Measurements of Sulfur Isotope Composition on Ultrasmall(80 Nanomole) Sulfide and Sulfate Samples by a Modified EA-IRMS

The traditional method for sulfur isotope measurement using EA-IRMS commonly requires sulfur content greater than 2 μmol. Such a large sample size limits its application to low-S materials, the size mainly being due to ineffective utilization of sample gas, almost 99.7% of which is discarded with carrier gas through the split port of the continuous-flow interface. A modified EA-IRMS system with a gas chromatographic(GC) column and a custom-built cryogenic concentration device is used in this study. We measured six reference materials to test the performance of this method. The results were consistent with those obtained through traditional EA-IRMS. Precisions ranging from ±0.24‰ to ±0.76‰(1σ)can be obtained with samples equivalent to ~80 nmol sulfur, which were similar to results obtained from an alternative method using an absorption column. Our improved method is a powerful tool for sulfur isotope measurement in ultrasmall sulfide and sulfate samples, which can be further applied to carbon, nitrogen and oxygen isotope analyses of samples at about 100 nmol level.

Identification of the bound residue composition derived from ^(14)C-labeled chlorsulfuron in soil by using LC-MS and isotope tracing method

A new method for extracting the bound residue(BR) derived from 14 C-labeled chlorsulfuron in soils was developed, and the technique of combining LC-MS with isotope tracing method was subsequently applied to identify the composition of the 14 C-BR in a loamy Fluvent derived from marine deposit. The results showed that the 14 C-[2-amino-4-methoxyl-6-methyl-1,3,5]-triazine, 14 C-[2-amino-4-hydroxyl-6-methyl-1,3,5]-triazine and 14 C-chlorsulfuron parent compound constituted the main composition of the 14 C-BR derived from 14 C-labeled chlorsulfuron in the soil. The radioactive ratio of three compounds accounted for 39.8%, 35.4% and 17.9% of total recovered radioactivity, respectively. However, a small amount(3.6% of total recovered radioactivity) of the complex of 14 C-[2-amino-4-hydroxyl-6-methyl-1,3,5]-triazine might have existed in the 14 C-BR in association with an unknown soil substrate. 2-chlorobenzenesulfonamide was also detected to be one of the components of the BR. The results could well explain the mechanism of phytotoxicity caused by the BR derived from chlorsulfuron in soil. In addition, the mechanism of BR formation in soil was also discussed in details.

An online method to determine chlorine stable isotope composition by continuous flow isotope ratio mass spectrometry (CF-IRMS) coupled with a Gasbench Ⅱ

An online method using continuous flow isotope ratio mass spectrometry (CF-IRMS) interfaced with a Gasbench Ⅱ was presented to determine chlorine stable isotope composition. Silver chloride (AgCl) was quantitatively derived from chloride by using silver nitrate (AgNO3), and then was reacted with iodomethane (CH3I) to produce methyl chloride (CH3Cl). A GasBench Ⅱ equipped with a PoraPlot Q column was used to separate CH3Cl from any other gas species. Finally, chlorine stable isotope analysis was carried out on CH3Cl introduced to the IRMS in a helium stream via an active open split. The minimum amount of Cl used in this method is of the order of 1.4μmol. Inter-laboratory and inter-technique comparisons show that the total uncertainty incorporating both the precision and accuracy of this method is better than 0.007%. Furthermore, ten seawaters sampled from different locations have a narrow δ 37 Cl value range from -0.008% to 0.010%, with a mean value of (0.000±0.006)%. This supports the assumption that any seawater can be representative of standard mean ocean chloride (SMOC) and used as an international reference material.

Decomposition of fissile isotope antineutrino spectra using convolutional neural network

Recent reactor antineutrino experiments have observed that the neutrino spectrum changes with the reactor core evolution and that the individual fissile isotope antineutrino spectra can be decomposed from the evolving data,providing valuable information for the reactor model and data inconsistent problems.We propose a machine learning method by building a convolutional neural network based on a virtual experiment with a typical short-baseline reactor antineutrino experiment configuration:by utilizing the reactor evolution information,the major fissile isotope spectra are correctly extracted,and the uncertainties are evaluated using the Monte Carlo method.Validation tests show that the method is unbiased and introduces tiny extra uncertainties.

Geochronology,Geochemistry,Fluid Inclusion and C,O Isotope Compositions of Calcite Veins in the Paleogene of the Jiangling Basin,South China:Implications for Fluid Evolution and Brine Potash Mineralization

Deep-seated potassium-rich brines were identified in the Jiangling Basin,South China.Although magmatichydrothermal sources have been proposed,the relationship between brine-type potash mineralization and volcanism remains unclear.In this study,U-Pb geochronology,geochemistry,fluid inclusion and C-O isotopic compositions of hydrothermal vein minerals in the Jiangling Basin are examined.Laser ablation U-Pb dating of calcite veins indicates that the ages are slightly younger than the formation age of the Balingshan basalt.Fluid inclusions in hydrothermal minerals show medium–low homogenization temperatures(160–220℃)and low salinities(0.14 to 4.9 wt%NaCl eqv.)and densities(0.882–0.944 g/cm^(3)).The liquid compositions of fluid inclusions in calcite veins from sedimentary strata have higher contents of potassium,compared with those from basalt.The coupled negativeδ^(13)CPDB(-10.3‰to-8.0‰)and positiveδ^(18)OSMOW(17.4‰to 20.7‰)values imply that calcite precipitation resulted from CO_(2)degassing of the basaltic magmatic fluids,as indicated by the gas composition of these inclusions in hydrothermal minerals.Rare earth element patterns indicate that water-rock interaction between hydrothermal fluids and sedimentary wall rocks contributed to the calcite precipitation in sedimentary strata.It is proposed that high-temperature water-rock interaction between magmatic fluids and sedimentary strata resulted in the potassium enrichment in fluids,interpreted as one of the sources of potassium-rich brines in the Jiangling Basin.

Rare earth elements(REE)and isotope composition(δ^(13)C andδ^(18)O)of manganese ores of Chiatura deposit(Georgia):features of ore formation and genesis

The rare earth elements(REE)geochemistry and the isotope(δ^(13)C,δ^(18)O)composition of manganese ores of the Chiatura(Georgia)deposit were studied.One of the major features of all types of manganese ores is negative cerium(Ce/Ce*_(PAAS))anomaly and the absence of europium(Eu/Eu*_(PAAS))anomaly.Oxide oolitic manganese ores were formed in oxic shallow marine environments.The content and distribution of REEs(in particular Ce and Eu)in these ores are connected mainly with ferrous oxides.The performed C-and O-isotope research in Mn-carbonates(oolitic and massive)has indicated that carbonate ores were formed by the participation of isotopic ally light CO_(2)which is a result of the oxidation of organic matter in the sediment strata by reducing environments of early diagenesis(and,partially,catagenesis)zone.Obtained negative cerium anomalies in the studied carbonate ores reflect the specific REE patterns in pore waters of sediments of earlier isdiagenesis zone of the Oligocene Chiatura's basin.The deficiency of cerium in this zone remains debatable and requires further study.Formation of manganese carbonates took place multistage by the input of incisional solutions of different chemistry into sea bottom waters and sediments.The absence of europium anomaly indicates about lack of hydrothermal solution input.

Ore Genesis for Stratiform Ore Bodies of the Dongfengnanshan Copper Polymetallic Deposit in the Yanbian Area, NE China:Constraints from LA-ICP-MS in situ Trace Elements and Sulfide S–Pb Isotopes

The Dongfengnanshan Cu polymetallic deposit is one representative deposit of the Tianbaoshan ore district in the Yanbian area, northeast(NE) China. There occur two types of ore bodies in this deposit, the stratiform ore bodies and veintype ones, controlled by the Early Permian strata and the Late Hercynian diorite intrusion, respectively. Due to the ambiguous genetic type of the stratiform ore bodies, there has been controversy on the relationship between them and veintype ore bodies. To determine the genetic type of stratiform ore bodies, laser ablation inductively coupled plasma mass spectrometry(LA-ICP-MS) in situ trace elements and S–Pb isotope analysis have been carried on the sulfides in the stratiform ore bodies. Compared with that in skarn, Mississippi Valley-type(MVT), and epithermal deposits, sphalerite samples in the stratiform ore bodies of the Dongfengnanshan deposit are significantly enriched in Fe, Mn, and In, while depleted in Ga, Ge, and Cd, which is similar to the sphalerite in volcanic-associated massive sulfide(VMS) deposits. Co/Ni ratio of pyrrhotites in the stratiform ore bodies is similar to that in VMS-type deposits. The concentrations of Zn and Cd of chalcopyrites are similar to those of recrystallized VMS-type deposits. These characteristics also reflect the intermediate ore-forming temperature of the stratiform ore bodies in this deposit. Sulfur isotope compositions of sulfides are similar to those of VMS-type deposits, reflecting that sulfur originated from the Permian Miaoling Formation. Lead isotope compositions indicate mixed-source for lead. Moreover, the comparison of the Dongfengnanshan stratiform ore bodies with some VMStype deposits in China and abroad, on the trace elements and S–Pb isotope characteristics of the sulfides reveals that the stratiform ore bodies of the Dongfengnanshan deposit belong to the VMS-type, and have closely genetic relationship with the early Permian marine volcanic sedimentary rocks.

In-situ LA-ICP-MS trace element and oxygen isotope signatures of magnetite from the Yamansu deposit,NW China,and their significance

The Yamansu iron deposit is hosted in submarine volcanic rocks in the Aqishan–Yamansu belt of Eastern Tianshan,NW China.A geological cross-section for the Carboniferous strata in the ore district shows that ore bodies in the Yamansu deposit are hosted in andesitic crystal tuff of the third cycle of the Carboniferous Yamansu Formation.This indicates an association between mineralization and volcanism.The orebodies are strata bound and lensoid and generally share the occurrence state of the host rocks.Magnetite mineralization mainly occurs asbreccia ores,ores in the mineralized volcanic rocks,massive ores,and sulfide-rich ores according to their structures and sequences of formation.Trace element compositions of magnetite from various types of ores were determined by LA-ICP-MS.The dataset indicates thatdifferent types of magnetite havedistinct trace element contents correlated to their formation environments.Magnetite crystals from breccia ores have high Ti,Ni,V,Cr,and Co and low Si,Al,Ca,and Mg contents,indicating crystallization from a volcanic magmatic eruption,which is consistent with field evidence of coexisting altered volcanic breccia.Magnetite crystals from ores in the mineralized volcanic rocks have moderate Ti,Ni,V,Cr,and Co contents.In contrast,magnetite from massive ores and sulfide-rich ores have low concentrations of Ti,Cr,Ni,and V,high concentrations of Si,Al,Ca,and Mg,and evidence of hydrothermal magnetite.In-situ magnetite compositions imply a magmatic-hydrothermal process.Although d18 O values for magnetite grains from Yamansu vary(?1.3 to?7.0%),they all plot in the range field of volcanic iron deposits,and they also record a magmatic-hydrothermal process.The compositions of Yamansu magnetites are interpreted as controlled mainly by temperature,fluid,host rock buffering,oxygen fugacity,and sulfur fugacity.The metallogenic conditions of the Yamansu deposit changed from high temperature and low oxygen fugacity to low temperature and high oxygen fugacity.However,more fluid-rock reactions and higher sulfur fugacity were involved during the deposition of massive ores and sulfiderich ores.

Fluid Inclusions and Isotope Geochemistry of the Emba Derho and the Debarwa VMS Deposits, Asmara District, Eritrea

Objective Recent exploration indicates several localities with significant gold, copper, and zinc resource potential in the Asmara district, Eritrea, including the Emba Derho and Debarwa volcanic-associated massive sulfide deposits. These deposits are hosted by the Neoproterozoic metamorphic volcanic rocks of Asmara green stone belt, which strike NNW-SSE and are 200 km long and 5-20 km wide, and the mineralization is often associated with the altered and deformed rocks. The Emba Derho deposit, located 12 km northwest of Asmara （Fig. la）, the capital of Eritrea, is the largest Cu-Zn-Au VMS deposit in the Asmara metallogeny belt. It is estimated that the Emba Derho deposit of the Asmara project contains total reserves of 49.8~106 tons of copper ores and 16.8~106 tons of zinc ores. The gold grade of this deposit is about 0.3 lg/t. The Debarwa deposit, situated 26 km southwest of Asmara, has similar ore features with the Emba Derho deposit.

Crustal Composition of China Continent Constrained from Heat Flow Data and Helium Isotope Ratio of Underground Fluid

Based on conservation of energy principle and heat flow data in China continent, the upper limit of 1.3 μW/m3 heat production is obtained for continental crust in China. Furthermore, using the data of heat flow and helium isotope ratio of underground fluid, the heat productions of different tectonic units in China continent are estimated in range of 0.58-1.12 μW/m3 with a median of 0.85 μW/m3. Accordingly, the contents of U, Th and K20 in China crust are in ranges of 0.83-1.76 μg/g, 3.16-6.69 μg/g, and 1.0%-2.12%, respectively. These results indicate that the abundance of radioactive elements in the crust of China continent is much higher than that of Archean crust; and this fact implies China＇s continental crust is much evolved in chemical composition. Meanwhile, significant lateral variation of crustal composition is also exhibited among different tectonic units in China continent. The crust of eastern China is much enriched in incompatible elements such as U, Th and K than that of western China; and the crust of orogenic belts is more enriched than that of platform regions. It can also be inferred that the crusts of eastern China and orogenic belts are much felsic than those of western China and platform regions, respectively, derived from the positive correlation between the heat production and SiO2 content of bulk crust. This deduction is consistent with the results derived from the crustal seismic velocity data in China. According to the facts of the lower seismic velocity of China than the average value of global crust, and the higher heat production of China continent compared with global crust composition models published by previous studies, it is deduced that the average composition models of global continent crust by Rudnick and Fountain （1995）, Rudnick and Gao （2003）, Weaver and Tarney （1984）, Shaw et al. （1986）, and Wedepohl （1995） overestimate the abundance of incompatible elements such as U, Th and K of continental crust.

Evolution of Carbon Isotope Composition in Potential Global Stratotype Section and Point at Luoyixi, South China, for the Base of the Unnamed Global Seventh Stage of Cambrian System

This work deals with the evolution of carbon isotope composition in the Luoyixi （罗依溪） Section, a candidate of the Global Standard Stratotype-section and Point （GSSP）, defining the base of the as-yet-undefined seventh stage of Cambrian System at the first appearance of the cosmopolitan agnostoid Lejopyge iaevigata. This level is favored in a vote of International Subcommission on Cambrian Stratigraphy （ISCS） as the biohorizon for defining the base of a global stage. Two hundred and sixty-four samples for carbon and oxygen isotope analysis have been collected from the carbonate successions at an interval of 0.25 to 0.5 m in this section. Results of the carbon isotope data exhibit a remarkable disciplinarian trend. The pattern of the carbon isotope evolution is gently undulant with a relatively long period during the underlying Drumian Stage, and then the values of δ13C fluctuate sharply with a short period in provisional seventh stage. The onset of sharp fluctuation in the δ13C values begins at the proposed GSSP level, defining the base of the global seventh stage, where δ13C values change from a gentle trend to a sharp trend. Distinct covariant-relationships among δ13C,δ18O, and sea level fluctuations suggest that a warming change in paleoclimate took place during the early global seventh stage, which led to a positive shift in δ13C values.

Zircon LA-ICP MS U-Pb Age,Sr-Nd-Pb Isotopic Compositions and Geochemistry of the Triassic Post-collisional Wulong Adakitic Granodiorite in the South Qinling,Central China,and Its Petrogenesis

The Indosinian post-collisional Wulong pluton intruded into the Mesoproterozoic Fuping Group, South Qinling, central China. In the southern part of the pluton, some mafic enclaves have sharp or gradational contact relationships with the host biotite granodiorite. Geochemistry, zircon LA-ICP MS （laser ablation inductively-coupled plasma mass spectrometry） U-Pb chronology and Sr- Nd-Pb isotope geochemistry of the pluton are reported in this paper. The biotite granodiorite shows close compositional similarities to high-silica adakite. Its chondrite-normalized REE patterns are characterized by strong HREE depletion （Yb = 0.33--0.96 10-6 and Y = 4.77-11.19 ×10^-6）, enrichment of Ba （775-1386 x 10-6） and Sr （643-1115 × 10^-6） and high Sr/Y （57.83-159.99） and Y/Yb （10.99-14.32） ratios, as well as insignificant Eu anomalies （6Eu = 0.70-0.83）, suggesting a feldspar-poor, garnet±amphibole-rich residual mineral assemblage. The mafic enclaves have higher MgO （4.15- 8.13%）, Cr （14.79-371.31 × 10-6）, Ni （20.00-224.24× 10^-6） and Nb/Ta （15.42-21.91） than the host granodiorite, implying that they are mantle-derived and might represent underplated mafic magma. Zircon LA-ICP MS dating of the granodiorite yields a ^206pb/^238U weighted mean age of 208±2 Ma （MSWD=0.50, 1σ）, which is the age of emplacement of the host biotite granodiorite. This age indicates that the Wulong pluton formed during the late-orogenic or post-collisional stage （〈242±21 Ma） of the South Qinling belt. The host biotite granodiorite displays ^87Sr/^86Sr = 0.7059-0.7062, Isr = 0.7044-- 0.7050,^143Nd/^144Nd = 0.51236-0.51238, εNd（t）= -2.26 to -2.66 to ^206Pb/^204pb = 18.099-18.209, ^207pb/^204pb = 15.873-15.979 and ^208pb/^204pb = 38.973-39.430. Those ratios are similar to those of the Mesoproterozoic Yaolinghe Group in the South Qinling. Furthermore, its Nd isotopic model age （-1.02 Ga） is consistent with the age （-1.1 Ga） of the Yaolinghe Group. Based on the integrated geological and geochemical studies, coupled with previous studies, the authors suggest that the Wulong adakitic biotite granodiorite was probably generated by dehydration melting of the Yaolinghe Group-like thickened mafic crust, triggered by underplating of mafic magma at the boundary of the thickened mafic crust and hot lithospheric mantle, and that the Wulong adakitic biotite granodiorite may have resulted from thinning and delamination of the lower crust or breakoff of the subducting slab of the Mianlue ocean during the Indosinian post-collisional orogenic stage of the Qinling orogenic belt.

Spatial structure and species composition of soil seed banks in moving sand dune systems of northeast China

Soil seed banks can provide a mechanistic for understanding the recruitment dynamics and can inform conservation management of ecosystems. To investigate the contribution of soil seed banks to vegetation restoration in moving sand dune systems, we compared seed structure and species similarity between soil seed banks and standing vegetation among moving sand dunes, ecotones and dune slacks in northeast China. Average seed density in dune slacks was greater than in ecotones or moving sand dunes. Seed density in the soil layer of 0-10 cm was greater than at 10-20 cm both in the moving sand dunes and the eco- tones, but seed densities were similar at depths of 10-20 and 20-30 cm in moving sand dunes. Moreover, the spatial autocorrelation of seed density on moving sand dunes was weak but was strong on the ecotones and dune slacks. The species in the soil seed bank of moving sand dune systems were nearly all annuals, and the low similarity was mainly due to the lack of perennial species that were common in standing vegetation. Consequently, vegetation restoration cannot mainly rely on the soil seed banks in the movingsand dunes and more attention should be paid to protection of the dune slacks because they are the main source of seed disperse and seedling recruitment in moving sand dune systems.

Coupled trace element and SIMS sulfur isotope geochemistry of sedimentary pyrite:Implications on pyrite growth of Caixiashan Pb-Zn deposit

Colloform pyrite with core-rim texture is commonly deposited in carbonate platforms associated with the sulfide ores such as the Caixiashan Pb-Zn deposit.However,the genesis of colloform pyrite in Pb-Zn deposits,its growth controls and their geological implication are insufficiently understood.Integration of in-situ trace element and SIMS sulfur isotopes has revealed geochemical variations among these pyrite layers.These colloform pyrite occur as residual phases of core-rim aggregates,the cores are made up of very fine-grained anhedral pyrite particles,with some rims being made up of fine-grained and poorlycrystallized pyrite,while the other rims were featured with euhedral cubic pyrite.which are cemented by fine-grained calcite and/or dolomite with minor quartz.Sulfur isotope analysis shows that some wellpreserved rims have negative δ^34 S values(-28.12‰to-0.49‰),whereas most of the cores and rims have positive δ^34 S values(>0 to+44.28‰;peak at+14.91‰).Integrating with the methane and sulfate were observed in previous fluid inclusion study,we suggest that the 34 S depleted rims were initially formed by bacteria sulfate reduction(BSR),whereas the positive δ^34 S values were resulted from the sulfate reduction driven by anaerobic methane oxidation(AOM).The well-developed authigenic pyrite and calcite may also support the reaction of AOM.Combined with petrographic observations,trace element composition of the colloform pyrite reveals the incorporation and precipitation behavior of those high abundance elements in the pyrite:Pb and Zn were present as mineral inclusion and likely precipitated before Fe,as supported by the time-resolved Pb-Zn signal spikes in most of the analyzed pyrite grains.Other metals,such as Hg,Co and Ni,may have migrated as chloride complexes and entered the pyrite lattice.Arsenic and Sb,generally influenced by complex-forming reactions rather than substitution ones,could also enter the pyrite lattice,or slightly predate the precipitation of colloform pyrite as mineral inclusions,which are controlled by their hydrolysis constant in the ore fluids.The colloform pyrite may have grown inward from the rims.The successive BSR reaction process would enrich H^32/2S in the overlying water column but reduce the metal content,the nucleation of these pyrite rims was featured by strongly negative sulfur isotopes.The following AOM process should be activated by deformation like the turbidity sediment of the mudstone as the sulfide deposition are associated with fault activities that caused the emission of methane migration upward and simultaneously replenishing the metal in the column.The higher AOM reaction rate and the higher metal supply(not only Fe.but with minor other metals such as Pb and Zn) caused by sediment movement enhanced the metal concentration within the pyrite lattice.

Geology and Lead-Sulphur Isotope Compositions of the Tongyu Volcanic-Hosted Massive Sulphide Copper Deposit in the Western Part of the North Qinling Orogen, China

The Tongyu copper deposit, located in the western part of the North Qinling Orogen, China, is one of several volcanic-hosted massive sulphide（VHMS） deposits with industrial value and is also a typical example of mineralization related to the subduction and metallogenesis during the Caledonian orogeny. We conducted systematic lead-sulphur isotope geochemical analyses of the Tongyu deposit to understand the possible ore-forming material sources and tectonic settings. Twenty-six sulphide samples yielded clustered δ^34SCDT values of 1.13‰-3.36‰, average 2.22‰, and show a tower-type distribution,implying that the sulphur of the Tongyu copper deposit mainly originated from a mantle source. The Pb isotope compositions of sulphides（^206Pb/^204Pb = 17.59225-18.56354, average 18.32020; ^207Pb/^204Pb =15.51770-15.69381, average 15.66217; ^208Pb/^204Pb= 37.99969-39.06953, average 38.52722） are close to the values of the volcanic host rocks（^206Pb/^204PbPb= 18.10678-18.26293, average 18.21158; ^207Pb/^204PbPb =15.63196-15.68188, average 15.65345; ^208Pb/^204PbPb= 38.43676-38.56360, average 38.49171）, thus consistent with the Pb in ores and volcanic host rocks having been derived from a common source that was island-arc Pb related to oceanic crust subduction. The northward subduction of the Palaeo-Qinling oceanic crust triggered dehydration of the slab, which generated a large amount of high-oxygen-fugacity aqueous hydrothermal fluid. The fluid rose into the mantle wedge, activated and extracted metallogenic material and promoted partial melting of the mantle wedge. The magma and ore-forming fluid welled up and precipitated, finally forming the Tongyu VHMS copper deposit.

Multi-collector ICP-MS Analysis of Pb Isotope Ratios in Rocks: Data, Procedure and Caution

The authors measured Pb isotope compositions of seven USGS rock referencestandards, i.e. AGV-1, AGV-2, BHVO-1, BHVO-2, BCR-2, BIR-1/1 and W-2, together with NBS 981 using amicromass isoprobe multi-collector inductively-coupled plasma mass spectrometer (MC-ICP-MS) at theUniversity of Queensland. ^(203)Tl-^(205)Tl isotopes were used as an internal standard to correctfor mass-dependant isotopic fractionation. The results for both NBS 981 and USGS rock standardsAGV-1 and BHVO-1 are comparable to or better than double- and triple-spike TIMS (thermal ionizationmass spectrometry) data in precision. The data for BHVO-2 and, to a lesser extent, AGV-2 and BCR-2are reproducibly higher for ^(206)Pb/^(204)Pb, ^(207)Pb/^(204)Pb and ^(208)Pb/^(204)Pb thandouble-spike TIMS data in the literature. The authors also obtained the Pb isotope data for BIR- 1/1and W-2, which may be used as reference values in future studies. It is found that linearcorrection for Pb isotopic fractionation is adequate with the results identical to those correctedfollowing an exponential law or a power law. Precise ^(207)Pb/^(206)Pb, ^(208)Pb/^(206)Pb and^(208)Pb/^(207)Pb ratios can be acquired for sample solutions with Pb>=1 ppb. However, Pb isotoperatios involving ^(204)Pb (i.e., ^(206)Pb/^(204)Pb, ^(207)Pb/^(204)Pb and ^(208)Pb/^(204)Pb) arereliable for solutions with Pb>=40 ppb. The errors for Pb isotope ratio analysis using the MC-ICP-MSare dominated by errors in the analysis of ^(204)Pb, which is commonly ascribed to the difficultyand imprecise correction for a ^(204)Hg isobaric interference. It is found however that the majorerrors on ^(204)Pb come from the tailings of mass ^(203)Tl and mass ^(205)Tl These mass tailingslead to over-subtraction of the baseline for ^(204)Pb, which is measured at +-0.5 amu on both sidesof mass-204 (i.e., at amu 203.5 and 204.5 respectively). Such errors are insignificant for Pb-richsample solutions (i.e., high Pb/Tl ratios), but can be severe for low-Pb sample solutions whenover-'spiked' with Tl. Experiments in this study suggest that a minimum concentration ratio ofPb/Tl>5 in Tl-'spiked' solutions be required to ensure reliable ^(206)Pb/^(204)Pb, ^(207)Pb/^(204)Pband ^(208)Pb/^(204)Pb isotopic ratios. The tailings of ^(203)Tl and ^(205)Tl can also lead toover-subtraction of baselines for ^(202)Hg (at amu 202.5) and ^(206)Pb (at amu 205.5). Therefore,the elegance of using ^(203)Tl and ^(205)Tl isotopes for mass fractionation correction becomes asevere problem in low-Pb rock solution-caution is required. Alternative internal standards for massfractionation correction may be considered. Of course, significant instrumental refinement inabundance sensitivity is in demand.

Determination of Fe,Ni,Cu,Zn,Cd and Pb in seawater by isotope dilution automatic solid-phase extraction—ICP-MS

A thorough understanding of the biogeochemical cycling of trace metals in the ocean is crucial because of the important role these elements play in regulating metabolism in marine biotas and thus,the climate.However,a precise and accurate analysis of trace metals in seawater is difficult because they are present at extremely low concentrations in a high salt matrix.In this study,we report an analytical method for the preconcentration and separation of six trace metals,Fe,Ni,Cu,Zn,Cd and Pb,in seawater using a sea FAST automatic solid-phase extraction device,analysis by a triple quadrupole collision/reaction technique with inductively coupled plasma mass spectrometry(ICP-MS),and quantification by the isotope dilution technique.A small volume(10 m L)of seawater sample was mixed with a multi-element isotope spike and subjected to sea FAST procedures.The preconcentrate solution was then analyzed using the optimized collision/reaction cell mode of ICP-MS,with NH_(3)gas for Fe and Cd with a flow rate of 0.22 m L/min and He for Ni,Cu,Zn and Pb with a flow rate of 4.0 m L/min.The procedure blanks were 130 pmol/L,3.0 pmol/L,6.8 pmol/L,37 pmol/L,0.29 pmol/L and 0.42 pmol/L,for Fe,Ni,Cu,Zn,Cd and Pb,respectively.The method was validated using five reference materials(SLRs-6,SLEW-3,CASS-6,NASS-7 and GEOTRACE-GSC),and our results were consistent with the consensus values.The method was further validated by measuring full-water-column seawater samples from the subtropical Northwest Pacific Ocean,and our results demonstrated good oceanic consistency.

Study on Material Composition and REE－host Forms of Ion－type RE Deposits in South China

in the ion-type RE deposite in South China, the host rocks of REE minerals are igneous and metamorphic rocks , such as granite, granite-porphyry, granitite, muscovite granite, granodiorite, rhyolite, tuff, lamprophyre, alkaline rocks, granite-gneiss, stuff, gneissic granite.These various types of rocks occurred in the environment of humid subtropical zone with a specific topographic relief. During a long-term geological process, they were weathered and alterated into montmorillonite, gibbstite, vermiculite and the dioctahedral type of clay minerals, such as kaolinite, halloysite-0. 7 nm , halloysite-1. 0 nm and ferrohalloysite. All of these clay minerals are the REE carriers. The REE in the ion-type RE deposits came from there source: 1) the REE -bearing rock-forming minerals in host rock, such as microcline and amphibole:2) the accessory minerals in host rocks, such as allanite, gadolinite-(Y), sphene , parisite-(Y), and fergusonite-(Y). For a long geological time the weathering and leaching processes caused the minerals to be disintegrated and to free REE ions. The REE cations can be adsorbed on various clay minerals associated. The categories of ion -type RE deposite depend on the species of RE minerals and the lithological characters of the host geological body in the ore deposit area.

ESSENTIAL NORMS OF PRODUCTS OF WEIGHTED COMPOSITION OPERATORS AND DIFFERENTIATION OPERATORS BETWEEN BANACH SPACES OF ANALYTIC FUNCTIONS

We obtain several estimates of the essential norms of the products of differen- tiation operators and weighted composition operators between weighted Banach spaces of analytic functions with general weights. As applications, we also give estimates of the es- sential norms of weighted composition operators between weighted Banach space of analytic functions and Bloch-type spaces.

Translocation and distribution of mercury in biomasses from subtropical forest ecosystems:evidence from stable mercury isotopes

To understand its source,distribution,storage,and translocation in the subtropical forest ecosystems,mercury(Hg)concentrations and stable isotopes in forest biomass tissues(foliage,branch,bark,and trunk)were investigated at Ailao Mountain National Nature Reserve,Southwest China.The total Hg(THg)concentrations in the samples show the following trend:mature foliage(57±19 ng g-1)>bark(11±4.0 ng g-1)>branch(5.4±2.5 ng g-1)>trunk(1.6±0.7 ng g-1).Using the measured THg concentrations and the quantity of respective biomasses,the Hg pools in the forest are:wood(60±26μg m-2)>bark(51±18μg m-2)>foliage(41±11μg m-2)>branch(26±8.3μg m-2).The tree biomasses displayed negativeδ202Hg(-1.83‰to-3.84‰)andΔ199Hg(-0.18‰to-0.62‰).The observedΔ200Hg(-0.08‰to 0.04‰)is not significantly from zero.AΔ199Hg/Δ201Hg ratio of 1.05 was found in tree biomasses,suggesting that mercury has undergone Hg(Ⅱ)photoreduction processes.A Hg-isotope based binary mixing model suggests that Hg in the tree biomasses mainly originated from foliage uptake of atmospheric Hg0,constituting 67%,80%,and 77%of Hg in wood,branch,and bark,respectively.Our study sheds new light on the transportation and sources of Hg in the subtropical forest ecosystems.