Achim J. Lilienthal Erik Schaffernicht Achim J. Lilienthal. AASS, Örebro University

Achim J. Lilienthal Erik Schaffernicht Mobile Achim J. Achim J. Lilienthal Room T1222 Robotics and Lilienthal Olfaction Room T1211 Lab, Erik Schaffernicht achim.lilienthal@oru.se AASS, Örebro University erik.schaffernicht@oru.se (often away please drop me an email in advance) (often there please drop me an email anyway) 46

2. Further Gas Sensing Technologies for Mobile Robots Beyond the Classical Electronic Nose o Optical sensor systems o Mass spectrometry (MS) 47

2. Mass Spectrometry (MS) Mass Spectrometry o Ionization of compounds http://antoine.frostburg.edu/chem/senese/101/atoms/images/ms3.jpg 48

2. Mass Spectrometry (MS) Mass Spectrometry o Ionization of compounds o Separation according to m/z» with electric or magnetic field http://antoine.frostburg.edu/chem/senese/101/atoms/images/ms3.jpg 49

2. Mass Spectrometry (MS) Mass Spectrometry o Ionization of compounds o Separation according to m/z» with electric or magnetic field o Detection of the ions with an electron multiplier http://antoine.frostburg.edu/chem/senese/101/atoms/images/ms3.jpg 51

2. Mass Spectrometry (MS) Mass Spectrometry o Ionization of compounds o Separation according to m/z» with electric or magnetic field o Detection of the ions with an electron multiplier o Disadvantages for robotics» Ionization unit required» Vacuum is required Not very convenient Costly 52

2. Further Gas Sensing Technologies for Mobile Robots Beyond the Classical Electronic Nose o Optical sensor systems o Mass spectrometry o Ion mobility spectrometry (IMS) 53

2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o Separation of ions by m/z and mobility Strukturuntersuchungen an (C60) n +-Clustern mit MRO-IPW'16 der Methode A. der J. Lilienthal Gasphasen-Ionenchromatographie & E. Schaffernicht (Sep 12, [Lilienthal 2016) 1998] 54

2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o Separation of ions by m/z and mobility» Ionization of compounds Strukturuntersuchungen an (C60) n +-Clustern mit MRO-IPW'16 der Methode A. der J. Lilienthal Gasphasen-Ionenchromatographie & E. Schaffernicht (Sep 12, [Lilienthal 2016) 1998] 55

2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o Separation of ions by m/z and mobility» Ionization of compounds» Separation of m/z Strukturuntersuchungen an (C60) n +-Clustern mit MRO-IPW'16 der Methode A. der J. Lilienthal Gasphasen-Ionenchromatographie & E. Schaffernicht (Sep 12, [Lilienthal 2016) 1998] 56

2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o Separation of ions by m/z and mobility» Ionization of compounds» Separation of m/z» Pulsed introduction to a drift region Larger ions with greater collision cross section are slower due to more collisions Strukturuntersuchungen an (C60) n +-Clustern mit MRO-IPW'16 der Methode A. der J. Lilienthal Gasphasen-Ionenchromatographie & E. Schaffernicht (Sep 12, [Lilienthal 2016) 1998] 57

2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o Separation of ions by m/z and mobility» Ionization of compounds» Separation of m/z» Pulsed introduction to a drift region» Detection of ion current Strukturuntersuchungen an (C60) n +-Clustern mit MRO-IPW'16 der Methode A. der J. Lilienthal Gasphasen-Ionenchromatographie & E. Schaffernicht (Sep 12, [Lilienthal 2016) 1998] 58

2. Ion Mobility Spectrometry (IMS) Ion Mobility Spectrometry o Separation of ions by m/z and mobility» Ionization of compounds» Separation of m/z» Pulsed introduction to a drift region» Detection of ion current o Disadvantages for robotics» Ionization unit required» Ion-ion interaction causes problems in complex mixtures» Drift cell with inert gas required (isolated from atmospheric air) Not very convenient Costly 59

2. Photoionization Detector (PID) Photoionization Detector (VOC monitor) o MS/IMS without m/z and mobility separation 60

2. Photoionization Detector (PID) Photoionization Detector (VOC monitor) o MS/IMS without m/z and mobility separation o Ionization with UV lamp» Max. 11.7 ev in RAE PIDs ( ethanol, acetone, methanol)» Cannot detect methane (IP between 12.6 and 13.6 ev [URL]) o Detection of current o Pros» Quick response to a wide range of gases» Calibrated readings if there is only one, known compound o Cons» Not suitable for classification» Too bulky (?)» Expensive 61

3 Signal Processing in Electronic Noses 64

3. E-Nose Signal Processing Components of an E-Nose Approach o Sampling system o Sensor array (physical or virtual) o Data evaluation algorithms» Reference data set Tasks o Detection o Discrimination o Identification o Quantification 66

3. E-Nose Signal Processing Components of an E-Nose Approach o Sampling system Traditional three-phase sampling Continuous (open) sampling with a mobile robot 67

3. E-Nose Signal Processing Components of an E-Nose Approach o Sampling system o Sensor array (physical or virtual)» Sensors with partial selectivity» Output of sensors is usually one feature per sensor (at a time) Resistance, fundamental frequency shift, etc. Preferably during an equilibrium-type or steady-state-type situation» Sensor array corresponds to feature space 68

3. E-Nose Signal Processing Components of an E-Nose Approach o Sampling system o Sensor array (physical or virtual)» Output of sensors is usually one feature per sensor (at a time)» Sensor array corresponds to feature space o Data evaluation algorithms» Data analysis using e.g. pattern recognition tools 69

4 Electronic Nose Applications 74

4. Electronic Nose Applications Application Areas o Food and beverage control ( human sense of smell) o Fire warning ( human sense of smell) o Pollution monitoring ( human sense of smell)» Environmental monitoring o Detection of hazardous substances and explosives (security macrosmatic mammals such as dogs) o Disease diagnosis» Lung cancer» Bacteria in blood o etc. 75

4. Electronic Nose Applications Environmental Monitoring o Detection of toxic compounds in the ambient atmosphere» At concentrations which will not have an immediate effect but are a longterm danger for human health Carbon monoxide, nitrogen oxides, sulfur oxides, volatile organic compounds, ammonia, ozone, and particulate matter» Compounds that are simply unpleasant 78

4. Electronic Nose Applications Environmental Monitoring o Detection of toxic compounds in the ambient atmosphere o Analytical instruments do not allow dense, continuous sampling o However, using e-noses is very challenging» Complex mixtures» Low detection thresholds» Sampling (where? when?) Samples must be representative and independent of variable ambient conditions Knowledge of spatial and time patterns of concentrations is important» Changes in temperature and humidity Sample pre-treatment and parametric compensation 79

4. Electronic Nose Applications Environmental Monitoring o For application the sensitivity of the electronic nose to the target substances and to potential interferents has to be known 81

4. Electronic Nose Applications Environmental Monitoring o For application the sensitivity of the electronic nose to the target substances and to potential interferents has to be known [Röck et al. 2008] 83

5 Literature 91

5. Literature Literature o [Pearce et al. 2003]» Handbook of Machine Olfaction Chapter 4 92

5. Literature Literature o [Pearce et al. 2003] o [Röck et al. 2008]» Electronic Nose: Current Status and Future Trends, Chem. Rev. 2008, 108, 705-725 93

5. Literature Literature o [Pearce et al. 2003] o [Röck et al. 2008] o [Hierlemann/Gutierrez-Osuna 2008]» Higher-Order Chemical Sensing, A. Hierlemann and R. Gutierrez-Osuna. Chem. Rev. 2008, 108, 563-613. 94

5. Literature Literature o [Pearce et al. 2003] o [Röck et al. 2008] o [Hierlemann/Gutierrez-Osuna 2008] o [Gardner/Bartlett 1999] Electronic Noses Principles and Applications, J. W. Gardner and P. N. Bartlett. Oxford Science Publications, 1999. 95

5. Literature Literature o [Pearce et al. 2003] o [Röck et al. 2008] o [Hierlemann/Gutierrez-Osuna 2008] o [Persaud and Dodd 1982]» Analysis of Discrimination Mechanisms in the Mammalian Olfactory System using a Model Nose. Nature, 1982, 299, 352 355. o [Kreutz et al. 2006]» High Frequency QuartzMicro Balances: A Promising Path to Enhanced Sensitivity of Gravimetric Sensors. Sensors 2006, 6, 335 340. 96