Iodine as a tracer of organic material: I results from gas hydrate systems and fore arc fluids

The strong association of iodine with organic material and the presence of the cosmogenic radioisotope ¹²⁹I make the iodine isotopic system useful in tracing and dating organic materials and their derivatives. We present here results from two new applications of this system, investigations of gas hydrates from the Peru Margin (ODP Leg 201, Site 1230) and of fluids collected from the fore arc region of the North Island, New Zealand. Pore fluids from Site 1230 are strongly enriched in iodine and show a distinct decrease in ¹²⁹I/I ratios from 920 × 10^− 15 close to the surface to 140 × 10^− 15 at a depth of 200 mbsf, suggesting the presence of a shallow, young source and deep, old source of fluids. The fore arc fluids from New Zealand are also enriched in iodine and show a similar range in ¹²⁹I/I ratios. In both cases minimum ages are calculated to be between 40 and 60 Ma for these fluids. The results are in good agreement with earlier investigations of gas hydrate systems at Blake Ridge and Nankai Trough and of fore arc fluids from Central America and Japan, but are not compatible with derivation from subducting sediments in active margins. The results indicate that continental margins contain large amounts of old iodine, reflecting the presence of large quantities of organic material stored in these regions. Results for gas hydrate systems and fore arc fluids show similar characteristics, but differ strongly from those obtained for fluids collected from the main zones of volcanic activity associated with active margins.     

Dating of Dissolved Iodine in Pore Waters from the Gas Hydrate Occurrence Offshore Shimokita Peninsula,Japan: 129I Results from the D/V Chikyu Shakedown Cruise

Iodine concentration and radioisotopic composition (¹²⁹I/I) were measured in the pore waters from the gas hydrate occurrence in the forearc basin offshore Shimokita Peninsula, north-eastern Japan, to determine the source formation of I and accompanying hydrocarbons. Iodine concentrations correlate well with the alkalinity and SO₄ patterns, reflecting degradation stages of I-rich buried organic matter, rapidly increasing in the sulfate reduction interval, and becoming constant below 250 meters below the seafloor with an upwelling flux of 1.5 × 10⁻¹¹ µmol cm⁻² year⁻¹. The ¹²⁹I/I ratios of 300 × 10⁻¹⁵–400 × 10⁻¹⁵ in deep pore waters suggest ages for iodine and hydrocarbon sources as old as 40 Ma. These ages correlate well with the coaly source formations of the Eocene age thought to be responsible for the conventional natural gas deposits underlying the gas hydrate stability zone. Similar profiles are observed in ¹²⁹I/I ratios of pore waters in the gas hydrate stability zone from the forearc basin in the eastern Nankai Trough, offshore central Japan, where pore waters are enriched in I and reach ages as old as ∼50 Ma through the sediment column. At the outer ridge site along the trough, on the other hand, relatively younger I are more frequently delivered probably through thrusts/faults associated with subduction. The nature of source formations of I and hydrocarbons in the offshore Shimokita Peninsula has a more terrestrial contribution compared with those in the Nankai Trough, but these formations are also considerably older than the host sediments, suggesting long-term transport of I and hydrocarbons for the accumulation of gas hydrates in both locations.     

Origin and history of waters associated with coalbed methane: I, Cl, and stable isotope results from the Fruitland Formation, CO and NM

The Fruitland Formation of the San Juan Basin was deposited during the late Cretaceous and is associated with significant reservoirs of coalbed methane (CBM). The purpose of this study is to determine the origin and history of waters associated with the formation, using long-lived cosmogenic and stable isotope systems. Ratios of ¹²⁹I/I and stable isotope values (δD and δ¹⁸O) were determined in waters from close to 100 wells, ³⁶Cl/Cl ratios for a subset of these samples. A significant group of samples has ¹²⁹I/I ratios between 100 × 10⁻¹⁵ and 200 × 10⁻¹⁵, indicating minimum iodine ages close to 60 Ma. If these ages are corrected for the addition of fissiogenic ¹²⁹I, they are compatible with the depositional age of the Fruitland Formation (Late Cretaceous).Several sets of waters are clearly present within the data. A group dominated by infiltration of recent surface waters is restricted to the uplifted basin margins, with a lateral extent of less than 5 km from outcrop, and is characterized by ¹²⁹I/I ratios in excess of 1500 × 10⁻¹⁵ and meteoric δD, δ¹⁸O, and ³⁶Cl/Cl signatures. The rest of the basin is characterized by several subsets of formation waters which have undergone variable degrees of iodine enrichment through diagenesis as well as variable degrees of dilution. The first subgroup is found in coals of relatively low vitrinite reflectance and moderate enrichment of iodine. This subgroup predominantly consists of entrapped pore fluids, although it may also contain waters which infiltrated the coals at the time of the Laramide uplift, between 25 and 30 Ma. A second subgroup consists of formation waters associated with coals of high vitrinite reflectance. Despite subsequent uplift, the high iodine concentrations and low ¹²⁹I/I ratios of this subgroup, as well as a moderate depletion of deuterium relative to ¹⁸O, suggest that these waters were not significantly altered since the time when diagenetic reactions occurred in the deepest portion of the basin. A third subgroup, with higher δD and δ¹⁸O values as well as higher ¹²⁹I/I ratios, extends roughly west to east at the New Mexico-Colorado state line and corresponds to a region of extensive fracturing of the coalbeds. In this case, the higher ¹²⁹I/I ratios are probably due to contributions of fissiogenic ¹²⁹I through fracture flow, perhaps from deeper formation waters. Our results do not support models of subsequent basin-wide groundwater migration in the Fruitland Formation. The combined use of ¹²⁹I and ³⁶Cl with stable isotope studies provides valuable information as to the hydrologic history of coalbed methane deposits, as well as their potential for commercial exploitation.     

Iodine budget in surface waters from Atacama: Natural and anthropogenic iodine sources revealed by halogen geochemistry and iodine-129 isotopes

Iodine enrichment in the Atacama Desert of northern Chile is widespread and varies significantly between reservoirs, including nitrate-rich “caliche” soils, supergene Cu deposits and marine sedimentary rocks. Recent studies have suggested that groundwater has played a key role in the remobilization, transport and deposition of iodine in Atacama over scales of millions-of-years. However, and considering that natural waters are also anomalously enriched in iodine in the region, the relative source contributions of iodine in the waters and its extent of mixing remain unconstrained. In this study we provide new halogen data and isotopic ratios of iodine (¹²⁹I/I) in shallow seawater, rivers, salt lakes, cold and thermal spring water, rainwater and groundwater that help to constrain the relative influence of meteoric, marine and crustal sources in the Atacama waters. Iodine concentrations in surface and ground waters range between 0.35 μM and 26 μM in the Tarapacá region and between 0.25 μM and 48 μM in the Antofagasta region, and show strong enrichment when compared with seawater concentrations (I = ∼0.4 μM). In contrast, no bromine enrichment is detected (1.3–45.7 μM for Tarapacá and 1.7–87.4 μM for Antofagasta) relative to seawater (Br = ∼600 μM). These data, coupled to the high I/Cl and low Br/Cl ratios are indicative of an organic-rich sedimentary source (related with an “initial” fluid) that interacted with meteoric water to produce a mixed fluid, and preclude an exclusively seawater origin for iodine in Atacama natural waters. Iodine isotopic ratios (¹²⁹I/I) are consistent with halogen chemistry and confirm that most of the iodine present in natural waters derives from a deep initial fluid source (i.e., groundwater which has interacted with Jurassic marine basement), with variable influence of at least one atmospheric or meteoric source. Samples with the lowest isotopic ratios (¹²⁹I/I from ∼215 to ∼1000 × 10⁻¹⁵) strongly suggest mixing between the groundwater and iodine storage in organic-rich rocks (with variable influence of volcanic fluids) and pre-anthropogenic meteoric water, while samples with higher values (∼2000–93,700 × 10⁻¹⁵) indicate the input of anthropogenic meteoric fluid. Taking into account the geological, hydrologic and climatic features of the Atacama region, we propose that the mean contribution of anthropogenic ¹²⁹I is associated with ¹²⁹I releases during nuclear weapon tests carried out in the central Pacific Ocean until the mid 1990's (¹²⁹I/I = ∼12,000 × 10⁻¹⁵). This source reflects rapid redistribution of this radioisotope on a global scale. Our results support the notion of a long-lived continental iodine cycle in the hyperarid margin of western South America, which is driven by local hydrological and climate conditions, and confirm that groundwater was a key agent for iodine remobilization and formation of the extensive iodine-rich soils of Atacama.     

Strontium isotope ratios in volcanic rocks from the south-eastern part of the Hellenic arc

Isotopic ratios of strontium in 9 volcanic rocks from the south-eastern part of the Hellenic arc range from 0.7037 to 0.7075. Within individual series of differentiation, there seems to be a correlation between Sr⁸⁷/Sr⁸⁶ and K₂O/SiO₂.All strontium isotope data for the Hellenic arc are reviewed. Comparable (but slightly smaller) ranges of Sr isotope ratios are found in other island arcs with continental basement. To explain the high values of Sr⁸⁷/Sr⁸⁶ ratio for the Hellenic arc, a selective addition of Sr⁸⁷ from the wall rock, and a process of assimilation involving water, perhaps from subducted sediments, are suggested. Since closely-spaced individual volcanic centres of similar ages have very different Sr isotope ratios, and since the range of Sr isotopic composition in individual centres is quite large, the variation is unlikely to be due to primary variation in mantle composition.     

Origin and age of pore waters in an actively venting gas hydrate field near Sado Island,Japan Sea: Interpretation of halogen and 129I distributions

A gas hydrate field with highly active venting of methane was recently found near Sado Island in the eastern Japan Sea. Piston cores were collected from active venting sites and nearby locations in the Umitaka Spur–Joetsu Knoll area during two cruises in 2004 (UT04) and 2005 (KY05-08). We report here halogen concentrations and ¹²⁹I/I ratios in pore waters associated with gas hydrates from these expeditions. The strongly biophilic behavior of I and, to a lesser degree, of Br together with the presence of the long-lived iodine radioisotope (¹²⁹I) allow evaluation of potential source materials for methane in gas hydrate systems. Depth profiles of all three halogens, particularly the very rapid downward increases of Br and I concentrations, strongly suggest input of deep fluids enriched in Br and I, but the profiles also display the effects of gas hydrate formation and dissociation. Although the ¹²⁹I/I ratios are modified by ¹²⁹I from seawater and sediments at shallow depth, likely ratios of the deep fluids are estimated to be between 400 × 10^− 15 and 600 × 10^− 15, equivalent to a Late Oligocene to Early Miocene age. Ages in the active methane venting sites typically are closer to the old end of this range than those in the reference sites. This age range suggests that the methane associated with venting and gas hydrate formation in this area is derived from organic materials accumulated during the initial opening of the Japan Sea. The Umitaka Spur–Joetsu Knoll gas hydrate field demonstrates the movement of deep fluids associated with the release of significant amounts of methane from the seafloor, processes which might be important components of mass transfer and carbon cycle in the shallow geosphere.     

Petrology and new data on the geochemistry of the Andahua volcanic group (Central Andes,southern Peru)

The Quaternary Andahua volcanic group is located within the Central Volcanic Zone in Southern Peru. The author presents new data on major and trace elements and ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios for Andahua rocks from all regions with volcanic centres. The TAS data identify the Andahua lavas as trachyandesites, basaltic trachyandesites and dacites. The phenocrysts are represented mainly by plagioclase, but olivine, clinopyroxene and hornblende are also present. In some cases the trachyandesites show Ca enrichment and their plagioclases have an andesine–bytownite composition. The plagioclase phenocrysts show a slight normal and occasionally reverse zonation. Their basaltic parental magmas were enriched in fluids derived from dehydration of the subducted oceanic crust. The chemical content of the Andahua volcanic rocks shows some similarity to both the slightly older and the contemporaneous and widespread Barroso Group rocks in this region.     

Magmatic evolution of the South Shetland Islands,Antarctica, and implications for continental crust formation

Lavas from the South Shetland Islands volcanic arc (northern Antarctic Peninsula) have been investigated in order to determine the age, petrogenesis and compositional evolution of a long-lived volcanic arc constructed on 32-km-thick crust, a thickness comparable with average continental crust. New ⁴⁰Ar–³⁹Ar ages for the volcanism range between 135 and 47 Ma and, together with published younger ages, confirm a broad geographical trend of decreasing ages for the volcanism from southwest to northeast. The migration pattern breaks down in Palaeogene time, with Eocene magmatism present on both Livingston and King George islands, which may be due to a change in both subduction direction and velocity after c. 60 Ma. The lavas range from tholeiitic to calc-alkaline, but there is no systematic change with age or geographic location. The compositions of lavas from the north-eastern islands indicate magma generation in a depleted mantle wedge with relatively low Sr and high Nd isotopic compositions and low U/Nb, Th/Nd and Ba/Nb ratios that was metasomatized by hydrous fluids from subducted basaltic oceanic crust. Lavas from the south-western islands show an additional sedimentary influence most likely due to fluid release from subducted sediments into the mantle wedge. Although magmatic activity in the South Shetland arc extended over c. 100 m.y., there is no evolution towards more enriched or evolved magmas with time. Few South Shetland arc lavas are sufficiently enriched with incompatible elements to provide a potential protolith for the generation of average continental crust. We conclude that even long-established subduction zones with magmatic systems founded on relatively thick crust do not necessarily form continental crustal building blocks. They probably represent only the juvenile stages of continental crust formation, and additional re-working, for example during subsequent arc-continental margin collision, is required before they can evolve into average continental crust.     

Fluid-rock interactions in a geothermal Rotliegend/Permo-Carboniferous reservoir (North German Basin)

Comprehensive data on the chemical composition of reservoir rocks and geothermal brines from the geothermal well doublet Groβ Schönebeck (North German Basin) drilled into a Rotliegend sedimentary and Permo-Carboniferous volcanic rock reservoir were sampled over the past years. They were characterized with respect to their major and minor elemental composition including various isotope ratios. The study considered the impact of drilling and reservoir operations on fluid composition and aimed at determining fluid–rock interactions to gain information on fluid origin and hydraulic pathways.The highly saline fluids (up to 265 g/L TDS) show δ ¹⁸O and δD of water (2.7–5.6 and −3.1–15, respectively) as well as δ ³⁴S of sulfate (3.6–5), and ⁸⁷Sr/⁸⁶Sr ratios (0.715–0.716) that resemble Rotliegend brines from an area located around 200 km in the west (the Altmark). Halogen ratios indicated that brines developed predominantly by evaporation of meteoric water (primary brine) together with halite dissolution brine (secondary brine). Indication for mixing with Zechstein brine or with younger meteoric water was not found.No geochemical distinction was possible between fluids deriving from different rock formations (dacites or sedimentary rocks, respectively). This is due to the evolution of the sediments from the effusive rocks resulting in a similar mineralogical and chemical composition and due to a hydraulic connectivity between the two types of rock. This connection existed probably already before reservoir stimulation as indicated by a set of faults identified in the area that could connect the Rotliegend formation with both, the volcanic rocks and the lower units of the Zechstein. Additional geochemical indication for a hydraulic connectivity is given by (1) the very high heavy metal contents (mainly Cu and Pb) in fluids and scaling that derive from the volcanic rocks and were that were also found in increased amounts up at the Zechstein border (Kupferschiefer formation). (2) The ⁸⁷Sr/⁸⁶Sr isotope ratios of fluid samples correspond to the ratios determined for the sedimentary rocks indicating that initially the fluids developed in the sedimentary rocks and circulated later, when faults structures were created by tectonic events into the volcanic rocks.     

Trapped Xe and I-Xe ages in aqueously altered CV3 meteorites

Twenty-two dark inclusions (DIs) from Allende (18), Leoville (2), Vigarano (1) and Efremovka (1) were studied by the I-Xe method. All except two of these DIs (Vigarano 2226 and Leoville LV2) produce well-defined isochrons, and precise I-Xe ages. The Allende DIs formed a tight group about 1.6 Ma older than Shallowater (4.566 ± 0.002 Ga), about 5 Ma older than four previously studied Allende CAIs. Most of the dark inclusions require trapped Xe with less ¹²⁹Xe (or more ¹²⁸Xe) than conventional planetary Xe (well restricted in composition by Q-Xe or OC-Xe). Studies of an irradiated/unirradiated DI pair from Allende demonstrate that the ¹²⁸Xe/¹³²Xe ratio in trapped is normal planetary, so that a ¹²⁹Xe/¹³²Xe ratio below planetary seems to be required. Yet, this is not possible given constraints on ¹²⁹Xe evolution in the early solar system. Trends among all of the Allende DIs suggest that an intimate mixture of partially decayed iodine and Xe formed a pseudo trapped Xe component enriched in both ¹²⁹Xe and ¹²⁷I, and subsequently in ¹²⁸Xe after n-capture during reactor irradiation. Enrichment in radiogenic ¹²⁹Xe, but with a ¹²⁹Xe/¹²⁷I ratio less than that observed in the iodine host phase, places closure of this trapped mixture ≥13 Ma after precipitation of the major iodine-bearing phase. Because the I-Xe isochron is a mixing line between iodine-derived and trapped Xe (pseudo or not), I-Xe ages, given by the slope of this mixing line, are not compromised by the presence of pseudo trapped Xe, and the precision of the I-Xe ages is given by the statistics of the line fit.     

Heterogeneous mantle source and magma differentiation of quaternary arc-like volcanic rocks from Tengchong,SE margin of the Tibetan Plateau

The Tengchong volcanic field north of the Burma arc comprises numerous Quaternary volcanoes in the southeastern margin of the Tibetan Plateau. The volcanic rocks are grouped into four units (1–4) from the oldest to youngest. Units 1, 3 and 4 are composed of olivine trachybasalt, basaltic trachyandesite and trachyandesite, and Unit 2 consists of hornblende dacite. The rocks of Units 1, 3, and 4 form a generally alkaline suite in which the rocks plot along generally linear trends on Harker diagrams with only slight offset from unit to unit. They contain olivine phenocrysts with Fo values ranging from 65 to 85 mol% and have Cr-spinel with Cr# ranging from 23 to 35. All the rocks have chondrite-normalized REE patterns enriched in LREE and primitive mantle-normalized trace element patterns depleted in Ti, Nb and Ta, but they are rich in Th, Ti and P relative to typical arc volcanics. Despite minor crustal contamination, ⁸⁷Sr/⁸⁶Sr ratios (0.706–0.709), εNd values (−3.2 to −8.7), and εHf values (+4.8 to −6.4) indicate a highly heterogeneous mantle source. The Pb isotopic ratios of the lavas (²⁰⁶Pb/²⁰⁴Pb = 18.02–18.30) clearly show an EMI-type mantle source. The underlying mantle source was previously modified by subduction of the Neo-Tethyan oceanic and Indian continental lithosphere. The present heterogeneous mantle source is interpreted to have formed by variable additions of fluids and sediments derived from the subducted Indian Oceanic lithosphere, probably the Ninety East Ridge. Magma generation and emplacement was facilitated by transtensional NS-trending strike-slip faulting.     

Tracing nitrogen in volcanic and geothermal volatiles from the Nicaraguan volcanic front

We report new chemical and isotopic data from 26 volcanic and geothermal gases, vapor condensates, and thermal water samples, collected along the Nicaraguan volcanic front. The samples were analyzed for chemical abundances and stable isotope compositions, with a focus on nitrogen abundances and isotope ratios. These data are used to evaluate samples for volatile contributions from magma, air, air-saturated water, and the crust. Samples devoid of crustal contamination (based upon He isotope composition) but slightly contaminated by air or air-saturated water are corrected using N₂/Ar ratios in order to obtain primary magmatic values, composed of contributions from upper mantle and subducted hemipelagic sediment on the down-going plate. Using a mantle endmember with δ¹⁵N = −5‰ and N₂/He = 100 and a subducted sediment component with δ¹⁵N = +7‰ and N₂/He = 10,500, the average sediment contribution to Nicaraguan volcanic and geothermal gases was determined to be 71%. Most of the gases were dominated by sediment-derived nitrogen, but gas from Volcán Mombacho, the southernmost sampling location, had a mantle signature (46% from subducted sediment, or 54% from the mantle) and an affinity with mantle-dominated gases discharging from Costa Rica localities to the south. High CO₂/N_{2 exc.} ratios (N_{2 exc.} is the N₂ abundance corrected for contributions from air) in the south are similar to those in Costa Rica, and reflect the predominant mantle wedge input, whereas low ratios in the north indicate contribution by altered oceanic crust and/or preferential release of nitrogen over carbon from the subducting slab. Sediment-derived nitrogen fluxes at the Nicaraguan volcanic front, estimated by three methods, are 7.8 × 10⁸ mol N/a from ³He flux, 6.9 × 10⁸ mol/a from SO₂ flux, and 2.1 × 10⁸ and 1.3 × 10⁹ mol/a from CO₂ fluxes calculated from ³He and SO₂, respectively. These flux results are higher than previous estimates for Central America, reflecting the high sediment-derived volatile contribution and the high nitrogen content of geothermal and volcanic gases in Nicaragua. The fluxes are also similar to but higher than estimated hemipelagic nitrogen inputs at the trench, suggesting addition of N from altered oceanic basement is needed to satisfy these flux estimates. The similarity of the calculated input of N via the trench to our calculated outputs suggests that little or none of the subducted nitrogen is being recycled into the deeper mantle, and that it is, instead, returned to the surface via arc volcanism.     

Geochemistry of halogens in the Milk River aquifer,Alberta, Canada

Analytical data are presented for Cl, Br and I on a regional scale for the Milk River aquifer. The three halides show strikingly similar spatial distributions and are highly correlated. Concentrations are low in the freshwater portions of the aquifer but increase by as much as two orders of magnitude along the margins. However, halide ratios reach nearly constant values moving down-gradient, suggesting the dominance of a common subsurface source for these ions. Ratios of Cl/I and Cl/Br are less than those of seawater and fit an origin derived from the diagenesis of organic matter in the sediments. Halide ratios rule out leakage and/or diffusion from the underlying Colorado Group as a major influence on the chemistry; the favored hypothesis is altered connate seawater diffusing from low-permeability units within the Milk River Formation as the primary source of salts. This hypothesis of an internal source has important implications for solute sources in other aquifers affected by saline waters because it does not require the importation of a distant fluid.The¹²⁹I/I ratio has a meteoric value in groundwater collected near the recharge area, but ratios for downflow waters are only 8–70% of this value. Due to the 16 Ma half-life of¹²⁹I, these data indicate that most of the increase in dissolved I cannot derive from concentration of a meteoric source by ion filtration, but must have a subsurface origin. Concentrations of¹²⁹I producedin situ by spontaneous fission of²³⁸U attain measurable levels only in the oldest waters sampled (ages≥ 10⁵a), in which it may account for nearly 90% of the total dissolved¹²⁹I concentration.Water ages based upon³⁶Cl/Cl data range up to 2 Ma if uncorrected for any dilution by subsurface sources of dead Cl. If one assumes that the subsurface contributions of Cl contribute at least 90% of total Cl in the distal portion, then the³⁶Cl-based ages are reduced to ∼ 1Ma, somewhat greater than those estimated by hydrodynamic modeling.     

Iodine-129 chronological study of brines from an Ordovician paleokarst reservoir in the Lunnan oilfield,Tarim Basin

Previous studies have shown that brines in an Ordovician paleokarst reservoir of the Lunnan oilfield in the Tarim Basin, China, are the product of mixing of paleo-evaporated seawater in the east with paleometeoric waters in the west. In order to put time constraints on the brine and related hydrocarbons in this field, 10 brine samples were collected, for which the iodine concentrations and ¹²⁹I/I ratios were measured and discussed. The iodine concentration (3.70–31.2 mg/L) and the ¹²⁹I/I ratio (189–897 × 10⁻¹⁵) show that the iodine in the paleoseawater and meteoric water (MW) had different origins and ¹²⁹I characteristics. The paleoseawater has a high iodine content (∼31 mg/L), indicating that iodine was introduced into the reservoir along with thermally generated hydrocarbons, possibly in the Cretaceous, from the Caohu Sag in the eastern area. Based on consideration of all possible origins of iodine and ¹²⁹I in the brines, it is suggested that the meteoric water maintained its initial iodine content (0.01 mg/L) and ¹²⁹I/I ratio (1500 × 10⁻¹⁵), whereas the iodine-enriched paloseawater (IPSW) exhibited a secular ¹²⁹I equilibrium (N_sq = 39 atom/μL) as a result of fissiogenic ¹²⁹I input in the reservoir over a long period of time. The model of brine evolution developed on that basis confirmed that meteoric water entered the reservoir in the Miocene at about 10 Ma, and partially mixed with the iodine-enriched paleoseawater. The movement of meteoric water was facilitated by faults created during the Himalayan orogeny, then became more dense after dissolving Paleogene halite and infiltrated into the reservoir at high pressure. The iodine and ¹²⁹I concentration in the brine contains information about the path and history of the fluid in the reservoir. This may be useful in oil exploration, since the movement of water was, to some extent, related to hydrocarbon migration.     

The Late Mesozoic tectonic evolution and magmatic history of west Zhejiang,SE China: implications for regional metallogeny

The granitoids and related polymetallic mineralization in the Zhejiang Province at the southeast margin of the Yangtze Block in China provide an important window to evaluate metallogeny associated with convergent margin magmatism. Here, we present geochronological, geochemical, and isotopic data from the granitic rocks of west Zhejiang, to constrain the timing of transformation of the tectonic setting of this region from volcanic arc to intra-plate during Late Mesozoic and its bearing on regional metallogeny. The granitic rocks in west Zhejiang can be geochemically subdivided into two groups. The first group is characterized by relatively steep rare earth element (REE) patterns with slight Eu anomalies, high Sr, low Yb, and negative Nb–Ta–Ti (NTT) anomalies, indicating a volcanic arc environment with a thickened crust in a convergent setting. The second group is featured by flat REE patterns with prominent negative Eu anomalies, low Sr, high Yb, and weak NTT anomalies, suggesting an intra-plate extensional environment with a thin crust. The geochronology of granitic rocks in west Zhejiang, combined with ages of regional tectonic basins and nappe structures, constrains the timing of the tectonic transformation to be in the range from 150 to 140 Ma. Sr–Nd isotopic data and a positive correlation displayed by oxygen fugacity (fO₂), and La/Sm and Ba/Th ratios (proxies of subducted sediments and slab dehydration fluids) suggest that the high oxygen fugacity is probably related to the melting of subducted sediments and slab dehydration. From 180 to 80 Ma, due to the increasing dip angle of the subducted Izanagi Plate, the volcanic arc belt migrated oceanward, leaving most of the interior of Zhejiang Province under an intra-plate environment where insufficient subducted components and upwelling mantle generated reduced magmas which were not favorable for Cu–Mo mineralization. Our model provides a plausible explanation for the absence of Cu–Mo porphyry deposits in the adjacent region of Zhejiang, Jiangxi, and Anhui provinces (Zhe-Gan-Wan region) after 140 Ma.     

Slab decarbonation and CO2 recycling in the Southwestern Colombian volcanic arc

The contribution of subducted carbonate sediments to the genesis of the Southwestern Colombian arc magmas was investigated using a comprehensive petrography and geochemical analysis, including determination of major and trace element contents and Sr, Nd, Hf and Pb isotope compositions. These data have been used to constrain the depth of decarbonation in the subducted slab, indicating that the decarbonation process continues into the sub-arc region, and ultimately becomes negligible in the rear arc. We propose on the basis of multi-isotope approach and mass balance calculations, that the most important mechanism to induce the slab decarbonation is the infiltration of chemically reactive aqueous fluids from the altered oceanic crust, which decreasingly metasomatize the mantle wedge, triggering the formation of isotopically different primary magmas from the volcanic front (VF) with relatively high ¹⁷⁶Hf/¹⁷⁷Hf, high ⁸⁷Sr/⁸⁶Sr, negative values of εNd and lower Pb isotopes compared to the rear arc (RA).The presence of more aqueous fluids at the volcanic front may increase the degree of decarbonation into carbonate-bearing lithologies. Moreover, with increasing pressure and temperature in the subduction system, the decrease in dehydration of the slab, leads to cessation of fluid-induced decarbonation reactions at the rear arc. This development allows the remaining carbonate materials to be recycled into the deep mantle.     

Thermal effects of massive CO2 emissions associated with subduction volcanism

Large volumes of CO₂ are emitted during volcanic activity at convergent plate boundaries, not only from volcanic centres. Their C isotopic signature indicates that this CO₂ is mainly derived from the decarbonation of subducted limestones or carbonated metabasalts, not as often admitted from magma degassing. On the example of Milos (Aegean Sea) it is argued that these fluids originate from intermediate depth in the mantle and carry sufficient heat to account for the generation of subduction-related magmas, as well as for the geothermal manifestations at the surface. The heat that is required for the decarbonation reactions is drawn by conduction from a wide zone surrounding the subducting slab and then rapidly transported upward by convection of the mixed CO₂–H₂O fluids that originate from the sediments in the slab. The transport takes place in a focused way through ‘chimneys’ in the upper mantle, where magmas are generated by the introduced heat and water. In the crust, the hot fluids cause thermal-dome-type metamorphism. In volcanic areas, magmas are commonly held responsible for the major part of heat transfer from the mantle to the surface. Here it is argued that most of the heat transfer is by hot gases. To cite this article: R.D. Schuiling, C. R. Geoscience 336 (2004).     

New insights into the origin of O–Hf–Os isotope signatures in arc lavas from Tonga–Kermadec

O, Hf and Os isotope data are presented for lavas from the highly depleted Tonga–Kermadec arc. O isotope values overlap with those of MORB limiting the amount of interaction with the arc crust. δ¹⁸O does not increase northwards as would be expected from the ~ 4 fold increase in subduction rate if slab-derived fluids had high ¹⁸O/¹⁶O ratios. Thus, the overall northward decrease in HFSE concentrations likely reflects depletion due to prior melt extraction, not increasing extents of melting. Hf isotopes are strongly negatively correlated with Be isotopes consistent with mixing of subducted pelagic sediment into the mantle wedge and do not require Hf to be fluid mobile. With the exception of a boninite from the north Tongan trench, the northern Tonga lavas do not overlap the Hf isotope composition of either the Samoan plume or the subducting Louisville volcaniclastic sediments. Thus, the Pb isotope signatures in these lavas must have been added by fluids and sediment melts derived from the Louisville volcaniclastics with minimal mobilisation of Hf. This suggests conservative behaviour for this element due to the formation of residual zircon during partial melting of the subducted sediments. ¹⁸⁷Os/¹⁸⁸Os ranges from 0.1275 to 0.4731 and the higher Os isotope ratios reflect the sensitivity of this system to even minor interaction with altered arc crust. Conversely, the lowest Os ratios are subchondritic and indicate that transfer of radiogenic Os from the slab is not all pervasive and provide an important constraint on the composition of the mantle wedge. Remarkably, the least radiogenic sample is a dacite demonstrating that evolved magmas can develop by fractionation from mantle-derived magmas with minimal interaction with the arc crust.     

Iodine-xenon analysis of Chainpur (LL3.4) chondrules

We present I-Xe analyses of ten chondrules from Chainpur LL3.4 by IR laser-stepped heating. Five chondrules provided isochrons of varying quality, giving a range of ages from 0.5 Ma before Shallowater to 17.8 after Shallowater. This confirms the extended range of Chainpur chondrule ages determined by previous data. We discuss evidence for fluid alteration, shock, and thermal events in explaining the chondrule ages and suggest that chondrule remelting events, presumably from bombardment of the parent body surface, are responsible for resetting the I-Xe chronometer. Previous data show a negative correlation between ¹³²Xe/¹²⁹Xe of the trapped Xe component and ¹²⁷I/¹²⁹I of an initial iodine component. This behaviour that requires the presence of a component with trapped ¹²⁹Xe/¹³²Xe lower than the planetary value has been cited as evidence for closed system evolution of the I-Xe system. We find no evidence of an unambiguous trapped component lower than planetary and no evidence of a negative correlation in our data. Therefore we suggest that open system behaviour more suitably explains the I-Xe systematics of Chainpur chondrules.     

Origin and evolution of geothermal fluids from Las Tres Vírgenes and Cerro Prieto fields,Mexico – Co-genetic volcanic activity and paleoclimatic constraints

Major and trace elements, noble gases, and stable (δD, δ¹⁸O) and cosmogenic (³H, ¹⁴C) isotopes were measured from geothermal fluids in two adjacent geothermal areas in NW-Mexico, Las Tres Vírgenes (LTV) and Cerro Prieto (CP). The goal is to trace the origin of reservoir fluids and to place paleoclimate and structural-volcanic constraints in the region. Measured ³He/⁴He (R) ratios normalized to the atmospheric value (R_a = 1.386 × 10⁻⁶) vary between 2.73 and 4.77 and are compatible with mixing between a mantle component varying between 42 and 77% of mantle helium and a crustal, radiogenic He component with contributions varying between 23% and 58%. Apparent U–Th/⁴He ages for CP fluids (0.7–7 Ma) suggest the presence of a sustained ⁴He flux from a granitic basement or from mixing with connate brines, deposited during the Colorado River delta formation (1.5–3 Ma). Radiogenic in situ ⁴He production age modeling at LTV, combined with the presence of radiogenic carbon (1.89 ± 0.11 pmC – 35.61 ± 0.28 pmC) and the absence of tritium strongly suggest the Quaternary infiltration of meteoric water into the LTV geothermal reservoir, ranging between 4 and 31 ka BP. The present geochemical heterogeneity of LTV fluids can be reconstructed by mixing Late Pleistocene – Early Holocene meteoric water (58–75%) with a fossil seawater component (25–42%), as evidenced by Br/Cl and stable isotope trends. CP geothermal water is composed of infiltrated Colorado River water with a minor impact by halite dissolution, whereas a vapor-dominated sample is composed of Colorado River water and vapor from deeper levels. δD values for the LTV meteoric end-member, which are 20‰–44‰ depleted with respect to present-day precipitation, as well as calculated annual paleotemperatures 6.9–13.6 °C lower than present average temperatures in Baja California point to the presence of humid and cooler climatic conditions in the Baja California peninsula during the final stage of the Last Glacial Pluvial period. Quaternary recharge of the LTV geothermal reservoir is related to elevated precipitation rates during cooler-humid climate intervals in the Late Pleistocene and Early Holocene. The probable replacement of connate water or pore fluids by infiltrating surface water might have been triggered by enhanced fracture and fault permeability through contemporaneous tectonic–volcanic activity in the Las Tres Vírgenes region. Fast hydrothermal alteration processes caused a secondary, positive δ¹⁸O-shift from 4‰ to 6‰ for LTV and from 2‰ to 4‰ for CP geothermal fluids since the Late Glacial infiltration.