Hydrology of a spring complex, studied by geochemical time-series data, Acquarossa, Switzerland

A case study of three springs in Switzerland is used to demonstrate the value of geochemical time-series data as a powerful tool to study the dynamics of groundwater systems. Values of repeatedly measured parameters revealed intermixings of two water types: (a) a 29°C water, circulating to a depth of 1100 m and containing approximately 700 mg/l Ca, 2000 mg/l SO₄, 700 mg/l HCO₃, 20 mg/l of Na and Cl, 6 mg/l Fe, at least 47 mg/l SiO₂, and with an isotopic composition of δD = − 73.0‰ and δ¹⁸ O = −10.9‰, and (b) a 12°C or colder water, shallow, and of a post-1953 age, containing 420 mg/l TDI or less, very low in Na and Cl (4 mg/l or less), isotopic values of δD = −71.0‰ and δ¹⁸ O = −10.5‰ and tritium as in recent (post-bomb) precipitation.     

Hydrochemical and isotopic characteristics of groundwater in the Souss Upstream Basin, southwestern Morocco

Heterogeneous shallow Plio-Quaternary formations of the Souss Plain represent the most important aquifer in southern High Atlas Mountains in Morocco. The present work was conducted in the Souss Upstream Basin to identify the chemical characteristics and the origin of groundwater in an aquifer under semi-arid climate. Isotopic and hydrochemical compositions combined with geological and hydrogeological data were used for this purpose. The total dissolved solids vary from 239 to 997 mg l⁻¹, and the following groundwater types are recognized: Ca²⁺–Mg²⁺–HCO₃⁻, Ca²⁺–Mg²⁺–SO₄²⁻ and Ca²⁺–Mg²⁺–Cl⁻. The groundwater is saturated and slightly supersaturated with respect to carbonate minerals and undersaturated with respect to evaporite minerals, which means that the groundwater composition is largely controlled by the dissolution of carbonate rocks known in the basin. The isotopic contents of groundwaters ranged from −8‰ to −5.2‰ for δ¹⁸O, from −52‰ to −34‰ for δD, and from 0 to 5.5 TU for tritium. The hydrogen (δD) and oxygen (δ¹⁸O) isotope signatures reveal a significant infiltration before evaporation takes place, indicating a major recharge directly from fractures in the crystalline and limestone formations of Atlas Mountains (above 800 m a.s.l.) and infiltration of surface water in the alluvial cones at the border of the Atlas basins. The very low tritium values suggest that the groundwater recharge follows a long flow path and a mixing between old and modern water is shown. However, a slight evaporation effect is noted in the southern part of the basin close to the Anti-Atlas Mountains.     

Geochemical characteristics of shallow groundwater in Datong basin, northwestern China

Located in semi-arid regions of northwestern China, Datong basin is a Quaternary sedimentary basin, where groundwater is the most important source for water supply. It is very important to study groundwater characteristics and hydrogeochemical processes for better management of the groundwater resource. We have identified five geochemical zones of shallow groundwater (between 5 and 80 m) at Datong: A. Leaching Zone (Zone I); B. Converging Zone (Zone II); C. Enriching Zone (Zone III); D. Reducing Zone (Zone IV); E. Oxidizing Zone (Zone V). In Zones I, II, and V and some parts of Zones III and IV, hydrolysis of albite/K-feldspar/chalcedony system and/or albite/K-feldspar/quartz system enhanced concentrations of Na⁺, K⁺, HCO₃⁻ and silicate. In Zone I, dissolution of carbonate and hydrolysis of feldspar generally controlled the groundwater chemistry. Infiltration of meteoric water promoted the formation of HCO₃⁻ in the water. In Zone II, the main geochemical processes influencing the groundwater chemistry were dissolutions of calcite and dolomite, ion exchange and evaporation. In Zones III and IV, in addition to ion exchange, evaporation and precipitation of calcite and dolomite, leaching of NaHCO₃ in saline–alkaline soils dominated the water quality. Zone IV was under anoxic condition, and reduction reactions led to the decrease of SO₄²⁻, NO₃⁻ and occurrence of H₂S, with the highest arsenic content (mean value of 366 μg/L), far exceeding Maximum Contaminant Level (MCL). Abnormal arsenic in the groundwater resulted in endemic disease of waterborne arsenic poisoning among local people. Zone V overlapped Zone I was intensively affected by coal mining activities. Sulfide minerals, such as pyrite, would have been oxidized when exposed to air due to coal mining, which directly added sulfate to groundwater and thus increased SO₄²⁻ concentration. Oxidization of sulfide minerals also decreased pH and promoted dissolutions of calcite and dolomite.     

Hydrochemistry and isotope compositions of groundwater from the Shihongtan sandstone-hosted uranium deposit, Xinjiang, NW China

Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO₃ type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ¹⁸O of − 8.3‰, δD of − 48.2‰,δ¹¹B of 1.5‰, and ⁸⁷Sr/⁸⁶Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO₄ type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ¹⁸O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ¹¹B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and ⁸⁷Sr/⁸⁶Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO₄ type water with the highest TDS (249.1 g/l, brine) and has δ¹⁸O of − 2.8‰, δD of − 45.8‰,δ¹¹B of 21.2‰, and ⁸⁷Sr/⁸⁶Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ¹¹B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.     

Chemistry and sulfur isotopic composition of precipitation at Bologna, Italy

Individual and monthly precipitation samples from the polluted atmosphere of Bologna (Emilia-Romagna province) were collected during March 1996 to May 1997 and analyzed for major ions in solution and S isotopes in dissolved SO₄.Weighted mean enrichment factors relative to seawater are found to be 1.0 for Na, 15.2 for K, 105 for Ca, 3.3 for Mg, 17.3 for SO₄ and 663 for HCO⁻₃. Very good positive correlations are observed for the Ca²⁺–Mg²⁺–HCO⁻₃–SO²⁻₄–NO⁻₃ system, indicating that dissolution of Ca (±Mg)-carbonate particles by H₂SO₄ and HNO₃ from combustion of oil and gas is a major process controlling the chemical composition of rain and snow. Na⁺ and Cl⁻ in monthly precipitation derive essentially from sea spray, but the contribution of Na⁺ from continental sources is appreciable in a number of individual rains. NH⁺₄ appears to be on average more abundant in spring and summer precipitation, its main sources being microbial activity in soils and application of fertilizers. K⁺ is probably of continental origin from soil dust.The S isotopic composition of SO₄ is systematically positive, with mean δ³⁴S values of +3.2±1.6‰ (n=40) in individual precipitation and +2.8±1.4‰ (n=12) in monthly precipitation. These isotopic compositions are interpreted in terms of a dominant contribution of S from anthropogenic emissions and subordinate contributions from biogenic and marine sources. Pollutant SO₄ is estimated to have a δ³⁴S value in the range +2.5 to +4.5‰, whereas a distinctive δ³⁴S of −4.5‰ or lower indicates SO₄ from oxidation of biogenic gases.The isotopic and chemical compositions of SO₄ do not depend on wind direction, thus testifying to a mostly local source for pollutant S in the Bologna atmosphere.     

Pollution par les nitrates des nappes phréatiques sous environnement semi-urbain non assaini: example de la nappe de Yeumbeul, Sénégal

High nitrate concentrations, above the WHO guideline of 50 mg l⁻¹, were observed in samples of shallow wells reaching the Yeumbeul suburb (Senegal) area groundwater. This groundwater is exploited by 7000 houses and therefore there are health implications. Correlations between parameters such as nitrate content (NO₃⁻) in the groundwater and soil water, the distance between shallow wells and family latrines, and soil water chloride (Cl⁻) and colon bacillus content led to two possible sources of groundwater pollution: first, contamination by non impervious and shallow latrines; and second, the leaching of soil NO₃⁻ from waste organic matter carried in groundwater.     

Controls on stable isotope profiles in the Chalk aquifer of north-east Norfolk, UK, with special reference to dissolved sulphate

Groundwater samples were collected at a site in N Norfolk, UK, comprising a borehole penetrating Upper Chalk and piezometers open within the overlyinf glacial deposits and intervening, weathered Putty Chalk. The samples were analyzed for δ¹⁸O (water), δ³⁴S and δ¹⁸O(SO₄) and δ¹³_C(HCO₃) as well as major ions. Variations in solute concentration and isotopic composition with depth were found to be caused by limited groundwater circulation at the site and incomplete flushing of old groundwater. The isotopic data prove the existence of a mineralized palaeowater at depth, which has undergone SO₄ reduction and is being slowly modified by mixing with recent groundwater circulating at a shallow depth in a more transmissive Chalk horizon. One measured δ¹⁸O (H₂O) value of −8.25‰_vsmow represents the lightest value reported for the Norfolk Chalk aquifer and is evidence for a component of Late Pleistocene recharge trapped at depth.The wide range of observed isotope ratios at the site, e.g.δ³⁴S and δ¹⁸O SO₄ between 7.8 to 27.8‰_cdt and 5.2 to 20.0‰_ovsmow respectively, demonstrates the importance of vertical stratification of solutes and the implications this has for interpreting spatial hydrochemical surveys of groundwater.     

Seasonal variations in the composition of mine drainage-contaminated groundwater in Dalarna, Sweden

Groundwater down-gradient from a mine rock dump in Dalarna, Sweden was sampled from the onset of snowmelt runoff (April) until October in order to investigate seasonal variations in groundwater composition. The results demonstrate that considerable variation in solute concentration (Al, Cu, Fe, SO₄²⁻, Zn) and acidity occurs in groundwater; the greatest change in solute concentrations occurs during the melting of the snow cover, when sulfide oxidation products are flushed from the rock dump. During this period, groundwater flow is concentrated near the soil surface with an estimated velocity of 1 m/day. Groundwater acidity varied by a factor of four closest to the rock dump during the sampling period, but these variations were attenuated with distance from the rock dump. Over a distance of 145 m, groundwater pH increases from 2.5 to 4.0 and acidity decreases from 3–13 to 0.8–1.1 meq/L, which is the combined effect of ferric iron precipitation and aluminosilicate weathering. As a result of flushing from the upper soil horizons, peaks in total organic carbon and ammonium concentrations in groundwater are observed at the end of snowmelt. In soils impacted by acidic surface runoff, the sequential extraction of C horizon soils indicates the accumulation of Cu in well-crystallized iron oxyhydroxides in the upper C horizon, while Cu, Fe, Ni and Zn accumulate in a well-crystallized iron oxyhydroxide hardpan that has formed 2.5m below the ground surface. Surface complexation modeling demonstrates that SO₄²⁻ and Cu adsorb to the abundant iron oxyhydroxides at pH < 4, while Zn adsorption in this pH range is minimal.     

Groundwater chemistry within a plateau neighboring Matsumoto city,Japan

The change in groundwater chemistry along the groundwater flow path in the Matsumoto tunnel vicinity was studied, and the origin of the groundwater and dissoluted substances was determined. The relationship between the concentration of HCO₃ ^–, Ca²⁺, and Na⁺, and CO₂ gas pressure in the groundwater indicated that the HCO₃ ^–, Ca²⁺, and Na⁺ were produced by the reaction of the CO₂ gas in the groundwater and feldspar in the rocks. The relationship between the concentration of NO₃ ^– and the Eh and pH values in the groundwater indicated that in an oxidative condition, ammonia-oxidizing and nitriteoxidizing bacteria used NH₄ ⁺ and produced NO₃ ^– and H⁺, and in a reductive condition, denitrifying bacteria used NO₃ ^– and produced N₂ gas and OH^–. The stable hydrogen and oxygen isotopic ratio in the groundwater and precipitation indicated that the groundwater originated from precipitation that had fallen on the area. The concentration of³H and the stable hydrogen and oxygen isotopic ratios in the groundwater suggested that it has been getting warmer climatically for more than 60 years. The stable carbon isotopic ratio indicated that the HCO₃ ^– in the groundwater, excluding deep well water, originated from CO₂ gas produced by organic matter in the soil. The deep well water, which had a higher concentration of HCO₃ ^– than the other groundwater sampled, was thought to have acquired HCO₃ ^– though contact with rocks. The³⁶Cl/Cl ratio indicated the recharge age of the deep well water sampled at a depth of 760 m at the foot of the plateau was recent.     

Further sulfur and carbon isotope studies of late Archean iron-formations of the Canadian shield and the rise of sulfate reducing bacteria

Sulfur and carbon contents and isotope ratios are reported for five Archean iron-formations, Helen, Nakina and Finlayson, Lumby and Bending Lake areas, distributed across 850 km of the Canadian shield all 2.7 Ga-old.A δ³⁴S profile through a complete stratigraphic column (oxide facies excluded) of the Helen iron-formation shows a δ³⁴S range of 30.2‰, mean δ³⁴S value of 2.5‰ and a standard deviation (δ_i) of 7.3‰ In sharp contrast to the sulfide and siderite facies, the oxide facies in the column shows a uniform δ³⁴S value close to zero. The δ³⁴S values obtained for the other four iron-formations are again wide ranging, highly variable in the sulfide and pyrite—siderite facies, but uniform and close to zero for the oxide facies.The carbon in the oxide, siderite, chert facies has δ¹³C values of +2.3 to −1.1‰ in the range of Phanerozoic marine carbonates. However, the carbonates in the graphite rich sulfide facies have δ¹³C values as low as −7.6‰. The mixing of reduced carbon with marine carbonate is suggested to explain the light carbonate values. The reduced carbon associated with the light carbonate is also relatively light at up to δ¹³C_org = 33.5‰, but is in the range of other Precambrian values. Distal, high temperature, abiogenic sulfate reduction as a source of highly fractionated sulfides in the Archean iron-formations is ruled out on the basis of both isotopic and geologic evidence. It is concluded that only the bacterial reduction of sulfate at low temperatures could produce the wide ranging, highly variable δ³⁴S values exhibited by these sulfides over large areas.     

Isotopic and molecular composition of coal-bed gas in the Amasra region (Zonguldak basin—western Black Sea)

Previous studies on the coal-bed methane potential of the Zonguldak basin have indicated that the gases are thermogenic and sourced by the coal-bearing Carboniferous units. In this earlier work, the origin of coal-bed gas was only defined according to the molecular composition of gases and to organic geochemical properties of the respective source rocks, since data on isotopic composition of gases were not available. Furthermore, in the western Black Sea region there also exist other source rocks, which may have contributed to the coal-bed gas accumulations. The aim of this study is to determine the origin of coal-bed gas and to try a gas-source rock correlation. For this purpose, the molecular and isotopic compositions of 13 headspace gases from coals and adjacent sediments of two wells in the Amasra region have been analyzed. Total organic carbon (TOC) measurements and Rock-Eval pyrolysis were performed in order to characterize the respective source rocks. Coals and sediments are bearing humic type organic matter, which have hydrogen indices (HI) of up to 300 mgHC/gTOC, indicating a certain content of liptinitic material. The stable carbon isotope ratios (δ¹³C) of the kerogen vary from −23.1 to −27.7‰. Air-free calculated gases contain hydrocarbons up to C₅, carbon dioxide (<1%) and a considerable amount of nitrogen (up to 38%). The gaseous hydrocarbons are dominated by methane (>98%). The stable carbon isotope ratios of methane, ethane and propane are defined as δ¹³C₁: −51.1 to −48.3‰, δ¹³C₂: −37.9 to −25.3‰, δ¹³C₃: −26.0 to −19.2 ‰, respectively. The δD₁ values of methane range from −190 to −178‰. According to its isotopic composition, methane is a mixture, partly generated bacterially, partly thermogenic. Molecular and isotopic composition of the gases and organic geochemical properties of possible source rocks indicate that the thermogenic gas generation took place in coals and organic rich shales of the Westphalian-A Kozlu formation. The bacterial input can be related to a primary bacterial methane generation during Carboniferous and/or to a recent secondary bacterial methane generation. However, some peculiarities of respective isotope values of headspace gases can also be related to the desorption process, which took place by sampling.     

Stable isotope and geochemical evidence of formation pore fluid evolution during diagenesis of Tertiary sandstones and mudrocks of the Niger Delta

Petrological data provide evidence that framboidal pyrite, Fe-carbonates and kaolinite are the major diagenetic minerals developed during burial diagenesis in the Tertiary Niger Delta sandstones and associated mudrocks. The pyrite sulphur, carbonate carbon and oxygen and kaolinite oxygen and hydrogen isotope compositions have been determined. These data (pyrite, δ³⁴S = −24.8 to 21.0‰; “siderite”, δ¹³C(PDB) = −14.7 to +5.0‰, δ¹⁸O(PDB) = −19.1 to −0.6‰; Fe-calcite, δ¹³C(PDB) = +17.5 to 17.9‰, δ¹⁸O(PDB) = −8.3 to −8.0‰; kaolinite, δ¹⁸O(SMOW) = +14.7 to 17.5‰, δD (SMOW) = −86 to −43‰) have been used to interpret the isotopic compositions of the precipitating pore fluids and/or the temperatures of mineral formation. The interpretation of these results indicate that in the deltaic depositional setting the syndepositional pore waters had a significant but variable marine influence that favoured the early formation of pyrite. Subsequently the subsurface influence of meteoric waters, showing varying degrees of modification involving organic and/or water-rock reactions, played an increasingly significant role in the development of later diagenetic cements in the sediments when abundant authigenic carbonates and kaolinites were formed.     

Vulnerability of the groundwater in the quaternary aquifer at El Shalal-Kema area, Aswan, Egypt

El Shalal-Kema area is located east of Aswan town and Nile River. The Quaternary sediments (unconsolidated material of sands, gravels, and clays intercalation) represent the main aquifer in the studied area. Its water is under unconfined condition, and the water table is shallow (vary from 7.5 to 16.3 m). The concerned aquifer is recharged mainly from Aswan Dam Lake, from the excess irrigation water and from septic tanks, where the area is not served by sewage system. The direction of the groundwater movement is generally from south to north. The transmissivity values of the Quaternary aquifer (from three pumping tests) are relatively high (vary from 1,996 to 3,029 m²/day). The exploitation of groundwater is carried out where there is continuous withdrawal for industrial and domestic uses with a total average quantity of groundwater of 71,304 m³ per day (25.67 million m³ per year). The hydrochemical characteristics of the Quaternary aquifer is studied based on the chemical analysis of 29 groundwater and four surface water samples collected from different sites. The chemical composition of the groundwater is dominated by calcium Ca²⁺ from the cations and bicarbonate (HCO ₃ ^? ) from the anions, and the order of cation abundance is Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ and HCO ₃ ^? > SO ₄ ^2? > Cl^? among the anions. The groundwater types are normal chloride water, normal sulfate water, and normal carbonate water. The hypothetical salt combination revealed the presence of different salts arranged in terms of their predominant as Ca(HCO₃)₂, Mg(HCO₃)₂, NaCl, Na₂SO₄, MgSO₄, KCL, NaHCO₃, MgCl₂, CaSO₄, and K₂SO₄. The analytical measurements to the NO₂ and NH₃ reveal that their values decrease in summer and increase in winter due to the stoppage of pumping which leads to the increase of the wastewater quantities that reach the groundwater. The chemical and microbiological analyses show that the aquifer in this area is contaminated with fecal and disease-causing bacteria. The main cause of this contamination is the outflow from the septic tanks; therefore, the construction of sewage network is a vital solution. Chlorination is important to disinfect the groundwater at the tanks before its distribution to the houses.     

Geology and geochemistry of the adjacent Changkeng gold and Fuwang silver deposits, Guangdong Province, South China

The Changkeng Au and Fuwang Ag deposits represent an economically significant and distinct member of the Au–Ag deposit association in China. The two deposits are immediately adjacent, but the Au and Ag orebodies separated from each other. Ores in the Au deposit, located at the upper stratigraphic section and in the southern parts of the orefield, contain low Ag contents (< 11 ppm); the Ag orebodies, in the lower stratigraphic section, are Au-poor (< 0.2 ppm). Changkeng is hosted in brecciated cherts and jasperoidal quartz and is characterized by disseminated ore minerals. Fuwang, hosted in the Lower Carboniferous Zimenqiao group bioclastic limestone, has vein and veinlet mineralization associated with alteration comprised of quartz, carbonate, sericite, and sulfides. Homogenization temperatures of fluid inclusions from quartz veinlets in the Changkeng and Fuwang deposits are in the range of 210 ± 80 °C and 230 ± 50 °C, respectively. Salinities of fluid inclusions from the two deposits range from 1.6 to 7.3 wt.% and 1.6 to 2.6 wt.% equiv. NaCl, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of the fluid inclusions from the Changkeng deposit range from − 80‰ to − 30‰, − 7.8‰ to − 3.0‰, − 16.6‰ to − 17.0‰ and 0.0100 to 0.0054 Ra, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of fluid inclusions from the Fuwang deposit range from − 59‰ to − 45‰, − 0.9‰ to 4.1‰, − 6.7‰ to − 0.6‰ and 0.5930 to 0.8357 Ra, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of the fluid inclusions suggest the ore fluids of the Changkeng Au-ore come from the meteoric water and the ore fluids of the Fuwang Ag-ore are derived from mixing of magmatic water and meteoric water. The two deposits also show different Pb-isotopic signatures. The Changkeng deposit has Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb: 18.580 to 19.251, ²⁰⁷Pb/²⁰⁴Pb: 15.672 to 15.801, ²⁰⁸Pb/²⁰⁴Pb: 38.700 to 39.104) similar to those (²⁰⁶Pb/²⁰⁴Pb: 18.578 to 19.433, ²⁰⁷Pb/²⁰⁴Pb: 15.640 to 15.775, ²⁰⁸Pb/²⁰⁴Pb: 38.925 to 39.920) of its host rocks and different from those (²⁰⁶Pb/²⁰⁴Pb: 18.820 to 18.891, ²⁰⁷Pb/²⁰⁴Pb: 15.848 to 15.914, ²⁰⁸Pb/²⁰⁴Pb: 39.579 to 39.786) of the Fuwang deposit. The different signatures indicate different sources of ore-forming material. Rb–Sr isochron age (68 ± 6 Ma) and ⁴⁰Ar–³⁹Ar age (64.3 ± 0.1 Ma) of the ore-related quartz veins from the Ag deposit indicate that the Fuwang deposit formed during the Cenozoic Himalayan tectonomagmatic event. Crosscutting relationships suggests that Au-ore predates Ag-ore. The adjacent Changkeng and Fuwang deposits could, however, represent a single evolved hydrothermal system. The ore fluids initially deposited Au in the brecciated siliceous rocks, and then mixing with the magmatic water resulted in Ag deposition within fracture zones in the limestone. The deposits are alternatively the product of the superposition of two different geological events. Age evidence for the Fuwang deposit, together with the Xiqiaoshan Tertiary volcanic-hosted Ag deposit in the same area, indicates that the Pacific Coastal Volcanic Belt in the South China Fold Belt has greater potential for Himalayan precious metal mineralization than previous realized.     

Comparison of microbial gases from the Middle America Trench and Scripps Submarine Canyon: implications for the origin of natural gas

Chemical and isotopic compositions have been measured on 62 microbial gases from Tertiary hemipelagic sediments in the Middle America Trench off Guatemala and from decaying kelp and surf grass currently accumulating in Scripps Submarine Canyon off southern California. Gases from the Middle America Trench have been generated primarily by the reduction of carbon dioxide; methane δ¹³C varies from −84‰ to −39‰, methane δD varies from −208‰ to −145‰, and carbon dioxide δ¹³ C varies from −27‰ to +28‰. Gases from Scripps Submarine Canyon have been generated primarily by acetate dissimilation; methane δ¹³ C varies from −63‰ to −43‰, methane δD varies from −331‰ to −280‰, and carbon dioxide δ¹³C varies from −17‰ to +3‰.Methane δ¹³C values as heavy as −40‰ appear to be uncommon for gases produced by carbon dioxide reduction and, in the Middle America Trench, are associated with unusually positive carbon dioxide δ¹³C values. However, based on the 25‰ intramolecular fractionation between acetate car☐yl carbon and methyl carbon estimated from the Scripps Submarine Canyon data, methane produced by acetate dissimilation may commonly have heavy δ¹³C values. The δD of methane derived from acetate is more negative than natural methanes from other origins. Microbial methane δD values appear to be controlled primarily by interstitial water δD and by the relative proportions of methane derived from carbon dioxide and acetate.The chemical and isotopic compositions of microbial gas and thermogenic gas overlap, making it difficult to determine the origins of many commercial natural gases from methane δ¹³C and C₂₊ hydrocarbon concentrations alone. Measurements of methane δD and carbon dioxide δ¹³C can provide useful additional information, and together with ethane δ¹³C data, help identify gases with mixed microbial and thermogenic origins.     

Integrated hydrochemical method of water quality assessment for irrigation in arid areas: application to the Jilh aquifer, Saudi Arabia

Water samples from 72 wells tapping the Jilh aquifer were collected and analyzed for 10 different water quality parameters. Using these data, a regional irrigation water quality was assessed using three techniques: (i) United States Department of Agriculture method (USDA), (ii) Food and Agriculture Organization (FAO) guidelines for water quality assessment, and (iii) Water-Types approach. The USDA method revealed that the aquifer water salinity, as represented by electrical conductivity, EC_w, ranges from high salinity (C3: EC_w > 0.75–2.25 dS/m) to a very high salinity (C4: EC_w > 2.25 dS/m). The sodium adsorption ratio (SAR) varied from low (S1) to very high (S4) sodicity. Therefore, the water of the Jilh aquifer is dominantly of the C4–S2 class representing 56% of the total wells followed by C4–S1, C4–S3, C3–S1 and C4–S4 classes at 19%, 14%, 8%, and 3% of the wells respectively. The FAO system indicated moderate to severe restriction on the use for irrigation and slight to moderate ion toxicities for Na⁺, Cl⁻, B⁺, NO₃⁻ and HCO₃⁻. It is clear that, both USDA and FAO systems condemn the Jilh groundwater as hazardous for irrigation due to its high salt content, unless certain measures for salinity control are undertaken. The dominant salt constituents in the water are Mg–Cl₂, Na–Cl and Ca–Cl₂ as per the Water-Types method. However, due to the complexity in classifying the aquifer groundwater for irrigation, a simplified approach acknowledging three class groups (I-suitable water, II-conditionally suitable water and III-unsuitable water) adopted from the three methods, is suggested in this paper. The simplified approach combines C–S classes of the USDA method among these three groups according to the lowest ratings. The salinity of the FAO method has been split arbitrarily into slight and moderate subclasses with values of 0.7–2.25 and >2.25 dS/m, respectively; to match with the C3-class of the USDA system. The Water-Types were classified assuming that Ca–Cl₂ is the least hazardous salt, followed by Mg–Cl₂ and Na–Cl. Using this integrated hydrochemical method, the majority of the wells (92%) contain unsuitable water for irrigation (Group III) while the remaining wells (8%) are in Group II with water considered conditionally suitable for irrigation.     

Origins of high nitrate in groundwater in Tanzania

Dodoma is located in a semi-arid climate (mean annual rainfall 550 mm) in an area of crystalline basement rock. The groundwater contains high nitrate with NO₃⁻ concentrations averaging 150 mg l⁻¹ and total mineralization between 1000–3000 mg l⁻¹. Factor analysis has been used for the identification of factors that bring about the chemical character of groundwater. Three rotated factors, explaining 77.2% of the total data variance, were extracted. The first factor accounts for 51.0% of the variance and shows high positive correlation with Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, SO₄²⁻, HCO₃⁻ and SEC and is attributed to the leaching of surface and soil salts together with mineral dissolution. The second factor accounts for 14.1% of the variance and is positively correlated with NO₃⁻ and negatively correlated with pH; this is explained by the nitrification process taking place on the sewage effluents. The third factor is highly positively correlated with ¹⁸O and ²H, accounting for 12.1% of the variance and is a consequence of evaporation processes. Nitrate concentrations greater than 100 mg l⁻¹ are commonly found in both deep and shallow groundwaters. It is concluded that the high nitrate concentrations have originated from the sewage effluents that are advecting and dispersing through macropores under bypass flow mechanisms.     

Molecular and carbon isotopic analysis of individual biological markers: evidence for sources of organic matter and paleoenvironmental conditions in the Upper Ordovician Maquoketa Group, Illinois Basin, U.S.A.

Variations in the carbon isotopic composition (δ¹³C) of pristane, phytane, n-heptadecane (n-C₁₇), C₂₉ ααα 20R sterane, and aryl isoprenoids provide evidence for a diverse community of algal and bacterial organisms in organic matter of the Upper Ordovician Maquoketa Group of the Illinois Basin. Carbon isotopic compositions of pristane and phytane from the Maquoketa are positively covariant (r = 0.964), suggesting that these compounds were derived from a common source inferred to be primary producers (algae) from the oxygenated photic zone. A variation of 3‰ in δ¹³C values (−31 to −34‰) for pristane and phytane indicates that primary producers utilized variable sources of inorganic carbon. Average isotopic compositions of n-C₁₇ (−32‰) and C₂₉ ααα 20R sterane (−31‰) are enriched in ¹³C relative to pristane and phytane (−33‰) suggesting that these compounds were derived from a subordinate group of primary producers, most likely eukaryotic algae. In addition, a substantial enrichment of ¹³C in aryl isoprenoids (−14 to −18‰) and the identification of tetramethylbenzene in pyrolytic products of Maquoketa kerogen indicate a contribution from photosynthetic green sulfur bacteria to the organic matter. The presence of anaerobic, photosynthetic green sulfur bacteria in organic matter of the Maquoketa indicates that anoxic conditions extended into the photic zone.The δ¹³C of n-alkanes and the identification of an unusual suite of straight-chain n-alkylarenes in the m/z 133 fragmentograms of Ordovician rocks rich in Gloeocapsomorpha prisca (G. prisca) indicate that G. prisca did not contribute to the organic matter of the Maquoketa Group.     

Geochemistry and occurrence of inorganic gas accumulations in Chinese sedimentary basins

Inorganic gases are commonly seen in eastern China and occasionally in southern China from the shallow water columns above hot and cold springs. The gases contain 68% to nearly 100% CO₂, with δ¹³C_CO2 and δ¹³C₁ values in the range of −1.18‰ to −6.00‰ and −19.48‰ to −24.94‰, respectively. All of the 34 large inorganic CO₂ and one inorganic methane accumulations discovered in China are distributed in eastern parts of the country, from both onshore and continental shelf basins. No commercial inorganic gas accumulation has been found in central and western China. This is a review of the occurrence and geochemical characteristics of inorganic gas accumulations in Chinese sedimentary basins. A detailed study of gas samples collected from four representative inorganic CO₂ pools and one possible inorganic methane pool indicates that inorganic alkane gases typically show δ¹³C₁ values greater than −10‰ versus PDB (mostly −30‰), with a positive stable carbon isotope sequence of δ¹³C₁ < δ ¹³C₂ < δ¹³C₃ < δ ¹³C₄. In contrast, the δ¹³C₁ values of biogenic alkane gases are lighter than −30‰, with a negative isotope sequence (i.e. δ¹³C₁ > δ¹³C₂ > δ ¹³C₃ > δ¹³C₄). Inorganic gases also tend to show less negative δ¹³C_CO2 values (−10‰) than biogenic gases (<−10‰).     

Petrological, geochemical, and stable isotope constraints on the genesis of the Miocene igneous rocks of Chetaibi and Cap de Fer (NE Algeria)

Miocene igneous rocks (diorites, andesites, dacites, rhyolites and microgranites) of Chetaibi and Cap de Fer massif, NE Algeria, are high-K calc-alkaline to shoshonitic rocks. Fresh diorites have δ³⁴S and δ¹⁸O values ranging between −2.5‰ and +5.9‰, +6.5‰ and +6.7‰ respectively, indicating a mantle origin. The relatively low δ³⁴S values (−5.4‰ to −12.2‰) and high δ¹⁸O (+8.3‰ to +9.0‰) of altered diorites indicate the input of a crustal component to the initial magma. The microgranites’ I-type signature is indicated by the geochemical data and the δ³⁴S and δ¹⁸O values of −1.2‰ and −3.6‰, and +7.8‰ to +10.4‰ respectively. The andesites show a large variation of δ³⁴S, between −33.2‰ and +25.7‰. Massive andesites with δ³⁴S between +6.8‰ and +7.6‰ preserve a ³⁴S-enriched mantle signature. The δ³⁴S of the lava flows between +25.7‰ and +25.8‰ are attributed to open system magma degassing, whereas the low δ³⁴S of two andesitic dyke samples (−13.7‰ and −33.2‰) strongly suggest a crustal sulphur input. High δ¹⁸O (+9.2‰ to +15.7‰) of andesites indicate post-magmatic alteration (mainly silicification); the flyschs with δ¹⁸O between of +13.3‰ and +21.7‰ are most likely the contaminant. Quartz veins within the andesites gave a δ¹⁸O value of +23.0‰ while silica-filling vesicles yielded a value of +13.8‰. Initial Sr-isotope data are rather high for all the rocks (diorites: 0.707–0.708, andesites: 0.707–0.710, and microgranites and rhyolites: 0.717–0.719), and because geochemical and stable isotope data do not indicate a substantial amount of crustal assimilation, an extensive enrichment of the mantle source by subducted sediments is called for. A metasomatized-mantle source, characterized by high radiogenic Sr and relatively high δ¹⁸O, has also been indicated for the genesis of similar Tertiary igneous rocks in the Western Mediterranean basin, e.g. the Volcanic Province of southeasten Spain [Benito, R., Lopez-Ruiz, J., Cebria, J.M., Hertogen, J., Doblas M., Oyarzun, R., Demaiffe, D., 1999. Sr and O isotope constraints on source and crustal contamination in the high-K calc-alkaline and shoshonitic neogene volcanic rocks of SE Spain. Lithos 46, 773–802] and some plutons of northeastern Algeria [Ouabadi, A., 1994. Pétrologie, géochimie et origine des granitoïdes peralumineux à cordiérite (Cap Bougaroun, Béni-Touffout et Filfila), Algérie nord-orientale. Thèse de Doctorat, Université de Rennes I, France, 257p; Fourcade, S., Capdevila, R., Ouabadi, A., Martineau, F., 2001. The origin and geodynamic significance of the Alpine cordierite-bearing granitoids of northern Algeria. A combined petrological, mineralogical, geochemical and isotopic (O, H, Sr, Nd) study. Lithos 57, 187–216].