ESF provides the COST Office

through a European Commission contractCOST is supported

by the EU Framework Programme

Dr Katarzyna RAULIN

WG4 member: Protocols & Standardisation Methods

ETHERA / France

European Network on New Sensing Technologies for Air Pollution Control and Environmental Sustainability - EuNetAir

COST Action TD1105

INTERNATIONAL WG1-WG4 MEETING on

New Sensing Technologies and Methods for Air-Pollution Monitoring

European Environment Agency - EEA

Copenhagen, Denmark, 3 - 4 October 2013

Action Start date: 01/07/2012 - Action End date: 30/06/2016 - Year 2: 2013-2014 (Ongoing Action)

DEVELOPMENT OF A FORMALDEHYDE CHEMICAL SENSOR FOR

INDOOR AIR QUALITY MONITORING AND ANALYSIS IN PASSIVE

MODE

Grenoble

Headquarter

Commercial & Marketing

2

Our markets

Public buildings

IAQ monitoring LEED building assessment

Private buildings

Personal Exposure Limits

assessment to chemical risk

Industry

Indoor Air QualityEnvironment Code

Industrial HygieneLabour Code

ETHERA created in 2010 Saclay

R&D and Production

3

Indoor chemical pollution status

0

5

10

15

20

25

Intérieur Extérieur

2-butoxy-éthylacétate

1-méthoxy-2propylacétate

styrène

trichloroéthylène

Acroléine

tétrachloroéthylène

2-butoxyéthanol

1 méthoxy2propanol

Benzène

Éthylbenzène

o-xylène

1,2,4-triméthylbenzène

1,4-dichlorobenzène

n-décane

m/p xylène

n-undécane

Acétaldéhyde

toluène

Hexaldéhyde

Formadéhyde

Co

nce

ntr

atio

n µ

g/m

3 Formaldéhyde

Acétaldéhyde

hexaldéhyde

acroléine

Source: French Indoor Air Quality Observatory 2006 –

Campaign based on 600 French representative dwellings

Aldehydes +

BTEX

=

> 80% of total

chemical pollution

Me

diim

Co

nc

en

tra

tio

n

Indoor Outdoor

4

ETHERA R&D

Development, validation

and industrialisation of new chemical sensors for the measurement of

indoor air pollutants

Development of new devices for indoor air

quality control especially

formaldehyde and trichloramine

Development of new devices for the

purification of indoor air

5

• Manufacturing from an industrial

Sol-Gel process

• Protected with 5 international

patents

• A operational pilot production line

Pollutant filtration and

concentration

A nanoporous Sol-Gel

material like a « sponge » Probe molecule integration

Direct optical detection

Specific reaction with the

pollutant creating a colorimetric

reaction

Direct ultra-sensitive

measurement of pollutant

concentration without lab

analysis

High trapping capacities

Selective and efficient

treatment of the pollutant with

integrated saturation indicator

EPURATION MEASURE

A Simple, Sensitive and

Selective technology

Polluant

ETHERA research based on an innovative

technology for IAQ measurement and treatment

6

Profil’air® product range : a modular approach

• Personal Exposure Limits (STOEL 15min)

• Short-term ambiant measurements

• Long-term ambiant measurements

• Personal Exposure Limits (TWA 8h)

• Emission source research

• Personal Exposure Limits (STOEL 15min)

• Short-term ambiant measurements

Passive

sampling

Active

sampling

Sensor

Badge for individual dosimetry PA-SDIxxx

Dynamic exposure module PA-MEX001

Pump module PA-MPO201

Emission measurement chamber PA-CMExxx

Ambiant diffuser PA-DFSxxx

Optical reader module

PA-MRF421

7 7

Main research equipments

Generation of calibrated gas

mixtures Generation of calibrated gas

mixtures in environmental

chamber

• [HCHO]

• T° (10 - 40°C),

• RH (20 – 80 %)

• Air velocity (0.1 - 2 m/s)

Passive measure development in controlled environments

in laboratory

Validation of the passive measure in real conditions:

measure campaigns in nurseries and schools of Grenoble

8

Phase : Calibrated conditions

y = 0,00025x + 0,18751R² = 0,999

y = 0,00024x + 0,18297R² = 0,995

y = 0,00012x + 0,10883R² = 0,999

y = 0,00013x + 0,14356R² = 0,998

0

0,2

0,4

0,6

0,8

1

1,2

1,4

1,6

1,8

0 1000 2000 3000 4000 5000

DO

Time (min)

100,7ppb

107,1ppb

107,0ppb 55,3ppb

50,9ppb

49,1ppb

active sampler ~107 ppb

~50 ppb

y = 0,989xR² = 1,000

y = 0,969xR² = 0,997

0

20

40

60

80

100

120

0 20 40 60 80 100 120

Co

nc

en

tra

tio

n p

as

siv

e s

am

pli

ng

(p

pb

)

Concentration active sampling /DNPH (ppb)

Linearity : sensor response is linear as

a function of time (1, 2, 3 and 4,5 days)

Linearity : sensor response is linear

as a function of the formaldehyde

concentration of 4.5 days

Correlation passive/active : Very good

correlation between passive and active

ETHERA measures

1: y = 2,35E-06xR² = 1,00E+00

2: y = 2,48E-06xR² = 9,97E-01

0,0E+00

5,0E-05

1,0E-04

1,5E-04

2,0E-04

2,5E-04

0 20 40 60 80 100

Re

ac

tio

n r

ate

(m

in-1

)

Concentration (ppb)

Correction coefficient

[HCHO]time

DOK

0

20

40

60

80

100

120

0,0

0,2

0,4

0,6

0,8

1,0

1,2

0 1 2 3 4

HR

(%

)

DO

(4

20

nm

)

Time (day)

0,0E+00

1,0E-06

2,0E-06

3,0E-06

4,0E-06

5,0E-06

6,0E-06

K (p

pb

-1.m

in-1

) 80%50%20%

0,0E+00

1,0E-06

2,0E-06

3,0E-06

4,0E-06

5,0E-06

6,0E-06

0,1 0,3 0,5

K *

10

6(m

in-1

.pp

b-1

)

Air speed (m/s)

CV = 3%

9

• Passive exposition on 1 day

• 50 % RH, 20°C, [HCHO] = 24 ppb

Low effect of the speed from 0.1 to

0.5 m/s

• 4.5 days à 28ppb de

HCHO

• 20°C, 0,1 m/s à

• 20, 50 et 80% RH

Little disruption of

moisture on sensors

Air speed

Variable relative humidity

Phase : Calibrated conditions

10

In presence of 50 ppb formaldehyde or not of:

• Toluene (500 and 2000 ppb)

• Acetaldehyde / Acroleine / Hexanal

• Acetone (some ppm in static)

• (other vapors: HNO3, acetic acid, H2O2…)

Study of potential interfering gaz

Phase : Calibrated conditions

No effect on measure with a mixture of acetaldéhyde, acroleine, hexanal in

the presence of formaldehyde except with acetaldehyde >100 ppb

No significant influence of toluene and acetone on the measure in the

presence of formaldehyde

y = 1,0015xR² = 0,8493

0

20

40

60

80

100

120

0 20 40 60 80 100

Passiv

e s

am

pli

ng

co

ncen

trati

on

(p

pb

)

DNPH concentration (ppb)

Phase : Real conditions

The passive sensor ETHERA was calibrated in real situations compared

with the Radiello® measures according to the humidity

Good correlation for the campaign

between Radiello ®/ ETHERA :

average = 21%

Absolute deviation < 5 ppb

Standard deviation inter-laboratory on

Radiello ®: approximately 18 %

Low standard deviation variation (CV = 8

%) according to the humidity

12

Performance comparable to a chromatographic analysis

Selective

Sensitive(ppb)

Simple

Non destructive

Result

Reproductibility (45 ppb, 50% RH, 24

hrs) 3.6%

Repeatability (45 ppb, 50% RH, 24

hrs) 1.9%

Detection limit (4.5 days of

exposition) 0.2 ppb

Quantification limit (4.5 days of

exposition) 0.8 ppb

Average accuracy / DNPH or

ETHERA active measure 3%

Performance of the method

Profil’air roadmap : planned activities

Aldehydes

BTEX

A progressive gas

extension

13

Chamber for emission

measurements

Ambiant

diffuser

Badge for personal

exposures

CO2, T°, HR

Formaldehyde

Trichloramine