Microplastics' analysis in water: Easy handling of samples by a new Thermal Extraction Desorption-Gas Chromatography-Mass Spectrometry (TED-GC/MS) methodology.

Thermal Extraction-Desorption (TED) using a thermobalance coupled to a gas chromatograph (GC) with mass spectrometer (MS) detector is an extended method for polymers identification in complex matrixes. A new TED-GC/MS method for microplastics identification is developed in this study, where the whole filter with solids collected from water is thermal treated in a furnace, instead of using a small portion in a Thermogravimetric analysis (TGA) device, avoiding sample handling. Pyrolyzing the whole filter in a tubular furnace has advantages with respect to the standard procedure of using a TGA with a small crucible in TED-GC/MS. The main advantage is the easy manipulation of the sample, since the filter does not have to be manipulated to extract the sample or cut some portions, avoiding sample losses during handling and ensuring that inhomogeneity on the filter surface is not a problem. Furthermore, there are no limitations on the weight of the sample beyond the adsorbent's ability to trap decomposition compounds without becoming saturated, so high intensity signals can be obtained in order to avoid confuse signals with noise, false negatives or values so close of the quantification limit.

New device for time-averaged measurement of volatile organic compounds (VOCs).

Contamination by volatile organic compounds (VOCs) in the environment is an increasing concern since these compounds are harmful to ecosystems and even to human health. Actually, many of them are considered toxic and/or carcinogenic. The main sources of pollution come from very diffuse focal points such as industrial discharges, urban water and accidental spills as these compounds may be present in many products and processes (i.e., paints, fuels, petroleum products, raw materials, solvents, etc.) making their control difficult. The presence of these compounds in groundwater, influenced by discharges, leachate or effluents of WWTPs is especially problematic. In recent years, law has been increasingly restrictive with the emissions of these compounds. From an environmental point of view, the European Water Framework Directive (2000/60/EC) sets out some VOCs as priority substances. This binding directive sets guidelines to control compounds such as benzene, chloroform, and carbon tetrachloride to be at a very low level of concentration and with a very high frequency of analysis. The presence of VOCs in the various effluents is often highly variable and discontinuous since it depends on the variability of the sources of contamination. Therefore, in order to have complete information of the presence of these contaminants and to effectively take preventive measures, it is important to continuously control, requiring the development of new devices which obtain average concentrations over time. As of today, due to technical limitations, there are no devices on the market that allow continuous sampling of these compounds in an efficient way and to facilitate sufficient detection limits to meet the legal requirements which are capable of detecting very sporadic and of short duration discharges. LABAQUA has developed a device which consists of a small peristaltic pump controlled by an electronic board that governs its operation by pre-programming. A constant flow passes through a glass cell containing adsorbent material where the VOCs are retained. The adsorbent used, made in LABAQUA, is a mixture of alginic acid and activated carbon. Due to its high permeability it allows the passage and retention of THMs in a suitable way, thus solving many of the problems of other common adsorbents. Also, to avoid degradation of the adsorbent, it is wrapped in a low density polyethylene (LDPE) membrane. After a sampling period of between 1 and 14 days, the adsorbent is collected and analyzed in the laboratory to quantify the VOC average concentration. This device resolves some of the limitations of the classical sampling system (spot samples), since we will take into account the fluctuations in the concentration of VOCs by averaging the same over time. This study presents the results obtained by the device for quantifying the VOCs legislated in the Directive 2000/60/EC. We present the validation of linearity over time and the limits of quantification, as well as the results of sample rate (Rs) obtained for each compound. The results demonstrate the high robustness and high sensitivity of the device. In addition the system has been validated in real waste water samples, comparing the results obtained with this device with the values of classical spot sampling, obtaining excellent results.

Analysis of chlorophenols, bisphenol-A, 4-tert-octylphenol and 4-nonylphenols in soil by means of ultrasonic solvent extraction and stir bar sorptive extraction with in situ derivatisation.

A novel method based on ultrasonic solvent extraction and stir bar sorptive extraction for the analysis of phenolic organic pollutants including chlorophenols, bisphenol-A, 4-tert-octylphenol and 4-nonylphenol in soil samples was developed. The different parameters that affect both the extraction of analytes from the soil samples, such as solvent selection, extraction time, and the partitioning from the solvent/water mix to poly(dimethylsiloxane) (PDMS) were studied. The final selected conditions consisted of the extraction of 1g of soil with 15 mL methanol by sonication for 30 min. The methanol extract was mixed with 85 mL of Milli-Q water and extracted by means of stir bar sorptive extraction with in situ derivatisation. The stir bars were analyzed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). The effects of the matrix on the recovery of the various pollutants under the developed method were studied using two soils with very different physicochemical properties. Method sensitivity, linearity, repeatability, and reproducibility were also studied. Validation and accuracy of the method were conducted by analyzing two commercial certified reference materials and by comparing the analysis of real samples with the proposed method and a classical method using pressurized solvent extraction (PSE)-GC-MS. The main advantage of this method is a substantial solvent reduction. For the extraction of only 1g of solid sample allowing limits of detection ranging from 0.2 to 1.7 microg kg(-1) dw. Repeatability and reproducibility variation were lower than 20% for all investigated compounds. Results of the certified reference materials and the real samples verify the high accuracy of this method.

Stir bar sorptive extraction for the analysis of short-chain chlorinated paraffins in water.

An optimised method using stir bar sorptive extraction (SBSE) and a thermal desorption-GC-electron capture detector (GC-ECD) for the determination of short-chain chlorinated paraffins from water samples was developed. Recoveries near to 100% were obtained by using 20 mm x 0.5 mm (length x film thickness) PDMS commercial stir bars from 200 mL spiked water samples and 20% methanol addition with an extraction period of 24 h. Method sensitivity, linearity and precision were evaluated for surface water and wastewater spiked samples. A LOD of 0.03 and 0.04 microg/L was calculated for surface and wastewater, respectively. The precision of the method given as an RSD was below 20% for both matrices. The developed method was applied for the analysis of two real samples from a contaminated river and a wastewater treatment plant. Results were in accordance with those obtained using a previously developed method based on solid phase microextraction (SPME).

Analysis of 51 persistent organic pollutants in soil by means of ultrasonic solvent extraction and stir bar sorptive extraction GC-MS.

A novel method based on ultrasonic solvent extraction and stir bar sorptive extraction (SBSE) for the analysis of 51 persistent organic pollutants including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and polybrominated diphenylethers (PBDEs) in soil samples was developed. The different parameters that affect both the extraction of analytes from the soil samples, such as solvent selection, solvent volume, mass of soil, and extraction time, and the partitioning from the solvent/water mixture to the PDMS were studied. The final selected conditions consisted of the extraction of 1 g of soil with 15 mL methanol by sonication for 30 min. The methanol extract was mixed with 85 mL of Milli-Q water and extracted by means of SBSE for 14 h at 900 rpm. The stir bars were analyzed by thermal desorption-GC-mass spectometry (TD-GC-MS). The effects of the matrix on the recovery of the various pollutants under the developed method were studied using two soils with very different physicochemical properties. Method sensitivity, linearity, repeatability, and reproducibility were also studied. Validation and accuracy of the method were conducted by analyzing two commercial certified reference materials (CRMs). The main advantage of this method resides in the fact that a small amount of a nontoxic solvent (methanol) is needed for the extraction of only 1 g of solid sample allowing LODs ranging from 0.01 to 2.0 microg/kg. Repeatability and reproducibility variations were lower than 20% for all investigated compounds. Results of the CRMs verify the high accuracy of this method.

Ultra trace determination of 31 pesticides in water samples by direct injection-rapid resolution liquid chromatography-electrospray tandem mass spectrometry.

A liquid chromatography-tandem mass spectrometry (LC-MS/MS)-based method for the detection of pesticides in tap and treated wastewater was developed and validated according to the ISO/IEC 17025:1999. Key features of this method include direct injection of 100 microL of sample, an 11 min separation by means of a rapid resolution liquid chromatography system with a 4.6 mm x 50 mm, 1.8 microm particle size reverse phase column and detection by electrospray ionization (ESI) MS-MS. The limits of detection were below 15 ng L(-1) and correlation coefficients for the calibration curves in the range of 30-2000 ng L(-1) were higher than 0.99. Precision was always below 20% and accuracy was confirmed by external evaluation. The main advantages of this method are direct injection of sample without preparative procedures and low limits of detection that fulfill the requirements established by the current European regulations governing pesticide detection.