Early Veins Research Articles

Miocene to Messinian deformation and hydrothermal activity in a pre-Alpine basement massif of the French western Alps: new U-Th-Pb and argon ages from the Lauzière massif

Abstract U-Pb and Th-Pb dating of monazite from hydrothermal quartz veins (“Alpine veins”) from the Lauzière massif (North Belledonne) together with Ar/Ar ages of adularias from the same veins constrain the age of the last tectono-metamorphic events that affected the External Crystalline Massifs (ECM). Ages obtained are surprisingly young. The study of the structural context of the veins combined with our chronological data, allow us to propose a tectonic scenario of the northern ECM for the 15-5 Ma period, which was poorly documented so far. The quartz veins are of two types: (i) the oldest are poorly mineralized (chlorite and epidote), flat-lying veins. The quartz fibres (= extension direction) are near vertical and seem to be associated with a subvertical dissolution schistosity superimposed upon an early Alpine deformation underlined by “mini-biotite”. They bear a sub-horizontal stretching lineation; (ii) the youngest veins are very rich in various minerals (anatase, rutile, phénacite, meneghinite, beryl, synchysite, ….). They are almost vertical. Their “en echelon” geometry as well as the horizontal attitude of their quartz fibres show a dextral strike-slip regime. Two groups of Th-Pb ages have been obtained: 11 to 10 Ma and 7 to 5 Ma. They were obtained from the most recent veins (vertical veins) sampled in different areas of the massif. The ca. 10 Ma ages are related to veins in the Lauzière granite and its metamorphic country-rocks at about 2 km from the eastern contact of the massif, while the ages of ca. 5 Ma correspond to veins occurring in mylonites along this contact. Adularias provided Ar/Ar ages at ca. 7 Ma. By contrast, a monazite from a vein of the Pelvoux massif (Plan du Lac) yielded a Th-Pb age of 17.6 Ma but in a different structural setting. Except fission track ages, there are very little ages of this range published in the recent literature on the Alps. The latter concern always gold mineralized veins (NE Mont Blanc and SW Lepontine dome). The last compressive tectonic regime dated between 15 and 12 Ma is coeval with (i) the late “Roselend thrust” event, which is recorded in the Mont Blanc by shear-zones with vertical lineation, (ii) the last movements in the basal mylonites of the Swiss Nappes, (iii) the horizontal Alpine veins from the Mont Blanc and Belledonne massifs (with vertical quartz fibres), which are similar to the early veins of the Lauzière. On the contrary, the vertical veins of the Lauzière, dated between 11 and 5 Ma, correspond to a dextral strike slip regime. This suggests that most of the strike-slip tectonics along the ECM took place during two stages (ca. 10 Ma and ca. 7-5 Ma) and not only at 18 Ma as had been proposed previously. Our ages are consistent with the late Miocene-Pliocene overlap of the Digne thrust to the South and to part of the normal movement along the Simplon fault to the North. Thus, all the external crystalline massifs were tectonically active during the late Miocene. This suggests that tectonic events in the external alpine belt may have contributed to some extent to the geodynamical causes of the Messinian crisis.

The Bingham Canyon Porphyry Cu-Mo-Au Deposit. II. Vein Geometry and Ore Shell Formation by Pressure-Driven Rock Extension

Copper, gold, and molybdenum in the Bingham Canyon deposit (Utah, United States) show a systematic distribution in grade and metal ratios. Most Cu-Au mineralization follows, both spatially and temporally, the emplacement of the quartz monzonite porphyry (QMP), a southwest-northeast-elongated thick dike intruding along the contact between the premineralization equigranular monzonite stock and surrounding sedimentary rocks. Copper ore grades define the shape of an inverted cup, which is centered on the QMP but has a much broader, near-circular footprint. Several deep root zones surround a barren core occupied by the same lithologic units and intense potassic alteration but insignificant metal tenor. Throughout the deposit, gold to copper ratio is systematically zoned. The distribution of molybdenum resembles that of copper and partly overlaps with it, but the molybdenum ore shell is generally displaced inward and downward from the copper ore shell. Systematic measurement of the abundance and orientation of three major vein types obtained at the pit surface were complemented with unoriented vein density data from drill core logging. Quartz stockwork veins, the earliest and most abundant of the mapped vein types, are related to potassic alteration and major Cu-Au mineralization. Their greatest vein density follows the intrusion of the QMP but extends far beyond, into sedimentary rocks and especially into adjacent parts of the pre-ore equigranular monzonite. Their orientation is predominantly steep, with a variable strike. Quartz-molybdenite veins postdate all intrusions and are less abundant than quartz stockwork veins. They show variable orientation of strikes and a weaker tendency to steep dips. Quartz-pyrite veins with sericitic alteration halos crosscut all intrusions and earlier veins. They are rare within the central high-grade part of the deposit and predominantly occur near and outside the northeastern and southwestern ends of the QMP. They have a strongly preferred orientation parallel to the porphyry dikes, with steep dips and strike directions fanning out radially from the center of the deposit. Repeated cycles of dike intrusions with distinct southwest-northeast orientation, followed by steep stockwork veins with variable strikes distributed over the broad ore shell and a final return to oriented postore veins are interpreted to result from alternation between two stress regimes. A regional, probably weakly transtensional regime controls the emplacement of dikes and postore veins. Ore vein formation and mineralization is controlled by active rock extension (increase in differential stress) in the roof area above a broad region of high fluid pressure in a subjacent magma chamber, rather than by local hydrofracturing caused by fluid exsolution from the porphyries (decrease in effective rock pressure and positive volume change upon magma crystallization). Shallow vein mineralization well above the lithostatic-to-hydrostatic transition is consistent with low (hydrostatic or even vapor-static) pressures of ore deposition indicated by a companion study of fluid inclusions. The process of pressure-driven roof extension favors the accumulation of metals in high-grade ore shells, compared to temperature-driven concepts according to which the porphyry mineralization is spread out vertically by following downward-retracting isotherms in a cooling magmatic-hydrothermal system.

High Cu grades in porphyry Cu deposits and their relationship to emplacement depth of magmatic sources

Observations at several porphyry Cu deposits indicate that in those formed above source magma chambers emplaced to relatively shallow levels (roofs ~3–4 km deep), zones of higher Cu grade are associated with the oldest intrusions of a central porphyry cluster, abundant early (A-type) quartz veins, secondary feldspar alteration, and usually high Fe/Fe + Cu, low S/Fe + Cu sulfide-oxide mineral assemblages. In deposits for which source magma chambers were deeper (roofs >5 km), porphyries closest in age to ore are spatially less directly related to mineralization. In these, higher Cu grades in early mineralization comprise swarms of veinlets with alteration halos that include sericite as well as secondary feldspar and biotite. Sulfide ± oxide assemblages are usually of lower Fe/Fe + Cu and higher S/Fe + Cu. These differences in deposit characteristics appear to correspond with a change from two-phase, chloride-bearing, aqueous fluids that would exsolve from magma at shallow depths, to one-phase fluids deeper.

Onset and Progression of Serpentinization and Magnetite Formation in Olivine-rich Troctolite from IODP Hole U1309D

Serpentinization of olivine-rich troctolite from core 227, Integrated Ocean Drilling Program (IODP) Hole U1309D ranges from 10 to 90. Two episodes of serpentinization are recognized. The first, dominant in weakly serpentinized samples, is an approximately isochemical (except for water) replacement of olivine (Fo(8485)) by a mixture of serpentine (antigorite, Mg-number 92) and brucite (amakinite-rich; Mg-number 65). The compositions of the minerals in type 1 veins are a reflection of FeMg exchange between olivine and the brucite serpentine formed during early serpentinization. The early serpentinite veins (type 1) are thin ( 005 mm), irregular, and exploit pre-existing cracks in olivine. The presence of antigorite suggests that early serpentinization occurred at T 300C. Type 1 veins reflect rock-dominated serpentinization, became isolated early in their history, and persist as relicts in all but the most altered samples. The main episode of serpentinization is manifested by through-going lizardite (average Mg-number 96)magnetite veins (type 2). Type 2 veins define an anastomosing foliation, may be several millimeters in width and appear to exploit pre-existing, favorably oriented type 1 veins. Type 2 veins reflect open-system serpentinization. Magnetite in these veins formed by oxidation of the Fe in brucite and serpentine, whereas addition of silica to the system converted the Mg-component of the brucite to serpentine. Magnetite forms one or more distinct bands in the interior of the vein and is never in direct contact with relict olivine. A bruciteserpentine mixture, similar to that found in type 1 veins, but with lizardite instead of antigorite, is commonly present at the margins of type 2 veins (i.e. where they are in reaction contact with relict olivine). We interpret type 2 veins as a steady-state system where brucite continually forms at the olivinevein contact and then reacts out in the interior of the vein. This continual formation and destruction of brucite imposes an exceptionally low a(SiO2) on the system. Magnetite and olivine are never in contact in type 2 veins (or anywhere else) because the olivine-out reaction yields ferroan brucite and not magnetite. The desilication of serpentine in the type 2 veins is a reflection of the inherent instability of Fe-rich serpentine with respect to magnetite at low silica activity. Thus, the composition of serpentine in equilibrium with magnetite in serpentinites is a function of serpentinemagnetite and not serpentineolivine equilbria.

Sediment-Hosted Gold Deposits in Guizhou, China: Products of Wall-Rock Sulfidation by Deep Crustal Fluids

Sediment-hosted gold deposits in Guizhou, China, are hosted in late Paleozoic and early Mesozoic sedimentary rocks along the southwest margin of the Precambrian Yangtze craton. They have characteristics similar to Carlin-type gold deposits in Nevada and are notably enriched in As, Sb, Hg, and Tl. The Shuiyindong and Yata deposits consist of disseminated, strata-bound sulfides in Permian bioclastic limestone and fault-controlled mineralization in Middle Triassic calcareous clastic rocks, respectively. Mineralization in both deposits consists of barren milky quartz veins, disseminated gold-bearing arsenian pyrite and arsenopyrite, stibnite, realgar, and orpiment. The barren milky quartz veins occur in the ore-controlling structures with an envelope of gold mineralization in the host rock consisting of disseminated gold-bearing arsenian pyrite and arsenopyrite and replacement-style quartz veinlets. Later drusy quartz, stibnite, realgar, and orpiment fill fractures and vugs on the periphery of gold mineralization. Petrography, microthermometry, laser Raman spectroscopy, and laser ablation inductively coupled plasma mass spectrometric (LA-ICP-MS) analyses of fluid inclusions are used to characterize the chemical evolution of ore fluids at Shuiyindong and Yata. Early barren milky quartz veins trapped aqueous fluid with moderate salinity (6.0 wt % NaCl equiv) and minor CO2 (<2.4 mol %) at a temperature of 230° ± 30°C. This fluid contains measurable B, Na, K, Cs, Sr, As, Sb, and Au (3.8 ± 0.5–5.7 ± 2.3 μ g/g) determined by LA-ICP-MS and is interpreted to approximate the mineralizing fluid responsible for precipitation of early barren quartz veins. Low-salinity (0.9–2.3 wt % NaCl equiv), CO2-bearing (6.3–8.4 mol %), aqueous fluids are recorded in replacement-style quartz veinlets. They formed gold-bearing arsenian pyrite and arsenopyrite and quartz veinlets at a temperature of 210° ± 20°C and pressures of 450 to 1,150 bars, corresponding to depths between 1.7 and 4.3 km under lithostatic conditions. Fluid inclusions in late stibnite-orpiment-realgar-quartz veins contain high CO2 (58–64 mol %) and N2 (19.2–23.7 mol %) with trace CH4 (up to 1.6 mol %). The increasing content of CO2 and decrease in the concentrations of Au and As in aqueous-carbonic inclusions are interpreted to result from carbonate dissolution at the level of the deposits during gold mineralization. Covariance of Au, As, Sb, and Sr concentrations in the fluids is interpreted to reflect deposition of As and Sb sulfides and gold concurrent with carbonate crystallization. Iron is below detection limit (~400 μ g/g) in all fluid inclusion types, suggesting that the ore fluids were Fe poor but possibly sulfur rich, possibly explaining their exceptionally high gold contents. Iron in sulfide minerals was probably derived from dissolution of ferroan minerals in the host rocks, sulfidized by H2S-rich fluids to precipitate arsenian pyrite, arsenopyrite, and gold. Pressure fluctuation induced by faulting resulted in local fluid immiscibility and led to late deposition of realgar, orpiment, stibnite, and calcite. Hydrogen and oxygen isotope compositions of ore fluids ( δ D(H2O) = −35 to −68‰, δ 18O(H2O) = 4–16.5‰) indicate a metamorphic origin, possibly related to crustal thickening and prograde metamorphism during the late Yanshanian orogeny.

The Empire Cu-Zn Mine, Idaho: Exploration Implications of Unusual Skarn Features Related to High Fluorine Activity

The Empire Cu-Zn skarn deposit is unusual because of the proximal position of Zn mineralization, abundance of endoskarn, and the extremely vermicular texture of quartz phenocrysts in the related intrusive rocks. Cu-Zn skarn occurs at the contact between Upper Mississippian White Knob limestone and the granite porphyry phase of the Mackay Stock which consists, from early to late, of quartz monzodiorite, granophyre, granite porphyry, porphyritic granite, and many dikes. The late phases have high F and also extremely vermicular quartz phenocrysts. Endoskarn is more abundant than exoskarn. The earliest alteration of the intrusive rocks consists of disseminated diopsidic pyroxene (Di64Hd36 to Di88Hd12), actinolite, and titanite. This assemblage was cut by early scapolite (Me18 to Me35, mostly Me18-26) and/or green pyroxene (Di14Hd80 to Di20Hd77) veinlets, with or without wollastonite halos. These early veins were then cut by main-stage endoskarn veins that typically have a garnet + minor pyroxene inner zone, a wollastonite and/or pyroxene ± Ca-rich plagioclase (An56 to An89) envelope, and a halo containing disseminated, fine-grained alteration minerals of the same assemblage as the envelope. Some veins contain only the envelope assemblage and are interpreted to represent the alteration front. The inner zone locally contains vesuvianite. Where many veins intersect, endoskarn is massive. Pyroxene is zoned around fluid conduits; the distal pyroxene is Fe rich (hedenbergitic) whereas the proximal pyroxene is Fe poor (diopsidic). The garnet changes in the opposite way, being Fe poor-Al rich (grossularitic) in locations distal to the fluid conduits, and Fe rich (andraditic) in proximal locations. In contrast, in the exoskarn, all pyroxene is diopsidic and garnet is andraditic. Weak, retrograde alteration composed of quartz + calcite + chlorite with minor fluorite, talc, and epidote overprinted both endoskarn and exoskarn. Magnetite precipitated after garnet-pyroxene in both endoskarn and exoskarn. Sphalerite precipitated together with chalcopyrite in proximal locations and is associated with retrograde alteration. Other ore minerals include minor molybdenite, bornite, pyrite, galena, arsenopyrite, native Au, as well as supergene minerals such as chrysocolla, malachite, azurite, native Cu, and limonite. Fluid xenoliths from pyroxene in early endoskarn veinlets homogenize at >600°C. Massive endoskarn and exoskarn replacing limestone inclusions in granite porphyry formed at 500° to >700°C, whereas the highest temperature inclusions, >700°C, occur in narrow garnet + minor pyroxene veins. Fluid inclusions in exoskarn replacing wall rock have homogenization temperatures of 500° to 650°C. Retrograde alteration and Cu-Zn mineralization occurred at 250° to 300°C. Fluid inclusions in prograde minerals contain daughter minerals, whereas fluid inclusions in retrograde minerals do not, indicating a decrease in salinity with time. Late-stage fluids have low eutectic temperatures, indicating the possible presence of KCl, NaCl, FeCl2, CaCl2, MgCl2, K2CO3, and/or Na2CO3. Formation of the unusually abundant endoskarn, the proximal position of Zn mineralization, and the extremely vermicular texture of quartz phenocrysts are all believed to have been promoted by the high F content of the magmatic fluid. These features may serve as exploration indicators of associated high F mineralization such as buried porphyry Mo deposits.

Genesis and evolution of the structurally controlled vein mineralization (Sb–Hg) in the Escarlati deposit (León, Spain): Evidence from fault population analysis methods, fluid-inclusion research and stable isotope data

The Escarlati deposit is located in the Cantabrian Zone of the Variscan Massif and is one of the best examples in the Iberian Peninsula of Sb and Hg both coexisting in the same paragenesis. The Sb–Hg mineralization appears filling hydraulic and collapse breccias hosted in Late-Variscan fractures affecting Carboniferous black limestones. The structural analysis and mineralogical, fluid-inclusion and stable isotopic characterization of the Escarlati Sb–Hg deposit (Señales pass, León province), have been performed. In this contribution we aim to show the close relationships between the structural control of the mineralization and the evolution of its mineralogical and thermodynamic formation conditions. An analysis of calcite vein sets and striated fault planes exposed in the old mine working areas using several methods of fault population analysis (FPA), in particular the right dihedra method (RDM) and the slip model (SM), enables us to determine that the ore concentration was favoured by reactivation of previous structures during the latest-tectonic regime. There was a first strike-slip tectonic event with a maximum compression orientation of NW-SE ( σ 1 = 00°/300°) and maximum extension trending NE-SW ( σ 3 = 00°/030°), which generated early unmineralized calcite veins. A second strike-slip reverse movement, which reactivated early structures, produced an intense stage of fracturing developing a first stage with mylonites and a second one with breccias (hydraulic and collapse calcareous breccias) and the rotation of the stress axes in a clockwise sense, with a maximum shortening direction N–S ( σ 1 = 00°/010°) and extension direction E–W ( σ 3 = 00°/100°). The final part of the younger tectonic event is recorded by striated fault planes, which indicate a latest strike-slip reverse tectonic event with maximum shortening direction NNE-SSW ( σ 1 = 17°/200°) and extension direction WNW-ESE ( σ 3 = 28°/100°), and also a new clockwise rotation is registered. Ore mineralogy is related to the second strike-slip reverse movement tectonic event and shows two different mineralogical associations, the first of which is related to the initial movements of the strike-slip reverse tectonics and is made up of quartz and pyrite followed by stibnite, fluorite and calcite filling hydraulic breccias. The final part of this tectonic regime promoted high fluid flow and is characterized by the deposition of cinnabar together with a second generation of pyrite and fluorite, mostly in collapse breccias. Fluid inclusions of the mineralizing event reveal a drop in temperature between the two mineralizing stages (from approximately 190 °C to less than 150 °C) and a remarkable pressure drop from lithostatic (1125 bar) to hydrostatic conditions (250 bar) during the first stage as well as sub-superficial pressures during Hg deposition, in agreement with the evolution in two parts of the second strike-slip reverse movement. The carbon of the hydrothermal carbonates is influenced by the organic matter of the Barcaliente Formation and their δ 13C and δ 18O isotopic composition reveal that we can not distinguish two different populations of hydrothermal carbonates. The heavy δ 34S of sulphides indicates its leaching from sedimentary sulphur that had its origin in an abiogenic fractionation process. The lighter δ 34S values in cinnabar than in stibnite indicate changes to more oxidant conditions during cinnabar deposition. These changes probably occurred as a result of the loss of volatile components from the mineralizing fluid during the transition from lithostatic to hydrostatic conditions, as revealed by the fluid-inclusion study.

Fluid Inclusion Evidence for Magmatic-Hydrothermal Fluid Evolution in the Porphyry Copper-Molybdenum Deposit at Butte, Montana

The porphyry Cu-Mo deposit in Butte, Montana, formed where magmatic hydrothermal fluids, introduced with injections of porphyrytic dikes, fractured and permeated the Butte Quartz Monzonite. These fluids formed a stockwork of quartz and quartz-sulfide veinlets with a variety of styles of potassic and sericitic alteration envelopes. The distribution of vein and alteration types and the distribution of fluid inclusions in these veins record the progressive pressure, temperature, and compositional evolution of the hydrothermal fluids that formed this world-class deposit. Deep drilling and 1,300 m of offset along the Continental fault provide a vertical view of almost 3 km through the Butte deposit. Deep veins within and below the highest Mo grades are quartz dominated with thin K-feldspar or, less commonly, biotitic alteration rims. Fluid inclusions in deep veins trapped a single phase aqueous fluid containing 2 to 5 wt percent NaCl equiv and 2 to 8 mol percent CO2 at temperatures between 575° and 650°C and pressures between 200 and 250 MPa, corresponding to depths between 6 and 9 km. Although Cu grades are low in this region, abundant chalcopyrite daughter minerals in fluid inclusions indicate that the fluids were Cu rich. Fluids that formed these veins transported Cu from the magma below, upward into the region of Cu mineralization with only minor Cu precipitation. Over a kilometer above the bulk of deep quartz and quartz-molybdenite veins, the highest Cu grades are in and around chalcopyrite-bearing quartz-sulfide veins with biotitic alteration (early dark micaceous veins), and their upward, equivalent magnetite-chalcopyrite-pyrite-quartz veins with wide K-feldspar, green sericite, and chlorite alteration (pale-green sericitic veins). These veins contain more evidence for brine-vapor unmixing than any other vein type. The upward progression of early dark micaceous veins to pale-green sericitic veins formed where low salinity, CO2-bearing fluids, similar to those trapped in deep quartz veins, ascended, de-pressurized, sometimes unmixed, and cooled from ~650°C at 90 MPa to ~475°C at ~50 MPa. As low salinity, CO2-bearing, aqueous fluids, similar in composition to fluids trapped in deep quartz veins, cooled at shallow depths, they formed late pyrite-quartz veins with sericitic alteration. These veins formed from fluid cooling at temperatures between 370° and 450°C at transiently hydrostatic pressures between 40 and 70 MPa, corresponding to depths of 4 to 7 km. Most pyrite-quartz veins formed at pressures and temperatures above the H2O-NaCl-CO2 solvus, but evidence for brine-vapor unmixing is also present. Pyrite-quartz veins formed at progressively greater depths as the hydrothermal system cooled, overprinting much previous mineralization. Late Cu-Pb-Zn-Ag-As-rich Main stage veins formed from dilute fluids containing <3 wt percent NaCl equiv and <2 mol percent CO2. These fluids were trapped between 230° and 400°C under hydrostatic pressures between 20 and 60 MPa and depths of 2 to 6 km. No evidence of boiling is observed in Main stage veins. Fluid inclusion phase relationships indicate that the Butte porphyry Cu-Mo deposit formed at 5 to 9 km depth, greater than any other porphyry-type deposit. At Butte, the similarity in bulk composition of fluids trapped in early quartz-rich veins with potassic alteration and late pyrite-quartz veins with sericitic alteration implies that an underlying magma continually provided low salinity, CO2-bearing fluids of relatively constant composition during the entire life of the hydrothermal system. We hypothesize that rather than resulting from changes in fluid chemistry due to magma crystallization, the entire suite of vein and alteration types and the ore metal distribution reflect the path of cooling, depressurization, and wall-rock interaction of a parental magmatic-derived fluid of relatively constant initial composition. Fluid inclusions, vein and alteration relations, and ore metal distribution indicate that Cu and Mo were introduced into the hydrothermal system by the same fluids, but that the mechanisms of precipitation of these metals were decoupled. Early dark micaceous and, to a greater extent, pale-green sericitic, veins have wide alteration envelopes and contain more evidence for fluid unmixing than any other vein type, which suggests that chalcopyrite precipitation was driven by a combination of fluid unmixing, fluid-rock reaction, and fluid cooling between 650° and 475°C. Most molybdenite mineralization, however, is in quartz-dominated veins with little or no alteration that are dominated by low salinity inclusions. These veins formed in response to pressure decrease rather than cooling. After chalcopyrite and molybdenite precipitation, low salinity fluids cooled, usually at temperatures and pressures above the H2O-NaCl-CO2 solvus, to produce significant acid and voluminous sericitic alteration accompanied by pyrite-quartz vein formation that overprints much of the deposit and contains anomalous but noneconomic Cu.

Serum concentration of procoagulant, endothelial and oxidative stress markers in early primary varicose veins

Endothelial disorders of the veins are considered to play a role in the pathogenesis of primary varicose veins and oxidative stress is implicated in these disorders. With this aim, we investigated vascular endothelial marker levels and the effect of endothelial damage on coagulation parameters and vasodilator substances to determine metabolic markers of oxidative stress in patients with varicose veins and vascular endothelial damage caused by oxidative stress. We investigated the levels of malondialdehyde (MDA), protein C, protein S, fibrinogen, von Willebrand factor (vWf), tissue plasminogen activator (tPA), vascular endothelial growth factor (VEGF), interleukin-6 (IL-6), interleukin-12 (IL-12) and nitric oxide (NO) in the blood taken from the brachial vein of 25 patients with primary varicose veins (study group) and compared the results with 25 healthy volunteers (control group). We also investigated the urinary levels of prostaglandin I2 (PGI2) in the study group and compared the results with the control group. There was no statistically significant difference between the study group and the control group with respect to the plasma levels of MDA, protein C, fibrinogen, tPA, IL-6, NO and urinary levels of PGI2. But plasma levels of protein S, vWf, VEGF and IL-12 were found to be statistically significantly higher in the study group than in the control group. Although the systemically measured levels of protein S, vWf, VEGF and IL-12 were found to be higher in patients of primary varicose veins, levels of protein C, fibrinogen, homocysteine and PGI2 were not found to be statistically significant. No systemic increased oxidative stress seems to be related to the early stages of chronic venous insufficiency. Further studies are warranted for understanding the role of molecules such as NO, oxidative stress parameters and cytokines.

Gold Mineralization at the Anomaly A Deposit, Clarence Stream Area, Southwestern New Brunswick: Distal Deposits of a Syn-Deformational Intrusion-Related Gold System?

Gold-bearing mineralization at Anomaly A occurs in polydeformed Ordovician turbidites of the Kendall Mountain Formation of the St. Croix belt in southwestern New Brunswick, and is hosted by WSW-trending, shallow-dipping, brittle–ductile high-strain zones associated with the latest stage of the second of four regional deformation events. Gold-bearing syn-deformational stockwork, massive, and multiply brecciated quartz-sulfide veined zones form irregular pods and sheets up to several meters thick, which contain arsenopyrite, pyrrhotite, pyrite, stibnite, and a variety of rare minerals that are gold-bearing. Mineralized zones are enveloped by locally auriferous, weakly to intensely altered wall rock. Vein paragenesis includes: (1) early (pre- to syn-D 2 ) quartz-chlorite veins that are largely the product of migration of quartz by pressure solution; (2) crosscutting, multiphase, vuggy quartz-sulfide veins that contain most of the gold and are interpreted to be structurally controlled; (3) late, crosscutting, nondeformed, non-gold-bearing veins containing laumontite, chlorite, muscovite, quartz, fluorite, and base metal sulfides. Carbonate-poor alteration associated with zones of gold mineralization is lithology-specific, and appears to reflect overprinting of multiple events. Major elements removed during alteration include Si, Na, Mn, and Mg. The minor and trace elements removed include Co, Li, Sc, and possibly Sr, Ni, and Zn. Minor and trace elements added include Au, Ag, As, Sb, S, and possibly F, Cu, Pb, and Zr. On the basis of proximity, time constraints, and a similar ore mineral assemblage, gold mineralization at Anomaly A is interpreted to be a distal equivalent of the intrusion-related gold mineralization at the nearby Clarence Stream Main zone deposit.

Three‐dimensional reconstruction of the remodeling of the systemic vasculature in early pig embryos

Current research on angiogenesis and vascular regression is mainly focused on pathological conditions such as tumor growth and diabetic retinopathy, while a suitable physiological model to study the controlling factors in these processes is still lacking. The remodeling pattern of the embryonic vasculature into the adult configuration, such as the branchial arch arterial system developing into the aorta or the early embryonic veins building the caudal vena cava can potentially serve as a model. However, practical applications of the embryonic vascular patterning are impeded by the current controversy over the exact development of the caudal vena cava in mammals. To elucidate these ambiguities, specific developmental stages of vascular development in pig embryos were mapped by means of computer-assisted 3D reconstructions starting from histological serial sections of Bouin's fixed embryos. Special attention was given to venous segments in the lumbar region, as their origin and fate are equivocally described in literature. Here we demonstrate that these venous segments originate from the caudal cardinal veins which are forced to migrate during development into a more dorsal position due to the expansion of the developing metanephroi and the more dorsal relocation of the umbilical arteries. These findings are in contrast with the generally accepted theory that the venous segments in the lumbar region arise from newly formed veins that are located dorsal to the early caudal cardinal system.

Production of carbonic fluids during metamorphism of graphitic pelites in a collisional orogen—An assessment from fluid inclusions

Fluid inclusions in quartz veins within Proterozoic metamorphic rocks in the Black Hills, South Dakota, were examined by microthermometry and Raman spectroscopy to assess the evolution of fluid compositions during regional metamorphism of organic-rich shales and late-orogenic magmatism, both of which were related to the collision of the Wyoming and Superior crustal blocks. Fluid inclusions occur in veins that began to be generated before or during regional compression and metamorphism that reached at least garnet-grade conditions, and in veins within the aureole of the Harney Peak Granite (HPG), where temperatures reached second-sillimanite grade conditions. Early veins in the schists have undergone recrystallization during heating and deformation that modified the composition of early CH 4 or CO 2 and N 2-dominated inclusions. These fluids were apparently trapped under conditions of immiscibility with a saline aqueous fluid phase. They are interpreted to represent components generated during maturation of organic matter and dehydration of phyllosilicates during incipient metamorphism at reducing fO 2 conditions. Most inclusions in the quartz veins are, however, secondary CO 2-bearing. They imply a transition to higher fO 2 conditions with increasing temperature of regional metamorphism. The fO 2 conditions may have been controlled by the mineral assemblage in the host metapelites. The prevalence of bimodal distributions of trapped CO 2–N 2 and aqueous endmembers in the biotite and garnet zones also suggests that two immiscible fluid phases existed during the regional metamorphism. In the aureole of the HPG, graphite was evidently consumed by influx of magmatic fluids. CO 2–H 2O fluid inclusions dominate, but they have significantly less N 2 than inclusions at lower metamorphic grades. All inclusions define secondary trails in mostly unstrained quartz. The bimodality of inclusion compositions is not as well defined as at lower grades, with many inclusions containing intermediate CO 2–H 2O compositions. This suggests that a single fluid phase existed at the high temperatures in the granite aureole, but then unmixed during cooling. A set of late quartz veins with graphitized and tourmalinized selvages in the granite aureole contains CH 4-bearing inclusions with little N 2. The existence of CH 4 in these inclusions is attributed to complexing of magmatic B with hydroxyl anions taken from the CO 2–H 2O fluid phase, effectively causing reduction in fO 2 and promoting precipitation of graphite.

Pb ISOTOPE COMPOSITIONS OF PYRITE FROM THE C QUARTZ-TOURMALINE VEIN OF THE SISCOE GOLD DEPOSIT, VAL D'OR, QUEBEC: CONSTRAINTS ON THE ORIGIN AND AGE OF THE GOLD MINERALIZATION

The Siscoe mine was one of the richest in the Val d’Or mining camp, producing 27.5 tonnes (t) of gold and 9.5 t of silver from 1929 to 1949. The C quartz-tourmaline vein at the Siscoe mine, which is the youngest auriferous vein on the property, is an excellent example of a high-grade Archean lode gold deposit; it contains an average of 45 g/t Au and locally up to 221 g/t Au. This vein cuts all dikes, the main regional foliation (S2), and several auriferous quartz-carbonate veins, and is interpreted to be a shear structure that formed during the development of a late- to post-D2 reverse fault. The vein comprises mainly alternating tourmaline- and quartz-rich layers, and gold occurs commonly in late fractures cutting the vein. The visible wall-rock alteration is characterized by the occurrence of tourmaline, pyrite, and calcite. In this study, we report the Pb isotope compositions of hydrothermal pyrite separates taken from the C quartz-tourmaline vein and its wall rock. Pyrite is abundant in the wall rock, where it occurs as grains with inclusions of chalcopyrite, gold, tetradymite, pyrrhotite, rutile, silicates, and carbonates. In the vein, it forms euhedra generally devoid of inclusions. Locally, the euhedra are fractured, and the fractures are filled with native gold, calcite, and tetradymite. Textural relationships suggest that pyrite precipitated synchronously with and/or after gold in the wall rock, but predated gold in the vein. Pyrite separates from the vein and its wall rock yielded similar 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios (13.63–13.83, 14.58–14.62, and 33.42–33.76, respectively), which are more radiogenic than those reported for volcanic supracrustal and syntectonic plutonic rocks of the southern Abitibi subprovince, but are very similar to those of the late- to posttectonic S-type granites in the Pontiac subprovince and Lacorne block. This suggests that the Pb originated from a reservoir similar to that of the magmas which produced these granites, or alternatively, that it was leached from the latter. The Pb ratios yield a model age of 2.57 ± 0.07 Ga, which is interpreted to date the cooling of the hydrothermal system that introduced and/or remobilized gold into the C quartz-tourmaline vein. These results, when considered in the context of the evolution of the southern Abitibi, indicate that widespread hydrothermal circulation occurred between 2.64 and 2.55 Ga, after the collision of the Pontiac and Abitibi subprovinces, and was caused by dewatering and S-type magmatism in the thickened unstable continental crust. This long-lived hydrothermal system promoted remobilization of gold from earlier veins and possibly introduction of gold from deeper zones, enhancing gold resources in the Siscoe deposit.

CO 2 metasomatism in a basalt-hosted petroleum reservoir, Nuussuaq, West Greenland

Extensive subaerial exposures of a basalt-hosted petroleum reservoir around Marraat Killiit on Nuussuaq, West Greenland, provide an unparalleled opportunity to investigate water–rock–hydrocarbon interactions in an unconventional petroleum system. Exposed sections in this locality include picritic and olivine-phyric basalts, with both subaerial and subaqueous textures that initially had significant primary porosity in the form of gas vesicles, scorias, and interclast voids within hyaloclastites. Alteration of these low-silica, high-magnesium basalts formed regionally-extensive, silica-deficient zeolite-facies mineral assemblages that dominantly consist of mixed-layer chlorite/smectite clays, thomsonite, natrolite, gonnardite, analcime and chabazite. In the study area, faulting and fracturing allowed petroleum migration from sediments into the overlying basalts. Migration of petroleum and the associated brine led to the pseudomorphic replacement of zeolite and clay mineral assemblages by carbonates (siderite, magnesite, dolomite and calcite) and quartz. Carbonates associated with petroleum migration are rich in Mg and Fe, reflecting the interaction of a CO 2-rich fluid with a picritic basalt and associated Fe- and Mg-rich smectites. Only late stage carbonates are calcium-rich, the result of depletion of aqueous magnesium and iron following precipitation of magnesite–siderite solid solutions. Values of δ 13C vPDB and δ 18O vSMOW of carbonates at Marraat form two distinct groups: (1) paragenetically early dolomite veins and magnesite–siderite replacement of low-grade metamorphic minerals that have δ 18O vSMOW between 12.6 and 20‰ and δ 13C vPDB in the approximate range of 0 ± 5‰, and (2) late stage calcite veins that are lighter in 18O ( δ 18O vSMOW between 6.4 and 8.7‰) and have a restricted range of δ 13C vPDB that is near zero. Comparison with isotopic properties of carbonates from petroleum reservoirs worldwide and carbonates formed from meteoric water in basalts from the North Atlantic Igneous Province suggests that the first group of carbonates are formed by reaction of oil field brines with basalts, but the latter group formed by reactions involving meteoric waters. Reservoir properties and quality are a sensitive function of the sequence of hydrothermal and deformation events affecting this region. Regional metamorphism resulted in extensive occlusion of primary porosity by mafic phyllosilicates and zeolites. Subsequent brittle deformation resulted in the formation of fracture sets that served as migration pathways for hydrocarbons and carbonate-rich brines. Interaction of these brines with the zeolite facies metabasalts resulted in extensive alteration reactions that replaced metamorphic mineral assemblages with carbonate + quartz, and generated significant secondary porosity that hosted the altering fluids and live hydrocarbons. Mineral paragenesis at Marraat indicates that zeolite and clay stability is a sensitive function of the oxidation state of the system and that this is controlled by water–hydrocarbon–basalt interactions.

Fracture sealing and fluid overpressures in limestones of the Jabal Akhdar dome, Oman mountains

AbstractFractures are important conduits for fluid flow in the Earth's crust. To better understand the spatial and temporal relations among fracturing, fracture sealing, and fluid flow, we have studied fractures, faults, and veins in a large dome (Jabal Akhdar) in the Oman mountains. Our work combines the results of meso‐ and microstructural analyses and stable isotope analyses. Seven generations of fractures and veins have been identified in the carbonate‐dominated dome. The earliest generations of veins developed during extension and subsidence of the Mesozoic basin. These veins formed in the inclined segments of bedding‐parallel stylolites and in extensional fractures that are perpendicular to bedding (#1 and #2, respectively). These extension‐related veins are truncated by bedding‐parallel veins (#4) that formed during top‐to‐north bedding‐parallel shear of both the northern and southern limbs of the dome. These veins are consistent with a change in stress regime and may be related to an earlier generation of strongly deformed pinch‐and‐swell veins (#3) that are exposed locally on the southern limb of the dome. Normal faults contain a set of en‐echelon tension gashes (#5) and veins emplaced in dilational jogs along the fault planes (#6). In the northern part of the dome, veins (#7) associated with thrusts post‐date the normal faults. Samples of veins and their host rocks were analyzed to provide information on fluid‐rock interaction in the dome and the scale(s) of fluid movement. Oxygen isotope values range from +16.2 to +29.3‰; carbon isotope values range from 0 to +3.6‰. The results of the structural and isotopic analyses are consistent with the early veins (#2–#5) having precipitated from overpressured fluid in a isotopically rock‐buffered system. During normal faulting (#5 and #6), a more open system allowed external fluid to infiltrate the dome at drained conditions and precipitate the youngest sets of veins (#6 and #7).

Late Paleozoic strike-slip faults and related vein arrays of Cape Elizabeth, Maine

Strike-slip faults and related quartz vein arrays of Late Paleozoic-age cut gently-dipping metasedimentary rocks at Cape Elizabeth in southern coastal Maine and formed in response to regional dextral shearing along the Norumbega fault system. Vertical quartz veins up to 20 m wide and 10s of meters long were emplaced orthogonal to the local shear zone-parallel elongation fabric, reflecting strain partitioning during transpression. Earlier veins were reoriented by clockwise rotation toward this NE-trending regional shear direction. The later brittle strike-slip faults are oblique to the regional shear direction and interpreted as a 10-km-scale R-shear array on the southeast flank of the Norumbega fault system. These left-stepping en échelon fault zones consist of the three Two Lights fault zones (∼200 m lengths and up to ∼5 m displacements) and the Richmond Island fault zone (∼1.6 km length and ∼40 m displacement). Displacements on these fault zones have developed fine-grained silicified, obliquely-foliated and laminated cataclasites and locally, millimeter-thin pseudotachylyte fault and injection veins. Individual fault core zones are up to 10s of centimeters thick as part of several complex anastamosing zones of faulting 10s of meters wide. Initial segments within each fault zone are typically terminated with oblique extension fractures in horsetail configurations. The left-stepping en échelon relationships between these segments led to dominantly contractional step-over zones where P-shear linkages created a through-going fault that truncated the ends of the earlier-formed terminated segments. This linkage-growth model for fault zone evolution works toward larger scales and longer fault lengths as displacement accumulates, within a limiting maximum displacement/length ratio characteristic of the host lithologies. Length–frequency data for fault segments within these zones suggest a transition to linkage-dominated growth once fault segments were longer than ∼15 m. Continued displacement was accommodated along the P-shear linked en échelon faults through imbrication, contractional duplexing and adhesive wear on the outcrop-scale. Core zone processes on the micro-scale reflect cataclasis and frictional sliding during coseismic slip as well as cataclastic flow and pressure solution during post-seismic creep. The development of foliated-to-laminated cataclasite was accompanied by pore volume collapse, pressure solution and fluid expulsion that, in turn, triggered the development of the late fault-related quartz vein arrays.

Intensity of quartz cathodoluminescence and trace-element content in quartz from the porphyry copper deposit at Butte, Montana

Textures of hydrothermal quartz revealed by cathodoluminescence using a scanning electron microscope (SEM-CL) refl ect the physical and chemical environment of quartz formation. Variations in intensity of SEM-CL can be used to distinguish among quartz from superimposed mineralization events in a single vein. In this study, we present a technique to quantify the cathodoluminescent intensity of quartz within individual and among multiple samples to relate luminescence intensity to specific mineralizing events. This technique has been applied to plutonic quartz and three generations of hydrothermal veins at the porphyry copper deposit in Butte, Montana. Analyzed veins include early quartz-molybdenite veins with potassic alteration, pyrite-quartz veins with sericitic alteration, and Main Stage veins with intense sericitic alteration. CL intensity of quartz is diagnostic of each mineralizing event and can be used to fingerprint quartz and its fluid inclusions, isotopes, trace elements, etc., from specific mineralizing episodes. Furthermore, CL intensity increases proportional to temperature of quartz formation, such that plutonic quartz from the Butte quartz monzonite (BQM) that crystallized at temperatures near 750 °C luminesces with the highest intensity, whereas quartz that precipitated at ~250 °C in Main Stage veins luminesces with the least intensity Trace-element analyses via electron microprobe and laser ablation-ICP-MS indicate that plutonic quartz and each generation of hydrothermal quartz from Butte is dominated by characteristic trace amounts of Al, P, Ti, and Fe. Thus, in addition to CL intensity, each generation of quartz can be distinguished based on its unique trace-element content. Aluminum is generally the most abundant element in all generations of quartz, typically between 50 and 200 ppm, but low-temperature, Main Stage quartz containing 400 to 3600 ppm Al is enriched by an order of magnitude relative to all other quartz generations. Phosphorous is present in abundances between 25 and 75 ppm, and P concentrations in quartz show little variation among quartz generations. Iron is the least abundant of these elements in most quartz types and is slightly enriched in CL-dark quartz in pyrite-quartz veins with sericitic alteration. Titanium is directly correlated with both temperature of quartz precipitation, and intensity of quartz luminescence, such that BQM quartz contains hundreds of ppm Ti, whereas Main Stage quartz contains less than 10 ppm Ti. Our results suggest that Ti concentration in quartz is controlled by temperature of quartz precipitation and that increased Ti concentrations in quartz may be responsible for increased CL intensities.

Association of pyrobitumen with copper mineralization from the Uchumi and Talcuna districts, central Chile

Abstract Pyrobitumen has been shown to be an essential component in formation of some Chilean manto-type (strata-bound) copper deposits and its presence has been observed in a number of other deposits but has received limited investigation. In this paper we present paragenetic and geochemical data from two central Chilean manto-type deposits from the Uchumi and Talcuna districts where solid pyrobitumen (residual petroleum) is intimately associated with copper sulfides. Pyrobitumen in the Uchumi deposit occurs in pore space within the host conglomerates and is adjacent to a granitoid stock; pyrobitumen predates bornite–chalcocite mineralization and may have reduced subsequent mineralizing fluids. Pyrobitumen from the Manto Delirio deposit, Talcuna District, fills the cores of early sphalerite veins and was partially replaced by later Cu–As mineralization; pyrobitumen is petrographically intergrown with Cu–Fe sulfides and light δ13C values of gangue calcite indicates the interaction of pyrobitumen with the mineralizing fluid. The presence of pyrobitumen within the ores of other manto-type copper deposits in the Lower Cretaceous basin of Chile suggests that degraded petroleum reservoirs, in particular if biodegradation generated authigenic pyrite, can be important controls for metallic mineralization derived from hydrothermal solutions of different sources.

Morphology, intersections, and syn/late-diagenetic origin of vein networks in pelites of the Lodève Permian Basin, Southern France

This paper presents the results of a field study aiming to describe and to interpret new types of relationships between vein sets. Three vein sets of the Lodève Permian Basin (Languedoc, Southern France) were studied. They consist of a family of N100E–N120E, widely opened sinuous veins with a composite infilling (sparite, calcite fibres, barite), hereafter called Sparitic Sinuous Veins, and of two orthogonal families of slim veins presenting a fibrous infilling of calcite, and oriented N10E–N20E and N90E–N100E, respectively. These two latter families are hereafter called N20 Fibrous Slim Veins and N90 Fibrous Slim Veins. The intersections between the three vein sets are shown to be original and more complex than those classically observed in the case of joint sets (abutting, crosscutting, …). The analysis of these intersections permitted a relative chronology of formation of the different vein sets to be established: the N20 Fibrous Slim Veins post-date the N90 Fibrous Slim Veins, which themselves post-date the Sparitic Sinuous Veins, the two former vein sets being shown to reopen contemporaneously. Furthermore, the vein intersections were not as simple as expected. Indeed, the successive propagating cracks of one set could in certain cases crosscut the pre-existing veins of an earlier set, or could be stopped at contact with earlier veins in other cases. This implies a physical change in the interface between the pre-existing veins and the host rock (pelites) during the formation of the latest cracks. Taking into account the well-known tectonic history of the Lodève basin, and the field observations (vein features, intersections, …), the origin of each vein set is discussed. We put forward that the Sparitic Sinuous Veins formed during the burial history of the basin: their morphological characteristics suggest that they appeared during the phase of active compaction of the basin, in response to the Permo-Triassic NS extension, and that their formation was assisted by fluid pressure. Second, we propose that the two orthogonal sets of Fibrous Slim Veins formed during the same extensional phase, their formation being favoured by the tectonic relaxation occurring at the beginning of the uplift of the basin at the end of the Permian. We attribute their particular characteristics (straight morphology of joints but systematic mineral infilling) to their origin in a medium already compacted but still incompletely lithified, and containing a large amount of fluids. We suggest that the fracturing history of the Lodève basin occurred in the time interval between the Late Permian (Thuringian) and the Middle Triassic (Anisian). Finally, the observed evolution in the propagation path between the Sparitic Sinuous Veins and the N90 Fibrous Slim Veins is discussed, and bears out the idea that the rock material was not completely lithified when the vein sets formed.

Compositions of magmatic hydrothermal fluids determined by LA-ICP-MS of fluid inclusions from the porphyry copper–molybdenum deposit at Butte, MT

We analyzed 85 fluid inclusions from seven samples from the porphyry Cu–Mo deposit in Butte, MT, using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The Butte deposit formed at unusually great depth relative to most porphyry deposits, and fluid inclusions in deep veins trapped a low-salinity, CO 2-bearing, magmatically derived, supercritical fluid as a single aqueous phase. This fluid is interpreted to be the parent fluid that cooled, decompressed, unmixed, and reacted with wall rock to form the gigantic porphyry Cu deposit at Butte. Few previous analyses of such fluids exist. Low-salinity, aqueous fluids from the earliest veins at Butte are trapped in deep veins with biotite-rich alteration envelopes (EDM veins). These veins, and the Butte quartz monzonite surrounding them, host much of the Butte porphyry Cu mineralization. Twenty fluid inclusions in one EDM quartz vein are dominated by Na, K, Fe (from ∼0.1 to ∼1 wt.%) and contain up to 1.3 wt.% Cu. These inclusions contain only small amounts (tens of ppm) of Pb, Zn, and Mn, and typically contain Li, B, Ca, As, Mo, Ag, Sn, Sb, Ba, and W in less than detectable quantities. The abundance of Cu in early fluids indicates that a low-salinity, Cu-rich, aqueous ore fluid can be directly produced by aqueous fluid separation from a granitic magma. Similar inclusions (eight) in an early deep quartz–molybdenite vein with a K-feldspar selvage have similar compositions but contain significantly less Cu than most inclusions in the biotite-altered vein. Analyzed inclusions in both veins contain less than detectable concentrations of Mo even though one is molybdenite-bearing. Low-salinity, CO 2-bearing aqueous fluids are also trapped in pyrite–quartz veins with sericitic selvages. These veins cut both of the above vein types and contain inclusions that were trapped at lower pressure and temperature. Thirty-nine inclusions in two such veins have compositions similar to early fluids, but are enriched by up to a factor of 10 in Mn, Pb, and Zn relative to early fluids, and are slightly depleted in Fe. Many of these inclusions contain as much or more Cu than early fluids, although little chalcopyrite is found in or around pyrite–quartz veins. Eighteen halite-bearing inclusions from three veins from both chalcopyrite-bearing and barren veins with both K-silicate and sericitic selvages were analyzed as well. Halite-saturated inclusions are dominated by Na, K, Fe, and in some inclusions Ca. Whereas these inclusions are significantly enriched in Ca, Mn, Fe, Zn, and Pb, fluids in all three veins contain significantly less Cu than early, high temperature, low-salinity inclusions. Analyses of all inclusion types show that whereas bulk-salinity of the hydrothermal fluid must be largely controlled by the magma, fluid–rock interactions have a significant role in controlling fluid compositions and metal ratios. Cu concentrations range over an order of magnitude, more than any other element, in all four samples containing low-salinity inclusions. We infer that variations are the result of fluid trapping after different amounts of fluid–rock reaction and chalcopyrite precipitation. Enrichment, relative to early fluids, of Mn, Pb, and Zn in fluids related to sericitic alteration is also likely the result of fluid–rock reaction, whereby these elements are released from biotite and feldspars as they alter to sericite. In halite-bearing inclusions, concentrations of Sr, Ca, Pb, and Ba are elevated in inclusions from the pyrite–quartz vein with sericitic alteration relative to halite-bearing inclusions from unaltered and potassically altered samples. Such enrichment is likely caused by the breakdown of plagioclase and K-feldspar in the alteration envelope, releasing Sr, Ca, Pb, and Ba.