1. Environmental monitoring Air quality monitoring Air and meteorological monitoring parameters

2. Environmental monitoring Air quality monitoring Classification of air pollutants Primary pollutants (emitted directly to the atmosphere) Secondary pollutants (formed by reactions involving primary pollutants and other constituents within the atmosphere) Classification of sources of air pollutants Stationary sources Mobile sources Sources Natural sources Anthropogenic sources Urban sources

3. Environmental monitoring Air quality monitoring Primary air pollutants Secondary air pollutants are formed from sunlight that results in photochemical reactions of O 2 with one or more of the primary air pollutants.

4. Environmental monitoring Air quality monitoring Legislation regarding the concentration limits Order no. 592/2002 revized by Order 448/2007 for establishing the limit values and the evaluation methods of several primary pollutants in the environmental air (imisii) PollutantHourly limit value (average 1 h) Daily limit value (average 24 h) Annually limit value for human health protection (average 1 year) Annually limit value for vegetation protection (average 1 year) SO 2 350 μg/m 3 125 μg/m 3 -20 μg/m 3 NO+NO 2 200 μg/m 3 -40 μg/m 3 30 μg/m 3 Particulate Matter (PM 10 ) -50 μg/m 3 20 μg/m 3 - Lead--0.5 μg/m 3 - Benzene--5 μg/m 3 - CO-10 mg/m 3 -- Ozone120 μg/m 3 -18.000 μg/m 3 h- Arsenic*--6 μg/m 3 - Cadmium*--5 μg/m 3 - Nickel*--20 μg/m 3 - *Added by Order 448/2007

5. Environmental monitoring Air quality monitoring Legislation regarding the concentration limits Order no. 592/2002 for establishing the limit values and the evaluation methods of several primary pollutants in the environmental air (imisii) SO 2 Fluorescence in ultraviolet NO+NO 2 Chemiluminescence Particulate Matter (PM 10 ) Collection of PM 10 on filters and mass measurement (gravimetric) or TEOM method LeadCollection of lead on filters and AAS BenzeneAspiration on a filter cartridge and gas chromatography CONondispersive infrared spectrophotometry (NDIR) OzoneUV photometry Reference methods for concentration measurement

6. Air quality monitoring National Network for Air Quality Monitoring (RNMCA) www.calitateaer.ro

7. Environmental monitoring Air quality monitoring Romanian legislation regarding the concentration limits Order no. 462/1993 regarding emissions from stationary sources (emisii) Refers to emissions produced by Stationary sources Vehicles Infrastructures designed to transportation Burning installations Fuel burning Measurements are mandatory for the installation owner. The results are to be registered and archived by the owner. The limits are given according to the source. If the limits are exceeded, the polluter pays.

8. Environmental monitoring Air quality monitoring Order no. 462/1993 Burner supplied with liquid fuel Thermal power [kW/t] PollutantUnit< 100100 - 300300 - 500> 500 Suspended particulatesmg/Nm 3 50 COmg/Nm 3 170 SO x (expressed in SO 2 )mg/Nm 3 1700 NO x (expressed in NO 2 )mg/Nm 3 450 Burner supplied with solid fuel Thermal power [kW/t] PollutantUnit< 100100 - 300300 - 500> 500 Suspended particulatesmg/Nm 3 100 COmg/Nm 3 250 SO x (expressed in SO 2 )mg/Nm 3 2000 400 NO x (expressed in NO 2 )mg/Nm 3 500400

9. Environmental monitoring Air quality monitoring Order no. 462/1993 Burner supplied with natural gas Thermal power [kW/t] PollutantUnit< 100100 - 300300 - 500> 500 Suspended particulatesmg/Nm 3 5555 COmg/Nm 3 100 SO x (expressed in SO 2 )mg/Nm 3 35 NO x (expressed in NO 2 )mg/Nm 3 350

10. Environmental monitoring Air quality monitoring Methods and instrumentation Passive sampling methods Active sampling methods Automatic methods Remote optical - long path analyzers Any instrument measures 3 types of values: Instantaneous value TWA (Time Weighted Average) STEL (Short Term Exposure Limits)

11. Environmental monitoring Air quality monitoring Methods and instrumentation Gas measurement using spectroscopic methods Spectrophotometry is based on the interaction of the gas molecules with light. Absorbtion techniques – it is measured the intensity of light after passing through a gaseous medium. Usually absorption is measured at several frequencies in order to avoid offests and interferences with other species. There are 4 principles: Differential Optical Absorption Spectroscopy (DOAS) Fourier Transform Infrared (FTIR) Non-Dispersive Infrared (NDIR) Tunable Laser Diode Absorption Spectroscopy (TLDAS)

12. Environmental monitoring Air quality monitoring Methods and instrumentation Gas measurement using spectroscopic methods Emission techniques – excite molecules of the gas and then examine the light emitted as they return to their ground state. The signal is passed through a narrow- band filter and measured with a photomultiplier tube. Flame photometry Chemiluminescence UV fluorescence

13. Environmental monitoring Air quality monitoring Measurement of carbon monoxide (CO) by IR photometry A = log(I/Io) = abC Beer’s law I0I0 I A = absorbance a = absorbtion coefficient b = path length C = concentration

14. Environmental monitoring Air quality monitoring Measurement of carbon monoxide (CO)

15. Environmental monitoring Air quality monitoring Measurement of carbon monoxide (CO) by IR photometry

16. Environmental monitoring Air quality monitoring Schematic of a NDIR head Measurement of carbon monoxide (CO) by IR photometry

17. Environmental monitoring Air quality monitoring Measurement of nitric oxides (NO x ) by chemiluminescence NO + O 3 ==> NO 2 + O 2 + hv (0.6 – 3 μm) Chemiluminescent reaction

18. Environmental monitoring Air quality monitoring Measurement of sulphur dioxide (SO 2 ) by UV fluorescence Excitation S 0 + hν ex → S 1 Fluorescence (emission) S 1 → S 0 + hν em + heat

19. Environmental monitoring Air quality monitoring Measurement of sulphur dioxide (SO 2 ) by UV fluorescence

20. Environmental monitoring Air quality monitoring Measurement of sulphur dioxide (SO 2 ) by UV fluorescence Teledyne 100E UV Fluorescence SO2 Analyzer Ranges: 0-50 ppb to 0-20,000 ppb full scale, user selectable or autoranging Units: ppb, ppm, µg/m 3, mg/m 3 Zero noise: < 0.2 ppb (RMS) Span noise: < 0.5% of reading (RMS) above 50 ppb Lower Detectable Limit (LDL): 0,4 ppb Linearity: 1% of full scale Precision: 0.5% of reading above 50 ppb Analog outputs: 10V, 5V, 1V, 0.1V, selectable Serial outputs: Serial Port 1: RS-232 (DB-9M) Serial Port 2: standard RS-232 or optional RS-485 (DB-9F), Ethernet

21. Environmental monitoring Air quality monitoring Gas chromatography (video clip)

22. Environmental monitoring Air quality monitoring Measurement of Volatile Organic Compounds (VOC) Photo-Ionization Detector (PID)

23. Environmental monitoring Air quality monitoring Measurement of Volatile Organic Compounds (VOC) Photo-Ionization Detector (PID)

24. Environmental monitoring Air quality monitoring FractionSize range PM 10 (thoracic fraction) ≤ 10 μm PM 2.5 (respirable fraction) ≤ 2.5 μm PM 2.5 – PM 10 (coarse fraction) 2.5 - 10 μm PM 1 (fine fraction) ≤ 1 μm Ultrafine (UFP or UP)≤ 0.1 μm Measurement of suspended particles (particulate matter – PM) Aerosol = particles + gas

25. Environmental monitoring Air quality monitoring Measurement of suspended particles (particulate matter – PM) Gravimteric method

26. Environmental monitoring Air quality monitoring Beta Attenuation Method Measurement of suspended particles (particulate matter – PM)

27. Environmental monitoring Air quality monitoring Beta Attenuation Method Measurement of suspended particles (particulate matter – PM) Technical specifications Source Carbon-14 (C-14), < 3.7 MBq Measurement Range 0 to 1.0, 2.0, 3.0, 5.0, 10.0 mg/m 3 0 to 100, 1,000, 2,000, 3,000, 5,000, 10,000 μg/m 3 Minimum Detection Limit 6 μg/m 3 (1/2 hour), 4 μg/m 3 (1hour) 3 μg/m 3 (3 hour), 1 μg/m 3 (24-hour) Resolution 0.1 μg/m 3 Precision ±2.0 μg/m 3 80 μg/m 3 (24-hour average) Accuracy (for mass measurement) ± 5% using NIST-traceable mass foil set Model: BAM-1020 EnviroTechnology

28. Environmental monitoring Air quality monitoring Measurement of suspended particles (particulate matter – PM) Optical method

29. Environmental monitoring Air quality monitoring Measurement of suspended particles (particulate matter – PM) Tapered Element Oscillating Microbalance (TEOM)

30. Environmental monitoring Air quality monitoring Measurement of gaseous pollutants using electrochemical sensors eV în prezenţa gazelor de reducere Gaz O2O2 E SnO 2-x eV în aer O2O2 O2O2 E SnO 2-x Metallic oxideDetected gases TiO 2, Fe 2 O 3, CoO, ZnO, ZrO 2, SnO 2, La 2 O 3 O2O2 Cr 2 O 3, NiO, ZnO, ZrO 2, SnO 2, In 2 O 3 CO Fe 2 O 3, Fe 3 O 4, Co 3 O 4, ZnOCH 4 SnO 2, VONO x ZnO, Al 2 O 3, SnO 2 halogens R = resistance A, α = constants C = gas concentration