Comparaison de Differentes Methodes Analytiques Appliquees au Dosage des Hydrocarbures Dissousdans L'Eaua L'etatde Traces

Abstract

Many physical-chemical methods are employed for the evaluation of trace hydrocarbons dissolved, in underground or surface waters.

Comparison is done of three techniques chosen amongst the most commonly used in the studies conducted on water pollution caused by oil products:

infrared spectroscopy;

ultraviolet spectrofluorimetry;

gas chromatography.

To enable the application of these techniques to very low concentrations of hydrocarbon all these techniques require a concentration step.

This can be carried out, either by the liquid-liquid extraction of the hydrocarbons with the assistance of an organic solvent and in this case, the concentration ratios are poor, or by the trapping technique, where the hydrocarbon concentration is effected by adsorption on a resin, followed by desorption by a relatively small amount of an appropriate organic solvent. The water amounts so treated can be 10 to 100 larger than those treated by a liquid-liquid extraction.

A trapping system is described which has been used in an initial phase for the detection and quantitation of aromatic hydrocarbons up to C₉. The operational conditions are described for the measurement of heavier hydrocarbons (sampled water quantity and flow, desorption solvent, amount of resin).

The importance of the concentration method and of the sensitivity of the analytical techniques chosen for the definition of the detection threshold of the dissolved hydrocarbons is pointed out.

In addition to the detection level problems for certain types of hydrocarbons, the selectivity of these techniques is considered.

In conclusion, the various methods are compared amongst themselves from the point of view of their application, of the quality of the results which are obtained and of their applicability to the different real water samples polluted by hydrocarbons.     

High Performance Liquid Chromatography Analysis of Sugar Cane Bagasse Hydrogenation Products. I. Group-Type Separation

Abstract

An HPLC Group-Type Separation was developed for the analysis of the liquefaction product of sugar cane wood fibers (bagasse). First, a liquid-liquid extraction technique was applied to separate the highly polar and polymerized aqueous fraction from the less polar organic fraction. This last fraction was then separated by HPLC into four classification groups: three hydrocarbons (saturates, olefins and aromatics) and a combination of polar compounds.

The application of these extraction and separation methods to the analysis of Brazilian sugar cane residue liquefaction products was very promising since the major group present in the extract is the aromatic hydrocarbons, suggesting its potential use as chemical feedstock, as well as a possible renewable source of energy. In addition, the method generates discrete and “clean” fractions for further detailed characterization when desired.     

一种新的光催化氧化体系用于化学需氧量的测定研究

基于KMnO₄能获得光生电子从而提高半导体光催化氧化能力的原理,建立了一种用纳米ZnO-KMnO₄协同体系光催化测定化学需氧量(COD)的新方法,探讨了催化氧化测定COD的机理,考察了测定COD的最佳反应条件.COD值浓度在1.5～10mg/L范围内与信号呈良好的线性关系,检测限为0.5mg/L.用本方法测定实际水样,结果和标准高锰酸盐指数法(COD_Mn法)相符.     

Study on photocatalytic oxidation for determination of the low chemical oxygen demand using a nano-TiO2-Ce(SO4)2 coexisted system

A new photocatalytic system, nano-TiO₂-Ce(SO₄)₂ coexisted system, which can be used to determine the low chemical oxygen demand (COD) is described. Nano-TiO₂ powders is used as photocatalyst in this system. The measuring method is based on direct determination of the concentration change of Ce(IV) resulting from photocatalytic oxidation of organic compounds. The mechanism of the photocatalytic oxidation for COD determination was discussed and the optimum experimental conditions were investigated. Under the optimum conditions, a good calibration graph for COD values between 1.0 and 12 mg l⁻¹ was obtained and the LOD value was achieved as low as 0.4 mg l⁻¹. When determining the real samples, the results were in good agreement with those from the conventional methods.     

光催化氧化法测定地表水化学需氧量的研究

用溶胶-凝胶法在石英管上制备了纳米TiO₂膜, 并采用光催化氧化法建立了一种测定地表水化学需氧量(COD)的新方法. 以Ce(IV)作为纳米TiO₂光生电子的接受体, 从而减少了纳米TiO₂光生电子和光生空穴的复合, 提高纳米TiO₂的光催化氧化能力. 以测定Ce(IV)的紫外吸收为手段探讨了光催化氧化测定COD的机理, 考察了测定COD的最佳反应条件. 实验结果表明, 该方法条件温和, 不会造成二次污染, 能够实现地表水等低COD值水样的快速准确测定. 在该实验所选择的条件下, 可准确地测定1.0～12 mg?L^－1之间的COD值, 检测限为0.4 mg?L^－1.     

纳米TiO2膜用于光催化氧化测定化学需氧量的研究

A photocatalytic oxidation method for determination of chemical oxygen demand （COD） using nano-TiO2 film, based on the use of a nano-TiO2-Ce（SO4）2 system and electrochemical detection, was proposed. The technique was originated from the direct determination of the Ce（Ⅲ） concentration change resulting from photocatalytic oxidation of organic compounds. Ce（Ⅲ）, which was produced by photocatalytic reduction of Ce（SO4）2, could be measured at a multi-walled carbon nanotubes （MWNT） chemically modified electrode （CME）. The COD values by this method were calculated from the differential pulse voltammetry （DPV） current of Ce（Ⅲ） at the CME. Under the optimal operation conditions, the detection limit of 0.5 mg·L^-1 COD with the linear range of 1-600 mg·L^-1 was achieved. This method was also applied to determination of various COD of ground water and wastewater samples. The resuits were in good agreement with those from the conventional COD methods, i.e., permanganate and dichromate ones.     

Sensitive and Green Method for Determination of Chemical Oxygen Demand Using a Nano‐copper Based Electrochemical Sensor

Copper nanoparticles (nano‐Cu) were electrodeposited on the surface of glassy carbon electrode (GCE) potentiostatically at −0.6 V vs. Ag/AgCl for 60 s. The developed nano‐copper modified glassy carbon electrode (nano‐Cu/GCE) was optimized and utilized for electrochemical assay of chemical oxygen demand (COD) using glycine as a standard. The surface morphology and chemical composition of nano‐Cu/GCE were investigated using scanning electron microscope (SEM) and energy dispersive X‐ray spectrometer (EDX), respectively. The electrochemical behavior was investigated using linear sweep voltammetry (LSV) which is characterized by a remarkable anodic peak at ∼0.6 V, compared to bare GCE. This indicates that nano‐Cu enhances significantly the electrochemical oxidation of glycine. The effect of different deposition parameters, such as Cu²⁺ concentration, deposition potential, deposition time, pH, and scan rate on the response of the developed sensor were investigated. The optimized nano‐Cu/GCE based COD sensor exhibited a linear range of 15 to 629.3 ppm, and a lower limit of detection (LOD) of 1.7 ppm (S/N=3). This developed method exhibited high tolerance level to chloride ion (0.35 M chloride ion has minimal influence). The analytical utility of the prepared COD sensor was demonstrated by investigating the COD recovery (99.8±4.3) and the assay of COD in different water samples. The results obtained were verified using the standard dichromate method.     

Study on photocatalytic oxidation for determination of chemical oxygen demand using a nano-TiO2-K2Cr2O7 system

A photocatalytic method for the determination of chemical oxygen demand (COD) using a nano-TiO₂-K₂Cr₂O₇ system is described. The measuring principle is based on direct determination of the change of Cr(III) concentration resulting from photocatalytic oxidation of organic compounds and simultaneous photocatalytic reduction of stoichiometrically involved K₂Cr₂O₇ in the solution. The operation conditions were optimized. The determinative COD value using this method was calculated from the absorbance of Cr(III). The operational characteristics of this method were demonstrated by use of a standard glucose solution as substrate. This method was also applied to the determination of the COD of wastewater samples. The results were in good agreement with those from the conventional (i.e., dichromate) COD methods.     

Microwave-Assisted Ionic Liquid Extraction of n-Alkanes and Isoprenoid Hydrocarbons from Petroleum Source Rock

Microwave-assisted ionic liquid extraction (MAILE) has been investigated for the extraction of n-alkanes and isoprenoid hydrocarbons from petroleum source rock and the conditions for maximum yield of the analytes were determined. An aqueous solution of an ionic liquid, 1-butyl-3-methylimidazolium bromide (BmimBr), was employed as the extracting medium. The results showed that the concentration of ionic liquid, extraction time and extraction temperatures have effects on extraction yields of aliphatic hydrocarbons with optimal conditions at: 3.0 mol L⁻¹ ionic liquid solution, 30 min and 120 °C, respectively. The extraction yields of all the n-alkanes and acyclic isoprenoid hydrocarbons were much higher using microwave-assisted ionic liquid extraction than with Soxhlet extraction and accelerated solvent extraction. There were good correlations of the diagnostic geochemical ratios calculated from the gas chromatographic (GC) data of MAILE, Soxhlet extraction and accelerated solvent extraction. The results of this study show that MAILE is an efficient and green analytical preparatory technique for geochemical evaluation of petroleum source rock.

     

Photoelectro‐Synergistic Catalysis at Ti/TiO2/PbO2 Electrode and Its Application on Determination of Chemical Oxygen Demand

In this paper, photoelectro‐synergistic catalysis oxidation of organics in water on Ti/TiO₂/PbO₂ electrode was investigated by the method of electrochemistry. Furthermore, the results were compared with those obtained from photocatalysis and electrocatalysis. The method proposed was applied to determine the chemical oxygen demand (COD) value, Ti/TiO₂/PbO₂ electrode functioning as the work electrode during the process. It was shown that the method of photoelectro‐synergistic catalysis had lower detection limit and wider linear range than the methods of electroassisted photocatalysis and electrocatalysis. The results obtained by the proposed method and conventional one were compared by carrying out the experiment on 8 wastewater samples. The correlation of the results using different methods was satisfactory and the relative bias was below ±6.0%.     

A Comparison of Two Sampling Devices for the Recovery of Organics from Aqueous Surface Films

Abstract

Teflon disc and wire screen type surface film samplers were compared as to their consistency and efficiency of retrieval of hydrocarbons, aromatics, and free fatty acids. Both laboratory and field experiments were conducted. The results obtained suggest that each device exhibits selectivity in its respective ability to recover organic compounds at the air-water interface.     

Electrochemical sensing chemical oxygen demand based on the catalytic activity of cobalt oxide film

Cobalt oxide sensing film was in situ prepared on glassy carbon electrode surface via constant potential oxidation. Controlling at 0.8 V in NaOH solution, the high-valence cobalt catalytically oxidized the reduced compounds, decreasing its surface amount and current signal. The current decline was used as the response signal of chemical oxygen demand (COD) because COD represents the summation of reduced compounds in water. The surface morphology and electrocatalytic activity of cobalt oxide were readily tuned by variation of deposition potential, time, medium and Co²⁺ concentration. As confirmed from the atomic force microscopy measurements, the cobalt oxide film, that prepared at 1.3 V for 40 s in pH 4.6 acetate buffer containing 10 mM Co(NO₃)₂, possesses large surface roughness and numerous three-dimensional structures. Electrochemical tests indicated that the prepared cobalt oxide exhibited high electrocatalytic activity to the reduced compounds, accompanied with strong COD signal enhancement. As a result, a novel electrochemical sensor with high sensitivity, rapid response and operational simplicity was developed for COD. The detection limit was as low as 1.1 mg L⁻¹. The analytical application was studied using a large number of lake water samples, and the accuracy was tested by standard method.     

Electrocatalytic Sensor for the Determination of Chemical Oxygen Demand Using a Lead Dioxide Modified Electrode

An amperometric method that makes use of a nano‐PbO₂ modified electrode as an electrocatalytic sensor for the determination of chemical oxygen demand (COD) is described. The sensor signal was observed as a result of the detection of the oxidation current due to electrocatalytic oxidation of organic compounds in the sample solution. This sensor responded linearly to the COD_Cr of standard samples in the range of 5–3 000 ppm and the detection limit was 2.5 ppm. When using the sensor to determine real samples, it displays short analysis time, simplicity and no sample pretreatment. The sensor was stable for over 20 days in real wastewater samples and has successfully been applied to the determination of COD in real wastewater samples.     

Comparison of Extraction Techniques and Surfactants for the Isolation of Total Polyphenols and Phlorotannins from the Brown Algae Lobophora variegata

Abstract

Surfactant-mediated extraction (SME), pressurized liquid extraction (PLE), and enzyme-assisted extraction (EAE) have been compared to improve the isolation of phlorotannins from the brown algae Lobophora variegata. Enzymatic treatment with Alcalase 2.4?L FG, Carezyme 4500?L, protease from Streptomyces griseus, pectinase from Aspergillus niger, Celluclast 1.5?L, protease from Bacillus licheniformis; surfactant extraction with triacetin and guaiacol and PLE with ethanol:water as extracting solvent, have been studied in terms of total phenolic content by the Folin–Ciocalteu method and total phlorotannin content using the DMBA assay. The results showed that SME yields the highest amount of phenols and phlorotannins by using food grade guaiacol as the surfactant. An extraction protocol was developed to maximize the amount of extract obtained from L. variegata. The effects of various parameters such as the type of surfactant, efficacy of surfactant, and optimum pH, on the extraction efficiency of polyphenols were examined. The simultaneous use of the enzyme and surfactant was also investigated. However, a synergistic effect between the enzymes and the surfactant for the extraction of polyphenols has not been observed. Considering total phenols and total phlorotannins in the extract, the extraction yield were obtained for total phenols as SME?>?EAE?>?PLE and for total phlorotannins as SME?>?PLE?>?EAE.     

Preparation of photocatalytic nano-ZnO/TiO2 film and application for determination of chemical oxygen demand

A composite nano-ZnO/TiO₂ film as photocatalyst was fabricated with vacuum vaporized and sol-gel methods. The nano-ZnO/TiO₂ film improved the separate efficiency of the charge and extended the range of spectrum, which showed a higher efficiency of photocatalytic than the pure nano-TiO₂ and nano-ZnO film. The photocatalytic mechanism of nano-ZnO/TiO₂ film was discussed, too. A new method for determination of low chemical oxidation demand (COD) value in ground water based on nano-ZnO/TiO₂ film using the photocatalytic oxidation technology was founded. This method was originated from the direct determination of the Mn(VII) concentration change resulting from photocatalytic oxidation of organic compounds on the nano-ZnO/TiO₂ film, and the COD values were calculated from the absorbance of Mn(VII). Under the optimal operation conditions, the detection limit of 0.1 mg l⁻¹, COD values with the linear range of 0.3-10.0 mg l⁻¹ were achieved. The results were in good agreement with those from the conventional COD methods.     

Direct Electrochemical Ritter-Type Amination of Electron-Deficient Arenes

Due to the high oxidation potentials of electron-deficient aromatic hydrocarbons, it is difficult to achieve the direct oxidative C(sp²)−H bonds functionalizations of such substrates. Herein, we develop a Ritter-type amination of electron-deficient aromatics by merging electricity and sulfate. This practical and straightforward method provides a series of acetanilides from simple electron-deficient arenes, including mono-, di- and tri-substituted arenes (22 examples, up to 75 %) with moderate to good yields under mild conditions. This method is characterized by cheap and readily available regents, atom and step economy.     

Characterization of Sediments in Aerated Lagoons and Waste Stabilization Ponds

Abstract

Sediments affect the performance of aerated lagoons and waste stabilization ponds in many ways. This paper presents the results of a three years study conducted on real-size facilities and implementing numerous analytical procedures. Sediment accumulation rates and physico-chemical characteristics are described as well as their activity in terms of oxygen consumption and exchange rates with overlying waters.

The deposits had a mean accumulation rate of 4.7 cm per year, their main characteristics being low viscosity and high organic content (>30%). They also accumulated numerous organic and mineral compounds, such as nutrients and heavy metals. Vertical concentration profiles, measured in the sediment and interstitial liquid phases, are presented and discussed. These results emphasize the importance of surface activity.

Sediment oxygen demand, which can be divided into biological and chemical components, ranged from 1 to 3 gO₂/m²·d. Finally, the exchange rates of COD, nitrates, ammonia and orthophosphates existing at sediment-water interface were quantified under several redox conditions and substrate additions.     

磺酰化修饰聚苯乙烯的合成及芳香烃萃取性能简

利用自由基聚合反应合成了低分子量聚苯乙烯,经过端基氧化和磺酰化反应,制备出一系列极性砜基修饰的低分子量聚苯乙烯. 通过红外光谱(FTIR)、核磁共振谱(NMR)、差示扫描量热分析(DSC)以及热重分析(TGA)等手段对聚合物的结构和性能进行了表征,并通过混合烃萃取分离实验对其芳香烃选择性进行了测试. 结果表明,随着磺化比例的增加,甲苯的选择系数和分布系数均显著提高,表明极性修饰聚苯乙烯对多种芳香烃/链烷烃混合物均具有明显的芳香烃选择性.     

Initial Validation of a New Procedure for Determining Aromatics in Petroleum Distillates

Abstract

The analytical data from an initial validation of a new method developed for determining aromatics in distillate fuels is reported. The method applies supercritical fluid chromatography (SFC) for the liquid chromatographic separation of total saturates and total aromatics, followed by flame ionization detection. A study was conducted to determine the validity of a SFC procedure after it was proposed to the Canadian national standard writing body for its adoption as a new standard method for determining aromatics. Inter-laboratory results suggest that SFC provides reproducible data among different laboratories and these SFC data correlate well with those obtained from other methods such as fluorescent indicator adsorption (FIA), nuclear magnetic resonance (NMR), and mass spectrometry (MS).     

One-pot conversion of aromatic bromides and aromatics into aromatic nitriles via aryllithiums and their DMF adduct

Various aromatic bromides and iodides were smoothly converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH₃. The same treatment of typical aromatics and heteroaromatics with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH₃ also provided the corresponding aromatic nitriles in good yields. Moreover, the same treatment of aromatic bromides and aromatics with half amount of DIH (1,3-diiodo-5,5-dimethylhydantoin) instead of molecular iodine worked effectively to give the corresponding aromatic nitriles, respectively, in good yields. These reactions are novel and environmentally benign one-pot methods for the preparation of aromatic nitriles from aromatic bromides and aromatics, respectively, through the formation of aryllithiums and their DMF adducts.