Laboratory and field evaluation of diffusive gradient in thin films (DGT) for monitoring levels of dissolved mercury in natural river water

The diffusive gradient in the thin films (DGT) technique was tested to measure dissolved mercury (Hg) both in laboratory aqueous solutions and in situ in river water. For this purpose, a commercial ready-to-use and specific-for-Hg DGT device was used. Each sampler consisted of a filter membrane-agarose gel as the diffusive layer and a Spheron-Thiol resin in polyacrylamide gel as the binding agent. Basic performance assays at the laboratory with this type of DGT unit confirmed the applicability of Fick's first law for DGT measurements. The diffusion coefficient of MeHg in the agarose diffusive gel was 8.50?×?10^?6?cm² s^?1 at 25°C. Several field studies were also carried out in two different rivers of the Ebro River basin (NE Spain) affected by Hg wastes released by the chlor-alkali industry. Hg concentrations determined by DGT were generally much lower than the results obtained through direct measurements of the river water. In addition, the results of a time series experiment also performed in the field show that the amount of Hg accumulated in the resin does not increase at all with the exposure time. This may be explained by the underestimation of the truly dissolved Hg fraction due to the formation of a biofilm layer on the surface of the samplers, thus clogging the filter and preventing Hg species from diffusing through it. Consequently, it was demonstrated that the DGT technique presents important limitations for measuring Hg in polluted rivers characterised by a high biomass load (eutrophic), whereas its performance was demonstrated to be correct in oligotrophic waters.     

Use of chemometric and geostatistical methods to evaluate pesticide pollution in the irrigation and drainage channels of the Ebro river delta during the rice-growing season

Data sets obtained from quantitative analysis of seventeen pesticides in water samples from a network of irrigation and drainage channels in the Ebro river delta (Catalonia, NE Spain) have been analysed by chemometric and geostatistical methods. Samples were taken at fourteen locations during the main rice-growing season, from May to August 2005. Principal-component analysis enabled investigation of the spatial and temporal distribution of the main pollution patterns caused by application of pesticides in the region under study. A first pesticide-contamination pattern from the Ebro river was differentiated from a second more specific pattern from the water-drainage channels of the delta, collected from the rice fields. The seasonal peak in this more specific rice pesticide source was observed in July. Coupling the results from chemometric data analysis with use of geostatistical methods was shown to be a useful procedure for discovery of the most significant spatial and monthly variations of the main pesticide-contamination patterns, taking into account the particular geographical structure of the area under study.     

基坑排水对城市内河水体溶解性有机质的影响研究

工程施工时基坑排水是保障基坑安全的必要措施,排出水进入城市内河,对内河及下游水生态安全产生影响。该研究采集哈尔滨市何家沟欧亚之窗公园段建筑工程施工过程中基坑排出水(W1)、排水口上游100 m处(W2)、排水口处(W3)、排水口下游50 m处(W4)、排水口下游100 m处(W5)、排水口下游200 m处(W6)的水体样品,应用三维荧光光谱-平行因子分析方法,测定溶解性有机质(DOM)的荧光光谱特征,分析DOM的组成和来源,探究基坑排水对城市内河水体环境的影响。结果表明：内河水体腐殖化指数(HIX)在0.337~0.381范围内,腐殖化程度低,W1,W3～W6的HIX差异不显著,均显著低于W2,说明排水进一步降低了内河水体腐殖化程度。荧光指数(FI₃₇₀)介于2.330~2.900范围内,生物指数(BIX)在0.897~1.140范围内,W1和W2的FI₃₇₀和BIX均显著高于W3~W6,两者具有极强的自生源特征,说明排水使下游水体自生源特征降低。水体样品DOM中共识别出2类4种有机组分：可见类富里酸组分(C1)、类色氨酸组分(C2)、紫外类富里酸组分(C3)和类酪氨酸组分(C4),即类富里酸物质(C1、C3)和类蛋白物质(C2、C4),两者间成负相关关系。FI₃₇₀与4种有机组分间均呈极显著的相关性,说明DOM组成简单。W2具有相对较高的DOM浓度,而排水口下游水体DOM浓度低,基本保持稳定。类蛋白物质在上游水体中占有相对较高的比重,在W4中,4种有机组分相对比重差异不显著,W5和W6类富里酸物质的相对比重有升高趋势,同样说明基坑排水导致内河水体自生源特征降低。除pH值升高外,下游水体样品溶解氧(DO)、总氮、总磷等理化指标含量均降低,pH值与类富里酸物质呈正相关,与类蛋白物质呈负相关,而DO、化学需氧量及水体养分指标与之相反。水体DOM有机组分与理化指标的相关性不同,可直接或间接影响DOM组成。因此,工程施工基坑排水可降低城市内河水体DOM浓度,改变了水体DOM组成。     

Strain induced topological transitions in twisted double bilayer graphene

We theoretically study the band structures and the valley Chern numbers of the AB–AB and AB–BA stacked twisted double bilayer graphene under heterostrain effect. In the absence of heterostrain, due to the constrains by the spatial symmetries, the central two flat bands of the AB–AB are topological trivial bands, while in the AB–BA they have a finite Chern number. The heterostrain breaks all the point group symmetries and the constrains are lifted, hence the topological properties of the two arrangements can be tuned by different strain magnitudes ϵ and directions ϕ. The heterostrain has dissimilar impacts on the Chern numbers of the AB–AB and AB–BA, owing to their different band gaps, and these gaps can be modified by a vertical electric field. Our results show that the topological transitions for both arrangements occur in the ϵ range of 0.1%–0.4%, which can be realized in the graphene-based sample.     

Vector valley Hall edge solitons in the photonic lattice with type-II Dirac cones

Topological edge solitons represent a significant research topic in the nonlinear topological photonics. They maintain their profiles during propagation, due to the joint action of lattice potential and nonlinearity, and at the same time are immune to defects or disorders, thanks to the topological protection. In the past few years topological edge solitons were reported in systems composed of helical waveguide arrays, in which the time-reversal symmetry is effectively broken. Very recently, topological valley Hall edge solitons have been demonstrated in straight waveguide arrays with the time-reversal symmetry preserved. However, these were scalar solitary structures. Here, for the first time, we report vector valley Hall edge solitons in straight waveguide arrays arranged according to the photonic lattice with innate type-II Dirac cones, which is different from the traditional photonic lattices with type-I Dirac cones such as honeycomb lattice. This comes about because the valley Hall edge state can possess both negative and positive dispersions, which allows the mixing of two different edge states into a vector soliton. Our results not only provide a novel avenue for manipulating topological edge states in the nonlinear regime, but also enlighten relevant research based on the lattices with type-II Dirac cones.     

Flow Injection On-Line Two-Stage Solvent Extraction Preconcentration Coupled with Et-Aas for Determination of Bismuth in Biological and Environmental Samples

ABSTRACT

A robust flow injection/sequential injection(FIA/SIA) on-line two-stage solvent extraction separation/preconcentration procedure coupled to electrothermal atomic absorption spectrometry (ETAAS) is described and demonstrated for the determination of trace-levels of bismuth. In 1-4% (v/v) nitric acid medium, diethyldithiophosphate (DDPA) chelates bismuth and the chelating complex formed is extracted into isobutyl methyl ketone (IBMK), which is separated from the aqueous phase by means of cavity gravitational phase separation. Both single and two-stage separations are used. In each case, 40 μl of the concentrate is entrapped and metered in a loop, and subsequently delivered via air-segmentation into a pyrolytically coated graphite tube. The ETAAS determination is performed in parallel with the preconcentration process of the ensuing sample. Enrichment factors of 17.8 and 31.5, detection limits of 12 ng 1^?1 and 10.5 ng 1^?1 for single and two-stage extractions, respectively, along with a sampling frequency of 13 h^?1 were obtained with 100 s of sample loading time at a sample flow rate of 5.4 ml min^?1. The relative standard deviations were 2.8% and 1.9% for single and two-stage extractions, respectively. The procedure was validated by determining the bismuth content in a certified reference material and i8543220 human urine samples.     

Inductively Coupled Plasma Mass Spectrometry for Sequential Determination of Trace Metals in Rain and River Waters Using Electrothermal Vaporization

Abstract

The sequential determination of 14 trace metals, Al, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Mo, Cd, Sb and Pb, in rain and river water samples has been investigated using an inductively coupled plasma mass spectrometry (ICP-MS) with a graphite rod electrothermal vaporizer (ETV) in the presence of the mixed modifier of palladium nitrate and magnesium nitrate. The sensitivity enhancements due to the presence of the modifier were observed for all analyte elements. Detection limits as high as 0.52, 0.13, 0.89, 0.35, 1.76, 0.5, 0.9, 0.5, 0.04, 1.03, 0.28, 0.07, 0.1 and 3.78 pg, respectively, for Al, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Mo, Cd, Sb and Pb have been achieved. For the determination of trace metals in both rain and river water samples by this method, the repeatibility of sample solution were very good, i.e. from 1% to 7% (as a coefficient variation) and the recoveries of elements were good enough, i.e. from 81% to 106%, by using a standard addition method. There was no difference between the results obtained by nebulizer ICP-MS and those obtained by this method, except for zinc and arsenic.     

同时测定无机离子的改良离子色谱法在河水和废水质量监控中的应用（英文）

In this study,our recent work on advanced ion chromatographic methods for the simultaneous determination of inorganic ionic species such as common anions(SO2-4,Cl-and NO-3) and cations(Na+,NH+4,K+,Mg2+,and Ca2+),nutrients(phosphate and silicate) and hydrogen ion/alkalinity are summarized first.Then,the applications using these methods for monitoring environmental water quality are also presented.For the determination of common anions and cations with nutrients,the separation was successfully performed by a polymethacrylate-based weakly acidic cation-exchange column of TSKgel Super IC-A/C(Tosoh,150 mm×6.0 mm i.d.) and a mixture solution of 100 mmol/L ascorbic acid and 4 mmol/L 18-crown-6 as acidic eluent with dual detection of conductivity and spectrophotometry.For the determination of hydrogen ion/alkalinity,the separation was conducted by TSKgel ODS-100Z column(Tosoh,150 mm×4.5 mm i.d.) modified with lithium dodecylsulfate and an eluent of 40 mmol/L LiCl/0.1 mmol/L lithium dodecylsulfate/0.05 mmol/L H2SO4 with conductivity detector.The differences of ion concentration between untreated and treated wastewater showed the variation of ionic species during biological treatment process in a sewage treatment plant.Occurrence and distribution of water-quality conditions were related to the bioavailability and human activity in watershed.From these results,our advanced ion chromatographic methods have contributed significantly for water quality monitoring of environmental waters.     

Analysis of Aluminum-Brass Corrosion Products in Sea Water and in Chloride Solutions

Abstract

A separation and chemical analysis method has been developed of corrosion products forming on aluminum brass surfaces immersed in sodium sulfate solutions at pH= 7.25 (simulating river water) and in sea water at pH= 8.2. This method is based upon a selective solubilization of various oxidation compounds with the aid of proper solvents (i.e. dissolving the metal matrix only to a negligible extent).

These analyses can be performed on oxidation films of more than 100 Å thickness. The following solvents were used:

1) Methanol for solubilization of Na⁺, Cu⁺⁺ and Zn⁺⁺ chlorides and sulfates;

2) Glycine to solubilize bivalent metal compounds:Cu and Zn oxydes oxysulfates, oxycarbonates, oxychlorides of Cu and Zn;

3) NH₄ OH to solubilize Cu⁺⁺ and aluminum compounds.

A fair agreement was observed between the formulae derived by stoichiometric calculation applied to chemical analyses and the values obtained by X-ray analysis.

Agreement was satisfactory for all compounds, except aluminum, determined by chemical analysis and identified by X-rays only in very thick oxidation films (≥ 10³ Å). The role of chemical analysis is therefore determinant to finalize the formation mechanism of aluminum brass passivation films.     

Coupling of a one-dimensional river routing model and a three-dimensional ocean model to predict overbank flows in a complex river–ocean system

River–ocean coupled models were developed to calculate overbank flows in a complex river–coastal ocean system comprising the Wu River and the adjacent coastal ocean of central Taiwan. The hydrodynamic quantities were exchanged between one-dimensional and three-dimensional domains during runtime to resolve the real-time exchange and interaction between the coastal waters and the river system. The coupled model was calibrated and verified with the observed water levels using data from three typhoon events. The results indicate a reasonable agreement between the model simulations and the observed data. The model was then used to calculate hydrographs of the overbank flow caused by Typhoon Kalmaegi, which occurred in 2008. The simulated overbank flows quantitatively agreed with the reported information. We also demonstrated that most of the overbank flows occurred at the upper reaches of the tributaries of the Wu River system, except for the tributary in the Fazi River.