6th international conference and exhibition on analytical & bioanalytical techniques, sep 1-3,...

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


W. Wardencki, R. J. Katulski, J. Stefański, J. Namieśnik, Crit. Rev. Anal. Chem., 38 (2008) 259–268

APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING


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).



M. Michulec, W. Wardencki, M. Partyka, J. Namieśnik, Crit. Rev. Anal. Chem., 35 (2005) 117–133



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.




The classification of sampling methods,

including simultaneous analyte

enrichmentbased on the

phenomena utilized for the analyte

enrichment


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


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


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




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


THE THEORY OF PASSIVE SAMPLING TECHNIQUE – FICK’S FIRST LAW OF DIFFUSION




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?


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


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


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


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


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?



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


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


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


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


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


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


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


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


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


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


ANALYTICAL PROCEDURE FOR DETERMINATION OF BTEX COMPOUNDS IN ATMOSPHERIC AIR


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


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


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


The study of the indoor air quality (IAQ) using passive samplers


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


M. Marć, J. Namieśnik, B. Zabiegała, Sci. Total Environ., 481 (2014) 35–46

CONCENTRATION LEVELS OF MONOTERPENES BEFORE AND AFTER FURNISHING


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


Study on the organic compounds emission rate (emitted from the surface of the indoor materials)

using small-scale passive emission chambers


Aliphatichydrocarbons

Aromatichydrocarbons

Aldehydes andketones

(formaldehyde)

Alcohols,phenols

Terpenes

Organic acids

ORGANIC COMPOUNDS EMITTED FROM INDOOR EQUIPMENT MATERIALS


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)


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)


SMALL-SCALE PASSIVE EMISSION CHAMBER (SSPEC)



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


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]


MEMBERS OF MY RESEARCH GROUP

6th international conference and exhibition on analytical & bioanalytical techniques, sep 1-3,...

Documents

applicable containers

variable volume containers

solid particles

gas molecules

simultaneous analyte

vapor molecules separation

useful tool

pparticulate matter