The influence of salinity on the solubility of Zn and Cd sulphides in the Scheldt estuary

In the estuary of the river Scheldt, where an oxygen gradient exists in addition to the salinity gradient, redox processes will be of major importance for trace metal mobilisation. In this study, the influence of salinity and pH on the redox processes of dissolved Zn and Cd sulphides is investigated together with the effects on the ratio of the dissolved Zn and Cd concentrations. The speciation of these metals is calculated with the chemical equilibrium programme +. Zn sulphides are oxidised at lower oxygen concentrations than Cd sulphides, due to lower stability constants, causing a sudden increase or peak in the dissolved Zn/Cd ratio. The formation of dissolved Cd chloride complexes when oxidation occurs at high salinities (S=15) increases the mobility of Cd, causing a decrease in the Zn/Cd peak of the total dissolved concentrations. The peak is three to four times smaller at S=15 than when oxidation occurs at S=2. The simple model calculations compare very well with field data. The Scheldt estuary is suitable to illustrate these calculations. In the 1970s, the anoxic part of the estuary reached S=15–20, but since the early 1980s it has dropped to S=2–10. Historic data on metals in the estuary from 1978, 1987 and the 1990s were used to compare with the equilibrium calculations. The increase of the dissolved Zn/Cd peak at low salinity as a consequence, of the decreasing anoxic region is confirmed well by the data. The good agreement between model calculations and field data is a proof of the extreme importance of redox processes for the solubility of Zn and Cd sulphides in the estuary.     

Silica-merrihueite/roedderite-bearing chondrules and clasts in ordinary chondrites: New occurrences and possible origin

Abstract Merrihueite (K,Na)₂(Fe, Mg)₅Si₁₂O₃₀ (na < 0.5, fe > 0.5, where na = Na/(Na + K), fe = Fe/(Fe + Mg) in atomic ratio) is a rare mineral described only in several chondrules and irregularly-shaped fragments in the Mezö-Madaras L3 chondrite (Dodd et al., 1965; Wood and Holmberg, 1994). Roedderite (Na,K)₂(Mg, Fe)₅Si₁₂O₃₀ (na > 0.5, fe < 0.5) has been found only in enstatite chondrites and in the reduced, subchondritic silicate inclusions in IAB irons (Fuchs, 1966; Rambaldi et al., 1984; Olsen, 1967). We describe silica-roedderite-bearing clasts in L/LL3.5 ALHA77011 and LL3.7 ALHA77278, a silica-roedderite-bearing chondrule in L3 Mezö-Madaras, and a silica-merrihueite-bearing chondrule in L/LL3.5 ALHA77115. The findings of merrihueite and roedderite in ALHA77011, ALHA77115, ALHA77278 and Mezö-Madaras fill the compositional gap between previously described roedderite in enstatite chondrites and silicate inclusions in IAB irons and merrihueite in Mezö-Madaras, suggesting that there is a complete solid solution of roedderite and merrihueite in meteorites. We infer that the silica- and merrihueite/roedderite-bearing chondrules and clasts experienced a complex formational history including: (a) fractional condensation in the solar nebula that produced Si-rich and Al-poor precursors, (b) melting of fractionated nebular solids resulting in the formation of silica-pyroxene chondrules, (c) in some cases, fragmentation in the nebula or on a parent body, (d) reaction of silica with alkali-rich gas that formed merrihueite/roedderite on a parent body, (e) formation of fayalitic olivine and ferrosilite-rich pyroxene due to reaction of silica with oxidized Fe on a parent body, and (f) minor thermal metamorphism, possibly generated by impacts.     

Differential subduction and exhumation of crustal slices in the Sulu HP-UHP metamorphic terrane: insights from mineral inclusions, trace elements, U-Pb and Lu-Hf isotope analyses of zircon in orthogneiss

Based on new evidence the Sulu orogen is divided from south‐east to north‐west into high‐pressure (HP) crustal slice I and ultrahigh‐pressure (UHP) crustal slices II and III. A combined set of mineral inclusions, cathodoluminescence images, U‐Pb SHRIMP dating and in situ trace element and Lu‐Hf isotope analyses was obtained on zircon from orthogneisses of the different slices. Zircon grains typically have three distinct domains that formed during crystallization of the magmatic protolith, HP or UHP metamorphism and late‐amphibolite facies retrogression, respectively: (i) oscillatory zoned cores, with low‐pressure (LP) mineral inclusions and Th/U > 0.38; (ii) high‐luminescent mantles (Th/U < 0.10), with HP mineral inclusions of Qtz + Grt + Arg + Phe + Ap for slice I zircon and Coe + Grt + Phe + Kfs + Ap for both slices II and III zircon; (iii) low‐luminescent rims, with LP mineral inclusions and Th/U < 0.08. Zircon U‐Pb SHRIMP analyses of inherited cores point to protolith ages of 785–770 Ma in all seven orthogneisses. The ages recorded for UHP metamorphism and subsequent retrogression in slice II zircon (c. 228 and c. 215 Ma, respectively) are significantly older than those of slice III zircon (c. 218 and c. 202 Ma, respectively), while slice I zircon recorded even older ages for HP metamorphism and subsequent retrogression (c. 245 and c. 231 Ma, respectively). Moreover, Ar‐Ar biotite ages from six paragneisses, interpreted as dating amphibolite facies retrogression, gradually decrease from HP slice I (c. 232 Ma) to UHP slice II (c. 215 Ma) and UHP slice III (c. 203 Ma). The combined data set suggests decreasing ages for HP or UHP metamorphism and late retrogression in the Sulu orogen from south‐east to north‐west. Thus, the HP‐UHP units are interpreted to represent three crustal slices, which underwent different subduction and exhumation histories. Slice I was detached from the continental lithosphere at ～55–65 km depth and subsequently exhumed while subduction of the underlying slice II continued to ～100–120 km depth (UHP) before detachment and exhumation. Slice III experienced a similar geodynamic evolution as slice II, however, both UHP metamorphism and subsequent exhumation took place c. 10 Myr later. Magmatic zircon cores from two types of orthogneiss in UHP slices II and III show similar mid‐Neoproterozoic crystallization ages, but have contrasting Hf isotope compositions (εHf_(～785) = ?2.7 to +2.2 and ?17.3 to ?11.1, respectively), suggesting their formation from distinct crustal units (Mesoproterozoic and Paleoproterozoic to Archean, respectively) during the breakup of Rodinia. The UHP and the retrograde zircon domains are characterized by lower Th/U and ¹⁷⁶Lu/¹⁷⁷Hf but higher ¹⁷⁶Hf/¹⁷⁷Hf(t) than the Neoproterozoic igneous cores. The similarity between UHP and retrograde domains indicates that late retrogression did not significantly modify chemical and isotopic composition of the UHP metamorphic system.     

A PETROGRAPHICAL STUDY OF THE CHINESE AGALMATOLITES

Ⅰ. INTRODUCTION. The most popular Chinese agalmatolites are Shoushanshih (壽山石), Changhuashih (昌化石), Chingtienshih (青田石) and Kwanglushih (廣綠石). They are named after the names of places, as the name Shoushanshih is from     

Unified modeling of flow liquefaction and cyclic mobility

Flow liquefaction and cyclic mobility are two different phenomena that are encountered during strong earthquakes. Flow liquefaction is associated with the contractive behavior of loose granular materials and cyclic mobility is associated with the dilative response of both loose and dense granular materials at low confining stresses. These two types of response pertain to the same material and therefore should be modeled in a consistent manner. Whether a soil in a given state exhibits contractive or dilative behavior is dependent on its dilatancy, d=d_v^p/d_q^p. A form of the dilatancy d=d(η,ψ,C) is proposed, where η=q/p is the stress ratio, and ψ and C denote the internal state variables and the intrinsic properties, respectively. It has been shown that such a state-dependent dilatancy is effective in describing both the contractive and dilative behavior. This allows the soil behavior associated with flow liquefaction and cyclic mobility during earthquakes to be modeled in a unified way.     

Petrology,mineralogy, and oxygen isotope compositions of aluminum‐rich chondrules from CV3 chondrites

Bulk major element composition, petrography, mineralogy, and oxygen isotope compositions of twenty Al‐rich chondrules (ARCs) from five CV3 chondrites (Northwest Africa [NWA] 989, NWA 2086, NWA 2140, NWA 2697, NWA 3118) and the Ningqiang carbonaceous chondrite were studied and compared with those of ferromagnesian chondrules and refractory inclusions. Most ARCs are marginally Al‐richer than ferromagnesian chondrules with bulk Al₂O₃ of 10–15 wt%. ARCs are texturally similar to ferromagnesian chondrules, composed primarily of olivine, pyroxene, plagioclase, spinel, Al‐rich glass, and metallic phases. Minerals in ARCs have intermediate compositions. Low‐Ca pyroxene (Fs_0.6–8.8Wo_0.7–9.3) has much higher Al₂O₃ and TiO₂ contents (up to 12.5 and 2.3 wt%, respectively) than that in ferromagnesian chondrules. High‐Ca pyroxene (Fs_0.3–2.0Wo_33–54) contains less Al₂O₃ and TiO₂ than that in Ca,Al‐rich inclusions (CAIs). Plagioclase (An_77–99Ab_1–23) is much more sodic than that in CAIs. Spinel is enriched in moderately volatile element Cr (up to 6.7 wt%) compared to that in CAIs. Al‐rich enstatite coexists with anorthite and spinel in a glass‐free chondrule, implying that the formation of Al‐enstatite was not due to kinetic reasons but is likely due to the high Al₂O₃/CaO ratio (7.4) of the bulk chondrule. Three ARCs contain relict CAIs. Oxygen isotope compositions of ARCs are also intermediate between those of ferromagnesian chondrules and CAIs. They vary from ?39.4‰ to 13.9‰ in δ¹⁸O and yield a best fit line (slope = 0.88) close to the carbonaceous chondrite anhydrous mineral (CCAM) line. Chondrules with 5–10 wt% bulk Al₂O₃ have a slightly more narrow range in δ¹⁸O (?32.5 to 5.9‰) along the CCAM line. Except for the ARCs with relict phases, however, most ARCs have oxygen isotope compositions (>?20‰ in δ¹⁸O) similar to those of typical ferromagnesian chondrules. ARCs are genetically related to both ferromagnesian chondrules and CAIs, but the relationship between ARCs and ferromagnesian chondrules is closer. Most ARCs were formed during flash heating and rapid cooling processes like normal chondrules, only from chemically evolved precursors. ARCs extremely enriched in Al and those with relict phases could have had a hybrid origin (Krot et al. 2002) which incorporated refractory inclusions as part of the precursors in addition to ferromagnesian materials. The occurrence of melilite in ARCs indicates that melilite‐rich CAIs might be present in the precursor materials of ARCs. The absence of melilite in most ARCs is possibly due to high‐temperature interactions between a chondrule melt and the solar nebula.     

Zircon U-Pb geochronology of Early Jurassic-Late cretaceous volcanic rocks in North Yellow Sea BasinEI北大核心CSCD

The X-drilling cores of the North Yellow Sea basin reveal two sets of Mesozoic clastic rocks, which are the dark rocks in lower part and the red rocks in upper part, respectively. There are two layers of volcanic rocks at the bottom and the upper part of the dark rock unit. The volcanic rocks at the bottom part are trachytic dacite while rocks at the upper part are clastic dacite. The zircon grains from the upper and lower units of volcanic rocks are euhedral-subhedral columnar crystals and show oscillatory zoning on cathodoluminescence images. 22 tests of zircons in the trachytic dacite from the bottom part yield an age of 141-151 Ma, with weighted mean 206Pb/238U age of 145±2 Ma. Whereas 18 tests of zircons from the sample at the upper part give 206Pb/238U ages around 139-149 Ma with weighted mean 206Pb/238U age of 141±2 Ma, which implies that the X well volcanic rocks belong to Late Jurassic-Early Cretaceous. Comparing with the age and geochemical characteristics of the Mesozoic igneous rocks in Shandong peninsula, we suggest that the igneous rocks from both the North Yellow Sea basin and Jiaolai basin were formed under same dynamic setting, i.e., the subduction related volcano arc and back-arc extension. ©, 2015, Science Press. All right reserved.     

A regime shift in sediment export from a coastal watershed during a record wet winter,California: Implications for landscape response to hydroclimatic extremes

Small, steep watersheds are prolific sediment sources from which sediment flux is highly sensitive to climatic changes. Storm intensity and frequency are widely expected to increase during the 21st century, and so assessing the response of small, steep watersheds to extreme rainfall is essential to understanding landscape response to climate change. During record winter rainfall in 2016–2017, the San Lorenzo River, coastal California, had nine flow peaks representing 2–10‐year flood magnitudes. By the third flood, fluvial suspended sediment showed a regime shift to greater and coarser sediment supply, coincident with numerous landslides in the watershed. Even with no singular catastrophic flood, these flows exported more than half as much sediment as had a 100‐year flood 35 years earlier, substantially enlarging the nearshore delta. Annual sediment load in 2017 was an order of magnitude greater than during an average‐rainfall year, and 500‐fold greater than in a recent drought. These anomalous sediment inputs are critical to the coastal littoral system, delivering enough sediment, sometimes over only a few days, to maintain beaches for several years. Future projections of megadroughts punctuated by major atmospheric‐river storm activity suggest that interannual sediment‐yield variations will become more extreme than today in the western USA, with potential consequences for coastal management, ecosystems, and water‐storage capacity. The occurrence of two years with major sediment export over the past 35 years that were not associated with extremes of the El Niño Southern Oscillation or Pacific Decadal Oscillation suggests caution in interpreting climatic signals from marine sedimentary deposits derived from small, steep, coastal watersheds, to avoid misinterpreting the frequencies of those cycles. Published 2018. This article is a U.S. Government work and is in the public domain in the USA.     

Recent Results from Studies of Electric Discharges in the Mesosphere

The paper reviews recent advances in studies of electric discharges in the stratosphere and mesosphere above thunderstorms, and their effects on the atmosphere. The primary focus is on the sprite discharge occurring in the mesosphere, which is the most commonly observed high altitude discharge by imaging cameras from the ground, but effects on the upper atmosphere by electromagnetic radiation from lightning are also considered. During the past few years, co-ordinated observations over Southern Europe have been made of a wide range of parameters related to sprites and their causative thunderstorms. Observations have been complemented by the modelling of processes ranging from the electric discharge to perturbations of trace gas concentrations in the upper atmosphere. Observations point to significant energy deposition by sprites in the neutral atmosphere as observed by infrasound waves detected at up to 1000 km distance, whereas elves and lightning have been shown significantly to affect ionization and heating of the lower ionosphere/mesosphere. Studies of the thunderstorm systems powering high altitude discharges show the important role of intracloud (IC) lightning in sprite generation as seen by the first simultaneous observations of IC activity, sprite activity and broadband, electromagnetic radiation in the VLF range. Simulations of sprite ignition suggest that, under certain conditions, energetic electrons in the runaway regime are generated in streamer discharges. Such electrons may be the source of X- and Gamma-rays observed in lightning, thunderstorms and the so-called Terrestrial Gamma-ray Flashes (TGFs) observed from space over thunderstorm regions. Model estimates of sprite perturbations to the global atmospheric electric circuit, trace gas concentrations and atmospheric dynamics suggest significant local perturbations, and possibly significant meso-scale effects, but negligible global effects.     

Volatile emissions and gas geochemistry of Hot Spring Basin,Yellowstone National Park,USA

We characterize and quantify volatile emissions at Hot Spring Basin (HSB), a large acid-sulfate region that lies just outside the northeastern edge of the 640 ka Yellowstone Caldera. Relative to other thermal areas in Yellowstone, HSB gases are rich in He and H₂, and mildly enriched in CH₄ and H₂S. Gas compositions are consistent with boiling directly off a deep geothermal liquid at depth as it migrates toward the surface. This fluid, and the gases evolved from it, carries geochemical signatures of magmatic volatiles and water–rock reactions with multiple crustal sources, including limestones or quartz-rich sediments with low K/U (or ^40?Ar/^4?He). Variations in gas chemistry across the region reflect reservoir heterogeneity and variable degrees of boiling. Gas-geothermometer temperatures approach 300 °C and suggest that the reservoir feeding HSB is one of the hottest at Yellowstone. Diffuse CO₂ flux in the western basin of HSB, as measured by accumulation-chamber methods, is similar in magnitude to other acid-sulfate areas of Yellowstone and is well correlated to shallow soil temperatures. The extrapolation of diffuse CO₂ fluxes across all the thermal/altered area suggests that 410 ± 140 t d^− 1 CO₂ are emitted at HSB (vent emissions not included). Diffuse fluxes of H₂S were measured in Yellowstone for the first time and likely exceed 2.4 t d^− 1 at HSB. Comparing estimates of the total estimated diffuse H₂S emission to the amount of sulfur as SO₄²⁻ in streams indicates ~ 50% of the original H₂S in the gas emission is lost into shallow groundwater, precipitated as native sulfur, or vented through fumaroles. We estimate the heat output of HSB as ~ 140–370 MW using CO₂ as a tracer for steam condensate, but not including the contribution from fumaroles and hydrothermal vents. Overall, the diffuse heat and volatile fluxes of HSB are as great as some active volcanoes, but they are a small fraction (1–3% for CO₂, 2–8% for heat) of that estimated for the entire Yellowstone system.