A miniaturized flow-injection analysis ( μ FIA) system with on-line chemiluminescence detection for the determination of iron in estuarine water

A miniaturized flow-injection analysis system constructed from a glass base plate and polydimethylsiloxane (PDMS) top plate was employed for the determination of iron in river water. Two designs were investigated, one utilizing a syringe pump and the other utilizing EOF pumping with a mini-filtration system incorporated. The syringe pump system was used to optimize the analytical method on chip, where the pump was used to deliver both the analyte and the reagents to the reactor chip. The highly sensitive chemiluminescence reaction between alkaline luminol (3-aminophthalhydrazide) and 0.1?M of hydrogen peroxide (H₂O₂) in the presence of iron(II) was utilized. The bright blue light (λ _max?～?440?nm) emitted was detected using a miniaturized photomultiplier tube interfaced directly under the chip. The light intensity signals were recorded, and the corresponding concentration of iron(II) concentration was determined. The calibration for iron(II) standards was linear up to 0.75?µg?mL^?1 (y?=?5.7839x?+?0.0378, r² ?=?0.9939) with a precision value of up to 3.72% RSD, for n?=?3. The limits of detection (blank?+?3s _y/x) were found to be 28?ng?mL^?1. The system which utilized EOF pumping and incorporated a minifiltration unit provided a linear calibration for 0–5?µg?mL^?1 (y?=?3.316x?+?0.1831; correlation coefficient, r ²?=?0.9996) over a working range of 0.0–0.5?µg?mL^?1. This system provided lower limits of detection 5.1?ng?mL^?1 and better repeatability (%RSD less than 0.5% for n?=?4), but problems occurred with the mini-filtration system at higher iron(II) concentrations. The EOF pumping system provided slightly higher results for the concentration of iron(II) in the Humber estuary (0.058?µg?mL^?1), but these results were in line with the results expected by the Environment Agency.     

Investigation of physicochemical properties of biooils produced from yellow poplar wood (Liriodendron tulipifera) at various temperatures and residence times

Fast pyrolysis of yellow poplar wood (Liriodendron tulipifera) was performed under different temperature ranges and residence times in a fluidized bed reactor to maximize the yield of biooil. In this study, the pyrolysis temperature ranged from 400 °C to 550 °C, and the residence time of pyrolysis products was controlled between 1.2 and 7.7 s by inert nitrogen gas flow. The results revealed that the distribution of thermal degradation products (biooil, biochar, and gas) from the woody biomass was heavily influenced by pyrolysis temperature, as well as residence time. The highest yield of biooil was approximately 68.5 wt% (wet basis), with pyrolysis conditions of 500 °C and 1.9 s of residence time. Water content of the biooils produced at different temperatures was 25-30 wt%, and their higher heating values were estimated to be between 15 MJ/kg and 17 MJ/kg. Using GC/MS analysis, 30 chemical components were identified from the biooil, which were classified into 5 main groups: organic acids, aldehydes, ketones, alcohols, and phenols. In addition, biochar was produced as a co-product of fast pyrolysis of woody biomass, approximately 10 wt%, at temperatures between 450 °C and 550 °C. The physicochemical features of the biochar, including elemental analysis, higher heating values, and morphological properties by SEM, were also determined.     

A membraneless gas-diffusion unit-multisyringe flow injection spectrophotometric method for ammonium determination in untreated environmental samples

A new design of a membraneless gas-diffusion (MGD) unit coupled to a multisyringe flow injection system is proposed. The spectrophotometric determination of ammonium using an acid-base indicator was chosen to show the feasibility of this approach. Hence, in alkaline medium, ammonium ions are transformed into ammonia (donor channel) which diffuses through the headspace into the acceptor stream (bromothymol blue solution), causing a pH change and subsequently a colour change. The exploitation of the enhanced potentialities of this re-designed MGD device was the main purpose of the present work. Hence, several strategies concerning flow management were studied seeking to characterize and improve the analytical features of the methodology and moreover, untreated environmental samples were analysed without previous filtration. Consequently, stopped flow in acceptor channel with continuous flow in donor channel was chosen for the application to wastewater and spiked river water samples. A linear concentration range between 10.0 and 50.0 mg L⁻¹ of NH₄⁺, a limit of detection of 2.20 mg L⁻¹ and a determination frequency of 11 h⁻¹ were obtained.     

测定黄磷中砷方法的样品前处理的改进

标准方法(GB 7816-1998)测定黄磷中砷时,采用敞开式消解法预处理样品。实践表明该方法耗时,易引入污染,造成测定误差,而且稍有不慎易使黄磷自燃。作为改进,提出了回流冷凝消解法,即2~3 g试样于硝酸(3+2)溶液60 mL中,在160℃电热板上加热回流消解。消解完成后的试液按Ag-DDTC方法进行砷的测定。结果表明:回流冷凝消解法不仅避免了试样的自燃,而且大大缩短了试样消解时间,所测得砷结果的准确度达到原标准方法的水平。     

Sensitivity of plume dynamics to the parameterization of vertical mixing

A three‐dimensional primitive equation, baroclinic numerical model incorporating a range of turbulence closure schemes is used to investigate the effects of vertical diffusion of momentum and density upon the spread of a freshwater plume, with particular reference to the Ebro plume. Initial calculations show that there are some differences in the horizontal spread and vertical mixing of the plume when diffusion coefficients are computed from a two‐equation turbulence energy model compared with a one‐equation model. To understand results from the turbulence energy models, the sensitivity of the plume dynamics to variations in the coefficient of vertical eddy viscosity and diffusivity is also considered, with increases in these parameters having a significant effect upon the cross‐shore and along‐shore spread of the plume. Also, increasing these parameters changes the plume characteristics from supercritical to subcritical and reduces the occurrence of meandering and baroclinic instability along the plume's off‐shore edge. However, differences in the southerly spread (the direction of Kelvin wave propagation in the model) of the plume (although not its northerly spread) produced by changes in diffusion coefficients are small compared with the influence of changes in the bottom slope, upon the along‐shore southerly spread of the plume, which moves in the direction of Kelvin wave propagation in the near coastal region. Results from the series of calculations are used as a guide in experimental design, with reference to a planned experiment in the Ebro region involving a coastal HF Radar deployment, as well as off‐shore measurements. Calculations suggest that surface current measurements from a coastal HF Radar, together with a detailed survey of the density field associated with the plume, may be an appropriate, although indirect, means of determining suitable mixing coefficients to use in plume discharge problems. Detailed measurements of water depth variation will also be required. Copyright © 1999 John Wiley & Sons, Ltd.     

Dynamical behavior of solutions of a reaction–diffusion model in river network

In this paper, we study the long-time behavior of solutions of a reaction–diffusion model in a one-dimensional river network, where the river network has two branches, and the water flow speeds in each branch are the same constant $\beta$. We show the existence of two critical values $c_0$ and 2 with $0<c_0<2$, and prove that when $-c_0\le \beta <2$, the population density in every branch of the river goes to 1 as time goes to infinity; when $-2<\beta <-c_0$, then, as time goes to infinity, the population density in every river branch converges to a positive steady state strictly below 1; when $\left|\beta \right|\ge 2$, the species will be washed down the stream, and so locally the population density converges to 0. Our result indicates that only if the water-flow speed is suitably small (i.e., $\left|\beta \right|<2$), the species will survive in the long run.