Matrix removal for the ion chromatographic determination of some trace elements in milk

An ion chromatographic method has been developed for the determination of some microelements in different types of milk. It involves oxidative photodegradation of the organic matrix with H₂O₂ in a UV digester, equipped with a high-pressure mercury lamp. The temperature of the sample is maintained at 85±5 °C by a combined air/water cooling system. This procedure provides an efficient alternative to traditional dry ashing and wet digestion methods. Milk degrades in less than 2 h, while inorganic constituents, except for iodide, nitrate, nitrite, sulfite and manganese (II), are unaffected by UV radiation. Depending upon the type of milk (whole, skimmed, powdered, evaporated, etc.) to be analysed, the amount of sample and the UV photolysis time can be adjusted as per requirements. The clear solution resulting from the UV digestion is diluted, filtered and injected onto an ion chromatograph equipped with both conductivity and variable-wavelength UV-Vis detectors. The method has been tested with standards and real milk samples and has been found to be satisfactory for the determination of total chloride, bromide, phosphorus (as phosphate) and sulfur (as sulfate), and of copper, nickel, zinc, cobalt, iron and lead.     

Determination of selenium in freshwaters by cathodic stripping voltammetry after UV irradiation

An analytical method was developed for the determination of total dissolved selenium in fresh waters, using linear sweep cathodic stripping voltammetry (CSV) in combination with UV photolytic digestion. Both the CSV method, based on the electrodeposition and stripping of Cu(2)Se, and the UV irradiation procedure were investigated in detail. In the presence of dissolved organic substances, as in freshwaters, Se(VI) is reduced to Se(IV) by UV irradiation in 0.1M hydrochloric acid. Glucose can be used as the carbon source in samples low in natural dissolved organic carbon (DOC). The photolytic yields of Se(IV) were about 90% in both cases. Five freshwater samples were analysed for total selenium by CSV after UV photolysis, and by hydride generation atomic absorption spectrometry (HG-AAS) after oxidative digestion followed by reduction with hydrochloric acid. The results agreed well and the concentrations were in the range 70-190 ng/l., well above the detection limit of the CSV method at 2 ng/l.     

Development and validation of a solid-phase microextraction method for the analysis of volatile organic compounds in groundwater samples

Summary Solid-phase microextraction is a relatively recent extraction technique for sample preparation. It has been used successfully to analyse environmental pollutants in a variety of matrices such as soils, water and air. In this work, a simple and rapid method for the analysis of volatile organic and polar compounds from polluted groundwater samples by SPME coupled with gas chromatography (GC) is described. Different types of fibres were studied and the extraction process was optimised. The fibre that proved to be the best to analyse this kind of samples was CAR-PDMS. The method was validated by analysis of synthetic samples and comparison with headspace—GC. The optimised method was successfully applied to the analysis of ground-water samples.     

Fast neutron activation: Sample preparation utilizing graphite as a diluent

A method has been developed for the preparation of irradiation samples which ensures that both standard and unknown samples are of the same size, shape, density and composition. Powdered standard and unknown samples were diluted with graphite to give homogeneous mixtures containing ≥80% graphite; these mixtures were pressed into cylindrical pellets. This method of sample preparation has been applied to the determination of nitrogen in organic and polymeric compounds. The results generally agree with Kjeldahl analyses within 5%. This work was supported by the United States Atomic Energy Commission.     

Simultaneous quantification of polar and non-polar volatile organic compounds in water samples by direct aqueous injection-gas chromatography/mass spectrometry

A direct aqueous injection-gas chromatography/mass spectrometry (DAI-GC/MS) method for trace analysis of 24 volatile organic compounds (VOCs) in water samples is presented. The method allows for the simultaneous quantification of benzene, toluene, ethyl benzene, and xylenes (BTEX), methyl tert-butyl ether (MTBE), tert-butyl alcohol (TBA), as well as a variety of chlorinated methanes, ethanes, propane, enthenes and benzenes. Applying a liquid film polyethylene glycol or a porous layer open tubular (PLOT) divinylbenzene GC capillary column to separate the water from the VOCs, volumes of 1-10 microL aqueous sample are directly injected into the GC. No enrichment or pretreatment steps are required and sample volumes as low as 100 microL are sufficient for accurate quantification. Method detection limits determined in natural groundwater samples were between 0.07 and 2.8 microg/L and instrument detection limits of <5 pg were achieved for 21 out of the 24 evaluated VOCs. DAI-GC/MS offers both good accuracy and precision (relative standard deviations 相似文献   

Sequential injection system for on-line analysis of total nitrogen with UV-mineralization

An automatic method for the determination of total nitrogen in wastewater by sequential injection analysis and mineralization with UV radiation has been developed. The method is based on the mineralization of the samples with sodium persulphate in basic medium under UV radiation. Small volumes of sample and reagents are firstly aspirated into a single channel and then propelled by flow reversal to the UV reactor and then to the detector. The organic and inorganic nitrogen compounds are oxidized to nitrate that is then measured at 226 nm. The sequential injection procedure has been optimized and the factors affecting the efficiency of the oxidation have been studied with a number of test substances with different chemical structures and properties. Solutions in the concentration range 1-56 g l⁻¹ of nitrogen can be analyzed with the described procedure. The sample rate is of 30-40 samples h⁻¹. The LOD is 0.6 mg l⁻¹ N and the reproducibility is 1.8% (28 mg l⁻¹ N). Organic carbon in the form of glucose was added to a number of test solutions to study the potential interference of organic matter.The method was compared with the Kjeldahl digestion method by analyzing 15 wastewater samples with both methods. The nitrate and nitrite content of the non-oxidized samples were subtracted from the corresponding nitrogen content determined after photo-oxidation and the value compared with the Kjeldahl nitrogen content.     

Analysis of aminobenzoic acids in waste water from a former ammunition plant with HPLC and combined diode array and fluorescence detection

 Aminobenzoic acids are of major interest in clinical analysis, but their determination in environmental samples has been rarely done. Therefore a method for the determination of 10 aminobenzoic acids in water has been developed, using high-performance liquid chromatography with combined diode array and fluorescence detection. A separation of the analytes has been achieved with a buffer pH 3/methanol gradient. The general elution order has been m-substituted<p-subst.<o-subst. aminobenzoic acids. UV and fluorescence data are presented. In a highly polluted water sample of the former ammunition plant Stadtallendorf/Hessen, 4-aminobenzoic acid, 2-amino- benzoic acid and 2-amino-4-nitrobenzoic acid have been detected. After passing a charcoal filter, only the concentration of 4-aminobenzoic acid in a sample from the same site has been above the detection limit. Besides the ten analytes investigated, several unknown compounds have been present in the samples. Received: 15 January 1996/Accepted 20 February 1996     

Analysis of aminobenzoic acids in waste water from a former ammunition plant with HPLC and combined diode array and fluorescence detection

 Aminobenzoic acids are of major interest in clinical analysis, but their determination in environmental samples has been rarely done. Therefore a method for the determination of 10 aminobenzoic acids in water has been developed, using high-performance liquid chromatography with combined diode array and fluorescence detection. A separation of the analytes has been achieved with a buffer pH 3/methanol gradient. The general elution order has been m-substituted<p-subst.<o-subst. aminobenzoic acids. UV and fluorescence data are presented. In a highly polluted water sample of the former ammunition plant Stadtallendorf/Hessen, 4-aminobenzoic acid, 2-amino- benzoic acid and 2-amino-4-nitrobenzoic acid have been detected. After passing a charcoal filter, only the concentration of 4-aminobenzoic acid in a sample from the same site has been above the detection limit. Besides the ten analytes investigated, several unknown compounds have been present in the samples. Received: 15 January 1996/Accepted 20 February 1996     

Simultaneous determination of benzophenone-type UV filters in water and soil by gas chromatography-mass spectrometry

A novel method has been developed to simultaneously determine and quantify seven organic UV filters employing liquid (solid)-liquid extraction, derivatization with N-methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA) and gas chromatography with mass spectrometric detection in various environmental matrices. The UV filters determined were: benzophenone (BP), benzhydrol (BH), 4-hydroxybenzophenone (HBP), 2-hydroxy-4-methoxybenzophenone (HMB), 2,4-dihydroxybenzophenone (DHB), 2,2'-dihydroxy-4-methoxybenzophenone (DHMB) and 2,3,4-trihydroxylbenzophenone (THB). Under optimal conditions, the analysis required 23 min and good linearity over the range of 10-2,500 ng/L in water and 100-25,000 ng/kg in soil for each UV filter obtained. The high recovery (62-114% and 60-125% for water and soil samples, respectively) and the low RSD values (less than 13.9 and 17.2% for water and soil samples, respectively) indicated the high performance of this method. The method detection limits (MDLs) were relatively low, ranging from 5 to 100 ng/L or kg and quantification limits ranged between 25 and 500 ng/L or kg for all test compounds. This validated method was applied in the analysis of seven BP-type UV filters collecting water and soil samples in Korea, between April and May 2003. The overall concentration of UV filters in the soil sample (500-18,380 ng/kg) was highly distributed in water sample (27-204 ng/L). The established method was successfully applied to monitor the residue measurement of the BP-type UV filters in environmental water and soil samples.     

Gamma ray decomposition of dissolved organic substances in river water without compositional change of metallic elements

A river water sample was irradiated with 60Co gamma-rays under aerobic conditions, and the changes of the organic substances in the sample were examined by the analyses of the dissolved organic carbon (DOC), organic composition, UV spectrum and molecular-weight distribution. By the irradiation, the DOC decreased with irradiation dose following the first-order kinetics. In addition, the changes of UV absorption and molecular-weight distribution showed that the considerable decomposition of polymeric aromatic structure, which is the characteristic of humic substances, took place by irradiation of relatively low dose. Since the gamma-ray decomposition does not require any oxidizing agents and pH control, it will cause no compositional change of metallic elements in the water samples and has less chance of contamination. Therefore the method will be useful in, for example, geochemical studies of trace metals in natural waters.     

Identification of free radicals induced by UV irradiation in collagen water solutions

Electron paramagnetic resonance (EPR) method has shown that hydrogen atoms and acetic acid free radicals appear in surrounding acetic acid-water solution of collagen under ultraviolet (UV) irradiation. These free radicals interact with the collagen molecule; consequently, seven superfine components of EPR spectrum with the split of aH = 11.3G and g-factor 2.001 appear. It is assumed that this spectrum is related to the free radical occurred on the proline residue in collagen molecule. In order to discover .OH hydroxyl radicals even in minor concentration, spin trap 5.5-dimethyl-1-pyrroline N-oxide (DMPO) has been applied. During the irradiation of collagen water solution in the presence of spin trap, EPR spectrum of the DMPO/.OH adduct has not been identified, while the above mentioned spectrum has been observed once the hydrogen peroxide H2O2 and FeSO4 were added to the sample. That means that water photolysis does not take place in collagen water-solution due to UV irradiation. It was suggested that occurrence of hydrogen radical is connected with the electron transmission to the hydrogen ion. The possible source of free electrons can be aromatic residues, photo ionization of which takes place in collagen molecule due to UV irradiation.     

Investigations of oxidative UV photolysis

Summary The behaviour of mercury during UV photolysis has been investigated. Mercury in the form of the inorganic compound mercury(II) nitrate and the organic compound methylmercury chloride was used in standards, model water samples and spiked municipal waste waters (10 g/l in each case). Despite the high digestion temperatures of ca. 90°C, losses due to evaporation are negligibly small, irrespective of the speciation of mercury.Part I: see [1]     

Photolytic and photocatalytic degradation of organic UV filters in contaminated water

UV filters as emerging contaminants are of great concern and their wide detection in aquatic environments indicates their chemical stability and persistence. This review summarized the photolytic and photocatalytic degradation of UV filters in contaminated water. The findings indicated that limited research has been conducted on the photolysis and photocatalysis of UV filters. Photolysis of UV filters through UV irradiation in natural water was a slow process, which was accelerated by the presence of photosensitisers e.g. triplet state of chromaphoric dissolved organic matter (³CDOM*) and nutrients but reduced by salinity, dissolved organic matter (DOM) and divalent cations. UV Photocatalysis of 4-methylbenzylidene camphor and 2-phenylbenzimidazole-5-sulfonic acid was very effective with 100% removal within 30 min and 90 min using medicated TiO₂/H₂O₂ and TiO₂, respectively. The radiation source, type of catalyst and oxygen content were key factors. Future research should focus on improved understanding of photodegradation pathways and by-products of UV filters.     

Sample Preparation Methods for the Determination of Chlorination Disinfection Byproducts in Water Samples

Chlorination has been widely used as a disinfection method for control of pathogens in drinking water and wastewater treatment plants. Chlorination disinfection byproducts (DBPs) are formed when organic matter is present in water, and they are harmful to human health. The main groups of compounds formed are trihalomethanes (THMs), haloacetic acids (HAAs) and haloacetonitriles (HANs). Analysis of THMs, HAAs and HANs in water samples has been reported. This paper reviews the various sample preparation methods in use for analysis of THMs, HAAs and HANs in water samples.

     

Optimization of a dispersive liquid-liquid microextraction method for the analysis of benzotriazoles and benzothiazoles in water samples

A simple and rapid dispersive liquid–liquid microextraction method has been developed for the determination of 11 benzotriazoles and benzothiazoles in water samples. Tri-n-butylphosphate (TBP) was used as extractant, thus avoiding the use of toxic water-immiscible chlorinated solvents. The influence of several variables (e.g., type and volume of dispersant and extraction solvents, sample pH, ionic strength, etc.) on the performance of the sample preparation step was systematically evaluated. Analytical determinations were carried out by high-performance liquid chromatography with fluorescence and UV detection and liquid chromatography–electrospray ionization-tandem mass spectrometry. The optimized method exhibited a good precision level with relative standard deviation values between 3.7% and 8.4%. Extraction yields ranging from 67% to 97% were obtained for all of these considered compounds. Finally, the proposed method was successfully applied to the analysis of benzotriazoles and benzothiazoles in real water samples (tap, river, industrial waters, and treated and raw wastewaters).     

Rapid, sensitive and on-line measurement of chemical oxygen demand by novel optical method based on UV photolysis and chemiluminescence

A novel on-line method based on the combination of UV photolysis and chemiluminescence detection was established and experimentally validated for the determination of chemical oxygen demand (COD). A quantitative amount of free radicals can be produced by analytes in the UV irradiation process. By utilizing the phenomenon that luminol can be oxidized by the free radicals to produce luminescence, COD was successfully determined indirectly. This new approach overcomes many problems associated with the conventional COD determination techniques such as long analysis time, tedious operations, consumption of expressive and toxic reagents, production of secondary toxic waste and poor reproducibility. The method was successfully applied to the determination of COD in synthetic samples, certified reference samples and real samples of river water and lake water. A limit of detection of 0.08 mg/L COD with a linear dynamic range of 0.2-20 mg/L was achieved under the optimum experimental conditions. The proposed method is a unique method that is environmentally friendly (without using any strong oxidizing reagent and any catalysts such as titanium dioxide), rapid (with only 5-10 min required for each sample), sensitive (with the lowest limit of detection for COD so far), simple (mainly with a photo-reactor and a chemiluminescence detector) and automated (using an intermittent flow system).     

Solid ink-printed filter paper as a green adsorbent material for the solid-phase extraction of UV filters from water samples

This work describes the development of a new green solid-phase extraction approach, which is based on the use of low-cost extraction discs composed of plain filter papers that are covered with a synthetic wax-like coating. The filter papers are printed in a commercial solid ink printer, which dispenses a synthetic wax-like ink on the surface of the paper, to cover the hydrophilic cellulose fibre matrix with an interface of lipophilic domains where non-polar analytes can partition through hydrophobic interactions. The modified paper filters were used to extract hydrophobic organic compounds from water samples following the customary procedure of solid-phase extraction without sorbent preconditioning and needless of high-vacuum sources. As a proof-of-concept application, a series of non-polar organic UV filters were used as model analytes to optimise the extraction parameters and evaluate the performance of the method in spiked water samples. Based on this principle, a new sample preparation platform with low environmental footprint has been developed that enables extraction to be carried out using low-cost, environmental benign and non-toxic conventional materials. The advantages and disadvantages of the method, alongside with its future prospects towards the development of custom-made ‘printed extraction kits’, are envisioned and discussed.     

185 nm UV降解水中4-CP、4-NP和Rh B的研究

本文以对氯苯酚(4-CP)、对硝基苯酚(4-NP)和罗丹明B(Rh B)为模型有机物(以4-CP和4-NP为小分子模型有机物,以Rh B为大分子模型有机物),分别研究了185 nm UV对水中这3种模型有机物的降解规律、性能和效果.研究结果表明,185 nm UV直接对水中4-CP、4-NP和Rh B有很好的降解效果.研究内容包括:185 nm UV降解模型有机物的浓度、TOC(Total organic carbon)浓度、185 nm UV降解模型有机物过程中溶液pH及电导率变化、以及降解模型有机物过程中产生的无机离子等几个方面.     

Effects of ultraviolet light on free and peptide-bound pyridinoline and deoxypyridinoline cross-links. Protective effect of acid pH against photolytic degradation

Little is known about the photodegradation of pyridinoline (Pyd) and deoxypyridinoline (Dpd), which are two mature cross-links stabilizing collagen within extracellular matrix. In this study, highly purified free Pyd and Dpd cross-links have been degraded by irradiation with ultraviolet light and we have shown that photolysis varies with the pH value. Assessment of photolysis in basic (pH 9) and neutral (pH 7) solutions by high-performance liquid chromatography as well as by UV absorbance measurement indicates that both cross-links are degraded after a 24 h UV exposure, while in acidic solution (pH 3) only Dpd is photolysed, suggesting that acid pH provides major protection against Pyd photolysis. Photodegradation products have been studied by amino-acid and mass spectral analysis. Both methods confirm the lack of Pyd degradation in acid pH. Furthermore, amino-acid analysis allows us to identify hydroxylysine and lysine as a result of Pyd and Dpd photolysis, respectively, indicating that the mechanism of photodegradation involves the cleavage of the pyridinium ring on each side of the quaternary nitrogen. Finally, we have also studied the photolysis of different molecular species of type I collagen peptides, obtained by digestion with collagenase of demineralized turkey bone. Our results indicate that even when they are part of the structure of collagen peptide, Pyd and Dpd can be photolysed. However, we have shown that the larger the peptide is, the smaller are the effects of UV irradiation.     

Critical comparison of two standard digestion procedures for the determination of total mercury in natural water samples by cold vapour atomic absorption spectrometry

Two pretreatment procedures for total mercury determinations in natural water samples were compared. The first, the Swedish Standard method (DP1), involves digestion of water in the presence of concentrated nitric acid at 120°C and under pressure for 30 min. In the West German Standard method (DP2), small volumes of nitric and sulphuric acids, permanganate and peroxodisulphate are added to the sample, and digestion proceeded at 50°C in an ultrasonic bath. Mercury was determined after both digestion procedures using a modified cold vapour atomic absorption spectrometric method, in which mercury generated on addition of a reducing agent is collected and subsequently atomized in a platinum-lined graphite furnace. The efficacy of the two digestion procedures was tested using various standard organic mercury compounds and it was found that only DP2 provided quantitative recoveries. Purification of the reagents required by DP2 was achieved using a mercury-selective ion-exchange resin, Chelite S, resulting in blank levels below 1.5 ng Hg l^?1. Both methods were applied to the determination of total mercury in an unpolluted marsh water sample, giving 2.0 ng Hg l^?1 (DP1) and 2.7 ng Hg l^?1 (DP2). The West German Standard digestion procedure (DP2) is recommended for the determination of total mercury in natural water samples.