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6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 1
APPLICATION OF PASSIVE SAMPLING TECHNIQUES AS A USEFUL TOOL IN
ENVIRONMENTAL QUALITY MONITORING
Jacek NamieśnikDepartment of Analytical Chemistry
Chemical FacultyGdańsk University of Technology
11/12 G. Narutowicza Str.80-233 Gdańsk, Poland
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 2
W. Wardencki, R. J. Katulski, J. Stefański, J. Namieśnik, Crit. Rev. Anal. Chem., 38 (2008) 259–268
APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 3
Direct and continuous measurements of the concentration level of organic and inorganic compounds as a result of applying relevant automatic monitors and analysers in the form of : stationary devices (measuring sets installed on
monitoring stations), mobile appliances (portable and transportable).
APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 4
M. Michulec, W. Wardencki, M. Partyka, J. Namieśnik, Crit. Rev. Anal. Chem., 35 (2005) 117–133
APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 5
Collection of air samples to applicable containers:o with a constant volume – stainless steel containers – SUMMA®,o with variable volume – containers made of such materials as:
Tedlar, Teflon, Nalofan.
The containers should
be transported to
a suitably equipped
laboratories.
APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 6
APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING
The classification of sampling methods,
including simultaneous analyte
enrichmentbased on the
phenomena utilized for the analyte
enrichment
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 7
A. Kloskowski , M. Pilarczyk, J. Namieśnik, Crit. Rev. Anal. Chem., 32 (2002) 301-335
The principle of gase and vapor molecules separation from solid particles in a cylindrical denuder:
1 — solid particles, 2 — gas molecules, 3 — film of the retaining medium, 4 — walls (F-force; indices: g–gas, p–particulate matter, d–diffusion, f–gas flow).
DENUDATION – A CONVENIENT METHOD OF ISOLATION/ENRICHMENT OF ANALYTES
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 8
DYNAMIC TECHNIQUE
PUMP
SO
RP
TIO
N
ME
DIU
M
FILTER
DE
NU
DE
RSTREAM OF GASEOUS MEDIUM PASSING THROUGH A TRAP
DENUDER TECHNIQUE
PUMP
PRINCIPLE OF OPERATION OF SAMPLING DEVICES USING DYNAMIC AND DENUDER TECHNIQUES
FILTER
Tube wall covered with thin film of
sorbent
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 9
c0
LM
x
c0
L
L
c0
medium trapping analytes
c
ME
MB
RA
NE
layer of still air
Analytemolecules
medium trapping analytes
DIFFUSIVE PASSIVE SAMPLER
PERMEATION PASSIVE SAMPLER
A. Kot-Wasik, B. Zabiegała, M. Urbanowicz, E. Dominiak, A. Wasik, J. Namieśnik, Anal. Chim. Acta, 602 (2007) 141-163
PASSIVE SAMPLING TECHNIQUE FOR COLLECTING ANALYTES SAMPLES FROM GASEOUS MEDIUM
DIFFUSIVE PASSIVE SAMPLER
PERMEATION PASSIVE SAMPLER
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 10
U – the diffusional mass-transfer rate of analyte [mol/s]A – the cross section of diffusion zone [cm2]D – diffusion coefficient of analyte [cm2/s]C – the analyte concentration inside diffusion zone of a sampler [mol/cm]C0 – the ambient concentration of analyte [mol/cm]
(p1-p2) – the difference in partial pressure of the analyte on both sides of the membrane
S – the analyte permeability coefficient dependent on the membrane material [cm2/min] L – length of diffusion zone [cm]Lm – the membrane thickness [cm]
CCL
DAU 0
mm L
pSA
L
ppSAU
)( 21
A. Kot-Wasik, B. Zabiegała, M. Urbanowicz, E. Dominiak, A. Wasik, J. Namieśnik, Anal. Chim. Acta, 602 (2007) 141-163
THE THEORY OF PASSIVE SAMPLING TECHNIQUE – FICK’S FIRST LAW OF DIFFUSION
DIFFUSIVE PASSIVE SAMPLER
PERMEATION PASSIVE SAMPLER
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 11
DIFFUSIVE PASSIVE SAMPLER:sampling rate: SR [ml/min]
PERMEATION PASSIVE SAMPLER:calibration constant: k [min/ml]
WHICH PARAMETER SHOULD BE DEFINED BEFORE THE EXPOSURE STAGE OF PASSIVE SAMPLER?
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 12
DIFFUSIVE PASSIVE SAMPLER ORSA 5
1. Diffusion barrier
(cellulose acetate),
2. Label,
3. Sorption medium
(activated charcoal, 400 mg),
4. Holder
http://www.mlhb.de/raumluft.html, A. Kot-Wasik et al., Anal. Chim. Acta, 602 141 (2007)
Air typeExposure/working
timeType of organic
compounds
Indoor air From 15 to 28 daysaromatic and
aliphatic hydrocarbons
Ambient air 14 daysthe BTEX
compounds
Analytes liberation technique
Solvent extraction using CS2
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 13
Exposure Collection of analyte samples
Transport and storage
Identification and determination of analytes
Passive devices Dynamic and denuder devices
Liberation of analytes
GENERAL ANALYTICAL PROTOCOL
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 14
19731973 – Determination of nitrogen dioxide using tubular diffusion passive sampler (Palms Tube)
E. D. Palmes, A. F. Gunnison, Am. Ind. Hyg. Assoc. J., 34 (1973) 78-81
MILESTONES IN THE FIELD OF PASSIVE SAMPLING TECHNIQUE – QUANTITATIVE APPROACH
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 15
19731973 – Determination of sulfur fioxide using a box-type permeation passive sampler
K. D. Reiszner, P. W. West, Environ. Sci. Technol., 7 (1973) 526-532
MILESTONES IN THE FIELD OF PASSIVE SAMPLING TECHNIQUE – QUANTITATIVE APPROACH
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 16
Simplicity of construction of devices,
Elimination of pumps and power supplies,
Possibility of determination of time-weighted average concentration based only upon exposure time, without knowledge of sample volume,
Suitability for long-term collection of analyte samples,
Possibility of collecting analyte samples in a confined places without supervision of qualified staff
WHY PASSIVE SAMPLING TECHNIQUE?
A. Kot-Wasik, B. Zabiegała, M. Urbanowicz, E. Dominiak, A. Wasik, J. Namieśnik, Anal. Chim. Acta, 602 (2007) 141-163
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 17
GENERAL CLASSIFICATION OF PASSIVE SAMPLERS APPLIED IN AIR MONITORING
M. Michulec, W. Wardencki, M. Partyka, J. Namieśnik, Crit. Rev. Anal. Chem., 35 (2005) 117–133
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 18
PORE WATER4%
GROUND WATER10%
OTHER10%
SOIL7%
AIR32% WATER
37%
AT
MO
SP
HE
RE
HY
DR
OS
PH
ER
E
LITOS
PH
ER
E
B. Zabiegała, A. Kot-Wasik, M. Urbanowicz, J. Namieśnik, Anal. Bioanal. Chem., 396 (2010) 273–296
APPLICATION AREAS OF PASSIVE SAMPLING IN MONITOR ING OF THE QUALITY OF DIFFERENT
ENVIRONMENTAL COMPARTMENTS
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 19
Permeation-type passive sampler
Diffusion-type passive sampler
Atmospheric air „Zero sink”
sorption medium
Diffusion path
Distance
Con
cent
ratio
n
Atmospheric air
Distance
Con
cent
ratio
n
S. Seethapathy, T. Górecki, X. Li, J. Chromatogr. A, 1184 (2008) 234–253
Concentration of analyte
Concentration of analyte
„Zero sink” sorption medium
GA
SE
OU
S M
ED
IUM
Membrane thickness
IDEAL CONCENTRATION PROFILES FOR TWO TYPES OF PASSIVE SAMPLERS
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 20
Type of sampled medium (indoor air, atmospheric air, ground water, soil etc.),
The nature of analytes (organic compounds, inorganic compounds),
Exposure time (8 hours, 24 hours, 7 days, 14 days, month, year),
The place of passive samplers installation (background, „hot spots”),
Metrological characteristics of passive sampler (sampling rate, sampler size),
Liberation technique of analytes retained on a sorption medium
The maintenance costs
CRITERIA OF PASSIVE SAMPLING TECHNIQUE SELECTION
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 21
Assessment of the quality of the atmosphere at the workplace, Collection of analyte samples from the human's breathing zone, Evaluation of indoor air quality (atmosphere at the indoor
environment), Estimation of atmospheric air quality (concentration levels of air
pollutants) Assessment of personal exposure (personal/individual samplers), Estimation of air quality exhaled by human, Evaluation of emission rate of chemical compounds emitted from
various types of indoor materials, Estimation of emission rate of chemical compounds emitted from
the surface of human skin, Assessment of the pollutants levels present in ground and surface
water, Evaluation of pollutants levels present in solid matrices (such as
soil, sediment, and compost)
PRACTICAL AREAS OF PASSIVE SAMPLING TECHNIQUE APPLICATION
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 22
B. Zabiegała, A. Kot-Wasik, M. Urbanowicz, J. Namieśnik, Anal. Bioanal. Chem., 396 (2010) 273–296 Time
Mas
s o
f an
alyt
e co
llec
ted
on
a
sorp
tio
n m
ediu
m
LIN
EA
R U
PTA
KE
RE
GIO
N
EQUILIBRIUM UPTAKE REGION
PASSIVE SAMPLERS WORKING IN AN EQULIBRIUM AREA
PASSIVE SAMPLERS WORKING IN A KINETIC AREA
TWO DIFFERENT ACCUMULATION REGIMES OF PASSIVE SAMPLING DEVICES
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 23
23
PASSIVE VS DYNAMIC SAMPLERS
ADVANTAGES
Passive Sampling Active Sampling
Relatively small, simple and light devices Flexible time resolution
Elimination of pumps and power supplies Ease of calibration
Low-cost sampling Large-volume samples can be collected
Possibility of determination of time-weighted average concentration based only upon exposure time, without knowledge of sample volume
Very effective enrichment
Suitability for long-term collection of analyte samples
Use of multisorbent sorption tubs allows to sampling wide spectrum of analytes with different volatility
S. Król, B. Zabiegała, J. Namieśnik, Trends Anal Chem., 29 (2010) 1101–1112
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 24
24
PASSIVE VS DYNAMIC SAMPLERS
DRAWBACKSPassive Sampling Active Sampling
Unsuitable for monitoring of short-term variations in analyte concentration
High cost of a single measurement
Lower enrichment efficiency compared to other techniques
Strongly labour-demanding
Sensitivity of enrichment efficiency to temperature fluctuations and air movement in the vicinity of a sampler
Calibrated pumps are needed (equipment needs regular servicing)
“Historical” nature of results – do not provide direct or real-time data
Energy is consumed
Impossible or very hard to automate A trap containing a desiccant has to be
used
The need to determine enrichment factors for individual analytes
Transport of power equipment (pumps, ventilators) to the sampling site is troublesome
S. Król, B. Zabiegała, J. Namieśnik, Trends Anal Chem., 29 (2010) 1101–1112
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 25
Passive sampling using badge type permeation passive samplers with silicone membranes is recommended for long-term monitoring of volatile organic compounds in indoor environment
Passive sampler in which a membrane and an organic solvent are a sorption medium (typically iso-octane or cyclohexane). It can be applied to transfer and isolate organic compounds like PAHs and chlorophenols from water
CONSTRUCTION SOLUTIONS IN THE FIELD OF PASSIVE SAMPLERS
DEVELOPED AT OUR DEPARTMENT
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 26
Determination of the concentration level of BTEX (benzene, toluene, ethylbenzene,
xylenes) compounds in ambient air in the Tri-City agglomeration area using passive
samplers at the step of handling of representative analyte samples
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 27
ANALYTICAL PROCEDURE FOR DETERMINATION OF BTEX COMPOUNDS IN ATMOSPHERIC AIR
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 28
M. Marć, J. Namieśnik, B. Zabiegała, Air Quality, Atmosphere & Health, doi:10.1007/s11869-014-0247-x, 2014
TIME-WEIGHT AVERAGE CONCENTRATION OF BENZENE MEASURED IN ATMOSPHERIC AIR IN TRI-
CITY AREA IN 2012
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 29
M. Marć, J. Namieśnik, B. Zabiegała, Air Quality, Atmosphere & Health, doi:10.1007/s11869-014-0247-x, 2014
CONCENTRATION PROFILE OF TOLUENE, ETHYLBENZENE AND XYLENES MEASURED IN ATMOSPHERIC AIR IN TRI-CITY AREA IN 2012
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 30
S. Król, B. Zabiegała, J. Namieśnik, Anal. Bioanal. Chem., 403 (2012) 1067-1082
COMPARISON OF THE SEASONAL BENZENE CONCENTRATION PROFILES OBTAINED BY PASSIVE
SANMPLING AND ON-LINE MONITORING
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 31
The study of the indoor air quality (IAQ) using passive samplers
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 32
ANALYSIS AND MONITORING OF INDOOR AIR POLLUTION – ISSUES AND CHALLENGES
Concentration of analytes present in indoor air may be at much higher concentration level than in atmospheric air due to endemic emission sources
Large variety of pollutants
Possibility of occurence of the same compound in a different concentration levels in the enclosed spaces characterized by similar dimensions and purpose
The need to conduct research during the normal exploitation of enclosed spaces
Lack of appropriate standards and reference materials
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 33
M. Marć, J. Namieśnik, B. Zabiegała, Sci. Total Environ., 481 (2014) 35–46
CONCENTRATION LEVELS OF MONOTERPENES BEFORE AND AFTER FURNISHING
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 34
0
0,5
1
1,5
2
2,5
3
3,5
4
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
Dwelling No.
Passive samplig technique
Dynamic sampling technique
Con
cen
trat
ion
[m
g/m
3 ]TOTAL VOLATILE ORGANIC COMPOUNDS (TVOC)
MEASURED IN INDOOR AIR
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 35
Study on the organic compounds emission rate (emitted from the surface of the indoor materials)
using small-scale passive emission chambers
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 36
Aliphatichydrocarbons
Aromatichydrocarbons
Aldehydes andketones
(formaldehyde)
Alcohols,phenols
Terpenes
Organic acids
ORGANIC COMPOUNDS EMITTED FROM INDOOR EQUIPMENT MATERIALS
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 37
The main advantages of passive flux samplers are: in-situ operation, no power source required, no inert gas line needed, contaminant emission flux(es) measured under real
conditions (as regards temperature, pressure, air humidity, ventilation rate and the furnishing of the room in question),
simplicity of operation, cheap to operate, installation possible at any point in the room without
affecting its functioning or disturbing its users.
M. Marć, B. Zabiegała, J. Namieśnik, Crit. Rev. Anal. Chem., 43 (2013) 55-61
PASSIVE FLUX SAMPLERS (PFS)
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 38
a weight (0.5 kg) placed on top of instrument to improve the tightness during use
a stainless steel container: area of opening: 452 cm2, height: 12 cm, volume of inner space: 3.65 dm3
a handle, which facilitates transport and installation of device anywhere in enclosed spaces
silicon seal in order to prevent air-leakage
Radiello® diffusive passive sampler placed inside in central point of chamber (graphitized carbon Carbograph 4 as a sorption medium)
M. Marć, J. Namieśnik, B. Zabiegała, Sci. Total Environ., 481 (2014) 35–46
SMALL-SCALE PASSIVE EMISSION CHAMBER (SSPEC)
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 39
M. Marć, J. Namieśnik, B. Zabiegała, Sci. Total Environ., 481 (2014) 35–46
Em
issi
on
rate
of
-Pin
en
e
[g
/2.h
]E
mis
sio
n ra
te o
f 3
-Ca
ren
e [
g/m
2.h
]E
mis
sio
n ra
te o
f D
-Lim
one
ne
[
g/m
2.h
]
EMISSION FLUX PROFILE OF MONOTERPENES EMITTED FORM INDOOR WOOD-BASED FURNITURE
Number of days
Number of days
Number of days
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 40
TraceSpec, 2016
15th Workshop on Progress in Trace Metal Speciation for Environmental Analytical
ChemistryGdansk, Poland, September 04-07, 2016
Info: Info: http://chem.pg.edu.pl/tracespec/http://chem.pg.edu.pl/tracespec/Contact: [email protected]: [email protected]
6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain 41
MEMBERS OF MY RESEARCH GROUP