[Indirect Photodegradation of Sulfamethoxazole in Water].

Indirect photodegradation is one of the primary approaches for the removal of pharmaceutical contaminants from water. This degradation process is dominated by chromophoric dissolved organic matter (CDOM). After illumination, CDOM produces many reactive intermediates, which can react with drug pollutants to achieve indirect photodegradation. In this article, we focused on four different sources of CDOM and factors affecting indirect sulfamethoxazole (SMZ) photolysis. The results show that the indirect photodegradation effect of SMZ is significantly influenced by CDOM. This indirect photodegradation has a dual nature. It promotes the indirect photodegradation of SMZ through the formation of various reactive intermediates and at the same time inhibits the photodegradation of SMZ through light shielding and masking of reactive intermediates. The indirect photodegradation of SMZ is mainly controlled by active intermediates such as 3CDOM*, HO·, and 1O2 produced by CDOM; 3CDOM* is the main participant in indirect photodegradation of SMZ. In addition, the pH, salinity, and nitrate ions have a significant effect on the indirect photodegradation of SMZ, while bicarbonate ions have no significant effect on the indirect photodegradation of SMZ.

[Assessment of the Spatial-temporal Distribution Characteristics and Main Affecting Factors of Chromophoric Dissolved Organic Matter in Spring and Summer at the Changjiang Estuary and Adjacent Areas].

The composition and distribution characteristics of chromophoric dissolved organic matter(CDOM) of Changjiang Estuary and its adjacent waters in spring (March 2015) and summer (July 2015) were evaluated by excitation-emission matrix spectroscopy (EEMs) in combination with parallel factor(PARAFAC) analysis. Three humic-like components[C1(370/495 nm),C2(330/405 nm),C3(365/440 nm)] and one protein-like component[C4(295/345 nm)] were identified. The distribution patterns of the four components in spring and summer were almost the same, showing a decreasing trend from Changjiang Estuary to adjacent waters. In spring, the high value areas of three humic-like components were located inside of Changjiang Estuary, and the high value areas of the protein-like component were located in the South Passage of Changjiang Estuary. In the surface layer, the CDOM was mainly from terrestrial input and human activities; the influence of terrestrial weakened in the middle layer because of the lower fluorescence intensity values; and in the bottom layer the fluorescence values were higher than those in the middle layer, which was caused by sediment resuspension. There were high value areas in the Daishan Island, which were related to human activities. In summer, the high value areas of CDOM were almost the same as those in spring, and all layers had similar fluorescence intensity values, which indicated that they were mixed evenly. CDOM in spring and summer had high humification index (HIX) values in the Changjiang Estuary, whereas for biological index (BIX), its high values appeared in the adjacent waters. Four components (C1-C4), a355 and DOC, TN, TP, DO, Chl-a, Salinity were evaluated by redundancy analysis (RDA), which indicated that C1-C4 and TN, TP were mainly affected by terrestrial input and human activities, and DOC was affected by terrestrial and marine source together. The use of EEMs-PARAFAC in combination with multivariate analysis to parse the composition of CDOM revealed the source of CDOM and main influencing factors in Changjiang Estuary and adjacent waters, and plays an important role in the biogeochemical research of biogenic elements in estuarine waters.

[Distribution Characteristics of Chromophoric Dissolved Organic Matter and Nutrients from the Yellow Sea and Bohai Sea in Autumn].

Water samples were collected from the Yellow and Bohai seas during November 2013 and the chromophoric dissolved organic matter (CDOM) and nutrients concentrations were investigated, including their composition, source and distribution characteristics. CDOM was analyzed by excitation-emission matrix spectroscopy (EEMS) in combination with a parallel factor analysis (PARAFAC). Three terrestrial humic-like substances (C1, C2, and C3) and one protein-like (C4) substances were identified. The three terrestrial humic-like components had a similar horizontal distribution, decreasing from inshore to offshore. The protein-like component, showed higher values for both inshore and offshore areas in the Yellow Sea at the surface layer and the middle layer of the Bohai Sea, while in other layers it had a similar distribution pattern as the terrestrial humic-like components. In the Bohai Sea, the dissolved inorganic nitrogen (DIN) concentration showed a decreasing trend from inshore to offshore areas and the concentration of dissolved inorganic phosphorus (DIP) gradually decreased from the Caofeidian coastal and central areas to other adjacent areas. The dissolved organic nitrogen (DON) showed an increasing from inshore to the central area of the Bohai Sea. DIN and DON were higher in surface layer than in the bottom layer and for DIP this was the opposite in the Bohai Sea. In the Yellow Sea, DON concentrations showed a decreasing trend from inshore to offshore areas. DIN and DIP had higher concentrations at inshore areas in the surface and middle layers, while in the bottom layer they had higher concentrations in offshore areas. The vertical distribution of the DIN and DIP showed higher values in the bottom layer than surface layers and for DON this was the opposite. These results also showed that the concentrations of DIN, DON, and DIP in the Bohai sea were overall higher than the Yellow Sea. A discriminant analysis was performed through redundancy analysis (RAD) of these water quality parameters, including the four fluorescent components, an absorption coefficient (a355), chlorophyll a concentration, conductivity, dissolved oxygen (DO), dissolved organic carbon (DOC), DIN, DON, and DIP. The RDA indicated that the four fluorescent components are mainly affected by terrestrial inputs. DOC was affected by both terrestrial and marine sources but terrestrial inputs were the major contributor. It was also indicated that the DIN concentration was affected by terrestrial inputs in the Bohai Sea area and by both terrestrial and marine sources in the Yellow Sea. DON concentrations were mainly affected by marine sources in the Bohai Sea and terrestrial inputs in the Yellow Sea. DIP concentrations were affected by both terrestrial and marine sources in the studied areas.

Absorption and Fluorescence Properties of Chromophoric Dissolved Organic Matter Produced by Algae.

Four kinds of diatom (Chaetoceros curvisetus, Phaeodactylum tricornutum, Nitzschia closterium f. minutissima and Navicula halophile) and two kinds of dinoflagellates (Prorocentrum donghaiense and Gymnodinium) were cultured under laboratory conditions. Variations of optical properties of chromophoric dissolved organic matter (CDOM) were studied with absorption and fluorescence excitation-emission matrix spectroscopy(EEM) during growth of marine microalgae in incubation experiment. Absorption spectrum revealed absorption coefficient a(355) (CDOM absorption coefficients at 355 nm) of 6 kinds of marine microalgae above increased by 64.8%, 242.3%, 535.1%, 903.2%, 836% and 196.4%, respectively. Simultaneously, the absorption spectral slope (Sg), determined between 270 and 350 nm, representing the size of molecular weight of CDOM and humic-like composition, decreased by 8.7%, 34.6%, 39.4%, 53.1%, 46.7%, and 35.7%, respectively. Applying parallel factor analysis (PARAFAC) together with EEM got four components of CDOM: C1(Ex/Em=350(260) nm/450 nm), C2 (Ex/Em=260(430) nm/525 nm), C3 (Ex/Em=325 nm/400 nm) and C4(Ex/Em=275 nm/325 nm), which were relative to three humic-like and one protein-like fluorescent components of Nitzschia closterium f. minutissima and Navicula halophile. In incubation experiment, fluorescence intensity of these four components during growth of Nitzschia closterium f. minutissima increased by, respectively, 8.68, 24.9, 7.19 and 39.8 times, and those of Navicula halophile increased by 2.64, 0.07, 4.39 and 12.4 times, respectively. Significant relationships were found between the fluorescence intensity of four components of CDOM, a(355) and Sg. All results demonstrated that both content and molecular weight of CDOM produced by diatom and dinoflagellate studied in incubation experiment increased, but these two parameters changed more obviously of the diatom than those of dinoflagellate; the proportion of humic-like components in the composition of CDOM also increased clearly with the growth of marine microalgae, but protein-like fluorescent component had only a slow growth. Furthermore, the absorption spectrum of CDOM produced by different species of algae changed obviously and the relative composition fluorescence intensity of CDOM produced by different microalgae were found to vary among different composition from EEM, which suggested CDOM produced by different microalgae make quite different contributions to CDOM in natural seawater.

[Characterization of Chromophoric dissolved organic matter (CDOM) in Zhoushan fishery using excitation-emission matrix spectroscopy (EEMs) and parallel factor analysis (PARAFAC)].

The composition, distribution characteristics and sources of chromophoric dissolved organic matter(CDOM) in Zhoushan Fishery in spring were evaluated by fluorescence excitation-emission matrix (EEM) combined with parallel factor analysis (EEMs-PARAFAC). Three humic-like components [C1 (330/420 nm)], C2 [(290) 365/440 nm] and C3 [(260) 370/490 nm)] and two protein-like components [C4(285/340 nm) and C5 (270/310 nm)] were identified by EEMs-PARAFAC. The horizontal distribution patterns of the five components were almost the same with only slight differences, showing decreasing trends with increasing distance from shore. In the surface and middle layers, the high value areas were located in the north of Hangzhou Bay estuary and the outlet of Xiazhimen channel, and the former's was higher in the surface layer while the latter's was higher in the middle layer. In the bottom layer, CDOM decreased gradiently from the inshore to offshore, with higher CDOM near Zhoushan Island. The distributions of fluorescence components showed an opposite trend with salinity, and no significant linear relationship with Chl-a concentration was found, which indicated that CDOM in the surface and middle layers were dominated by terrestrial input and human activities of Zhoushan Island and that of the bottom layer was attribute to human activities of Zhoushan Island. The vertical distribution of five fluorescent components along 30.5 degrees N transect showed a decreasing trend from the surface and middle layers to bottom layer with high values in inshore and offshore areas, which were correlated with the lower salinity and higher Chl-a concentration, respectively. On this transect, CDOM was mainly affected by Yangtze River input in coastal area but by bioactivities in offshore waters. Along the 30 degrees N transect, the vertical distribution patterns of CDOM were similar to those of 30.5 degrees N transect but there was a high value area in the bottom layer near the shore, attributing to the CDOM release from the marine sediment pore water to the water body because of physical force role like tidal, the underlying upwelling and so on. A strong correlation occurred between C1 and C3, C4, indicating that they had similar sources; a weak correlation was found between C1 and C2, C5, reflecting some differences among their sources. CDOM in Zhoushan Fishery in spring had low humification index (HIX) values, which reflected a low degree of humification, poor stability and a short resident time in the environment. For biological index (BIX), its higher values appeared in the offshore waters and the lower values occurred in the inshore area, reflecting a greater influence of human and biological activities, respectively.

[Lake algae chemotaxonomy technology based on fluorescence excitation emission matrix and parallel factor analysis].

An in vivo three-dimensional fluorescence method for the determination of algae community structure was developed by parallel factor (PARAFAC) analysis and CHEMTAX. The PARAFAC model was applied to fluorescence excitation-emission matrix (EEM) of 23 algae species and 12 fluorescent components were identified according to the residual sum of squares and specificity of the composition profiles of fluorescent. Based on the 12 fluorescent components, the algae species at different growth stages were correctly classified at the division level using Bayesian discriminant analysis (BDA). Then the reference fluorescent component ratio matrix was constructed for CHEMTAX, and the EEM-PARAFAC-CHEMTAX method was developed to differentiate taxonomic groups of algae. When the fluorometric method was used for 531 single-species samples, the average correct discrimination ratio (CDR) was 99.1% and the correct discrimination ratios (CDRs) were 100% at the division level except Chlorophyta, the CDR of which was 97.5%. The CDRs for 95 mixtures were above 98.5% for the dominant algae species and above 90.5% for the subdominant algae species, with average relative contents of 69.7% and 26.4%, respectively. This technique would be of great aid when low-cost and rapid analysis is needed for samples in a large batch.

[Resolving characteristic of CDOM by excitation-emission matrix spectroscopy combined with parallel factor analysis in the seawater of outer Yangtze Estuary in Autumn in 2010].

The distribution and estuarine behavior of fluorescent components of chromophoric dissolved organic matter in the seawater of outer Yangtze Estuary were determined by fluorescence excitation emission matrix spectra combined with parallel factor analysis. Six individual fluorescent components were identified by PARAFAC models, including three terrestrial humic-like components C1 [330 nm/390(430) nm], C2 (390 nm/480 nm), C3 (360 nm/440 nm), marine biological production component C5 (300 nm/400 nm) and protein-like components C4 (290 nm/350 nm) and C6 (275 nm/300 nm). The results indicated that C1, C2, and C3 showed a conservative mixing behavior in the whole estuarine region, especially in high-salinity region. And the fluorescence intensity proportion of C1 and C3 decreased with increase of salinity and fluorescence intensity proportion of C2 kept constant with increase of salinity in the whole estuarine region. While C4 showed conservative mixing behavior in low-salinity region and non-conservative mixing behavior in high-salinity region, and fluorescence intensity proportion of C4 increased with increase of salinity. However, C5 and C6 showed a non-conservative mixing behavior and fluorescence intensity proportion increased with increase of salinity in high-salinity region. Significantly spatial difference was recorded for CDOM absorption coefficient in the coastal region and in the open water areas with the highest value in coastal region and the lowest value in the open water areas. The scope of absorption coefficient and absorption slope was higher in coastal region than that in the open water areas. Significantly positive correlations were found between CDOM absorption coefficient and the fluorescence intensities of C1, C2, C3, and C4, but no significant correlation was found between C5 and C6, suggesting that the river inputs contributed to the coastal areas, while CDOM in the open water areas was affected by terrestrial inputs and phytoplankton degradation.

[Fluorescence discrimination technique for phytoplankton based on the wavelet analysis].

Daubechies7 (db7) wavelet was selected to decompose the 3-D fluorescence spectra of 27 species of phytoplankton belonging to 22 generas of 6 divisions found in major lakes, then the scale vectors and time-series vectors were obtained as candidates for feature spectra. The third scale vector (Ca3) of db7 was chosen as feature spectra by Bayesian discriminant analysis, and the reference spectra were obtained via hierarchical cluster analysis to feature spectra. Based on the above data, a fluorescence discrimination technique was developed by multiple linear regression resolved by non-negative least squares. For single species algae cultures, the average correct discrimination ratio (CDR) was 98.6%, with the average relative content of 90.8% at division level. Furthermore, the noise immunity of reference spectra was tested by adding noise at different proportions. For the dominant division of laboratory mixed samples, the average CDR was 97.0%, with the average relative content of 67.7% at division level, and the average CDR of subdominant division was 90.7%, with the average relative content of 32.3%. The results showed that the technique is feasible to some extent.

[Research on using 3-D fluorescence spectroscopy-wavelet transform-PSO for rapid discrimination of compositions of phytoplankton population].

Three-dimensional fluorescence of 17 red tide algae species that belong to 13 genera of five divisions was measured by fluorescence excitation-emission matrix spectroscopy. And 2-D wavelet db7 was selected to decompose the spectra at different levels to choose the alternative characteristic spectra. Based on the norm reference spectra constructed by cluster analysis, the linear regression model was solved by particle swarm optimization (PSO) algorithm and the discrimination method was established at the division and genus level. Some samples were tested: for single algal samples, and the correct discrimination ratios (CDRs) were 96.1% and 73.6%, respectively; For simulative mixed algal samples, when the dominance were 60%, 75%, 80% and 90% of the total biomass, the CDRs of the dominant algae were 86.7%, 96.9%, 98.7% and 99.4% with the average relative contents of 62.6%, 72.7%, 76.0% and 81.6%, respectively at the division level. And the CDRs were 51.0%, 68.9%, 72.0%, and 78.8% at the genus level, respectively. For 364 actual mixture samples, the CDRs of the dominant species (75%) were 99.4% at the division level and 75.9% at the genus level . For the particular field samples from mesocosm experiment and corrected from Jiaozhou Bay, results showed that the method can be used to realize the identification of red tide algae population and estimate the relative abundance of different classes, especially between diatoms and dinoflagellates.

[Research on the 3D discrete fluorescence spectrum technique for differentiation of phytoplankton population].

The present research was targeted to develop a fluorescence analyser for phytoplankton population which uses a series of LEDs as the light source. So the 3D discrete fluorescence spectra with 12 excitation wavelengths (400, 430, 450, 460,470, 490, 500, 510, 525, 550, 570 and 590 nm) were determined by fluorescence spectrophotometer for 43 phytoplankton species. Then, the wavelet, Daubechies-7 (Db7), and Bayes Classifier were applied to extract the characteristics for each classes from the 3D discrete fluorescence spectra. Lastly, the fluorescence differentiation method for phytoplankton populations was established by multivariate linear regression and non-negative least squares, which could differentiate phytoplankton populations at the levels of both divisions and genus. This method was tested: for simulatively mixed samples(the dominant species accounted for 70%, 80%, 90% and 100% of the gross biomass, respectively) from 32 red tide algal species, and the correct discrimination rates at the level of genus were 67.5%, 75.8%, 81.4% and 79.4%, respectively. For simulatively mixed samples (the dominant divisions algae accounted for 50%, 75% and 100% of the gross biomass, respectively) from 43 algal species, the discrimination rates at the level of division were 95.2%, 99.7% and 91.9% with average relative content of 38.1%, 63.2% and 90.5%, respectively.

[Toxic effects of chloride tributyltin on the predominant phytoplankton species of China coastal sea].

Toxic effects of tributyltin (TBT) on the growth, peak diameter and photosynthetic activity (F(v)/F(m)) of fifteen predominant phytoplankton species in China coastal sea of Leptocylindru danicus, Skeletonema marinoi, Asterionella japonica, Bacilaria paxillifera, Chaetoceros debilis, Chaetoceros socialis, Thalassiosira, Amphidinium carterae, Karenia mikimotoi, Prorocentrum minimum, Gymnodinium sp., Scrippsiella trochoidea, Gymnodinium simplex, Prorocentrum triestinum and Heterosigma akashiwo were systematically studied. 96 h-EC50 of TBT were 136.42, 3.55, 3.15, 2.95, 1.90, 1.08, 0.70, 21.60, 7.71, 4.77, 3.81, 2.04, 0.53, 0.51, 1.76 microg/L, respectively. The no detectation effect concentration were 112.62, 1.19, 1.17, 3.70, 0.95, 1.07, 0.80, 6.28, 1.84, 0.99, 3.73, 1.63, 0.23, 0.16, 1.76 microg/L, respectively. The results indicated that the toxic effects of TBT were very different among different phytoplankton species and the resistance of Leptocylindru danicus was stronger than those of other microalgae. The TBT not only inhibited the growth of phytoplankton, but also changed the peak diameter and decreased the photosynthetic activity (F(v)/F(m)). Besides that, we infer that there may have a relationship between the toxicity of TBT and the composition of predominant phytoplankton population in harbour.

[Evaluation on biodegradability of hydrocarbon biomarkers in two crude oils under laboratory conditions].

Biodegradabilities of several hydrocarbon biomarker groups, including isoprene, hopanes and steranes in a medium-crude oil BZ34-1 and a heavy-crude oil SZ36-1 from offshore, were determined under laboratory conditions. The results of GC-MS analysis showed that isoprene biomarkers such as pristane and phytane in both crude oils degraded obviously in 60-day experiment period. The degradation ratios of pristane and phytane in the medium-crude oil BZ34-1 reached 20.2% and 15.0%, respectively; while those in the heavy-crude oil SZ36-1 reached 95.6% and 75.4%, respectively. Pristane and phytane in the heavy-crude oil SZ36-1 were degraded in the early period of biodegradation, but these two biomarkers in the medium-crude oil BZ34-1 were degraded in middle and late biodegradation phases. However, hopanes and steranes in the both oils were not biodegraded obviously during the whole period. These results indicated that pristane and phytane could be used to evaluate bioremediation efficiency in the early biodegradation phase for light or medium oils, while hopanes and steranes could be used to evaluate bioremediation efficiency within the whole given experiment process.

[Research on the 3D fluorescence spectra differentiation of phytoplankton by coiflet2 wavelet].

In the present paper, the authors utilize the wavelet base function coiflet2 (coif2) to analyze the 3D fluorescence spectra of 37 phytoplankton species belonging to 30 genera of 7 divisions, and these phytoplankton species include common species frequently causing harmful algal blooms and most predominant algal species in the inshore area of China Sea. After the Rayleigh and Raman scattering peaks were removed by the Delaunay triangulation interpolation, the fluorescence spectra of those phytoplankton species were transformed with the coiflet2 wavelet, and the scale vectors and the wavelet vectors were candidate for the feature spectra. Based on the testing results by Bayesian analysis, the 3rd scale vectors were the best feature segments at the division level and picked out as the fluorescence division feature spectra of those phytoplankton species, and the group of the 3rd scale vectors, the 2nd and 3rd wavelet vectors were the best feature segments at the genus level and chosen as the fluorescent genus feature spectra of those phytoplankton species. The reference spectra of those phytoplankton species at the division level and that at the genus level were obtained from these feature spectra by cluster analysis, respectively. The reference spectra base for 37 phytoplankton species was composed of 107 reference spectra at the division level and 155 ones at the genus level. Based on this reference spectra base, a fluorometric discriminating method for phytoplankton populations was established by multiple linear regression resolved by the nonnegative least squares. For 1 776 samples of single phytoplankton species, a correct discriminating rate of 97.0% at genus level and 98.1% at division level can be obtained; The correct discriminating rates are more than 92.7% at the genus level and more than 94.8% at the division level for 384 mixed samples from two phytoplankton species.

[Discrimination of Red Tide algae by fluorescence spectra and principle component analysis].

Fluorescence discrimination technology for 11 species of the Red Tide algae at genus level was constructed by principle component analysis and non-negative least squares. Rayleigh and Raman scattering peaks of 3D fluorescence spectra were eliminated by Delaunay triangulation method. According to the results of Fisher linear discrimination, the first principle component score and the second component score of 3D fluorescence spectra were chosen as discriminant feature and the feature base was established. The 11 algae species were tested, and more than 85% samples were accurately determinated, especially for Prorocentrum donghaiense, Skeletonema costatum, Gymnodinium sp., which have frequently brought Red tide in the East China Sea. More than 95% samples were right discriminated. The results showed that the genus discriminant feature of 3D fluorescence spectra of Red Tide algae given by principle component analysis could work well.

[Research on characterization analysis of synchronous fluorescence spectra of living phytoplankton].

The synchronous fluorescence spectra of five phytoplankton species growing under three temperatures (25, 20 and 15 degrees C)and three illuminations (7000, 4100 and 1100 Lx)were measured and processed by multinomial smoothness and autoscaling to obtain the characteristic spectra. Principal component analysis was used to obtain standard spectra. The analysis shows that at different temperatures, the characteristic spectra of Skeletonema costatuma, Isochrysis galbana, and Platymonas helgolanidica show high similarities, while the spectra similarities of Alexandrium tamarense and Gymnodinium stein are not as good as the above three species. The standard spectrum of Skeletonema costatuma, which belongs to Bacillariophyta, is quite different from those of Alexandrium tamarense and Gymnodinium stein, which belong to Dinophyta.

[Study on the characters of phytoplankton chlorophyll fluorescence excitation spectra based on fourth-derivative].

Chlorophyll fluorescence excitation spectra of six phytoplankton species, belonging to Bacillariophyta and Dinophyta, were dealt by fourth-derivative analysis with the Matlab program. The results show that between 350 nm and 550 nm six fluorescence peaks were found in the fourth-derivative spectra, which are representatives of non-pigments, chlorophylls and carotenoides respectively. The method makes Bacillariophyta and Dinophyta more distinguishable when the fourth-derivative spectra are compared with the chlorophyll fluorescence excitation spectra. It can be used not only to discriminate the two groups of algaes, but also to reduce the effect of noise. The fluorescence peaks in the fourth-derivative spectra are proved to be stable.

[Chip-based capillary electrophoresis on-line coupled with atomic fluorescence spectrometry and its application to rapid speciation analysis].

Chip-based capillary electrophoresis (chip-CE) is under rapid progress due to its high efficiency, fast separation, little sample consumption and integration. Due to the short optical path (30-50 microm), the conventional UV absorbance cannot satisfy the chip detection needs. Atomic fluorescence spectrometer (AFS) is a selective and sensitive detector for hydride-forming elements. With the strong points of low cost and easy operation, AFS is attractive as an ideal detector of chip-CE for mercury, arsenic and selenium, etc. A few important practical aspects of coupling chip-CE to AFS are critically discussed. These include the design of the chip, chip-AFS interface, gas-liquid separator, AFS atomizer, and elimination of the effect of backpressure on separation. The application of the developed chip-CE-AFS to the mercury speciation analysis is highlighted.

Speciation analysis of inorganic arsenic by microchip capillary electrophoresis coupled with hydride generation atomic fluorescence spectrometry.

A novel method for speciation analysis of inorganic arsenic was developed by on-line hyphenating microchip capillary electrophoresis (chip-CE) with hydride generation atomic fluorescence spectrometry (HG-AFS). Baseline separation of As(III) and As(V) was achieved within 54 s by the chip-CE in a 90 mm long channel at 2500 V using a mixture of 25 mmol l(-1) H3BO3 and 0.4 mmol l(-1) CTAB (pH 8.9) as electrolyte buffer. The precisions (RSD, n=5) ranged from 1.9 to 1.4% for migration time, 2.1 to 2.7% for peak area, and 1.8 to 2.3% for peak height for the two arsenic species at 3.0 mg l(-1) (as As) level. The detection limits (3sigma) for As(III) and As(V) based on peak height measurement were 76 and 112 microg l(-1) (as As), respectively. The recoveries of the spikes (1 mg l(-1) (as As) of As(III) and As(V)) in four locally collected water samples ranged from 93.7 to 106%.

A polymeric master replication technology for mass fabrication of poly(dimethylsiloxane) microfluidic devices.

A protocol of producing multiple polymeric masters from an original glass master mold has been developed, which enables the production of multiple poly(dimethylsiloxane) (PDMS)-based microfluidic devices in a low-cost and efficient manner. Standard wet-etching techniques were used to fabricate an original glass master with negative features, from which more than 50 polymethylmethacrylate (PMMA) positive replica masters were rapidly created using the thermal printing technique. The time to replicate each PMMA master was as short as 20 min. The PMMA replica masters have excellent structural features and could be used to cast PDMS devices for many times. An integration geometry designed for laser-induced fluorescence (LIF) detection, which contains normal deep microfluidic channels and a much deeper optical fiber channel, was successfully transferred into PDMS devices. The positive relief on seven PMMA replica masters is replicated with regard to the negative original glass master, with a depth average variation of 0.89% for 26-microm deep microfluidic channels and 1.16% for the 90 mum deep fiber channel. The imprinted positive relief in PMMA from master-to-master is reproducible with relative standard deviations (RSDs) of 1.06% for the maximum width and 0.46% for depth in terms of the separation channel. The PDMS devices fabricated from the PMMA replica masters were characterized and applied to the separation of a fluorescein isothiocyanate (FITC)-labeled epinephrine sample.

Development of a new hybrid technique for rapid speciation analysis by directly interfacing a microfluidic chip-based capillary electrophoresis system to atomic fluorescence spectrometry.

This paper represents the first study on direct interfacing of microfluidic chip-based capillary electrophoresis (chip-CE) to a sensitive and selective detector, atomic fluorescence spectrometry (AFS) for rapid speciation analysis. A volatile species generation technique was employed to convert the analytes from the chip-CE effluent into their respective volatile species. To facilitate the chip-CE effluent delivery and to provide the necessary medium for subsequent volatile species generation, diluted HCl solution was introduced on the chip as the makeup solution. The chip-CE-AFS interface was constructed on the basis of a concentric "tube-in-tube" design for introducing a KBH4 solution around the chip effluent as sheath flow and reductant for volatile species generation as well. The generated volatile species resulting from the reaction of the chip-CE effluent and the sheath flow were separated from the reaction mixture in a gas-liquid separator and swept into the AFS atomizer by an argon flow for AFS determination. Inorganic mercury (Hg(II)) and methylmercury (MeHg(I)) were chosen as the targets to demonstrate the performance of the present technique. Both mercury species were separated as their cysteine complexes within 64 s. The precision (relative standard deviation, RSD, n = 5) of migration time, peak area, and peak height for 2 mg.L(-1) Hg(II) and 4 mg.L(-1) MeHg(I) (as Hg) ranged from 0.7 to 0.9%, 2.1 to 2.9%, and 1.5 to 1.8%, respectively. The detection limit was 53 and 161 microg.L(-1) (as Hg) for Hg(II) and MeHg(I), respectively. The recoveries of the spikes of mercury species in four locally collected water samples ranged from 92 to 108%.