Geochemistry of Quaternary travertines in the region north of Rome (Italy): structural, hydrologic and paleoclimatic implications

In the Tyrrhenian region of central Italy, late Quaternary fossil travertines are widespread along two major regional structures: the Tiber Valley and the Ancona-Anzio line. The origin and transport of spring waters from which travertines precipitate are elucidated by chemical and isotopic studies of the travertines and associated thermal springs and gas vents. There are consistent differences in the geochemical and isotopic signatures of thermal spring waters, gas vents and present and fossil travertines between east and west of the Tiber Valley. West of the Tiber Valley, δ¹³C of CO₂ discharged from gas vents and δ¹³C of fossil travertines are higher than those to the east. To the west the travertines have higher strontium contents, and gases emitted from vents have higher ³He/⁴He ratios and lower N₂ contents, than to the east. Fossil travertines to the west have characteristics typical of thermogene (thermal spring) origin, whereas those to the east have meteogene (low-temperature) characteristics (including abundant plant casts and organic impurities). The regional geochemical differences in travertines and fluid compositions across the Tiber Valley are interpreted with a model of regional fluid flow. The regional Mesozoic limestone aquifer is recharged in the main axis of the Apennine chain, and the groundwater flows westward and is discharged at springs. The travertine-precipitating waters east of the Tiber Valley have shallower flow paths than those to the west. Because of the comparatively short fluid flow paths and low (normal) heat flow, the groundwaters to the east of the Tiber Valley are cold and have CO₂ isotopic signatures, indicating a significant biogenic contribution acquired from soils in the recharge area and limited deeply derived CO₂. In contrast, spring waters west of the Tiber Valley have been conductively heated during transit in these high heat-flow areas and have incorporated a comparatively large quantity of CO₂ derived from decarbonation of limestone. The elevated strontium content of the thermal spring water west of the Tiber Valley is attributed to deep circulation and dissolution of a Triassic evaporite unit that is stratigraphically beneath the Mesozoic limestone. U-series age dates of fossil travertines indicate three main periods of travertine formation (ka): 220-240, 120-140 and 60-70. Based on the regional flow model correlating travertine deposition at thermal springs and precipitation in the recharge area, we suggest that pluvial activity was enhanced during these periods. Our study suggests that travertines preserve a valuable record of paleofluid composition and paleoprecipitation and are thus useful for reconstructing paleohydrology and paleoclimate.     

The origin,typology, spatial distribution and detrimental effects of the sinkholes developed in the alluvial evaporite karst of the Ebro River valley downstream of Zaragoza city (NE Spain)

Three types of sinkhole have been mapped in a 50 km² stretch of the Ebro River valley downstream of Zaragoza: large collapse sinkholes, large shallow subsidence depressions and small cover-collapse sinkholes. The sinkholes relate to the karstification of evaporitic bedrock that wedges out abruptly downstream, giving way to a shale substratum. Twenty-three collapse sinkholes, up to 50 m in diameter by 6 m deep, and commonly hosting saline ponds, have been identified in the floodplain. They have been attributed to the upward stoping of dissolutional cavities formed within the evaporitic bedrock by rising groundwater flows. Twenty-four large shallow subsidence depressions were mapped in the floodplain. These may reach 850 m in length and were formed by structurally controlled interstratal karstification of soluble beds (halite or glauberite? and gypsum) by rising groundwater flow and the progressive settlement of the overlying bedrock and overburden sediments. A total of 447 small cover-collapse, or dropout, sinkholes have been recognized in a perched alluvial level along the southern margin of the valley. These sinkholes result from the upward propagation of voids through the alluvial mantle caused by the downward migration of detrital sediments into dissolutional voids. The majority of these sinkholes, commonly 1·5–2 m in diameter, are induced by human activities. Over the karstic bedrock, there is a significant increase in sinkhole density downstream. This is interpreted as being a result of the evaporitic bedrock wedging out and the convergence of the groundwater flow lines in the karstic aquifer. The collapse sinkholes in this area, locally with a probability of occurrence higher than 140 sinkholes/km²/year, cause substantial damage to the linear infrastructures, buildings and agriculture, and they might eventually cause the loss of human lives. Copyright © 2006 John Wiley & Sons, Ltd.     

Mg isotopic composition of carbonate: insight from speleothem formation

Simultaneous high-precision measurement of ²⁴Mg, ²⁵Mg and ²⁶Mg isotopic compositions were made by multiple collector inductively coupled mass spectrometry (MC-ICP-MS) relative to the international standard SRM980. Data are presented on low-Mg calcite speleothems and their associated host rocks and waters from four caves, one in the French Alps and three in Israel, covering various climate conditions. In addition, data are presented on three dolostones and three limestones from the Himalaya. The overall variation is 4.13‰ and 2.14‰ in δ²⁶Mg and δ²⁵Mg, respectively. This is 35 times the uncertainty of the measurements and clearly demonstrates that the terrestrial isotopic composition of Mg is not unique. Each speleothem shows a characteristic range of δ²⁶Mg values that are attributed to the isotopic composition of the local water. Differences between the isotopic composition of Mg in the water dripping from stalactites and that of the modern speleothem are interpreted as being due to Mg isotopic fractionation during carbonate precipitation in the temperature range of 4-18°C. The low-Mg calcite is enriched in light isotopes by 1.35‰/AMU and the dependence on temperature has been found to be less than 0.02‰/AMU/°C. Despite various geological settings, the δ²⁶Mg of the studied dolostones is 2.0±1.2‰ higher than the δ²⁶Mg of the limestones. All together, these results suggest a strong mineralogical control and a weak temperature effect on the Mg isotopic composition of carbonate.     

Isotopic and hydrochemistry spatial variation of sulfate for groundwater characterization in karstic aquifers

The Sierra Gorda aquifer is one of the most extensive of southern Spain. The main groundwater discharge is produced at its northern boundary through several high‐flow springs. In this study, stable isotopes of dissolved sulfate (δ³⁴S and δ¹⁸O) and groundwater chemistry were used to determine the origin of the sulfate and to characterize the groundwater flow. We sampled the main springs, as well as other minor outlets related to perched water tables, in order to determine the different sources of SO₄^2? (e.g., dissolution of evaporites and atmospheric deposition). The substantial difference in the amount of dissolved SO₄^2? between the springs located in its northwestern part (≈25 mg/L) and those elsewhere in the northern part (≈60 mg/L) suggests zones with separate groundwater flow systems. A third group of springs, far from the northeastern boundary of the permeable outcrops, shows higher SO₄^2? content than the rest (≈125 mg/L). The isotopic range of sulfate (?0.3‰ to 14.82‰ V‐CTD) points to several sources, including dissolution of Triassic or Miocene evaporites, atmospheric deposition, and decomposition of organic material in the soil. Among these, the dissolution of Triassic gypsum—which overlies the saturated zone as a consequence of the folds and faults that deform the aquifer—is the main source of SO₄^2? (range from 12.79‰ to 14.82‰ V‐CTD). This range is typical for Triassic gypsum. The higher karstification in the western sector, together with important differences in the saturated thickness between the western and eastern sectors, would also be due to the tectonic structure and could explain the difference in SO₄^2? contents in the water. This singular arrangement may cause a higher residence time of groundwater in the eastern sector; thus, a higher contact time with Triassic evaporitic rocks is inferred. Accordingly, the stable isotopes of SO₄^2? are found to be a valuable tool for identifying areas with different flow systems in the saturated zone of karstic aquifers, as well as for evaluating aspects such as the degree of karstification .     

Natural gas seepage in the Gulf of Mexico

Hydrocarbon compositions and δ¹³C values for methane of fourteen natural seep gases and four underwater vents in the northwestern Gulf of Mexico are reported. The C₁/(C₂ + C₃) ratios of the seep gas samples ranged from 68 to greater than 1000, whereas δ_PDB¹³C values varied from ?39.9 to ?65.5‰. Compositions suggest that eleven of the natural gas seeps are produced by microbial degradation whereas the remaining three have a significant thermocatalytically produced component. Contradictions in the inferences drawn from molecular and isotopic compositions make strict interpretation of the origins of a few of the samples impossible.     

Stable isotope‐based mean catchment altitudes of springs in the Lebanon Mountains

Stable isotopes of water are known to provide information on mean altitudes of spring recharge areas, which is an important parameter for groundwater resources management especially in karstic environments. Very often, a lack of precipitation input data limits the possibility for an appropriate estimation of mean catchment altitudes. In the Jeita spring catchment, Lebanon, a characterization of precipitation input was possible with samples collected at six stations at varying altitudes (88 amount‐weighted monthly samples). A local meteoric water line for the Jeita spring catchment was characterized as δ²H = 6.04 * δ¹⁸O + 8.45 (R ² = .92) for a 2‐year observation period between October 2012 and September 2014. Integral samples from the snow layer were collected at 22 sites at altitudes ranging from 1,000 to 2,300 m above sea level at the end of February 2012 and February 2013, when snow height reached a maximum of more than 6 m at the highest peak in the catchment. Water samples were continuously collected from six springs (Jeita, Kashkoush, Labbane, Assal, Afqa, and Rouaiss). Jeita spring water samples were collected additionally in daily time steps during the snowmelt season in 2012. Mean isotope values of the sampled springs range from ?6.8‰ to ?8.2‰, and from ?33‰ to ?44‰, for δ¹⁸O and δ²H, respectively. The stable isotope data show that input variability (space and time, snow cover, and rainfall) has direct impacts on mean altitude estimates of spring catchments. A more profound interpretation of spring response to rainfall for six local springs in the Lebanon Mountains was possible in comparison to four earlier described springs collected in the Anti‐Lebanon Mountains in Syria.     

Using environmental isotopes to investigate the groundwater recharge mechanisms and dynamics in the North-eastern Basin,Palestine

ABSTRACT

This study aims to differentiate the potential recharge areas and flow mechanisms in the North-eastern Basin, Palestine. The results differentiate the recharge into three main groups. The first is related to springs and some of the deep wells close to the Anabta Anticline, through the Upper Aquifer (Turonian) formation, with depleted δ¹⁸O and δ²H. The second is through the Upper Cenomanian formation surrounding the Rujeib Monocline in the southeast, where the lineament of the Faria Fault plays an important role, with relatively enriched δ¹³C_DIC values of about ?4‰ (VPDB). The third is the Jenin Sub-series, which shows higher δ¹³C_DIC values, with enriched δ¹⁸O and δ²H and more saline content. The deep wells from the Nablus area in the south of the basin indicate low δ¹³C_DIC values due to their proximity to freshwater infiltrating faults. The deep wells located to the northwest of the basin have δ¹³C_DIC values from ?8 to ?9‰ (VPDB), with enriched δ¹⁸O signatures, indicating slow recharge through thick soil.     

Controls on Methane Occurrences in Aquifers Overlying the Eagle Ford Shale Play,South Texas

Assessing natural vs. anthropogenic sources of methane in drinking water aquifers is a critical issue in areas of shale oil and gas production. The objective of this study was to determine controls on methane occurrences in aquifers in the Eagle Ford Shale play footprint. A total of 110 water wells were tested for dissolved light alkanes, isotopes of methane, and major ions, mostly in the eastern section of the play. Multiple aquifers were sampled with approximately 47 samples from the Carrizo‐Wilcox Aquifer (250‐1200 m depth range) and Queen City‐Sparta Aquifer (150‐900 m depth range) and 63 samples from other shallow aquifers but mostly from the Catahoula Formation (depth <150 m). Besides three shallow wells with unambiguously microbial methane, only deeper wells show significant dissolved methane (22 samples >1 mg/L, 10 samples >10 mg/L). No dissolved methane samples exhibit thermogenic characteristics that would link them unequivocally to oil and gas sourced from the Eagle Ford Shale. In particular, the well water samples contain very little or no ethane and propane (C1/C2+C3 molar ratio >453), unlike what would be expected in an oil province, but they also display relatively heavier δ¹³C_methane (>?55‰) and δD_methane (>?180‰). Samples from the deeper Carrizo and Queen City aquifers are consistent with microbial methane sourced from syndepositional organic matter mixed with thermogenic methane input, most likely originating from deeper oil reservoirs and migrating through fault zones. Active oxidation of methane pushes δ¹³C_methane and δD_methane toward heavier values, whereas the thermogenic gas component is enriched with methane owing to a long migration path resulting in a higher C1/C2+C3 ratio than in the local reservoirs.     

Geology, ore deposits and hydrothermal venting in Bahía Concepción, Baja California Sur, Mexico

Abstract Bahía Concepción is located in the eastern coast of the Baja California peninsula and it is shaped by northwestern–southeastern normal faults. These are associated with a 12–6 Ma rifting episode, although some have been reactivated since the Pliocene. The most abundant rocks correspond to the arc related Comondú Group, Oligocene to Miocene, which forms a mainly calc‐alkaline volcanic and volcaniclastic sequence. There are less extensive outcrops of sedimentary rocks, lava flows, domes and pyroclastic rocks of Pliocene to Quaternary ages. The Neogene volcanism in the area indicates a shift from a subduction regime to an intraplate volcanism related to continental extension and the opening of an oceanic basin. The Bahía Concepción area contains numerous Mn ore deposits, being the biggest at El Gavilán and Guadalupe. The Mn deposits occur as veins, breccias and stockworks, and are composed by Mn oxides (pyrolusite, coronadite, romanechite), dolomite, quartz and barite. The deposits are hosted in volcanic rocks of the Comondú Group and, locally, in Pliocene sedimentary rocks. Thus, the Mn deposits formed between the Middle Miocene and the Pliocene. The mineralized structures are associated with Miocene northwestern–southeastern fault systems, which are analogous to those associated with the Cu‐Co‐Zn‐Mn deposits of El Boleo. The Bahía Concepción area also bears subaerial and submarine hot springs, which are associated with the same fault systems and host rocks. The submarine and subaerial geothermal manifestations south of the bay are possibly related with recent volcanism. The geothermal manifestations within the bay are intertidal hot springs and shallow submarine diffuse venting areas. Around the submarine vents (5–15 m deep, 87°C), Fe‐oxyhydroxide crusts with pyrite and cinnabar precipitate. In the intertidal vents (62°C), aggregates of opal, calcite, barite and Ba‐rich Mn oxides occur covered by silica‐carbonate stromatolitic sinters. Some 10–30 cm thick crustiform veins formed by chalcedony, calcite and barite are also found close to the vents. The hydrothermal fluids exhibit mixed isotopic compositions between δ¹⁸O‐enriched meteoric and local marine water. The precipitation of Ba‐rich Mn oxides around the vent sites could be an active analog for the processes that produced Miocene to Pliocene hydrothermal Mn‐deposits.     

Geochemistry and Provenance of Springs in a Baja California Sur Mountain Catchment

Fractured rock aquifers cover much of Earth's surface and are important mountain sites for groundwater recharge but are poorly understood. To investigate groundwater systematics of a fractured-dominated aquifer in Baja California Sur, Mexico, we examined the spatial patterns of aquifer recharge and connectivity using the geochemistry of springs. We evaluate a range of geochemical data within the context of two endmember hypotheses describing spatial recharge patterns and fracture connectivity. Hypothesis 1 is that the aquifer system is segmented, and springs are fed by local recharge. Hypothesis 2 is that the aquifer system is well connected, with dominant recharge occurring in the higher elevations. The study site is a small <15 km² catchment. Thirty-four distinct springs and two wells were identified in the study area, and 24 of these sites were sampled for geochemical analyses along an elevation gradient and canyon transect. These analyses included major ion composition, trace element and strontium isotopes, δ¹⁸O and δ²H isotopes, radiocarbon, and tritium. δ¹⁸O and δ²H isotopes suggest that the precipitation feeding the groundwater system has at least two distinct sources. Carbon isotopes showed a change along the canyon transect, suggesting that shorter flowpaths feed springs in the top of the transect, and longer flowpaths discharge near the bottom. Geochemical interpretations support a combination of the two proposed hypotheses. Understanding of the connectivity and provenance of these springs is significant as they are the primary source of water for the communities that inhabit this region and may be impacted by changes in recharge and use.     

Local vs. Regional Groundwater Flow Delineation from Stable Isotopes at Western North America Springs

The recharge location for many springs is unknown because they can be sourced from proximal, shallow, atmospheric sources or long‐traveled, deep, regional aquifers. The stable isotope (¹⁸O and ²H) geochemistry of springs water can provide cost‐effective indications of relative flow path distance without the expense of drilling boreholes, conducting geophysical studies, or building groundwater flow models. Locally sourced springs generally have an isotopic signature similar to local precipitation for that region and elevation. Springs with a very different isotopic composition than local meteoric inputs likely have non‐local recharge, representing a regional source. We tested this local vs. regional flow derived hypothesis with data from a new, large springs isotopic database from studies across Western North America in Arizona, Nevada, and Alberta. The combination of location‐specific precipitation data with stable isotopic groundwater data provides an effective method for flow path determination at springs. We found springs in Arizona issue from a mix of regional and local recharge sources. These springs have a weak elevation trend across 1588 m of elevation where higher elevation springs are only slightly more depleted than low elevation springs with a δ¹⁸O variation of 5.9‰. Springs sampled in Nevada showed a strong elevation‐isotope relationship with high‐elevation sites discharging depleted waters and lower elevation springs issuing enriched waters; only a 2.6‰ difference exists in ¹⁸O values over an elevation range of more than 1500 m. Alberta's springs are mostly sourced from local flow systems and show a moderate elevation trend of 1200 m, but the largest range in δ¹⁸O, 7.1‰.     

The hydrothermal system of Nevado del Ruiz volcano,Colombia

Hot springs and steam vents on the slopes of Nevado del Ruiz volcano provide evidence regarding the nature of hydrothermal activity within the summit and flanks of the volcano. At elevations below 3000 m, alkali-chloride water is discharged from two groups of boiling springs and several isolated warm springs on the western slope of Nevado del Ruiz. Chemical and isotopic geothermometers suggest that the boiling springs are fed by an aquifer having a subsurface equilibration temperature of at least 175°C, and the sampled warm spring is fed by an aquifer having a subsurface equilibration temperature near 150°C. Similarities in conservative solute ratios (e.g., B/Cl) indicate that the alkali-chloride waters may be related to a single reservoir at depth. Isotopic ratios of hydrogen and oxygen indicate that recharge for the alkali-chloride aquifers comes mostly from higher elevations on the volcano. Steam vents and steam-heated bicarbonate-sulfate springs at higher elevations, along a linear structural trend with the alkali-chloride springs, may be derived partly from the alkali-chloride water at depth by boiling. Steam from the vents (84°C) yields a gas geothermometer temperature of 209°C. Acid-sulfate-chloride and acid-sulfate waters are discharged widely from warm springs above 3000 m on the northern and eastern slopes of Nevado del Ruiz. Similarities in B/Cl and SO₄/Cl ratios suggest that the acid waters are mixtures of water from an acid-sulfate-chloride reservoir with various proportions of shallow, dilute groundwater. The major source of sulfate, halogens, and acidity for the acid waters may be high-temperature magmatic gases. Available data on hot spring temperatures and compositions indicate that they have remained fairly stable since 1968. However, the eruption of November 13, 1985 apparently caused an increase in sulfate concentration in some of the acid springs that peaked about a year after the eruption. Long-term monitoring of hot spring compositions over many years will be required to better define the effects of volcanic activity on the Nevado del Ruiz hydrothermal system.     

Carbonatitic volcanic ashes in Northern Tanganyika

In the Neogene volcanic province of Northern Tanganyika are surface limestones which cover large areas, despite variation and unsuitability of the bedrock. Field mapping has proved the existence of bedded carbonate tuffs dipping off Recent vents, and the field relationships and the trace element analyses prove the tuffs to be carbonatitic. Trace element analyses of some of the «surface limestones» show that they also have carbonatitic affinities, and the inference is that some, if not all, of the limestones are consolidated carbonatitic ashes. The presence of limestone in the area surrounding other carbonatite volcanoes is examined in the light of this evidence.     

Biogeochemical processes involving dissolved CO2 and CH4 at Albano, Averno, and Monticchio meromictic volcanic lakes (Central–Southern Italy)

This paper focuses on the chemical and isotopic features of dissolved gases (CH₄ and CO₂) from four meromictic lakes hosted in volcanic systems of Central–Southern Italy: Lake Albano (Alban Hills), Lake Averno (Phlegrean Fields), and Monticchio Grande and Piccolo lakes (Mt. Vulture). Deep waters in these lakes are characterized by the presence of a significant reservoir of extra-atmospheric dissolved gases mainly consisting of CH₄ and CO₂. The δ¹³C-CH₄ and δD-CH₄ values of dissolved gas samples from the maximum depths of the investigated lakes (from ?66.8 to ?55.6?‰ V-PDB and from ?279 to ?195?‰ V-SMOW, respectively) suggest that CH₄ is mainly produced by microbial activity. The δ¹³C-CO₂ values of Lake Grande, Lake Piccolo, and Lake Albano (ranging from ?5.8 to ?0.4?‰ V-PDB) indicate a significant CO₂ contribution from sublacustrine vents originating from (1) mantle degassing and (2) thermometamorphic reactions involving limestone, i.e., the same CO₂ source feeding the regional thermal and cold CO₂-rich fluid emissions. In contrast, the relatively low δ¹³C-CO₂ values (from ?13.4 to ?8.2?‰ V-PDB) of Lake Averno indicate a prevalent organic CO₂. Chemical and isotopic compositions of dissolved CO₂ and CH₄ at different depths are mainly depending on (1) CO₂ inputs from external sources (hydrothermal and/or anthropogenic); (2) CO₂–CH₄ isotopic exchange; and (3) methanogenic and methanotrophic activity. In the epilimnion, vertical water mixing, free oxygen availability, and photosynthesis cause the dramatic decrease of both CO₂ and CH₄ concentrations. In the hypolimnion, where the δ¹³C-CO₂ values progressively increase with depth and the δ¹³C-CH₄ values show an opposite trend, biogenic CO₂ production from CH₄ using different electron donor species, such as sulfate, tend to counteract the methanogenesis process whose efficiency achieves its climax at the water–bottom sediment interface. Theoretical values, calculated on the basis of δ¹³C-CO₂ values, and measured δ¹³C_TDIC values are not consistent, indicating that CO₂ and the main carbon-bearing ion species (HCO₃ ^?) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO₂ and CH₄. This study demonstrates that the vertical patterns of the CO₂/CH₄ ratio and of δ¹³C-CO₂ and δ¹³C-CH₄ are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO₂ input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes.     

Flow rates in the axial hot springs of the East Pacific Rise (21°N): Implications for the heat budget and the formation of massive sulfide deposits

The first in-situ measurements of flow rates in submarine hot springs (temperatures between 275° and 350°C) were made in the hot springs of the East Pacific Rise at 21°N during November, 1981. The flow rates ranged between 0.7 and 2.4 m/s. We estimate that the total rates at which heat and mass are transported from the three hot spring areas—OBS, National Geographic, and Southwest Vents—are ca. 2.2×10⁸ W and 150 kg of fluid/s respectively. The very high rate of heat loss precludes the existence of hot springs as steady state features of the East Pacific Rise at 21°N. We estimate that hot springs are active for a maximum of ca. 40,000 years. Chemical and/or mechanical clogging of the vents can drastically reduce the lifetime of the hot springs.Using a simple model of plume development [1], we calculated that less than 3% of the sulfide particles that are entrained in the hydrothermal plumes at 21°N settle from the plumes before dispersal by a lateral submarine current at a height of ca. 250 m above the seafloor [2]. The time that is required to form the sulfide mounds that surround the hot springs by the accumulation of sulfide particles that settle from the plumes is ca. 70–85 years. The current rate at which sulfide particles settle from the hydrothermal plumes and accumulate near the hot springs appears to be too small to lead to the formation of large massive sulfide deposits such as the Mavrouni deposit on Cyprus [3], within the time limits that are suggested by our thermal energy balance calculations.     

Geochemische und 13C/12C-isotopenchemische Untersuchung zur Herkunft der Kohlensäure in mineralhaltigen Wässern Nordhessens (Deutschland)

Geochemical and ¹³C/¹²C-isotopical Investigation of Mineral Waters in Northern Hessia (Germany) and the Origin of their CO₂ Content The dissolved carbonate originates from three sources: 1. biogenetic soil-CO₂, 2. volcanic CO₂ related to the evaporites of the Zechstein formation, and 3. carbonate derived from the dissolution of limestones and dolomites. Miocenic basaltic melts penetrated the evaporites of the Zechstein, and the related CO₂ was trapped in the intra- and intergranulars of the salt minerals. Circulating meteoric waters dissolve the salt minerals releasing CO₂ gas. Thus, the occurrence of basalt is related to the CO₂ contents of the evaporites, and the dissolution of only small amounts of salts rich in CO₂ may result in a high concentration of carbonic acid. In waters rich in carbonate, where volcanic CO₂ dominates over the other two sources of carbon, a δ¹³C-value of “salt-CO₂” of about –1‰ (PDB) is obtained. Water with less dissolved carbonate species have smaller quantities of salt-CO₂ down to about 20%.     

Characterizing spatial and temporal variation in 18O and 2H content of New Zealand river water for better understanding of hydrologic processes

Time series of hydrogen and oxygen stable isotope ratios (δ²H and δ¹⁸O) in rivers can be used to quantify groundwater contributions to streamflow, and timescales of catchment storage. However, these isotope hydrology techniques rely on distinct spatial or temporal patterns of δ²H and δ¹⁸O within the hydrologic cycle. In New Zealand, lack of understanding of spatial and temporal patterns of δ²H and δ¹⁸O of river water hinders development of regional and national-scale hydrological models. We measured δ²H and δ¹⁸O monthly, together with river flow rates at 58 locations across New Zealand over a two-year period. Results show: (a) general patterns of decreasing δ²H and δ¹⁸O with increasing latitude were altered by New Zealand's major mountain ranges; δ²H and δ¹⁸O were distinctly lower in rivers fed from higher elevation catchments, and in eastern rain-shadow areas of both islands; (b) river water δ²H and δ¹⁸O values were partly controlled by local catchment characteristics (catchment slope, PET, catchment elevation, and upstream lake area) that influence evaporation processes; (c) regional differences in evaporation caused the slope of the river water line (i.e., the relationship between δ²H and δ¹⁸O in river water) for the (warmer) North Island to be lower than that of the (cooler, mountain-dominated) South Island; (d) δ²H seasonal offsets (i.e., the difference between seasonal peak and mean values) for individual sites ranged from 0.50‰ to 5.07‰. Peak values of δ¹⁸O and δ²H were in late summer, but values peaked 1 month later at the South Island sites, likely due to greater snow-melt contributions to streamflow. Strong spatial differences in river water δ²H and δ¹⁸O caused by orographic rainfall effects and evaporation may inform studies of water mixing across landscapes. Generally distinct seasonal isotope cycles, despite the large catchment sizes of rivers studied, are encouraging for transit time analysis applications.     

Geothermal springs of the West Florida continental shelf: Evidence for dolomitization and radionuclide enrichment

On the sea bed of the West Florida continental shelf about 45 km SSW of Ft. Myers, Florida, an 85-km² area has been discovered in which six thermal springs discharge warm, chemically altered seawater from vents and seepage zones. The spring water apparently originates in the subsurface ocean around the Florida Platform and penetrates the highly porous strata of the platform about 500–1000 meters below sea level. It percolates toward the interior of the platform and is geothermally heated to about 40°C en route. Then it rises along more vertical flow channels and is discharged in warm submarine springs.Beneath the platform, several chemical processes alter the percolating seawater. One process seems to be a secondary dolomitization of the limestone of the platform because, in the discharging seawater, magnesium is lower by 2.7 mmole/kg and calcium higher by 3.6 mmole/kg than in normal seawater with the same chlorinity. Other reactions within the sediments of the platform enrich the spring effluents 1000-fold in²²⁶Ra, 10,000-fold in²²²Rn, and 90-fold in²²⁸Ra compared to the seawater surrounding the platform. Thus, the springs may be important sources of radionuclides for the Gulf of Mexico. The percolating seawater also loses all of its oxygen and nitrate to reduction processes, loses most of its phosphate and 40% of its²³⁸U, and roughly quadruples its silica content.Coastal carbonate platforms are fairly common geological features. Thus, processes like those beneath the West Florida Shelf may function on a world-wide basis to play an important role in the diagenesis of carbonate sediments.     

Springflow hydrographs: eogenetic vs. telogenetic karst

Matrix permeability in the range of 10(-11) to 10(-14) m(2) characterizes eogenetic karst, where limestones have not been deeply buried. In contrast, limestones of postburial, telogenetic karst have matrix permeabilities on the order of 10(-15) to 10(-20) m(2). Is this difference in matrix permeability paralleled by a difference in the behavior of springs draining eogenetic and telogenetic karst? Log Q/Q(min) flow duration curves from 11 eogenetic-karst springs in Florida and 12 telogenetic-karst springs in Missouri, Kentucky, and Switzerland, plot in different fields because of the disparate slopes of the curves. The substantially lower flow variability in eogenetic-karst springs, which results in the steeper slopes of their flow duration curves, also makes for a strong contrast in patterns (e.g., "flashiness") between the eogenetic-karst and telogenetic-karst spring hydrographs. With respect to both spring hydrographs and the flow duration curves derived from them, the eogenetic-karst springs of Florida are more like basalt springs of Idaho than the telogenetic-karst springs of the study. From time-series analyses on discharge records for 31 springs and published time-series results for 28 additional sites spanning 11 countries, we conclude that (1) the ratio of maximum to mean (Q(max)/Q(mean)) discharge is less in springs of eogenetic karst than springs of telogenetic karst; (2) aquifer inertia (system memory) is larger in eogenetic karst; (3) eogenetic-karst aquifers take longer to respond to input signals; and (4) high-frequency events affect discharge less in eogenetic karst. All four of these results are consistent with the hypothesis that accessible storage is larger in eogenetic-karst aquifers than in telogenetic-karst aquifers.