UV camera measurements of fumarole field degassing (La Fossa crater,Vulcano Island)

The UV camera is becoming an important new tool in the armory of volcano geochemists to derive high time resolution SO₂ flux measurements. Furthermore, the high camera spatial resolution is particularly useful for exploring multiple-source SO₂ gas emissions, for instance the composite fumarolic systems topping most quiescent volcanoes. Here, we report on the first SO₂ flux measurements from individual fumaroles of the fumarolic field of La Fossa crater (Vulcano Island, Aeolian Island), which we performed using a UV camera in two field campaigns: in November 12, 2009 and February 4, 2010. We derived ~ 0.5 Hz SO₂ flux time-series finding fluxes from individual fumaroles, ranging from 2 to 8.7 t d^?1, with a total emission from the entire system of ~ 20 t d^?1 and ~ 13 t d^?1, in November 2009 and February 2010 respectively. These data were augmented with molar H₂S/SO₂, CO₂/SO₂ and H₂O/SO₂ ratios, measured using a portable MultiGAS analyzer, for the individual fumaroles. Using the SO₂ flux data in tandem with the molar ratios, we calculated the flux of volcanic species from individual fumaroles, and the crater as a whole: CO₂ (684 t d^?1 and 293 t d^?1), H₂S (8 t d^?1 and 7.5 t d^?1) and H₂O (580 t d^?1 and 225 t d^?1).     

Primitive neon and helium isotopic compositions of high-MgO basalts from the Kerguelen Archipelago,Indian Ocean

The geochemical characteristics of mildly alkalic basalts (24–25 Ma) erupted in the southeastern Kerguelen Archipelago are considered to represent the best estimate for the composition of the enriched Kerguelen plume end-member. A recent study of picrites and high-MgO basalts from this part of the archipelago highlighted the Pb and Hf isotopic variations and suggested the presence of mantle heterogeneities within the Kerguelen plume itself. We present new helium and neon isotopic compositions for olivines from these picrites and high-MgO basalts (6–17 wt.% MgO) both to constrain the enriched composition of the Kerguelen plume and to determine the origin of isotopic heterogeneities involved in the genesis of Kerguelen plume-related basalts. The olivine phenocrysts have extremely variable ⁴He / ³He compositions between MORB and primitive values observed in OIB (∼90,000 to 40,000; i.e., R / R_a ∼8 to 18) and they show primitive neon isotopic ratios (average ²¹Ne / ²¹Ne_ext ∼0.044). The neon isotopic systematics and the ⁴He / ³He ratios that are lower than MORB values for the Kerguelen basalts clearly suggest that the Kerguelen hotspot belongs to the family of primitive hotspots, such as Iceland and Hawaii. The rare gas signature for the Kerguelen samples, intermediate between MORB and solar, is apparently inconsistent with mixing of a primitive component with a MORB-like source, but may result from sampling a heterogeneous part of the mantle with solar ³He / ²²Ne and with a higher (U, Th) / ³He ratio compared to typically high R / R_a hotspot basalts such as those from Iceland and Hawaii.     

Spatiotemporal patterns of fault slip rates across the Central Sierra Nevada frontal fault zone

Patterns in fault slip rates through time and space are examined across the transition from the Sierra Nevada to the Eastern California Shear Zone–Walker Lane belt. At each of four sites along the eastern Sierra Nevada frontal fault zone between 38 and 39° N latitude, geomorphic markers, such as glacial moraines and outwash terraces, are displaced by a suite of range-front normal faults. Using geomorphic mapping, surveying, and ¹⁰Be surface exposure dating, mean fault slip rates are defined, and by utilizing markers of different ages (generally, ~ 20 ka and ~ 150 ka), rates through time and interactions among multiple faults are examined over 10⁴–10⁵ year timescales.At each site for which data are available for the last ~ 150 ky, mean slip rates across the Sierra Nevada frontal fault zone have probably not varied by more than a factor of two over time spans equal to half of the total time interval (~ 20 ky and ~ 150 ky timescales): 0.3 ± 0.1 mm year^? 1 (mode and 95% CI) at both Buckeye Creek in the Bridgeport basin and Sonora Junction; and 0.4 + 0.3/?0.1 mm year^? 1 along the West Fork of the Carson River at Woodfords. Data permit rates that are relatively constant over the time scales examined. In contrast, slip rates are highly variable in space over the last ~ 20 ky. Slip rates decrease by a factor of 3–5 northward over a distance of ~ 20 km between the northern Mono Basin (1.3 + 0.6/?0.3 mm year^? 1 at Lundy Canyon site) to the Bridgeport Basin (0.3 ± 0.1 mm year^? 1). The 3-fold decrease in the slip rate on the Sierra Nevada frontal fault zone northward from Mono Basin is indicative of a change in the character of faulting north of the Mina Deflection as extension is transferred eastward onto normal faults between the Sierra Nevada and Walker Lane belt.A compilation of regional deformation rates reveals that the spatial pattern of extension rates changes along strike of the Eastern California Shear Zone-Walker Lane belt. South of the Mina Deflection, extension is accommodated within a diffuse zone of normal and oblique faults, with extension rates increasing northward on the Fish Lake Valley fault. Where faults of the Eastern California Shear Zone terminate northward into the Mina Deflection, extension rates increase northward along the Sierra Nevada frontal fault zone to ~ 0.7 mm year^? 1 in northern Mono Basin. This spatial pattern suggests that extension is transferred from more easterly fault systems, e.g., Fish Lake Valley fault, and localized on the Sierra Nevada frontal fault zone as the Eastern California Shear Zone–Walker Lane belt faulting is transferred through the Mina Deflection.     

Contrasting punctuated zircon growth in two syn-erupted rhyolite magmas from Tarawera volcano: Insights to crystal diversity in magmatic systems

Two mineralogically and chemically distinct rhyolite magmas (T1 and T3) were syn-erupted from the same conduit system during the 21.9 ka basalt intrusion-triggered Okareka eruption from Tarawera volcano, New Zealand. High spatial resolution U–Th disequilibrium dating of zircon crystals at the ~ 3–5 μm scale reveals a protracted yet discontinuous zircon crystallization history within the magmatic system. Both magma types contain zircon whose interiors predate the eruption by up to 200 ka. The dominant age peak in the T1 magma is ~ 30 ka with subordinate peaks at ~ 45, ~ 75, and ~ 100 ka, whereas the T3 magma has a dominant zircon interior age peak at ~ 90 ka with smaller modes at ~ 35 and ~ 150 ka. These patterns are consistent with isolated pockets of crystallization throughout the evolution of the system. Crystal rim analyses yield ages ranging from within error of the eruption age to at least ~ 90 ka prior to eruption, highlighting that zircon crystallization frequently stalled long before the eruption. Continuous depth profiling from crystal rims inward demonstrates protracted growth histories for individual crystals (up to ~ 100 ka) that were punctuated by asynchronous hiatuses of up to 30 ka in duration. Disparate zircon growth histories can result from localized thermal perturbations caused by mafic intrusions into a silicic reservoir. The crystal age heterogeneity at hand-sample scale requires considerable crystal transport and mixing. We propose that crystal mixing was achieved through buoyancy instabilities caused by mafic magma flow through crystal mush. A terminal pre-eruptive rejuvenation event was capable of mobilizing voluminous melts that erupted, but was too short (< 10²–10³ years) to result in extensive zircon growth. The contrasting, punctuated zircon histories argue against closed-system fractional crystallization models for silicic magmatism that require protracted cooling times following a mostly liquid starting condition.     

Systematic tapping of independent magma chambers during the 1 Ma Kidnappers supereruption

The 1.0 Ma Kidnappers supereruption (~ 1200 km³ DRE) from Mangakino volcanic centre, Taupo Volcanic Zone, New Zealand, produced a large phreatomagmatic fall deposit followed by an exceptionally widespread ignimbrite. Detailed sampling and analysis of glass shards and mineral phases have been undertaken through a proximal 4.0 m section of the fall deposit, representing the first two-thirds of erupted extra-caldera material. Major and trace element chemistries of glass shards define three distinct populations (types A, B and C), which systematically change in proportion through the fall deposit and are inferred to represent three magma types. Type B glass and biotite first appear at the same level (~ 0.95 m above base) in the fall deposit suggesting later tapping of a biotite-bearing magma. Plagioclase and Fe–Ti oxide compositions show bimodal distributions, which are linked to types A and B glass compositions. Temperature and pressure (T–P) estimates from hornblende and Fe–Ti oxide equilibria from each magma type are similar and therefore the three magma bodies were adjacent, not vertically stacked, in the crust. Most hornblende model T–P estimates range from 770 to 840 °C and 90 to 170 MPa corresponding to storage depths of ~ 4.0–6.5 km. Hornblende model T–P estimates coupled with in situ trace element fingerprinting imply that the magma bodies were individually well mixed, and not stratified. Compositional gaps between the three glass compositional types imply that no mixing between these magmas occurred. We interpret these data, coupled with the systematic changes in shard compositional proportions through the fall deposit, to reflect that three independent melt-dominant bodies of magma contributed large (A, ~ 270 km³), medium (B, ~ 90 km³) and small (C, ~ 40 km³) volumes (as reflected in the fall deposits) and were systematically tapped during the eruption. We propose that the systematic evacuation of the three independent magma bodies implies that there was tectonic triggering and linkage of eruptions. Our results show that supereruptions can be generated by near simultaneous multiple eruptions from independent magma chambers rather than the evacuation of a large single unitary magma chamber.     

Cosmogenic 3He and 21Ne dating of biotite and hornblende

Stable cosmogenic isotopes such as ³He and ²¹Ne are useful for dating of diverse lithologies, quantifying erosion rates and ages of ancient surfaces and sediments, and for assessing complex burial histories. Although many minerals are potentially suitable targets for ³He and ²¹Ne dating, complex production systematics require calibration of each mineral–isotope pair. We present new results from a drill core in a high-elevation ignimbrite surface, which demonstrates that cosmogenic ³He and ²¹Ne can be readily measured in biotite and hornblende. ²¹Ne production rates in hornblende and biotite are similar, and are higher than that in quartz due to production from light elements such as Mg and Al. We measure ²¹Ne_hbl/²¹Ne_qtz = 1.35 ± 0.03 and ²¹Ne_bio/²¹Ne_qtz = 1.3 ± 0.02, which yield production rates of 25.6 ± 3.0 and 24.7 ± 2.9 at g^? 1 yr^? 1 relative to a ²¹Ne_qtz production rate of 19.0 ± 1.8 at g^? 1 yr^? 1. We show that nucleogenic ²¹Ne concentrations produced via the reaction ¹⁸O(α,n)²¹Ne are manageably small in this setting, and we present a new approach to deconvolve nucleogenic ²¹Ne by comparison to nucleogenic ²²Ne produced from the reaction ¹⁹F(α,n)²²Ne in F-rich phases such as biotite. Our results show that hornblende is a suitable target phase for cosmogenic ³He dating, but that ³He is lost from biotite at Earth surface temperatures. Comparison of ³He concentrations in hornblende with previously measured mineral phases such as apatite and zircon provides unambiguous evidence for ³He production via the reaction ⁶Li(n,α)³H → ³He. Due to the atypically high Li content in the hornblende (~ 160 ppm) we estimate that Li-produced ³He represents ~ 40% of total ³He production in our samples, and must be considered on a sample-specific basis if ³He dating in hornblende is to be widely implemented.     

The origins and concentrations of water,carbon, nitrogen and noble gases on Earth

The isotopic compositions of terrestrial hydrogen and nitrogen are clearly different from those of the nebular gas from which the solar system formed, and also differ from most of cometary values. Terrestrial N and H isotopic compositions are in the range of values characterizing primitive meteorites, which suggests that water, nitrogen, and other volatile elements on Earth originated from a cosmochemical reservoir that also sourced the parent bodies of primitive meteorites. Remnants of the proto-solar nebula (PSN) are still present in the mantle, presumably signing the sequestration of PSN gas at an early stage of planetary growth. The contribution of cometary volatiles appears limited to a few percents at most of the total volatile inventory of the Earth. The isotope signatures of H, N, Ne and Ar can be explained by mixing between two end-members of solar and chondritic compositions, respectively, and do not require isotopic fractionation during hydrodynamic escape of an early atmosphere.The terrestrial inventory of ⁴⁰Ar (produced by the decay of ⁴⁰K throughout the Earth's history) suggests that a significant fraction of radiogenic argon may be still trapped in the silicate Earth. By normalizing other volatile element abundances to this isotope, it is proposed that the Earth is not as volatile-poor as previously thought. Our planet may indeed contain up to ~ 3000 ppm water (preferred range: 1000–3000 ppm), and up to ~ 500 ppm C, both largely sequestrated in the solid Earth. This volatile content is equivalent to an ~ 2 (± 1) % contribution of carbonaceous chondrite (CI-CM) material to a dry proto-Earth, which is higher than the contribution of chondritic material advocated to account for the platinum group element budget of the mantle. Such a (relatively) high contribution of volatile-rich matter is consistent with the accretion of a few wet planetesimals during Earth accretion, as proposed by recent dynamical models.The abundance pattern of major volatile elements and of noble gases is also chondritic, with two notable exceptions. Nitrogen is depleted by one order of magnitude relative to water, carbon and most noble gases, which is consistent with either N retention in a mantle phase during magma generation, or trapping of N in the core. Xenon is also depleted by one order of magnitude, and enriched in heavy isotopes relative to chondritic or solar Xe (the so-called “xenon paradox”). This depletion and isotope fractionation might have taken place due to preferential ionization of xenon by UV light from the early Sun, either before Earth's formation on parent material, or during irradiation of the ancient atmosphere. The second possibility is consistent with a recent report of chondritic-like Xe in Archean sedimentary rocks that suggests that this process was still ongoing during the Archean eon (Pujol et al., 2011). If the depletion of Xe in the atmosphere was a long-term process that took place after the Earth-building events, then the amounts of atmospheric ¹²⁹Xe and ^131–136Xe, produced by the short-lived radioactivities of ¹²⁹I (T_1/2 = 16 Ma) and ²⁴⁴Pu (T_1/2 = 82 Ma), respectively, need to be corrected for subsequent loss. Doing so, the I–Pu–Xe age of the Earth becomes ≤ 50 Ma after start of solar system formation, instead of ~ 120 Ma as computed with the present-day atmospheric Xe inventory.     

Safety of Italian dams in the face of flood hazard

Most rivers in Italy are segmented by dams that need rehabilitation because of (1) safety requirements by increasingly risk-averse societies, (2) changes in the downstream river and riparian system after dams building, (3) poor initial design at the time of completion and (4) modified priorities of watershed management. Safe design of flood spillways is a major concern, and requires to cope with low frequency flood hazard. One must estimate flood figures with high return periods (R ⩾ 1000–10,000 years) but statistical methods involve large uncertainties because of the short length of the available records. This paper investigates the return period of the design flood of existing spillways R_S of large dams in Italy. We used re-normalized flood frequency approach and regionalization using the Generalized Extreme Value distribution. The estimation of the site specific index flood is carried out by simple scaling with basin area at the regional level. The result show that 55% (245) of the 448 examined dams are equipped by spillway with R_S > 10,000; and 71% (315) of the dams have R_S > 1000. Conversely, 29% (130) of the dams display R_S < 1000 years, lower than acceptable hazard. The spillway of 14% (62) of the dams has R_S < 100 years, indicating potential exceedance of spillways capacity. Reservoir routing may dampen the outflow hydrograph, but one should carefully account for the need of achieving accurate dam safety assessment of these dams based on site specific investigations, also accounting for global change forcing.     

Radiogenic heat production in the lithosphere of Sulu ultrahigh-pressure metamorphic belt

The Chinese Continental Scientific Drilling (CCSD) project is located at the Sulu ultrahigh-pressure metamorphic (UHPM) belt. It offers a unique opportunity for studying the radiogenic heat production of both shallower and deeper rocks. Based on the concentrations of radiogenic elements U, Th and K on 349 samples from main hole of CCSD (CCSD MH), pilot holes and exposures, we determined radiogenic heat productions of all major rock types in the Sulu UHPM belt. Results show the mean values of orthogneiss and paragneiss are respectively 1.65 ± 0.81 and 1.24 ± 0.61 µW m^? 3. Due to different composition and grade of retrogressive metamorphism, the eclogites display significant scatter in radiogenic heat production, ranging from 0.01 to 2.85 µW m^? 3, with a mean of 0.44 ± 0.55 µW m^? 3. The radiogenic heat production in ultramafic rocks also varies within a large range of 0.02 to 1.76 µW m^? 3, and the average turns out to be 0.18 ± 0.31 µW m^? 3. Based on the measurements and crustal petrologic model, the vertical distribution model of heat production in Sulu crust is established. The resulting mean heat production (0.76 µW m^? 3) contributes 24 mW m^? 2 to the surface heat flow. 1-D thermal model indicates that the temperature at the Moho reaches above 750 °C, and the thermal thickness of the lithosphere is ~ 75 km, in good agreement with the geophysical results. The high teat flow (~ 75 mW m^? 2) together with thin lithosphere presents strong support for the extension events during the late Cretaceous and Cenozoic.     

Decoupled warming and monsoon precipitation in East Asia over the last deglaciation

Our understanding of the continental climate development in East Asia is mainly based on loess–paleosol sequences and summer monsoon precipitation reconstructions based on oxygen isotopes (δ¹⁸O) of stalagmites from several Chinese caves. Based on these records, it is thought that East Asian Summer Monsoon (EASM) precipitation generally follows Northern Hemisphere (NH) summer insolation. However, not much is known about the magnitude and timing of deglacial warming on the East Asian continent. In this study we reconstruct continental air temperatures for central China covering the last 34,000 yr, based on the distribution of fossil branched tetraether membrane lipids of soil bacteria in a loess–paleosol sequence from the Mangshan loess plateau. The results indicate that air temperature varied in phase with NH summer insolation, and that the onset of deglacial warming at ~ 19 kyr BP is parallel in timing with other continental records from e.g. Antarctica, southern Africa and South-America. The air temperature increased from ~ 15 °C at the onset of the warming to a maximum of ~ 27 °C in the early Holocene (~ 12 kyr BP), in agreement with the temperature increase inferred from e.g. pollen and phytolith data, and permafrost limits in central China.Comparison of the tetraether membrane lipid-derived temperature record with loess–paleosol proxy records and stalagmite δ¹⁸O records shows that the strengthening of EASM precipitation lagged that of deglacial warming by ca. 3 kyr. Moreover, intense soil formation in the loess deposits, caused by substantial increases in summer monsoon precipitation, only started around 12 kyr BP (ca. 7 kyr lag). Our results thus show that the intensification of EASM precipitation unambiguously lagged deglacial warming and NH summer insolation, and may contribute to a better understanding of the mechanisms controlling ice age terminations.     

New insights into the origin and evolution of Lake Vida,McMurdo Dry Valleys,Antarctica — A noble gas study in ice and brines

Unlike other lakes in the McMurdo Dry Valleys, Antarctica, Lake Vida has a thick (~ 19 m) ice cover sealing a liquid brine body of unusually high salinity (~ 245 g/L) from the atmosphere. To constrain the conditions under which the atypical Lake Vida ice cover formed and evolved, 19 ice samples were collected down to a depth of ~ 14 m, together with three brine samples trapped in the ice at ~ 16 m for analysis of helium, neon, argon, krypton, and xenon concentrations. The broad pattern of noble gas concentrations for Lake Vida samples is fundamentally different from that of air saturated water (ASW) at 0 °C and an elevation of 340 m for salinities of 0 (ice) and 245 g/L (brine). Overall, ice samples are enriched in He and depleted in Ne with saturation relative to ASW averages of 1.38 and 0.82, respectively, and strongly depleted in Ar, Kr, and Xe with relative saturations of 0.10, 0.06, and 0.05, respectively. By contrast, brine samples are generally depleted in He and Ne (relative saturation averages of 0.33 and 0.27, respectively) but enriched in Ar, Kr, and Xe, with relative saturation averages of 1.45, 3.15, and 8.86, respectively. A three-phase freezing partitioning model generating brine, ice and bubble concentrations for all stable noble gases was tested and compared with our data. Measured brine values are best reproduced for a salinity value of 175 g/L, a pressure of 1.1 atm, and a bubble volume of 20 cm³ kg^?1. Sensitivity tests for ice + bubble samples show an ideal fit for bubble volumes of ~ 1–2 cm³ kg^?1. Our results show that the conditions under which ice and brine formed and evolved at Lake Vida are significantly different from other ice-covered lakes in the area. Our brine data suggest that Lake Vida may be transitioning from a wet to a dry-based lake, while the ice + bubble data suggest at least partial re-equilibration of residual liquid with the atmosphere as ice forms at the top of Lake Vida ice cover.     

Pliocene climate change of the Southwest Pacific and the impact of ocean gateways

The transition from the early Pliocene “Warmhouse” towards the present “Icehouse” climate and the role of Gateway dynamics are intensively debated. Both, the constrictions of the Central American Seaway and the Indonesian Gateway affected ocean circulation and climate during the Pliocene epoch. Here, we use combined δ¹⁸O and Mg/Ca ratios of planktonic foraminifera (marine protozoa) from surface and subsurface levels to reconstruct the thermal structure and changes in salinities from the Southwest Pacific Deep Sea Drilling Project (DSDP) Site 590B from 6.5 to 2.5 Ma. Our data suggest a gradual cooling of ~ 2 °C and freshening of the sea surface during ~ 4.6–4 Ma with an increased meridional temperature gradient between the West Pacific Warm Pool and the Southwest Pacific when the closing of the Central American Seaway reached a critical threshold. After ~ 3.5 Ma, the restricted Indonesian Gateway might have amplified the East Australian Current, allowing enhanced heat transport towards the Southwest Pacific with reduced meridional temperature gradients when the global climate gradually cooled. At the same time our data suggest a cooling and freshening of Subantarctic Mode Water (SAMW) or/and an increased northward flow of SAMW towards Site 590B, possibly a first step towards the present Antarctic Frontal System.     

Vertical distribution of HTO and 125I− transport parameters in Boom Clay in the Essen-1 borehole (Mol,Belgium)

In the frame of the R&D activities performed on the Boom Clay for assessing the suitability of deep clayey formations for radioactive waste disposal, the transferability of the scientific results obtained on the Boom Clay in Mol to the whole Campine Basin is investigated. Boreholes were drilled at different locations (e.g. Mol, Doel, Essen) and cores were sampled over the entire thickness of the Boom Clay formation on which the migration parameters for iodide and tritiated water (HTO) are determined.At Essen, the transport parameters in the Boom Clay can be considered as homogeneous in the range from 159 m to 241 m Below Drilling Table. The average hydraulic conductivity is (5.4 ± 1.7) × 10⁻¹² m/s. The average ηR value for iodide is 0.25 ± 0.03 and 0.42 ± 0.05 for HTO. For HTO, this high value is mainly due to a higher value in the Putte Member (0.46 ± 0.03) compared to the other members (0.39 ± 0.02). The apparent diffusion coefficient is (1.3 ± 0.1) × 10⁻¹⁰ m²/s for HTO and (1.1 ± 0.2) × 10⁻¹⁰ m²/s for iodide. The expected effect of ionic strength (increasing with depth) on the ηR value of iodide is of the same size as the measurement error, what might explain why it was not observed.On a lateral (horizontal) level, the hydraulic conductivity at the Essen-1 borehole (5.4 × 10⁻¹² m/s) lies between that of Boom Clay in Mol-1 (2.5 × 10⁻¹² m/s) and that of Boom Clay in Doel-2b (1.4 × 10⁻¹¹ m/s). For iodide, the higher ηR value in Essen-1 and Doel-2b (ηR ≈ 0.25) than in Mol-1 (ηR ≈ 0.16) can partly be explained by a higher ionic strength of the pore water. Apart from the Putte Member at Essen-1, the HTO porosities of the Terhagen Member and the Transition zone in Essen are in the range of the average porosities observed in Mol and Doel (ηR ≈ 0.37–0.39). For both iodide and HTO, the value of the apparent diffusion coefficient D_app is similar in Mol-1 and in Doel-2b, with a clearly higher value for HTO than for iodide. In Essen-1, the apparent diffusion coefficients for iodide and HTO are nearly equal, and slightly smaller than the iodide value in Mol-1/Doel-2b. Accordingly, the HTO apparent diffusion coefficient is considerably smaller in Essen-1 than in Mol-1/Doel-2b.     

Age and nature of eclogites in the Huwan shear zone,and the multi-stage evolution of the Qinling-Dabie-Sulu orogen,central China

In situ LA-ICPMS U-Pb, trace element, and Hf isotope data in zircon demonstrate a Carboniferous age for eclogite-facies metamorphism in Siluro-Devonian protoliths in the Huwan shear zone, Dabie Mountains, Central China. This age contrasts with the more prevailing Triassic age for high- to ultrahigh pressure (HP to UHP) metamorphism in the Qinling-Dabie-Sulu orogen. Metamorphic zircon in two eclogite samples from Sujiahe is characterized by low Th/U ratios, small negative Eu anomalies, flat HREE patterns, and low ¹⁷⁶Lu/¹⁷⁷Hf ratios. These geochemical signatures suggest that the zircon crystallized in the presence of garnet and in the absence of plagioclase feldspar. Furthermore, temperatures of ~ 655 and ~ 638 °C, calculated using the Ti content of zircon, are consistent with their formation during eclogite-facies metamorphism. The weighted mean ²⁰⁶Pb/²³⁸U age of 309 ± 4 Ma (2δ) for this zircon improves previous age estimates for eclogite-facies metamorphism in the Huwan shear zone, ranging from 420 to 220 Ma. Metamorphic zircon from one eclogite sample from Hujiawan, most likely formed during prograde metamorphism, yields an equivalent age estimate of 312 ± 11 Ma. Magmatic zircon cores in the three samples yield ages for the magmatic protoliths of the eclogites ranging from 420 ± 7 to 406 ± 5 Ma, and post-dating the middle Paleozoic collision of the North China and the Qinling terrain. The zircon crystals in the three eclogite samples display a large variation of ε_Hf (t) values of ? 4.9 to 21.3. The metamorphic zircon overgrowths show the same range of ε_Hf (t) values as those of the inherited magmatic crystal interiors. This suggests that the metamorphic zircon overgrowths may have formed by dissolution-reprecipitation of pre-existing magmatic zircon thereby preserving their original Hf isotopic composition. The high ε_Hf (t) values suggest that the protoliths were derived from depleted mantle sources, most likely Paleotethyan oceanic crust; while the low ε_Hf (t) values are attributed to crustal contamination. Some eclogites in the Huwan shear zone have a distinctive signature of continental crust most probably derived from the Yangtze Craton. The coexistence of Paleozoic oceanic crust and Neoproterozoic continental crust with similar metamorphic ages in the Huwan shear zone implies that Paleozoic Paleotethyan oceanic crust was produced within a marginal basin of the northern Yangtze Craton. The opening of the Paleo-Tethyan ocean was slightly younger than the collision of the North China Craton and the Qinling terrain during the Late Paleozoic in the Qinling-Dabie-Sulu orogen. Subduction of the Paleo-Tethyan oceanic crust and associated continental basement resulted in the 309 ± 2 Ma (2σ) eclogite-facies metamorphism in the Huwan shear zone. The subsequent Triassic continent-continent collision led to the final coalescence of the Yangtze and Sino-Korean cratons. Amalgamation of the Yangtze and North China cratons was, therefore, a multistage process extending over at least 200 Ma.     

Remote sensing based water quality monitoring in Chivero and Manyame lakes of Zimbabwe

Lakes Chivero and Manyame are amongst Zimbabwe’s most polluted inland water bodies. MEdium Resolution Imaging Spectrometry level 1b full resolution imagery for 2011 and 2012 were used to derive chlorophyll-a (chl_a) and phycocyanin (blue-green algae) concentrations using a semi-empirical band ratio model; total suspended matter (TSM) concentrations were derived from the MERIS processor. In-situ measured chl_a was used to validate the remotely sensed values. Results indicate that remote sensing measurements are comparable with in situ measurements. A strong positive correlation (R² = 0.91; MAE = 2.75 mg/m³ (8.5%)) and p < 0.01 (highly significant)) between measured and modeled chl_a concentrations was obtained. Relationships between optically active water constituents were assessed. Measured chl_a correlated well with MERIS modeled phycocyanin (PC) concentration (R² = 0.9458; p < 0.01 (highly significant)) whilst chl_a and TSM gave (R² = 0.7344; p < 0.05 (significant)). Modeled TSM and PC concentrations manifested a good relationship with each other (R² = 9047; p < 0.001 (very highly significant)). We conclude that remote sensing data allow simultaneous retrieval of different water quality parameters as well as providing near real time and space results that can be used by water managers and policy makers to monitor water bodies.     

Helium isotopes in the Izu Peninsula,Japan: Relation of magma and crustal activity

The relation of magma and crustal activity has been studied from spatial distribution of ³He/⁴He ratios of gas and/or water samples over the Izu Peninsula, where significant crustal deformation associated with seismic swarm activities has been observed since 1970s. The air-corrected values of ³He/⁴He ratios ranged from 3.5 to 8.2 R_A, where R_A is the atmospheric ³He/⁴He ratio = 1.4 × 10^? 6, indicating that helium is mostly of magmatic origin. Among the three pressure sources proposed to explain the crustal deformation, two inflation sources beneath the inland of northeast and the mid east coast of the Izu Peninsula locate in the broad distribution of high ³He/⁴He ratios, which supports relation of magma to the crustal uplift. In contrast, the distribution of ³He/⁴He ratios around the tensile fault assumed in the area of seismic swarms appears not to indicate existence of significant amount of magma below the tensile fault. Alternatively, the results suggest magma below a point several kilometers south of the tensile fault. The seismic swarms are explained either by fluid pressurization of thermal water heated by this magma or by intrusion of magma to the tensile fault moved obliquely from the deep magma reservoir.     

Magnesium isotopes constraints on the origin of Mg-rich olivines from the Allende chondrite: Nebular versus planetary?

High precision Mg isotope measurements by multi-collector ion microprobe show that refractory olivines from the Allende chondrite, either olivines isolated in the matrix (2 samples studied) or olivines in type I chondrules (6 samples studied), have variable δ²⁶Mg* enrichments and deficits (calculated in permil as the ²⁶Mg deviation from the instrumental mass fractionation line) relative to the Earth. Most average δ²⁶Mg* (noted δ²⁶Mg*_av) values (between 10 and 20 analyses per chondrule) are negative but the total range is from ?0.029 (± 0.010) ‰ (2 sigma errors) to + 0.011 (± 0.011) ‰ with an exception of one olivine at + 0.043 (± 0.023) ‰. These variations in δ²⁶Mg*_av reflect the formation of the olivines from reservoirs enriched in various amounts of ²⁶Mg by the decay of short-lived ²⁶Al (T_1/2 = 0.73 Ma). Similarly, 30 analyses of olivines from the Eagle Station pallasite show a δ²⁶Mg*_av value of ?0.033 ± 0.008‰, as negative as some olivines from Allende chondrules and the Solar system initial δ²⁶Mg* value of ?0.038 ± 0.004‰ (defined at the time of formation of type B Ca–Al-rich inclusions – CAIs – when ²⁶Al/²⁷Al = 5.23 × 10^?5, Jacobsen et al., 2008).Because olivines are Al-poor and because their Mg isotopic compositions are not reset during the chondrule forming events, their δ²⁶Mg*_av can be used to calculate model crystallization ages relative to various theoretical Mg isotope growth curves. The two end-member scenarios considered are (i) a “nebular” growth in which the Al/Mg ratio remains chondritic and (ii) a “planetary” growth in which a significant increase of the Al/Mg ratio can be due to, for instance, olivine magmatic fractionation. The low δ²⁶Mg*_av value of olivines from the Eagle Station pallasite demonstrate that metal-silicate differentiation occurred as early as ~ 0. 15_- 0. 23^+ 0. 29 Ma after CAIs in either of the growth scenarios. Similarly the variable δ²⁶Mg*_av values of refractory olivines can be understood if they were formed in planetesimals which started to differentiate as early as the Eagle Station parent body. Accretion of these planetesimals must have been coeval to the formation of CAIs and their disruption could explain why their fragments (Mg-rich olivines) were distributed in the chondrule forming regions of the disk.     

Effect of prolonged hypoxia on food consumption,respiration, growth and reproduction in marine scavenging gastropod Nassarius festivus

The effects of prolonged exposure to reduced oxygen levels (3.0 and 1.5 mg O₂ l⁻¹) on marine scavenging gastropods Nassarius festivus were studied for 8 weeks. The percentages of individuals engaged in feeding and amount of food consumed were reduced as oxygen level decreased; absorption efficiency, however, did not vary significantly with oxygen level. Oxygen consumption rates and specific oxygen consumption rates were lower at reduced oxygen levels. Reproduction occurred at all oxygen levels with less egg capsules being produced at lower oxygen levels. Egg size and number of eggs per capsule, however, were not significantly affected by oxygen level. The increase in shell length was 12%, 6% and 5% at 6.0 mg O₂ l⁻¹ (normoxia), 3.0 mg O₂ l⁻¹ and 1.5 mg O₂ l⁻¹, respectively. At the end of the experiment, the amount of energy allocated to growth and reproduction decreased at reduced oxygen levels with values obtained at 3.0 mg O₂ l⁻¹ and 1.5 mg O₂ l⁻¹ being 48% and 70% lower than those at 6.0 mg O₂ l⁻¹. At all oxygen levels, most of the accumulated energy was allocated to shell growth and reproduction, and the amount allocated to somatic growth was relatively insignificant. The reduction in energy allocated to reproduction was greater than that to shell growth as the oxygen level was reduced, indicating a strategic energy allocation of marine scavengers under stressful conditions to enhance survival.     

Cave air ventilation and CO2 outgassing by radon-222 modeling: How fast do caves breathe?

In general, the rate and timing of calcite precipitation is in part affected by variations in cave air CO₂ concentrations. Knowledge of cave ventilation processes is required to quantify the effect variations in CO₂ concentrations have on speleothem deposition rates and thus paleoclimate records. In this study we use radon-222 (²²²Rn) as a proxy of ventilation to estimate CO₂ outgassing from the cave to the atmosphere, which can be used to infer relative speleothem deposition rates. Hollow Ridge Cave, a wild cave preserve in Marianna, Florida, is instrumented inside and out with multiple micro-meteorological sensor stations that record continuous physical and air chemistry time-series data. Our time series datasets indicate diurnal and seasonal variations in cave air ²²²Rn and CO₂ concentrations, punctuated by events that provide clues to ventilation and drip water degassing mechanisms. Average cave air ²²²Rn and CO₂ concentrations vary seasonally between winter (²²²Rn = 50 dpm L^? 1, where 1 dpm L^? 1 = 60 Bq m^? 3; CO₂ = 360 ppmv) and summer (²²²Rn = 1400 dpm L^? 1; CO₂ = 3900 ppmv). Large amplitude diurnal variations are observed during late summer and autumn (²²²Rn = 6 to 581 dpm L^? 1; CO₂ = 360 to 2500 ppmv).We employ a simple first-order ²²²Rn mass balance model to estimate cave air exchange rates with the outside atmosphere. Ventilation occurs via density driven flow and by winds across the entrances which create a ‘venturi’ effect. The most rapid ventilation occurs 25 m inside the cave near the entrance: 45 h^? 1 (1.33 min turnover time). Farther inside (175 m) exchange is slower and maximum ventilation rates are 3 h^? 1 (22 min turnover time). We estimate net CO₂ flux from the epikarst to the cave atmosphere using a CO₂ mass balance model tuned with the ²²²Rn model. Net CO₂ flux from the epikarst is highest in summer (72 mmol m^? 2 day^? 1) and lowest in late autumn and winter (12 mmol m^? 2 day^? 1). Modeled ventilation and net CO₂ fluxes are used to estimate net CO₂ outgassing from the cave to the atmosphere. Average net CO₂ outgassing is positive (net loss from the cave) and is highest in late summer and early autumn (about 4 mol h^? 1) and lowest in winter (about 0.5 mol h^? 1). Modeling of ventilation, net CO₂ flux from the epikarst, and CO₂ outgassing to the atmosphere from cave monitoring time-series can help better constrain paleoclimatic interpretations of speleothem geochemical records.     

Variability of the dissolved nutrient (N,P, Si) concentrations in the Bay of Annaba in relation to the inputs of the Seybouse and Mafragh estuaries

Dissolved inorganic nitrogen (DIN), phosphate (PO₄) and silicic acid (Si(OH)₄) loads from the Seybouse and the Mafragh estuaries into the Bay of Annaba, Algeria, were assessed at three stations of the Bay over three years. The Seybouse inputs had high levels of DIN and PO₄, in contrast to the Mafragh estuary’s near-pristine inputs; Si(OH)₄ levels were low in both estuaries. The DIN:PO₄ molar ratios were over 30 in most samples and the Si(OH)₄:DIN ratio was less than 0.5 in the Seybouse waters, but nearly balanced in the Mafragh. The specific fluxes of Si–Si(OH)₄ (400–540 kg Si km⁻² yr⁻¹) were comparable in the two catchments, but those of DIN were several-fold higher in the Seybouse (373 kg N km⁻² yr⁻¹). The inner Bay affected by the Seybouse inputs had high levels of all nutrients, while the Mafragh plume and the outer marine station were less enriched.