Sulfur isotopes and origin of some sulfide deposits,New England,Australia

The S-isotopic compositions of sulfide deposits from Steinmann, granitoid and felsic volcanic associations have been examined. Ores of Steinmann association have ³⁴S values close to zero per mil (³⁴S=+0.3±3.1) it appears they are of mantle origin. Isotopically, ores of granitoid association regularly show a variable enrichment in ³²S relative to meteoritic (³⁴S=–2.7±3.3). The composition is in accord with an upper mantle/lower crustal source. Two stratiform accumulations of felsic volcanic association show a narrow spread of ³⁴S values (+0.2 to 2.4); a mantle origin for the sulfur in these deposits is favored. In contrast, vein, stockwork and cement ores are moderately enriched in ³²S relative to meteoritic (³⁴S=–4.0±6.4). These ores are polygenetic; sulfur and metals appear to have been leached from local country rocks where volcanogenic and biogenic sulfur predominate.     

Stable isotope geochemistry and phase equilibria of coesite-bearing whiteschists,Dora Maira Massif,western Alps

Peak metamorphic temperatures for the coesite-pyrope-bearing whiteschists from the Dora Maira Massif, western Alps were determined with oxygen isotope thermometry. The ¹⁸O(smow) values of the quartz (after coesite) (¹⁸O=8.1 to 8.6, n=6), phengite (6.2 to 6.4, n=3), kyanite (6.1, n=2), garnet (5.5 to 5.8, n=9), ellenbergerite (6.3, n=1) and rutile (3.3 to 3.6, n=3) reflect isotopic equilibrium. Temperature estimates based on quartz-garnet-rutile fractionation are 700–750 °C. Minimum pressures are 31–32 kb based on the pressure-sensitive reaction pyrope + coesite = kyanite + enstatite. In order to stabilize pyrope and coesite by the temperature-sensitive dehydration reaction talc+kyanite=pyrope+coesite+H₂O, the a(H₂O) must be reduced to 0.4–0.75 at 700–750 °C. The reduced a(H₂O) cannot be due to dilution by CO₂, as pyrope is not stable at X(CO₂)>0.02 (T=750 °C; P=30 kb). In the absence of a more exotic fluid diluent (e.g. CH₄ or N₂), a melt phase is required. Granite solidus temperatures are 680 °C/30 kb at a(H₂O)=1.0 and are calculated to be 70°C higher at a(H₂O)=0.7, consistent with this hypothesis. Kyanite-jadeite-quartz bands may represent a relict melt phase. Peak P-T-f(H₂O) estimates for the whiteschist are 34±2 kb, 700–750 °C and 0.4–0.75. The oxygen isotope fractionation between quartz (¹⁸O=11.6) and garnet (¹⁸O=8.7) in the surrounding orthognesiss is identical to that in the coesitebearing unit, suggesting that the two units shared a common, final metamorphic history. Hydrogen isotope measurements were made on primary talc and phengite (D(_SMOW)=-27 to-32), on secondary talc and chlorite rite after pyrope (D=-39 to -44) and on the surrounding biotite (D=-64) and phengite (D=-44) gneiss. All phases appear to be in nearequilibrium. The very high D values for the primary hydrous phases is consistent with an initial oceanicderived/connate fluid source. The fluid source for the retrograde talc+chlorite after pyrope may be fluids evolved locally during retrograde melt crystallization. The similar D, but dissimilar ¹⁸O values of the coesite bearing whiteschists and hosting orthogneiss suggest that the two were in hydrogen isotope equilibrium, but not oxygen isotope equilibrium. The unusual hydrogen and oxygen isotope compositions of the coesite-bearing unit can be explained as the result of metasomatism from slab-derived fluids at depth.     

Isotopic Composition (δ13C, δ18O) and Origin of Manganese Carbonate Ores of the Usa Deposit (Kuznetskii Alatau)

Isotopic compositions of carbon and oxygen are studied in different (rhodochrosite, calcareous-rhodochrosite, and chlorite–rhodochrosite) types of manganese carbonate ores from the Usa deposit (Kuznetskii Alatau). The ¹³C value varies from –18.4 to –0.7, while the ¹⁸O value ranges between 18.4 and 23.0. Host rocks are characterized by higher values of ¹³C (–1.9 to 1.0) and ¹⁸O (21.2 to 24.3). The obtained isotope data suggest an active participation of oxidized organic carbon in the formation of manganese carbonates. Manganese carbonate ores of the deposit are probably related to metasomatic processes.     

Oxygen isotope geochemistry of hydrothermally-altered synmetamorphic granitic rocks from South-Central Maine,USA

Hydrothermally-altered mesozonal synmetamorphic granitic rocks from Maine have whole-rock ¹⁸O (SMOW) values 10.7 to 13.8. Constituent quartz, feldspar, and muscovite have ¹⁸O in the range 12.4 to 15.2, 10.0 to 13.2, and 11.1 to 12.0, respectively. Mean values of _Q–F ( ¹⁸O_quartz– ¹⁸O_feldspar)=2.4 and _Q–M ( ¹⁸O_quartz– ¹⁸O_muscovite)=3.3 are remarkably uniform (standard deviations of both are 0.2). Measured _Q–F and _Q–M values demonstrate that the isotopic compositions of the minerals are altered from primary magmatic ¹⁸O values but that the minerals closely approached oxygen isotope exchange equilibrium at subsolidus temperatures. Analyzed muscovites have D (SMOW) values in the range –65 to –82.Feldspars in the granitic rocks are mineralogically altered to either (a) muscovite+calcite, (b) muscovite+calcite+epidote, (c) muscovite+epidote, or (d) muscovite only. A consistent relation exists between the assemblage of secondary minerals and the oxygen isotope composition of whole rocks, quartz, and feldspar. Rocks with assemblage (a) have whole-rock ¹⁸O>12.1 and contain quartz and feldspar with ¹⁸O>13.8 and >11.4, respectively. Rocks with assemblages (b), (c), and (d) have whole-rock ¹⁸O<11.4 and contain quartz and feldspar with ¹⁸O< 13.1 and <11.0, respectively. The correlation suggests that the mineralogical alteration of the rocks was closely coupled to their isotopic alteration.Three mineral thermometers in altered granite suggest that the hydrothermal event occurred in the temperature range 400°–150° C, 100°–150° C below the peak metamorphic temperature inferred for country rocks immediately adjacent to the plutons. Calculations of mineral-fluid equilibria indicate that samples with assemblage (a) coexisted during the event with CO₂-H₂O fluids of and ¹⁸O=10.8 to 12.2 while samples with assemblages (b), (c), or (d) coexisted with fluids of and ¹⁸O=9.4 to 10.1. Compositional variations of the hydrothermal fluids were highly correlated: fluids enriched in CO₂ were also enriched in ¹⁸O. Because CO₂ was added to the granites during hydrothermal alteration and because fluids enriched in CO₂ were enriched in ¹⁸O, some or all of the variation in ¹⁸O of altered granites may have been caused by addition of ¹⁸O to the rocks during the hydrothermal event. The source of both the CO₂ and ¹⁸O could have been high-¹⁸O metasedimentary country rocks. The inferred change in isotopic composition of the granites is consistent with depletion of the metacarbonate rocks in ¹⁸O close to the plutons and with large volumes of fluid that were inferred from petrologic data to have infiltrated the metacarbonate rocks during metamorphism.A close approach of minerals to oxygen isotope exchange equilibrium in altered mesozonal rocks from Maine is in marked contrast to hydrothermally-altered epizonal granites whose mineral commonly show large departures from oxygen isotope exchange equilibrium. The difference in oxygen isotope systematics between altered epizonal granites and altered mesozonal granites closely parallels a differences between their mineralogical systematics. Both differences demonstrate the important control that depth exerts on the products of hydrothermal alteration. Deeper hydrothermal events occur at higher temperature and are longer-lived. Minerals and fluid have sufficient time to closely approach both isotope exchange and heterogeneous chemical equilibrium. Shallower hydrothermal events occur at lower temperatures and are shorter-lived. Generally there is insufficient time for fluid to closely approach equilibrium with all minerals.     

The role of magmatic and hydrothermal processes in the chemical evolution of the Strange Lake plutonic complex,Québec-Labrador

The Strange Lake plutonic complex consists of three annular Mid-Proterozoic arfvedsonite-aegirine-bearing alkali granites emplaced in the Rae province of the Canadian Shield. The mineralogy, chemistry and structural setting of the complex are very similar to that of many peralkaline central salic complexes associated with the development of the Gardar rift in southern Greeland. The Strange Lake granites are highly fractionated (Rb/Sr=5 to 160 and K/Rb=27 to 120) and carry unusually high abundances of HFSE and REE-bearing exotic minerals (e.g. pyrochlore, gittinsite, elpidite, gadolinite and kainosite) which are reflected in the elevated HFSE (e.g.Zr=307 to 16800 ppm) and REE (e.g. La=84 to 1337 ppm) contents of the granites. HFSE and REE increase from the oldest intrusive unit, which is hypersolvus and unaltered, to the youngest, which is subsolvus and metasomatized. The unaltered granites display a restricted range of ¹⁸O values (+8.2 to+9.6) and low ¹⁸O signatures for fresh arfvedsonite/aegirine (+4.8 to+5.2). Anomalously high CaO (0.7 to 3.2 wt%) and MgO (0.1 to 0.6wt%) concentrations characterize the altered subsolvus granites. These rocks also have elevated whole rock ¹⁸O values (+9.6 to +11.9), negative ¹⁸O_{quartz-alk.feld.} (-0.1 to-1.6), and high ¹⁸O values of altered arfvedsonite (i.e.+6.5 to 13.75) that correlates positively with whole rock ¹⁸O values. The chemical and isotopic data are consistent with a model in which the least evolved alkali granites are formed through differentiation from trachytic (syenitic) parents. Extreme HFSE and REE-enrichment may have been accomplished by differentiation through fractional crystallization and heterogenous distribution of F-rich silicic residual melts in which the REE and HFSE are transported as fluorocomplexes. The O-isotopic values are consistent with the circulation of low temperature (lt;200°C) hydrothermal fluids in the youngest subsolvus intrusive unit which caused extensive Ca (Mg and Sr) metasomatism and fluorine leaching, widespread hematization, and remobilization of the HFSE and REE.     

Boron isotopic variations in hydrous rhyolitic melts: a case study from Long Valley,California

In this paper, we present boron isotope analyses of variably degassed rhyolitic glasses from Long Valley, California. The following results indicate that pre-eruptive boron isotopic signatures were preserved in degassed glasses: (1) averaged secondary ionization mass spectrometry (SIMS) measurements of H₂O-rich (~3 wt%) melt inclusions from late erupted Bishop Tuff pumice are indistinguishable from positive thermal ionization mass spectrometry (PTIMS) analysis of vesiculated groundmass glass (¹¹B=+5.0±0.9 and +5.4±5, respectively); (2) SIMS spot-analyses on H₂O-poor obsidian (~0.15 wt% H₂O) from younger Glass Mountain Dome YA (average ¹¹B=+5.2±1.0) overlap with compositionally similar late Bishop Tuff melt inclusions; and (3) four variably degassed obsidian samples from the 0.6 ka Mono Craters (H₂O between 0.74 and 0.10 wt%) are homogeneous with regard to boron (average ¹¹B=+3.2±0.8, MSWD=0.4). Insignificant variations in ¹¹B between early and late Bishop Tuff melt inclusion glasses agree with published experimental data that predict minor ¹¹B depletion in hydrous melts undergoing gas-saturated fractional crystallization. Melt inclusions from two crystal-rich post-caldera lavas (Deer Mountain and South Deadman Dome) are comparatively boron-rich (max. 90 ppm B) and have lower ¹¹B values (average ¹¹B=+2.2±0.8 and –0.4±1.0 ) that are in strong contrast to the boron isotopic composition of post-caldera crystal-poor rhyolites (27 ppm B; ¹¹B=+5.7±0.8). These variations in ¹¹B are too large to be caused by pre-eruptive degassing. Instead, we favor assimilation of ¹¹B depleted low-temperature hydrothermally altered intrusive rocks subsequent to fresh rhyolite recharge.Editorial responsibility: J. HoefsAn erratum to this article can be found at     

The genesis of emeralds and their host rocks from Swat,northwestern Pakistan: a stable-isotope investigation

Emerald deposits in Swat, northwestern Pakistan, occurring in talc-magnesite and quartz-magnesite assemblages, have been investigated through stable isotope studies. Isotopic analyses were performed on a total of seven emeralds, associated quartz (seven samples), fuchsite (three samples) and tourmaline (two samples) from the Mingora emerald mines. The oxygen isotopic composition ( ¹⁸O SMOW) of emeralds shows a strong enrichment in¹⁸O and is remarkably uniform at + 15.6 ± 0.4 (1,n = 7). Each of the two components of water in emerald (channel and inclusion) has a different range of hydrogen isotopic composition: the channel waters being distinctly isotopically heavier (D = –51 to –32 SMOW) than the other inclusion waters (D = –96 to –70 SMOW). Similarly the oxygen isotopic compositions of tourmaline and fuchsite are relatively constant ( ¹⁸O = + 13 to + 14 SMOW) and show enrichment in¹⁸O. The ¹⁸O values of quartz, ranging from + 15.1 to + 19.1 SMOW, are also high (+ 16.9 ± 1.4 1, n = 7). The meanD of channel waters measured from emerald (–42 ± 6.6 SMOW) and that of fluid calculated from hydrous mineralsD_calculated (–47 ± 7.1 SMOW) are consistent with both metamorphic and magmatic origin. However, the close similarity between the measuredD values of the hydroxyl hydrogen in fuchsite (–74 to –6 SMOW) and tourmaline (–84 and –69 SMOW) with pegmatitic muscovite and tourmaline suggests that the mineralization was probably caused by modified (¹⁸O-enriched) hydrothermal solutions derived from an S-type granitic magma. The variation in the carbon and oxygen isotopic composition of magnesite, locally associated with emerald mineralization, is also very restricted ( ¹³ –3.2 ± 0.7%, PDB; ¹⁸O + 17.9 ± 1.27 SMOW). On the basis of the isotopic composition of fluid ( ¹³C –1.8 ± 0.7 PDB; ¹⁸O + 13.6 ± 1.2 SMOW calculated for the 250-550 °C temperature), it is proposed that the Swat magnesites formed due to the carbonation of previously serpentinized ultramafic rocks by a CO₂-bearing fluid of metamorphic origin.     

The isotopic constitution of sulphur in some stratiform lead-zinc sulphide ores

Sulphur isotope measurements on five Australian stratiform lead-zinc sulphide ores are presented. Each deposit is characterised by a conspicuously narrow spread of values, mean ³⁴S heavier than meteoritic, average crustal, and, where sampled stratigraphically, ³⁴S related to stratigraphy rather than propinquity. When considered with other deposits of the same class from elsewhere, several seemingly general features appear: Mean ³⁴S heavier than meteoritics; ranges for individual deposits narrow and rarely more than 8 with standard deviation approximately 1 to 2; individual values for the whole group spread between, but almost entirely restricted by, the values for meteoritic S and seawater SO₄ ^—; no age effect; no apparent relationship between ³⁴S and lead type; and, where investigated, a stratigraphical affiliation. While no positive interpretation of these features is made, it is suggested that the sulphur concerned has been derived neither from migrant hydro-thermal solutions nor from the H₂S of normal biological sulphate reduction in seawater.

---

Zusammenfassung Es werden Meßergebnisse von fünf australischen geschichteten Blei-Zink-Sulfid-Lagerstätten mitgeteilt: Jedes Vorkommen ist durch einen bemerkenswert engen Schwankungsbereich der Werte, Mittelwert ³⁴S schwerer als meteoritischer Schwefel/Durchschnittswert aus der Erdkruste, gekennzeichnet. Wo die Proben in stratigraphischer Abfolge entnommen wurden, zeigt der Wert ³⁴S eine stärkere Affinität zur Stratigraphie als zu absoluter Entfernung der Muster. Vergleicht man diese Werte mit solchen von anderen Vorkommen der nämlichen Lagerstättengruppe, so liegen einige allgemeine Eigenheiten auf der Hand: Für einige Vorkommen ist der Mittelwert ³⁴S schwerer als meteoritischer Schwefel; für einzelne Lagerstätten ist der Bereich eng und überschreitet kaum mehr als 8 mit der Standardabweichung von ungefähr 1 bis 2; Einzelwerte für die gesamte Lagerstättengruppe fallen fast ausschließlich zwischen die Werte für meteoritischen Schwefel und SO₄ ^2–-Ionen im Meerwasser; es herrscht kein dem geologischen Alter zuzuschreibender Effekt; auch gibt es keine augenscheinliche Beziehung zwischen dem ³⁴S-Wert und dem Blei-Typ; in jenen Fällen aber, wo Untersuchungsergebnisse vorliegen, ist eine Beziehung der Werte zur Stratigraphie zu erkennen. Obwohl keine positive Interpretation dieser Phänomena angestellt wurde, wird die Vermutung geäußert, daß der betreffende sulfidische Schwefel weder von wandernden hydrothermalen Lösungen noch vom H₂S einer normalen biologischen Sulfatreduktion im Meerwasser abgeleitet werden kann.

     

Changes in stable isotope ratios of metapelites and marbles during regional metamorphism,Mount Lofty Ranges,South Australia: implications for crustal scale fluid flow

The Mount Lofty Ranges comprises interlayered marbles, metapsammites, and metapelites that underwent regional metamorphism during the Delamarian Orogeny at 470–515 Ma. Peak metamorphic conditions increased from lowermost biotite grade (350–400°C) to migmatite grade (700°C) over 50–55 km parallel to the lithological strike of the rocks. With increasing metamorphic grade, ¹⁸O values of normal metapelites decrease from 14–16 to as low as 9.0, while ¹⁸O values of calcite in normal marbles decrease from 22–24 to as low as 13.2 These isotopic changes are far greater than can be accounted for by devolatilisation, implying widespread fluid-rock interaction. Contact metamorphism appears not to have affected the terrain, suggesting that fluid flow occurred during regional metamorphism. Down-temperature fluid flow from synmetamorphic granite plutons (¹⁸O=8.4–8.6) that occur at the highest metamorphic grades is unlikely to explain the resetting of oxygen isotopes because: (a) there is a paucity of skarns at granite-metasediment contacts; (b) the marbles generally do not contain low-XCO₂ mineral assemblages; (c) there is insufficient granite to provide the required volumes of water; (d) the marbles and metapelites retain a several permil difference in ¹⁸O values, even at high metamorphic grades. The oxygen isotope resetting may be accounted for by along-strike up-temperature fluid flow during regional metamorphism with time-integrated fluid fluxes of up to 5x10⁹ moles/m² (10⁵ m³/m²). If fluid flow occurred over 10⁵–10⁶ years, estimated intrinsic permeabilities are 10^-20 to 10^-16m². Variations in ¹⁸O at individual outcrops suggest that time-integrated fluid fluxes and intrinsic permeabilities may locally have varied by at least an order of magnitude. A general increase in XCO₂ values of marble assemblages with metamorphic grade is also consistent with the up-temperature fluid-flow model. Fluids in the metapelites may have been derived from these rocks by devolatilisation at low metamorphic grades; however, fluids in the marbles were probably derived in part from the surrounding siliceous rocks. The marble-metapelite boundaries preserve steep gradients in both ¹⁸O and XCO₂ values, suggesting that across-strike fluid fluxes were much lower than those parallel to strike. Up-temperature fluid flow may also have formed orthoamphibole rocks and caused melting of the metapelites at high grades.This paper is a contribution to IGCP Project 304 Lower Crustal Processes     

Seawater-sediment-basalt interactions: stable isotope (H,O) and elemental fluxes within the Ordovician volcano-sedimentary sequence of Erquy (Brittany,France)

The Ordovician volcano-sedimentary succession of Erquy (northern Brittany) is made of immature sediments thermally metamorphosed at the contact of intruding basic sills. Pillow lavas constitute the upper part of the sequence. The trace element geochemistry of sills and pillow lavas suggests that they were derived from a tholeiitic source located beneath a passive margin. This volcanic sequence was metamorphosed under low to moderate greenschist facies conditions. In this study the direction and amplitude of chemical and isotopic fluxes in the basalt-sediment-water system were established and the oxygen and hydrogen isotope compositions of the aqueous fluid that reacted with the volcanic rocks were characterized. Cationic thermometry on chlorites and isotopic thermometry on plagioclase-chlorite pairs indicate closure metamorphic temperatures in the range 200–250°C for the basaltic sills. Stable isotope compositions of iron-rich chlorites (¹⁸O-5.5; D from-60 to-50) and plagioclases (¹⁸O from +9 to +10) reveal that the source of the fluid was certainly seawater. The ¹⁸O variations within the sills are strongly correlated with the rate of progress of the main metamorphic reaction:clinopyroxene+plagioclase+ilmenite chlorite+albite+epidote+quartz+sphene that produced major element mobility at the scale of the volcanosedimentary sequence. Calculation of elemental fluxes by mass balance combined with oxygen isotopic compositions of basalts shows that the highest water-rock ratios (1) were at sill-sediment boundaries and within pillow lavas at the top of the pile. The volcanosedimentary sequence of Erquy was a net sink for Na and a source for Ca. No Mg uptake could be detected whereas the hydrothermal alteration of the sediments released Fe, Si, and K trapped by the volcanic rocks. The ¹⁸O value of the fluid reacting with sills appears to have shifted no more than +4 after percolation at low temperature through immature sediments (¹⁸O12). The Erquy volcano-sedimentary sequence represents a marine hydrothermal system dominated by low-temperature exchange which allowed a general ¹⁸O-enrichment of the volcanic rocks and a ¹⁸O-depletion of sediments.     

Textural and isotopic variations in graphite from plutonic rocks,South-Central New Hampshire

Graphite occurs in two distinct textural varieties in syntectonic granitoids of the New Hampshire Plutonic Series and in associated metasedimentary wall rocks. Textural characteristics indicate that coarse graphite flakes were present at an early stage of crystallization of the igneous rocks and thus may represent xenocrystic material assimilated from the wall rocks. The range of ¹³C values determined for flake graphite in the igneous rocks (–26.5 to –13.8) overlaps the range for flake graphite in the wall rocks (–26.0 to –16.7), and spatial correlation of some ¹³C values in the plutons and wall rocks supports the assimilation mechanism. The textures of fine-grained irregular aggregates or spherulites of graphite, on the other hand, indicate that they formed along with secondary hydrous silicates and carbonates during retrograde reactions between the primary silicates and a carbon-bearing aqueous fluid phase. Relative to coexisting flake graphite, spherulitic graphite shows isotopic shifts ranging from 1.9 higher to 1.4 lower in both igneous and metasedimentary samples.The observed isotopic shifts and the association of spherulitic graphite with hydrous silicates are explained by dehydration of C-O-H fluids initially on or near the graphite saturation boundary. Hydration of silicates causes dehydration of the fluid and drives the fluid composition to the graphite saturation surface. Continued dehydration of the fluid then requires coprecipitation of secondary graphite and hydrous silicates and drives the fluid toward either higher or lower CO₂/CH₄ depending upon the inital bulk composition. Isotopic shifts in graphite formed at successive reaction stages are explained by fractionation of ¹³C between secondary graphite and the evolving fluid because ¹³C is preferentially concentrated into CO₂ relative to CH₄.Epigenetic graphite in two vein deposits assiciated with the contacts of these igneous rocks is generally enriched in ¹³C (–15.7 to –11.6) relative to both the igneous and wall-rock ¹³C values. Values of ¹³C vary by up to 3.4 within veins, with samples taken only 3 cm apart differing by 2.0 These variations in ¹³C correlate with textural evidence showing sequential deposition of different generations of graphite in the veins from fluids which differed in proportions of carbon species or isotopic composition (or both).     

Reconstruction of palaeohydrological conditions in a lagoon during the 2nd Zechstein cycle through simultaneous use of δD values of individual n-alkanes and δ<Superscript>18</Superscript>O and δ<Superscript>13</Superscript>C values of carbonates

For the first time ¹⁸O and ¹³C values from carbonates and D values of individual n-alkanes were used to reconstruct palaeohydrological conditions in a lagoon at the southern margin of the Central European Zechstein Basin (CEZB). A 12-m core covering the complete Ca2 interval and adjacent anhydrites (A1 and A2) was analyzed for ¹⁸O and ¹³C values of dolomitized carbonates and D values of individual n-alkanes. ¹⁸O_carb values (+2 to +5 vs. VPDB) were strongly influenced by evaporation and temporal freshwater input into the lagoon. The ¹³C_carb values (–1 to +4 vs. VPDB) were controlled mainly by changes in primary production. Both isotopic ratios show an inverse relationship throughout most of the core, contradicting diagenetic alteration, since ¹³C_carb values are not altered significantly during dolomitization. Assuming a temperature range of 35–40 °C in the lagoon, ¹⁸O_carb values of +2.5 to +8 (vs. VSMOW) for the lagoonal water can be reconstructed. The lagoon may have desiccated twice during the Ca2 interval, as indicated by very high ¹⁸O_carb and low ¹³C_carb values, coinciding with increasing amount of anhydrite in the analyzed sample. These events seem to reflect not just local but a regional intra-Ca2 cyclicity. Measured D values of the short-chain n-alkanes, namely n-C₁₆ and n-C₁₈ which are widely used as indicators for photosynthetic bacterial and algal input, reflect the isotopic composition of the lagoonal water. Assuming constant fractionation during incorporation of hydrogen into lipids of –160, an average D value of +70 (vs. VSMOW) can be reconstructed for the lagoonal water, accounting for very arid conditions. The long-chain n-alkanes n-C₂₇, n-C₂₈, n-C₂₉ and n-C₃₀, thought to be derived from the leaf waxes of terrestrial higher plants, were shown to be depleted in D relative to the short-chain alkanes, therefore indicating a different hydrogen source. Terrestrial plants in arid areas mainly use water supplied by precipitation. By using a smaller fractionation of –120 due to evaporation processes in the leaves, reconstructed values vary between –74 and –9 (vs. VSMOW). These values are not indicating extremely arid conditions, implying that the long-chain n-alkanes were transported trough wind and/or rivers into the lagoon at the Zechstein Sea coast. D_water values, reconstructed using the n-C₁₆ alkane and ¹⁸O _water values, independently reconstructed on the same sample using the temperature dependant fractionation for dolomites are good agreement and suggest high amounts of evaporation affecting the coastal lagoon. Altogether, our results indicate that hydrogen isotopic ratios of n-alkanes give information on their origin and are a useful proxy for palaeoclimatic reconstruction.     

A stable isotope study of retrograde alteration in SW Connemara,Ireland

Dalradian metamorphic rocks, Lower Ordovician meta-igneous rocks (MGS) and Caledonian granites of the Connemara complex in SW Connemara all show intense retrograde alteration. Alteration primarily involves sericitization and saussuritization of plagioclase, the alteration of biotite and hornblende to chlorite and the formation of secondary epidote. The alteration is associated with sealed microcracks in all rocks and planes of secondary fluid inclusions in quartz where it occurs, and was the result of a phase of fluid influx into these rocks. In hand specimen K-feldspar becomes progressively reddened with increasing alteration. Mineralogical alteration in the MGS and Caledonian granites took place at temperatures 275±15°C and in the MGS P_fluid is estimated to be 1.5 kbar during alteration. The °D values of alteration phases are:-18 to-29 (fluid inclusions),-47 to-61 (chlorites) and-11 to-31 (epidotes). Chlorite ¹⁸O values are +0.2 to +4.3, while ¹⁸O values for quartz-K-feldspar pairs show both positively sloped (MGS) and highly unusual negatively sloped (Caledonian granites) arrays, diverging from the normal magmatic field on a - plot. The stable isotope data show that the fluid that caused retrogression continued to be present in most rocks until temperatures fell to 200–140°C. The retrograde fluid had D -20 to-30 in all lithologies, but the fluid ¹⁸O varied both spatially and temporally within the range-4 to +7. The fO₂ of the fluid that deposited the epidotes in the MGS varied with its ¹⁸O value, with the most ¹⁸O-depleted fluid being the most oxidizing. The D values, together with low (<0) ¹⁸O values for the retrograde fluid in some lithologies indicate that this fluid was of meteoric origin. This meteoric fluid was probably responsible for the alteration in all lithologies during a single phase of fluid infiltration. The variation in retrograde fluid ¹⁸O values is attributed to the effects of variable oxygen isotope shifting of this meteoric fluid by fluid-rock interaction. Infiltration of meteoric fluid into this area was most likely accomplished by convection of pore fluids around the heat anomaly of the Galway granite soon after intrusion at 400 Ma. However convective circulation of meteoric water and mineralogical alteration could possible have occurred considerably later.     

Deep crustal oxygen isotope variations: the Wawa-Kapuskasing crustal transect,Ontario

We have studied the oxygen isotopic composition of rocks from a 100 km transect through the central Superior province of Ontario, representing progressively the shallower terrains of the Kapuskasing structural zone (KSZ), the Wawa gneiss terrane (WGT), and the Michipicoten greenstone belt (MGB). These rocks range in age from 2.76 to 2.60 Ga, and correspond to a section through approximately 20 km of crustal thickness. Equivalent lithologic types have similar range of ¹⁸O values at each crustal level: tonalitic to granodioritic rocks: 6.4 to 9.5; dioritic and anorthositic rocks: 5.5 to 7.6; mafic gneisses: group 1 (majority): 5.7 to 7.1; group 2: 8.1 to 9.5. ¹⁸O values exhibit a remarkable correlation with SiO₂ values, similar to that observed in unaltered plutonic rocks of equivalent composition. Paragneisses have significantly higher ¹⁸O values: 9.3 to 12.2. Low-grade metavolcanic and metasedimentary rocks of the MGB are ¹⁸O-enriched compared to their high-grade equivalents in the KSZ and WGT: 7.4 to 13.3 for mafic to felsic metavolcanic rocks; 11.4 to 14.7 for clastic metasediments. Coexisting minerals exhibit ¹⁸O-fractionation consistent with equilibrium, but corresponding to uniform isotopic temperatures about 553 to 584°C across the entire transect, lower than the inferred metamorphic temperatures in the highest-grade (KSZ) terrane. The lack of distinctive isotopic differences between equivalent rock types in the KSZ, WGT and MGB suggests that there is no significant gradient in ¹⁸O with depth in the crust. The majority of mafic gneisses (group 1) appear to have been emplaced either as subaerial extrusives, intrusive sills, or, less likely, as submarine extrusives that were hydrothermally altered at high temperatures. The less abundant group 2 mafic rocks have the ¹⁸O values typical of greenstones that were altered at low temperature by seawater, and isotopically resemble low-grade rocks in the Michipicoten and Abitibi belts. In general, no major changes in whole-rock isotopic composition appear to have occurred during granulite facies metamorphism, implying limited flux of water or CO₂. The continuous linear gradient in ¹⁸O versus SiO₂ in the high-grade rocks cannot be due to differentiation of a mafic source magma. A model involving an association between mantle-derived mafic magma and ¹⁸O-enriched crustal materials is more consistent with the oxygen isotopic and the REE data.McMaster Isotopic, Nuclear and Geochemical Studies Group Publication 163; LITHOPROBE Publication 168.     

Oxygen Isotopic Composition in Riphean Mudstones of the Yudoma–Maya Trough: Implication for Isotopic Dating

In Riphean mudstones of the Yudoma–Maya Trough (southeastern Siberian Platform), which underwent deep catagenetic and metagenetic transformations, ¹⁸O values range from 11.2 to 18.9 (¹⁸O_aver= 14.4), which are 5–7 lower than those in similar Cenozoic rocks. The isotopic shift is caused by postsedimentary alterations at temperatures up to 200°C under the influence of a moderate influx of metamorphogenic solutions and relative geochemical insulation of rock formations from each other. Within separate formations, we have revealed a distinct positive correlation between ¹⁸O and SiO₂, which is typical for thermodynamically ordered metamorphic rocks composed of minerals in isotopic equilibrium.     

Hydrothermal alteration and oxygen and hydrogen isotope geochemistry of the D-68 zone Cu-Zn Massive Sulfide Deposit,Noranda District,Quebec, Canada

Summary Pervasive hydrothermal alteration zones in quartz-feldspar porphyry domes underly all massive sulfide lenses in the D-68 Zone Cu-Zn deposit, Noranda. Alteration pipes are mineralogically zoned and contain chloritic cores consisting of stringer sulfides, enveloped by sericitic haloes. Silicified rocks are found locally.Alteration took place at nearly constant volume. Na depletion, and K enrichment relative to the least altered rocks, are found in all alteration zones. Fe and Mg have been added to the chloritic zone and subtracted in the sericitic and silicic zones. Ca and Si are enriched mainly in the silicic zone. Al, Ti and Zr were the least mobile of the elements studied.Whole-rock ¹⁸O values vary from +5.6 to +6.2 per mil in chloritized rocks, +5.8 to + 7.3 per mil in sericitized rocks and + 7.2 to + 8.3 per mil in silicified rocks. D values for two chloritized samples are – 63 and – 70 per mil whereas in two sericitized samples they are close to –62 per mil. Quartz from the chlorite alteration zone is isotopically heavier (¹⁸O = 8.6 per mil) than that from the sericite alteration zone (¹⁸O = 6.4 per mil), suggesting equilibration with different hydrothermal fluid or different temperature of alteration. Assuming an alteration temperature of 300° + 50°C the fluid in equilibrium with quartz and chlorite had ¹⁸O and D values of about 1.5 ± 2.0 per mil and –23 ± 5 per mil, respectively. The fluid in equilibrium with quartz and sericite had ¹⁸O and D values of about –0.5 ± 2 per mil and –30 ± 5 per mil, respectively. On the basis of isotopic data, seawater was probably the major constituent of the hydrothermal fluids.

---

Hydrothermale Umwandlung und Sauerstoff-Wasserstoff-Isotopengeochemie der Zone D-68 Cu-Zn Derberz Sulfidlagerstätte, Noranda District, Quebec, Canada

Zusammenfassung Hydrothermale Umwandlungszonen in porphyrischen Quarz-Feldspat Gesteinskörpern liegen unterhalb von Derberz Sulfidlinsen in der D-68 Zone Cu-Zn Lagerstätte, Noranda. Umgewandelte pipes sind mineralogisch zoniert; sie enthalten aus Sulfiden bestehende chloritische Kerne, die von sericitischen Höfen umhüllt werden. Lokal treten silicifizierte Gesteine auf.Die Umwandlung ging bei annähernd konstantem Volumen vor sich. Na-Verarmung und K-Anreicherung, bezogen auf die am wenigsten umgewandelten Gesteine, liegen in allen Umwandlungszonen vor. Fe und Mg wurden der Chloritzone zugeführt, in den Sericit- und Si-Zonen abgeführt. Ca und Si sind vor allem in der Si-Zone angereichert. Al, Ti und Zr waren von den untersuchten Elementen am wenigsten mobil.Gesamtgesteins-¹⁸O Werte variieren von +5,6 bis +6,2 in den chloritisierten Gesteinen, von +5,8 bis 7,3 in sericitisierten Gesteinen und von +7,2 bis +8,3 in den silicifizierten Gesteinen. Die D Werte für zwei chloritisierte Proben betragen –63 und –70, in zwei sericitisierten Proben liegen sie hingegen nahe bei –62. Quarz von der Chlorit-Umwandlungszone ist isotopisch schwerer (¹⁸O = 8,6) als von der Sericit-Umwandlungszone (¹⁸O = 6.4), was eine Gleichgewichtseinstellung mit verschiedenen hydrothermalen Lösungen oder eine verschiedene Umwandlungstemperatur nahelegt. Bei einer angenommenen Umwandlungstemperatur von 300 ± 50°C, hatte die im Gleichgewicht mit Quarz und Chlorit stehende Lösung ¹⁸O und D Werte von etwa 1,5 ± 2 bzw. –23 + 5. Die im Gleichgewicht mit Quarz und Sericit befindliche Lösung hatte ¹⁸O und D Werte von etwa –0,5 ± 2%o bzw. –30 ± 5. Aufgrund der Isotopendaten war wahrscheinlich Meerwasser der Hauptbestandteil der hydrothermalen Lösungen.

---

---

With 7 Figures     

Oxygen isotopes in mantle related and geothermally altered magmatites of the Transhimalayan (Gangdese) ranges

In closed magma systems SiO₂ approximately measures differentiation progress and oxygen isotopes can seem to obey Rayleigh fractionation only as a consequence of the behaviour of SiO₂. The main role of ¹⁸O is as a sensitive indicator of contamination, either at the start of differentiation ( ¹⁸O_init) or as a proportion of fractionation in AFC. Plots of ¹⁸O vs SiO₂-allow to determine initial ¹⁸O values for different sequences for source comparison. For NBS-28=9.60, the ¹⁸O at 48% SiO₂-varies between a high 6.4 for Kiglapait (Kalamarides 1984), 5.9 for Transhimalaya, 5.8 for Hachijo-Jima (Matsuhisa 1979), 5.6 for Koloula (Chivas et al. 1982) and a low 5.3 for the Darran Complex, New Zealand. The Transhimalayan batholiths (Gangdese belt) were emplaced in the Ladakh-Lhasa terrane, between the present-day Banggong-Nujiang, and Indus-Yarlung Tsangbo suture zones, after its accretion to Eurasia. The gradient of the least contaminated continuous ( ¹⁸O vs SiO₂-igneous trend line is similar to that of Koloula, and AFC calculations suggest a low secondary assimilation rate of less than 0.05 times the rate of crystallisation. Outliers enriched in ¹⁸O are frequent in the Lhasa, and apparently rare in the Ladakh transsect. Low- ¹⁸O (5.0–0) granitoids and andesites on the Lhasa-Yangbajain axis are the result of present day or recent near-surface geothermal activity; their quartzes still trace the granitoids to the Transhimalaya ¹⁸O trend line, but the distribution of low total rock or feldspar ¹⁸O values could be a guide to more recent heat flow and thermally marked tectonic lineaments. Two ignimbrites from Maqiang show hardly any ¹⁸O-contamination by crustal material.     

The Candelaria silver deposit,Nevada — preliminary sulphur,oxygen and hydrogen isotope geochemistry

The pre-Cenozoic geology at Candelaria, Nevada comprises four main lithologic units: the basement consists of Ordovician cherts of the Palmetto complex; this is overlain unconformably by Permo-Triassic marine clastic sediments (Diablo and Candelaria Formations); these are structurally overlain by a serpentinitehosted tectonic mélange (Pickhandle/Golconda allochthon); all these units are cut by three Mesozoic felsic dike systems. Bulk-mineable silver-base metal ores occur as stratabound sheets of vein stockwork/disseminated sulphide mineralisation within structurally favourable zones along the base of the Pickhandle allochthon (i.e. Pickhandle thrust and overlying ultramafics/mafics) and within the fissile, calcareous and phosphatic black shales at the base of the Candelaria Formation (lower Candelaria shear). The most prominent felsic dike system — a suite of Early Jurassic granodiorite porphyries — exhibits close spatial, alteration and geochemical associations with the silver mineralisation. Disseminated pyrites from the bulk-mineable ores exhibit a ³⁴S range from — 0.3 to + 12.1 (mean ³⁴S = +6.4 ± 3.5, 1, n = 17) and two sphalerites have ³⁴S of + 5.9 and + 8.7 These data support a felsic magmatic source for sulphur in the ores, consistent with their proximal position in relation to the porphyries. However, a minor contribution of sulphur from diagenetic pyrite in the host Candelaria sediments (mean ³⁴S = — 14.0) cannot be ruled out. Sulphur in late, localised barite veins ( ³⁴S = + 17.3 and + 17.7) probably originated from a sedimentary/seawater source, in the form of bedded barite within the Palmetto basement ( ³⁴S = + 18.9). Quartz veins from the ores have mean ¹⁸O = + 15.9 ± 0.8 (1, n = 10), which is consistent, over the best estimate temperature range of the mineralisation (360°–460°C), with deposition from ¹⁸O-enriched magmatic-hydrothermal fluids (calculated ¹⁸O fluid = + 9.4 to + 13.9). Such enrichment probably occurred through isotopic exchange with the basement cherts during fluid ascent from a source pluton. Whole rock data for a propylitised porphyry ( ¹⁸O = + 14.2, D = — 65) support a magmatic fluid source. However, D results for fluid inclusions from several vein samples (mean = — 108 ± 14, 1, n = 6) and for other dike and sediment whole rocks (mean = — 110 ± 13, 1, n = 5) reveal the influence of meteoric waters. The timing of meteoric fluid incursion is unresolved, but possibilities include late-mineralisation groundwater flooding during cooling of the Early Jurassic progenitor porphyry system and/or meteoric fluid circulation driven by Late Cretaceous plutonism.     

Geological,fluid inclusion and stable isotope studies of Mo mineralization,Galway Granite,Ireland

Mo mineralization within the Galway Granite at Mace Head and Murvey, Connemara, western Ireland, has many features of classic porphyry Mo deposits including a chemically evolved I-type granite host, associated K- and Si-rich alteration, quartz vein(Mace Head) and granite-hosted (Murvey) molybdenite, chalcopyrite, pyrite and magnetite mineralization and a gangue assemblage which includes quartz, muscovite and K-feldspar. Most fluid inclusions in quartz veins homogenize in the range 100–350°C and have a salinity of 1–13 eq. wt.% NaCl. They display Th-salinity covariation consistent with a hypothesis of dilution of magmatic water by influx of meteoric water. CO₂-bearing inclusions in an intensely mineralized vein at Mace Head provide an estimated minimum trapping temperature and pressure for the mineralizing fluid of 355°C and 1.2 kb and are interpreted to represent a H₂O-CO₂ fluid, weakly enriched in Mo, produced in a magma chamber by decompression-activated unmixing from a dense Mo-bearing NaCl-H₂O-CO₂ fluid. ³⁴S values of most sulphides range from c. 0 at Murvey to 3–4 at Mace Head and are consistent with a magmatic origin. Most quartz vein samples have ¹⁸O of 9–10.3 and were precipitated from a hydrothermal fluid with ¹⁸O of 4.6–6.7. Some have ¹⁸O of 6–7 and reflect introduction of meteoric water along vein margins. Quartz-muscovite oxygen isotope geothermometry combined with fluid inclusion data indicate precipitation of mineralized veins in the temperature range 360–450°C and between 1 and 2 kb. Whole rock granite samples display a clear ¹⁸O-D trend towards the composition of Connemara meteoric waters. The mineralization is interpreted as having been produced by highlyfractionated granite magma; meteoric water interaction postdates the main mineralizing event. The differences between the Mace Head and Murvey mineralizations reflect trapping of migrating mineralizing fluid in structural traps at Mace Head and precipitation of mineralization in the granite itself at Murvey.     

Isotope studies on the Rosebery,Mount Farrell and Mount Lyell ores,Tasmania

Preliminary studies have been made on the distributions of oxygen and sulphur isotopes in the Rosebery, Mount Farrell, and Mount Lyell ores. These ores lie in Cambrian geosynclinal volcanic rocks in West Tasmania. At each locality the sulphur of the sulphide minerals has a distinctive degree of enrichment in ³⁴S in relation to sulphur in meteorites and a narrow range of ³⁴S values. The dominant ore at Mount Lyell (mainly pyrite-chalcopyrite) has an average ³⁴S value of +7.0, the main lode at Rosebery (pyrite-sphalerite-galenachalcopyrite) averages +10.9, and the Mount Farrell ore (galena-sphalerite) averages +14.1. The degree of enrichment does not appear to be related to local, near-surface geological factors. Other ores of geosynclinal volcanic type with similar mineralogy also show narrow ranges in ³⁴S and varying enrichments in ³⁴S. Barite from a concordant sulphide-barite-carbonate lode at Rosebery has an average ³⁴S of +38.1 and an average ¹⁸O of +10.7. Barite from veins at Mount Lyell has an average ³⁴S of +25.3 and an average ¹⁸O of +10.6.

---

Die Verteilung von Sauerstoff- und Schwefel-Isotopen in den Erzkörpern von Rosebery, Mount Farrell und Mount Lyell wurde untersucht. Die Erzkörper sind in kambrische, geosynklinale vulkanische Gesteine Westtasmaniens eingebettet. An jeder dieser Lagerstätten zeigt der Schwefel der Sulfiderze einen charakteristischen Anreicherungsgrad an ³⁴S im Verhältnis zum Meteoritenschwefel und einen eng begrenzten Bereich der ³⁴S-Werte. Die Erze des Mount Lyell-Lagers (hauptsächlich Pyrit-Chalkopyrit) zeigen überwiegend einen ³⁴S-Durchschnittswert von +7.0, das Hauptlager von Rosebery (Pyrit-Sphalerit-Galenit-Chalkopyrit) +10.9, und des Mount Farrell-Erz (Galenit-Sphalerit) +14.1. Der Anreicherungsgrad scheint nicht mit den lokalen geologischen Faktoren verbunden zu sein. Auch andere Erzkörper geosynklinaler vulkanischer Art von ähnlicher mineralogischer Struktur zeigen eng begrenzte ³⁴S-Werte und ³⁴S-Anreicherungsvariationen. Der Baryt des konkordant aufgebauten Sulfid-Baryt-Carbonat-Lagers bei Rosebery hat einen ³⁴S-Durchschnitt von +38.1 und einen ¹⁸O-Durchschnitt von +10.7. Der Baryt aus den Erzgängen von Mount Lyell ist durch einen ³⁴S-Durchschnitt von +25.3 und einen ¹⁸O-Durchschnitt von +10.6 charakterisiert.