Novel method for the determination of five carbamate pesticides in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography

A novel method for the determination of five carbamate pesticides （metolcarb, carbofuran, carbaryl, isoprocard and diethofencard） in water samples was developed by dispersive liquid-liquid microextraction （DLLME） coupled with high performance liquid chromatography-diode array detector （HPLC-DAD）. Some experimental parameters that influence the extraction efficiency were studied and optimized to obtain the best extraction results. Under the optimum conditions for the method, the calibration curve was linear in the concentration range from 5 to 1000 ng mL^-1 for all the five carbamate pesticides, with the correlation coefficients （r^2） varying from 0.9984 to 0.9994. Good enrichment factors were achieved ranging from 80 to 177- fold, depending on the compound. The limits of detection （LODs） （S/N = 3） were ranged from 0.1 to 0.5 ng mL^-1. The method has been successfully applied to the analysis of the pesticide residues in environmental water samples.

DESIGN OF NOVEL HIGH PRESSURE-RESISTANT HYDROTHERMAL FLUID SAMPLE VALVE

Sampling study is an effective exploration method, but the most extreme environments of hydrothermal vents pose considerable engineering challenges for sampling hydrothermal fluids. Moreover, traditional sampler systems with sample valves have difficulty in maintaining samples in situ pressure. However, decompression changes have effect on microorganisms sensitive to such stresses. To address the technical difficulty of collecting samples from hydrothermal vents, a new bidirectional high pressure-resistant sample valve with balanced poppet was designed. The sample valve utilizes a soft high performance plastic ＂PEEK＂ as poppet. The poppet with inapposite dimension is prone to occur to plastic deformation or rupture for high working pressure in experiments. To address this issue, based on the fmite element model, simulated results on stress distribution of the poppet with different structure parameters and preload spring force were obtained. The static axial deformations on top of the poppet were experimented. The simulated results agree with the experimental results. The new sample valve seals well and it can withstand high working pressure.

Neutron Diffraction of Large-Volume Samples at High Pressure Using Compact Opposed-Anvil Cells

Neutron diffraction techniques of large-volume samples at high pressure using compact opposed-anvil cells are developed at a reactor neutron source, China＇s Mianyang research reactor. We achieve a high-pressure condition of in situ neutron diffraction by means of a newly designed large-volume opposed-anvil cell. This pressure calibration is based on resistance measurements of bismuth and the neutron diffraction of iron. Pressure calibration experiments are performed at room temperature for a new cell using the tungsten carbide anvils with a tapered angle of 30°, Φ4.5 mm culet diameter and the metal-nonmetal composite gasket with a thickness of 2 mm. Transitions in Bi（Ⅰ–Ⅱ 2.55 GPa, Ⅱ–V 7.7 GPa） are observed at 100 and 300 kN, respectively, by resistance measurements.The pressure measurement results of neutron diffraction are consistent with resistance measurements of bismuth.As a result, pressures up to about 7.7 GPa can routinely and stably be achieved using this apparatus, with the sample volume of 9 mm^3.

A New High-throughput Real-time PCR Assay for the Screening of Multiple Antimicrobial Resistance Genes in Broiler Fecal Samples from China

Objective Antimicrobial resistance(AMR)has become a global concern and is especially severe in China.To effectively and reliably provide AMR data,we developed a new high-throughput real-time PCR assay based on microfluidic dynamic technology,and screened multiple AMR genes in broiler fecal samples.Methods A high-throughput real-time PCR system with an new designed integrated fluidic circuit assay were performed AMR gene detection.A total of 273 broiler fecal samples collected from two geographically separated farms were screened AMR genes.Results The new assay with limits of detection ranging from 40.9 to 8,000 copies/reaction.The sensitivity rate,specificity rate,positive predictive value,negative predictive value and correct indices were 99.30%,98.08%,95.31%,99.79%,and 0.9755,respectively.Utilizing this assay,we demonstrate that AMR genes are widely spread,with positive detection rates ranging from 0 to 97.07%in 273 broiler fecal samples.bla CTX-M,bla TEM,mcr-1,fex A,cfr,optr A,and int I1 showed over 80%prevalence.The dissemination of AMR genes was distinct between the two farms.Conclusions We successfully established a new high-throughput real-time PCR assay applicable to AMR gene surveillance from fecal samples.The widespread existence of AMR genes detected in broiler farms highlights the current and severe problem of AMR.

The determination of 52 elements in marine geological samples by an inductively coupled plasma optical emission spectrometry and an inductively coupled plasma mass spectrometry with a high-pressure closed digestion method

An improved analytical method to determine the content of 52 major, minor and trace elements in marine geological samples, using a HF-HCl-HNO_3 acid system with a high-pressure closed digestion method（HPCD）, is studied by an inductively coupled plasma optical emission spectrometry（ICP-OES） and an inductively coupled plasma mass spectrometry（ICP-MS）. The operating parameters of the instruments are optimized, and the optimal analytical parameters are determined. The influences of optical spectrum and mass spectrum interferences, digestion methods and acid systems on the analytical results are investigated. The optimal spectral lines and isotopes are chosen, and internal standard element of rhodium is selected to compensate for matrix effects and analytical signals drifting. Compared with the methods of an electric heating plate digestion and a microwave digestion, a high-pressure closed digestion method is optimized with less acid, complete digestion,less damage for digestion process. The marine geological samples are dissolved completely by a HF-HCl-HNO_3 system, the relative error（RE） for the analytical results are all less than 6.0%. The method detection limits are 2–40μg/g by the ICP-OES, and 6–80 ng/g by ICP-MS. The methods are used to determine the marine sediment reference materials（GBW07309, GBW07311, GBW07313）, rock reference materials（GBW07103, GBW07104,GBW07105）, and cobalt-rich crust reference materials（GBW07337, GBW07338, GBW07339）, the obtained analytical results are in agreement with the certified values, and both of the relative standard deviation（RSD） and the relative error（RE） are less than 6.0%. The analytical method meets the requirements for determining 52 elements contents of bulk marine geological samples.

Distribution and Migration of Heavy Metals in Undisturbed Forest Soils:A High Resolution Sampling Method

The vertical distribution and migration of Cu,Zn,Pb,and Cd in two forest soil profiles near an industrial emission source were investigated using a high resolution sampling method together with reference element Ti.One-meter soil profile was sectioned horizontally at 2 cm intervals in the first 40 cm,5 cm intervals in the next 40 cm,and 10 cm intervals in the last 20 cm.The migration distance and rate of heavy metals in the soil profiles were calculated according to their relative concentrations in the profiles,as calibrated by the reference element Ti.The enrichment of heavy metals appeared in the uppermost layer of the forest soil,and the soil heavy metal concentrations decreased down the profile until reaching their background values.The calculated average migration rates of Cd,Cu,Pb,and Zn were 0.70,0.33,0.37,and 0.76 cm year-1,respectively,which were comparable to other methods.A simulation model was proposed,which could well describe the distribution of Cu,Zn,Pb,and Cd in natural forest soils.

Characteristics analysis on high density spatial sampling seismic data

China＇s continental deposition basins are characterized by complex geological structures and various reservoir lithologies. Therefore, high precision exploration methods are needed. High density spatial sampling is a new technology to increase the accuracy of seismic exploration. We briefly discuss point source and receiver technology, analyze the high density spatial sampling in situ method, introduce the symmetric sampling principles presented by Gijs J. O. Vermeer, and discuss high density spatial sampling technology from the point of view of wave field continuity. We emphasize the analysis of the high density spatial sampling characteristics, including the high density first break advantages for investigation of near surface structure, improving static correction precision, the use of dense receiver spacing at short offsets to increase the effective coverage at shallow depth, and the accuracy of reflection imaging. Coherent noise is not aliased and the noise analysis precision and suppression increases as a result. High density spatial sampling enhances wave field continuity and the accuracy of various mathematical transforms, which benefits wave field separation. Finally, we point out that the difficult part of high density spatial sampling technology is the data processing. More research needs to be done on the methods of analyzing and processing huge amounts of seismic data.

Silicon PIN photodiode applied to acquire high-frequency sampling XAFS spectra

Experimental techniques based on SR facilities have emerged with the development of synchrotron radiation(SR)sources.Accordingly,detector miniaturization has become significant for the development of SR experimental techniques.In this study,the miniaturization of a detector was achieved by coupling a commercial silicon PIN photodiode(SPPD)into a beamstop,aiming for it not only to acquire X-ray absorption fine structure(XAFS)spectra,but also to protect the subsequent two-dimensional detector from high-brilliance X-ray radiation damage in certain combination techniques.This mini SPPD detector coupled to a beamstop was used as the rear detector in both the conventional sampling scheme and novel high-frequency(HF)sampling scheme to collect the transmission XAFS spectra.Traditional ion chambers were also used to collect the transmission XAFS spectra,which were used as the reference.These XAFS spectra were quantitatively analyzed and compared;the results demonstrated that the XAFS spectra collected by this SPPD in both the conventional sampling scheme and HF sampling scheme are feasible.This study provides a new detector-selection scheme for the acquisition of the quick-scanning XAFS(QXAFS)and HF sampling XAFS spectra.The SPPD detector presented in this study can partially meet the requirements of detector miniaturization.

Standard-sample bracketing calibration method combined with Mg as an internal standard for silicon isotopic compositions using multi-collector inductively coupled plasma mass spectrometry

Silicon isotope analysis traditionally uses a standard-sample bracketing （SSB） method that relies upon greater instrument stability than can be consistently expected. The following proposed method reduces the level of instrumental stability required for the analysis process and provides a valid solution for high-precision and accurate studies of Si isotopic compositions. Rock samples were dissolved by using alkali fusion and acidification. Silicon isotopes were purified with an ion exchange resin. Interfering peaks for isotopes were separated by using a Nu Plasma 1700 multi-collector inductively coupled plasma mass spectrometry （MS） system in high-resolution mode （M/AM 〉 8000 RP）. Two magnesium isotopes （25Mg and 26Mg） and three silicon isotopes （28Si, 29Si, and 3;Si） were analyzed in the same data collection cycle. Mg isotopes were used as an internal standard to calibrate the mass discrimination effects in MS analysis of Si isotopes in combination with the SSB method in order to reduce the effects of MS interference and instrumental mass dis- crimination on the accuracy of measurements. The conventional SSB method without the Mg internal standard and the proposed SSB method with Mg calibration delivered consistent results within two standard deviations. When Mg was used as an internal standard for calibration, the analysis precision was better than 0.05 %0 amu.

Rapid determination of atrazine in environmental water samples by a novel liquid phase microextraction

A novel method was described for the rapid determination of atrazine using dispersive liquid phase microextraction in combination with high performance liquid chromatography （HPLC）. Possible impact parameters such as sample pH, extraction and disperser solvents, salting-out effect, and extraction time were investigated. The experimental results indicated that proposed method possessed an excellent analytical performance, The linear range, detection limit, and precision （R.S.D.） were 0.1- 50 ng mL- 1 （R2 = 0.9955）, 0.601 ng mL- 1 and 6,4%, respectively. The proposed method was validated with the real water samples, and the spiked recoveries were in the range of 69.9-89.8%, respectively. These results indicated that the established method with high enrichment factor, short extraction time was an excellent alternative for the routine analysis of atrazine in environmental samples. 2007 Qing Xiang Zhou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

An Improved Algorithm for Imbalanced Data and Small Sample Size Classification

Traditional classification algorithms perform not very well on imbalanced data sets and small sample size. To deal with the problem, a novel method is proposed to change the class distribution through adding virtual samples, which are generated by the windowed regression over-sampling (WRO) method. The proposed method WRO not only reflects the additive effects but also reflects the multiplicative effect between samples. A comparative study between the proposed method and other over-sampling methods such as synthetic minority over-sampling technique (SMOTE) and borderline over-sampling (BOS) on UCI datasets and Fourier transform infrared spectroscopy (FTIR) data set is provided. Experimental results show that the WRO method can achieve better performance than other methods.

FAST ALGORITHM FOR NON-UNIFORMLY SAMPLED SIGNAL SPECTRUM RECONSTRUCTION

In this paper, a fast algorithm to reconstruct the spectrum of non-uniformly sampled signals is proposed. Compared with the original algorithm, the fast algorithm has a higher computational efficiency, especially when sampling sequence is long. Particularly, a transformation matrix is built, and the reconstructed spectrum is perfectly synthesized from the spectrum of every sampling channel. The fast algorithm has solved efficiency issues of spectrum reconstruction algorithm, and making it possible for the actual application of spectrum reconstruction algorithm in multi-channel Synthetic Aperture Radar (SAR).

The effect of frequency and sample shape on fatigue behaviors of DZ125 superalloy

The effect of frequency and sample shape on fatigue behaviors of DZ125 superalloy are systematically studied.The results show that fatigue fracture still occurs above the cycle of 10~8 for tests carried out at the frequency of f=20 kHz and stress ratio R =-1,so the traditional fatigue limit at cycle of 10~7 is not appropriate for fatigue design.Fatigue fracture surfaces are perpendicular to stress axis for cylindrical and plate specimens,and the fatigue cracks originate from the extra surface of the specimens.Fatigue crack is apt to propagate from cutting direction to forward direction,which occurs mainly in the second propagation stage at higher stress amplitude. There is an obvious frequency effect for DZ125 superalloy.The higher the test frequency is,the more serious the effect of frequency on fatigue behaviors of the alloy.After the frequency correction,the ultra-high cycle fatigue S-N curve well coincide with the traditional fatigue S-N curve.

基于固相萃取-高效液相色谱-串联质谱测定孕妇尿液中8种邻苯二甲酸酯代谢物及新生儿出生结局评价

邻苯二甲酸酯(PAEs)是一种环境内分泌干扰物,广泛存在于日常生活中,并可通过多种途径进入机体。孕妇作为一类特殊人群,若暴露于PAEs,将会对子代的生长发育造成不良影响。研究建立了固相萃取-高效液相色谱-串联质谱(SPE-HPLC-MS/MS)同时检测孕妇尿液中8种PAEs代谢物(mPAEs)的分析方法。尿液样品经β-葡萄糖苷酶酶解后,采用Bond Elut Plexa固相萃取柱净化,样品经洗脱、浓缩、复溶后,进行HPLC-MS/MS分析。采用Agilent Eclipse Plus C18色谱柱(100 mm×3 mm,3.5μm)进行分离,以0.1%乙酸水溶液和0.1%乙酸乙腈作为流动相进行梯度洗脱,在多反应监测(MRM)模式下检测,内标法定量。结果表明,8种mPAEs在0.1~200 ng/mL范围内线性关系良好,检出限为0.015~0.048 ng/mL,定量限为0.050~0.160 ng/mL。在低、中、高3个加标水平(1、10、50 ng/mL)下,8种mPAEs的加标回收率为80.2%~99.7%。采用此方法对鄂州市妇幼保健院497名孕妇尿液中的8种mPAEs水平进行检测,结果表明,497名孕妇广泛暴露于PAEs,其中邻苯二甲酸单丁酯(MBP)的含量最高,中位数水平为104.46 ng/mL;邻苯二甲酸单苄酯(MBzP)的含量最低,中位数水平为0.22 ng/mL。同时,研究还对新生儿的出生结局进行了评估,线性回归模型表明,孕妇尿液中的邻苯二甲酸单乙酯(MEP)每增加一个自然对数(ln)水平,孕周减少0.11周(95%置信区间(CI):-0.18~-0.03);孕妇尿液中的邻苯二甲酸(2-乙基-5-氧己基)酯(MEOHP)和邻苯二甲酸单(2-乙基己基)酯(MECPP)每增加一个ln水平,新生儿出生体重分别降低39.28 g(95%CI:-76.48~-2.09)和39.62 g(95%CI:-73.73~-5.52)。该方法操作简便,检出限低,具有较高的准确度和精密度,通过此方法测定了孕妇尿液中的8种mPAEs,并结合新生儿的出生结局发现,孕期PAEs暴露会影响新生儿的生长发育。

Simulation method for reliability of TT&C mission with high redundancy and small time horizon

The tracking, telemetry and command （TT＆C） mission is extremely reliable for its characters of small time horizon and high redundancy. The combined forcing and failure biasing （CFFB） method that is usually used for simulating the unreliability of the highly dependable mission system seems not so efficient for the TT＆C mission. The concept about the importance of failure transition is proposed based on the logical relationship between TT＆C mission and its involved resources. Then, the importance is used for readjusting the transition rate of the failure transition when using the forcing and failure biasing during the simulation. Examples show that the improved CFFB method can evidently increase the occurrence of the TT＆C mission failure event and decrease the sample variance. More redundancy of the TT＆C mission leads to the improved CFFB method more efficient.

High Voltage Digital Transient State Measuring System

This paper presents main functions of a high voltage,high speed and extensive memory transient measurementequipment and design of associate hardware and software. Thepaper also introduces the hardware design of high speed hugememory data sampler, explains the know-how of data analysissoftware, program-controlled voltage divider andanti-interference measurement, with which the equipmentperforms excellent on--site.This equipment reallies automatic measurement and satisfiesthe requirement of high voltage digital measurment.

Diffusion Process of High Concentration Spikes in a Quasi-Homogeneous Turbulent Flow

When a mass spreads in a turbulent flow, areas with obviously high concentration of the mass compared with surrounding areas are formed by organized structures of turbulence. In this study, we extract the high concentration areas and investigate their diffusion process. For this purpose, a combination of Planar Laser Induced Fluorescence (PLIF) and Particle Image Velocimetry (PIV) techniques was employed to obtain simultaneously the two fields of the concentration of injected dye and of the velocity in a water turbulent channel flow. With focusing on a quasi-homogeneous turbulence in the channel central region, a series of PLIF and PIV images were acquired at several different downstream positions. We applied a conditional sampling technique to the PLIF images to extract the high concentration areas, or spikes, and calculated the conditional-averaged statistics of the extracted areas such as length scale, mean concentration, and turbulent diffusion coefficient. We found that the averaged length scale was constant with downstream distance from the diffusion source and was smaller than integral scale of the turbulent eddies. The spanwise distribution of the mean concentration was basically Gaussian, and the spanwise width of the spikes increased linearly with downstream distance from the diffusion source. Moreover, the turbulent diffusion coefficient was found to increase in proportion to the spanwise distance from the source. These results reveal aspects different from those of regular mass diffusion and let us conclude that the diffusion process of the spikes differs from that of regular mass diffusion.

HIGH-EFFICIENCY CODING FOR PAL COLOR TELEVISION SIGNAL

Proceeding from the specific characteristics of PAL television signals adopted in China this paper points out that if the fs = 2fsc of sub-Nyquist sampling and DPCM encoding is used for PAL complete signal and if the blanking time is utilized to transmit code of effective area, it is possible to transmit a color TV signal over PCM three-group channel.

Trace Determination of Tamoxifen in Biological Fluids Using Hollow Fiber Liquid-Phase Microextraction Followed by High-Performance Liquid Chromatography-Ultraviolet Detection

The applicability of hollow fiber liquid-phase microextraction (HF-LPME) combined with high-performance liquid chromatography-ultraviolet detection (HPLC-UV) was evaluated for the extraction and determination of tamoxifen (TAM) in biological fluids including human urine and plasma. The drug was extracted from a 15 mL aqueous sample (source phase;SP) into an organic phase impregnated in the pores of the hollow fiber (membrane phase;MP) followed by the back-extraction into a second aqueous solution (receiving phase;RP) located in the lumen of the hollow fiber. The effects of several factors such as the nature of organic solvent, compositions of SP and RP solutions, extraction time, ionic strength and stirring rate on the extraction efficiency were examined and optimized. An enrichment factor of 360 along with substantial sample clean up was obtained under the optimized conditions. The calibration curve showed linearity in the range of 1 - 500 ng?mL–1 and the limit of detection was found to be 0.5 ng?mL–1 in aqueous medium. A reasonable relative recovery (≥89%) and satisfactory intra-assay (3.7% - 4.2%, n = 3) and inter-assay (7.5% - 7.8%, n = 3) precision illustrated good performance of the analytical procedure in spiked human urine and plasma samples.