M. H. Yang

New method of gold-film electrode preparation for anodic stripping voltammetric determination of arsenic (III and V) in seawater

A new method of efficient rotating gold-film glassy-carbon electrode preparation prior to the determination of As(III) and As(V) in seawater by anodic stripping voltammetry (ASV) is described. Factors affecting sensitivity and precision including pH, deposition time and potential, rotation and scan rate, and the nature of working electrode were investigated. Electroinactive As(V) was reduced to As(III) by gaseous SO(2) prior to ASV determination. For a deposition time of 4 min the determination limit was approximately 0.19 ppb. Precision of the proposed method was very good (RSD=2-0.6% at 1-5 ppb) and a relatively good accuracy determined by analysis of certified reference seawater (CASS-1) and seawater samples spiked with an arsenic standard solution, was also obtained.

The chemical fate of the Cd/Se/Te-based quantum dot 705 in the biological system: toxicity implications

QD705 is a cadmium/selenium/tellurium (Cd/Se/Te)-based quantum dot with good potential for biomedical applications. Although the biological fate of QD705 is established, its chemical fate in the biological system is still unknown. Since the chemical nature of Cd in QD705 (either stays as bounded Cd or becomes free Cd) is closely related to the toxicity of this nanocrystal, information on its chemical fate is critically needed. In this study we investigated the chemical fate of QD705 in the kidneys of mice. We used the molar ratio of Cd and Te (increased Cd/Te ratio signifies increased Cd release from QD705) and the induction of tissue metallothionein (MT) as markers for elevated free Cd in tissues. Our study indicated that 100% of QD705 (measured as Cd) was still retained in the body 16 weeks after exposure, with significant time redistribution to the kidneys. Furthermore, there were an elevation in both the molar Cd/Te ratio and MT-1 expression in the kidneys, suggesting that free Cd was released from QD705. Thus QD705 is not as stable or biologically inert as many may have once believed. Our study demonstrated that free Cd indeed can be released from QD705 in the kidneys and increases the risk of renal toxicity.

Arsenic, selenium, and zinc in patients with blackfoot disease

Blackfoot disease is a peripheral vascular disease resulting in gangrene of the lower extremities. Extensive epidemiological study implicates that high arsenic content in artesian well water is the responsible causal factor of the disease. In the present study the concentrations of arsenic, selenium, and zinc in the body fluids and hair of patients with Blackfoot disease, in comparison to age- and sex-matched normal controls, are investigated. Two analytical techniques that include atomic absorption spectrometry and neutron activation analysis were used for the analysis of urine, serum, hair, and whole blood. The analytical results indicate that hair arsenic of the patients is significantly higher than that of the controls, but still below the critical value of 1 μg/g. In addition, the patients showed significantly lower concentrations of Se and Zn in the urine and blood than the normal controls. The possible connection of these elements with the etiology of the disease is discussed.

The use of radioactive zinc oxide nanoparticles in determination of their tissue concentrations following intravenous administration in mice

The increasing uses of zinc oxide nanoparticles (ZnONPs) in coatings, paints, personal care products and many other products increase the possibility of the bodys exposure to ZnONPs. Accurate and quantitative profiling on the tissue distribution and body clearance of ZnONPs, which is an important factor to clarify the acute and chronic safety concerns of ZnONPs, is interfered by the abundance of the bodys endogenous zinc moiety. In this report, radioactive zinc oxide nanoparticles (R-ZnONPs) generated from neutron activation were employed for the in vivo bio-distribution studies using mice as the animal model. Gamma-ray emitting radioactive R-ZnONPs were produced from neutron activation. Zeta potentials of the ZnONPs before and after the neutron irradiation remained about the same, and R-ZnONPs largely remained its original nano-particulate form after neutron irradiation. After intravenous administration into ICR mice, R-ZnONPs exhibited a primary retention in lung (43.6% injected dose (ID)/g tissue wet weight) for the first hour and began to be translocated to intestinal tract for feces excretion at a later stage. This type of labeling free and radioactive nanoparticles retains the surface property and can be a convenient protocol for studying bio-distribution of nanoparticles in pristine chemical form.

Automated, continuous, and dynamic speciation of urinary arsenic in the bladder of living organisms using microdialysis sampling coupled on-line with high performance liquid chromatography and hydride generation atomic absorption spectrometry

An on-line and fully automated method was developed for the continuous and dynamic in vivo monitoring of four arsenic species [arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA)] in urine of living organisms. In this method a microdialysis sampling technique was employed to couple on-line with high performance liquid chromatography (HPLC) and hydride generation atomic absorption spectrometry (HGAAS). Dialysates perfused through implanted microdialysis probes were collected with a sample loop of an on-line injector for direct and automated injection into HPLC system hyphenated with HGAAS. The saline (0.9% NaCl) solution was perfused at the rate of 1 microl min(-1) through the microdialysis probe and the dialysate was loaded into 50 microl of sample loop. The separation conditions were optimally selected to be in phosphate buffer solution at a pH 5.2 with a flow rate of 1.2 ml min(-1). The effluent from the HPLC was first mixed on-line at the exit of the column with HCl (1 M) solution and then mixed with a NaBH4 (0.2% m/v) solution. Based on the optimal conditions obtained, linear ranges of 2.5-50 ng ml(-1) for AsIII and 6.75-100 ng ml(-1) for the other three arsenic species were obtained. Detection limits of 1.00, 2.18, 1.03 and 2.17 ng ml(-1) were obtained for AsIII, DMA, MMA and AsV, respectively. Typical precision values of 3.4% (AsIII), 5.4% (DMA), 3.6% (MMA) and 7.5% (AsV) were obtained, respectively, at a 25 ng ml(-1) level. Recoveries close to 100%, relative to an aqueous standard, were observed for each species. The average in vivo recoveries of AsIII, DMA, MMA and AsV in rat bladder urine were 56+/-5%, 60+/-9%, 49+/-3% and 55+/-7%, respectively. The use of an on-line microdialysis-HPLC-HGAAS system permitted the determination of four urinary arsenic species in the bladder of an anesthetized rat with a temporal resolution of 50 min sampling.

Spectrophotometric determination of trace and ultratrace levels of boron in silicon and chlorosilane samples

SummarySpectrophotometric methods for the determination of boron in the low μg/g and ng/g range in high-purity silicon and dichloro- and trichlorosilanes were investigated in detail. The procedures established involve dissolution of silicon samples and the hydrolyzed products of chlorosilane samples in hydrofluoric acid-containing reagents followed by evaporation of the silicon matrix as H2SiF6. The boron retained in the treated sample solution was then determined by a spectrophotometric method using carminic acid as a chromatic reagent. Special effort has been paid to the control of the analytical blank and reproducible determination of boron. The results indicate that addition of mannitol and proper control of the evaporation process are effective in preventing volatilization of boron during the evaporation of silicon matrix and can thus attain high recovery of boron and reproducible analysis. Through meticulous control of the analytical blank and experimental conditions, the limit of detection for boron determination with the established method can be as low as ng/g levels. Application of the methods to the determination of boron in various stages of purification of silicon and trichlorosilane as well as in borophosphosilicate film was conducted.

Direct impurity analysis of semiconductor photoresist samples with laser ablation ICP-MS

A high-throughput method involving laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was developed for the determination of critical elements in semiconductor photoresist samples. An innovative procedure, including a sequence of spiking, mixing, spin-coating, and baking, was developed for the preparation of photoresist film standards to be used for calibration in the direct analytical process. The homogeneity of the photoresist sample was then evaluated using the radiotracer technique, and the effects of silicon substrate reflection, spin rate and baking temperature on the signal response of the analytes in the photoresist film were subsequently studied. The results indicated that sample pretreatment conditions (i.e., spin rate and baking temperature) strongly influenced the signal intensity. The signal variations with respect to photoresist thickness, due to the changes in spin rate, could be corrected by using an internal standard, while those due to the changes in baking temperature could not. Visual evidence of shock-wave motion, via a laser induced plasma, on the photoresist film was presented in the SEM images using a Nd-YAG laser in the Q-switched mode. For direct determination of impurities in photoresist samples, various calibration methods, including a matrix-matched external calibration curve, an internal standard with the major matrix element (i.e., carbon), and an internal standard with metal spiking (i.e., Co and Tl), were evaluated independently. The recoveries of spike metals (Al, Cu, Pt, Au, Th and U) ranged from 81 to 112%, with detection limits in the 20–285 ng mL−1 range for all elements except Al. The analytical throughput of the developed method was up to 12 samples per hour.

Trace Elements in Hair of Blackfoot Disease

Blackfoot disease is a peripheral vascular disease resulting in gangrene of the lower extremities. Though extensive epidemiological study has implicated that high arsenic content in artesian well water of the endemic area, bears some important connection with the disease, the etiology of the disease is still unknown. In this study, attention is paid to multielement determination in order to find out whether the trace elements in hair of Blackfoot disease patients are different from those of the controls.Experimental results indicate that the concentrations of As and Se in hair of patients are significantly higher than those of the controls, but Ca and Zn are significantly lower than those of the controls. The possible connection of these elements with the etiology of the disease is discussed.

Determination of major, minor and trace elements in urinary stones by neutron activation analysis

In five kinds of human urinary stones 18 elements have been identified by instrumental neutron activation analysis (INAA). From the results it may be concluded that calcium is the most important initiating cation, magnesium is the second most significant one, and Na, Cl, Sr, Zn, Fe, Br and Co may also play an important role in the stone formation. The results indicate also that ions like Ca, Br and Cu are easily incorporated into the nucleus to form a urate stone; Mg and Sr, into the nucleus to form a magnesium ammonium phosphate stone; and Zn, into the nucleus to form a calcium oxalate combined with apatite stone. The differences in elemental composition among the different kinds of stones as well as across the layers of stones are statistically evaluated.

Development of an on-line isotope dilution laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method for determination of boron in silicon wafers

A method has been developed based on an on-line isotope dilution technique couple with laser ablation/inductively coupled plasma mass spectrometry (LA-ICP-MS), for the determination of boron in p-type silicon wafers. The laser-ablated sample aerosol was mixed on-line with an enriched boron aerosol supplied continuously using a conventional nebulization system. Upon mixing the two aerosol streams, the isotope ratio of boron changed rapidly and was then recorded by the ICP-MS system for subsequent quantification based on the isotope dilution principle. As an on-line solid analysis method, this system accurately quantifies boron concentrations in silicon wafers without the need for an internal or external solid reference standard material. Using this on-line isotope dilution technique, the limit of detection for boron in silicon wafers is 2.8x10(15)atomscm(-3). The analytical results obtained using this on-line methodology agree well with those obtained using wet chemical digestion methods for the analysis of p-type silicon wafers containing boron concentrations ranging from 1.0x10(16) to 9.6x10(18)atomscm(-3).