On-line voltammetric monitoring of dissolved Cu and Ni in the Gulf of Cadiz, south-west Spain

Geochemical processes in estuarine and coastal waters often occur on temporally and spatially small scales, resulting in variability of metal speciation and dissolved concentrations. Thus, surveys, which are aimed to improve our understanding of metal behaviour in such systems, benefit from high-resolution, interactive sampling campaigns. The present paper discusses a high-resolution approach to coastal monitoring, with the application of an automated voltammetric metal analyser for on-line measurements of dissolved trace metals in the Gulf of Cadiz, south-west Spain. This coastal sea receives metal-rich inputs from a metalliferous mining area, mainly via the Huelva estuary. On-line measurements of dissolved Cu, Zn, Ni and Co were carried out on-board ship during an eight-day sampling campaign in the study area in June 1997. A pumping system operated continuously underway and provided sampled water from a depth of ca. 4 m. Total dissolved metal concentrations measured on-line in the Gulf of Cadiz ranged between <5 nM Cu (<3 nM Ni) ca. 50 km off-shore and 60–90 nM Cu (5–13 nM Ni) in the vicinity of the Huelva estuary. The survey revealed steep gradients and strong tidal variability in the dissolved metal plume extending from the Huelva estuary into the Gulf of Cadiz. Further on-line measurements were carried out with the automatic metal monitor from the bank of the Odiel estuary over a full tidal cycle, at dissolved metal concentrations in the μM range. The application confirmed the suitability of the automated metal monitor for coastal sampling, and demonstrated its adaptability to a wide range of environmental conditions in the dynamic waters of estuaries and coastal seas. The near-real time acquisition of dissolved metal concentrations at high resolution enabled an interactive sampling campaign and therefore the close investigation of tidal variability in the development of the Huelva estuary metal plume.

Determination of Hg(II) in waters by on-line preconcentration using Cyanex 923 as a sorbent - Cold vapor atomic absorption spectrometry

Using a solid phase extraction mini-column home-made from a neutral extractant Cyanex 923, inorganic Hg could be on-line preconcentrated and simultaneously separated from methyl mercury. The preconcentrated Hg (11) was then eluted with 10% HNO3 and subsequently reduced by NaBH4 to form Hg vapor before determination by cold vapor atomic absorption spectrometry (CVAAS). Optimal conditions for and interferences on the Hg preconcentration and measurement were at 1% HCl, for a 25 mL sample uptake volume and a 10 mL min(-1) sample loading rate. The detection limit was 0.2 ng L-1 and much lower than that of conventional method (around 15.8 ng L-1). The relative standard deviation (RSD) is 1.8% for measurements of 40 ng L-1 of Hg and the linear working curve is from 20 to 2000 ng L-1 (with a correlation coefficient of 0.9996). The method was applied in determination of inorganic Hg in city lake and deep well water (from Changchun, Jilin, China), and recovery test results for both samples were satisfactory.

The research of cellulose derivatives as chiral stationary phases and high performance liquid chromatography with polarimeter as on-line detector

Three cellulose derivatives were synthesized and used as chiral stationary phases based on silica gel. The effects of adsorbances on the column numbers and stabilities have been investigated. These stationary phases exhibited high chiral recognition for various racemates. At the same time, the on-line curves of polarimeter were obtained by high performance liquid chromatography with polarimeter as on-line detector.

On-line concentration of proteins in pressurized capillary electrochromatography coupled with electrospray ionization-mass spectrometry

Pressurized capillary electrochromatography (pCEC) and electrospray ionization-mass spectrometry (ESI-MS) have been hyphenated for protein analysis. Taken cytochrome c, lysozyme, and insulin as samples, the limits of detection (LODs) for absolute concentrations are 10(-11) mol (signal-to-noise ratio S/N = 3) with relative standard deviations (RSDs) of retention time and peak area, respectively, of less than 1.7% and 4.8%. In order to improve the detection sensitivity, on-line concentration by field-enhanced sample-stacking effect and chromatographic zone-sharpening effect has been developed, and parameters affecting separation and detection, such as pH and electrolyte concentration in the mobile phase, separation voltage, as well as enrichment voltage and time, have been studied systematically. Under the optimized conditions, the LODs of the three proteins could be decreased up to 100-fold. In addition, the feasibility of such techniques has been further demonstrated by the analysis of modified insulins at a concentration of 20 mu g/mL.

On-line concentration of peptides and proteins with the hyphenation of polymer monolithic immobilized metal affinity chromatography and capillary electrophoresis

An iminodiacetic acid (IDA)-type adsorbent is prepared at the one end of a capillary by covalently bonding IDA to the monolithic rods of macroporous poly(glycidyl methacrylate-co-ethylene dimethacrylate). Cu(II) is later introduced to the support via the interaction with IDA. By this means, polymer monolithic immobilized metal affinity chromatography (IMAC) materials are prepared. With such a column, IMAC for on-line concentration and capillary electrophoresis (CE) for the subsequent analysis are hyphenated for the analysis of peptides and proteins. The reproducibility of such a column has been proved good with relative standard deviations (RSDs) of dead time of less than 5% for injection-to-injection and 12% for column-to-column (n = 3). Through application on the analysis of standard peptides and real protein samples, such a technique has shown promising in proteome study.

Development of a biotic index using the correlation of protozoan communities with chemical water quality

A method of comparing data on protozoan communities with chemical parameters is presented. Using data from an extensive survey of the River Hanjiang in China, each species of protozoa has been given a species pollution value (SPV) related to its occurrence in waters with different degrees of pollution. A comprehensive chemical index is calculated for each site based on water quality standards for eight chemical parameters. The index is calculated from the relationship between the observed levels of each chemical at a site, compared with the limits of the drinking water quality standards of the People's Republic of China. From the distribution of each species at sites with differing chemical index values, a SPV is calculated. The SPV for each species is obtained by summing the logarithmic value of 10 times the chemical pollution divided by the number of chemical parameters, then divided by the stations where the species occurs. The community pollution value (CPV), which is the average SPVs of all protozoa at a site, is used to evaluate water quality. The CPV has been shown to have a close correlation with the degree of water pollution. It is not necessary for all the protozoa in a sample to have SPVs listed in this paper, provided at least 56% of the protozoa in a sample have an SPV value, the CPV will be applicable.

The effect of Be-doping structure in negative electron affinity GaAs photocathodes on integrated photosensitivity

A new structure of GaAs photocathode was introduced. The Be-doping concentration is variable in the new structure compared with the constant concentration of Be in the normal photocathode. Negative electron affinity GaAs photocathodes were fabricated by alternate input of Cs and O. The spectral response results measured by the on-line spectral response measurement system show that the integrated photosensitivity of the photocathodes with the new structure is enhanced by at least 50% as compared to those with the monolayer structure. Accordingly, two main factors leading to the enhanced photosensitivity of the photocathodes were discussed. (c) 2005 Elsevier B.V. All rights reserved.

Studies on the flavones using liquid chromatography-electrospray ionization tandem mass spectrometry

Fragmentation pathways of nine flavone compounds have been studied by using electrospray ionization multi-stage tandem mass spectrometry (ESI-MSn). Analyzing the product ion spectra of flavonoids and aglycones, we observed some diagnostic neutral losses, such as *CH3, H2O, residue of glucose and gluconic acid, which are very useful for the identification of the functional groups in the structures. Furthermore, specific retro Diels-Alder (RDA) fragments for flavones with different hydroxyl substitution have also been discussed. The information is helpful for the rapid identification of the location site of hydroxyl substitution on flavones. Fragmentation pathways of C-glycosidic flavonoid have also been discussed using ESI-MSn, demonstrating ions [M-H-60](-), [M-H-90](-), [M-H-120](-) are characteristic ions of C-glycosidic flavonoid. According to the fragmentation mechanism of mass spectrometry and HPLC-MS data, the structures of seven flavones in Scutellaria baicalensis Georgi have been identified on-line without time-consuming isolation. The HPLC-ESI-MSn method for analyzing constituents in the Scutellaria baicalensis Georgi has been established.

Tank cultivation of the red alga Palmaria palmata: Effects of intermittent light on growth rate, yield and growth kinetics

Tank cultivation of marine macroalgae involves air-agitation of the algal biomass and intermittent light conditions, i.e. periodic, short light exposure of the thalli in the range of 10 s at the water surface followed by plunging to low light or darkness at the tank bottom and recirculation back to the surface in the range of 1-2 min. Open questions relate to effects of surface irradiance on growth rate and yield in such tumble cultures and the possibility of chronic photoinhibition in full sunlight. A specially constructed shallow-depth tank combined with a dark tank allowed fast circulation times of approximately 5 s, at a density of 4.2 kg fresh weight (FW) m(-2) s(-1). Growth rate and yield of the red alga Palmaria palmata increased over a wide range of irradiances, with no signs of chronic photoinhibition, up to a growth-saturating irradiance of approximately 1600 mumol m(-2) s(-1) in yellowish light supplied by a sodium high pressure lamp at 16 h light per day. Maximum growth rate ranged at 12% FW d(-1), and maximum yield at 609 g FW m(-2) d(-1). This shows that high growth rates of individual thalli may be reached in a dense tumble culture, if high surface irradiances and short circulation times are supplied. Another aspect of intermittent light relates to possible changes of basic growth kinetics, as compared to continuous light. For this purpose on-line measurements of growth rate were performed with a daily light reduction by 50% in light-dark cycles of 1, 2 or 3 min duration during the daily light period. Growth rates at 10degreesC and 50 mumol photon m(-2) s- 1 dropped in all three intermittent light regimes during both the main light and dark periods and reached with all three periodicities approximately 50% of the control, with no apparent changes in basic growth kinetics, as compared to continuous light.