Mixing of magmatic CO2 into volcano groundwater flow at Aso volcano assessed combining carbon and water stable isotopes

To understand deep groundwater flow systems and their interaction with CO₂ emanated from magma at depth in a volcanic edifice, deep groundwater samples were collected from hot spring wells in the Aso volcanic area for hydrogen, oxygen and carbon isotope analyses and measurements of the stable carbon isotope ratios and concentrations of dissolved inorganic carbon (DIC). Relations between the stable carbon isotope ratio (δ¹³C_DIC) and DIC concentrations of the sampled waters show that magma-derived CO₂ mixed into the deep groundwater. Furthermore, groundwaters of deeper areas, except samples from fumarolic areas, show higher δ¹³C_DIC values. The waters' stable hydrogen and oxygen isotope ratios (δD and δ¹⁸O) reflect the meteoric-water origin of that region's deep groundwater. A negative correlation was found between the altitude of the well bottom and the altitude of groundwater recharge as calculated using the equation of the recharge-water line and δD value. This applies especially in the Aso-dani area, where deeper groundwater correlates with higher recharge. Groundwater recharged at high altitude has higher δ¹³C_DIC of than groundwater recharged at low altitude, strongly suggesting that magmatic CO₂ is present to a much greater degree in deeper groundwater. These results indicate that magmatic CO₂ mixes into deeper groundwater flowing nearer the magma conduit or chamber.     

Invasion of anthropogenic CO<Subscript>2</Subscript> recorded in planktonic foraminifera from the northern Gulf of Aqaba

The stable carbon isotopic composition of the planktonic foraminifera Globigerinoides sacculifer and G. ruber (white) and sedimentary organic matter from the northern Gulf of Aqaba have been investigated to estimate changes in ¹³C_DIC in surface waters during the last 1,000 years. The high sedimentation rates at the core sites (about 54 cm/Kyear) provide high temporal resolution (~10 years). Recent sediments at the top of the cores reflect conditions younger than 1950. The ¹³C records of the planktonic foraminifera from three multicores display similar trends, showing a uniform and consistent pattern before the 1750s, and a gradual decrease of approximately 0.63 over the last two centuries. This decrease seems to track the decrease of ¹³C_DIC in surface waters, which is mainly caused by the increase of anthropogenic input of ¹³C-depleted CO₂ into the atmosphere. Similarly, a trend towards lighter values of the carbon isotopic composition of sedimentary organic matter (¹³C_org) during the last 200 years supports the interpretation obtained from the planktonic foraminiferal ¹³C. Furthermore, direct measurements of seawater show that ¹³C of the dissolved inorganic carbon (DIC) in the northern Gulf of Aqaba has decreased by about 0.44 during the period 1979–2000. The average annual decrease is 0.021, which is similar to that observed globally. The ¹³C values of planktonic foraminifera combined with organic matter ¹³C from marine sediments are good indicators for reconstructing past changes in atmospheric CO₂ concentrations from the northern Gulf of Aqaba.     

Evolution of the Yunkai Terrane, South China: Evidence from SHRIMP zircon U–Pb dating, geochemistry and Nd isotope

The Yunkai Terrane is one of the most important pre-Devonian areas of metamorphosed supracrustal and granitic basement rocks in the Cathaysia Block of South China. The supracrustal rocks are mainly schist, slate and phyllite, with local paragneiss, granulite, amphibolite and marble, with metamorphic grades ranging from greenschist to granulite facies. Largely on the basis of metamorphic grade, they were previously divided into the Palaeo- to Mesoproterozoic Gaozhou Complex, the early Neoproterozoic Yunkai ‘Group’ and early Palaeozoic sediments. Granitic rocks were considered to be Meso- and Neoproterozoic, or early Palaeozoic in age. In this study, four meta-sedimentary rock samples, two each from the Yunkai ‘Group’ and Gaozhou Complex, together with three granite samples, record metamorphic and magmatic zircon ages of 443–430 Ma (Silurian), with many inherited and detrital zircons with the ages mainly ranging from 1.1 to 0.8 Ga, although zircons with Archaean and Palaeoproterozoic ages have also been identified in several of the samples. A high-grade sillimanite–garnet–cordierite gneiss contains 242 Ma metamorphic zircons, as well as 440 Ma ones. Three of the meta-sedimentary rocks show large variations in major element compositions, but have similar REE patterns, and have t_DM model ages of 2.17–1.91 Ga and ε_Nd (440 Ma) values of −13.4 to −10.0. Granites range in composition from monzogranite to syenogranite and record t_DM model ages of 2.13–1.42 Ga and ε_Nd (440 Ma) values of −8.4 to −1.2. It is concluded that the Yunkai ‘Group’ and Gaozhou Complex formed coevally in the late Neoproterozoic to early Palaeozoic, probably at the same time as weakly to un-metamorphosed early Palaeozoic sediments in the area. Based on the detrital zircon population, the source area contained Meso- to Neoproterozoic rocks, with some Archaean material. Palaeozoic tectonothermal events and zircon growth in the Yunkai Terrane can be correlated with events of similar age and character known throughout the Cathaysia Block. The lack of evidence for Palaeo- and Mesoproterozoic rocks at Yunkai, as stated in earlier publications, means that revision of the basement geology of Cathaysia is necessary.     

Hydrologic and climatic implications of stable isotope and minor element analyses of authigenic calcite silts and gastropod shells from a mid-Pleistocene pluvial lake, Western Desert, Egypt

Authigenic calcite silts at Wadi Midauwara in Kharga Oasis, Egypt, indicate the prolonged presence of surface water during the Marine Isotope Stage 5e pluvial phase recognized across North Africa. Exposed over an area of  4.25 km², these silts record the ponding of water derived from springs along the Libyan Plateau escarpment and from surface drainage. The δ¹⁸O values of these lacustrine carbonates (− 11.3‰ to − 8.0‰ PDB), are too high to reflect equilibrium precipitation with Nubian aquifer water or water of an exclusively Atlantic origin. Mg/Ca and Sr/Ca of the silts have a modest negative covariance with silt δ¹⁸O values, suggesting that the water may have experienced the shortest residence time in local aquifers when the water δ¹⁸O values were highest. Furthermore, intra-shell δ¹⁸O, Sr/Ca, and Ba/Ca analyses of the freshwater gastropod Melanoides tuberculata are consistent with a perennially fresh water source, suggesting that strong evaporative effects expected in a monsoonal climate did not occur, or that dry season spring flow was of sufficient magnitude to mute the effects of evaporation. The input of a second, isotopically heavier water source to aquifers, possibly Indian Ocean monsoonal rain, could explain the observed trends in δ¹⁸O and minor element ratios.     

Effects of nitrogen on the ecosystem respiration,CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O emissions to the atmosphere from the freshwater marshes in northeast China

Freshwater marshes could be a source of greenhouse gases emission because they contain large amounts of soil carbon and nitrogen. These emissions are strongly influenced by exogenous nitrogen. We investigate the effects of exogenous nitrogen on ecosystem respiration (CO₂), CH₄ and N₂O emissions from freshwater marshes in situ in the Sanjiang Plain Northeast of China during the growing seasons of 2004 and 2005, using a field fertilizer experiment and the static opaque chamber/GC techniques. The results show that there were no significant differences in patterns of seasonal variations of CO₂ and CH₄ among the fertilizer and non-fertilizer treatments, but the seasonal patterns of N₂O emission were significantly influenced by the exogenous nitrogen. Seasonal averages of the CO₂ flux from non-fertilizer and fertilizer were 987.74 and 1,344.35 mg m ⁻² h ⁻¹, respectively, in 2004, and 898.59 and 2,154.17 mg m ⁻² h ⁻¹, respectively, in 2005. And the CH₄ from the control and fertilizer treatments were 6.05 and 13.56 mg m ⁻² h ⁻¹ and 0.72 and 1.88 mg m ⁻² h ⁻¹, respectively, in 2004 and 2005. The difference of N₂O flux between the fertilizer and non-fertilizer treatments is also significant either in 2004 and 2005. On the time scale of 20-, 100-, and 500-year periods, the integrated global warming potential (GWP) of CO₂ + CH₄ + N₂O released during the two growing seasons for the treatment of fertilizer was 97, 94 and 89%, respectively, higher than that for the control, which suggested that the nitrogen fertilizer can enhance the GWP of the CH₄ and N₂O either in long time or short time scale.     

Zircon SHRIMP U–Pb and in-situ Lu–Hf isotope analyses of a tuff from Western Beijing: Evidence for missing Late Paleozoic arc volcano eruptions at the northern margin of the North China block

Zircon SHRIMP U–Pb and in-situ Lu–Hf isotopic analyses via laser ablation microprobe-inductively coupled plasma mass spectrometer (LAM-ICPMS) of a tuff within the Upper Paleozoic from Western Beijing were carried out to give new constraints on volcano eruption ages and source area of the tuffs within the North China block (NCB). SHRIMP U–Pb zircon dating of the tuff yielded a ²⁰⁶Pb/²³⁸U weighted mean age of 296 ± 4 Ma (95% confidence, MSWD = 3.3), which is very similar to the emplacement age of the newly discovered Carboniferous calc-alkaline, I-type continental arc granitoid plutons in the Inner Mongolia Paleo-uplift (IMPU) on the northern margin of the NCB. In-situ Lu–Hf analysis results of most zircons from the tuff yielded initial ¹⁷⁶Hf/¹⁷⁷Hf ratios from 0.282142 to 0.282284 and ε_Hf(t) values from − 15.9 to − 10.7. These Lu–Hf isotopic compositions are very similar to those of the Late Carboniferous granitoids in the IMPU, but are very different to those of the Central Asian Orogenic Belt (CAOB). Together with the sedimentary and tectonic analyses results, we inferred that the source area of the tuffs within the NCB is the IMPU instead of the CAOB. Therefore, some arc volcanoes once existed in the IMPU on northern margin of the NCB during the Late Carboniferous, but they were entirely eroded due to strong exhumation and erosion of the IMPU during the Late Carboniferous to Early Jurassic.     

Hydrochemical and isotope characteristics of spring water and travertine in the Baishuitai area (SW China) and their meaning for paleoenvironmental reconstruction

A method of combining hydrochemical data logging and in situ titrating with measurement of stable carbon and oxygen isotopes was used to reveal the hydrochemical and isotopic characteristics in the Baishuitai travertine scenic area of SW China. It was found that the travertine-forming springs have a very high concentration of calcium and bicarbonate, and accordingly very high CO₂ partial pressures, which are not likely to be produced by biological activity in soil alone. Further analysis of the stable carbon isotopes of the springs shows that the high pressure of CO₂ is mainly related to an endogenic CO₂ source. That means the Baishuitai travertine is endogenic in origin. This is contrast to the commonly accepted saying that the travertine deposition in this study simply is a product of warm and humid conditions in a karst ecological environment. Rapid CO₂ degassing from the water is triggered by the much higher partial pressures in water than that of the surrounding air. Consequently, as the waters flow downstream of the spring the pH increases, the waters become supersaturated with respect to calcite, and travertine is deposited. The preferential release of ¹²CO₂ to the atmosphere results in a progressive increase of travertine ¹³C downstream. This is concluded with a preliminary discussion of variation in travertine-forming water temperatures, according to differences in stable oxygen isotopic compositions of the travertine formed in different epochs at Baishuitai. It was found that the change in water temperature is as high as 13 °C, i.e., from 23 °C at about 2500 years b.p., to 10 °C at present. This may mainly reflect that the effect of geothermal source on water temperature is decreasing. The problems involved in paleoenvironmental reconstruction with endogene travertine are also discussed. They are the impacts of "dead carbon" in radiocarbon dating and the enrichment in ¹³C of travertine by endogenic CO₂ and degassing of CO₂ from water, which has to be considered in paleovegetation reconstruction when using ¹³C data of the endogene carbonate deposits.     

Detection of petroleum contamination in river sediments from Quebec City region using GC–IRMS

Isotopic analysis by compound specific gas chromatography–isotope ratio mass spectrometry (GC–IRMS) is used to detect and characterize petroleum pollution in surficial sediments along the St Lawrence River, near Quebec City. Unusually mature n-alkane distributions have been found in some recent intertidal sediments in the region. GC–IRMS results suggest that the n-alkanes are not derived from indigenous organic sources because they carry δ¹³C values between −30.0 and −27.0‰, as well as very small isotopic differences between odd and even numbered n-alkanes, which are both typically associated with petroleum products. Comparison of these sediments with bunker fuel, an oil used in the shipping industry, has shown a close isotopic correlation in some sites, which is further supported by biomarkers. Overall, the contamination has been dispersed along the river but is generally localized around the industrial region where hydrocarbon transfer from shore storage to ships takes place. This study illustrates how GC–IRMS can be used effectively in the detection and characterization of petroleum pollutants in sediments.     

First Reliable Re–Os Ages of Pyrite and Stable Isotope Compositions of Fe(‐Cu) Deposits in the Hami Region,Eastern Tianshan Orogenic Belt,NW China

The Eastern Tianshan Orogenic Belt (ETOB) in NW China is composed of the Dananhu–Tousuquan arc belt, the Kanggurtag belt, the Aqishan–Yamansu belt and the Central Tianshan belt from north to south. These tectonic belts have formed through arc–continent or arc–arc collisions during the Paleozoic. A number of Fe(‐Cu) deposits in the Aqishan–Yamansu belt, including the Heifengshan, Shuangfengshan and Shaquanzi Fe(‐Cu) deposits, are associated with Carboniferous–Early Permian volcanic rocks and are composed of vein‐type magnetite ores. Metallic minerals are dominated by magnetite and pyrite, with minor chalcopyrite. Calcite, chlorite, and epidote are the dominant gangue minerals. Pyrite separates of ores from those three deposits have relatively high and variable Re contents ranging from 3.7 to 184 ppb. All pyrite separates have very low common Os, allowing us calculation of single mineral model ages for each sample. Pyrite separates from the Heifengshan Fe deposit have an ¹⁸⁷Re–¹⁸⁷Os isochron age of 310 ± 23 Ma (MSWD = 0.04) and a weighted mean model age of 302 ± 5 Ma (MSWD = 0.17). Those from the Shuangfengshan Fe deposit have an isochron age of 295 ± 7 Ma (MSWD = 0.28) and a weighted mean model age of 292 ± 5 Ma (MSWD = 0.33). The Shaquanzi Fe‐Cu deposit has pyrite with an isochron age of 295 ± 7 Ma (MSWD = 0.26) and a weighted mean model age of 295 ± 6 Ma (MSWD = 0.23). Pyrite separates from these Fe(‐Cu) deposits have δ³⁴S_CDT ranging from ?0.41‰ to 4.7‰ except for two outliers. Calcite from the Heifengshan Fe deposit and Shaquanzi Fe‐Cu deposit have similar C and O isotope compositions with δ¹³C_PDB and δ¹⁸O_SMOW ranging from ?5.5‰ to ?1.0‰ and from 10‰ to 12.7‰, respectively. These stable isotopic data suggest that S, C, and O are magmatic‐hydrothermal in origin. The association of low‐Ti magnetite and Fe/Cu‐sulfides resembles those of Iron–Oxide–Copper–Gold (IOCG) deposits elsewhere. Our reliable Re–Os ages of pyrite suggest that the Fe(‐Cu) deposits in the Aqishan–Yamansu belt formed at ～296 Ma, probably in a back‐arc extensional environment.     

Variations of foliar carbon isotope discrimination and nutrient concentrations in Artemisia ordosica and Caragana korshinskii at the southeastern margin of China’s Tengger Desert

Seasonal variations in foliar stable carbon isotope discrimination (Δ) of Artemisia ordosica and Caragana korshinskii and correlations of foliar Δ with N, P, and K concentrations were studied under different planting regimes at the southeastern margin of China’s Tengger Desert. Foliar Δ, N, P, and K concentrations and the correlations of Δ with N, P, and K differed between the species and planting regimes. Foliar Δ, P and K concentrations in A. ordosica were markedly higher than in C. korshinskii, while foliar N concentrations in C. korshinskii was significantly higher than in A. ordosica. There were no significant differences in N, P, and K concentrations in C. korshinskii between planting regimes, but foliar Δ was significantly increased after June in mixed-species planting. In A. ordosica foliar N concentrations in mixed-species planting and foliar Δ in single-species planting were significantly higher than those of corresponding planting regimes. According to water-use efficiency (WUE) calculated based on foliar Δ, and on N, P, and K concentrations, C. korshinskii’s survival may profit from its higher WUE, whereas A. ordosica can avoid drought damage by its higher P and K concentrations in leaves in arid or semi-arid environments. The complex correlations of foliar Δ with foliar N, P and K suggested that water in C. korshinskii and water and P nutrition in A. ordosica were the key factors limiting their growth.     

Evidence of NAO control on subsurface ice accumulation in a 1200 yr old cave-ice sequence, St. Livres ice cave, Switzerland

Mid-latitude ice caves are assumed to be highly sensitive to climatic changes and thus represent a potentially interesting environmental archive. Establishing a precise chronology is, however, a prerequisite for the understanding of processes driving the cave-ice mass balance and thus allows a paleoenvironmental interpretation. At St. Livres ice cave (Jura Mountains, Switzerland), subfossil trees and organic material are abundant in the cave-ice deposit, therefore allowing the dating of individual ice layers. The dendrochronological analysis of 45 subfossil samples of Norway spruce (Picea abies (L.) Karst.) from the overhanging front of the ice outcrop as well as the dating of seven wood samples with ¹⁴C dating allowed for a reconstruction of the St. Livres cave-ice sequence and for the determination of periods of ice accumulation and ablation. Results suggest a maximal age of 1200 ± 50 ¹⁴C yr BP for the observed ice sequence and indicate the presence of four major deposition gaps dated to the 14th, 15th, mid-19th and late 19th century, which can be related with periods of positive North Atlantic Oscillation anomalies (NAO+) over the winter half-year and/or anthropogenic cave-ice abstraction. Similarly, there is evidence that periods of cave-ice accumulation as observed between AD 1877-1900 and AD 1393-1415 would correspond with phases of negative NAO indices. Cave ice represents therefore an original climate archive for the winter half-year and is complementary to other continental proxies recording preferentially summer conditions (e.g., tree rings, varves).     

Geochronology and Genesis of the Tiegelongnan Porphyry Cu(Au) Deposit in Tibet: Evidence from U–Pb,Re–Os Dating and Hf,S, and H–O Isotopes

The Tiegelongnan Cu (Au) deposit is the largest copper deposit newly discovered in the Bangong–Nujiang metallogenic belt. The deposit has a clear alteration zoning consisting of, from core to margin, potassic to propylitic, superimposed by phyllic and advanced argillic alteration. The shallow part of the deposit consists of a high sulphidation‐state overprint, mainly comprising disseminated pyrite and Cu–S minerals such as bornite, covellite, digenite, and enargite. At depth porphyry‐type mineralization mainly comprises disseminated chalcopyrite, bornite, pyrite, and a minor vein molybdenite. Mineralization is disseminated and associated with veins contained within the porphyry intrusions and their surrounding rocks. The zircon U–Pb ages of the mineralized diorite porphyry and granodiorite porphyry are 123.1 ± 1.7 Ma (2σ) and 121.5 ± 1.5 Ma (2σ), respectively. The molybdenite Re–Os age is 121.2 ± 1.2 Ma, suggesting that mineralization was closely associated with magmatism. Andesite lava (zircon U–Pb age of 111.7 ± 1.6 Ma, 2σ) overlies the ore‐bodies and is the product of post‐mineralization volcanic activity that played a critical role in preserving the ore‐bodies. Values of ?4.6 ‰ to + 0.8 ‰ δ³⁴S for the metal sulfides (mean ? 1.55 ‰) suggest that S mainly has a deep magmatic source. The H and O isotopic composition is (δD = ?87 ‰ to ?64 ‰; δ¹⁸O_H2O = 5.5 ‰ to 9.0 ‰), indicating that the ore‐forming fluids are mostly magmatic‐hydrothermal, possibly mixed with a small amount of meteoric water. The zircon ε_Hf(t) of the diorite porphyry is 3.7 to 8.3, and the granodiorite porphyry is 1.8 to 7.5. Molybdenite has a high Re from 382.2 × 10^?6 to 1600 × 10^?6. Re and Hf isotope composition show that Tiegelongnan has some mantle source, maybe the juvenile lower crust from crust–mantle mixed source. Metallogenesis of the Tiegelongnan giant porphyry system was associated with intermediate to acidic magma in the Early Cretaceous (~120 Ma). The magma provenance of the Tiegelongnan deposit has some mantle‐derived composition, possibly mixed with the crust‐derived materials.     

The variations of stable carbon isotope ratio of land plant-derived n-alkanes in deep-sea sediments from the Bering Sea and the North Pacific Ocean during the last 250,000 years

Two piston cores, one located far from the continents (The North Pacific Ocean: ES core), and another located comparatively closer to the continents (The Bering Sea: BOW-8a core) were investigated to reconstruct environmental changes on source land areas. The results show significant contribution of terrestrial organic matter to sediments in both cores. The δ¹³C values of n-C₂₇, n-C₂₉, and n-C₃₁ alkanes in sediments from the North Pacific ES core show significant glacial to interglacial variation whereas those from the Bering Sea core do not. Variations of δ¹³C values of land plant n-alkanes are related to the environmental or vegetational changes in the source land areas. Environmental changes, especially, aridity, rainfall, and pCO₂ during glacial/interglacial transitional periods can affect vegetation, and therefore C₃ / C₄ plant ratios, resulting in δ¹³C changes in the preserved land plant biomarkers. Maximum values of δ¹³C as well as maximum average chain length values of long chain n-alkanes in the ES core occur mostly at the interglacial to glacial transition zones reflecting a time lag related to incorporation of living organic matter into soil and transportation into ocean basins via wind and/or ability of C₄ plants to adapt for a longer period before being replaced by C₃ plants when subjected to gradual climatic changes. Irregular variations with no clear glacial to interglacial trends in the BOW-8a core may result from complex mixture of aerosols from westerly winds and riverine organic matter from the Bering Sea catchments. In addition, terrestrial organic matter entering the Bering Sea could originate from multiple pathways including eolian, riverine, and ice rafted debris, and possibly be disturbed by turbidity and other local currents which can induce re-suspension and re-sedimentation causing an obliterated time relation in the Bering Sea biomarker records.     

Role of fluid mixing and wallrock sulfidation in gold mineralization at the Semna mine area, central Eastern Desert of Egypt: Evidence from hydrothermal alteration, fluid inclusions and stable isotope data

The Semna gold deposit is one of several vein-type gold occurrences in the central Eastern Desert of Egypt, where gold-bearing quartz veins are confined to shear zones close to the boundaries of small granitoid stocks. The Semna gold deposit is related to a series of sub-parallel quartz veins along steeply dipping WNW-trending shear zones, which cut through tectonized metagabbro and granodiorite rocks. The orebodies exhibit a complex structure of massive and brecciated quartz consistent with a change of the paleostress field from tensional to simple shear regimes along the pre-existing fault segments. Textural, structural and mineralogical evidence, including open space structures, quartz stockwork and alteration assemblages, constrain on vein development during an active fault system. The ore mineral assemblage includes pyrite, chalcopyrite, subordinate arsenopyrite, galena, sphalerite and gold. Hydrothermal chlorite, carbonate, pyrite, chalcopyrite and kaolinite are dominant in the altered metaggabro; whereas, quartz, sericite, pyrite, kaolinite and alunite characterize the granodiorite rocks in the alteration zones. Mixtures of alunite, vuggy silica and disseminated sulfides occupy the interstitial open spaces, common at fracture intersections. Partial recrystallization has rendered the brecciation and open space textures suggesting that the auriferous quartz veins were formed at moderately shallow depths in the transition zone between mesothermal and epithermal veins.Petrographic and microthermometric studies aided recognition of CO₂-rich, H₂O-rich and mixed H₂O–CO₂ fluid inclusions in the gold-bearing quartz veins. The H₂O–CO₂ inclusions are dominant over the other two types and are characterized by variable vapor: liquid ratios. These inclusions are interpreted as products of partial mixing of two immiscible carbonic and aqueous fluids. The generally light δ³⁴S of pyrite and chalcopyrite may suggest a magmatic source of sulfur. Spread in the final homogenization temperatures and bulk inclusion densities are likely due to trapping under pressure fluctuation through repeated fracture opening and sealing. Conditions of gold deposition are estimated on basis of the fluid inclusions and sulfur isotope data as 226–267 °C and 350–1100 bar, under conditions transitional between mesothermal and epithermal systems.The Semna gold deposit can be attributed to interplay of protracted volcanic activity (Dokhan Volcanics?), fluid mixing, wallrock sulfidation and a structural setting favoring gold deposition. Gold was transported as Au-bisulfide complexes under weak acid conditions concomitant with quartz–sericite–pyrite alteration, and precipitated through a decrease in gold solubility due to fluid cooling, mixing with meteoric waters and variations in pH and fO₂.