Determination of total arsenic by photo-decomposition of organoarsenic compounds and hydride generation electrothermal atomic absorption spectrometry

A method was developed for the determination of total arsenic concentration in less than ng/ml level by decomposition of organoarsenicals using photo -oxidation combined with in situ trapping of arsenic hydride on a palladium coated graphite tube with subsequent atomization and detection by AAS. The organoarsenicals include monomethylarsenic, dimethylarsenic, arsenobetaine, arsenocholine, o -aminobenzenarsenate and p -aminobenzenarsenate. The method is simple and sensitive. Detection limit was obtained from different arsenic compounds over the range from 0. 058 to 0.063 ng/ml as As (based on three times of the standard deviation of 10 blank measurements) and the relative standard deviations for ten replicate measurements were from 2.0 to 3.8%. The calibration curves of arsenic compounds including inorganic and organic arsenicals were linear over the range from 0.1 to 3.0 ng/ml as As. The recommended method has been applied to the determination of total arsenic in tap and lake water samples at ng/ml levels.

DETERMINATION OF ANTIMONY IN WATER SAMPLES BY FLOW-INJECTION HYDRIDE GENERATION ATOMIC ABSORPTION SPECTROMETRY WITH ON-LINE ION-EXCHANGE COLUMN PRECONCENTRATION

On-line ion-exchange separation and preconcentration were combined with flow-injection hydride generation atomic absorption spectrometry (HGAAS) to determine ultra-trace amounts of antimony in water samples. Antimony(Ⅲ) was preconcentrated on a micro-column packed with CPG-8Q chelating ion-exchanger using time-based sample loading and eluted by 4 mol l^(-1) HCl directly into the hydride generation AAS system. A detection limit (3σ) of 0.0015μg l^(-1) Sb(Ⅲ) was obtained on the basis of a 20 fold enrichment and with a sampling frequency of 60h^(-1). The precision was 1.0% r.s.d.(n=11) at the 0.5μg l^(-1) Sb(Ⅲ) level. Recoveries for the analysis of antimony in tap water, snow water and sea water samples were in the range 97-102%.

Determination of Mecruy at Trace Level in Natural Water Samples by Hydride Generation Atomic Absorption Spectrophotometry after Cloud Point Extraction Preconcentration

A method for the determination of trace mercury in water samples by hydride generation atomic absorption spectrophotometry after cloud point extraction was proposed in the present work. The effects of pH, concentration of surfactant, and equilibration time on cloud point extraction were discussed. The enhancement factor of 20 and the detection limit of 0.039 μg/L were obtained for mercury with relative standard deviation of 4.8% （n = 11）.

Effect of sample treatment on determination of arsenic （Ⅲ） and arsenic （Ⅴ） in aqueous and tissue samples by hydride generation atomic absorption spectrometry

The purpose of this procedure was to optimize and improve a method that used for the determination of arsenic （Ⅲ） and arsenic （Ⅴ） in biological and environmental samples. The method is based on hydride generation and atomic absorption spectrometry. For both As （Ⅲ） and As （Ⅴ） the parameters such as NaBH4, HCI concentration, and pH were optimized. Absorption signal of As （Ⅴ） was approximately 17% of As （Ⅲ） signal. Therefore, for estimation of As （Ⅲ） and As （Ⅴ） concentrations in various samples the difference between the absorbance obtained for arsenic, without and with previous treatment of samples with potassium iodide （KI）, can be applied. The calibration graphs were linear （r〉0.99）, and the detection limits of the method based on three times the standard deviation of the blank were 0.14 and 0.64 μL^-1 for As （Ⅲ） and As （Ⅴ）, respectively. The relative standard deviation （R.S.D.） of measurements was less than 10%. As a means of checking performance method, water samples were spiked with known concentrations of both As （Ⅲ） and As （Ⅴ）, and recovery above 94% was obtained. The proposed method was applied successfully to determine inorganic As （Ⅲ） and As （Ⅴ） in various environmental and total As in biological samples.

Computational Modelling of the Hydride Generation Reaction in a Tubular Reactor and Atomization in a Quartz Cell Atomizer

In this study, we present a model whereby the centre of the atomization channel is shown to be the optimal location for the spectrometric data acquisition in a quartz cell atomizer. The study aims to explore the hydride generation technique which is normally coupled with efficient thermal source to apply determination of heavy metals in water samples via spectrometric analysis. The arsenic hydride generation process and the atomization of the generated hydride in a quartz cell atomizer were studied analytically as model case studies. The hydride generation (HG) process was analyzed by adopting two hypotheses, the nascent hydrogen and formation of intermediate hydroboron species, where the results based on the second hypothesis are found to be more realistic for design purposes. Moreover, the release of the generated hydride from the liquid phase and their transport to the gas phase is simulated in a helical tubular section, in which the actual tubular section length required for separation is deduced. The analytical results have been verified experimentally by measuring the signal intensity for the free arsenic atoms against several reaction tube lengths, in which increasing the tubular section length from 12 cm to 100 cm results in signal amelioration by no more than 6.6%. Furthermore, the atomization of the hydride and the distribution of the generated free atoms are deduced in two configurations of tubular quartz atomizers. The results obtained from both studied cases illustrate that a high concentration of the free analyte atoms is generated in the first part of the atomization channel, saturates to a maximum in a position at the atomizer centre, and dissipates at the inside wall of the tubular atomizer before reaching the atomizer outlet edge, which is found to be in total agreement with the current understanding of atomization mechanism in tubular atomizer and emphasizes the fact that the centre of the quartz cell atomizer is the best location for the spectrometric data acquisition.

Determination of Phosphorus by Inductively Coupled Plasma Atomic Emission Spectroscopy after Hydride Generation

A continuous phosphine (PH3) generation was developed and applied to the sensitive detection of phosphorus by ICP-AES. Phosphate ion in aqueous solution was converted to phosphine by passing the sample solution through an incandescent copper silica-tube. Detection limit is 2 ng/mL. The relative standard deviation is 4.2% for 20 ng/mL. The method is rapid and simple with low contamination and high sensitivity.

Determination of Cadmium in TSP, PM10 in urban areas by hydride generation atomic fluorescence spectrometry

In this paper, two different diameter particles （TSP, PM10） were collected by TH-16A four-channels classification air sampler. The samples were treated by HNO3. Analysis of cadmium was carried out by hydride generation atomic fluorescence spectrometry （HG-AFS） method, and distribution proportions of elements in four phases were calculated. This method was based on the reaction of cadmium with 1.5% （m/v） KBH4 solution and 0.5% KOH（m/v） solution to form the hydride gas in medium of 2% （v/v） HCl. The detection limit for cadmium as low as 0.008μg/L was obtained. The lineally correlation coefficient was 0.99992. The relative standard deviation （n=5, C=1.00μg/L） was 3.26%. The proposed method was applied for the determination of cadmium in atmosphere aerosol samples and the recoveries in the range of 95-102.2% were obtained. This method was simple, rapid, less matrix interference and high sensitivity.

Determination of Hg in soil by ultrasonic slurry sampling hydride generation atomic fluorescence spectrometry

Ultrasonic aided slurry sampling hydride generation atomic fluorescence spectrometry （USS-HG-AFS） was developed for the determination of Hg in soil samples from a sewage-irrigated farm. 500 mg grounded soil was suspended in agar solution by an ultrasound water bath before the HG-AFS determination. The results for the reference material of soil （serial number GBW-07411） agreed satisfactorily with the certified values. Results obtained by the developed procedure compared well with those after traditional acid digestion of samples. The detection limit are 6.7ngL-1 for Hg respectively, with average relative standard deviation values of 6.4% for analysis of a series of soil samples of different origin. The recoveries of the anatytes varied in the range from 95 to 107%. This observation has stimulated interest in fast, accurate and sensitive analytical methods for determination of metals in soil.

Influence of chloride salts on hydrogen generation via hydrolysis of MgH_2 prepared by hydriding combustion synthesis and mechanical milling

The effects of chloride salts(NaCl,MgCl2and NH4Cl)on the hydrolysis kinetics of MgH2prepared by hydridingcombustion synthesis and mechanical milling(HCS+MM)were discussed.X-ray diffraction(XRD)analyses show that high-purityMgH2was successfully prepared by HCS.Hydrolysis performance test results indicate that the chloride salt added during the millingprocess is favorable to the initial reaction rate and hydrogen generation yield within60min.A MgH2?10%NH4Cl composite exhibitsthe best performance with the hydrogen generation yield of1311mL/g and a conversion rate of85.69%in60min at roomtemperature.It is suggested that the chloride salts not only play as grinding aids in the milling process,but also create fresh surface ofreactive materials,favoring the hydrolysis reaction.

Nonlinear High Harmonics Generation in REB-Plasma System

The interaction of a relativistic electron beam (REB) with inhomogeneous, magneto-active, relativistic warm plasma is theoretically investigated. The nonlinear formation of waves at second and triple frequency at the inlet of the beam into the plasma is investigated. Effects of external static or oscillating magnetic field are considered. Nonlinear effects associated with the generation of second and triple harmonics, play an important role in the process of energy transfer from the beam to the plasma as compared with linear stage.

Electricity generation by Pseudomonas putida B6-2 in microbial fuel cells using carboxylates and carbohydrate as substrates

Microbial fuel cells(MFCs)employing Pseudomonas putida B6-2(ATCC BAA-2545)as an exoelectrogen have been developed to harness energy from various conventional substrates,such as acetate,lactate,glucose,and fructose.Owing to its metabolic versatility,P.putida B6-2 demonstrates adaptable growth rates on diverse,cost-effective carbon sources within MFCs,exhibiting distinct energy production characteristics.Notably,the anode chamber’s pH rises with carboxylates’(acetate and lactate)consumption and decreases with carbohydrates’(glucose and fructose)utilization.The MFC utilizing fructose as a substrate achieved the highest power density at 411 mW m^(−2).Initial analysis revealed that P.putida B6-2 forms biofilms covered with nanowires,contributing to bioelectricity generation.These microbial nanowires are likely key players in direct extracellular electron transport through physical contact.This study established a robust foundation for producing valuable compounds and bioenergy from common substrates in bioelectrochemical systems(BESs)utilizing P.putida as an exoelectrogen.

Current Situation and Application in Coal-Generated Hydrocarbons

The characteristics and research methods of terrigenous organic hydrocarbon-generated source rock in coal measures are studied in this thesis. After abundance of organic matters, pyrolysis parameter of rocks and hydrocarbon generated capacity of macerals are basically discussed in coal measures of the Cretaceous Muleng-Chengzihe formation in Suibin depression in Sanjang basin, the hydrocarbon generated grade in coal-genera^ted source rock is ascertained in this depression. At last, we think that it is a main attack prospect in coal-genera^ted hydrocarbons study in the future to research the macerals of coal measures organic source rock and to build a criterion to classify the coal-generated hydrocarbons in Northeast region.

Comparison of masking agents for antimony speciation analysis using hydride generation atomic fluorescence spectrometry

A sensitive atomic spectrometric method for the redox speciation analysis of Sb in water is described. The proposed method is based on the selective generation of stibine from Sb（III） in a continuous flow system using non-dispersive atomic fluorescence spectrometry for detection. The effects of the HCI concentration on the fluorescence intensities of Sb（III） and Sb（V） were investigated. The results indicated that atomic fluorescence emission due to Sb（V） can constructively interfere with the determination of Sb（III）. For the determination of Sb（III）, four compounds were tested as masking agents to inhibit the generation of stibine from Sb（V）. The effects of the concentrations of the masking agents and of HC1 on the fluorescence signals from Sb（III） and Sb（V） were studied. The results indicated that citric acid and NaF can successfully suppress hydride generation from Sb（V）. To evaluate the developed methodology and the influence of the matrix, the recovery of Sb（III） from natural water that was spiked with different Sb（III） and Sb（V） concentrations was tested.

Determination of Inorganic Arsenic Species by Electrochemical Hydride Generation Atomic Absorption Spectrometry with Selective Electrochemical Reduction

A new direct procedure for the determination of inorganic arsenic species was developed by electrochemical hydride generation atomic absorption spectrometry （EcHG-AAS） with selective electrochemical reduction. The determination of inorganic arsenic species is based on the fact that As（Ⅲ） shows significantly higher absorbance at low electrolytic currents than As（Ⅴ） in 0.3 mol·L^-1 H2SO4. The electrolytic current used for the determination of As（Ⅲ） without considerable interferences of As（Ⅴ） was 0.4 A, whereas the current for the determination of As（Ⅲ） and As（Ⅴ） was 1.2 A. For equal concentrations of As（Ⅲ） and As（Ⅴ） in a sample, the interferences of As（Ⅴ） during the As（Ⅲ） determination were smaller than 5%. The absorbance for As（Ⅴ） could be calculated by subtracting that for As（Ⅲ） measured at 0.4 A from the total absorbance for As（Ⅲ） and As（Ⅴ） measured at 1.2 A, and then the concentration of As（Ⅴ） can be obtained by its calibration curve at 1.2 A. The methodology developed provided the detection limits of 0.3 and 0.6 ng·mL^-1 for As（Ⅲ） and As（Ⅴ）, respectively. The relative standard deviations were of 3.5% for 20 ng·mL^-1 As（Ⅲ） and 3.2% for 20 ng·mL^-1 As（Ⅴ）. The method was successfully applied to determination of soluble inorganic arsenic species in Chinese medicine.

Formation conditions and exploration direction of large natural gas reservoirs in the oil-prone Bohai Bay Basin, East China

The Bohai Bay Basin is a typical oil-prone basin, in which natural gas geological reserves have a small proportion. In this basin, the gas source rock is largely medium-deep lake mudstone with oil-prone type Ⅱ2-Ⅱ1 kerogens, and natural gas preservation conditions are poor due to active late tectonic movements. The formation conditions of large natural gas fields in the Bohai Bay Basin have been elusive. Based on the exploration results of Bohai Bay Basin and comparison with large gas fields in China and abroad, the formation conditions of conventional large-scale natural gas reservoirs in the Bohai Bay Basin were examined from accumulation dynamics, structure and sedimentation. The results show that the formation conditions of conventional large natural gas reservoirs in Bohai Bay Basin mainly include one core element and two key elements. The core factor is the strong sealing of Paleogene "quilt-like" overpressure mudstone. The two key factors include the rapid maturation and high-intensity gas generation of source rock in the late stage and large scale reservoir. On this basis, large-scale nature gas accumulation models in the Bohai Bay Basin have been worked out, including regional overpressure mudstone enriching model, local overpressure mudstone depleting model, sand-rich sedimentary subsag depleting model and late strongly-developed fault depleting model. It is found that Bozhong sag, northern Liaozhong sag and Banqiao sag have favorable conditions for the formation of large-scale natural gas reservoirs, and are worth exploring. The study results have important guidance for exploration of large scale natural gas reservoirs in the Bohai Bay Basin.

Ultrasensitive determination of mercury by solution anode glow discharge atomic emission spectrometry coupled with hydride generation

An innovative method for the ultrasensitive detection of mercury by solution anode glow discharge atomic emission spectroscopy(SAGD-AES) coupled with hydride generation(HG) was first investigated.In this method,the mercury vapor generated by the HG was transmitted to the SAGD through the miniature hollow tungsten tube for excitation and detected by a miniaturized spectrograph.A thorough parametric evaluation of the HG and SAGD system was performed,including the type and concentration of ca rrier acid,He flow rate,concentrations of NaBH4,discha rge current and discharge gap.Under optimal operating conditions,the detection limit for Hg^(2+) achieved 0.03 μg/L,with a relative standard deviation of 1.1% at the Hg^(2+) concentration of 5 μg/L.Moreover,the correlation coefficient of the calibration curve was 0.9996 in the range between 0.1 and 10 μg/L.The accuracy and practicability of HG-SAGD-AES were verified by measuring GBW09101 b(human hair),GBW10029(fish),soil and rice samples.The results showed good agreement with the certified values and values from direct mercury analyzer(DMA).

Characterization of Cd1-xZnxTe（0≤x≤1） Nanolayers Grown by Atomic Layer Deposition on GaSb and GaAs（001） Oriented Substrates

ZnTe, CdTe, and the ternary alloy CdZnTe are important semiconductor materials used widely for the detection of an important range of electromagnetic radiation as gamma ray and X-ray. Although, recently these materials have acquired renewed importance due to the new explored nanolayer properties of modern devices. In addition, as shown in this work they can be grown using uncomplicated synthesis techniques based on the deposition in vapour phase of the elemental precursors. This work presents the results obtained from the deposition of nanolayers of these materials using the precursor vapour on GaAs and GaSb (001) substrates. This growth technique, extensively known as atomic layer deposition (ALD), allows the layers growth with nanometric dimension. The main results presented in this work are the used growth parameters and the results of the structural characterization of the layers by the means of Raman spectroscopy measurements. Raman scattering shows the peak corresponding to longitudinal optical (LO)-ZnTe, which is weak and slightly redshift in comparison with that reported for the ZnTe bulk at 210 cm^-1. For the case of the CdTe nanolayer, Raman spectra presented the LO-CdTe peak, which is indicative of the successful growth of the layer. Its weak and slightly redshift in comparison with that reported for the CdTe bulk can be related with the nanometric characteristic of this layer. The performed high-resolution X-ray diffraction (HR-XRD) measurement allows to study some important characteristics such as the crystallinity of the grown layer. In addition, the HR-XRD measurement suggests that the crystalline quality has dependence on the growth temperature.

ANTI-IDIOTYPIC MONOCLONAL ANTIBODIES AGAINST ANTI-OVARIAN CARCINOMA MONOCLONAL ANTIBODY COC166-9 GENERATION AND APPLICATION

Anri-idiotypic monoclonal antibody (Mab Ab2 ) by MAb COC166-9 against ovarian serous papillary adenocarcinoma was prepared. Hybridomas of Ab2 screened by sandwich ELISA and immunocompetitive inhibition tests were procured and named as 6B11 and 1H12. The number of their chromosomes were 93 and 91, and DNA analysis also proved the characteristics of hybridomas. These Ab2s could induce delayed type hypersensitivity (DTH), the cellular immune response. The results of the immune reaction of 6B11 with SKOV3 (ovarian carcinoma cell line) were similar to OC166-9 (Ag), the positive control, while 1H12 was weaker. Anti-and-idiotypic antibody (Ab3) was also raised by 6B11 and 1H12 respectively. They all showed positive immunohistochemical stainings with ovarian serous adenocarcinoma tissue sections and immunocytochemical stainings with SKOV3 cells as was shown by COC166-9. In the antibody dependent cell mediated cytotoxicity (ADCC) tests, they showed no differences against SKOV3 as compared with COC166-9. We anticipate that 6B11 and 1H12 may be used as vaccines against ovarian carcinoma and may provide a clue for its prevention and treatment.

黄皮叶中5种重金属元素的含量测定

黄皮叶药材经硝酸－高氯酸（10＋2）湿法消解后，采用原子吸收分光光度法测定铜元素含量，采用原子荧光法测定砷、汞、铅、镉元素的含量，建立了黄皮叶药材中5种重金属元素的含量测定方法，并测定了不同产地及批次黄皮叶药材中这5种元素的含量。5种元素回收率在94．25％～104．1％之间，8批黄皮叶中铜、砷和铅元素含量均低于国家限量标准，部分产地和批次药材中的重金属汞、镉元素含量高于国家限量标准。

Enhanced nitrate reduction in water by a combined bio-electrochemical system of microbial fuel cells and submerged aquatic plant Ceratophyllum demersum

High nitrate(NO_3^-)loading in water bodies is a crucial factor inducing the eutrophication of lakes.We tried to enhance NO_3^-reduction in overlying water by coupling sediment microbial fuel cells(SMFCs)with submerged aquatic plant Ceratophyllum demersum.A comparative study was conducted by setting four treatments:open-circuit SMFC(Control),closed-circuit SMFC(SMFC-c),open-circuit SMFC with C.demersum(Plant),and closed-circuit SMFC with C.demersum(P-SMFC-c).The electrochemical parameters were documented to illustrate the bio-electrochemical characteristics of SMFC-c and P-SMFC-c.Removal pathways of NO_3^- in different treatments were studied by adding quantitative^(15)NO_3^- to water column.The results showed that the cathodic reaction in SMFC-c was mainly catalyzed by aerobic organisms attached on the cathode,including algae,Pseudomonas,Bacillus,and Albidiferax.The oxygen secreted by plants significantly improved the power generation of SMFC-c.Both electrogenesis and plants enhanced the complete removal of NO_3^- from the sediment–water system.The complete removal rates of added^(15)N increased by 17.6% and 10.2% for SMFC-c and plant,respectively,when compared with control at the end of experiment.The electrochemical/heterotrophic and aerobic denitrification on cathodes mainly drove the higher reduction of NO_3^- in SMFC-c and plant,respectively.The coexistence of electrogenesis and plants further increased the complete removal of NO_3^- with a rate of 23.1%.The heterotrophic and aerobic denitrifications were simultaneously promoted with a highest abundance of Flavobacterium,Bacillus,Geobacter,Pseudomonas,Rhodobacter,and Arenimonas on the cathode.