Characteristics of strontium isotopes and their implications in the Qixing Cave of Guizhou,China

The strontium isotopic compositions (87Sr/86Sr) of samples including soils, bedrock, soil waters, drip waters and their corresponding speleothems in the Qixing Cave (QXC), Guizhou Province, China, were systemically measured and analyzed. The results indicate that there are significant Sr isotopic differences among samples. The mean 87Sr/86Sr ratios in drip water for the samples 1#, 4# and 9# were 0.709568, 0.709139 and 0.708761, respectively, which possibly result from different flow paths, residence times, and other hydrogeological processes in the unsaturated zone overlying QXC. Meanwhile, levels of 40.8%, 57.6% and 72.4% of Sr in drip waters for 1#, 4# and 9#, respectively, were derived from bedrock dissolution, which was calculated by the mixture model of the two end-members (soil and bedrock). There is, however, no positive correlation between the relative proportion from bedrock dissolution (δ13C value is 1.8‰) and drip water δ13CDIC values. The mean drip water δ13CDIC value in 1# is the heaviest (–4.5‰) with the lowest contribution rate of bedrock dissolution, whereas the value in 9# is the lightest (–9.3‰) with the highest contribution rate of bedrock dissolution. The proportion from host rock dissolution in 4# is higher than that in 1# and lower than that in 9#, while its mean drip water δ13CDIC value (–8.6‰) is higher than that of 9# and lower than that for 1#. This suggests that the prior calcite precipitation (PCP) processes in the unsaturated zone overlying the cave are responsible for the δ13CDIC value differences between different drip waters, and not bedrock dissolution. Furthermore, this study also demonstrates that the 87Sr/86Sr ratios of speleothems in the 1# and 4# mainly reflect the variation in the relative proportions from the soil system (soil water) and bedrock dissolution overlying the cave. It is, therefore, feasible to use the strontium isotopic signals of speleothems as an indicator for soil chemical weathering intensity, and consequently as a monsoon proxy in the study area.     

Biomineralization process occurring in iron mud of coastal seepage area of Zhoushan Island, Zhejiang province

The biomineralization process of iron oxidizing bacteria and its influence on accumulation of metals were investigated by modern biological observation techniques （i.e., SEM and TEM） and geochemical methods, in coastal area of Zhoushan Island, Zhejiang province where a thick ancient wood layers were buried, Results show that the iron mud samples mainly contain Leptothrix-like sheaths and Gallionella-like stalks, which are known as neutrophilic iron-oxidizing bacteria. These two bacteria are present as obviously different abundance in two sampling sites, which may be regulated by the geochemistry of seepage water. The biomineralization product of iron oxidizing bacteria is ferrihydrite, a poorly ordered iron oxide, and formation of amorphous mineral is affected by the factors of bacteria, minor Si and temperature preventing any further transformation into more crystalline phases. Organic functional groups, extracellular polymers and surface charges can provide favorable nucleation sites or template for formation of iron precipitates on the bacterial surface. The mineralization process of the iron oxidizing bacteria is divided into different stages, i.e., extracellular mineralization, intracellular mineralization and the whole cell mineralization. Furthermore, due to BIOS containing the bacterial organic matter, the accumulation capacity of metals specially Fe and Co is highly increased, suggesting that BIOS exert a degree of controlling in the cycling of metal elements in seepage area.     

Variable diffusion boundary layer and diffusion flux at sediment-water interface in response to dynamic forcing over an intertidal mudflat

The diffusion boundary layer (DBL) significantly limits the exchange between sediment and overlying water and therefore becomes a bottleneck of diffusive vertical flux at the sediment-water interface (SWI). Variable DBL thickness and diffusion flux in response to dynamic forcing may influence replenishment of nutrients and secondary pollution in coastal waters. In situ measurements of velocity in the bottom boundary layer (BBL) and oxygen concentration in the DBL were made over an intertidal mudflat, using an acoustic Doppler current and mini profiler. A linear distributed zone in the oxygen profile, the profile slope discontinuity and variance of concentration can be used to derive accurate DBL thickness. Diffusion fluxes calculated from the water column and sediment are identical, and their bias is less than 6%. A numerical model PROFILE is used to simulate the in situ dissolved oxygen profile, and layered dissolved oxygen consumption rates in the sediment are calculated. The DBL thickness (0.10-0.35 mm) and diffusion flux (15.4-53.6 mmol m 2 d 1) vary with a factor of 3.5 during a tidal period. Over an intertidal mudflat, DBL thickness is controlled by flow speed U in the BBL, according to δDBL=1686.1DU 1+0.1 (D is the molecular diffusion coefficient). That is, the DBL thickness δDBL increases with decreasing flow speed U. Changes of diffusion flux at the SWI are caused by variations in the water above the sediment and the turbulent mixing intensity. The diffusion flux is positively related to the turbulent dissipation rate, friction velocity and turbulent energy. Under the influence of dynamics in the BBL, DBL thickness and flux vary significantly.     

Synthesis and structure of Cu5(BTA)6(TTA)4 · 5DMF, a copper-nitrogen cluster containing η Π3-benzotriazolate

The title cluster compound—Cu₅(BTA)₆(TTA)₄·5DMF was prepared using thenyltrifluoroacetone and benzotriazolate ligands. The crystal structure indicates that a tetrahedral array of Cu(1), Cu(2), Cu(3) and Cu(4) ions surrounding a central Cu(5) ion are held together by bridging tridentate BTA^- and terminated by TTA^- bond cap. The three nitrogen atoms of a BTA^- bond three different copper ions to form a η³-benzotriazolate. The central Cu ion has a distorted octahedral structure and the surrounding Cu ions are 5 coordinated forming distorted tetragonal structures. The distances between the surrounding Cu(Ⅱ) ions and the central Cu(Ⅱ) ion are in the range of 0.3561—0.3755 nm and those between the surrounding Cu(Ⅱ) ions are in the range of 0.5785—0.6301 nm.     

Chemiluminescence determination of tetracycline and oxytetracycline in pharmaceutical preparations using Ru (bipy)3 2+-cerium (IV) system

A new chemiluminescence (CL) method for the determination of tetracycline and oxytetracycline is developed, based on the CL reaction of tetracycline and oxytetracycline with Ru (bipy)₃ ²⁺ and Ce (IV). In sulfuric acid medium, the CL emission is generated upon continuous oxidtion of Ru(bipy)₃ ²⁺ by cerium (IV). The emission intensity is greatly enhanced when tetracycline and oxytetracycline are introduced into the reaction system after acid degradation. Under the optimum conditions, the calibration curves are linear over the range of 8.0×10⁻⁸∼4.0×10⁻⁶ mol/L for tetracycline and of 2.0×10⁻⁷∼4.0×10⁻⁵ mol/L for oxytetracycline, with the detection limits are 4.2×10⁻⁸ mol/L for tetracycline and 1.5×10⁻⁷ mol/L for oxytetracycline, respectively. The proposed method was used for the determination of tetracycline and oxytetracycline in pharmaceutical formulations with good results. Foundation item: Supported by the National Natural Science Foundation of China and the Natural Science Foundation of Hubei Province. Biography: HAH He-you (1962), male, Associate profeddor, Ph.D graduate candidate. Present address, Department of Chemistry, Huainan Teacher's College, Huainan.     

Lipids of sulfate-reducing bacteria and sulfur-oxidizing bacteria found in the Dongsheng uranium deposit

U-bearing sandstones from the Dongsheng deposit in Ordos Basin contain abundant C15-C18 fatty acids. The fatty acids may have been derived from modern and ancient organisms including organisms from the intervals of U mineralization. A certain amount of i15:0, a15:0, a17:0 fatty acids coexist with small amounts of i17:1ω7c and 10me16:0, characteristic biomarkers of Desulfovibrio and Desulfobacter sp., respectively. This indicates the existence of sulfate-reducing bacteria (SRB) in the sandstones. The presence of sulfur-oxidizing bacteria (SOB), such as Beggiatoa and Thioploca, is indicated by significant amounts of 16:1ω7c and 18:1ω7c fatty acids. The existence of the SRB in the deposit, as inferred from the fatty acids, is consistent with results from fossilized microorganisms and isotopic compositions of ore-stage pyrite. This suggests that the environment may have been favorable for the SRB to grow since ore formation (9.8-22 Ma). The bacteria may have degraded hydrocarbons directly, or indirectly utilized hydrocarbons degraded by oxic microbes in the deposits. This process may have produced 12C-rich calcite and prominent baseline humps of unresolved complex mixtures (UCM), and 25-demethylated hopanes and tricyclic terpanes. The existence of sulfur-oxidizing bacteria and sulfate-reducing bacteria in the deposit may have resulted in bacterial sulfate reduction to sulfide, re-oxidization of the sulfide to sulfate and subsequent reduction of the sulfate to sulfide. This assertion is supported by ore-stage pyrite with δ34S values as low as-39.2‰, and the lightest sulfate (about 11‰) measured during the Phanerozoic, a difference of more than 46‰.     

Investigation of Ru （ phen ）3^2＋-Hydrazine-Ce（Ⅳ） Chemiluminescence System and Its Analytical Application

0 IntroductionThbiep ycroidmipnlee)xru ctahteinoinu mof(Ⅱ r)u t(he Rniuu(mbip,y m)3ai2n +ly) atrnids- t(r2is -,(21’ -,10-phenanthroline)ruthenium(Ⅱ) (Ru(phen)32 +) ,is a kindof sensitive analytical reagent for electrogenerated chemilumi-nescence(ECL) and chemiluminescence(CL) ,on which a par-ticular review has been presented[1]. The earliest publicationon the synthesis of Ru(bipy)32 +appeared in 1936[2], andduringthefollowing30 years ,theinvestigations relatedtothissubstance were only in…     

鲜枣中糖精的快速、无标签检测

糖精是食品工业中最古老的人造甜味剂之一,因为没有卡路里而被广泛使用,但其滥用是非法的,食品中最大允许添加量为8.189×10^-4mol·L^-1.介绍了以六磷酸肌醇（IP₆）为保护剂合成的银（Ag）纳米粒子（Ag NPs）,即Ag NPs@IP₆,并提出了一种基于表面增强拉曼散射（SERS）的快速方法.探讨了食品中糖精的测定,用最佳SERS法测定水中糖精的最低可检测浓度可达50 nmol·L^-1,符合食品添加剂耐受性水平的国家食品安全标准.提出了基于便携式拉曼的AgNPs@IP₆的SERS方法,可用于现场检测食品中的糖精,如新鲜枣果.     

Application of Constructed Wetlands on Wastewater Treatment for Aquaculture Ponds

A group of constructed wetlands （CWs） were applied to the recirculating aquaculture system. This study assessed the performance of CWs in treating the aquaculture wastewater, examined the water quality condition of aquaculture ponds and the growth and the survival rate of ＂target＂ species （Ictalurus punctatus and Megalobrama amblycephala）. The results showed that CWs were effective on reducing the concentrations of 5-day biochemical oxygen demand （BOD5, at 70.5%）, total suspended solids （TSS, at 81.9%）, chlorophyll a （Chl-a, at 91.9%）, ammonium （NH4^＋, at 61.5%） and nitrate nitrogen （NOa-N, at 68.0%）. Effect of CWs on phosphate （PO43 -P） removal was relatively lower （at 20.0%）. The concentrations of BODs, TSS, Chl-a, NH4^＋ and TN, TP in the recirculating culture pond were significantly lower than that in the control pond（ p〈0.05 ）. CWs could help to increase total yield, survival rate of the ＂target＂ species and significantly decrease feed conversion ratio （ p〈0.05 ）.     

Effect of CO<Subscript>2</Subscript> concentrations on the activity of photosynthetic CO<Subscript>2</Subscript> fixation and extracelluar carbonic anhydrase in the marine diatom <Emphasis Type="Italic">Skeletonema costatum</Emphasis>

The growth and activity of photosynthetic CO2 uptake and extracellular carbonic anhydrase (CAext) of the marine diatom Skeletonema costatum were investigated while cultured at different levels of CO2 in order to see its physio-logical response to different CO2 concentrations under either a low (30 靘ol·m-2·s-1) or high (210 靘ol·m-2·s-1) irradiance. The changes in CO2 concentrations (4—31 靘ol/L) affected the growth and net photosynthesis to a greater extent under the low than under the high light re-gime. CAext was detected in the cells grown at 4 mol/L CO2 but not at 31 and 12 靘ol/L CO2, with its activity being about 2.5-fold higher at the high than at the low irradiance. Photo- synthetic CO2 affinity (1/ K1/2(CO2)) of the cells de-creased with increased CO2 concentrations in culture. The cells cultured under the high-light show significantly higher photosynthetic CO2 affinity than those grown at the low-light level. It is concluded that the regulations of CAext activity and photosynthetic CO2 affinity are dependent not only on CO2 concentration but also on light availability, and that the de-velopment of higher CAext activity and CO2 affinity under higher light level could sufficiently support the photosyn-thetic demand for CO2 even at low level of CO2.     

Third-order optical nonlinearities for lanthanum (III) complexes with 1, 10-phenanthroline components

The nonlinear refractive indexesn ₂ for the ethanol solutions of 1, 10-phenanthroline (2.0 × 10⁻³ mol · L⁻¹), [bis(l, 10-phenanthroline) lanthanum (III)] nitrate (1.0 × 10⁻³ mol · L⁻¹), and [nitrato-fluoracil-bis (1, 10_{-phenanthroline}) lanthanum (III) ] nitrate (1.0 × 10⁻³ mol · L⁻¹) are first measured, the third-order nonlinear optical susceptibilities χ(³) and 〈γ〉 are calculated, and the mechanisms of the third-order optical nonlinearities enhanced by lanthanum (III) are discussed preliminarily.     

Anaerobic oxidation of methane: Geochemical evidence from pore-water in coastal sediments of Qi’ao Island (Pearl River Estuary), southern China

The concentrations of CH4 and SO4^2- in pore-water and the carbon isotope compositions of total dissolved inorganic （TCO2） and OH4 were determined for three coastal sedimentary cores collected from Qi＇ao Island （Pearl River Estuary）, southern China. Results show that methane concentration changes dramatically at the base of the sulfate-reducing zone and sulfate concentration gradients are linear for all stations. In addition, the carbon isotope of methane becomes heavier at the sulfate-methane transition （SMT）, which causes ∑CO2-δ^13C to become the minimum. The geochemical profiles of pore-water render indirect evidence for anaerobic oxidation of methane （AOM）. Based on numerical modeling of AOM and sulfate-reducing rates, the portion of total sulfate reduction occurring via AOM is 9.0%, 84% and 45.5%, respectively, and the percentage of TCO2 added to the pore-water is 4.7%, 72.4% and 29.45% correspondingly for three sites. Furthermore, it is found that the methane concentration, methane diffusive flux and the depth of SMT are controlled by the quantity and quality of sedimentary organic matter incorporated into the sediments. The great amount of organic material is favorable for rapid depletion of sulfate via sedimentary organic matter degradation, and on the other hand, causes the increase of the methane flux in the SMT, which results in a portion of sulfate reduction supported by AOM. Accordingly, the SMT was shifted towards the sediment surface.     

A theoretical study of the proton transfer process in the spin-forbidden reaction ^1HNO（^1A＇） ＋ OH^-→^ 3NO^-（^3∑^-） ＋ H2O

The spin-forbidden reaction 1HNO（^1A＋OH^-→3NO^-（^3∑^-）＋H2O has been extensively explored using vari- ous CASSCF active spaces with MP2 corrections in several basis sets. Natural bond orbital （NBO） analysis, together with the NBO energetic （deletion） analysis, indicates that the two isomers have nearly equal total energy and could compete with each other in the title reaction. More significantly, the singlet/triplet surface crossing regions have been examined and the spin-orbit coupling （SOC） and energetics have been computed. The computational results indicate that the SOC is very large at the crossing point T1/S0 trans （ca. 40.9 cm^-1）. Moreover, the T1/S0 trans has a low energy of 10.67 kcal/mol relative to that of trans-So. Therefore, the surface crossing to the triplet state seems much more efficient at the T1/S0 trans region along the minimum energy path （MEP）, However, The values of single （P1^ISC） and double （P2^ISC） passes estimated at T1/S0 trans show that the ISC occurs with a little probability.     

分子印迹电化学发光传感器检测毒死蜱

石墨相氮化碳纳米薄片（g-C₃N₄NSs）具有优良的电化学发光（ECL）性能和良好的成膜特性.以g-C₃N₄NSs作为ECL材料,利用其良好的成膜性能将其固定在玻碳电极（GCE）上,再以毒死蜱（CPF）作模板分子,甲基丙烯酸（MAA）作功能单体,通过分子自组装制备分子印迹聚合物（MIP）.将该聚合物引入g-C₃N₄NSs修饰电极,构建了一个MIP-ECL传感器.除去模板分子的传感器能够选择性识别CPF,利用CPF对g-C₃N₄NSs ECL信号的淬灭作用实现了CPF的高灵敏、高选择性检测.传感器对CPF的线性响应范围是1.0×10^-8~1.0×10^-4mol·L^-1,检出限（LOD）是5.0 nmol·L^-1,用于蔬菜中CPF残留量检测,结果令人满意.     

Application of Nanometer-Size Titanium Dioxide in Extreme-Trace V（Ⅴ） Analysis

0Introduction Vanadiumplaysanimportantroleinmodernindustry,es peciallyinsteelandchemicalindustry.Forinstance,itscompoundsarewidelyappliedintheproceduresofvitrioland petroleumchemicalmanufactureascatalyzers[14].Vanadium hasseveralvalences,butgenerallyitslowvalencesturnintohighoneseasilyinenvironment[5].BecauseV(Ⅴ)isthemost stableandpoisonousone,weoftenlayemphasisonitinenvi ronmentalpollutioncontrol.Vanadiumexistsinenvironmentalwaterwithextremelylowconcentration.Inseawateritscontentislessthan…     

Organic media enhanced spectrofluorimetric determination of L-ascorbic acid

A novel spectrofluorimetric method for the determination of L-ascorbic acid is proposed. It is based on the inhibition of L-ascorbic acid on the formation of 2,3-diaminophenazine, which is an oxidation product ofo-phenylenediamine catalyzed by laccase. The fluorescence (at λ_cx/λ_cm=464 nm /530 nnm) was enhanced strongly in the presence of organic media. The mechanism ofo-phenylenediamine oxidation reaction catalyzed by laccase in the presence of L-ascorbic acid is discussed. L-ascorbic acid is determined in the ethanol, 1,4-dioxane and acetone over the linear range of 4.0×10⁻⁷≈1.2×10⁻⁴ mol/L, 4.0×10⁻⁷≈8.0×10⁻⁵ mol/L and 4.0×10⁻⁷≈1.0×10⁻⁴ mol/L with a detection limit of 1.20×10⁻⁵ mol/L, 1.19×10⁻⁵ mol/L and 1.24×10⁻⁸ mol/L, respectively. The method has been successfully applied to the simple and rapid determination of L-ascorbic acid in pharmaceuticals and milk powder. Supported by National Natural Science Foundation of China and the Special Funds of State Education Committe for Doctorate Research Huang Zuyun: born in Aug. 1963. Ph.D     

TFEL of Ce3+ in zine sulpho-oxide

A new TFEL material ZnS_xO_1−x: Ce³⁺ is prepared. The EL brightness of ZnS_xO_1−x: Ce³⁺ is at least one order higher than that of ZnS: Ce³⁺ at the same doping concentration of Ce³⁺. The EL emission wavelength of ZnS_xO_1−x: Ce³⁺ (X = 0.5) ranges from 400 to 600 nm. The emission of ZnS_xO_1−x: Ce³⁺ may be used as the blue part of white TFEL.     

季铵盐改性MWNTs制备具有抗菌性和自清洁性的PVDF超滤膜

叔铵盐2-二甲氨基氯乙烷盐酸盐(DCH)作为季铵盐的前驱体,通过环氧氯丙烷接枝到氧化多壁碳纳米管(O-MWNTs)上,得到的季铵盐改性多壁碳纳米管(MWNTs)(即N~+-MWNTs)作为添加剂加入铸膜液制备聚偏氟乙烯(PVDF)平板超滤膜(PVDF/N~+-MWNTs膜).场发射扫描电子显微镜(FESEM)用来观测不同的N~+-MWNTs添加量对膜形貌的影响.结果表明,制得的PVDF/N~+-MWNTs复合膜表面粗糙度明显减小,同时亲水性得到明显改善.在对牛血清白蛋白(BSA)的污染-清洗循环实验中,PVDF/N~+-MWNTs复合膜相比于纯PVDF膜,纯水通量由110.5×10~(-5)L·m~(-2)·h~(-1)·Pa~(-1)上升至197.4×10~(-5)L·m~(-2)·h~(-1)·Pa~(-1).此外,通量恢复率(FRR)明显提高,尤其在3次循环之后,对BSA的截留性能没有下降.在对大肠杆菌和金黄色葡萄球菌的抗菌实验中,PVDF/N~+-MWNTs复合膜展现出优异的抑菌性,且在膜的抗菌性再生循环中,3次循环之后PVDF/N+-MWNTs复合膜的抑菌率依然维持在较高的水平.     

Flow-injection microcolumn on-line preconcentration for the determination of chromium (VI)

A rapid and sensitive on-line preconcentration method for spectrophotometric determination of chromium (VI) in nature water is described. Preconcentration and determination are based on (i) the quantitative and fast adsorption of chromium (VI) on the high surface area nanometer-size TiO₂ (anatase) powders, which prepared by a sol-gel method from hydrolysis of TiCl₄ and (ii) the quantitative and reproducible elution of Cr (VI) by 2.0 mol·L⁻¹ HCl. A mini-column system for preconcentration is developed, Cr(VI) on the mini-column is eluted and merged with a stream water and DPCB (1,5-diphenylcarbazide) as the chromogenic reagent. The proposed system permits throughputs of 6 sample h⁻¹ (0.001 μg·mL⁻¹ Cr(VI)) or 20 sample h⁻¹ (0.1 μg·mL⁻¹ Cr(VI)). The preconcentration factor is 55. The detection limit is 0.8 ng · mL⁻¹ Cr(VI). The reproducibility is satisfactory with a relative standard deviation of less than 3.35% (0.01 μg·mL⁻¹ Cr(VI),n=5). Supported by the National Natural Science Foundation of China Ma Wanhong: born in 1961, Ph. D. Graduate student, Associate professor     

Preconcentration of vanadium(V) on crosslinked chitosan and determination by graphite furnace atomic absorption spectrometry

A new method is proposed for the preconcentration of vanadium(V) with crosslinked chitosan (CCTS) and determination by graphite furnace atomic absorption spectrometry (GFAAS). The adsorption rate of vanadium(V) by CCTS was 97% at pH 4.0, and vanadium(V) was eluted from crosslinked chitosan with 2 mL 2.0 mol·L⁻¹ chlorhydric acid and determined by GFAAS. The detection limit (3σ,n=7) for vanadium (V) was 4.8×10⁻¹²g and the relative standard deviation (R.S.D) at concentration level of 2.6 μg·L⁻¹ is less than 3.6%. The method shows a good selectivity and high sensity, and it was applied to determination of vanadium(V) in oyster and water samples. The analytic recoveries are (97±5)%. Biography: Wu Wei (1975-), female, Master candidate, research direction: environmental & analytical chemistry.