Classification or air types

emission air, ambient air, workplace air, indoor air.

Different analytical and legal aspects!

Legal aspects: ambient air

COUNCIL DIRECTIVE 96/62/EC of 27 September 1996 on ambient air quality assessment and management
LIST OF ATMOSPHERIC POLLUTANTS TO BE TAKEN INTO CONSIDERATION IN THE ASSESSMENT AND MANAGEMENT OF AMBIENT AIR QUALITY 1. Sulphur dioxide 2. Nitrogen dioxide 3. Fine particulate matter such as soot (including mw 10) 4. Suspended particulate matter 5. Lead 6. Ozone 7. Benzene 8. Carbon monoxide 9. Poly-aromatic hydrocarbons 10. Cadmium 11. Arsenic 12. Nickel
13. Mercury

Directive 2000/69/EC of the European Parliament and of the Council of 16 November 2000 relating to limit values for benzene and carbon monoxide in ambient air Directive 2002/3/EC of the European Parliament and of the Council of 12 February 2002 relating to ozone in ambient air Directive 2004/107/EC of the European Parliament and of the Council of 15 December 2004 relating to arsenic, cadmium, mercury, nickel and polycyclic aromatic hydrocarbons in ambient air

Legal aspects: workplace air

Directive 91/322/EEC - indicative limit values of 29 May 1991 on establishing indicative limit values by implementing Council Directive 80/1107/EEC on the protection of workers from the risks related to exposure to chemical, physical and biological agents at work.

Directive 2006/15/EC - indicative occupational exposure limit values of 7 February 2006 establishing a second list of indicative occupational exposure limit values in implementation of Council Directive 98/24/EC and amending Directives 91/322/EEC and 2000/39/EC

Dcret no 2007-1539 du 26 octobre 2007 fixant des valeurs limites dexposition professionnelle contraignantes pour certains agents chimiques et modifiant le code du travail

Commission Directive 2009/161/EU of 17 December 2009 establishing a third list of indicative occupational exposure limit values in implementation of Council Directive 98/24/EC and amending Commission Directive 2000/39/EC

Workplace air vs. Indoor air

Workplace air
known health risk, adults

Indoor air
no sufficient information about risks, sensitive population, changed health status (illnesses,

healthy, regularly examined, known sources, detailed legislation.

pregnancy) unknown sources, guidelines.

mg/m3

g/m3

Workplace air vs. Indoor air

Workplace air
Sampling breathing zone (150-160 cm), fixed sampling time (EN standards) Analytical methods spectrophotometry, GC, HPLC, ICP-OES, AAS many standards (ISO, EN, NIOSH, OSHA)

Indoor air: sampling and analysis

Indoor air
Sampling purpose of room, variation of breathing height customized sampling time

Analytical methods HPLC TD- GC/MS

Choises for air analyis and sampling

Zoltn Filep WESSLING Hungary Kft.

Choices for air analyis and sampling

systematization of air polluting substances,

choices in sampling and analysis,

sampling prcedures, sampling equipment.

Choises for air analyis and sampling

SYSTEMATIZATION OF AIR POLLUTING SUBSTANCES

Systematization of air polluting substances

Sources
Natural - antropogen
Emission of methane: animal husbandry, 28% mining 23% rice cultivation 28% Allergens in indoor air dust mites, molds, bacterias, viruses, endotoxins.

Volcanos, Fumaroles vagy mofettes (Mtraderecske) CO2, HCl, H2S, SO2, S

chemical properties (organic- inorganic) health effect, toxicity, etc., boiling point, vapour pressure, (state)

Classification according to boiling point

Megnevezs Very Volatile Organic Compounds Volatile Organic Compounds Semi-Volatile Organic Compounds Particulate Organic Matter

Rvidts VVOC VOC SVOC POM

Forrspont tartomny (C) <0- (50-100) (50-100)-(240-260) (240-260)-(380-400) >380

Classification according to boiling point

Influencing factors atmospherical conditions,

temperature, humidity, pressure

other factors
aerosol concentration, reactive gases

Choices in sampling and analysis

METHODS FOR SAMPLING AND ANALYSIS

Analytical methods

Direct methods On-site

spectromety (flue gas analyzers, pariculate concentration analyzer) (para) magnetic analyzer (oxygen) ionization (PID, FID) electrochemical sensor mass spectrometry

Sampling and analysis Off-site

-

sampling with preconcentration

sampling without preconcentration

Analysis
titration, photometry, chromatography

Sampling without preconcentration

glass bulbs,
cheap, fragile,

polymer bags (Tedlar , Teflor , Cali-5-Bond)

cost effective, easy to use, sample storage time?
11,00 mg/m3 10,80 10,60 10,40 10,20 0 3 5 days 11 16

TCE RSD<3%

Sampling without preconcentration

Canisters
robust design-> longer lifetime, undisturbed sampling (whole air) , EPA method (TO-15), CEN, ISO -> non standard, special intrument need, limited use, high cost

Choices in sampling and analysis

SAMPLING WITH PRECONTENTRATIONPROCESSES

Fizikai-kmiai folyamatok

Sampling processes
phase separation, chemical reaction or dissolution, surface sorption (adsorption and chemisorption), diffusion.

Physico-chemical processes: phase separation

Filters
geometria, material:
chemical resistivity, compatibility with the analysis method, filtration process.

MCE
depth type

GLASS PC

PP

PVC PC

PVDF

screen type

Size selective sampling of aerosols

TSP PM10 PM2.5 nanoparticles

Physico-chemical processes: chemical processes

diazomethane: octanoic acid coated XAD-2 resin (NIOSH 2515)

2,4-toluoldiisocyanate (NIOSH 2535)
HN

N C O

+
N C O

O2N
N O N N O N

NO2

acrolein, (NIOSH 2501), 9-vinyl-1-aza-8-oxabicyclo [4.3.0] nonane formaldehyde (NIOSH 2016), 2, 4-dinitrophenyl hydrazone
NH N

NH O2N NO2

NH2

R1

CH

O2N

NO2 R1

R1: H formaldehid

Surface sorption (adsorption and chemisorption)

K A(g) A(s) H

f(T, p)

Active charcoal by SEM

-solvent desorption -thermodesorption

Sorbent Active coal (coconut shell pyrolizate) XAD-2 Tenax Silicagel XAD-2 phosphoric acid coated Chromosorb Porapak-Q

Chemical name styrene-divinylbenzene copolymer Poly (2,6-diphenyil-p-phenylene-oxide) Silicagel styrene-divinylbenzene copolymer + phosphoric acid polystyrene polyvinylpyrrolidone

Use hydrocarbons, slightly polar substances pesticide, SVOC C6-C16, phtalates acids, polar compounds amines organophosphorous pestcides dimethyl sulfate, diethyl sulphate

Sorbents for thermodesorption

Sorbent Quartz wool Carbograph 2TD Carbograph 5TD Strength Very weak Weak Medium/strong Max. Temp >450 >450 >450 Features Very inert, non-water retentive Hydrophobic Minimal (<0.1 ng) e artefacts Friable 40/60 mesh recommended to minimise back pressure Hydrophobic Minimal (<0.1 ng) artefacts Friable. 40/60 mesh recommended to minimise back pressure Inert; not hydrophobic Individual artefacts below 0.1 ng Must be conditioned slowly Requires extensive purge to remove permanent gases Hydrophobic Low inherent artefacts (<1 ng) Inert suitable for labile components

Carboxen 1003

Very strong

>450

Tenax TA

Weak

350

Sampling for volatile organic compounds: literature

SUPELCO Air Method Guide 2nd Ed., SUPELCO Technical Report : A Tool for Selecting an Adsorbent for Thermal Desorption Applications Note 5: Advice on Sorbent Selection and Conditioning Sample Tubes MARKES Int. Martin Harper :Sorbent trapping of volatile organic compounds from air Journal of Chromatography A, 885 (2000) 12915 Elizabeth Woolfenden: Sorbent-based sampling methods for volatile and semi-volatile organic compounds in air Part 1: Sorbent-based air monitoring options Journal of Chromatography A, 1217 (2010) 26742684 Elizabeth Woolfenden: Sorbent-based sampling methods for volatile and semi-volatile organic compounds in air. Part 2. Sorbent selection and other aspects of optimizing air monitoring methods Journal of Chromatography A, 1217 (2010) 26852694 Maria Rosa Rasa, Francesc Borrull, Rosa Maria Marc: Sampling and preconcentration techniques for determination of volatile organic compounds in air samples , TrAC Trends in Analytical Chemistry Volume 28, Issue 3, March 2009, 347361 Kumar, Anuj, Vden, Ivan: Volatile Organic Compounds: Sampling Methods and Their Worldwide Profile in Ambient Air, Environmental Monitoring and Assessment, Volume 131, Issue 1, 301-321, 2007 Krl, Sylwia, Zabiegala, Bozena, Namiesnik, Jacek: Monitoring VOCs in atmospheric air II. Sample collection and preparation, TrAC Trends in Analytical Chemistry, Volume 29, Issue 9, 1101-1112, 2010 Salthammer, Tunga - Uhde, Erik: Organic Indoor Air Pollutants, Wiley VCH Verlag GmbH, 2009

Choice of sample volume

V0 V<<BV VSSV V>BV

Safe sampling volume (SSV) Breakthrough volume (BV) BV f(T, p, %RH) Sample volume?

SSV boiling point relation

Sznhidrognek hydrocarbons 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0 0 100 200 300 ketonok ketones

-aim of analysis, -guidance given by standard, -performance of analytical method, -previous results.

SSV (g/l)

How to handle breakthrough:

-appropriate sorbent, - control zones or, -backup tubes.
bp (oC)

Sampling processes: diffusion

c0

l
A

ci

dmi dc Di A i (1) dt dl mi A Di (ci c0 ) (2) t l A Qi Di l m c i i (3) t Qi

A 2 r h dmi dc Di 2 r h i (4) dt dr dmi dc Di 2 r h i (5) dt dr r ln d ra 1 ci mi t Di 2 h

ra rd