APPLICATION OF PASSIVE SAMPLING TECHNIQUES AS A USEFUL

APPLICATION OF PASSIVE SAMPLING TECHNIQUES AS A USEFUL TOOL IN ENVIRONMENTAL QUALITY MONITORING Jacek Namieśnik Department of Analytical Chemistry Chemical Faculty Gdańsk University of Technology 11/12 G. Narutowicza Str. 80 -233 Gdańsk, Poland 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 1

APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING W. Wardencki, R. J. Katulski, J. Stefański, J. Namieśnik, Crit. Rev. Anal. Chem. , 38 (2008) 259– 268 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 2

APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING q 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). 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 3

APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING M. Michulec, W. Wardencki, M. Partyka, J. Namieśnik, Crit. Rev. Anal. Chem. , 35 (2005) 117– 133 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 4

APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING q 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. 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 5

APPLICATION AREAS OF ENVIRONMENTAL ANALYSIS AND MONITORING The classification of sampling methods, including simultaneous analyte enrichment based on the phenomena utilized for the analyte enrichment 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 6

DENUDATION – A CONVENIENT METHOD OF ISOLATION/ENRICHMENT OF ANALYTES 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). A. Kloskowski , M. Pilarczyk, J. Namieśnik, Crit. Rev. Anal. Chem. , 32 (2002) 301 -335 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 7

PRINCIPLE OF OPERATION OF SAMPLING DEVICES USING DYNAMIC AND DENUDER TECHNIQUES DYNAMIC TECHNIQUE DENUDER TECHNIQUE PUMP DENUDER SORPTION MEDIUM FILTER Tube wall covered with thin film of sorbent FILTER STREAM OF GASEOUS MEDIUM PASSING THROUGH A TRAP 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 8

PASSIVE SAMPLING TECHNIQUE FOR COLLECTING ANALYTES SAMPLES FROM GASEOUS MEDIUM DIFFUSIVE PASSIVE SAMPLER medium trapping analytes c 0 L c c 0 x L LM MEMBRANE layer of still air PERMEATION PASSIVE SAMPLER medium trapping analytes Analyte molecules A. Kot-Wasik, B. Zabiegała, M. Urbanowicz, E. Dominiak, A. Wasik, J. Namieśnik, Anal. Chim. Acta, 602 (2007) 141 -163 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 9

THE THEORY OF PASSIVE SAMPLING TECHNIQUE – FICK’S FIRST LAW OF DIFFUSION DIFFUSIVE PASSIVE SAMPLER PERMEATION PASSIVE SAMPLER U – the diffusional mass-transfer rate of analyte [mol/s] A – the cross section of diffusion zone [cm 2] D – diffusion coefficient of analyte [cm 2/s] C – the analyte concentration inside diffusion zone of a sampler [mol/cm] C 0 – the ambient concentration of analyte [mol/cm] (p 1 -p 2) – the difference in partial pressure of the analyte on both sides of the membrane S – the analyte permeability coefficient dependent on the membrane material [cm 2/min] L – length of diffusion zone [cm] Lm – the membrane thickness [cm] A. Kot-Wasik, B. Zabiegała, M. Urbanowicz, E. Dominiak, A. Wasik, J. Namieśnik, Anal. Chim. Acta, 602 (2007) 141 -163 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 10

WHICH PARAMETER SHOULD BE DEFINED BEFORE THE EXPOSURE STAGE OF PASSIVE SAMPLER? q. DIFFUSIVE PASSIVE SAMPLER: Øsampling rate: SR [ml/min] q. PERMEATION PASSIVE SAMPLER: Øcalibration constant: k [min/ml] 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 11

DIFFUSIVE PASSIVE SAMPLER ORSA 5 Air type Indoor air Ambient air Analytes liberation technique Exposure/working time Type of organic compounds From 15 to 28 days aromatic and aliphatic hydrocarbons 14 days the BTEX compounds Solvent extraction using CS 2 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) 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 12

GENERAL ANALYTICAL PROTOCOL Passive devices Dynamic and denuder devices Exposure Collection of analyte samples Transport and storage Liberation of analytes Identification and determination of analytes 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 13

MILESTONES IN THE FIELD OF PASSIVE SAMPLING TECHNIQUE – QUANTITATIVE APPROACH 1973 – 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 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 14

MILESTONES IN THE FIELD OF PASSIVE SAMPLING TECHNIQUE – QUANTITATIVE APPROACH 1973 – Determination of sulfur fioxide using a box-type permeation passive sampler K. D. Reiszner, P. W. West, Environ. Sci. Technol. , 7 (1973) 526 -532 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 15

WHY PASSIVE SAMPLING TECHNIQUE? 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 A. Kot-Wasik, B. Zabiegała, M. Urbanowicz, E. Dominiak, A. Wasik, J. Namieśnik, Anal. Chim. Acta, 602 (2007) 141 -163 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 16

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 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 17

HYDROSPHERE ATM OSP HER E APPLICATION AREAS OF PASSIVE SAMPLING IN MONITOR ING OF THE QUALITY OF DIFFERENT ENVIRONMENTAL COMPARTMENTS E ER PH OS LIT B. Zabiegała, A. Kot-Wasik, M. Urbanowicz, J. Namieśnik, Anal. Bioanal. Chem. , 396 (2010) 273– 296 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 18

IDEAL CONCENTRATION PROFILES FOR TWO TYPES OF PASSIVE SAMPLERS Atmospheric air Concentration of analyte Permeation-type passive sampler Concentration Diffusion path Atmospheric air Membrane thickness „Zero sink” sorption medium Distance „Zero sink” sorption medium Concentration of analyte GASEOUS MEDIUM Concentration Diffusion-type passive sampler Distance S. Seethapathy, T. Górecki, X. Li, J. Chromatogr. A, 1184 (2008) 234– 253 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 19

CRITERIA OF PASSIVE SAMPLING TECHNIQUE SELECTION q q q q 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 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 20

PRACTICAL AREAS OF PASSIVE SAMPLING TECHNIQUE APPLICATION 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) 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 21

TWO DIFFERENT ACCUMULATION REGIMES OF PASSIVE SAMPLING DEVICES RE GI ON EA R UP TA KE PASSIVE SAMPLERS WORKING IN AN EQULIBRIUM AREA LIN Mass of analyte collected on a sorption medium EQUILIBRIUM UPTAKE REGION PASSIVE SAMPLERS WORKING IN A KINETIC AREA Time B. Zabiegała, A. Kot-Wasik, M. Urbanowicz, J. Namieśnik, Anal. Bioanal. Chem. , 396 (2010) 273– 296 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 22

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 timeweighted 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 23 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 23

PASSIVE VS DYNAMIC SAMPLERS DRAWBACKS Passive Sampling Active Sampling û Unsuitable for monitoring of short-term variations in analyte concentration û High cost of a single measurement û Lower enrichment efficiency compared to other techniques û Strongly labour-demanding û Sensitivity of enrichment efficiency to temperature fluctuations and air movement in the vicinity of a sampler û Calibrated pumps are needed (equipment needs regular servicing) û “Historical” nature of results – do not provide direct or real-time data û Energy is consumed û Impossible or very hard to automate û A trap containing a desiccant has to be used û The need to determine enrichment factors for individual analytes û 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 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 24 24

CONSTRUCTION SOLUTIONS IN THE FIELD OF PASSIVE SAMPLERS DEVELOPED AT OUR DEPARTMENT q Passive sampling using badge type permeation passive samplers with silicone membranes is recommended for long-term monitoring of volatile organic compounds in indoor environment q Passive sampler in which a membrane and an organic solvent are a sorption medium (typically isooctane or cyclohexane). It can be applied to transfer and isolate organic compounds like PAHs and chlorophenols from water 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 25

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 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 26

ANALYTICAL PROCEDURE FOR DETERMINATION OF BTEX COMPOUNDS IN ATMOSPHERIC AIR 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 27

TIME-WEIGHT AVERAGE CONCENTRATION OF BENZENE MEASURED IN ATMOSPHERIC AIR IN TRICITY AREA IN 2012 M. Marć, J. Namieśnik, B. Zabiegała, Air Quality, Atmosphere & Health, doi: 10. 1007/s 11869 -014 -0247 -x, 2014 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 28

CONCENTRATION PROFILE OF TOLUENE, ETHYLBENZENE AND XYLENES MEASURED IN ATMOSPHERIC AIR IN TRI-CITY AREA IN 2012 M. Marć, J. Namieśnik, B. Zabiegała, Air Quality, Atmosphere & Health, doi: 10. 1007/s 11869 -014 -0247 -x, 2014 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 29

COMPARISON OF THE SEASONAL BENZENE CONCENTRATION PROFILES OBTAINED BY PASSIVE SANMPLING AND ON-LINE MONITORING S. Król, B. Zabiegała, J. Namieśnik, Anal. Bioanal. Chem. , 403 (2012) 1067 -1082 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 30

The study of the indoor air quality (IAQ) using passive samplers 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 31

ANALYSIS AND MONITORING OF INDOOR AIR POLLUTION – ISSUES AND CHALLENGES q Concentration of analytes present in indoor air may be at much higher concentration level than in atmospheric air due to endemic emission sources q Large variety of pollutants q Possibility of occurence of the same compound in a different concentration levels in the enclosed spaces characterized by similar dimensions and purpose q The need to conduct research during the normal exploitation of enclosed spaces q Lack of appropriate standards and reference materials 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 32

CONCENTRATION LEVELS OF MONOTERPENES BEFORE AND AFTER FURNISHING M. Marć, J. Namieśnik, B. Zabiegała, Sci. Total Environ. , 481 (2014) 35– 46 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 33

Concentration [mg/m 3] TOTAL VOLATILE ORGANIC COMPOUNDS (TVOC) MEASURED IN INDOOR AIR 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 34

Study on the organic compounds emission rate (emitted from the surface of the indoor materials) using small-scale passive emission chambers 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 35

ORGANIC COMPOUNDS EMITTED FROM INDOOR EQUIPMENT MATERIALS Terpenes Organic acids Aliphatic hydrocarbons Aromatic hydrocarbons Aldehydes and ketones (formaldehyde) Alcohols, phenols 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 36

PASSIVE FLUX SAMPLERS (PFS) q 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 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 37

SMALL-SCALE PASSIVE EMISSION CHAMBER (SSPEC) q a weight (0. 5 kg) placed on top of instrument to improve the tightness during use q a stainless steel container: area of opening: 452 cm 2, height: 12 cm, volume of inner space: 3. 65 dm 3 q a handle, which facilitates transport and installation of device anywhere in enclosed spaces q silicon seal in order to prevent air-leakage q 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 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 38

Emission rate of a-Pinene [mg/2. h] EMISSION FLUX PROFILE OF MONOTERPENES EMITTED FORM INDOOR WOOD-BASED FURNITURE Emission rate of 3 -Carene [mg/m 2. h] Number of days Emission rate of D-Limonene [mg/m 2. h] Number of days M. Marć, J. Namieśnik, B. Zabiegała, Sci. Total Environ. , 481 (2014) 35– 46 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 39

INVITATION Trace. Spec, 2016 15 th Workshop on Progress in Trace Metal Speciation for Environmental Analytical Chemistry Gdansk, Poland, September 04 -07, 2016 Info: http: //chem. pg. edu. pl/tracespec/ Contact: chemanal@pg. gda. pl 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 40

MEMBERS OF MY RESEARCH GROUP 6 th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1 -3, 2015 Valencia, Spain 41