Single-walled carbon nanotubes as solid-phase microextraction adsorbent for the determination of low-level concentrations of butyltin compounds in seawater

Carbon nanotubes are a kind of new carbon-based nanomaterials, which have drawn great attention in many application fields. The potential of single-walled carbon nanotubes (SWCNTs) as solid-phase microextraction (SPME) adsorbent for the preconcentration of environmental pollutants has been investigated in recent years. In the present study, the feasibility of SWCNTs as SPME adsorbent for the determination of monobutyltin, dibutyltin and tributyltin in seawater samples was studied. To achieve this aim, the potential factors affecting the SPME efficiency, including extraction time, extraction temperature, desorption time, desorption temperature, and salinity were optimized. The developed method showed good performance according to the ICH (International Conference on Harmonization of Technical Requirements for Analytical Methods) criteria. The acquired calibration curves were linear (r ≥ 0.992) over the concentration range from ≤12 to 2000 ng L⁻¹. For all of the analytes, the limit of detection at signal-to-noise ratio of 3 was below 5 ng L⁻¹. Furthermore, in comparison with the commercial carboxen/polydimethylsiloxane fiber, the developed SWCNT fiber showed better thermal stability (over 350 °C) and longer life span (over 150 times). The application of the proposed method in environmental analyses was shown by analyzing seawater samples from the harbors on the Persian Gulf for butyltin residues. Some of the butyltins were detected in the analyzed samples. Results of the present study demonstrate the feasibility of the SWCNTs as SPME adsorbent for the determination of butyltins in seawater samples.     

Surface Changes at Platinized Platinum Based Hydrogen Gas Electrodes Following Use in Highly Saline Aqueous Solutions

Platinized platinum based hydrogen gas electrodes, Pt(Pt)|H₂(g)|H⁺(aq), and silver‐silver chloride electrodes, Ag|AgCl|Cl^? (aq), make up the Harned cell, without transfer, working in the potentiometric mode at Cl^? concentrations and ionic strengths, I, below 0.1 mol kg^?1, for assigning primary pH values to reference pH buffer solutions. This work reports on experiments performed at higher I and Cl^? solutions up to 0.7 mol kg^?1, aiming at addressing seawater conditions with results of equally high quality. In the course of measurements, the occasional occurrence of highly unstable potentials denoted electrode malfunction; Pt metal surfaces observed by SEM/EDS and XRD exhibit strong Ag and Cl peaks corresponding to the presence of AgCl crystals deposited at both surfaces.     

New ion exchange membrane derived from sulfochlorated polyether sulfone for electrodialysis desalination of brackish water

The purpose of this work is to study the desalination of brackish water using a new ion exchange membrane, made from sulfochlorated polyethersulfone (Cl‐PES), and crosslinked using aminated polyethersulfone (NH2‐PES) as a crosslinking reagent. This membrane, named ClNH2 membrane, has been obtained by reaction between Cl‐PES with 1.3 SO₂Cl groups per monomer unit and 0.2 equivalent amount of NH2‐PES. ClNH2 membrane has been characterized in terms of contact angle, transport number, intrinsic conductivity, and water uptake (as a function of temperature). Electrodialysis performances of the newly synthetized membranes have been measured using an electrodialysis cell at a laboratory scale and compared to commercial membranes. All the experiments have been performed using synthetic brackish water solutions prepared from sodium chloride salts with different concentrations (varying from 0.5 to 5.0 g/L). The concentration of different water samples obtained has been found to be below the amount recommended by the World Health Organization (WHO) for drinking water.     

水通道蛋白启发下的人工水通道研究进展

受水通道蛋白(AQP)结构与功能启发,含有生物水通道或人工水通道(AWC)的仿生膜近年来取得了显著进展.借鉴AQP的传输特性,所制备的AWC获得了高度的选择性及水快速运输能力.通过对AQP的结构原型进行分析,对标AWC中H2O分子选择性和渗透特性,尝试提出了"门控效应"、"润湿效应"和"排队效应"3种效应,并对现有嵌入...     

Determination of total arsenic in seawater by hydride generation atomic fluorescence spectrometry

In this work, the determination of total As in seawater by hydride generation atomic fluorescence spectrometry was studied. The influence of the chemical, flow and instrumental parameters were investigated and optimized. The pre-reduction of As(V) to As(III) was performed using KI plus ascorbic acid in 3.5 mol L^− 1 HCl medium. No multiplicative interference was present and external aqueous calibration could be used. The limit of detection was 36 ng L^− 1, while the repeatability was 2% (n = 10), at a 500 ng L^− 1 concentration level. The sample throughput was 15 h^− 1 if triplicate measurements were made. The accuracy was assessed by the analysis of a seawater certified reference material and excellent agreement between the obtained and certified values was verified. The procedure was used for the analysis of seawater offshore samples collected at the Brazilian coast and results ranging from 860 to 1200 ng L^− 1 were found.     

Study on the matrix effect in the determination of selected pharmaceutical residues in seawater by solid-phase extraction and ultra-high-performance liquid chromatography–electrospray ionization low-energy collision-induced dissociation tandem mass spectrometry

Matrix effect is a major problem when trace level pharmaceuticals in seawater were analyzed using solid-phase extraction (SPE) combined with high-performance liquid chromatography–electrospray ionization tandem mass spectrometry (HPLC–ESI–MS–MS). Therefore, efforts should be devoted to diminish matrix effect as much as possible. The present study investigates the matrix effect during the analysis of selected pharmaceutical residues (naproxen, ibuprofen, diclofenac and gemfibrozil) in seawater samples with ultra-high-performance liquid chromatography (UHPLC)–ESI low-energy collision-induced dissociation (CID) MS–MS. Solutions to reduce matrix effect were studied through optimization of SPE procedure and the employment of isotope-labeled analogues. Results showed that 30 mL of deionized water can efficiently diminish matrix effect and satisfactory absolute mean recoveries ranging from 73.5% to 120.5% were obtained in the optimized SPE condition. Isotope-labeled analogues employed as surrogates were found to be efficient to further compensate for matrix effect, with the relative mean recoveries ranging from 85.5% to 110.5%. The optimized method has been successfully applied for the analysis of target pharmaceutical residues in different seawater samples.     

Dissolved oxygen in the bottom water of the Sea of Japan as a sensitive alarm for global climate change

The Sea of Japan, a semi-closed marginal sea (greatest depth ∼3700 m) in the northwestern-most Pacific Ocean, has an independent, deep convection system, which is driven by the formation and the sinking of cool, saline surface water towards the bottom in severe winters. Continuous measurement of dissolved oxygen using highly precise versions of the Winkler titration method has revealed 8-10% decreases in the bottom concentration of oxygen (O₂) over the past 30 years. The temporal decrease in O₂ means an imbalance between the supply of O₂ from the surface and the in situ consumption of O₂ in decomposing organic matter, suggesting that the change in the deep convection pattern of the Sea of Japan is probably caused by global climate change to reduce winter cooling of surface seawater.     

Comparison of Alternate Reactants for pM Level Cobalt Analysis in Seawater by the Use of Catalytic Voltammetry

The analysis of Cobalt (Co) at low pM concentrations in seawater with Adsorptive Cathodic Stripping Voltammetry involves high concentrations of sodium nitrite (NaNO₂) to enhance the signal in an electrocatalytic reaction. In this study we found three substitutes for NaNO₂ that critically affected the sensitivity. Optimisation of a method with potassium bromate (KBrO₃) resulted in an excellent detection limit (0.9 pM) after a 90 s adsorption period. Reactant concentration and consumption were 10× reduced compared to protocols with NaNO₂ and reagent blanks were lower. Accuracy and precision were verified with SAFe intercalibration standards and the method was applied using open ocean seawater samples. The reaction mechanism is discussed and differences to NaNO₂ are shown.     

High-precision measurements of seawater Pb isotope compositions by double spike thermal ionization mass spectrometry

A new method for the determination of seawater Pb isotope compositions and concentrations was developed, which combines and optimizes previously published protocols for the separation and isotopic analysis of this element. For isotopic analysis, the procedure involves initial separation of Pb from 1 to 2 L of seawater by co-precipitation with Mg hydroxide and further purification by a two stage anion exchange procedure. The Pb isotope measurements are subsequently carried out by thermal ionization mass spectrometry using a ²⁰⁷Pb–²⁰⁴Pb double spike for correction of instrumental mass fractionation. These methods are associated with a total procedural Pb blank of 28 ± 21 pg (1sd) and typical Pb recoveries of 40–60%. The Pb concentrations are determined by isotope dilution (ID) on 50 mL of seawater, using a simplified version of above methods. Analyses of multiple aliquots of six seawater samples yield a reproducibility of about ±1 to ±10% (1sd) for Pb concentrations of between 7 and 50 pmol/kg, where precision was primarily limited by the uncertainty of the blank correction (12 ± 4 pg; 1sd). For the Pb isotope analyses, typical reproducibilities (±2sd) of 700–1500 ppm and 1000–2000 ppm were achieved for ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, ²⁰⁸Pb/²⁰⁴Pb, respectively. These results are superior to literature data that were obtained using plasma source mass spectrometry and they are at least a factor of five more precise for ratios involving the minor ²⁰⁴Pb isotope. Both Pb concentration and isotope data, furthermore, show good agreement with published results for two seawater intercomparison samples of the GEOTRACES program. Finally, the new methods were applied to a seawater depth profile from the eastern South Atlantic. Both Pb contents and isotope compositions display a smooth evolution with depth, and no obvious outliers. Compared to previous Pb isotope data for seawater, the ²⁰⁶Pb/²⁰⁴Pb ratios are well correlated with ²⁰⁷Pb/²⁰⁶Pb, underlining the significant improvement achieved in the measurement of the minor ²⁰⁴Pb isotope.     

A miniature and field-applicable multipumping flow analyzer for ammonium monitoring in seawater with fluorescence detection

In this article, a simple, economic, and miniature flow analyzer for ammonium in seawater based on the solenoid micropumps is presented. A single reagent of sodium tetraborate, ortho-phthaldialdehyde (OPA), and sodium sulfite was used and optimized applying the modified SIMPLEX method. A special-made detection cell for fluorescence detection of the reaction product isoindol-1-sulfonat was made and combined with a commercial photomultiplier tube, a long-pass optical filter, and an UV-LED as excitation light source. A LOD down to 13 nmol/L was achieved. The fabrication and application of a miniature reaction coil heating device for reaction rate enhancement is further described. The system featured an injection frequency of 32 h⁻¹ at average standard deviation of 3%.