Evaluating a Rapid Atmospheric Pressure Photoionization - Mass - - PowerPoint PPT Presentation

Evaluating a Rapid Atmospheric Pressure Photoionization - Mass Spectrometry (APPI-MS) Method for the Detection of Polychlorinated Dibenzodioxins (PCDD) and Furans (PCDF) in Real Environmental Samples Collected within the Vicinity

• f Industrial Incinerators

LIFE12 ENV/ES/000729-DIOXDETECTOR project

Álvaro A. Mc Culloch R. Del Castillo J.C. Amo-González M. Gómez M. Martín J.M. Cuesta R. Sociedad Europea de Análisis de Movilidad S.L. SEADM (Spain) Centro Tecnológico CARTIF (Spain)

Project Objective

Application of a new analytical technique for the quantification

• f dioxin, tracking continuous PCDDs/PCDFs concentrations in

air, soil and biota (vegetable matter) in the surroundings of a municipal solid waste incineration facility.

Project Outline

• Identification of the sampling area
• Sampling collection and sample preparation
• Analyzer Definition
• APPI Ionization
• PCDD/F Limit of Detection
• Analysis Results
• Conclusions
• Future actions
• Acknowledgements

Identification of the sampling areas

ADMS Input data:

• Type and characteristics of the

emission source

• Position coordinates of the source
• Meteorological data in the area of

study SURFER Output data:

• The model estimates immission concentrations

in the long term or short term

• Dioxin dispersion map showing the most

affected areas

• Two sampling areas were defined with two

sampling points for each sampling area

Sampling collection and sample preparation

• Air, soil and vegetable matter samples were taken

monthly during a year at the four sampling points.

• PCDD/F extraction, clean-up and concentration were

carried out according to the norm UNE-EN 1948-2.

Air ≈ 700 m3 Soil ≈ 5 grams Vegetable matter ≈ 20 grams

Analyzer definition: PCCD/PCDF isomer separation by ion mobility

DMA resolution was not adequate for isomer separation. A high resolution DMA is being developed by SEADM, but for the time being the DMA is not incorporated into the Analyzer:

Architecture of the APPI-MS analyzer

SEADM´s Custom APPI ion Source Sciex´s Qtrap 3200 Triple Quadrupole MS

APPI Ionization

• SEADM´s ESI/SESI Sources are ideal for polars, but not suitable for non-polars.
• SEADM´s APCI Source is suitable for non-polars, but did not have enough sensitivity .
• A new APPI Source has been developed with high ionization efficiency for both polar

and non-polar compounds.

Analysis

• Samples dissolved in toluene solvent infused into the nebulizer at

2µL/min

• Sample is vaporized in the nebulizer at 400⁰C using 99.999% N2 as

nebulizer gas

• PCDD/PCDF ionization: [M-Cl+O]-
• Ions are transmitted to the MS using electric fields and analyzed

in negative Multiple Reaction Monitoring mode.

PCDD/F Limit of Detection

• Analysis of air sampled blanks and air

samples loaded with liquid standards

• LODs ranging from 0.15 to 1.40 pg;
• Homologues detected with a LOD

around 1 pg

• Method used for comparison

purposes:

• NDAMN1 - (HR-GC-MS)

1) The National Dioxin Air Monitoring Network (NDAMN) – Report of the Results of Atmospheric Measurements of Polychlorinated Dibenzo-p-Dioxins (PCDDs), Polychlorinated Dibenzofurans (PCDFs) and Dioxin-Like-Polychlorinated Biphenyls (PCBs) in Rural and Remote areas of the United States from June 1998 through November 2004.

Log scale

Results of the Analysis – Location nº2

• The results correspond to

the concentration of each homologue group.

• Since isomers were not

separated, no Toxicity Equivalence Factor was applied to the results. Blue – January, Red – February, Green - March

Conclusions

• The APPI-MS/MS analyzer developed allows detection limits around

1 pg for each PCDD/F homologue.

• Operational costs of the analyzer are considerably lower than

present techniques: Cost per analysis ≈ 25 Euros.

• According to project plan, the Analyzer will be improved at the end
• f 2016 with a high resolution DMA, which will allow isomer

separation.

Future actions to improve the Analyzer: Ion Mobility Mass Spectrometry

Isomer separation using SEADM´s High Resolution DMA will be possible allowing analysis in a few seconds. Since the DMA significantly reduces the chemical background it is expected an improvement in the LOD of the Analyzer

0.0 0.2 0.4 0.6 0.8 1.0 5400 5500 5600

Electrometer Voltage (V)

DMA Voltage (V)

THA+ Mobility Peak acquired in SEADM´s high resolution DMA P5

FWHM Resolving Power = 115

Acknowledgements

• LIFE+ Program (LIFE12 ENV/ES/000729-DIOXDETECTOR project)
• SEADM
• CARTIF

You can follow the progress of the project and the final results by visiting the project website:

http://www.dioxdetector.eu

• Thank you for your attention-