Water isotopic composition traces source and dynamics of water supply in a semi-arid agricultural landscape

Changes in seasonality and form of precipitation alter the structure and function of grassland and steppe ecosystems and pose challenges for land management and crop production in regions like the Northern Great Plains, North America. This research uses isotopic composition of water (δ¹⁸O and δ²H) to explore the sources and fate of soil water in lower-elevation agricultural areas of the Judith River watershed, in the headwaters of the Missouri River, USA. Extensive non-irrigated cereal crop production in this area occurs on well-drained soils and depends on careful water management. Our observations indicate that colder precipitation contributes isotopically distinct water to cultivated terrace soils relative to downgradient groundwaters and streams. Riparian waters also exhibit a higher fraction of contributions from colder precipitation relative to terrace groundwaters and streams. Apparent contributions from colder precipitation in terrace and riparian soil waters suggest that snowmelt is a key component of the water supply to these systems. Riparian waters also show evidence of evaporation suggesting that water spends sufficient time in some ponds and open channels in the riparian corridor to reflect fractionation by evaporation. The evolution of water isotopic composition from soils to shallow aquifers to stream corridors indicates source water partitioning as precipitation moves through this semi-arid agricultural landscape. The apparent mixing processes evident in this evolution reveal source water dynamics that are necessary to understand plant transpiration, solute processing, and contaminant leaching processes.     

Linking snowmelt‐derived fluxes and groundwater flow in a high elevation meadow system,Sierra Nevada Mountains,California

Quantifying snowmelt‐derived fluxes at the watershed scale within hillslope environments is critical for investigating local meadow scale groundwater dynamics in high elevation riparian ecosystems. In this article, we investigate the impact of snowmelt‐derived groundwater flux from the surrounding hillslopes on water table dynamics in Tuolumne Meadows, which is located in the Sierra Nevada Mountains of California, USA. Results show water levels within the meadow are controlled by a combination of fluxes at the hillslope boundaries, snowmelt within the meadow and changes in the stream stage. Observed water level fluctuations at the boundaries of the meadow show the hydrologic connection and subsequent disconnection between the hillslope and meadow aquifers. Timing of groundwater flux entering the meadow as a result of spring snowmelt can vary over 20 days based on the location, aspect, and local geology of the contributing area within the larger watershed. Identifying this temporal and spatial variability in flux entering the meadow is critical for simulating changes in water levels within the meadow. Model results can vary significantly based on the temporal and spatial scales at which watershed processes are linked to local processes within the meadow causing errors when boundary fluxes are lumped in time or space. Without a clear understanding of the surrounding hillslope hydrology, it is difficult to simulate groundwater dynamics within high elevation riparian ecosystems with the accuracy necessary for understanding ecosystem response. Copyright © 2010 John Wiley & Sons, Ltd.     

Geochronologic and paleomagnetic evidence defining the relationship between the Miocene Hiko and Racer Canyon tuffs, eccentric outflow lobes from the Caliente caldera complex, southeastern Great Basin, USA

 Outflow sheets of the Hiko tuff and the Racer Canyon tuff, which together extend over approximately 16 000 km² around the Caliente caldera complex in southeastern Nevada, have long been considered to be products of simultaneous or near-simultaneous eruptions from inset calderas in the west and east ends, respectively, of the caldera complex. New high-precision ⁴⁰Ar/³⁹Ar geochronology and paleomagnetic data demonstrate that emplacement of the uppermost part of the Racer Canyon tuff at 18.33±0.03 Ma was nearly synchronous with emplacement of the single outflow cooling unit of the much larger overlying Hiko tuff at 18.32±0.04 Ma. Based on comparison with the geomagnetic polarity time scale derived from the sea-floor spreading record, we conclude that emplacement of the first of several outflow cooling units of the Racer Canyon tuff commenced approximately 0.5 m.y. earlier. Only one paleomagnetic polarity is found in the Hiko tuff, but at least two paleomagnetic reversals have been found in the Racer Canyon tuff. The two formations overlap in only one place, at and near Panaca Summit northeast of the center of the Caliente caldera complex; here the Hiko tuff is stratigraphically above the Racer Canyon tuff. This study demonstrates the power of combining ⁴⁰Ar/³⁹Ar and paleomagnetic data in conjunction with phenocryst compositional modes to resolve problematic stratigraphic correlations in complex ash-flow sequences where use of one method alone might not eliminate ambiguities. Received: 13 January 1997 / Accepted: 7 May 1997     

Geochemical evidence for strong ongoing methanogenesis in Sanhu region of Qaidam Basin

Sanhu depression of Qaidam Basin is the largest biogenic gas production region in China.Headspace samples were collected from two wells in this region,and hydrogen and propylene compounds were detected in these samples with a certain concentration.The stable hydrogen isotope ratio of H 2 is relatively light (-700‰--820‰).The stable carbon isotope ratio of propylene ranges from -27‰ to -40‰,which coincides with the rule of change of the stable carbon isotope of kerogen at the corresponding horizon.The charac...     

Stable isotopic and geochemical identification of groundwater evolution and recharge sources in the arid Shule River Basin of Northwestern China

Stable isotopic (δD_VSMOW and δ¹⁸O_VSMOW) and geochemical signatures were employed to constrain the geochemical evolution and sources of groundwater recharge in the arid Shule River Basin, Northwestern China, where extensive groundwater extraction occurs for agricultural and domestic supply. Springs in the mountain front of the Qilian Mountains, the Yumen‐Tashi groundwater (YTG), and the Guazhou groundwater (GZG) were Ca‐HCO₃, Ca‐Mg‐HCO₃‐SO₄ and Na‐Mg‐SO₄‐Cl type waters, respectively. Total dissolved solids (TDS) and major ion (Mg²⁺, Na⁺, Ca²⁺, K⁺, SO₄^2?, Cl^? and NO₃^?) concentrations of groundwater gradually increase from the mountain front to the lower reaches of the Guazhou Basin. Geochemical evolution in groundwater was possibly due to a combination of mineral dissolution, mixing processes and evapotranspiration along groundwater flow paths. The isotopic and geochemical variations in melt water, springs, river water, YTG and GZG, together with the end‐member mixing analysis (EMMA) indicate that the springs in the mountain front mainly originate from precipitation, the infiltration of melt water and river in the upper reaches; the lateral groundwater from the mountain front and river water in the middle reaches are probably effective recharge sources for the YTG, while contribution of precipitation to YTG is extremely limited; the GZG is mainly recharged by lateral groundwater flow from the Yumen‐Tashi Basin and irrigation return flow. The general characteristics of groundwater in the Shule River Basin have been initially identified, and the results should facilitate integrated management of groundwater and surface water resources in the study area. Copyright © 2015 John Wiley & Sons, Ltd.     

Modern stable isotopic (δ18O, δ2H, δ13C) variation in terrestrial,fluvial, estuarine and marine waters from north‐central Sarawak,Malaysian Borneo

Stable isotope data on humid tropical hydrology are scarce and, at present, no such data exist for Borneo. Delta¹⁸O, δ²H and δ¹³C were analysed on 22 water samples from different parts of the Sungai (river) Niah basin (rain, cave drip, rainforest pool, tributary stream, river, estuary, sea) in north‐central Sarawak, Malaysian Borneo. This was done to improve understanding of the modern stable isotope systematics of the Sungai Niah basin, essential for the palaeoenvironmental interpretation of the Late Quaternary stable isotope proxies preserved in the Great Cave of Niah. The Niah hydrology data are put into a regional context using the meteoric water line for Southeast Asia, as derived from International Atomic Energy Agency/World Meteorological Organization isotopes in precipitation network data. Although the Niah hydrological data‐set is relatively small, spatial isotopic variability was found for the different subenvironments of the Sungai Niah basin. A progressive enrichment occurs towards the South China Sea (δ¹⁸O ?4·6‰; δ²H ?29·3‰; δ¹³C ?4·8‰) from the tributary stream (δ¹⁸O ?8·4‰; δ²H ?54·7‰; δ¹³C ?14·5‰) to up‐river (δ¹⁸O c. ?8‰; δ²H c. ?51‰; δ¹³C c. ?12‰) and down‐river values (δ¹⁸O c. ?7·5‰; δ²H c. ?45‰; δ¹³C c. ?11‰). This is thought to reflect differential evaporation and mixing of different components of the water cycle and a combination of depleted biogenic δ¹³C (plant respiration and decay) with enriched δ¹³C values (due to photosynthesis, atmospheric exchange, mixing with limestone and marine waters) downstream. Cave drip waters are relatively enriched in δ¹³C as compared to the surface waters. This may indicate rapid degassing of the cave drips as they enter the cave atmosphere. Copyright © 2005 John Wiley & Sons, Ltd.     

Spatial,seasonal, and source variability in the stable oxygen and hydrogen isotopic composition of tap waters throughout the USA

To assess spatial, seasonal, and source variability in stable isotopic composition of human drinking waters throughout the entire USA, we have constructed a database of δ¹⁸O and δ²H of US tap waters. An additional purpose was to create a publicly available dataset useful for evaluating the forensic applicability of these isotopes for human tissue source geolocation. Samples were obtained at 349 sites, from diverse population centres, grouped by surface hydrologic units for regional comparisons. Samples were taken concurrently during two contrasting seasons, summer and winter. Source supply (surface, groundwater, mixed, and cistern) and system (public and private) types were noted. The isotopic composition of tap waters exhibits large spatial and regional variation within each season as well as significant at‐site differences between seasons at many locations, consistent with patterns found in environmental (river and precipitation) waters deriving from hydrologic processes influenced by geographic factors. However, anthropogenic factors, such as the population of a tap's surrounding community and local availability from diverse sources, also influence the isotopic composition of tap waters. Even within a locale as small as a single metropolitan area, tap waters with greatly differing isotopic compositions can be found, so that tap water within a region may not exhibit the spatial or temporal coherence predicted for environmental water. Such heterogeneities can be confounding factors when attempting forensic inference of source water location, and they underscore the necessity of measurements, not just predictions, with which to characterize the isotopic composition of regional tap waters. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

Carbon stable isotopic composition of karst soil CO2 in central Guizhou, China

The δ¹³c values of soil CO₂ are less than that of atmosphere CO₂ in the karst area. On the soil-air interface, the δ¹³c vlaues of soil CO₂ decrease with the increase in soil depth; below the soil-air interface, the δ¹³c values of soil CO₂ are invariable. The type of vegetation on the land surface has an influence on the δ¹³C values of soil CO₂. Due to the activity of soil microbes, the δ¹³C values of soil CO₂ are variable with seasonal change in ps. Isotopic tracer indicates that atmosphere CO₂ has a great deal of contribution to soil CO₂ at the lower parts of soil proflie. Project supported by the National Natural Science Foundation of China (Grant Nos. 49703048 and 49833002)     

藏南普莫雍错流域水体离子组成与空间分布及其环境意义

对藏南普莫雍错湖水及其周围人湖河流水体进行了离子化学成分分析,对部分湖泊和河流水样作氧同位紊分析.结果显示,不同入湖河流离子组成与湖水本身离子组成有较大差异.湖水的主要离子组合是Mg2 -Ca2 -HCO3-SO42-,而主要补给河流加曲为Ca2 -Mg2 -HCO3-.加曲人湖河口2m水深以内水化学性质差异大,湖泊其他地区差异小.加曲对河口三角洲之上湖水影响显著.其他河流对河口处湖水影响较小.Gibbs图显示湖水离子的组成主要与流域内的岩石风化有关.离子比例和三角图分析说明控制入湖河水离子主要过程是碳酸盐、黄铁矿和硅酸盐风化.湖泊与河流水体离子的组成差异较大,原因可能是蒸发浓缩导致的CaCO3的沉淀.其结果有助于正确理解湖泊沉积碳酸盐的环境指示意义.     

Application of geochemical and stable isotopic tracers to investigate groundwater salinity in the Ochi-Narkwa Basin,Ghana

Rainwater, groundwater and soil-water samples were analysed to assess groundwater geochemistry and the origin of salinity in the Ochi-Narkwa basin of the Central Region of Ghana. The samples were measured for major ions and stable isotopes (δ¹⁸O, δ²H and δ¹³C). The Cl^? content in rainwater decreased with distance from the coast. The major hydrochemical facies were Na-Cl for the shallow groundwaters and Ca-Mg-HCO₃, Na-Cl and Ca-Mg-Cl-SO₄ for the deep groundwaters. Groundwater salinization is caused largely by halite dissolution and to a minor extent by silicate weathering and seawater intrusion. Stable isotope composition of the groundwaters followed a slope of 3.44, suggesting a mixing line. Chloride profiles in the soil zone revealed the existence of salt crusts, which support halite dissolution in the study area. A conceptual flow model developed to explain the mechanism of salinization showed principal groundwater flow in the NW–SE direction.

EDITOR D. Koutsoyiannis

ASSOCIATE EDITOR K. Heal     

Geochemical and Sm–Nd isotopic characteristics of metabasites from central Hainan Island, South China and their tectonic significance

Abstract   Major and trace elements and Sm–Nd isotopic data are presented for metabasites that are present as lenses within Paleozoic metasediments in the Chenxing and Bangxi regions, central Hainan Island, Southeast (SE) China. Most metabasites are metamorphosed cumulated gabbroic rocks tholeiitic in nature, and characterized by varying degrees of depletion in Th, Nb, Ta and light rare earth elements (LREE). Moreover, they show high positive ∈Nd(T) values of approximately +7, similar to those of mid-ocean ridge basalts (MORB). A Sm–Nd isochron age of 333 ± 12 Ma obtained for the metabasites is interpreted as their crystallization age. The combined geochemical and Sm–Nd isotopic data suggest that the metabasites were generated by dynamic partial melting from a MORB-like mantle source in an oceanic regime. These rocks probably represent remnants of fragmented oceanic crust of the eastern part of Paleo-Tethys. They were obducted onto the continental crust as part of the 'Shilu Mélange' in earliest Mesozoic time when southern Hainan (part of the Indochina block) collided with northern Hainan (part of South China). Alternatively, they could be formed in a volcanic rifted passive margin at the sea-floor spreading stage as part of MORB-like seaward-dipping reflector break-up packages.     

Evolution study of a regional groundwater system using hydrochemistry and stable isotopes in Songnen Plain,northeast China

Groundwater is often a critical source of water for municipal, industrial and agricultural uses, especially in arid and semi‐arid environments. Songnen Plain, located in the central part of northeast China, is such a region, it being an important productive base of commodity grain in this country. In the past two decades, groundwater quality in the region, especially salinization, has deteriorated under natural changes and human activities, and has become a crucial factor restricting sustainable eco‐environmental and socio‐economic development. In this paper, The Taoer River catchment, situated in the middle of the region, was selected as the study area for the groundwater quality evolution study using hydrochemistry and stable isotopes to obtain a better understanding of the system. Fifty‐two groundwater samples were collected with systematic design during the low‐water and high‐water periods in 2003. A series of comprehensive quality data interpretations, e.g. statistics, ratios of ions and Piper diagrams, together with stable isotope data, have been used to gain an insight into the spatial and temporal variations and evolution laws of groundwater hydrochemistry. The following main hydrochemical processes were identified as controlling the water quality of the groundwater system: weathering–dissolution, evaporation–condensation, ion‐exchange reactions and groundwater salinization. This latter process, salinization, is the most important process and is caused by the leaching of superficial or near‐surface salts from the saline–alkaline soil into shallow groundwater. Copyright © 2006 John Wiley & Sons, Ltd.     

Channel mobility drives a diverse stratigraphic architecture in the dryland Mojave River (California,USA)

The links between flood frequency and rates of channel migration are poorly defined in the ephemeral rivers typical of arid regions. Exploring these links in desert fluvial landscapes would augment our understanding of watershed biogeochemistry and river morphogenesis on early Earth (i.e. prior to the greening of landmasses). Accordingly, we analyse the Mojave River (California), one of the largest watercourses in the Great Basin of the western United States. We integrate discharge records with channel-migration rates derived from dynamic time-warping analysis and chronologically calibrated subsidence rates, thereby constraining the river's formative conditions. Our results reveal a slight downstream decrease in bankfull discharge on the Mojave River, rather than the downstream increase typically exhibited by perennial streams. Yet, the number of days per year during which the channel experiences bankfull or higher stages is roughly maintained along the river's length. Analysis of historical peak flood records suggests that the incidence of channel-formative events responds to modulation in watershed runoff due to the precipitation in the river's headwaters over decades to centuries. Our integrated analysis finally suggests that, while maintaining hydraulic geometries that are fully comparable with many other rivers worldwide, ephemeral desert rivers akin to the Mojave are capable of generating a surprisingly wide range of depositional geometries in the stratigraphic record. © 2020 John Wiley & Sons, Ltd.     

Elemental and isotopic signatures of particulate organic carbon in the Zengjiang River,southern China

Riverine total suspended sediment (TSS) at the lower reach section of the Zengjiang River, a low‐turbidity river in the southern China, was sampled on a 4‐week basis from March 2002 to February 2003. The gross TSS was divided into sedimentary and suspended fractions (SED and SUS) by the sedimentation method. Organic carbon and nitrogen, ¹⁴C and ¹³C were analysed using an elemental analyser and accelerator mass spectrometer respectively. The results show that particulate organic carbon (POC) yield is 0·8 × 10⁶ g km^?2 year^?1 in the Zengjiang River drainage basin, which is about one‐tenth of that in the Zhujiang (Pearl) River drainage basin. The C/N ratio demonstrates that aquatic biomass is the major contributor to POC in the Zengjiang River. The average share of aquatic biomass in the SUS‐fraction POC and SED‐fraction POC is about 88·89% and 62·76% respectively, with a substantial seasonal variation. δ¹³C values of SUS‐fraction POC (?26·56 to ? 22·89‰) is slightly lighter than that of SED‐fraction POC (?25·05 to ? 22·20‰), indicating that the contribution of aquatic biomass to δ¹³C values is more pronounced in the SUS‐fraction POC than in the SED‐fraction POC. The ‘bomb’–¹⁴C signature is not detected in the POC of Zengjiang River, and the contribution from geological organic carbon is very little. Δ¹⁴C values of the SED‐fraction POC vary from ? 44 to ? 223‰, and the Δ¹⁴C values of the SUS‐fraction POC vary from ? 33 to ? 165‰. For most paired samples, the SED‐fraction POC is generally more depleted in ¹⁴C than that of its counterpart SUS‐fraction POC. Compared with other small mountainous rivers, the ¹⁴C enrichment of POC in the Zengjiang River indicates slight drainage basin erosion. Copyright © 2006 John Wiley & Sons, Ltd.     

Geochemical characteristics and origin of gases from the Upper,Lower Paleozoic and the Mesozoic reservoirs in the Ordos Basin,China

The Ordos Basin,the second largest sedimentary basin in China,contains the broad distribution of natural gas types.So far,several giant gas fields have been discovered in the Upper and Lower Paleozoic in this basin,each having over 1000×10 8 m 3 of proven gas reserves,and several gas pools have also been discovered in the Mesozoic.This paper collected the data of natural gases and elucidated the geochemical characteristics of gases from different reservoirs,and then discussed their origin.For hydrocarbons preserved in the Upper Paleozoic,the elevatedδ13C values of methane,ethane and propane indicate that the gases would be mainly coal-formed gases;the singular reversal in the stable carbon isotopes of gaseous alkanes suggests the mixed gases from humic sources with different maturity.In the Lower Paleozoic,theδ13C 1 values are mostly similar with those in the Upper Paleozoic,but theδ13C 2 andδ13C 3 values are slightly lighter,suggesting that the gases would be mixing of coal-type gases as a main member and oil-type gases.There are multiple reversals in carbon isotopes for gaseous alkanes,especially abnormal reversal for methane and ethane(i.e.δ13C 1 >δ13C 2 ),inferring that gases would be mixed between high-mature coal-formed gases and oil-type gases.In the Mesozoic,the δ13Cvalues for gaseous alkanes are enriched in 12C,indicating that the gases are mainly derived from sapropelic sources;the carbon isotopic reversal for propane and butane in the Mesozoic is caused by microbial oxidation and mixing of gases from sapropelic sources with different maturity.In contrast to the Upper Paleozoic gases,the Mesozoic gases are characterized by heavier carbon isotopes of iso-butane than normal butane,which may be caused by gases generated from different kerogen types. Finally,according toδ13C 1 -Ro relationship and extremely low total organic carbon contents,the Low Paleozoic gases would not be generated from the Ordovician source as a main gas source,bycontrast, the Upper Paleozoic source as a main gas source is contributed to the Lower Paleozoic gases.     

Factors controlling diurnal variation in the isotopic composition of atmospheric water vapour observed in the taiga,eastern Siberia

Deciduous forest covers vast areas of permafrost under severe dry climate in eastern Siberia. Understanding the water cycle in this forest ecosystem is quite important for climate projection. In this study, diurnal variations in isotopic compositions of atmospheric water vapour were observed in eastern Siberia with isotope analyses of precipitation, sap water of larch trees, soil water, and water in surface organic layer during the late summer periods of 2006, 2007, and 2008. In these years, the soil moisture content was considerably high due to unusually large amounts of summer rainfall and winter snowfall. The observed sap water δ¹⁸O ranged from ?17.9‰ to ?13.3‰, which was close to that of summer precipitation and soil water in the shallow layer, and represents that of transpired water vapour. On sunny days, as the air temperature and mixing ratio rose from predawn to morning, the atmospheric water vapour δ¹⁸O increased by 1‰ to 5‰ and then decreased by about 2‰ from morning to afternoon with the mixing ratio. On cloudy days, by contrast, the afternoon decrease in δ¹⁸O and the mixing ratio was not observed. These results show that water vapour that transpired from plants, with higher δ¹⁸O than the atmospheric water vapour, contributes to the increase in δ¹⁸O in the morning, whereas water vapour in the free atmosphere, with lower δ¹⁸O, contributes to the decrease in the afternoon on sunny days. The observed results reveal the significance of transpired water vapour, with relatively high δ¹⁸O, in the water cycle on a short diurnal time scale and confirm the importance of the recycling of precipitation through transpiration in continental forest environments such as the eastern Siberian taiga. Copyright © 2012 John Wiley & Sons, Ltd.     

Identifying the origin of groundwater for water resources sustainable management in an arid oasis,China

ABSTRACT

Many oases are experiencing severe groundwater depletion due to increased population, expanding agriculture and economic development. For sustainable development, quantifying groundwater recharge resources are fundamentally important. In this study, stable isotope techniques were employed to identify recharge sources of groundwater and quantitatively evaluate their contribution ratios in the Dunhuang Oasis, northwest China. Our findings indicate that heavy isotopes in shallow groundwater are more negative than those in deep groundwater, which is attributed to shallow groundwater that was modern and deep groundwater that was old. Irrigated return water and lateral groundwater flow from the Qilian Mountains are considered as the two main sources of shallow groundwater, accounting for 35% and 65% of the total recharge, respectively. Thus, as the main groundwater source of the Dunhuang Oasis, the Qilian Mountain Front should be protected against over-exploitation. Our results provide not only fundamental knowledge for groundwater management of aquifers of the Oasis, but also valuable water management information for other similar arid oases worldwide.     

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.     

Geochemistry of water and gas discharges from the Mt. Amiata silicic complex and surrounding areas (central Italy)

The Mt. Amiata volcano in central Italy is intimately related to the post-orogenic magmatic activity which started in Pliocene times. Major, trace elements, and isotopic composition of thermal and cold spring waters and gas manifestations indicate the occurrence of three main reservoir of the thermal and cold waters in the Mt. Amiata region. The deepest one is located in an extensive carbonate reservoir buried by thick sequences of low-permeability allochthonous and neo-autochthonous formations. Thermal spring waters discharging from this aquifer have a neutral Ca-SO₄ composition due to the presence of anhydrite layers at the base of the carbonate series and, possibly, to absorption of deep-derived H₂S with subsequent oxidation to SO₄²⁻ in a system where pH is buffered by the calcite–anhydrite pair (Marini and Chiodini, 1994). Isotopic signature of these springs and N₂-rich composition of associated gas phases suggest a clear local meteoric origin of the feeding waters, and atmospheric O₂ may be responsible for the oxidation of H₂S. The two shallower aquifers have different chemical features. One is Ca-HCO₃ in composition and located in several sedimentary formations above the Mesozoic carbonates. The other one has a Na-Cl composition and is hosted in marine sediments filling many post-orogenic NW–SE-trending basins. Strontium, Ba, F, and Br contents have been used to group waters associated with each aquifer. Although circulating to some extent in the same carbonate reservoir, the deep geothermal fluids at Latera and Mt. Amiata and thermal springs discharging from their outcropping areas have different composition: Na-Cl and Ca-SO₄ type, respectively. Considering the high permeability of the reservoir rock, the meteoric origin of thermal springs and the two different composition of the thermal waters, self-sealed barriers must be present at the boundaries of the geothermal systems. The complex hydrology of the reservoir rocks greatly affects the reliability of geothermometers in liquid phase, which understimate the real temperatures of the discovered geothermal fields. More reliable temperatures are envisaged by using gas composition-based geothermometers. Bulk composition of the 67 gas samples studied seems to be the result of a continuous mixing between a N₂-rich component of meteoric origin related to the Ca-SO₄ aquifer and a deep CO₂-rich component rising largely along the boundaries of the geothermal systems. Nitrogen-rich gas samples have nearly atmospheric N₂/Ar (=83) and

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(δ=0‰) ratios whereas CO₂-rich samples show anomalously high

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values (up to +6.13 ‰), likely related to N₂ from metamorphic schists lying below the carbonate formations. On the basis of average

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isotopic ratio (

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around 0‰), CO₂ seems to originate mainly from thermometamorphic reactions in the carbonate reservoir and/or in carbonate layers embedded in the underlying metamorphic basement. Distribution of

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isotopic ratios indicates a radiogenic origin of helium in a tectonic environment that, in spite of the presence of many post-orogenic basins and mantle-derived magmatics, can presently be considered in a compressive phase.