TOC-Bestimmung in Schlämmen,Sedimenten und Schwebstoffen — Beschreibung des Verfahrens und begleitender Qualitätssicherungsmaßnahmen Determination of TOC in Sludge,Sediment and Suspended Solids — Description of the Analytical Procedure and Accompanying Quality Control Procedures

The total organic carbon (TOC) is calculated by subtracting the inorganic carbon (IC) from the total carbon (TC). For TC determination, the carbon in a sample is completely converted to CO₂ by decomposition/combustion in an oxygen stream. To determine IC, inorganic carbon (carbonate) is liberated by adding acid and by heating in an oxygen stream. In both cases, CO₂ is quantified by infrared spectrometry. To gain reliable and reproducable results for sludge, sediment and suspended solids, at least the following conditions have to be met: particle size has to be smaller than 200 μm; weightout has to be selected in such a way, that the signal area is not below and the signal maximum is not above specific instrument dependent parameters; combustion/decomposition has to be complete (TC: ≥ 1300 °C, no soot) and rules for analytical quality assurance must be followed. The TC quantification of calcium carbonate is used for system calibration. Daily working procedures include calibration checks by mean control charts for TC determination of calcium carbonate and IC determination of sodium carbonate as well as for control sediment TC and IC quantifications.     

Historical variations in autochthonous and allochthonous sediment supplies to the largest freshwater lake in Central India

Lacustrine sediment preserves high-resolution biogeochemical records of past variations in watershed processes controlling lake sedimentation. The current study explores historical variations in autochthonous and allochthonous sediment supplies to a large tropical freshwater lake system (Upper Lake, Bhopal) protected under the international Ramsar Convention of 2002 against anthropogenic pressures. For this purpose, multi-proxy biogeochemical data are presented for organic matter (total organic carbon, total nitrogen, phosphorous, and loss on ignition [LOI] at 550 °C), carbonate (LOI at 950 °C), lithic sediment (aluminum, titanium, iron, calcium, magnesium, sodium, potassium, manganese, zirconium, niobium, hafnium, tantalum, thorium, uranium, and rare earth elements), and anthropogenic inputs (lead) measured in a 38 cm long sediment core retrieved from the lake. In addition to the lacustrine sediment core, the samples of catchment bedrock, surface soils, major stream sediment, and eolian dust collected from the lake periphery also are analyzed. The systematic biogeochemical excursions in the upper core section (top ～8 cm) indicate increased anthropogenic inputs, watershed denudation by agricultural activities, artificially reduced fluvial sediment supply, relatively increased dust inputs and lake eutrophication in the last few decades. The current study underscores the roles of anthropogenic land-use and wetland conservation practices in the rapid alteration of autochthonous and allochthonous sediment supplies to open aquatic ecosystems. Further, rising lake eutrophication levels despite a managed reduction in allochthonous sediment supplies seem challenging to control due to dissolved nutrient supply from urban sewage discharge and runoff from agricultural land in the watershed.     

Melting relationships in CaO-CO2 and MgO-CO2 to 36 kilobars with comments on CO2 in the mantle

The melting curves of CaCO₃ and MgCO₃ have been extended to pressures of 36 kb by experiments in piston-cylinder apparatus. At 30 kb, the melting temperatures of calcite and magnesite are 1610°C and 1585°C, respectively. New data for the magnesite dissociation reaction permit the location of an invariant point for the assemblage magnesite + periclase + liquid + vapor near 26 kb-1550°C. New data are also presented for the calcite-aragonite transition at 800°C, 950°C and 1100°C. At pressures above 36–50 kb, calcite and magnesite melt at temperatures lower than the solidus of dry mantle peridotite. Natural and experimental evidence suggests that carbon dioxide in the Earth's mantle could be present in a variety of forms: (a) a free vapor phase, (b) vapor dissolved in silicate magma, (c) crystalline carbonate, (d) carbonatite liquid, (e) carbon-bearing silicate analogs, or (f) carbonato-silicates (such as scapolite, spurrite, tilleyite, and related compounds).     

On the use of loss‐on‐ignition techniques to quantify fluvial particulate organic carbon

The fluvial flux of carbon (C) from terrestrial to marine environments represents an important component of the global C‐cycle, which can transfer C from the atmosphere to sedimentary storage. Fluvial fluxes of C are also an essential resource for freshwater ecosystems, critical for habitat heterogeneity and function. As such it is crucial that we are able to quantify this flux accurately. However, at present there are a number of different techniques used to quantify concentrations of fluvial C, and these techniques vary in their accuracy. In this article, we compare particulate organic carbon (POC) measurements derived from two commonly‐used techniques; a simple combustion and loss‐on‐ignition (LOI) technique, and an oxidative–combustion and carbon dioxide (CO₂) detection technique. The techniques were applied to water samples collected from 10 contrasting reference‐condition, temperate river ecosystems. The POC measurements derived from the LOI technique were up to 16 times higher (average four times higher), than those derived from the oxidative–combustion and CO₂ detection technique. This difference was highly variable both across the different river ecosystems and within each river ecosystem over time, suggesting that there is no simple way of converting the mass measured by LOI to estimates of fluvial POC. It is suggested that the difference in POC measured by these two techniques is a consequence of: (1) the loss of inorganic carbon at LOI combustion temperatures of > 425 °C, (2) the potential during the LOI combustion stage to lose hygroscopic and intercrystalline water, not completely driven off by the drying stage at temperatures of < 150 °C, and (3) the variable C content of fluvial organic matter, meaning that the simple application of a fixed correction factor to values obtained from the LOI technique may not be appropriate. These findings suggest that oxidative–combustion and CO₂ detection techniques are preferential for quantifying fluvial POC. Copyright © 2013 John Wiley & Sons, Ltd.     

On the distribution of noble gases in Allende: a differential oxidation study

We have developed a closed-system combustion technique and utilized it to progressively oxidize a gas-rich, highly carbonaceous acid residue and a fine-grained (<4 μm) matrix sample from the Allende C3V meteorite and analyze the released gases mass spectrometrically. For the residue complete gas mobilization occurs at temperatures below 600°C. The temperature interval over which most of the gases are released coincides with that for combustion of most of the carbon. Release is primarily due to chemical attack rather than thermal activation of the gases. There are somewhat different oxidation thresholds for the heavy gases (Ar, Kr, and Xe) and the light gases (He, Ne), indicating chemically different sites for the two groups. Relative enhancement of isotopically anomalous components near 600°C is as large as in any open-system oxidation method. Differential combustion of the matrix sample reveals three distinct outgassing peaks, the first matching the release from the carbonaceous residue (“combustibles”), the second attributed to sulfides, and the third tentatively assigned to silicates. They comprise about 53%, 7% and 40% of the total heavy gases respectively. While the “sulfides” exhibit a small fission-like component, the Xe in the “silicates” appears isotopically uniform with roughly AVCC composition. The “combustibles” of the matrix contain relatively less excess¹²⁹Xe than the residue, perhaps indicating that ～10% of the total¹²⁹Xe in the residue was acquired from “silicates” by redistribution during acid treatment. We cannot rule out the possibility that planetary gases assigned to “sulfides” or “silicates” actually reside in carbonaceous phases somehow sheltered within soluble mineral assemblages, or in acid-soluble carbonaceous phases resistant to oxidation. Integrated releases below and above 600°C during the matrix combustion exhibit virtually identical heavy gas elemental composition, implying similar fractionation during planetary gas entrapment in various materials or in the same material in various environments.     

Isotope distribution of dissolved carbonate species in southeastern coastal aquifers of Sicily (Italy)

Concentrations of major ions and the δ¹³C composition of dissolved inorganic carbon in groundwater and submarine groundwater discharges in the area between Siracusa and Ragusa provinces, southeastern Sicily, representing coastal carbonate aquifers, are presented and discussed. Most of groundwater analysed belongs to calcium bicarbonate type, in agreement with the geological nature of carbonate host rocks. Carbonate groundwater acquires, besides the dissolution of carbonate minerals, dissolved carbon (and the relative isotopic composition) from the atmosphere and from soil biological activity. In fact, δ¹³C values and total dissolved inorganic carbon contents show that both these sources contribute to carbon dissolved species in the waters studied. Finally, mixing with seawater in the second main factor of groundwater mineralization Copyright © 2007 John Wiley & Sons, Ltd.     

柴达木盆地托素湖不同位置岩芯沉积物指标对比及其环境意义

湖泊不同位置岩芯沉积物相同代用指标的变化是否一致对于重建可靠的区域气候变化历史至关重要.目前多数研究仅利用深水区单一的沉积岩芯来反演区域的气候环境变化,对于不同位置岩芯重建结果的异同尚缺乏研究.本文选择托素湖不同位置、不同水深的4根短钻岩芯沉积物,在放射性核素(210 Pb和137 Cs)定年的基础上,对比分析各岩芯沉积物粒度、碳酸盐含量等代用指标的变化情况.结果显示,湖泊内相近的沉积岩芯沉积物粒度变化相似,但相距较远的岩芯之间粒度变化差异较大;浅水区的沉积物粒度(粒径或组分含量)在短时间尺度上变化很大,而深水区的沉积环境比较稳定,在百年尺度上的变化不明显;有机质与碳酸盐含量总体变化趋势一致且有较好的相关性,表明碳酸盐可能受到湖泊生产力的影响.碳酸盐含量、碳酸盐氧同位素(δ18 O)和TL06孔孢粉的A/C比值变化基本一致,反映的有效湿度变化与同期气象记录的相对湿度一致,但与降水量和蒸发量的变化不一致.因此,托素湖粒度指标仅指示不同位置钻孔沉积环境状况,与气候变化的关系并不明显,用碳酸盐及其同位素等地球化学指标恢复区域气候变化历史更可靠.     

Carbon and nutrients transfer from primary producers to lake sediments – A stoichiometric approach

We aimed to demonstrate different input of organic and inorganic carbon, nitrogen and phosphorus from three main groups of primary producers (phytoplankton, charophytes and vascular submerged macrophytes) to respective lake sediments. Studies were carried out in one eutrophic and two mesotrophic lakes. Samples of sediments were taken from profundal and from littoral zones, the latter divided into such overgrown by charophytes and others covered by vascular submerged macrophytes. We applied a stoichiometric approach to illustrate variable functional carbon to nutrients relationships. Among profundal sediments, the lowest organic to inorganic carbon ratio was found in sediments from the eutrophic lake due to precipitation of calcium carbonate during algal blooms. Extremely low inorganic carbon input to profundal sediment of one of the mesotrophic lakes may be explained by low phytoplankton production but also by dissolution of once deposited calcium carbonates. Charophyte-dominated littoral sediments contained significantly more inorganic carbon than other littoral and profundal sediments. Comparison of stoichiometric ratios between plant standing crop and underlying littoral sediments showed significant enrichment of sediments in nitrogen manifested by reduction of organic carbon to total nitrogen ratio during plant decomposition taking place both in charophyte and in vascular plant stands. We also attempted to divide phosphorus pool in sediments into organic P and calcium-bound P present in charophyte stands and in profundal sediments of eutrophic lake. In the former, calcium-bound P was estimated at 17–19 % of the total P pool while in profundal sediments it amounted 42 % of the total P. This difference suggests that calcium carbonate settling during algal blooms in a eutrophic lake may be more effective in P trapping than calcite encrustations covering charophyte plants in littoral sites. In conclusions, we underline the need of considering often neglected inorganic fractions of carbon and phosphorus to get better insight into carbon and nutrient burial in lake sediments.     

Age and intensity of thermal events by fission track analysis: The Ries impact crater

A thermal event reduces the number of previously registered fission tracks in a mineral dependent upon the track retention properties of the individual mineral. Apatite, sphene and zircon have retention properties over a wide range of temperatures (from 100° to 550°C); apatite data reveal information at lowest temperatures while sphene and zircon data are useful for higher temperatures.Thermal events within this temperature range of 100°C to about 550°C are suitable for study with this technique. The age of the event is determined from samples in which the fission tracks are completely erased, while minerals containing partially removed (erased) tracks provide information on the temperatures occurring during the thermal event.As a test case, the analysis of the temperatures developed by the meteorite impact which produced the Ries crater at 14.7 m.y. ago is presented.     

Oxidation of titanomagnetites in mafic and felsic intrusive rocks

We report opaque mineralogical observations and magnetic properties of primary titanomagnetites in Tertiary submarine gabbros from DSDP, Legs 30 and 37 and in a late Archean, continental granitic pluton, the Shelley Lake granite. The titanomagnetites and silicates in all the submarine gabbros have been deuterically oxidized. There is no indication of subsequent low-temperature oxidation, although serpentization of olivines is pervasive in the deeper Leg 37 units. The Leg 30 samples, from a single thick sill, contain abundant coarse (≈100 μm) titanomagnetites with fully developed ilmenite exsolution lamellae. Curie temperatures are 515–550°C; there are no low Curie temperatures that would indicate surviving unoxidized titanomagnetite. The unserpentinized Leg 37 gabbros contain scarce opaques with pure magnetite Curie points that are barely resolvable microscopically; most occur as inclusions in pyroxene. In the Shelley Lake granite, on the other hand, many samples exhibit bimodal blocking-temperature spectra, with blocking temperature peaks at 250–300°C and 550–575°C. The low-blocking-temperature phase is unidentified. No pyrrhotite was seen in thin section. Optically homogeneous grains coexist with fully exsolved neighbours, but the electron microprobe indicates no titanium. The lamellae appear to be haematite, not ilmenite, and the primary composition of the opaques is pure magnetite. The oxidation state of the opaques is very inhomogeneous, even on a fine scale.     

Are feldspar SAR protocols appropriate for post-IR IRSL dating?

Recently proposed post-infrared infrared stimulated luminescence (post-IR IRSL or pIR) dating protocols have largely overcome problems associated with anomalous fading and have become increasingly important for age determination of Quaternary sediments. Here, we investigate the suitability of the proposed post-IR IRSL protocols for accurate equivalent-dose estimation on K-feldspar extracts. Our research focuses on potential sensitivity changes between the natural signal and the first test dose signal in single-aliquot regenerative dose (SAR) procedures that are not detected and thus not corrected using test-dose responses.For these investigations, we employed the Single Aliquot Regeneration and Added dose (SARA) procedure, which combines equivalent-dose estimation with a dose recovery test. Results indicated that high-temperature preheats (>260 °C for 60 s) may induce a trapping sensitivity change in IRSL signals measured at low temperature (<100 °C). As this sensitivity change cannot be detected through test dose responses in the SAR protocol, it may result in an invalid equivalent-dose estimation. However, trapping sensitivity changes were not observed after low temperature preheats (<260 °C for 60 s), nor in pIR signals measured at elevated temperature (>100 °C) after a high temperature preheat. Our results indicate that the SAR protocol is appropriate for equivalent-dose determination using elevated-temperature pIR signals (e.g. pIR at 290 °C or multiple elevated temperature pIR at 250 °C). The SAR protocol may also be appropriate for equivalent-dose determination using low temperature pIR signals, provided that the combination of preheat and measurement temperature is carefully chosen to avoid the unwanted effects of sensitivity change during the first preheat.     

Reinvestigation and application of olivine-quartz-orthopyroxene barometry

Experiments in a piston-cylinder apparatus have been carried out at 700–1050°C, 10–16 kbar to determine the stability of ferrosilite (FeSiO₃) relative to fayalite + quartz. Reaction reversals within 0.1-kbar intervals locate the equilibrium at 10.5, 11.0, 11.5, 12.0, 12.6, 13.3, 14.1 and 14.8 kbar at 700, 750, 800, 850, 900, 950, 1000, and 1050°C, respectively, reflecting the intercept with the α-β quartz transition at about 880°C. The tight reversals severely constrain the reaction slope, providing a basis for limited extrapolation and calculations. However, the lack of accurate activity and cation-distribution data for orthopyroxene and olivine generates substantial uncertainties when considering the effects of large proportions of additional components such as MgO. Experiments and calculations indicate that additional components dramatically extend the pyroxene stability field and that pressures that have been inferred from ferrosilite-rich pyroxenes in natural assemblages are 1–3 kbar too high.     

Luminescence determination of firing temperature of archaeological pure sand related to ancient Dian bronze casting,China

In the present paper, we have investigated the thermal history of an archaeological ‘core sand’ from a cow-shaped bronze ornament attached to a cowrie container. It was unearthed at the Lijiashan site, located in southwest China, in the area of central Yunnan, and dates from the Han period (3 c. BC–2 c. AD). We compared the archaeological sample and a control sample of the modern quartz, examining the sensitivity of 110 °C TL and 210° C TL glow peaks, and sensitization characteristics of 110° C TL and OSL. Large differences between the ‘core sand’ samples and the control sand samples have been observed in our work. The firing temperature of the ‘core sand’ was determined to be 550–700 °C. The results offer a key to understanding the ‘core sand’ as a unique casting technique in Bronze Age Yunnan. These luminesence techniques form a new method for determining the historical firing temperature of archaeological material.     

Siliceous productivity changes in Gulf of Ancud sediments (42°S, 72°W), southern Chile,over the last ∼150 years

We evaluated changes in siliceous export production and the source of organic matter preserved in sediment core MD07-3109H recovered from the Gulf of Ancud, Chiloé Inner Sea (42°S, 72°W, water column depth: 328 m), southern Chile. We analyzed the abundance of siliceous microfossils (diatoms, silicoflagellates, sponge spicules, Chrysophyte cysts, phytoliths), geochemical proxies (weight percent silicon %Si_OPAL, organic carbon, total nitrogen, C/N molar), and sediment stable isotopes (δ¹³C_org, δ¹⁵N). Chronology based on ²¹⁰Pb and ¹⁴C provided an accumulated age of 144 years at the base of the core.Sediments of core MD07-3109H are predominantly marine in origin, averaging δ¹³C_org=–20.75‰±0.82, δ¹⁵N=8.7±0.35‰, and C/N=8.76±0.36. Marine diatoms compose 94% of the total assemblage of siliceous microfossils. Our record of productivity based on the mass accumulation rates of organic carbon, total nitrogen, Si_OPAL, and total diatoms showed high values between 1863 and 1869 AD followed by a declining trend until 1921 AD, a transition period from 1921 to 1959 AD with fluctuating values, and a clear decreasing pattern from 1960 AD to the present. This marked reduction in productivity was associated with decreased precipitation and Puelo River streamflow (41°S), as well as a warmer and more stratified water column, especially since the 1980s.     

Environmental records of carbon in recent lake sediments

Based on careful sampling and accurate analysis of recent sediments in Lake Chenghai, this paper discusses the staggered positive/negative correlation between organic carbon (OC) concentration and inorganic carbon (IC) concentration. The result indicates that temperature change, and its induced relative changes are the main factors affecting the relationship between IC concentration, δ¹³C of carbonate and OC concentration. When temperature and its induced photosynthesis strength change control autochthonous calcite precipitation, OC concentration is positively correlated with IC concentration and δ¹³C of carbonate. When temperature and its induced physical/chemical changes dominate, OC concentration displays negative correlation with IC concentration and δ¹³C of carbonate. IC concentration and δ¹³C of carbonate in sediments of Lake Chenghai are good proxies for climatic warm/cold changes.     

Quantifying the carbon source of pedogenic calcite veins in weathered limestone: implications for the terrestrial carbon cycle

The continent is the second largest carbon sink on Earth’s surface.With the diversification of vascular land plants in the late Paleozoic,terrestrial organic carbon burial is represented by massive coal formation,while the development of soil profiles would account for both organic and inorganic carbon burial.As compared with soil organic carbon,inorganic carbon burial,collectively known as the soil carbonate,would have a greater impact on the long-term carbon cycle.Soil carbonate would have multiple carbon sources,including dissolution of host calcareous rocks,dissolved inorganic carbon from freshwater,and oxidation of organic matter,but the host calcareous rock dissolution would not cause atmospheric CO2drawdown.Thus,to evaluate the potential effect of soil carbonate formation on the atmospheric p CO2level,different carbon sources of soil carbonate should be quantitatively differentiated.In this study,we analyzed the carbon and magnesium isotopes of pedogenic calcite veins developed in a heavily weathered outcrop,consisting of limestone of the early Paleogene Guanzhuang Group in North China.Based on the C and Mg isotope data,we developed a numerical model to quantify the carbon source of calcite veins.The modeling results indicate that4–37 wt%of carbon in these calcite veins was derived from atmospheric CO2.The low contribution from atmospheric CO2might be attributed to the host limestone that might have diluted the atmospheric CO2sink.Nevertheless,taking this value into consideration,it is estimated that soil carbonate formation would lower 1 ppm atmospheric CO2within 2000 years,i.e.,soil carbonate alone would sequester all atmospheric CO2within 1 million years.Finally,our study suggests the C–Mg isotope system might be a better tool in quantifying the carbon source of soil carbonate.     

Diamond formation in metal–carbonate interactions

Reduced silicon alloyed with Fe metal was shown to chemically react with FeCO₃ siderite at pressures of 10–25 GPa and temperatures of 1700–1800 °C according to2 FeCO_{3 siderite}+3 Si _{in metal}=2 Fe _{in metal}+3 SiO2 stishovite+2 C_diamondSince no carbon seeds were introduced, the only source of carbon for diamond formation was the carbonate phase. This observation provides a mechanism of diamond formation, possibly relevant to the early Earth. Thermodynamic modelling of the observed reactions shows that the stishovite/silicon oxygen fugacity buffer is far more reducing than the carbonate/diamond equilibrium, implying that, at Earth mantle conditions, no silicon-bearing metal can coexist with carbonates. Diamond formation by reactions between carbonates and highly reducing metal phases containing significant amounts of silicon might have occurred in the early Earth upon mixing of oxidized and reduced accretion components at pressures and temperature exceeding 10 GPa and 1700 °C.     

Lead isotopes and age of Hawaiian lherzolite nodules

The reaction between enstatite (En_95.3Fs_4.7) and CaCO₃ has been studied at pressures between 23 and 77 kbars and at temperatures between 800° and 1400°C. At 1000°C enstatite and CaCO₃ react to form dolomite and diopside solid solutions at pressures below approximately 45 kbars and magnesite and diopside solid solutions at higher pressures. The curve for the reaction dolomite_ss + enstatite_ss ? magnesite_ss + diopside_ss lies between 40 to 45 kbars at 1000°C and between 45 and 50 kbars at 1200°C. It is very close to the graphite-diamond transition curve. These experimental results indicate that calcite (or aragonite) is unstable in the presence of enstatite, and that dolomite and magnesite are the stable carbonates at high pressures. The forsterite + aragonite assemblage is, however, stable to at least 80 kbars at 800°C. It is suggested that in the upper mantle where enstatite is present, dolomite is stable to depths of about 150 km and magnesite is stable at greater depths in the continental regions, assuming that the partial pressure of CO₂ is equal or close to the total pressure. It is also suggested that carbonate inclusions in pyroxene can be used as an indicator of the depth of their equilibration; dolomite inclusions in enstatite would be formed at depths shallower than 150 km and magnesite inclusions in diopside at greater depths. Eclogite and peridotite inclusions in kimberlite may be classified on this basis.     

Measurements of thermal magnetic susceptibility of hematite and goethite

Magnetic susceptibility (MS) of natural specimens of hematite and goethite is studied under continuous heating with various additives: with carbon (sugar), nitrogen (carbamide), and elemental sulfur. It is found that heating of hematite with carbon above 450°C results in the formation of single-domain magnetite, while the magnetic susceptibility rises by a factor of 165. The increase in magnetic susceptibility on heating of hematite with nitrogen above 540°C reflects the generation of a single-domain maghemite with the Curie point of about 650°C, which is stable to heating. After the first heating, the magnetic susceptibility increases by 415 times. The subsequent cycle of thermal treatment results in the transition of maghemite to hematite, a decrease of MS, and an increase of coercivity. Heating with sulfur produces a stable single-domain magnetite at a temperature above the Curie point, which is manifested in the cooling curves. Here, the MS increases by a factor of 400. The heating curves for goethite exhibit a sharp drop in susceptibility to a temperature of 350–360°C, which reflects the transition of hematite to goethite. Heating of hematite with carbon produces stable maghemite at above 530°C, and with sulphur and nitrogen, it produces magnetite. When heated with pyrite, hematite reduces to magnetite under the action of sulfur released from pyrite.     

Experimental hydrogen isotope studies,II. Fractionations in the systems epidote-NaCl-H2O,epidote-CaCl2-H2O and epidote-seawater,and the hydrogen isotope composition of natural epidotes

The hydrogen isotope fractionation factors between epidote and aqueous 1 M and 4 M NaCl, 1 M CaCl₂ solutions, and between epidote and seawater, have been measured over the temperature range 250–550°C over which the degree of dissociation of dissolved species varies significantly. Measured fractionations at 350°C are decreased by up to 12‰, 9‰ and 7‰ relative to pure water in seawater, 1 M CaCl₂ and 1 M NaCl respectively, while above 500°C fractionations are not measurably dependent on fluid composition. Water—solution fractionation factors are derived which are generally applicable to the correction of mineral—water hydrogen isotope fractionations for the composition of the fluid phase.The hydrogen isotope compositions of natural epidotes are interpreted in the light of experimental fractionation data for situations where temperature, δD (fluid), and, in some cases, fluid chemistry, are independently known. Epidotes from active geothermal systems have hydrogen isotope quench temperatures consistent with or close to measured well temperatures unless the measured temperature has declined substantially since epidote formation or there is uncertainty in the D/H ratio of the water associated with the epidote because of isotopic heterogeneity in the well waters. Hydrothermal and metamorphic epidotes show closure temperatures of 175–225°C and 200–250°C. There is no evidence that retrograde metamorphic fluids, if present, are isotopically different from prograde fluids.The water-solution fractionations indicate strong solute-solvent interactions between 250 and 450°C and imply that both dissociated and associated species contribute to the fractionation effects through modification of the orientations and structure of the water molecules. Solute-solvent interactions become negligible at temperatures around 550°C.