Competitive Doping Chemistry for Nickel-Rich Layered Oxide Cathode Materials.

Chemical modification of electrode materials by heteroatom dopants is crucial for improving storage performance in rechargeable batteries. Electron configurations of different dopants significantly influence the chemical interactions inbetween and the chemical bonding with the host material, yet the underlying mechanism remains unclear. We revealed competitive doping chemistry of Group IIIA elements (boron and aluminum) taking nickel-rich cathode materials as a model. A notable difference between the atomic radii of B and Al accounts for different spatial configurations of the hybridized orbital in bonding with lattice oxygen. Density functional theory calculations reveal, Al is preferentially bonded to oxygen and vice versa, and shows a much lower diffusion barrier than BIII . In the case of Al-preoccupation, the bulk diffusion of BIII is hindered. In this way, a B-rich surface and Al-rich bulk is formed, which helps to synergistically stabilize the structural evolution and surface chemistry of the cathode.

P3/O3 Integrated Layered Oxide as High-Power and Long-Life Cathode toward Na-Ion Batteries.

Low-cost and stable sodium-layered oxides (such as P2- and O3-phases) are suggested as highly promising cathode materials for Na-ion batteries (NIBs). Biphasic hybridization, mainly involving P2/O3 and P2/P3 biphases, is typically used to boost their electrochemical performances. Herein, a P3/O3 intergrown layered oxide (Na2/3 Ni1/3 Mn1/3 Ti1/3 O2 ) as high-rate and long-life cathode for NIBs via tuning the amounts of Ti substitution in Na2/3 Ni1/3 Mn2/3- x Tix O2 (x = 0, 1/6, 1/3, 2/3) is demonstrated. The X-ray diffraction (XRD) Rietveld refinement and aberration-corrected scanning transmission electron microscopy show the co-existence of P3 and O3 phases, and density functional theory calculation corroborates the appearance of the anomalous O3 phase at the Ti substitution amount of 1/3. The P3/O3 biphasic cathode delivers an unexpected rate capability (≈88.7% of the initial capacity at a high rate of 5 C) and cycling stability (≈68.7% capacity retention after 2000 cycles at 1 C), superior to those of the sing phases P3-Na2/3 Ni1/3 Mn2/3 O2 , P3-Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 , and O3-Na2/3 Ni1/3 Ti2/3 O2 . The highly reversible structural evolution of the P3/O3 integrated cathode observed by ex situ XRD, ex situ X-ray absorption spectra, and the rapid Na+ diffusion kinetics, underpin the enhancement. These results show the important role of P3/O3 biphasic hybridization in designing and engineering layered oxide cathodes for NIBs.

Dynamic Evolution of a Cathode Interphase Layer at the Surface of LiNi0.5Co0.2Mn0.3O2 in Quasi-Solid-State Lithium Batteries.

Intensive understanding of the surface mechanism of cathode materials, such as structural evolution and chemical and mechanical stability upon charging/discharging, is crucial to design advanced solid-state lithium batteries (SSLBs) of tomorrow. Here, via in situ atomic force microscopy monitoring, we explore the dynamic evolution process at the surface of LiNi0.5Co0.2Mn0.3O2 cathode particles inside a working SSLB. The dynamic formation process of the cathode interphase layer, with an inorganic-organic hybrid structure, was real-time imaged, as well as the evolution of its mechanical property by in situ scanning of the Derjaguin-Muller-Toporov modulus. Moreover, different components of the cathode interphase layer, such as LiF, Li2CO3, and specific organic species, were identified in detailat different stages of cycling, which can be directly correlated with the impedance buildup of the battery. In addition, the transition metal migration and the formation of new phases can further exacerbate the degradation of the SSLB. A relatively stable cathode interphase is key to improving the performance of SSLBs. Our findings provide deep insights into the dynamic evolution of surface morphology, chemical components and mechanical properties of the cathode interphase layer, which are pivotal for the performance optimization of SSLBs.

Highly efficient electrochemical gas reduction on a three-dimensional foam electrode: mechanism and application for the determination of hazardous mercury in complex matrix.

For the first time a nickel foam electrode (NFE) is applied in the field of electrochemical vapor generation (EVG) to carry out the electrochemical vapor phase conversion of mercury. Systematical electrochemical and morphological research has demonstrated that the specific surface area of the NFE was several times larger than that of the metal/non-metal electrode with the same geometric size. At the same time, the 3D porous channel composed of multi-layer nickel wire ensures the full contact between reactant and interface. The evident enhancement of spectral signals on a Ni electrode (283%), compared with Pt (27%) and graphite (109%), confirmed that the NFE effectively enhances the yield of mercury reduction. The NFE exhibits low limit of detection (0.017 µg L-1) and a wide linear range (0.2-20 µg L-1) with recoveries of actual samples in the range 87.8-117% towards Hg2+. Although the NFE has no advantage in electronic transmission and catalytic performance, its excellent stability, especially anti-interference and other characteristics, is sufficient for the analysis of hazardous mercury in complex matrix including certified reference materials and real samples.

High sensitivity atomic fluorescence spectroscopy for the detection of AsIII by selective electrolysis of arsenic on nanoflowers-like Fe/NFE.

Modified electrosynthetic sample introduction technique is a reliable means of solving the problem of high sensitivity analysis of trace arsenite. This article attempts to achieve selective electroreduction of AsIII through the construction of electrode surfaces with different structures and materials from the perspective of interface reactions. Among the four transition metal modifiers, the iron modified nickel foam electrode with nano-flower structure documented higher efficiency in inducing arsenic reduction and better species selectivity. Systematic electrochemical and spectroscopic tests suggest that strong adsorption effect between Fe and AsIII, appropriate hydrogen evolution potential, and catalytic activity jointly promote efficient electroreduction of AsIII. Optimization based on electrode materials and electrolysis conditions, with high sensitivity, wide linear range (0.1-50 µg L-1), and excellent species selectivity, this paper offers an efficient and economic sample introduction method for trace AsIII/V selective atomic spectroscopy direct determination.

Highly sensitive analysis of trace germanium derived from the efficient electrosynthesis and spectral introduction of GeH4 on foam electrode.

BACKGROUND: The electrochemical hydride generation technology, which uses electrolysis instead of chemical reagents to generate reducing species to achieve gaseous transformation and sample introduction of the tested elements, has received widespread attention in the field of atomic spectroscopy due to its simple, economical, and green characteristics. However, limited by the effective area of the electrode, the introduction efficiency and spectral signal of most elements (e.g., germanium) in practical applications are lower than traditional chemical hydride generation. RESULTS: In this paper, an efficient electrochemical hydride generation (EHG) method based on metal foam electrode for µg L-1 level germanium was constructed. Systematic electrochemical and spectral tests showed that the low charge transfer resistance and the high electrochemical activity of nickel-based foam electrodes jointly promoted the efficient electroreduction of Ge(IV). Besides, the porous network structure of the metal foam material improves the contact probability of reactants while reducing the gas-evolution effect caused by bubble accumulation. Interestingly, adequate reaction sites are crucial for the conversion of germanium, but large foam electrodes are not always compatible with analytical performance. After coupling atomic fluorescence spectroscopy, this new electrolysis method has been proven to be suitable for efficient conversion and quantitative detection of Ge over a wide concentration range (5-150 µg L-1). SIGNIFICANCE: Our proposal to improve the electrosynthesis efficiency of germanane (GeH4) by using metal foam electrode is extremely effective for the detection of trace or ultra-trace germanium. The exploration of electrode material, structure, and especially effective area will also provide ideas for the establishment of highly sensitive analysis methods in the future.

A novel green analytical procedure for monitoring of azoxystrobin in water samples by a flow injection chemiluminescence method with off-line ultrasonic treatment.

A simple and green flow injection chemiluminescence (FI-CL) method for determination of the fungicide azoxystrobin was described for the first time. CL signal was generated when azoxystrobin was injected into a mixed stream of luminol and KMnO4 . The CL signal of azoxystrobin could be greatly improved when an off-line ultrasonic treatment was adopted. Meanwhile, the signal intensity increases with the analyte concentration proportionally. Several variables, such as the ultrasonic parameters, flow rate of reagents, concentrations of sodium hydroxide solution and CL reagents (potassium permanganate, luminol) were investigated, and the optimal CL conditions were obtained. Under optimal conditions, the linear range of 1-100 ng/mL for azoxystrobin was obtained and the detection limit (3σ) was determined as 0.13 ng/mL. The relative standard deviation was 1.5% for 10 consecutive measurements of 20 ng/mL azoxystrobin. The method has been applied to the determination of azoxystrobin residues in water samples.

Ultrasonic assisted magnetic solid phase extraction of ultra-trace mercury with ionic liquid functionalized materials.

Due to the agglomeration between particles, the inherent adsorption characteristics of magnetic powder materials are usually difficult to fully display. Taking ionic liquid functional materials as an example, the enrichment behavior of these adsorbents for trace mercury (Hg2+) in ultrasonic (US) assisted dispersion mode was systematically studied. The dissociation of protonic ionic liquids (IL) occur in the process of dispersion and the strong electrostatic attraction can improve the diffusion and adhesion of mercury on the adsorbent surface. Spectral measurement data showed that with the help of US, the more uniform dispersion of magnetic materials accelerated the adsorption of trace Hg2+. Ultrasonic intrinsic parameters such as frequency, power and radiation duration significantly affect the dispersion and apparent adsorption properties of magnetic functional materials. In the range of experimental parameters, the dye/paper image experimental results documents that there is a positive correlation between cavitation effect and ultrasonic frequency/power. The enrichment degree of fixed adsorbate (0.1 µg L-1) under high frequency (59 kHz) or high-power input (100%) is 1-2 times higher than that under low frequency (40 kHz) or low power (60%) input. This is a valuable conclusion for the subsequent study of US dispersion of magnetic and even non-magnetic powder materials. In addition, the in-situ desorption and accurate measurement of adsorbed mercury were realized by combining slurry vapor generation atomic fluorescence spectroscopy (SVG-AFS). The constructed US assisted magnetic solid phase extraction (US-MSPE) method has the characteristics of low detection limit (0.36 ng L-1), high recovery (>90%), sustainable utilization (>3) and reasonable measurement deviation (<5%), which can meet the requirements of ultra-trace Hg2+ (0.01-1.0 µg L-1).

Speciation of inorganic- and methyl-mercury in biological matrixes by electrochemical vapor generation from an L-cysteine modified graphite electrode with atomic fluorescence spectrometry detection.

A novel nonchromatographic speciation technique for ultratrace inorganic mercury (Hg(2+)) and methylmercury (CH(3)Hg(+)) in biological materials is developed and validated by electrolytic vapor generation (EVG) coupled with atomic fluorescence spectrometry (AFS). The studies show that CH(3)Hg(+) and Hg(2+) can be converted to Hg vapor efficiently on an l-cysteine modified graphite cathode, which has never been reported before. We observe that only Hg(2+) can be converted efficiently to Hg vapor at low current mode (0.2 A). While at high current mode (2.2 A), both CH(3)Hg(+) and Hg(2+) can be reduced efficiently. As a result, we successfully establish an exact and sensitive method based on the current control to detect mercury speciation for the first time. The factors of electrolytic conditions have been optimized, and the potential mechanism is discussed. Under the optimal conditions, the detection limits (3s) of Hg(2+) and CH(3)Hg(+) in aqueous solutions are 0.098 and 0.073 µg L(-1), respectively. The relative standard deviations for 6 replicate determinations of 2 µg L(-1) Hg are determined as 3.2% and 4.7% for Hg(2+) and CH(3)Hg(+). The accuracy of the method is verified through the analysis of certified reference materials (CRM, NRC-DORM-2), and the proposed method has been applied satisfactorily to the determination of mercury speciation in several seafood samples by calibration curve mode.

A novel electrooxidation vapor generation technique for the direct analysis of trace Os in ore/water samples.

All electrolytic vapor generation technologies are based on cathodic reduction, but this paper focuses on how to use anodic oxidation to realize the gaseous transformation of noble metal Os. Supported by RuO2-based dimensionally stable anode (DSA), we found that the conversion from trivalent/tetravalent Os to the OsO4 can be carried out continuously and stably, even at the µg L-1 level. Interestingly, there was a negative correlation between the conversion of OsO4 and the RuO2 content in the DSA. The decrease of oxygen absorption potential and the increase of current density suggest that the oxidation process of Os belongs to electrocatalytic behavior. The catalytic activity of the material has an obvious influence on the conversion of osmium while the formation of free radical may be crucial for the effective oxidation. Under the optimum conditions, this electrocatalytic synthesis of OsO4 combined with ICP-MS can realize the same effect of oxidation and detection of two osmium species [Os(III) and Os(IV)]. The proposed method exhibits a low limit of detection (5 pg kg-1), a wide linear range (0.1-100 µg L-1) and excellent anti-interference performance, which promotes the direct analysis of total Os in real ore samples without separation. Considering the catalytic activity of OsO4 in specific reactions, this green anodic electrosynthesis technology is also expected to provide more possibilities.

Ultrasound-assisted dispersive solid phase extraction for promoting enrichment of ng L-1 level Hg2+ on ionic liquid coated magnetic materials.

Herein, we investigated the enrichment behavior of inorganic mercury (Hg2+) on magnetic adsorbent with different ultrasound (US) energy field input. The enrichment rate of 0.10 µg L-1 mercury is increased by 4.5 times after US instead of stirring as dispersion mode. The input of higher frequency and power ultrasound can accelerate the enrichment of magnetic ionic liquid adsorbent and reduce the Hg2+ residue, importantly, which has not been reported. The positive correlation between cavitation effect and acoustic frequency and power in imaging experiments documents that US parameters are the key factors affecting the magnetic solid phase extraction. In addition, in-situ desorption and detection of adsorbate and recovery of adsorbent can be realized by slurry vapor generation (SVG) technology. The recovery of Hg2+ in four cycles is more than 90%, which indicates that the structure and properties of the material are not affected by the application of US. Hence, the degradation of adsorption properties caused by agglomeration of magnetic materials can be improved by introducing dispersion methods such as US. At the same time, 95% enrichment efficiency and 0.01-1.0 µg L-1 linear calibration range corresponding to 150 mL sample documents that magnetic ionic liquid adsorbent combined with US and sensitive spectral detector can meet the needs of ng L-1 level Hg2+ analysis in natural water samples.

Ultrasound enhanced solid-phase extraction of ultra-trace arsenic on Fe3O4@AuNPs magnetic particles.

Using ultrasound (US) to reduce the agglomeration of magnetic materials has attracted many researchers' attention in the field of magnetic solid phase extraction (MSPE). This paper showed that even the simple magnetic material (Fe3O4@AuNPs) can stimulate excellent arsenic (As) enrichment performance with the assistance of US. Compared with stirring dispersion, the extraction efficiencies of Fe3O4@AuNPs for 0.2 µg L-1 As(III) and As(V) improved by a factor of about 6.2- and 5.7-times with ultrasonic agitation, respectively. Importantly, when the ultrasonic frequency and power are varied within a certain range, the extraction efficiency was increased by about 50% and 130%, respectively. This effect of ultrasonic frequency and power on the enrichment of arsenic by magnetic materials has never been reported. The number, dispersion uniformity and energy released by the bursting of cavitation bubbles under different conditions are considered to be the main reasons for the above phenomena. Additionally, the As(III) or As(V) can be converted into a gaseous product by in-situ slurry chemical hydride generation (SCHG) technology, and the material adsorbed by the material can be effectively removed, thereby ensuring that the complex is repeated at least 5 times or more. Under the optimized conditions, the whole enrichment process can be shortened from ~1 h to several minutes in the presence of US. At the same time, the linear calibration range was 0.01-3.0 µg L-1 documenting that this US-assisted dispersive MSPE method coupled with a sensitive spectral detector (e.g. atomic fluorescence spectrometer, AFS) is suitable for analysis of inorganic As in natural water samples. The content of arsenic in five kinds of natural water samples ranged from 34 ng L-1 to 2.3 µg L-1.

Rapid extraction of arsenic species from traditional Chinese herbal by dual-frequency ultrasound-assisted enzymatic digestion prior to spectral analysis.

Considering the huge difference of biological toxicity, it is extremely significant to recognize the exact content of arsenic species in actual samples. In this paper, a novel pretreatment technique for the efficient extraction of arsenic species from herbal samples is developed by dual-frequency ultrasound-assisted enzymatic digestion (DUED). The preservation of arsenic original form, reduction of the actual analysis time, environmental friendliness and free-interference in subsequent detection make this method over the traditional method such as wet digestion, ashing and some solvent extraction technologies. The combination of DUED and atomic fluorescence spectrometry realize the speciation analysis of arsenic in traditional Chinese medicine. The optimizations of experimental parameters have been achieved, and the potential mechanism is discussed. The experimental data showed that cellulase is suitable for the digestion of herbal matrix than α-amylase and papain. Ultrasound can significantly increase the rate of enzymatic hydrolysis of biological molecules, especially under dual-frequency ultrasound irradiation. The highest relative extraction efficiency can be obtained by combining 40 kHz ultrasonic bath (UB) with 20 kHz ultrasonic probe (UP). Two certified reference materials [CRMs, GBW(E)090066 and GBW(E)090067] and four practical herbs were used to evaluate the accuracy and practicability of the method. Inorganic arsenic, including trivalent arsenic and pentavalent arsenic, was the main species in the four herbal samples.

Magnetic graphitic carbon nitride nano-composite for ultrasound-assisted dispersive micro-solid-phase extraction of Hg(II) prior to quantitation by atomic fluorescence spectroscopy.

A nanosheet structure of Fe3O4/g-C3N4 magnetic composite has been prepared and utilized as adsorbent for the ultrasound-assisted dispersive magnetic micro-solid-phase extraction of the ultra-trace inorganic mercury [Hg(II)]. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Fouries transform infrared spectroscopy images manifested that the hydrothermal systhesis promoted the binding of Fe3O4 particles with g-C3N4. The enrichment performance of composites depended on their compositions, and the recovery of Hg(II) on C-m30 (with Fe3O4/g-C3N4 mass ratio 2:3) was higher than that on other ratios. Recorded data showed that ultrasound wave was an effective method for reducing the agglomeration of magnetic materials and enhancing their adsorption properties. The Hg signal obtained by 80% power input is 3.2 times stronger than the signal by strring mode. X-ray diffraction characterization of the recovered adsorbent showed that g-C3N4 needed to be updated after repeated use for four times. In addition, competitive adsorption may be main factor affecting the inhibitory effect of high concentration methylmercury on inorganic mercury. Under the optimized conditions, the detection limit of the proposed method was 1.4 ng L-1 and relative standard deviation of 4.6% for 0.05 µg L-1 Hg(II) was obtained. The linear calibration range was 0.005-0.4 µg L-1. The accuracy of the method was verified through analysis of the certificated reference materials. The proposed method has been applied in the determination of inorganic Hg in natural water samples.

Dual-frequency ultrasound assisted-enzyme digestion coupled with atomic fluorescence spectrometry as a green and efficient tool for cadmium detection in rice flour samples.

A sample treatment technique based on a duel frequency ultrasonic device for enzymatic digestion of rice is reported. The ultrasonic device combines a high intensity ultrasonic probe and the temperature control function of ultrasonic water bath, which can effectively extract cadmium from rice within only 160 s under the optimized conditions. Compared with the traditional ultrasonic assisted enzymatic digestion, the new method not only shortens the time significantly (e.g., from the 90 min of ultrasonic water bath to the present few minutes), but also increases the extraction efficiency of cadmium (such as ~ 75% from ultrasonic probe to app. 100%). Through the optimization of ultrasonic mode, ultrasonic frequency, power and the type of enzyme, we found that enzyme played a dominant role in ultrasound assisted enzymatic digestion. Compared with a-amylase and pepsin, trypsin is more suitable for the extraction of cadmium from rice. Furthermore, ultrasound energy is beneficial to enzymatic hydrolysis of bimolecular, and this promotion is related to the frequency of ultrasound. The reliability of this method was evaluated by analyzing the content of cadmium in the certified reference materials (CRMs, GBW10045, GBW08510, GBW08511 and GBW08512) based on atomic fluorescence spectrometry combined with a modified chemical vapor generation. The proposed method has been applied satisfactorily in the determination of Cd in several rice samples.

Fabrication of a porous hydrangea-like Fe3O4@MnO2 composite for ultra-trace arsenic preconcentration and determination.

Fe3O4@MnO2 magnetic composite microsphere with hierarchical shells structure has been synthesized through a facile two-step hydrothermal reaction for ultra-trace arsenic enrichment. Scanning electron microscopy and transmission electron microscopy images clearly indicated that the as-synthesized material is a porous hydrangea-like morphology, as well as the size of the composite microspheres and the widths of pore are related to the reaction conditions. The N2 adsorption-desorption isotherms demonstrated that the specific surface areas and pore volume of Fe3O4@MnO2 with 8 h hydrothermal synthesis are 121.9260 m2 g-1 and 0.21 cm3 g-1, respectively. The enrichment performance of composites depends on their compositions, and the recovery of As(III) on Fe3O4@MnO2 with Mn/Fe ratio 1:2 was 1-2.3 times of that on other ratios. In comparison with As(V), experimental data indicated that the prepared composites have faster adsorption rate for As(III). In addition, slurry sampling chemical hydride generation technology can effectively remove and reduce the adsorbed As(III) or As(V) to the gaseous product, thus ensuring that the composite is at least repeated over 5 times. Under the optimized conditions, the detection limit of the proposed method was 2.9 ng L-1 and relative standard deviation of 4.8% for 0.1 µg L-1 As(III) was obtained. The linear calibration range was 0.01-1.5 µg L-1. The accuracy of the method was verified through analysis of the certificated reference materials. The proposed method has been applied to the determination of inorganic As in natural water samples.

Highly efficient electrocatalytic vapor generation of methylmercury based on the gold particles deposited glassy carbon electrode: A typical application for sensitive mercury speciation analysis in fish samples.

A gold particle deposited glassy carbon electrode (Au/GCE) was first used in electrochemical vapor generation (ECVG) technology and demonstrated to have excellent catalytic property for the electrochemical conversion process of aqueous mercury, especially for methylmercury (CH3Hg+), to gaseous mercury. Systematical research has shown that the highly consistent or distinct difference between the atomic fluorescence spectroscopy signals of CH3Hg+ and Hg2+ can be achieved by controlling the electrolytic parameters of ECVG. Hereby, a new green and accurate method for mercury speciation analysis based on the distinguishing electrochemical reaction behavior of Hg2+ and CH3Hg+ on the modified electrode was firstly established. Furthermore, electrochemical impedance spectra and the square wave voltammetry displayed that the ECVG reaction of CH3Hg+ may belong to the electrocatalytic mechanism. Under the selected conditions, the limits of detection of Hg2+ and CH3Hg+ are 5.3 ng L-1 and 4.4 ng L-1 for liquid samples and 0.53 pg mg-1 and 0.44 pg mg-1 for solid samples, respectively. The precision of the 5 measurements is less than 6% within the concentration of Hg2+ and CH3Hg+ ranging from 0.2 to 15.0 µg L-1. The accuracy and practicability of the proposed method was verified by analyzing the mercury content in the certified reference material and several fish as well as water samples.

Sensitive determination of Se(IV) and tSe in rice and water samples using L-cysteine modified carbon paste electrode-based electrolytic hydride generation and atomic fluorescence spectrometry analysis.

This work illustrates an accurate method for determination of Se by electrolytic hydride generation technique based on a novel carbon paste electrode for sample introduction combined with atomic fluorescence spectral analysis. The studies show that Se(IV) can be converted efficiently to SeH2 on an L-cysteine modified carbon paste electrode (CMCPE), which has never been reported before. Significantly, generation from Se(IV) implies that the use of carbon paste electrode-based electron-induced hydride generation system to achieve efficiency is almost 90% to that obtained by chemical hydride generation, and the response obtained from CMCPE is 2 and 3 times of that from the Pb and graphite electrode, respectively. Results also display that the lifetime and the stability of the CMCPE is superior to that of L-cysteine ornamented graphite electrode fabricated by covalently bonding. Under the optimal conditions, a low concentration limit of detection 0.065µgL-1 of Se(IV) is achieved. The repeatability denoted as % RSD is 2.2% for 1.0µgL-1 Se(IV). The utility of the studied method is compared with certified reference materials as well as several edible samples. The advantages and limitations of this method, compared with existing techniques, are also discussed.

Selective and sensitive determination of As(III) and tAs in Chinese herbal medicine samples using L-cysteine modified carbon paste electrode-based electrolytic hydride generation and AFS analysis.

A novel non-chromatographic speciation technique for ultra-trace arsenite [As(III)] and total arsenic (tAs) in Chinese herbal medicine (CHM) is developed and validated by electrolytic hydride generation (EHG) coupled with atomic fluorescence spectrometry (AFS). The studies show that As(III) can be converted efficiently to AsH3 on an L-cysteine modified carbon paste electrode (CMCPE), which has never been reported before. Significantly, other arsenic species such as arsenate [As(V)], monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) do not form any or only less volatile hydrides at low applied current mode (<1.0 A). The results also demonstrate that L-cysteine and graphite powder play different roles in the electrolytic generation of AsH3. Comparing with the traditional graphite electrode, CMCPE has better stability, sensitivity and interference tolerance. Under the optimal conditions, the limit of detection (LOD) of tAs and As(III) for this method are 0.087µgL-1 and 0.095µgL-1 respectively. The accuracy of the method is verified through the analysis of reference materials (CRM 08231 and SRM1568a), and the proposed method has been applied satisfactorily to the determination of As(III) and tAs in several CHM samples.

Evaluation of Pyridaben Residues on Fruit Surfaces and Their Stability by a Novel On-Line Dual-Frequency Ultrasonic Device and Chemiluminescence Detection.

In this paper, we first report the development of a highly sensitive and economical method for accurate analysis of pyridaben residues on fruits based on dual-frequency ultrasonic treatment (DFUT) and flow injection chemiluminescence (CL) detection. The DFUT device is made by integrating an ultrasonic bath with an ultrasonic probe. Two quartz glass coils (QGC) with different structures have been designed and applied to evaluate the function of DFUT in the detection process. Recorded data showed that DFUT is an effective method for improving the pyridaben CL signal. The signal of pyridaben in response to DFUT is 2.0-3.3 times stronger than the response to only the ultrasonic probe at 20 kHz or the ultrasonic bath at 40 kHz. In addition, the response obtained from the concentric circle QGC is 2.1 times stronger than the response to the spiral tube QGC. Under the optimized condition, the proposed method has advantages, such as a wide linear range (0.8-100.0 µg L-1), a high sensitivity (limit of detection of 0.085 µg L-1), and good stability (RSDs ≤ 4.7% in the linear range) for pyridaben determination. We apply this method to monitor the residue pyridaben on some fruits. The data show that the maximum amounts of the residue on fruit surfaces after soaking in water (50 mg L-1, 5 min) are 0.583 mg kg-1 (apple), 0.794 mg kg-1 (orange), and 0.351 mg kg-1 (pear). However, the concentration of pyridaben in the presence of sunlight decreases rapidly, showing its poor light stability.