title: An innovative ultrasound assisted extraction micro-scale cell combined with gas chromatography/mass spectrometry in negative chemical ionization to determine persistent organic pollutants in air particulate matter.
abstract: New clean technologies are needed to determine concentration of organic pollutants without generating more pollution. A method to extract Persistent Organic Pollutants (POPs) from airborne particulate matter was developed using a novel technology recently patented called ultrasound assisted extraction micro-scale cell (UAE-MSC). This technology extracts, filters, collects the sample, and evaporates the solvent, on-line. No sample transfer is needed. The cell minimizes sample manipulation, solvent consumption, waste generation, time, and energy; fulfilling most of the analytical green chemistry protocol. The methodology was optimized applying a centred 23factorial experimental design. Optimum conditions were used to validate and determine concentration of 16 organochlorine pesticides (OCls) and 6 polybrominated diphenyl ethers (PBDEs). The best conditions achieved were 2 extractions with 5mL (each) of dichloromethane over 5min (each) at 60°C and 80% ultrasound potency. POPs were determined by gas chromatography/mass spectrometry in negative chemical ionization (GC/MS-NCI). Analytical method validation was carried out on airborne particles spiked with POPs at seven concentration levels between 0.5 and 26.9pgm-3. This procedure was done by triplicate (N=21). Recovery, ranged between 65.5±2.3% and 107.5±3.0% for OCls and between 79.1±6.5% and 105.2±3.8% for PBDEs. Linearity (r2) was ≥0.94 for all compounds. Method detection limits, ranged from 0.5 to 2.7pgm-3, while limits of quantification (LOQ), ranged from 1.7 to 9.0pgm-3. A Bias from -18.6% to 9% for PBDEs was observed in the Standard Reference Material (SRM) 2787. SRM 2787 did not contain OCls. OCls recoveries were equivalent by UAE-MSC and Soxhlet methods UAE-MSC optimized extraction conditions reduced 30 times less solvent and decreased the extraction time from several hours to ten minutes, respect to Soxhlet. UAE-MSC was applied to 15 samples of particles less than 2.5μm (PM2.5) from three seasons (warm dry, rainy, and cold dry) collected in five sites around Mexico City. OCls (4,4'-DDE and endrin aldehyde) concentrations ranged from <LOQ to 12.6pgm-3, while PBDEs levels were below the quantification limit, although BDE-99 was detected in all samples. UAE-MSC is a novel technology to determine organic compounds present in trace concentrations in particulate matter. This technology can be extended to extract organic compounds in different solid matrices to minimize time extraction and solvent consumption.
authors.affiliation: Centro de Ciencias de la Atmósfera, Universidad Nacional Autónoma de México, Circuito exterior, 04510, México City, Distrito Federal, Mexico.
authors.forename: E
authors.initials: E
authors.lastname: Beristain-Montiel
authors.affiliation: Centro de Ciencias de la Atmósfera, Universidad Nacional Autónoma de México, Circuito exterior, 04510, México City, Distrito Federal, Mexico.
authors.forename: R
authors.initials: R
authors.lastname: Villalobos-Pietrini
authors.affiliation: Centro de Ciencias de la Atmósfera, Universidad Nacional Autónoma de México, Circuito exterior, 04510, México City, Distrito Federal, Mexico.
authors.forename: G E
authors.initials: GE
authors.lastname: Arias-Loaiza
authors.affiliation: Centro de Ciencias de la Atmósfera, Universidad Nacional Autónoma de México, Circuito exterior, 04510, México City, Distrito Federal, Mexico.
authors.forename: S L
authors.initials: SL
authors.lastname: Gómez-Arroyo
authors.affiliation: Centro de Ciencias de la Atmósfera, Universidad Nacional Autónoma de México, Circuito exterior, 04510, México City, Distrito Federal, Mexico. Electronic address: oam@atmosfera.unam.mx.
authors.forename: O
authors.initials: O
authors.lastname: Amador-Muñoz
mesh_terms: D002138:Calibration; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D055768:Halogenated Diphenyl Ethers / Q000032:analysis; D008800:Mexico; D009930:Organic Chemicals / Q000032:analysis*; D052638:Particulate Matter / Q000032:analysis*; D015203:Reproducibility of Results; D012621:Seasons; D012997:Solvents; D014465:Ultrasonics / Q000379:methods*
chemical_list: D055768:Halogenated Diphenyl Ethers; D009930:Organic Chemicals; D052638:Particulate Matter; D012997:Solvents
keywords: Mexico; Micro scale extraction; PM(2.5); Persistent organic pollutants