6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain1 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 Gdańsk, Poland

6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain2 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, Spain3  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, Spain4 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, Spain5  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, Spain6 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

6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain7 A. Kloskowski, M. Pilarczyk, J. Namieśnik, Crit. Rev. Anal. Chem., 32 (2002) 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, Spain8 DYNAMIC TECHNIQUE PUMP SORPTION MEDIUM FILTER DENUDER STREAM 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, Spain9 c0c0 LMLM x c0c0 L L c0c0 medium trapping analytes c MEMBRANE layer of still air Analyte molecules 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) 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, Spain10 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] L m – the membrane thickness [cm] A. Kot-Wasik, B. Zabiegała, M. Urbanowicz, E. Dominiak, A. Wasik, J. Namieśnik, Anal. Chim. Acta, 602 (2007) 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, Spain11  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, Spain12 DIFFUSIVE PASSIVE SAMPLER ORSA 5 1.Diffusion barrier (cellulose acetate), 2. Label, 3. Sorption medium (activated charcoal, 400 mg), 4. Holder A. Kot-Wasik et al., Anal. Chim. Acta, (2007) Air type Exposure/working time Type of organic compounds Indoor airFrom 15 to 28 days aromatic and aliphatic hydrocarbons Ambient air14 days the BTEX compounds Analytes liberation technique Solvent extraction using CS 2

6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain13 Exposure Collection of analyte samples Transport and storage Identification and determination of analytes Passive devicesDynamic and denuder devices Liberation of analytes GENERAL ANALYTICAL PROTOCOL

6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain – Determination of nitrogen dioxide using tubular diffusion passive sampler (Palms Tube) E. D. Palmes, A. F. Gunnison, Am. Ind. Hyg. Assoc. J., 34 (1973) 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 – Determination of sulfur fioxide using a box-type permeation passive sampler K. D. Reiszner, P. W. West, Environ. Sci. Technol., 7 (1973) MILESTONES IN THE FIELD OF PASSIVE SAMPLING TECHNIQUE – QUANTITATIVE APPROACH

6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain16 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)

6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain17 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, Spain18 ATMOSPHERE HYDROSPHERE LITOSPHERE 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, Spain19 Permeation-type passive sampler Diffusion-type passive sampler Atmospheric air „Zero sink” sorption medium Diffusion path Distance Concentration Atmospheric air Distance Concentration S. Seethapathy, T. Górecki, X. Li, J. Chromatogr. A, 1184 (2008) 234–253 Concentration of analyte „Zero sink” sorption medium GASEOUS MEDIUM 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, Spain20  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, Spain21 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, Spain22 B. Zabiegała, A. Kot-Wasik, M. Urbanowicz, J. Namieśnik, Anal. Bioanal. Chem., 396 (2010) 273–296 Time Mass of analyte collected on a sorption medium LINEAR UPTAKE REGION 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, Spain23 PASSIVE VS DYNAMIC SAMPLERS ADVANTAGES Passive SamplingActive 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, Spain24 PASSIVE VS DYNAMIC SAMPLERS DRAWBACKS Passive SamplingActive 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, Spain25  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, Spain26 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, Spain27 ANALYTICAL PROCEDURE FOR DETERMINATION OF BTEX COMPOUNDS IN ATMOSPHERIC AIR

6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain28 M. Marć, J. Namieśnik, B. Zabiegała, Air Quality, Atmosphere & Health, doi: /s 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, Spain29 M. Marć, J. Namieśnik, B. Zabiegała, Air Quality, Atmosphere & Health, doi: /s 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, Spain30 S. Król, B. Zabiegała, J. Namieśnik, Anal. Bioanal. Chem., 403 (2012) 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, Spain31 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, Spain32 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, Spain33 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, Spain34 Concentration [mg/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, Spain35 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, Spain36 Aliphatic hydrocarbons Aromatic hydrocarbons Aldehydes and ketones (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, Spain37  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) PASSIVE FLUX SAMPLERS (PFS)

6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain38  a weight (0.5 kg) placed on top of instrument to improve the tightness during use  a stainless steel container: area of opening: 452 cm 2, height: 12 cm, volume of inner space: 3.65 dm 3  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, Spain39 M. Marć, J. Namieśnik, B. Zabiegała, Sci. Total Environ., 481 (2014) 35–46 Emission rate of  -Pinene [  g/ 2. h] Emission rate of 3-Carene [  g/m 2. h] Emission rate of D-Limonene [  g/m 2. h] EMISSION FLUX PROFILE OF MONOTERPENES EMITTED FORM INDOOR WOOD-BASED FURNITURE Number of days

6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain40 TraceSpec, th Workshop on Progress in Trace Metal Speciation for Environmental Analytical Chemistry Gdansk, Poland, September 04-07, 2016 Info: Contact:

6th International Conference and Exhibition on Analytical & Bioanalytical Techniques, Sep 1-3, 2015 Valencia, Spain41 MEMBERS OF MY RESEARCH GROUP