Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwaveassisted extraction and liquid chromatography

A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4±8.8 to 112.0±1.1%, for all the compounds except for naphthalene (62.3±18.0%) and anthracene (67.3±5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m3 for benzo( a)anthracene to 0.089 ng/m3 for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m3.

A multiresidue method for the analysis of carbamate and urea pesticides from soils by microwave-assisted extraction and liquid chromatography with photodiode array detection

A multiresidue approach using microwave-assisted extraction and liquid chromatography with photodiode array detection was investigated for the determination of butylate, carbaryl, carbofuran, chlorpropham, ethiofencarb, linuron,metobromuron, and monolinuron in soils. The critical parameters of the developed methodology were studied. Method validation was performed by analyzing freshly and aged spiked soil samples. The recoveries and relative standard deviations reached using the optimized conditions were between 77.0 ± 0.46% and 120 ± 2.9% except for ethiofencarb (46.4 ± 4.4% to 105 ± 1.6%) and butylate (22.1 ± 7.6% to 49.2 ± 11%). Soil samples from five locations of Portugal were analysed.

Soil vapor extraction in sandy soils: influence of airflow rate

Airflow rate is one of the most important parameters for the soil vapor extraction of contaminated sites, due to its direct influence on the mass transfer occurring during the remediation process. This work reports the study of airflow rate influence on soil vapor extractions, performed in sandy soils contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene and perchloroethylene. The objectives were: (i) to analyze the influence of airflow rate on the process; (ii) to develop a methodology to predict the remediation time and the remediation efficiency; and (iii) to select the most efficient airflow rate. For dry sandy soils with negligible contents of clay and natural organic matter, containing the contaminants previously cited, it was concluded that: (i) if equilibrium between the pollutants and the different phases present in the soil matrix was reached and if slow diffusion effects did not occur, higher airflow rates exhibited the fastest remediations, (ii) it was possible to predict the remediation time and the efficiency of remediation with errors below 14%; and (iii) the most efficient remediation were reached with airflow rates below 1.2 cm3 s 1 standard temperature and pressure conditions.

Determination of chlorfenvinphos in soils by microwave-assisted extraction and stripping voltammetry with an ultramicroelectrode

A methodology for the determination of the pesticide chlorfenvinphos by microwave-assisted solvent extraction and square-wave cathodic stripping voltammetry at a mercury film ultramicroelectrode in soil samples is proposed. Optimization of microwave solvent extraction performed with two soils, selected for having significantly different properties, indicated that the optimum solvent for extracting chlorfenvinphos is hexane-acetone (1:1, v/v). The voltammetric procedure is based on controlled adsorptive accumulation of the insecticide at the potential of -0.60 V (vs. Ag/AgCl) in the presence of Britton-Robinson buffer (pH 6.2). The detection limit obtained for a 10 s collection time was 3.0 x 10-8 mol l-1. The validity of the developed methodology was assessed by recovery experiments at the 0.100 µg g-1 level. The average recoveries and standard deviations for the global procedure reached byMASE-square-wave voltammetry were 90.2±2.8% and 92.1±3.4% for type I (soil rich in organic matter) and type II (sandy soil) samples, respectively. These results are in accordance to the expected values which show that the method has a good accuracy.

Determination of carbamate and urea pesticide residues in fresh vegetables using microwave-assisted extraction and liquid chromatography

An analytical multiresidue method for the simultaneous determination of seven pesticides in fresh vegetable samples, namely, courgette (Cucurbita pepo), cucumber (Cucumis sativus), lettuce (Lactuca sativa, Romaine and Iceberg varieties) and peppers (Capsicum sp.) is described. The procedure, based on microwave-assisted extraction (MAE) and analysis by liquid chromatography– photodiode array (LC–PDA) detection was applied to four carbamates (carbofuran, carbaryl, chlorpropham and EPTC) and three urea pesticides (monolinuron, metobromuron and linuron). Extraction solvent and the addition of anhydrous sodium sulphate to fresh vegetable homogenate before MAE were the parameters optimised for each commodity. Recovery studies were performed using spiked samples in the range 250–403 µgkg- 1 in each pesticide. The pesticide residues were extracted using 20mL acetonitrile at 60 ºC, for 10 min. Acceptable recoveries and RSDs were attained (overall average recovery of 77.2% and RSDs are lower than 11%). Detection limits ranged between 5.8 µgkg- 1 for carbaryl to 12.3 µgkg- 1 for carbofuran. The analytical protocol was applied for quality control of 41 fresh vegetable samples bought in Oporto Metropolitan Area (North Portugal). None of the samples contained any detectable amounts of the studied compounds.

Screening of carbamates and ureas in fresh and processed tomato samples using micowave-assisted extraction and liquid chromatography

An analytical method, based on microwave-assisted extraction and liquid chromatography with diode array detection, for the determination of six carbamate and three urea pesticides in fresh and processed tomato samples is described. Significant parameters affecting extraction efficiency were optimized. Under optimum microwave-assisted extraction conditions (20mL acetonitrile, for 10 minutes, at 60º C), pesticides were extracted with recoveries ranging from 57.6 to 102% (RSDs<7%). Quantification limits between 6.5 and 39.6 µg=kg were obtained. A total number of 28 different fresh tomato samples and 6 processed tomato products were analysed. Confirmation of suspicious samples was performed by LC-MS.

Multi-criteria design optimization study of solvent extraction in mixer–settler units

Solvent extraction is considered as a multi-criteria optimization problem, since several chemical species with similar extraction kinetic properties are frequently present in the aqueous phase and the selective extraction is not practicable. This optimization, applied to mixer–settler units, considers the best parameters and operating conditions, as well as the best structure or process flow-sheet. Global process optimization is performed for a specific flow-sheet and a comparison of Pareto curves for different flow-sheets is made. The positive weight sum approach linked to the sequential quadratic programming method is used to obtain the Pareto set. In all investigated structures, recovery increases with hold-up, residence time and agitation speed, while the purity has an opposite behaviour. For the same treatment capacity, counter-current arrangements are shown to promote recovery without significant impairment in purity. Recycling the aqueous phase is shown to be irrelevant, but organic recycling with as many stages as economically feasible clearly improves the design criteria and reduces the most efficient organic flow-rate.

DNA-based biosensor for the electrocatalytic determination of antioxidant capacity in beverages

Reactive oxygen species (ROS) are produced as a consequence of normal aerobic metabolism and are able to induce DNA oxidative damage. At the cellular level, the evaluation of the protective effect of antioxidants can be achieved by examining the integrity of the DNA nucleobases using electrochemical techniques. Herein, the use of an adenine-rich oligonucleotide (dA21) adsorbed on carbon paste electrodes for the assessment of the antioxidant capacity is proposed. The method was based on the partial damage of a DNA layer adsorbed on the electrode surface by OH• radicals generated by Fenton reaction and the subsequent electrochemical oxidation of the intact adenine bases to generate an oxidation product that was able to catalyze the oxidation of NADH. The presence of antioxidant compounds scavenged hydroxyl radicals leaving more adenines unoxidized, and thus, increasing the electrocatalytic current of NADHmeasured by differential pulse voltammetry (DPV). Using ascorbic acid (AA) as a model antioxidant species, the detection of as low as 50nMof AA in aqueous solution was possible. The protection efficiency was evaluated for several antioxidant compounds. The biosensor was applied to the determination of the total antioxidant capacity (TAC) in beverages.

Determination of ametryn in soils via microwave-assisted solvent extraction coupled to anodic stripping voltammetry with a gold ultramicroelectrode

An extraction-anodic adsorptive stripping voltammetric procedure using microwave-assisted solvent extraction and a gold ultramicroelectrode was developed for determining the pesticide ametryn in soil samples. The method is based on the use of acetonitrile as extraction solvent and on controlled adsorptive accumulation of the herbicide at the potential of 0.50 V (vs. Ag/AgCl) in the presence of Britton-Robinson buffer (pH 3.3). Soil sample extracts were analysed directly after drying and redissolution with the supporting electrolyte but without other pre-treatment. The limit of detection obtained for a 10 s collection time was 0.021 µg g-1. Recovery experiments for the global procedure, at the 0.500 µg g-1 level, gave satisfactory mean and standard deviation results which were comparable to those obtained by HPLC with UV detection.

Electrochemical DNA-sensor for evaluation of total antioxidant capacity of flavours and flavoured waters using superoxide radical damage

In this paper, a biosensor based on a glassy carbon electrode (GCE) was used for the evaluation of the total antioxidant capacity (TAC) of flavours and flavoured waters. This biosensor was constructed by immobilising purine bases, guanine and adenine, on a GCE. Square wave voltammetry (SWV) was selected for the development of this methodology. Damage caused by the reactive oxygen species (ROS), superoxide radical (O2·−), generated by the xanthine/xanthine oxidase (XOD) system on the DNA-biosensor was evaluated. DNA-biosensor encountered with oxidative lesion when it was in contact with the O2·−. There was less oxidative damage when reactive antioxidants were added. The antioxidants used in this work were ascorbic acid, gallic acid, caffeic acid, coumaric acid and resveratrol. These antioxidants are capable of scavenging the superoxide radical and therefore protect the purine bases immobilized on the GCE surface. The results demonstrated that the DNA-based biosensor is suitable for the rapid assess of TAC in beverages.

Remediation efficiency of vapour extraction of sandy soils contaminated with cyclohexane: influence of air flow rate, water and natural organic matter content

Abstract This work reports the analysis of the efficiency and time of soil remediation using vapour extraction as well as provides comparison of results using both, prepared and real soils. The main objectives were: (i) to analyse the efficiency and time of remediation according to the water and natural organic matter content of the soil; and (ii) to assess if a previous study, performed using prepared soils, could help to preview the process viability in real conditions. For sandy soils with negligible clay content, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) the increase of soil water content and mainly of natural organic matter content influenced negatively the remediation process, making it less efficient, more time consuming, and consequently more expensive; and (ii) a previous study using prepared soils of similar characteristics has proven helpful for previewing the process viability in real conditions.

Electrocatalytic evaluation of DNA damage by superoxide radical for antioxidant capacity assessment

The integrity of DNA purine bases was herein used to evaluate the antioxidant capacity. Unlike other DNA-based antioxidant sensors reported so far, the damaging agent chosen was the O 2 radical enzymatically generated by the xanthine/xanthine oxidase system. An adenine-rich oligonucleotide was adsorbed on carbon paste electrodes and subjected to radical damage in the presence/absence of several antioxidant compounds. As a result, partial damage on DNA was observed. A minor product of the radical oxidation was identified by cyclic voltammetry as a diimine adenine derivative also formed during the electrochemical oxidation of adenine/guanine bases. The protective efficiency of several antioxidant compounds was evaluated after electrochemical oxidation of the remaining unoxidized adenine bases, by measuring the electrocatalytic current of NADH mediated by the adsorbed catalyst species generated. A comparison between O 2 and OH radicals as a source of DNA lesions and the scavenging efficiency of various antioxidant compounds against both of them is discussed. Finally, the antioxidant capacity of beverages was evaluated and compared with the results obtained with an optical method.

Analysis of PCBs in soils and sediments by microwave-assisted extraction, headspace-SPME and high resolution gas chromatography with ion-trap tandem mass spectrometry

A procedure for the determination of seven indicator PCBs in soils and sediments using microwave-assisted extraction (MAE) and headspace solid-phase microextraction (HS-SPME) prior to GC-MS/MS is described. Optimization of the HS-SPME was carried out for the most important parameters such as extraction time, sample volume and temperature. The adopted methodology has reduced consumption of organic solvents and analysis runtime. Under the optimized conditions, the method detection limit ranged from 0.6 to 1 ng/g when 5 g of sample was extracted, the precision on real samples ranged from 4 to 21% and the recovery from 69 to 104%. The proposed method, which included the analysis of a certified reference material in its validation procedure, can be extended to several other PCBs and used in the monitoring of soil or sediments for the presence of PCBs.

Use of solvent extraction to remediate soils contaminated with hydrocarbons

The main objective of this research is to exploit the possibility of using an ex situ solvent extraction technique for the remediation of soils contaminated with semi-volatile petroleum hydrocarbons. The composition of the organic phase was chosen in order to form a single phase mixture with an aqueous phase and simultaneously not being disturbed (forming stable emulsions) by the soil particles hauling the contaminants. It should also permit a regeneration of the organic solvent phase. As first, we studied the miscibility domain of the chosen ternary systems constituted by ethyl acetate–acetone–water. This system proved to satisfy the previous requirements allowing for the formation of a single liquid phase mixture within a large spectrum of compositions, and also allowing for an intimate contact with the soil. Contaminants in the diesel range within different functional groups were selected: xylene, naphthalene and hexadecane. The analytical control was done by gas chromatography with FID detector. The kinetics of the extractions proved to be fast, leading to equilibrium after 10 min. The effect of the solid–liquid ratio on the extraction efficiency was studied. Lower S/L ratios (1:8, w/v) proved to be more efficient, reaching recoveries in the order of 95%. The option of extraction in multiple contacts did not improve the recovery in relation to a single contact. The solvent can be regenerated by distillation with a loss around 10%. The contaminants are not evaporated and they remain in the non-volatile phase. The global results show that the ex situ solvent extraction is technically a feasible option for the remediation of semi-volatile aromatic, polyaromatic and linear hydrocarbons.

Agar extraction from integrated multitrophic aquacultured Gracilaria vermiculophylla: Evaluation of a microwave-assisted process using response surface methodology

Microwave-assisted extraction (MAE) of agar from Gracilaria vermiculophylla, produced in an integrated multitrophic aquaculture (IMTA) system, from Ria de Aveiro (northwestern Portugal), was tested and optimized using response surface methodology. The influence of the MAE operational parameters (extraction time, temperature, solvent volume and stirring speed) on the physical and chemical properties of agar (yield, gel strength, gelling and melting temperatures, as well as, sulphate and 3,6-anhydro-Lgalactose contents) was evaluated in a 2^4 orthogonal composite design. The quality of the extracted agar compared favorably with the attained using traditional extraction (2 h at 85ºC) while reducing drastically extraction time, solvent consumption and waste disposal requirements. Agar MAE optimum results were: an yield of 14.4 ± 0.4%, a gel strength of 1331 ± 51 g/cm2, 40.7 ± 0.2 _C gelling temperature, 93.1 ± 0.5ºC melting temperature, 1.73 ± 0.13% sulfate content and 39.4 ± 0.3% 3,6-anhydro-L-galactose content. Furthermore, this study suggests the feasibility of the exploitation of G. vermiculophylla grew in IMTA systems for agar production.