Static headspace versus head space solid-phase microextraction (HS-SPME) for the determination of volatile organochlorine compounds in landfill leachates by gas chromatography

The determination of five volatile organochlorine compounds, VOX (chloroform, 1,1,1-trichloroethane, carbon tetrachloride, trichloroethene and tetrachloroethene) in raw landfill leachates and biologically cleansed leachates by GC-MS is investigated. Two extraction and preconcentration procedures were evaluated for recovery of such analies from the samples, including static headspace (HS) and solid phase microextraction by sampling the headspace above the sample (HS-SPME). Optimisation of operating parameters for the best performance of both, sampling and preconcentration techniques was described. Detection limits, time of analysis, precision and linear ranges of both introduction techniques have been established. Application of proposed methods to the determination of the five VOX under study in the above referred samples revealed the absence of such analytes in both leachates. Then both methods were applied to the determination to the five organochlorine compounds under study on spiked leachates samples. While HS-GC-MS offered better analytical precision than HS-SPME-GC-MS, this last technique gave a faster analytical response because no dilution must be done for a reliable VOX determination in landfill leachates. In any case, both sample introduction techniques tested provides excellent recoveries and good analytical precision (ranged from 1 to 3%).     

Pretreatment of landfill leachate by chemical oxidation processes

Kinetics and efficiency of Fenton’s and ozonation processes for the pretreatment of two landfill leachates (fresh and mature) resulting from municipal waste disposal were studied. Both samples presented high organic load, high toxicity and low biodegradability. These were the reasons why oxidative treatment was proposed. Fresh and mature leachate showed different behaviors in the oxidation experiments. The final extents of removal were attained in comparable time intervals in both oxidation systems. Maximal removal of organics by the Fenton’s oxidation reached more than 50 % according to COD. Zero or first order kinetics were found the best to describe the organic components (in terms of COD and DOC) removal by the Fenton’s oxidation for both landfill leachates. Higher reaction rate values of the Fenton’s oxidation were achieved with fresh leachate samples. The efficiency of initial organics removal with ozone was about 70 % for mature leachate, while in case of the fresh one only 41 % of COD were removed. The best fits of COD and DOC experimental data from oxidation of fresh and mature leachates were obtained by a combined kinetic model. No significant improvement of the biodegradability of landfill leachates was achieved using these treatment procedures. Regarding toxicity, ozonation showed to be more effective than the Fenton’s oxidation. Advanced oxidation experiments confirmed that the Fenton’s oxidation and ozonation are comparable oxidative treatment techniques for the reduction of organic pollution in the investigated municipal landfill leachates. However, neither of them is effective enough to be used as a pretreatment method followed by biological treatment.     

Direct determination of chlorophenols in landfill leachates by solid-phase micro-extraction-gas chromatography-mass spectrometry

Landfill leachates represent a serious environmental concern with regard to trace priority pollutants introduced into the aquatic environment. From the analytical point of view, they constitute complex matrices because of their high organic matter content and competition with the trace analytes in the extraction procedure. Although the use of SPME to extract chlorophenols in leachates has already been described in several publications, the limited number of chlorophenols restricts this analysis field of application. This paper presents a new analytical methodology to determine 13 chlorophenols and phenol by SPME-GC-MS in landfill leachates. The overall analysis was performed in 90 min and the detection limits range from 0.005 microg/l (pentachlorophenol) to 2.5 microg/l (phenol). Reproducibility, expressed by the coefficient of variation of repeated extractions at different concentration levels of the analytes, was on average inferior to 10%. Recovery, evaluated by standard addition to leachates, was 86.2% on average. Pentachlorophenol, 2,3,4,5-tetrachlorophenol and 2,3,4,6-tetrachlorophenol were the sole analytes detected at nanogram level in the landfill leachates analysed.     

Co/Bi催化剂催化湿法氧化降解垃圾渗滤液中的氨氮

采用催化湿法氧化(CWAO)技术,以Co/Bi为催化剂,对垃圾渗滤液中氨氮(NH₃-N)进行降解处理,并利用GC-MS检测了垃圾渗滤液中含氮有机物的相对含量.结果表明,随着反应温度的升高,CWAO对NH₃-N的降解能力逐渐增强,在220,240,260和280℃条件下,NH₃-N降解规律符合一级动力学反应(r>0.93,n=6).在升温过程(20～300℃)中,NH₃-N浓度变化经历了先升后降两个阶段,并在220℃时达到最大值.GC-MS检测结果表明,在第一阶段,垃圾渗滤液中几种含氮有机物因催化氧化而生成NH₃-N;第二阶段,NH₃-N逐渐被氧化降解,达到了CWAO技术同时降解有机物和NH₃-N的目的.同时,选取垃圾渗滤液中一种含氮有机物2-巯基苯并噻唑进行含氮有机物氮降解机理的验证实验.     

Simultaneous speciation of mercury and butyltin compounds in natural waters and snow by propylation and species-specific isotope dilution mass spectrometry analysis

A robust method has been developed for simultaneous determination of mercury and butyltin compounds in aqueous samples. This method is capable of providing accurate results for analyte concentrations in the picogram per liter to nanogram per liter range. The simultaneous determination of the mercury and tin compounds is achieved by species-specific isotope dilution, derivatization, and gas chromatography–inductively coupled plasma mass spectrometer (GC–ICP–MS). In derivatization by ethylation and propylation, reaction conditions such as pH and the effect of chloride were carefully studied. Ethylation was found to be more sensitive to matrix effects, especially for mercury compounds. Propylation was thus the preferred derivatization method for simultaneous determination of organomercury and organotin compounds in environmental samples. The analytical method is highly accurate and precise, with RSD values of 1 and 3% for analyte concentrations in the picogram per liter to nanogram per liter range. By use of cleaning procedures and SIDMS blank measurements, detection limits in the range 10–60 pg L^–1 were achieved; these are suitable for determination of background levels of these contaminants in environmental samples. This was demonstrated by using the method for analysis of real snow and seawater samples. This work illustrates the great advantage of species-specific isotope dilution for the validation of an analytical speciation method—the possibility of overcoming species transformations and non-quantitative recovery. Analysis time is saved by use of the simultaneous method, because of the use of a single sample-preparation procedure and one analysis.     

Indirect resolution of beta-blocker agents by reversed-phase capillary electrochromatography

The indirect resolution of five beta-adrenoreceptor blocking agents (propranolol, oxprenolol, pindolol, metoprolol, and atenolol) using precolumn derivatization with (+)-1-(9-fluorenyl)ethyl chloroformate (FLEC), and capillary electrochromatography (CEC) is reported. Three octadecylsilanized (ODS) silica gel-based stationary phases, differing in particle diameter and carbon surface density for suitability of determination of the enantiomeric composition of these substances in drugs and biological fluids, were studied. Under optimum separation conditions, all the investigated compounds were baseline-resolved within acceptable analysis times (i.e., between 10-16 min). The resolution values ranged between 1.80 and 1.14, and the separation factors were in no case less than 1.07. The possible use of the developed CEC method for the determination of enantiomeric composition of beta-adrenoreceptor blocking agents in drug substances was investigated. A study, in which the enantiomers of metoprolol were examined regarding specificity, reproducibility, limit of detection, and ruggedness, was developed in accordance with some analytical procedures for method validation.     

In situ aqueous derivatization and determination of non-steroidal anti-inflammatory drugs by salting-out-assisted liquid-liquid extraction and gas chromatography-mass spectrometry

A new analytical method for the determination of trace levels of five non-steroidal anti-inflammatory drugs (NSAIDs: clofibric acid, ibuprofen, naproxen, diclofenac and ketoprofen) in water samples is described. The analytical procedure involves in situ aqueous derivatization with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA) and salting-out liquid-liquid extraction (SALLE), followed by gas chromatography-programmed temperature vaporizer-mass spectrometry (GC-PTV-MS). The influence of several parameters on the efficiency of the derivatization (stirring time, reaction time, reagent concentration and pH), and the extraction (solvent, volume, salts and stirring time) and injection steps (liner, injection volume, liner temperature, injection time, venting time and venting flow) was investigated. The detection limits of the method in water varied from 0.042 μg/L for ibuprofen to 1.2 μg/L for ketoprofen. The relative standard deviations (RSD) values were found to be relatively low (<10% for all compounds). The methodology developed was applied to the determination of NSAIDs in several environmental matrices including tap, river, sea and influent and effluent waste water samples. The results obtained show the presence of ibuprofen and naproxen in the influent waste water sample.     

Simultaneous quantification of neutral and acidic pharmaceuticals and pesticides at the low-ng/l level in surface and waste water

A new analytical method is presented that allows simultaneous determination of neutral and acidic pharmaceuticals and pesticides in natural waters. The compounds investigated include frequently used pharmaceuticals, i.e., the anti-epileptic carbamazepine, four analgesic/anti-flammatory drugs (ibuprofen, diclofenac, ketoprofen and naproxen) and the lipid regulator clofibric acid and important pesticides including triazines, acetamides and phenoxy acids. Sample enrichment was achieved in one step with a newly developed solid-phase extraction procedure using the Waters Oasis HLB sorbent. The neutral compounds were analyzed by GC-MS in a first step, and then the acidic compounds after derivatization with diazomethane. Relative recoveries using isotope labeled internal standards were between 71 and 118% and the detection limits were in the range of 1 to 10 ng/l in drinking water, surface water and waste water treatment plant effluents (precision: 1-15%). The developed analytical method proved to be very durable during a 3-month field study and the target analytes were detected in concentrations of 5-3,500 ng/l in waste water treatment plant effluents, river water and lake water.     

Developing an on-line derivatization of FAs by microwave irradiation coupled to HPLC separation with UV detection

The development of analytical methods for routine simultaneous identification and quantification of carboxylic fatty acids (CFAs) are required in different fields, such as, pharmaceutical cosmetics, food products and formulations of water–microemulsion–oil systems. Determination of CFAs has been developed mainly by gas chromatography (GC). As an alternative to GC, liquid chromatography (LC) has better sensitivity and selectivity. However, most CFAs show no useful absorption in ultraviolet–violet (UV–Vis) region, one of the more used detection technique in high-performance liquid chromatography (HPLC). In order to allow the use of UV–Vis detection, the use of pre-column derivatization has been reported to increase sensitivity and selectivity. Therefore, establishment of a simpler and faster on-line method with complete separation is needed for the screening of large numbers of samples. 2,4-Dinitrophenylhydrazine (2,4-DNPH.), benzoil chloride (BC), and phenylhydrazine (PH) were used for derivatization of different FAs by microwaves radiation (MW). After the on-line derivatization, products were separated and quantified by HPLC. Reactor coil was placed inside of microwaves oven at 450 W. Parameters as flow, amount of reagents, irradiation time, and chromatographic conditions were optimized. The continuous analysis using the MW–HPLC–UV system provided high sensitivity and reduced both the amount of reagent used and the analysis times. This proposed method can be used for the routine analysis of FAs contained in water–microemulsion–oil systems, to quantify the total acid fraction in each phase.     

Characterization of volatile and semivolatile compounds in waste landfill leachates using stir bar sorptive extraction–GC/MS

Stir bar sorptive extraction in combination with thermal desorption coupled online to capillary gas chromatography–mass spectrometry was applied to investigate volatile and semivolatile fractions in two waste leachate samples: old and fresh ones. The present study helps to improve our knowledge of waste leachate organic composition. The aim is to then make use of this knowledge afterwards in order to generate more reliable and specific treatment processes for waste leachates and thus to respect the environmental statute law regarding their rejection. The volatile and semivolatile compounds appeared to be mainly anthropogenic in origin. Moreover, lactic acid and cyclic octaatomic sulfur could potentially be used as microbiological activity indicators, since they occur during organic matter degradation processes within waste leachates. Figure TDU-CGC-MS analytical equipment     

Development and application of an analytical protocol for evaluation of treatment processes for landfill leachates. I. Development of an analytical protocol for handling organic compounds in complex leachate samples

A strategy is presented for evaluation of treatment procedures for landfill leachate with emphasis on organic pollutants. An analytical scheme, the LAQUA protocol, was developed as a guide for the analytical work. The protocol includes organic as well as metals, inorganic ions, water-quality parameters, and toxicity. The proposed strategy considers the behaviour of both polar and non-polar organic substances at trace levels. For polar substances, phenols were chosen as markers and determined with an automated supported liquid membrane extraction device, coupled on-line to HPLC with a diode-array detector. For non-polar substances, PCBs and 10 unidentified compounds were chosen as markers and analysed by solid-phase extraction combined with supercritical fluid extraction with GC analysis. The chosen measurement strategy, based on the use of marker substances, difference measurements, and versatile data-handling procedures, provided essential information about complex systems at relatively low cost.     

Speciation of organolead compounds in water samples by GC-AAS after in situ butylation with tetrabutylammonium tetrabutylborate

A simple and reliable analytical method for the determination of organolead compounds in water samples has been developed by means of a gas chromatographic-atomic absorption system (GC-AAS). The derivatization of the organolead cations, necessary before their determination, was directly achieved in the water samples by the reagent tetrabutylammonium tetrabutylborate. Hexane/pentane was used to extract the butylated tetraorganolead compounds. The organic layer was dried and purified with sodium sulfate, concentrated by evaporation and injected into a GC-AAS system. The effects of various parameters on the derivatization and extraction procedures were studied and discussed.     

Comparison of two analytical methods for the determination of organotin compounds in marine organisms

Two analytical procedures were used for the determination of butyltin compounds in mussels.Both methods include extraction with methanol containing tropolone, derivatization, purification on Florisil and GC–MS analysis. The main difference between the procedures is in the derivatization step: one employs a Grignard reagent (n-pentylmagnesium bromide) while the other uses sodium tetraethylborate (STEB).Quantitative determinations were carried out in single ion monitoring using tripropyltin as internal standard. The accuracy of the procedures was verified on a certified reference material (ERM 477), providing good results for both methods.All the considered compounds showed lower detection limits with STEB derivatization; in particular for tributyltin (TBT), the difference between the two methods overcame one order of magnitude.An in vivo experiment was then performed, exposing mussels (Mytilus galloprovincialis) to known amount of TBT for 7 days; control and contaminated tissues were analyzed using the STEB derivatization method. Results showed the accumulation of TBT, especially in the gills.     

Comparison and evaluation of analysis procedures for the quantification of (2-methoxyethoxy)acetic acid in urine

Several extraction and derivatization procedures were evaluated for the quantification of (2-methoxyethoxy)acetic acid (MEAA) in urine. MEAA is a metabolite and a biomarker for exposure to 2-(2-methoxyethoxy)ethanol, a glycol ether with widespread use in various industrial applications and the specific use as an anti-icing additive in the military jet fuel formulation JP-8. Quantification of glycol ether biomarkers is an active area of analytical research. Various sample preparation procedures were evaluated: liquid–liquid extraction (LLE) using ethyl acetate yielded the highest recovery, and solid-phase extraction (SPE) gave low recovery of MEAA. Two derivatization procedures were thoroughly investigated and validated, namely, silylation of MEAA with N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA), and esterification of MEAA using ethanol. Quantification was performed by gas chromatography (GC) with a mass spectrometer as detector and using a polydimethylsiloxane (HP-1) capillary column. Deuterated 2-butoxyacetic acid (d-BAA) was used as an internal standard. Recovery studies of spiked human urine demonstrated the accuracy and precision of both procedures. The limit of detection (LOD) and other figures of merit for both derivatization procedures will be discussed in detail. Applications of these analysis procedures are also discussed. Disclaimers Mention of company names and/or products does not constitute endorsement by the Centers for Disease Control and Prevention (CDC). The findings and conclusions in this report are those of the authors and do not necessarily represent the views of the National Institute for Occupational Safety and Health.     

Ion chromatographic investigations of leachates from a hazardous-waste landfill

Leachates from different areas of a modern hazardous-waste landfill were investigated. In addition, samples of the waste to be buried were taken, and leachability tests in accordance with German standards were performed. The composition of the leachates from the landfill and the leachates produced by the leachability tests varied over a wide range, depending on the kind and volume of hazardous waste buried and the weather conditions. High concentrations of some anions were often found in combination with low concentrations of other anions. In the leachates the following concentration ranges were found: Cl⁻, 30–6000 mg/l; NO₂⁻, 0–150 mg/l; NO₂⁻, 0–150 mg/l; SO₂ ²⁻, 100–6000 mg/l. Therefore, several dilutions of one sample often had to be measured. The complex matrix often also requires several sample preparation steps for the elimination of interfering effects. Experience to date has shown that ion chromatography in this application field is efficient.     

Field-portable X-ray fluorescence spectrometry as rapid measurement tool for landfill mining operations: comparison of field data vs. laboratory analysis

Landfill mining applied in reclamation at the territories of old dump sites and landfills is a known approach tended to global economic and environmental benefits as recovery of metals and energy is an important challenge. The aim of this study was to analyse the concentration of several metallic elements (Ca, Cu, Cr, Fe, K, Mn, Pb, Zn) in the fine fraction of waste derived in the landfill and to compare the results of measurements obtained by field-portable equipment with the data gained by advanced analytical tools. Atomic absorption spectrometry (AAS) and inductively coupled plasma mass spectrometry (ICP-MS) were used for the quantitative detection of metallic elements at the laboratory; whereas field-portable X-ray fluorescence spectrometry (FPXRF) was applied for rapid sample characterisation in the field (on-site). Wet digestion of samples (fine fraction of waste at landfill) was done prior analytical procedures at the laboratory conditions, but FPXRF analysis was performed using raw solid samples of waste fine fraction derived in the Kudjape Landfill in Estonia. Although the use of AAS and ICP-MS for the measurements of metals achieves more precise results, it was concluded that precision and accuracy of the measurements obtained by FPXRF is acceptable for fast approximate evaluation of quantities of metallic elements in fine fraction samples excavated from the waste at landfills. Precision and accuracy of the results provided by express method is acceptable for quick analysis or screening of the concentration of major and trace metallic elements in field projects; however, data correction can be applied by calculating moisture and organic matter content dependent on sample matrix as well as special attention must be paid on sample selection and homogenisation and number of analysed samples.     

Capillary zone electrophoresis determination of oxytetracycline in pig tissue samples at maximum residue limits

Summary The determination of the antibiotic oxytetracycline (OTC), in pig tissues was investigated by capillary zone electrophoresis (CZE) with a prior solid-phase extraction (SPE) using alkyl-bonded silica and polymeric cartridges. The methodology developed allows determination of OTC in pig kidney, liver and muscle samples with detection limits below maximum residue limit values, and the procedures to extract OTC and clean-up the matrix are simple and reliable. The limit of detection for OTC was 160, 120 and 85 μg kg⁻¹ for kidney, liver and muscle samples, respectively. The average recoveries from spiked samples (200 μg kg⁻¹ and 1600 μg kg⁻¹) were in excess of 63% with coefficients of variation between 2.0 and 9.8%. This method would be useful for routine monitoring of oxytetracycline residues in pig tissues.     

Monitoring of veterinary drug residues by a combination of continuous flow techniques and column-switching high-performance liquid chromatography. I. Sulphonamides in egg, meat and milk using post-column derivatization with dimethylaminobenzaldehyde

By using a combination of a low-pressure continuous flow module and a column-switching high-performance liquid chromatographic system, procedures have been developed for the automated residue analysis of sulphonamides and selected other drugs in meat, egg and milk. Aqueous extracts are purified by on-line dialysis and subsequent trace enrichment on a short column containing silica-based or polymer material. After backflush to the analytical column, detection is performed either at 280 nm or, after post-column derivatization with p-dimethylaminobenzaldehyde, at 450 nm. With these procedures the fully automated determination of both polar and apolar sulphonamides and dapsone above 5-20 micrograms/kg is possible. Coefficients of variation are 4-10%, recoveries compared to standards are 85-90%. The methods developed were tested in routine veterinary drug control.     

Treatment of Sanitary Landfill Leachates in a Lab-Scale Gradual Concentric Chamber (GCC) Reactor

Sanitary landfill leachates are a major environmental problem in South American countries where sanitary landfills are still constructed and appropriate designs for the treatment of these leachates remain problematic. The performance of a lab-scale Gradual Concentric Chamber (GCC) reactor for leachates treatment is presented in this study. Two types of sanitary landfill residuals were evaluated, one directly collected from the garbage trucks (JGL), with high organic strength (84 g COD/l) and the second one, a 6-month-generated leachate (YL) collected from the lagoon of the sanitary landfill in Quito, Ecuador, with an organic strength of 66 g COD/l. Different operational parameters, such as organic loading rate (OLR), temperature, recycling and aeration, were tested. The GCC reactor was found to be a robust technology to treat these high-strength streams with organic matter removal efficiencies higher than 65%. The best performance of the reactors (COD removal efficiencies of 75–80%) was obtained at a Hydraulic Retention Time (HRT) of around 20 h and at 35 °C, with an applied OLR up to 70 and 100 g COD/l per day. Overall, the GCC reactor concept appears worth to be further developed for the treatment of leachates in low-income countries.     

High Performance Liquid Chromatography (HPLC) with Fluorescence Detection for Quantification of Steroids in Clinical,Pharmaceutical, and Environmental Samples: A Review

Steroids are compounds widely available in nature and synthesized for therapeutic and medical purposes. Although several analytical techniques are available for the quantification of steroids, their analysis is challenging due to their low levels and complex matrices of the samples. The efficiency and quick separation of the HPLC combined with the sensitivity, selectivity, simplicity, and cost-efficiency of fluorescence, make HPLC coupled to fluorescence detection (HPLC-FLD) an ideal tool for routine measurement and detection of steroids. In this review, we covered HPLC-FLD methods reported in the literature for the steroids quantification in clinical, pharmaceutical, and environmental applications, focusing on the various approaches of fluorescent derivatization. The aspects related to analytical methodology including sample preparation, derivatization reagents, and chromatographic conditions will be discussed.