REVIEW OF THALLIUM,ITS GEOCHEMISTRY,MINERALOGY, PRINCIPAL GENETIC TYPES OF DEPOSITS,AND GEOCHEMICAL PROVINCES BY V.V. IVANOV,V.YU. VOLGIN,A.A. KRASNOV AND N.V. LIZUNOV

This book review takes the authors to task for omitting numerous references when they wrote this first comprehensive work on thallium. Among the omissions noted are; 1) the extreme toxicity of thallium; 2) the occurrence of thallium in various minerals:

REVIEW OF THALLIUM, ITS GEOCHEMISTRY, MINERALOGY, PRINCIPAL GENETIC TYPES OF DEPOSITS, AND GEOCHEMICAL PROVINCES BY V.V. IVANOV, V.YU. VOLGIN, A.A. KRASNOV AND N.V. LIZUNOV

All authors

V. V. Mogarovskiy

https://doi.org/10.1080/00206816409473950

Published online:

20 September 2010

Table     

CONTRIBUTION TO THE DESCRIPTION OF THE AKTAS FAULT ZONE,CENTRAL KAZAKHSTAN

Vernadskiy's views on the origin of oil, as originally expressed in 1924 in the first French edition of Geochemistry and more extensively in his Essays in Geochemistry (especially in the fourth or second Russian edition, 1934), are evaluated and praised in light of more recent information. The principal reference is the second Russian edition, in six essays. The several points of Vernadskiy's thesis, that oil is of organic origin, are noted and discussed with reference to data more extensive than that available to him. Vernadskiy's interest in the origin of oil was subordinate to his major interest in the geochemistry of carbon and its history in the crust, and in biogeochemistry — the role of living matter in the development of the upper geosphere. To him the emergence of oil was “one of the momentous manifestations of a transfer of solar energy to deeper reaches of our planet, by means of living substance.” Vernadskiy, in light of Trask's work, even conceded the possibility of oil originating from organic matter of continental fresh-water basins. He read widely in his field and appreciated the need for understanding the history of thought on the subject. The organic theory, he strongly believed, was born in 1763 with the publication of Lomonosov's On Terrestrial Layers. — W.D. Lowry.     

Electronic Microprobe Analysis and Scanning Electronic Microscopy in Geology, by S. J. B. Reed. Cambridge University Press, Cambridge, 1996. Hardback: {pound}50. Paperback: {pound}17.95.

Anyone in the Earth Sciences community involved in the trainingof postgraduate students new to electron microprobe and scanningelectron microscope instrumentation has, in the past, alwayshad problems answering the inevitable question regarding textsthat the student may study. There are a number of excellentbooks that could be recommended. Chapman (1986), Goldstein etal. (1992), Scott et al. (1995) and, dare I say it, Reed (1993)would feature on any reading list. Unfortunately, other thanChapman (1986), such books are for the specialist. They aretheoretical, comprehensively detailed, and highly numerical.When practical aspects are discussed (as in Goldstein et al.)these are heavily biased towards the materials scientist orbiologist. On the other hand,     

The Bomber's Baedeker -target book for strategic bombing in the Economic Warfare against German Towns 1943–45

In 1943, the British Ministry of Economic Warfare (MEW) issued the Bomber's Baedeker. A Guide to the Economic Importance of German Towns and Cities, followed by a second extended edition in 1944. Both editions have now been analysed completely for the first time. Based on information taken from the second edition, the analysis on the macro-level allows statements about the spatial distribution of the most important war-economic targets of the German Reich within the borders of 1937, as seen from the British point of view, just as about the distribution of target priorities within the town hierarchy, classified by population size, and on the micro-level about the information density provided for any single town. The final picture to emerge of the destruction of German towns at the end of the war reveals that quite a number were bombed which the MEW had not recommended for attack. This was due to the economically orientated target selection of the MEW being eclipsed and intermingled with the aims of those who promised to decide the war by demoralising the German population through general dehousing as well as by bombardments in support of ground forces advancing into the German hinterland at the end of the war.     

Physical evolution of Grande Ronde Basalt magmas, Columbia River Basalt Group, north-western USA

Summary In this paper we present what is, to the best of our knowledge, the first comprehensive study of clinopyroxenes and plagioclases contained in the flows of the Grande Ronde Basalt member of the Columbia River Basalt Group (northwestern USA). The rocks have MgO(wt%)<6%, and trace amounts of Cr and Ni. About 56% of extracted solid containing normative clinopyroxene and plagioclase explains the liquid line of descent from the more mafic sample (MgO wt%=5.89) to the most evolved. The most ubiquitous phases in the basalts are plagioclase and augite. Ilmenite and magnetite are accessories in all rocks. Olivine is present in small amount only in one sample (RT 89-7). Based on principles of Ca–Na plagioclase–liquid exchange, estimates of pre-eruptive magmatic water are < 2.4wt%. From clinopyroxene–liquid equilibria, calculated pressures and temperatures of ascending magmas are between 1atm and 0.617GPa, and 1068°C and 1166°C, respectively. Compositions of magnetite–ilmenite pairs and olivine–clinopyroxene–oxide assemblages yield post-eruptive oxygen fugacities of NNO=–1.923, and one pre-eruptive value of NNO=– 2.455. A simple model of asthenospheric melting and magma ponding in the lower crust fits the physical parameters.Supplementary material to this paper is available in electronic form at http://dx.doi.org/10.1007/s00710-003-0017-1     

Petrology, geothermobarometry and C-O-H-S fluid compositions in the environs of Rampura-Agucha Zn-(Pb) ore deposit, Bhilwara District, Rajasthan

The massive Zn-(Pb) sulfide ore body at Rampura-Agucha in Bhilwara district, Rajasthan, occurs within graphitic metapelites surrounded by garnet-biotite-sillimanite gneiss containing concordant bodies of amphibolite. These rocks and the sulfide ores have been studied to estimate the pressure, temperature and fluid composition associated with upper amphibolite facies metamorphism. Geothermobarometric calculations involving garnet-biotite and garnet-hornblende pairs, as well as sphalerite-hexagonal pyrrhotite-pyrite and garnet-plagioclase-sillimanite-quartz assemblages indicate that the most pervasive P-T condition during peak of regional metamorphism was 650°C and 6 kb, and was attained between the first and second deformations in the region. Some temperature-pressure estimates also cluster around 500°C–5.1 kb which probably represent retrograde cooling during unloading. Consideration of devolatilization equilibria in the C-O-H-S system at the pervasive metamorphic conditions mentioned above shows that the metamorphic fluid was H₂O-rich ( ) but also had a substantial component of . and were the other important phases in the fluid. CO (X_CO = 0.002) and were the minor phases in the fluid. It is probable that a part of this aqueous fluid was consumed by re-/neocrystallization of hydrous silicate phases like chlorite during the retrogressive metamorphic path, so that fluid entrapped in quartz below 450°C was rendered CO₂-rich (Holleret al 1996).     

Platinum-group elements in rocks from the voikar-syninsky ophiolite complex,Polar Urals,U.S.S.R.

Analyses of platinum-group elements (PGE) in rocks collected from the Voikar-Syninsky ophiolite in the Polar Urals suggest that the distribution and geochemistry of PGE in this Paleozoic ophiolite are similar to those in Mesozoic ophiolites from elsewhere. Chondrite-normalized PGE patterns for chromitite, the tectonite unit, and ultramafic and mafic cumulate unit have negative slopes. These results are similar to those found for chromitites from other ophiolites; stratiform chromities show positive slopes. If the magmas that form both types of chromitite originate from similar mantle source material with respect to PGE content, the processes involved must be quite different. However, the distinct chondrite-normalized PGE patterns may reflect differing source materials.     

The asiatic clam,Corbicula fluminea (Müller), in the tidal Potomac River,Maryland

The Asiatic clam,Corbicula fluminea (Müller), has extended its range to include the tidal fresh-water portion of the Potomac River, Maryland. Though patchily distributed, the clams have attained densities of 665 m^?2. Size-class distributions indicate that the clams first appeared in 1975. About 90% of the population belong to year-class I and were less than 12 mm in length. Elsewhere, this species has created severe water quality problems; it should be closely watched in the Potomac.     

A cordierite-bearing granite suite from the New England Batholith,N.S.W., Australia

A suite of cordierite-bearing biotite-muscovite intrusive granites in the New England Batholith, New South Wales, outcrops over 3400 sq km and is the largest reported occurrence of granites of this type. Compositionally the granites are close to the low temperature minimum and display only limited chemical variation. The corundum-normative nature of the granites suggests a pelitic sedimentary parentage. Cordierite with an average 100 Mg/ Mg + Fe of 55 occurs as large tabular crystals and is considered to be a refractory phase brought up from the zone of partial melting. The presence of cordierite and the absence of garnet in these granites suggests a partial melting at a pressure maximum of 6 kb, equivalent to 22 km depth.     

Sr,Nd and Pb isotopic and REE geochemistry of St. Paul's Rocks: the metamorphic and metasomatic development of an alkali basalt mantle source

Surface samples of peridotites and hornblendite mylonites from St. Paul's Rocks, and dredge samples from the flanks of the massif, have been analyzed for Sr, Nd and Pb isotopic ratios and Rb, Sr, and REE concentrations. This data, coupled with previous K and REE data, are used to develop a self-consistent model for the genesis of these ultramafic rocks. This model involves metasomatism of an ocean island-type mantle about 155 m.y. ago by a strongly light-REE-enriched metasomatic fluid, probably derived from the same mantle. This metasomatism produced light-REE-enriched materials which were isotopically homogeneous on a small scale (100 m), and isotopically heterogeneous on a large (km) scale. The geochemical relationships between the peridotites and the hornblendites were established by metamorphic equilibration on a relatively small scale (<10 m). The average mantle produced by these events is characterized by⁸⁷Sr/⁸⁶Sr=0.7034,¹⁴³Nd/¹⁴⁴Nd=0.51291,²⁰⁶Pb/²⁰⁴Pb=19.33 and 207/204=15.63. An alkali basalt which postdates the mylon-itization of the ultramafic massif has an isotopic character which is identical to the average ultramafic massif; it also lies on the five-dimensional isotopic mantle plane of Zindler et al. (1982). With respect to major elements, trace elements, and Sr, Nd and Pb isotopes, the average ultramafic rock of the St. Paul's massif is an ideal candidate for a mantle source from which alkali basalts can be derived by partial melting; the St. Paul's massif is in fact the first such example of an ultramafic rock which meets all the requirements to be an alkali basalt source.     

Correlations between U, Th Content and Metamorphic Grade in the Western Namaqualand Belt, South Africa, with Implications for Radioactive Heating of the Crust

The digital image of airborne radiometric data across SouthAfrica reveals that the largest anomaly, 100 nGy/h, is causedby the granulite-facies rocks of the Namaquan metamorphic complex,whereas most of the country is <60 nGy/h. This observationis consistent with geochemical data that show that the 1900± 100 Ma greenschist-facies Richtersveld Terrane nearNamibia (max. U = 3·4 ppm; Th = 20·1 ppm) andthe adjacent, 1100 ± 100 Ma, amphibolite-facies Aggeneys/SteinkopfTerranes (max. U 10 ppm; Th 52 ppm) are the least enrichedin U, Th and K. In contrast, the lower-T granulite-facies OkiepTerrane near Springbok hosts more enriched granites (max. U 17 ppm; Th 66 ppm) and noritic intrusions (max. U = 14 ppm;Th = 83 ppm). The most enriched rocks are found in the 1030Ma higher-T granulite-facies core of the Namaquan belt and includequartzo-feldspathic gneisses (max. U = 46 ppm; Th = 90 ppm)and charnockites (max. U = 52 ppm; Th = 400 ppm). Our findingscontradict the notion that granulite-facies terrains are characteristicallydepleted in U and Th. In this study we modeled the heat productionin the core of the Namaquan complex, where the granulites havehad a very unusual metamorphic history, and show that ultra-high-T(1000°C, P 10 kbar) metamorphic conditions could have beenachieved by radiogenic heating without invoking external heatsources. However, monazite-rich veins of charnockite and patchesof granulites mark the passage of CO₂-dominated melts and fluidsderived from fractionated noritic intrusions. KEY WORDS: charnockite; granulite; Namaqualand; thorium; uranium; radioactive heating; metamorphism     

Elpasolite from hyperalkaline pegmatite of the Khibiny pluton, Kola Peninsula. Symmetry of elpasolite

Elpasolite, K₂NaAlF₆, has been found for the first time in a pegmatite related to peralkaline foid syenite at Mt. Koashva, Khibiny alkaline pluton, Kola Peninsula, Russia, as pale pink octahedral crystals up to 2 mm in size within cavities in the natrolite core of pegmatite in association with amicite, sodalite, aegirine, pectolite, catapleiite, sitinakite, lemmleinite-K, and vinogradovite. The chemical composition determined with an electron microprobe is as follows, wt %: 31.53 K; 9.22 Na; 11.20 Al; 47.21 F; total is 99.16. The empirical formula is K_1.96Na_0.98Al_1.01F_6.05. The infrared spectrum is given. The crystal structure has been refined to R = 0.030, space group Fm $ \bar 3 Elpasolite, K₂NaAlF₆, has been found for the first time in a pegmatite related to peralkaline foid syenite at Mt. Koashva, Khibiny alkaline pluton, Kola Peninsula, Russia, as pale pink octahedral crystals up to 2 mm in size within cavities in the natrolite core of pegmatite in association with amicite, sodalite, aegirine, pectolite, catapleiite, sitinakite, lemmleinite-K, and vinogradovite. The chemical composition determined with an electron microprobe is as follows, wt %: 31.53 K; 9.22 Na; 11.20 Al; 47.21 F; total is 99.16. The empirical formula is K_1.96Na_0.98Al_1.01F_6.05. The infrared spectrum is given. The crystal structure has been refined to R = 0.030, space group Fm m, a = 8.092 ?. The result of a special X-ray powder diffraction study confirmed the suggestion made by Morss (1974) that reflections violating space group Fm m in some published X-ray powder patterns of natural elpasolite are Kβ-lines. Original Russian Text ? I.V. Pekov, N.V. Chukanov, N.N. Kononkova, N.V. Zubkova, M.Kh. Rabadanov, D.Yu. Pushcharovsky, 2007, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2007, No. 6, pp. 76–84.     

A re-appraisal of the chemical formula of nealite,Pb4Fe(AsO3)2Cl4 . 2H2O,on the basis of a crystal structure determination

Summary A crystal structure determination of the mineral nealite, Pb₄Fe(AsO₃)₂Cl₄ . 2H₂O, (a = 6.548(4), b = 10.243(8), c = 5.587(3) [Å]; = 96.2(1), = 89.6(1), = 97.7(1) [°]; Z = 1; space group ) was performed using single crystal X-ray data and a direct method strategy; the structural parameters were fitted by least squares techniques. The structure is characterized by isolated FeO₂Cl₂(H₂O)₂ octahedra (Fe-O: 2.08 Å, 2x, and 2.12 Å, 2x, Fe-Cl: 2.60 Å, 2x) and AsO₃ pyramids (As-O from 1.79 to 1.89 Å) which are connected by PbO₄Cl₄ and PbO₅Cl₄ polyhedra to a framework (with Pb-O distances from 2.22 to 3.34 Å, Pb-Cl distances from 3.10 to 3.54 Å). Oscillation photographs, exposed for 20 h, show very faint streaks indicating a doubling of c, probably caused by a partial ordering of a split lead atom position. Nealite is the first mineral found to contain a divalent iron atom coordinated to oxygen and chlorine atoms simultaneously.

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Änderung der chemischen Formel des Nealits, Pb₄Fe(AsO₃)₂Cl₄ . 2H₂O, basierend auf der Kristallstrukturbestimmung

Zusammenfassung Die Kristallstrukturbestimmung des Minerals Nealit, Pb₄Fe(AsO₃)₂Cl₄ . 2H₂O, a = 6.548(4), b = 10.243(8), c = 5.587(3) [Å]; = 96.2(1), = 89.6(1), = 97.7(1) [°]; Z = 1; Raumgruppe ) wurde anhand von röntgenographischen Einkristalldaten mit direkten Methoden durchgeführt und die Strukturparameter nach der Methode der kleinsten Quadrate verfeinert. Die Kristallstruktur ist charakterisiert durch isolierte FeO₂Cl₂(H₂O)₂-Oktaeder (Fe-O: 2.08 Å, 2x, und 2.12 Å, 2x, Fe-Cl: 2.60 Å, 2x) und AsO₃-Pyramiden (As-O von 1.79 Å bis 1.89 Å), welche durch PbO₄Cl₄ und PbO₅Cl₄-Polyeder zu einem Gerüst verknüpft sind (Pb-O von 2.22 bis 3.34 Å und Pb-Cl von 3.10 bis 3.54 Å). Schwenkaufnahmen, etwa 20 h belichtet, zeigen sehr feine Schwärzungsstreifen, die auf eine Verdopplung von c hinweisen, möglicherweise durch eine teilweise Ordnung einer aufgespaltenen Position eines Bleiatoms hervorgerufen. Nealit ist das erste Mineral, in dem ein zweiwertiges Eisenatom gleichzeitig an Sauerstoff- und Chloratome gebunden ist.

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Dedicated to Prof. Dr. Josef Zemann (Vienna) on the occasion of his 70^th birthday

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With 1 Figure     

Alkaline rocks and carbonatites of Amba Dongar and adjacent areas,Deccan Alkaline Province,Gujarat, India. 2. Complexly zoned clinopyroxene phenocrysts

Summary Clinopyroxene phenocrysts in six samples, representing the compositional range in the alkaline rocks of the region, range overall from aluminian titanian diopside (mg = Mg/[Mg + Fe _t ] = 92) to aegirine (mg = 17), but Ca-pyroxenes are dominant (90% of 851 analyses), Ca-Na pyroxenes minor ( 10%) and Na-pyroxenes rare ( 1%). Pyroxenes in associated subalkaline rocks (dolerites and basalts) are lower-Ca augites of distinct trend. Al and Ti correlate positively in the alkaline rock pyroxenes, but negatively with Si, mirroring decreasing CaTiAl₂O₆ and CaSiAl₂O₆ components in more felsic host-rocks. Although the most evolved pyroxenes in each host-rock show increasingna (Na/[Na + Ca]) and Zr and decreasingmg as host-rock mg decreases, the most primitive pyroxenes in each host-rock do not change, implying they are not at equilibrium. Over 40 paired logitudinal and lateral traverses across 21 phenocrysts reveal very complex zoning, in which up to five growth zones can be recognized in one crystal, separated by either sharp contacts or gradual transitions. These individual zones may show one of seven zoning trends:normal (na asmg moving outwards towards the rim),reverse (na asmg ),inverse (na asmg ),converse (na asmg ),unzoned (no change),symmetric (na andmg display complementary and trends), oroscillatory (superimposed on normal, reverse or unzoned). Ten distinct crystal types can also be recognized, showing particular sequences of zoning trends: for example, Type 1 shows a green, relatively sodic core surrounded by a more primitive rim or overgrowth, and has similar longitudinal and lateral zoning; whereas Type 6 shows extremely erratic variations which differ longitudinally and laterally. Up to four of these types were found in one host-rock, with little pattern in their distribution between different host-rocks. These pyroxenes are believed to record an intricate history of stop-start differentiation, complicated by magma-mixing, entry or disappearance of coprecipitating phases, and inheritance of high-pressure precipitates. Apparently random superimposed variations of Al, Ti and Si within some individual growth zones most probably reflect kinetic (disequilibrium) effects, due to rapid growth and/or supercooling.

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Alkaligesteine und Karbonatite von Amba Dongar und Umgebung Deccan Alkali-Provinz, Gujarat, Indien. 2. Komplex zonierte Klinopyroxenkristalle

Zusammenfassung Klinopyroxenkristalle in sechs Proben, die das ganze Spektrum der Zusammensetzung der Alkaligesteine des Gebietes repräsentieren, schwanken von Aluminium-Titandiopsid (mg = Mg/[Mg + Fe _t ] = 92) bis Aegirin (mg = 17), aber C-Pyroxene dominieren (90% von 851 Analysen). Ca-Na-Pyroxene sind Nebengemengteile (10%) und Na-Pyroxene sind selten ( 1%). Pyroxene in assoziierten subalkalischen Gesteinen (Dolerite und Basalte) sind Ca-arme Augite eines eigenständigen Trendes. Al und Ti korrelieren positiv in den Pyroxenen der Alkaligesteine, aber negativ mit Si, und dies spiegelt abnehmende CaTiAl₂O₆ und CaSiAl₂O₆ Komponenten in den mehr felsischen Wirtsgesteinen wider. Obwohl Pyroxene in jedem Wirtsgestein zunehmende na-Werte (Na/[Na + Ca]) und Zr-Gehalte und mit demmg des Wirtsgesteines auch abnehmendemg-Werte zeigen, lassen die primitivsten Pyroxene in jedem Wirtsgestein keine Änderung erkennen. Dies weist darauf hin, daß sie nicht im Gleichgewicht sind. Über vierzig paarweise angelegte Längs- und Quertraversen über 21 Kristalle zeigen sehr komplexen Zonarbau, in dem bis zu fünf Wachstumszonen in einem Kristall erkannt werden können, die entweder von scharfen Kontakten oder von graduellen Übergangszonen getrennt werden. Diese individuellen Zonen können einen der folgenden sieben Trends erkennen lassen: Normal (na ;mg ; von innen gegen den Rand zu), reverse (na ,mg ), invers (na undmg ), konvers (na ,mg ), unzoniert (keine Änderung), symmetrisch (na undmg zeigen komplementäre und Trends), oder oszillierend (überlagert den normalen, reversen oder unzonierten Trend). Weiters können zehn definierte Kristalltypen erkannt werden, die besondere Abfolgen von Trends der Zonierung erkennen lassen. Zum Beispiel zeigt Typ 1 einen grünen, relativ Na-reichen Kern, umgeben von einem mehr primitiven Rand oder Überwachsungen, wobei die Zonierung in Längs- und Querrichtung ähnlich ist. Demgegenüber zeigt Typ 6 außerordentlich unregelmäßige Zonierungen, die in Längs- und Querschnitten verschieden sind. Bis zu vier dieser Typen wurden in einem Wirtsgestein nachgewiesen, und sie ließen keine deutlichen Verteilungsmuster zwischen verschiedenen Wirtsgesteinen erkennen. Es wird angenommen, daß diese Pyroxene eine komplexe geschichte von stop-start Differentiation wiedergeben, die durch Magmamischung, durch die Zufuhr oder das Verschwinden von gleichzeitig ausfallenden Phasen und durch die Übernahme von Hochdruck-Bildungen weiter kompliziert wird. Unregelmäßig überlagerte Variationen von Al, Ti und Si innerhalb einzelner Wachstumszonen reflektieren sehr wahrscheinlich kinetische (Ungleichgewicht) Effekte, die auf sehr rasches Wachstum und/oder Überkühlung zurückgehen.

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With 11 Figures     

Rare earth element geochemistry of the Fen alkaline complex,Norway

Determination of rare earth element (REE) abundances in rocks of the Fen complex has shown that within rocks of the first magmatic series REE abundances increase in the order urtiteFen magmas are discussed and it is considered that parental magmas had relatively high La/Yb ratios (40–60). Utilizing petrological evidence from other alkaline complexes coupled with experimental studies it is considered that the parental magma was a carbonated nephelinite produced by limited (<10%) partial melting of the mantle. All the Fen rocks are placed in a petrogentic scheme in which a carbonated nephelinite magma undergoes liquid immiscibility, differentiation and volatile transport.     

Sulfur redox reactions: Hydrocarbons,native sulfur,Mississippi Valley-type deposits,and sulfuric acid karst in the Delaware Basin,New Mexico and Texas

Hydrocarbons, native sulfur, Mississippi Valley-type (MVT) deposits, and sulfuric acid karst in the Delaware Basin, southeastern New Mexico, and west Texas, USA, are all genetically related through a series of sulfur redox reactions. The relationship began with hydrocarbons in the basin that reacted with sulfate ions from evaporite rock to produce isotopically light ( ³⁴S = -22 to -12) H₂S and bioepigenetic limestone (castiles). This light H₂S was then oxidized at the redox interface to produce economic native sulfur deposits ( ³⁴S = -15 to +9) in the castiles, paleokarst, and along graben-boundary faults. This isotopically light H₂S also migrated from the basin into its margins to accumulate in structural (anticlinal) and stratigraphic (Yates siltstone) traps, where it formed MVT deposits within the zone of reduction ( ³⁴S = -15 to +7). Later in time, in th zone of oxidation, this H₂S reacted with oxygenated water to produce sulfuric acid, which dissolved the caves (e.g., Carlsbad Cavern and Lechuguilla Cave, Guadalupe Mountains). Massive gypsum blocks on the floors of the caves ( ³⁴S = -25 to +4) were formed as a result of this reaction. The H₂S also produced istopically light cave sulfur ( ³⁴S = -24 to -15), which is now slowly oxidizing to gypsum in the presence of vadose drip water.