO2 values are distributed between −19.5‰ and −10.3‰. The δ13C1 values of ultra-deep gas in marine craton carbonate rocks are distributed between −54.4‰ and −33.3‰, with an average of −42.6‰. δ13C2 values are distributed between −41.1‰ and −29.4‰, with an average of −33.8‰, and δ13CCO2 values are distributed between −28.2‰–0.6‰. According to the identification chart, it can be seen that the ultra-deep gas in the sandstone reservoir of the Kuqa foreland is mainly coal-derived gas in the high over-mature stage, and the reversal of carbon isotopic series may be caused by the mixing of natural gas of the same type and different sources. The natural gas in carbonate reservoirs of marine craton is mainly oil-type gas with complex sources, including both kerogen cracking gas and oil cracking gas. CO2 can be formed by organic and inorganic genesis. Inorganic CO2 is most likely to be generated by the dissolution of carbonate rocks under acid formation water.

Chemical Quality and Hydrogeological Settings of the El-Farafra Oasis (Western Desert of Egypt) Groundwater Resources in Relation to Human Uses

In the Egyptian deserts, new land reclamation projects have been recently established to meet the increasing-population growth rate and food demand. These projects mainly depend on the different groundwater aquifers. El-Farafra Oasis is one of the “1.5-million-feddan reclamation project” areas recently established in the Western Desert of Egypt where the only available water source is the world’s largest fossil freshwater reservoir “the Nubian Sandstone Aquifer System (NSAS)”. Groundwater-dependent springs, and their artificial counterpart “drilled wells”, are reliable water systems throughout the world. In the present study, hydrochemical parameters were collected in 2015 from 16 different springs and wells of the El-Farafra Oasis, and analyzed using the different water quality indices. The calculated water quality index (WQI), its correlations with the water quality parameters Gibbs, Piper, US Salinity-Lab Staff and Wilcox diagrams, and Principal Component Analysis (PCA) were used to evaluate the groundwater suitability for human drinking and irrigation purposes. WQI values revealed good-to-excellent groundwater quality for human drinking. In addition, the spring and well water samples investigated showed good indices for irrigation activities. Gibbs and Piper’s diagrams were presented, with most samples falling into the rock-dominance category, and belonging to hydrogeochemical facies determining the following water types: Mg(HCO3)2 type water (37.5% of the samples), no dominant ions (mixed water-type category; Ca/MgCl2) (50% of the samples), and, finally, NaCl water type (the remaining 12.5%). The groundwater chemistry in the study area is mainly controlled by rock-water interactions, particularly the dissolution of carbonate rocks and silicate weathering. The elevated nutrient concentrations, in particular nitrates, are most likely due to agricultural activities, indicating substantial anthropogenic activities in the area studied.

Carbon Dioxide and its Carbon Isotopic Composition of Natural Gas in the Sichuan Basin, SW China

The Sichuan Basin, covering an area of 180 × 103 km2, has the following advantages in natural gas geology: The sedimentary rocks are 6,000–12,000 m thick with high maturity of source rocks, and nine sets of primary gas source rocks are developed in the basin with a gas–oil ratio of 80:1, and thus it is a gas basin. The remaining recoverable reserves of conventional and unconventional natural gas are up to 13.6404 × 1012 m3. Multiple gas-bearing systems are developed with 25 conventional and tight oil and gas producing layers and 135 discovered gas fields, and the total proved geological reserves and cumulative production of natural gas by the end of 2019 were 5.7966 × 1012 m3 and 648.8 × 109 m3, respectively. The CO2 components and the correlation with relevant parameters for 243 samples from 22 gas fields indicate that CO2 in the Sichuan Basin display the following two characteristics: (1) Relatively low CO2 content of 0.02%–22.90% with an average of 2.96%, which guaranteed the commerciality of natural gas exploration and production; (2) cratonic CO2, which is characterized by low CO2 contents (<5%) and low R/Ra ratios (<0.24). According to the δ13CCO2 values and the relationship with R/Ra, δ13C1, CO2 contents, and wetness coefficient (W) for 263 gas samples, the δ13CCO2 values display three characteristics: (1) The highest δ13CCO2 value (10.4‰) in China is found in the Fuling shale gas field, which extends the interval values from previous −39‰–7‰ to −39‰–10.4‰. (2) The δ13CCO2 values can be applied to identify the CO2 origin of natural gas in the Sichuan Basin: type A, organic origin from thermal decomposition of organic matter, with an average δ13CCO2 value of −12.8‰ and average wetness coefficient of 7.8% for 44 samples; type B, organic origin from thermal cracking of organic matter, with an average δ13CCO2 value of −15.7‰ and average wetness coefficient of 1.30% for 34 samples; type C, inorganic origin from thermal decomposition or organic acid dissolution of carbonate rocks or minerals, with an average δ13CCO2 value of −1.8‰ and average wetness coefficient of 0.85% for 175 samples. (3) δ13CCO2>δ13CCH4. This is a common characteristic shared by all geological age (from Z2dn to J2s) gas reservoirs and various gas types (coal-derived gas, oil-associated gas, and shale gas).

Hydrogeochemistry Characteristics of Groundwater in the Nandong Karst Water System, China

The hydrogeochemical characteristics of groundwater are an important element in the study of the spatial and temporal variation of groundwater resources, which is crucial to water resources utilization, ecological environmental protection, and human development. Water samples were collected at eight observation of Nandong Karst Water System (NKWS) sites in each month of 2019, and the main ions and isotopes of the water samples were examined. The hydrogeochemistry characteristics of groundwater and its differences with surface water were explored by using the methods of multivariate statistics, Gibbs model. Results showed that the water chemistry types of groundwater were mainly HCO3–Ca and HCO3–Ca·Mg. The analysis of hydrogen and oxygen isotope showed that the initial recharge source of surface water and groundwater were atmospheric precipitation, and the measured hydrogen and oxygen isotopes of surface water were heavier due to the strong evaporation effect. The natural and anthropogenic processes contributed to the chemical composition of surface water and groundwater in the study area. However, the main factor affecting the quality of surface water and groundwater was the input of anthropogenic contaminants. In terms of natural factors, the main chemical ions of surface water and groundwater were mainly controlled by water-rock action originating from weathering and hydrolysis of rocks and soils. Ca2+, Mg2+, and HCO3− mainly originated from natural dissolution of carbonate rocks. K+, Na+, SO42−, and Cl− were partly from atmospheric precipitation. For human activities, Na+ and Cl− were partly from domestic water for local residents. SO42− in surface water mainly came from mining. NO3− in groundwater mainly came from chemical fertilizers, and NO3− in surface water were mainly from human waste and domestic sewage.

Hydrochemical characteristics and health risk assessment of groundwater in karst areas of southwest China: A case study of Bama, Guangxi

The southwest karst area is considered to have the most vulnerable groundwater environment in China. Groundwater quality is an important factor restricting sustainable economic development. In this study, traditional water chemistry method, water quality index (WQI), and hazard index (HI) were applied to comparatively analyze the hydrochemical characteristics of groundwater and the water quality in the exposed karst region (EKR) and buried karst region (BKR) in Bama, a typical karst area in southwest China. Generally, the main water type was Ca/Mg–HCO3. Due to the predominance of dissolution of carbonate rocks in EKR and silicate rocks in BKR, higher total dissolved solids (TDS), Ca and HCO3− concentrations, and lower H2SiO3 content were detected in groundwater in EKR compared with BKR. As affected by weathering of rocks such as lead-zinc ore, the maximum concentrations of Zn and Sr were 11.23 mg/L and 13.30 mg/L, showing that mineral water resources are widely distributed in Bama. The ion ratios and isotope abundances (δD and δ18O) in groundwater samples indicated stronger evaporation and rock-water interaction in EKR than BKR. Human activities exerted a more significant influence on the water quality in EKR compared to BKR. The mean WQI value also suggested that the groundwater quality was better in BKR (9.56) than EKR (12.17). Although 95.7% of the water samples in the study area were classified as excellent based on their WQI values, 4.3% of the water samples still had significant health risks (HI > 1) due to the high Sb, Zn, As, and Sr concentrations. It is recommended to reduce anthropogenic pollution in EKR and develop a plan for clean production of mineral water industry according to local conditions, which will help the sustainable development of the local economy.

Soil phosphorus status and P nutrition strategies of European beech forests on carbonate compared to silicate parent material

Sustainable forest management requires understanding of ecosystem phosphorus (P) cycling. Lang et al. (2017) [Biogeochemistry,https://doi.org/10.1007/s10533-017-0375-0] introduced the concept of P-acquiring vs. P-recycling nutrition strategies for European beech (Fagus sylvatica L.) forests on silicate parent material, and demonstrated a change from P-acquiring to P-recycling nutrition from P-rich to P-poor sites. The present study extends this silicate rock-based assessment to forest sites with soils formed from carbonate bedrock. For all sites, it presents a large set of general soil and bedrock chemistry data. It thoroughly describes the soil P status and generates a comprehensive concept on forest ecosystem P nutrition covering the majority of Central European forest soils. For this purpose, an Ecosystem P Nutrition Index (ENIP) was developed, which enabled the comparison of forest P nutrition strategies at the carbonate sites in our study among each other and also with those of the silicate sites investigated by Lang et al. (2017). The P status of forest soils on carbonate substrates was characterized by low soil P stocks and a large fraction of organic Ca-bound P (probably largely Ca phytate) during early stages of pedogenesis. Soil P stocks, particularly those in the mineral soil and of inorganic P forms, including Al- and Fe-bound P, became more abundant with progressing pedogenesis and accumulation of carbonate rock dissolution residue. Phosphorus-rich impure, silicate-enriched carbonate bedrock promoted the accumulation of dissolution residue and supported larger soil P stocks, mainly bound to Fe and Al minerals. In carbonate-derived soils, only low P amounts were bioavailable during early stages of pedogenesis, and, similar to P-poor silicate sites, P nutrition of beech forests depended on tight (re)cycling of P bound in forest floor soil organic matter (SOM). In contrast to P-poor silicate sites, where the ecosystem P nutrition strategy is direct biotic recycling of SOM-bound organic P, recycling during early stages of pedogenesis on carbonate substrates also involves the dissolution of stable Ca-Porg precipitates formed from phosphate released during SOM decomposition. In contrast to silicate sites, progressing pedogenesis and accumulation of P-enriched carbonate bedrock dissolution residue at the carbonate sites promote again P-acquiring mechanisms for ecosystem P nutrition.

Hydrogeochemistry of karst groundwater for the environmental and health risk assessment: The case of the suburban area of Chongqing (Southwest China)

Karst groundwater is a vital resource for drinking, living and irrigation purposes in karst agricultural areas of the world. Due to the vulnerability of karst aquifers, surface pollutants are easily transferred to the subsurface and make karst groundwater be deteriorated, thereby restricting the rational exploitation of karst groundwater resource. In view of this, 49 karst groundwater samples were collected from spring (SW) and underground river (URW) sites in the suburban area of Chongqing City and analyzed for various hydrochemical components. Particularly, the karst groundwater quality was comprehensively uncovered by combining characteristics of hydrogeochemical evolution and health risks caused by nitrate and fluoride. The results revealed that the karst groundwater was slightly alkaline in nature and the water types were mainly characterized by Ca-HCO3 accounting for 93.88% of the total samples due to the heavy dissolution of carbonate rock. The relatively high concentrations of Na+, SO42− and NO3− up to 271.88 mg/L, 277.94 mg/L and 56.94 mg/L were over the corresponding maximum acceptable limits for drinking water, which can be predominately attributed to the emissions of industrial park, dissolution of gypsum and pyrite and excessive application of chemical fertilizers. Although agricultural activities were stopped and chemical fertilizers were no longer applied during the sampling period, long-term application of fertilizers have a persistent adverse effect on the karst groundwater NO3−. The pollution index of the karst groundwater (PIG) revealed that the low pollution and potential pollution zones were noticed in the northwestern parts of the study area. With respect of the SW, all the total hazard index (HI) values were below 1 suggesting no significant health risk. On the contrary, HI values of 0.11–1.16 for adults, 0.15–1.61 for children and 0.17–1.83 for infants in the URW indicated significant noncarcinogenic health risks. Particularly, infants and children were more vulnerable to karst groundwater NO3− than adults. Furthermore, the noncarcinogenic health risks of karst groundwater can be mainly attributed to NO3−, confirmed by the higher contribution ratio (66.55%) to the HI values. Therefore, special and targeted measures need to be taken to decrease the NO3− concentration in agricultural area.

Hydrogeological Assessment and Modified Conceptual Model of a Dinaric Karst Island Aquifer

Vis Island is situated in southern Croatia. The island is mostly composed of karstified carbonate rocks and belongs to the Dinaric karst region, which is a locus typicus of karst landforms. Located far from the mainland, Vis island has maintained a successful water supply from its own karst aquifer for decades. Hydrogeological research has been undertaken to protect this excellent karst aquifer by establishing sanitary protection zones and to explore the possibility of increasing the pumping yield. New groundwater velocity data obtained via a tracer test were in accordance with the rock mass hydraulic conductivity calculated from previous pumping tests. The hydrochemical interpretation indicated several different phenomena, from carbonate and sulfate rock dissolution to seawater mixing with groundwater. A conceptual model of the island’s aquifer was improved, and two main catchments were delineated according to tracer test results, and connected with the geological setting, hydrochemical data, and new climatological insights. Such an approach is applicable for similar karst aquifers, in which topographic and hydrogeological divides usually do not coincide.

Dissolution-After-Precipitation (DAP): a simple microfluidic approach for studying carbonate rock dissolution and multiphase reactive transport mechanisms.

We propose a simple microfluidic approach: Dissolution-After-Precipitation (DAP), to investigate regimes of carbonate rock dissolution and multiphase reactive transport. In this method, a carbonate porous medium is created in a glass microchannel via calcium carbonate precipitation, after which an acid is injected into the channel to dissolve the precipitated porous medium. Utilizing the DAP method, for the first time we realized all five classical single-phase carbonate rock dissolution regimes (uniform, compact, conical, wormhole, ramified wormholes) in a microfluidic chip. The results are validated against the established theoretical dissolution diagram, which shows good agreement. Detailed analysis of these single-phase dissolutions suggests that the heterogeneity of the porous medium may significantly impact how the dissolution patterns evolve over time. Furthermore, DAP is utilized to investigate multiphase dissolution. As examples we tested the cases of an oleic phase (tetradecane) and a gaseous phase (CO2). Results show that the presence of a nonaqueous phase in pore spaces induces the formation of wormholes despite weak advection, and these wormholes ultimately become pathways for nonaqueous phase transport. However, the transport of tetradecane in the wormhole is very slow, causing acid breakthrough into neighboring regions. This mechanism enhances lateral connectivity between wormholes and may lead to a wormhole network. In contrast, CO2 moves rapidly and continuously seeks to enter a widening wormhole from a narrower wormhole or the porous regions, generating phenomena such as ganglia redistribution and counterflow (flow of gas opposite to acid flow). Extensive independent experiments are conducted to verify the reproducibility of the observed phenomena/mechanisms and further analyze them. Real-time monitoring of fluid pressure drop during dissolution is implemented to complement microscopy image analysis. Our method can be implemented repeatedly on the same chip, which offers a convenient and inexpensive option to study pore-scale reactive transport mechanisms.

Impact of geology and climate change on wetlands: Case of Lake Aguelmam Azegza (Middle Atlas, Morocco)

The AguelmamAzegza lake is located in the Middle Atlas mountain range, this region consists of carbonate rocks of Lias. It is the best-watered and richest region in Morocco in terms of wetlands, especially natural lakes, rivers and fresh springs. The lake’s water supply is ensured by the inflows of water in the form of underwater sources fed by precipitation (rain and snow) following tectonics and the genesis of karstic formations by the dissolution of carbonate rocks. The declining trend in lake levels in recent years results from the decrease in precipitation which decreases during these years.