Yuh-Chang Sun

Solid-phase microextraction for determining the distribution of sixteen US Environmental Protection Agency polycyclic aromatic hydrocarbons in water samples

A solid-phase microextraction (SPME) procedure has been developed for the determination of 16 US Environmental Protection Agency promulgated polycyclic aromatic hydrocarbons (PAHs). Five kinds of SPME fibers were used and compared in this study. The extracted sample was analyzed by gas chromatography with flame ionization detection or mass spectrometry. Parameters affecting the sorption of analyte into the fibers, including sampling time, thickness of the fiber coating, and the effect of temperature, have been examined. Moreover, the feasibility of headspace SPME with different working temperatures was evaluated. The method was also applied to real samples. The 85-microm polyacrylate (PA) and 100-microm poly(dimethylsiloxane) (PDMS) fibers were shown to have the highest affinities for the selected PAHs. The PA fiber was more suitable than the PDMS fiber for the determination of low-ring PAHs while high sensitivity of high-ring PAHs was observed when a 100-microm PDMS fiber was used. The method showed good linearity between 0.1 and 100 ng/ml with regression coefficients ranging from 0.94 to 0.999. The reproducibility of the measurements between fibers was found to be very good. The precisions of PA and PDMS fibers were from 3 to 24% and from 3 to 14%, respectively. Headspace SPME is a valid alternative for the determination of two- to five-ring PAHs. A working temperature of 60 degrees C provides significant enhancement in sensitivity of two- to five-ring PAHs having low vapor pressures (>10(-6) mmHg at 25 degrees C) (1 mmHg = 133.3 Pa) and low Henrys constants (>10 atm ml/mol) (1 atm = 1.01 x 10(5) Pa).

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.

Direct determination of molybdenum in seawater by adsorption cathodic stripping square-wave voltammetry

A reliable and very sensitive procedure for the determination of trace levels of molybdenum in seawater is proposed. The complex of molybdenum with 8-hydroxyquinoline (Oxine) is analyzed by cathodic stripping square-wave voltammetry based on the adsorption collection onto a hanging mercury drop electrode (HMDE). This procedure of molybdenum determination was found to be more favorable than differential pulse cathodic stripping voltammetry because of inherently faster scan rate and much better linearity obtained through the one-peak (instead of one-of-two peaks) calibration. The variation of polarographic peak and peak current with a pH, adsorption time, adsorption potential, and some instrumental parameters such as scan rate and pulse height were optimized. The alteration of polarographic wave and its likely mechanism are also discussed. The relationship between peak current and molybdenum concentration is linear up to 150 mug l(-1). Under the optimal analytical conditions, the determination limit of 0.5 mug l(-1) Mo was reached after 60 s of the stirred collection. The estimated detection limit is better than 0.1 mug l(-1) of Mo. The applicability of this method to analysis of seawater was assessed by the determination of molybdenum in two certified reference seawater samples (CASS-2 and NASS-2) and the comparison of the analytical results for real seawater samples (study on a vertical distribution of Mo in the seawater column) with the results obtained by Zeeman-corrected electrothermal atomization atomic absorption spectrometry (Zeeman ETAAS). A good agreement between two used methods of molybdenum determination was obtained.

Characterization and composition of heavy metals and persistent organic pollutants in water and estuarine sediments from Gao-ping River, Taiwan.

The objective of this study was to determine the concentrations and possible sources of heavy metals and persistent organic pollutants (POPs) in water and estuarine sediments from Gao-ping River in order to evaluate the environmental quality of aquatic system in southern Taiwan. High concentrations of heavy metals including Cr, Zn, Ni, Cu and As, ranging from 10.7 to 180 mg/kg-dry weight (dw), were detected in sediments from Gao-ping River. When normalized to the principal component analysis (PCA), swinery and electroplating wastewaters were found to be the most important pollution sources for heavy metals. Of various organochlorine pesticide (OCP) residues detected, aldrin and total-hexachlorocyclohexane (HCH) were frequently found in sediments. The total concentrations of OCPs were in the range 0.47-47.4 ng/g-dw. Also, the total-HCH, total-cyclodiene, and total-dichlorodiphenyltrichloroethane (DDT) were in the range 0.37-36.3, 0.21-19.0, and 0.44-1.88 ng/g-dw, respectively. The polychlorinated biphenyl (PCB) concentrations in sediments from Gao-ping River ranged between 0.37 and 5.89 ng/g-dw. The PCB concentrations are positively correlated to the organic contents of the sediment particles. alpha-HCH was found to be the dominant compound of HCH in the sediments, showing that long-range transport may be the possible source for the contamination of HCH in sediments from Gao-ping River. In summary, trace amounts of POPs in estuarine sediments from Gao-ping River were detected, showing that there still exist a wide variety of POP residues in the river sediments in Taiwan. These POP residues may be mainly from long-range transport and weathered agricultural soils, while heavy metal contamination is primarily from the swinery and industrial wastewaters.

Magnetic nano-adsorbent integrated with lab-on-valve system for trace analysis of multiple heavy metals

A novel system for trace analysis of multiple heavy metals was developed wherein we have integrated a magnetic nano-adsorbent with a lab-on-valve system and coupled this to an inductively coupled plasma mass spectrometer. The magnetic nano-adsorbent was prepared by surface modification of iron-based magnetic nanoparticles with polyacrylic acid (MNPs-PAA). The MNPs-PAA possessing the superparamagnetic nature of MNPs could be controllably immobilized in PTFE tubing by an external magnetic force. The high surface density of PAA (3.30 × 1011 molecules cm−2) on MNPs-PAA significantly reduced the amounts of adsorbent needed for adsorption of heavy metals (Mn2+, Co2+, Cu2+, Zn2+, and Pb2+). A detection limit of 0.04–0.06 µg L−1 (except 0.6 µg L−1 for Cu2+ and Zn2+), a precision smaller than 4% (RSD, n = 3), and a linear range of 0.5–50 µg L−1 were obtained by directly injecting an aliquot of 20 µL fortified standard solution analyzed at 5 min per sample. The accuracy was evaluated by analyzing certified reference materials of SRM 2670a (trace elements in urine, low level) and CASS-2 (nearshore seawater reference material for trace metals). Good agreement between the measured and certified values demonstrated that the system is useful for trace analysis of multiple heavy metals in environmental and biological aqueous samples. The potential of integrating functionalized nano-materials to improve the performance of existing analytical systems as an alternative approach to green analytical chemistry is foreseen.

Comparative determination of Ba, Cu, Fe, Pb and Zn in tea leaves by slurry sampling electrothermal atomic absorption and liquid sampling inductively coupled plasma atomic emission spectrometry

The comparative determination of barium, copper, iron, lead and zinc in tea leaf samples by two atomic spectrometric techniques is reported. At first, slurry sampling electrothermal atomization atomic absorption spectrometry (ETAAS) was applied. The results of Ba and Pb determination were calculated using the method of standard additions, and results of Cu, Fe and Zn from the calibration graphs based on aqueous standards. These results were compared with the results obtained after microwave-assisted wet (nitric+hydrochloric+hydrofluoric acids) digestion in closed vessels followed by inductively coupled plasma-atomic emission spectrometric (ICP-AES) determination with the calibration by means of aqueous standards. The exception was lead determined after a wet digestion procedure by ETAAS. The accuracy of the studied methods was checked by the use of the certified reference material Tea GBW-07605. The recoveries of the analytes varied in the range from 91 to 99% for slurry sampling ETAAS, and from 92.5 to 102% for liquid sampling ICP-AES. The advantages of slurry sampling ETAAS method are simplicity of sample preparation and very good sensitivity. Slurry sampling ETAAS method is relatively fast but if several elements must be determined in one sample, the time of the whole microwave-assisted digestion procedure and ICP-AES determination will be shorter. However, worse detection limits of ICP-AES must also be taken into the consideration in a case of some analytes.

Determination of antimony(III,V) in natural waters by coprecipitation and neutron activation analysis

Abstract A simple and quantitative method for separating antimony(III) from antimony(V) by coprecipitation with thionalide is described. The total concentration of antimony is determined through addition of tin(II) chloride followed by thionalide coprecipitation and antimony(V) is determined by substraction. The coprecipitation system was investigated with the use of 122 Sb radiotracer. The precipitate was collected on a membrane filter for neutron activation analysis. The dectection limit of antimony was found to be in the order of ng l −1 under the experimental conditions. The reliability was checked with National Research Council of Canada standard reference material.

Determination of methylmercury and inorganic mercury by coupling short-column ion chromatographic separation, on-line photocatalyst-assisted vapor generation, and inductively coupled plasma mass spectrometry

We have combined short-column ion chromatographic separation and on-line photocatalyst-assisted vapor generation (VG) techniques with inductively coupled plasma mass spectrometry to develop a simple and sensitive hyphenated method for the determination of aqueous Hg(2+) and MeHg(+) species. The separation of Hg(2+) and MeHg(+) was accomplished on a cation-exchange guard column using a glutathione (GSH)-containing eluent. To achieve optimal chromatographic separation and signal intensities, we investigated the influence of several of the operating parameters of the chromatographic and photocatalyst-assisted VG systems. Under the optimized conditions of VG process, the shortcomings of conventional SnCl(2)-based VG techniques for the vaporization of MeHg(+) was overcome; comparing to the concentric nebulizer-ICP-MS system, the analytical sensitivity of ICP-MS toward the detection of Hg(2+) and MeHg(+) were also improved to 25- and 7-fold, respectively. With the use of our established HPLC-UV/nano-TiO(2)-ICP-MS system, the precision for each analyte, based on three replicate injections of 2 ng/mL samples of each species, was better than 15% RSD. This hyphenated method also provided excellent detection limits--0.1 and 0.03 ng/mL for Hg(2+) and MeHg(+), respectively. A series of validation experiments--analysis of the NIST 2672a Standard Urine Reference Material and other urine samples--confirmed further that our proposed method could be applied satisfactorily to the determination of inorganic Hg(2+) and MeHg(+) species in real samples.

Three-dimensional printed sample load/inject valves enabling online monitoring of extracellular calcium and zinc ions in living rat brains.

We have developed a simple and low-cost flow injection system coupled to a quadruple ICP-MS for the direct and continuous determination of multi-element in microdialysates. To interface microdialysis sampling to an inductively coupled plasma mass spectrometer (ICP-MS), we employed 3D printing to manufacture an as-designed sample load/inject valve featuring an in-valve sample loop for precise handling of microliter samples with a dissolved solids content of 0.9% NaCl (w/v). To demonstrate the practicality of our developed on-line system, we applied the 3D printed valve equipped a 5-μL sample loop to minimize the occurrence of salt matrix effects and facilitate an online dynamic monitoring of extracellular calcium and zinc ions in living rat brains. Under the practical condition (temporal resolution: 10h(-1)), dynamic profiling of these two metal ions in living rat brain extracellular fluid after probe implantation (the basal values for Ca and Zn were 12.11±0.10mg L(-1) and 1.87±0.05μg L(-1), respectively) and real-time monitoring of the physiological response to excitotoxic stress elicited upon perfusing a solution of 2.5mM N-methyl-d-aspartate were performed.

Fully 3D-Printed Preconcentrator for Selective Extraction of Trace Elements in Seawater.

In this study, we used a stereolithographic 3D printing technique and polyacrylate polymers to manufacture a solid phase extraction preconcentrator for the selective extraction of trace elements and the removal of unwanted salt matrices, enabling accurate and rapid analyses of trace elements in seawater samples when combined with a quadrupole-based inductively coupled plasma mass spectrometer. To maximize the extraction efficiency, we evaluated the effect of filling the extraction channel with ordered cuboids to improve liquid mixing. Upon automation of the system and optimization of the method, the device allowed highly sensitive and interference-free determination of Mn, Ni, Zn, Cu, Cd, and Pb, with detection limits comparable with those of most conventional methods. The systems analytical reliability was further confirmed through analyses of reference materials and spike analyses of real seawater samples. This study suggests that 3D printing can be a powerful tool for building multilayer fluidic manipulation devices, simplifying the construction of complex experimental components, and facilitating the operation of sophisticated analytical procedures for most sample pretreatment applications.