Isotopes of deuterium and oxygen-18 in thermal groundwater in China

Compositions of deuterium and ¹⁸O isotopes of 90 representative samples indicate that thermal groundwater in most parts of China is meteoric in origin. Latitude, altitude, and continent effects have significant bearing on the values of δD and δ¹⁸O of the hot water samples. Oxygen-18 shift is not significant in most of the thermal groundwater, especially the hot water of low-to-moderate temperature. Slight oxygen-18 shift is only found in some hot springs of high temperature in Tibet and western Yunnan and in thermal groundwater of low-to-moderate temperature in the deep-seated carbonate aquifers in the northern North China Plain (including the Tianjin area). Near-surface boiling may causes the shift of the former and the latter may be attributed to exchange of oxygen-18 between water and carbonates in the geothermal systems of taphrogenic basin-type. Hot springs in Tibet and western Sichuan have very low contents of δD and δ¹⁸O, possibly due to recharge of precipitation and snow-melting water of extremely depleted δD and δ¹⁸O values at high latitudes of several thousands of meters.     

Isotopes of hydrogen and oxygen in nitrogen hot springs of Baikal Rift Zone in terms of interaction in the water-rock system

The negative correlation between values δD and δ¹⁸O and concentrations of dissolved silicon in nitrogen hot springs is ascertained, which attests to the directed alteration of their hydroisotopic composition towards being depleted in heavy isotopes during interaction in the water-rock system. This fact can be allowed for the cases of the lighter isotopic composition of the hot springs of meteogenic origin relative to that of local atmospheric precipitation. The shifts in points of isotopic composition of hot springs from the global meteoric water line can be caused by alterations in either oxygen or hydrogen composition.     

Hydrochemistry of urban groundwater in Seoul, South Korea: effects of land-use and pollutant recharge

The ionic and isotopic compositions (δD, δ¹⁸O, and ³H) of urban groundwaters have been monitored in Seoul to examine the water quality in relation to land-use. High tritium contents (6.1–12.0 TU) and the absence of spatial/seasonal change of O–H isotope data indicate that groundwaters are well mixed within aquifers with recently recharged waters of high contamination susceptibility. Statistical analyses show a spatial variation of major ions in relation to land-use type. The major ion concentrations tend to increase with anthropogenic contamination, due to the local pollutants recharge. The TDS concentration appears to be a useful contamination indicator, as it generally increases by the order of forested green zone (average 151 mg/l), agricultural area, residential area, traffic area, and industrialized area (average 585 mg/l). With the increased anthropogenic contamination, the groundwater chemistry changes from a Ca–HCO₃ type toward a Ca–Cl(+NO₃) type. The source and behavior of major ions are discussed and the hydrochemical backgrounds are proposed as the basis of a groundwater management plan.     

Isotopic constraints on the origin of groundwater in the Ordos Basin of northern China

Despite its extreme aridity, the Ordos Basin in northern China is rich in groundwater. Many artesian wells or springs with large fluxes are utilized for drinking, irrigation and industrial production. In a search for the origin of the groundwater, a detailed investigation of the stable isotopes of oxygen and hydrogen in the local precipitation, the river water, the springs, the well water, as well as the soil water extracted from six soil profiles in the Ordos Basin, was carried out. The data show that δD, δ¹⁸O and TDS values of the river water are similar to those of groundwater, while the TDS values of the soil water are about ten times greater than those of groundwater. Furthermore, the mean isotopic compositions of the local precipitation are significantly higher than those of river water and groundwater. Based on the chloride mass balance method, the estimated recharge rates range from 5.2 to 17.2 mm/year, with a mean value of 10.5 mm/year. The results show that the main source of recharge of the groundwater in the Ordos Basin is not the local precipitation, but must come from a region where the precipitation is characterized by much lower δD and δ¹⁸O values. In addition, the groundwater in the Ordos Basin contains a component of mantle-derived ³He and crust-derived ⁴He suggesting that the groundwater may partly derive from flows through basement faults beneath the Ordos Basin.     

Groundwater recharge and flow in the Lower Cretaceous Nubian Sandstone aquifer in the Sinai Peninsula, using isotopic techniques and hydrochemistry

The present work was conducted in the Sinai Peninsula (1) to identify the recharge and flow characteristics and to evaluate the continuity of the Lower Cretaceous Nubian Sandstone aquifer; and (2) to provide information for the aquifer's rational appraisal. Isotopic and hydrochemical compositions combined with the geological and hydrogeological settings were used for this purpose. A considerable depletion in isotopic content (oxygen-18 and deuterium) and low d-excess values exist in the studied groundwater, reflecting the contribution of old meteoric water that recharged the aquifer in pluvial times. Modern recharge also occurs from precipitation that falls on the aquifer outcrops. The wide scatter of the data points around the two meteoric lines, the global meteoric water line (GMWL) and Mediterranean meteoric water line (MMWL), in the δ¹⁸O–δD diagram indicates considerable variation in recharge conditions (amount, altitude, temperature, air masses, distances from catchment, overland flow, etc.). The isotopic composition in the El-Bruk area is minimum (¹⁸O=–9.53‰), very close to the average value of the Western Desert Nubian Sandstone (¹⁸O=–10‰), where the local structural and lithologic conditions retard groundwater flow and the main bulk of water becomes noncyclic. The continuity of the aquifer in northern and central Sinai is evidenced by the isotopic similarity between samples taken from above and below the central Sinai Ragabet El-Naam fault, the distribution of potentiometric head, and hydrogeological cross sections. The combination of isotopic composition in terms of ¹⁸O and chemical composition in terms of TDS and salt contents is the basis for separating the studied groundwater into groups that reflect the recharge sources and isotopic and chemical modifications during flow. Electronic Publication     

Migration of recharge waters downgradient from the Santa Catalina Mountains into the Tucson basin aquifer, Arizona, USA

 Aquifers in the arid alluvial basins of the southwestern U.S. are recharged predominantly by infiltration from streams and playas within the basins and by water entering along the margins of the basins. The Tucson basin of southeastern Arizona is such a basin. The Santa Catalina Mountains form the northern boundary of this basin and receive more than twice as much precipitation (ca. 700 mm/year) as does the basin itself (ca. 300 mm/year). In this study environmental isotopes were employed to investigate the migration of precipitation basinward through shallow joints and fractures. Water samples were obtained from springs and runoff in the Santa Catalina Mountains and from wells in the foothills of the Santa Catalina Mountains. Stable isotopes (δD and δ¹⁸O) and thermonuclear-bomb-produced tritium enabled qualitative characterization of flow paths and flow velocities. Stable-isotope measurements show no direct altitude effect. Tritium values indicate that although a few springs and wells discharge pre-bomb water, most springs discharge waters from the 1960s or later. Received, February 1997 · Revised, September 1997 · Accepted, September 1997     

Oxygen and hydrogen isotopic ratios in groundwaters and river waters from India

A comprehensive set of measurements of oxygen and hydrogen isotopic ratios in groundwaters as well as waters from rivers, lakes, hot springs etc. taken from a variety of locations in India has been carried out for the first time. Isotopically the most depleted samples occur in the high altitude precipitations in the Himalayas e.g. in the lakes of Bhutan and the source water of the Ganga. The shallow groundwater data display a continental effect where the heavy isotope content decreases with distance from the coast (about 4 to 6 per mil decrease in δ¹⁸O per 1000 km). The δ D and δ¹⁸O of these fresh waters are linearly related and an analysis of this relation vis-a-vis the meteoric water line shows the unambiguous effect of enrichment due to evaporation from soils.     

Using chemical and microbiological indicators to track the impacts from the land application of treated municipal wastewater and other sources on groundwater quality in a karstic springs basin

Multiple chemical constituents (nutrients; N, O, H, C stable isotopes; 64 organic wastewater compounds, 16 pharmaceutical compounds) and microbiological indicators were used to assess the impact on groundwater quality from the land application of approximately 9.5 million liters per day of treated municipal sewage effluent to a sprayfield in the 960-km² Ichetucknee Springs basin, northern Florida. Enriched stable isotope signatures (δ¹⁸O and δ²H) were found in water from the effluent reservoir and a sprayfield monitoring well (MW-7) due to evaporation; however, groundwater samples downgradient from the sprayfield have δ¹⁸O and δ²H concentrations that represented recharge of meteoric water. Boron and chloride concentrations also were elevated in water from the sprayfield effluent reservoir and MW-7, but concentrations in groundwater decreased substantially with distance downgradient to background levels in the springs (about 12 km) and indicated at least a tenfold dilution factor. Nitrate-nitrogen isotope (δ¹⁵N–NO₃) values above 10 ‰ in most water samples were indicative of organic nitrogen sources except Blue Hole Spring (δ¹⁵N–NO₃ = 4.6–4.9 ‰), which indicated an inorganic source of nitrogen (fertilizers). The detection of low concentrations the insect repellent N,N-diethyl-metatoluamide (DEET), and other organic compounds associated with domestic wastewater in Devil’s Eye Spring indicated that leakage from a nearby septic tank drainfield likely has occurred. Elevated levels of fecal coliforms and enterococci were found in Blue Hole Spring during higher flow conditions, which likely resulted from hydraulic connections to upgradient sinkholes and are consistent with previoius dye-trace studies. Enteroviruses were not detected in the sprayfield effluent reservoir, but were found in low concentrations in water samples from a downgradient well and Blue Hole Spring during high-flow conditions indicating a human wastewater source. The Upper Floridan aquifer in the Ichetucknee Springs basin is highly vulnerable to contamination from multiple anthropogenic sources throughout the springs basin.     

Water—Rock Interaction in Tarim Basin：Constraints from Oilfield Water Geochemistry

Olifeld waters from Cenoxoic and Mesozoic terrestrial and Paleozoic marine environments in the Tarim Basin show no obvious difference in water chemistry except Br and isotopic compositions.The Paleozoic marine strata have higher Br concentrations than the terrestrial sediments,and the lack of obvious relationship between Br and I suggests that Br is not,for the most part,derived from the degradation of organic matter.The oilfield waters are characterized by high TDS(total dissolved solids),ranging from 120000mg/L to 320000mg/L relatively low Mg,high Ca,Sr,and CF relative to Br of evaporating seawater,suggestive of enhanced water-rock interaction,OAA(organic acid anions)concentrations are generally lower than 1500mg/L with high values occurring over the temperature range from 95℃ to 140℃,in the Cambrian to Jurassic systems,and nearby unconformities.Organic acids are considered to be generated mainly from thermal maturation of kerogens during progressive burial of the Jurassic-Triassic and Cambrian-Ordovician systems,biodegradation of crude oils nearby unconformities,and thermochemical sulfate reduction in part of the Cambrian and Ordovician strata.High Al concentrations up to 3mg/L to 5.5mg/L tend to occur in the waters of high OAA or petroleum-bearing intervals,suggesting the presence of organic complexing agents.Calculation by SOLMINEQ.88 with updated database shows that AlAc^2 may account for more than 30% of the total Al.Isotopic measurements(δD,δ18O)provide evidence for the following types of waters:diagenetically-modified connate meteoric water from the Jurassic and Triassic strata;diagenetically-modified connate marine water from the Cambrian and Ordovician strata;subaerially-evaporated water from the Cenozoic and Cretaceous strata;and mixed meteoric-evaporated or/and diagenetically modified connate water from the Carboniferous strata and reservoirs adjacent to the J/C and T/C unconformities.Those waters with very negative δD values from -51.30‰to-53.80‰(SMOW) and positive δ18O values from 2.99‰to 4.99‰(SMOW)in the continuous burial of the Cambrian-Ordovician system are explained to have resulted from hydrocarbon-water and water-rock interactions.     

Study of shallow groundwater quality evolution under saline intrusion with environmental isotopes and geochemistry

Evolution of the shallow groundwater quality under saline intrusion in porous aquifer system has been studied with environmental isotopes and geochemistry in the Laizhou Bay area, China. Two campaigns of water sampling from various sources were carried out in spring and winter for environmental isotopic and chemical analyses. The origin of groundwater salinity from intrusion of both modern seawater and deep brine water was identified by analysing the correlations between ¹⁸O, D, T, Cl⁻, SO₄²⁻ and electrical conductivity. The results indicate that the brine is originated from evaporating and concentrating of intruded seawater and its δD and δ¹⁸O are different from modern seawater but similar to those of mixture of seawater with fresh groundwater. It is hard to distinguish the salinity origin in this area by the δD–δ¹⁸O relationship alone. The relations between δ¹⁸O and conductivity, Cl⁻ and SO₄²⁻ have been used to identify the salinity origin due to the distinct difference in salinity between the brine and seawater, conjunctively with use of T. A threshold of T = 12 TU was adopted to identify the origin of saline groundwater.     

Changes of δ<Superscript>18</Superscript>O and δD along the Dousitu River,Inner Mongolia,China, and their evidence of river water evaporation

On the basis of the hydrogeology of the Dousitu River drainage basin, the changes of water flow rate, δ¹⁸O and δD along the Dousitu River are discussed according to measured and analytical results. Changes of flow rate along the Dousitu River agree well with groundwater level contours and the recharge and discharge of groundwater to the river. When compared with other types of water in the area, it is obvious that the ¹⁸O and D of river waters have experienced evaporation. The changes of δ¹⁸O and δD along the Dousitu River are mainly caused by combined effects of groundwater recharge and river water evaporation. The recharge of groundwater makes δ¹⁸O and δD of the river water decrease. Evaporation makes δ¹⁸O and δD of the river water increase. The evaporation fractions of the river water are calculated using the kinetic fractionation theory. Results showed as much as 10–30% of water was evaporated in different segments of Dousitu River.     

A hydrogeochemical survey of Kilimanjaro (Tanzania): implications for water sources and ages

Kilimanjaro, Tanzania, the highest mountain in Africa, has undergone extensive hydrologic changes over the past century in an area where water resources are critical. A hydrochemical and isotopic synoptic sampling program in January 2006 is used to characterize hydrogeology, hydrology, and water quality of the area. Samples were collected from the summit and southern side of Kilimanjaro and the Moshi region (Tanzania). Sample sources included four glaciers, seven groundwater wells, 12 rivers, 10 springs, precipitation, and a lake. Analyses included major ion chemistry, stable isotopes of water (¹⁸O and D); in addition, seven samples were analyzed for tritium. The samples generally have good water quality with the exception of three samples with elevated fluoride concentrations (>3 mg/L) and elevated nitrate concentrations (>2.5 mg/L NO₃ as N). There is a strong elevation control on stable isotopes, with an apparent elevation effect of – 0.1 ‰ δ¹⁸O per 100 m rise in elevation (R ² = 0.79). The results, including the tritium values, show that the hydrogeologic system is comprised of both local and regional flow systems, and that regional rivers are receiving significant inflow from shallow groundwater, and at very high elevations the hydrologic system is derived from groundwater, precipitation, and glacial melt water.     

The origin of salinity and sulphate contamination of groundwater in the Colima State, Mexico, constrained by stable isotopes

Chemical compositions and stable isotope ratios of water and sulphate were used to characterise sources and processes responsible for elevated concentrations of sulphate and other constituents in groundwater from aquifers at Colima State along Mexico’s Pacific Coast. The δ¹⁸O and δ²H values of the groundwater were similar to those of precipitation indicating a meteoric origin, and recharge processes are relatively uniform in large parts of the study area with only slight local evaporation effects. δ³⁴S_sulphate and δ¹⁸O_sulphate analyses indicated that high sulphate concentrations of up to 1,480 mg/l are mainly due to dissolution of evaporites and volcanic exhalations. Chloride is largely related to sources other than seawater. The Marabasco sub basin is affected by anthropogenic contamination through manganese and iron ore mining activities. The obtained knowledge regarding sources and areas of contamination will be essential for the development and design of a water quality monitoring program in the study area.     

Hydrochemical and isotopic evidence of recharge,apparent age,and flow direction of groundwater in Mayo Tsanaga River Basin,Cameroon: bearings on contamination

Unplanned exploitation of groundwater constitutes emerging water-related threats to MayoTsanaga River Basin. Shallow groundwater from crystalline and detrital sediment aquifers, together with rain, dams, springs, and rivers were chemically and isotopically investigated to appraise its evolution, recharge source and mechanisms, flow direction, and age which were used to evaluate the groundwater susceptibility to contamination and the basin’s stage of salinization. The groundwater which is Ca–Na–HCO₃ type is a chemically evolved equivalent of surface waters and rain water with Ca–Mg–Cl–SO₄ chemistry. The monsoon rain recharged the groundwater preferentially at an average rate of 74 mm/year, while surface waters recharge upon evaporation. Altitude effect of rain and springs show a similar variation of −0.4‰ for δ¹⁸O/100 m, but the springs which were recharged at 452, 679, and 773 m asl show enrichment of δ¹⁸O through evaporation by 0.8‰ corresponding to 3% of water loss during recharge. The groundwater which shows both local and regional flow regimes gets older towards the basins` margin with coeval enrichment in F⁻ and depletion in NO₃ ⁻. Incidentally, younger groundwaters are susceptible to anthropogenic contamination and older groundwaters are sinks of lithologenic fluoride. The basins salinization is still at an early stage.     

Fluid flow in marbles at Jervois, central Australia: oxygen isotope disequilibrium and zoning produced by decoupling of mineralogical and isotopic resetting

The Jervois region of the Arunta Inlier, central Australia, contains para- and orthogneisses that underwent low-pressure amphibolite facies metamorphism (P = 200–300 MPa, T = 520–600 °C). Marble layers cut by metre-wide quartz + garnet ± epidote veins comprise calcite, quartz, epidote, clinopyroxene, grandite garnet, and locally wollastonite. The marbles also contain locally discordant decimetre-thick garnet and epidote skarn layers. The mineral assemblages imply that the rocks were infiltrated by water-rich fluids (XCO₂ = 0.1–0.3) at ∼600 °C. The fluids were probably derived from the quartz-garnet vein systems that represent conduits for fluids exsolved from crystallizing pegmatites emplaced close to the metamorphic peak. At one locality, the marble has calcite (Cc) δ¹⁸O values of 9–18‰ and garnet (Gnt) δ¹⁸O values of 10–14‰. The δ¹⁸O(Gnt) values are only poorly correlated with δ¹⁸O(Cc), and the δ¹⁸O values of some garnet cores are higher than the rims. The isotopic disequilibrium indicates that garnet grew before the δ¹⁸O values of the rock were reset. The marbles contain  ≤15% garnet and, for water-rich fluids, garnet-forming reactions are predicted to propagate faster than O-isotopes are reset. The Sm-Nd and Pb-Pb ages of garnets imply that fluid flow occurred at 1750–1720 Ma. There are no significant age differences between garnet cores and rims, suggesting that fluid flow was relatively rapid. Texturally late epidote has δ¹⁸O values of 1.5–6.2‰ implying δ¹⁸O(H₂O) values of 2–7‰. Waters with such low-δ¹⁸O values are probably at least partly meteoric in origin, and the epidote may be recording the late influx of meteoric water into a cooling hydrothermal system. Received: 29 April 1996 / Accepted: 12 March 1997     

Temporal and spatial differences in salinity and water chemistry in SW Florida estuaries: Effects of human-impacted watersheds

Three estuaries near Naples, Florida with variably modified watersheds have been investigated to understand the chemical consequences of altering drainage patterns. Blackwater River (near natural drainage, control site), Henderson Creek (moderately modified watershed), and Faka-Union Canal (severe channelization) were sampled for temperature, salinity, δ¹⁸O, δ¹³C of dissolved inorganic carbon (DIC), molality of CO₂ (ΣCO₂), and Mg:Ca and Sr:Ca ratios between freshwater and marine water end members over a 17-mo period. Carbon isotope composition followed similar seasonal patterns as salinity. Freshwater and seawater end members are more negative than the global average, likely reflecting equilibration with local carbon sources derived from mangrove leaf litter and groundwater. δ¹³C responds to differences in primary productivity between estuaries. Henderson Creek has higher primary productivity than Blackwater River (probable due to higher sewage input and agricultural runoff) and has more positive δ¹³C and lower ΣCO₂. δ¹⁸O is affected by seasonal input of freshwater from atmospheric precipitation, evaporation, and groundwater. Late summer and fall rains lower the δ¹⁸O of estuarine water, whereas evaporative conditions in the dry season elevate δ¹⁸O to values that can be more positive upstream than those from the Gulf of Mexico (estuarine inversion). Evaporation produces water in the Gulf of Mexico that is >1‰ more positive than the global sea surface average most of the year. The very negative δ¹⁸O values in Blackwater River and Henderson Creek likely reflect atmospheric and groundwater contribution. Mg:Ca and Sr:Ca ratios of Gulf water from all three estuaries are similar to global averages at low latitudes. Freshwater end members among estuaries are different in that Blackwater River has higher ratios, suggesting a groundwater contribution. Dolomitic rocks in the subsurface likely provide a source of Mg ions.     

Geology and geochemistry of jasperoids from the Gold Bar district, Nevada

Gold Bar is one of several Carlin-type gold mining districts located in the Battle Mountain–Eureka trend, Nevada. It is composed of one main deposit, Gold Bar; five satellite deposits; and four resources that contain 1.6 Moz (50 t) of gold. All of the deposits and resources occur at the intersection of north-northwest- and northeast-trending high-angle faults in slope facies limestones of the Devonian Nevada Group exposed in windows through Ordovician basin facies siliciclastic rocks of the Roberts Mountains allochthon. Igneous intrusions and magnetic anomalies are notably absent. The Gold Bar district contains a variety of discordant and stratabound jasperoid bodies, especially along the Wall Fault zone, that were mapped and studied in some detail to identify the attributes of those most closely associated with gold ore and to constrain genetic models. Four types of jasperoids, J₀, J₁, J₂, and J₃, were distinguished on the basis of their geologic and structural settings and appearance. Field relations suggest that J₀ formed during an early event. Petrographic observations, geochemistry, and δ¹⁸O values of quartz suggest it was overprinted by the hydrothermal event that produced ore-related J₁, J₂, and J₃ jasperoids and associated gold deposits. The greater amount of siliciclastic detritus present in J₀ jasperoids caused them to have higher δ¹⁸O values than J_1,2,3 jasperoids hosted in underlying limestones. Ore-related jasperoids are composed of main-ore-stage replacements and late-ore-stage open-space filling quartz with variable geochemistry and an enormous range of δ¹⁸O values (24.5 and −3.7‰). Jasperoids hosted in limestones with the most anomalous Au, Ag, Hg, ±(As, Sb, Tl) concentrations and the highest δ¹⁸O values are associated with the largest deposits. The 28‰ range of jasperoid δ¹⁸O values is best explained by mixing between an ¹⁸O-enriched fluid and an ¹⁸O-depleted fluid. The positive correlation between the sizes of gold deposits and the δ¹⁸O composition of jasperoids indicates that gold was introduced by the ¹⁸O-enriched fluid. The lowest calculated δ¹⁸O value for water in equilibrium with late-ore-stage quartz at 200°C (−15‰) and the measured δD value of fluid inclusion water extracted from late-ore-stage orpiment and realgar (−116‰) indicate that the ¹⁸O-depleted fluid was composed of relatively unexchanged meteoric water. The source of the ¹⁸O-enriched ore fluid is not constrained. The δ³⁴S values of late-ore-stage realgar, orpiment, and stibnite (5.7–15.5‰) and barite (31.5–40.9‰) suggest that H₂S and sulfate were derived from sedimentary sources. Likewise, the δ¹³C and δ¹⁸O values of late-stage calcite (−4.8 to 1.5‰ and 11.5 to 17.4‰, respectively) suggest that CO₂ was derived from marine limestones. Based on these data and the apparent absence of any Eocene intrusions in the district, Gold Bar may be the product of a nonmagmatic hydrothermal system.     

Imprint of meteoric water on the stable isotope compositions of igneous and secondary minerals,Kap Edvard Holm Complex,East Greenland

 Hydrogen and oxygen isotope analyses have been made of hydrous minerals in gabbros and basaltic xenoliths from the Eocene Kap Edvard Holm intrusive complex of East Greenland. The analyzed samples are of three types: (1) primary igneous hornblendes and phlogopites that crystallized from partial melts of hydrothermally altered basaltic xenoliths, (2) primary igneous hornblendes that formed during late–magmatic recrystallization of layered gabbroic cumulates, and (3) secondary actinolite, epidote and chlorite that formed during subsolidus alteration of both xenoliths and gabbros. Secondary actinolite has a δ¹⁸O value of −5.8‰ and a δD value of −158‰. These low values reflect subsolidus alteration by low–δ¹⁸O, low–δD hydrothermal fluids of meteoric origin. The δD value is lower than the −146 to −112‰ values previously reported for amphiboles from other early Tertiary meteoric–hydrothermal systems in East Greenland and Scotland, indicating that the meteoric waters at Kap Edvard Holm were isotopically lighter than typical early Tertiary meteoric waters in the North Atlantic region. This probably reflects local climatic variations caused by formation of a major topographic dome at about the time of plutonism and hydrothermal activity. The calculated isotopic composition of the meteoric water is δD=−110 ± 10‰, δ¹⁸O ≈−15‰. Igneous hornblendes and phlogopites from pegmatitic pods in hornfelsed basaltic xenoliths have δ¹⁸O values between −6.0 and −3.8‰ and δD values between −155 and −140‰. These are both much lower than typical values of fresh basalts. The oxygen isotope fractionations between pegmatitic hornblendes and surrounding hornfelsic minerals are close to equilibrium fractionations for magmatic temperatures, indicating that the pegmatites crystallized from low–δ¹⁸O partial melts of xenoliths that had been hydrothermally altered and depleted in ¹⁸O prior to stoping. The pegmatitic minerals may have crystallized with low primary δD values inherited from the altered country rocks, but these values were probably overprinted extensively by subsolidus isotopic exchange with low–δD meteoric–hydrothermal fluids. This exchange was facilitated by rapid self–diffusion of hydrogen through the crystal structures. Primary igneous hornblendes from the plutonic rocks have δ¹⁸O values between +2.0 and +3.2‰ and δD values between −166 and −146‰. The ¹⁸O fractionations between hornblendes and coexisting augites are close to equilibrium fractionations for magmatic temperatures, indicating that the hornblendes crystallized directly from the magma and subsequently underwent little or no oxygen exchange. The hornblendes may have crystallized with low primary δD values, due to contamination of the magma with altered xenolithic material, but the final δD values were probably controlled largely by subsolidus isotopic exchange. This inference is based partly on the observation that coexisting plagioclase has been extensively depleted in ¹⁸O via a mineral–fluid exchange reaction that is much slower than the hydrogen exchange reaction in hornblende. It is concluded that all hydrous minerals in the study area, whether igneous or secondary, have δD values that reflect extensive subsolidus isotopic equilibration with meteoric–hydrothermal fluids. Received: 22 March 1994 / Accepted: 26 January 1995     

Recharge source and hydrogeochemical evolution of shallow groundwater in a complex alluvial fan system,southwest of North China Plain

Many cities around the world are developed at alluvial fans. With economic and industrial development and increase in population, quality and quantity of groundwater are often damaged by over-exploitation in these areas. In order to realistically assess these groundwater resources and their sustainability, it is vital to understand the recharge sources and hydrogeochemical evolution of groundwater in alluvial fans. In March 2006, groundwater and surface water were sampled for major element analysis and stable isotope (oxygen-18 and deuterium) compositions in Xinxiang, which is located at a complex alluvial fan system composed of a mountainous area, Taihang Mt. alluvial fan and Yellow River alluvial fan. In the Taihang mountainous area, the groundwater was recharged by precipitation and was characterized by Ca–HCO₃ type water with depleted δ¹⁸O and δD (mean value of −8.8‰ δ¹⁸O). Along the flow path from the mountainous area to Taihang Mt. alluvial fan, the groundwater became geochemically complex (Ca–Na–Mg–HCO₃–Cl–SO₄ type), and heavier δ¹⁸O and δD were observed (around −8‰ δ¹⁸O). Before the surface water with mean δ¹⁸O of −8.7‰ recharged to groundwater, it underwent isotopic enrichment in Taihang Mt. alluvial fan. Chemical mixture and ion exchange are expected to be responsible for the chemical evolution of groundwater in Yellow River alluvial fan. Transferred water from the Yellow River is the main source of the groundwater in the Yellow River alluvial fan in the south of the study area, and stable isotopic compositions of the groundwater (mean value of −8.8‰ δ¹⁸O) were similar to those of transferred water (−8.9‰), increasing from the southern boundary of the study area to the distal end of the fan. The groundwater underwent chemical evolution from Ca–HCO₃, Na–HCO₃, to Na–SO₄. A conceptual model, integrating stiff diagrams, is used to describe the spatial variation of recharge sources, chemical evolution, and groundwater flow paths in the complex alluvial fan aquifer system.