Anal Bioanal Chem (2009) 393:467472 DOI 10.

1007/s00216-008-2464-3

TRENDS

Chemosensors in environmental monitoring: challenges in ruggedness and selectivity

Peter A. Lieberzeit & Franz L. Dickert

Published online: 4 November 2008 # Springer-Verlag 2008

Abstract Environmental analysis is a potential key application for chemical sensors owing to their inherent ability to detect analytes on-line and in real time in distributed systems. Operating a chemosensor in a natural environment poses substantial challenges in terms of ruggedness, longterm stability and calibration. This article highlights current trends of achieving both the necessary selectivity and ruggedness: one way is deploying sensor arrays consisting of robust broadband sensors and extracting information via chemometrics. If using only a single sensor is desired, molecularly imprinted polymers offer a straightforward way for designing artificial recognition materials. Molecularly imprinted polymers can be utilized in real-life environments, such as water and air, aiming at detecting analytes ranging from small molecules to entire cells. Keywords Environmental monitoring . In situ sensing . Artificial recognition materials . Real-life application . Molecular imprinting

Introduction In both academic and industrial research, the design of novel sensor systems has attracted substantial interest, because it inherently generates small measuring devices that can be operated independently of a well-equippedand hence costlylaboratory and trained personnel. These properties make them promising tools every time a defined class of
P. A. Lieberzeit (*) : F. L. Dickert Department of Analytical Chemistry and Food Chemistry, University of Vienna, Waehringer Strasse 38, 1090 Vienna, Austria e-mail: peter.lieberzeit@univie.ac.at

analytes has to be monitored on-line, in real life or in a distributed way, such as in environmental analysis. Despite excellent scientific progress in designing novel chemosensors including novel transducers as well as functionalities on the nanoscale, they mostly have been tested in laboratories rather than being exposed to natural environments. The commercially available exceptions are the Taguchi or Figaro sensor for detecting combustible gases indoors and the lambda probe for surveying the oxygen content of automotive exhaust gases. In contrast to this, a larger number of physical sensors are available, including systems measuring strain, temperature, pressure, acceleration and conductivity, among others. Therefore, the intriguing question is: What are the reasons for the comparably small number of chemical sensors on the market? One answer is their inherently higher complexity [1] when compared with physical sensors: whereas in the case of a physical measurement a suitable transducer platform has to be found, chemical sensors usually additionally require a sensor layer guaranteeing the necessary selectivity between related compounds (with some fibre-optic systems being the notable exception). Furthermore, analyte concentrations in a real-life environment can be very low down to parts per billion or parts per trillionthus requiring outstanding sensitivity. However, often sensitivity and ruggedness have to be traded off against one another. Therefore, operating a sensor in a real-life environment over an extended period of time requires optimizing selectivity and sensitivity, robustness and complexity, taking also recalibration into account. In this paper, we summarize recent efforts (published roughly within the last 5 years) addressing one or more of these issues published in peer-reviewed journals and hence undertaking analysis in a non-standardized, real-life matrix. Furthermore, we focus on contaminants and leave out natural analytes in water (e.g. CO2, O2, etc.), because this topic has been extensively covered by Greenwood et al. [2]

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and Johnson et al. [3], the latter including sensor platforms deployed in marine environments. In a similar way, Chapman and Owusu [4] have reviewed rapid analysis and destruction of toxins affecting drinking water quality and availability.

Novel in-field systems and distributed sensors To date, only a limited number of reports of chemical sensor applications in real-life environments have been published. Most of these applications have in common that they correlate a physical signal directly with the incidence of a chemical phenomenon and hence do not require sophisticated selective layers. One example for such an approach is a thin-film resistor for detecting steel corrosion [5] mounted directly on the respective substrate. When exposed to corrosive environments, the system slowly dissolves, which can be detected by the increase in resistivity. Strictly speaking this is not a sensor system but a dosimeter owing to the lack of reversibility. True sensing, however, has been performed by a grid measurement system for detecting landfill or oil tank leaching by monitoring conductivity [6]. Figure 1 shows the principal setup and sketches the results: each intersection point of any two wires of the grid contains a conductivity sensor. Solutions from landfill leakage usually contain substantial amounts of ions and polar compounds and hence increase local conductivity, whereas the opposite

is true in the case of oil tanks. This allows for rapidly localizing leaks and repair before substantial amounts of groundwater are contaminated. In environmental sensing, also the oxidationreduction potential of water is an ecologically important measurand. A group around Papautsky [7] developed a microelectrode system consisting of four individual electrodes with a length of 1 cm, diameters in the range of 90 m, an interelectrode spacing of 450900 m and tip sizes around 200 nm. These systems are excellently suitable for being immersed into natural aquatic systems and directly measure the respective redox potential without the necessity of a selective layer material. Similarly, Je et al. [8] designed a mobile walk-in hood for disposing of organics at a hazardous-waste facility including physical sensors for monitoring volatile organics. The devices are based on photoionization directly assessing the overall amount of organics occurring in the hood, in the filter system and in the exhaust to ensure that the air emitted meets the requirements of maximum contaminant concentration. Deploying established, robust detectors within a suitable housing in an environment of interest has also been demonstrated, e.g. with Cherenkov counters monitoring 90Sr in the groundwater near nuclear facilities [9]. In going from physical to chemical measurements, metal oxide semiconductors represent a class of miniaturized sensors having found widespread application in gas sensing. When they are used in long-term, on-site measure-

Fig. 1 a Setup of a conductive sensor grid for early detection of leakages in landfill sites or buried oil tanks. b Sample sensor response patterns in the case of leakage. (Adapted from [6])

(A)

(B)

landfill leakage

oil leakage

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ments, they have to be regularly recalibrated because of signal drift. An example for this is monitoring NOx values in Tokyo over several weeks with a distributed sensor system consisting of four individual sensors [10]. The tin dioxide sensors correctly reproduce the NOx values in the parts per billion range at the different measuring stations when referencing by the respective temperature and humidity levels. However, the drift of the individual sensor signals makes recalibration necessary about once every 10 days. For this purpose, the authors developed a routine readjusting the baseline at times when all four sensors of the grid show low sensor responses and only minimal difference in NOx concentration among each other, i.e. in the case of no or only little traffic in the respective area. Otherwise, sensors located near main streets should show effects substantially differing from the ones mounted in more tranquil neighbourhoods. Under the abovementioned circumstances, the system could recalibrate all four sensors using the average signal of the other three and thus validate the monitoring network by a commercial NOx analyser, resulting in measuring campaigns of at least several months. Feng et al. [11] proposed a different and very generally applicable strategy: when applying an external stimulus to a wireless sensor network, the response pattern caused can be utilized to recalibrate each individual system within the network. The authors proved the concept by light sensors, where they used a single light bulb to irradiate at once all sensors in a sensor grid during the absence of ambient light and to recalibrate the system using the dynamic response behaviour to the incident beam. In principle, this strategy is not restricted to optical sensors but can also be applied for any transducer that can be rationally influenced by an external stimulus.

Sensor arrays Commercially available electronic noses, i.e. sensor arrays for gas-phase measurements, mostly rely on metal oxide semiconductor, conductive polymer or mass-sensitive sensors. The first two can be designed with different selectivity by modifying the transducer material itself; in the case of mass-sensitive devicesmainly the quartz crystal microbalance (QCM)they have to be coated prior to use. Nake et al. [13] assessed two different commercial portable products for measuring volatile emissions from wastewater plants. For this purpose, they sampled air at different locations of the wastewater plant on different days. The metal oxide sensor data were clustered with some minor outliers, which also correctly reproduced the fact that the smell was similar on all days. However, the conductive polymer signals formed groups correlated to the day of measurement, thus showing a substantial influence of ambient humidity. Hence, owing to their transduction strategy based on polymer swelling, they in this case would require thorough referencing. On the other hand, metal oxide semiconductor sensors need higher operating temperatures and thus consume more energy, so from this point of view the two transducer systems do not differ substantially with respect to the desired application. Similarly, a group from NASA reported on spacecraft on-board monitoring of toxic vapours based on an array of different Taguchi sensors [14] monitoring 11 different compounds. Though this is a rather non-typical environment, the challenges for sensors are similar, because in the case of accidental leakage of toxic compounds into the atmosphere, a spacecraft cannot be simply evacuated. Aside from longterm stability, rapid sensor responses are also fundamental: a leak contaminating the air requires fast countermeasures. Metal oxide sensors, where the analyte interacts directly with the transducer rather than forming a (diffusion-controlled) equilibrium with a selective material, meet this necessity. A further straightforward and robust way for achieving detection in analytical chemistry is making use of colorimetric reactions for the detection of both cations and anions. This approach of course has a long history, but modern methods such as CCD readout and chemometry make it, for instance, possible to screen large numbers of water samples in a parallelized way with microtitre plates [15] and characterize them by their respective ion load. Choosing a broadband approach has another advantage: it allows detection of odours as such even without knowing their detailed composition. However, if the analyte is not exactly known, fundamental analytical features such as the limit of detection can no longer be utilized [16]. For monitoring composting processes, Nicolas and Romain [17] overcame this problem in a tin dioxide sensor based system on comparing the resistance change caused by odour

Generating selectivity In addition to sensitivity, environmental analysis requires high selectivity owing to the complexity of the respective matrices. Currently, two different strategies attempt to overcome the limited ruggedness of natural recognition systems (e.g. antibodies). The first is introducing suitable multisensory arrays consisting of broadband sensors, i.e. electronic noses [12], and the second is designing novel, robust selector materials (Fig. 2). In the former case, selectivity is generated in silico by chemometry assessing the qualitative or quantitative composition of an environmental matrix and hence calculating it from the response pattern of an array. The latter case comprises designing man-made materials with bioanalogous affinity known to be stable over extended periods of time. Both strategies have been developed far enough that reports of the first applications in real-life environments have been published.

470 Fig. 2 Approaches for generating selectivity in real-life environmental applications: a chemometric calculations from multiselective arrays; b generating adapted recognition sites in artificial materials

P.A. Lieberzeit, F.L. Dickert

A) Multiselective Arrays

B) Selective Materials

samples above a composter with the calibration curves for ethanol. They then defined the limit of detection by the dilution factor necessary to obtain a resistance shift higher than 3 times the baseline noise. Generally, the limit of detection of the electronic nose is still higher than the resolution limit of a human testing panel. However, in the long term this approach shall replace the rather subjective panels as a more quantitative approach. Relying on a different transducer, Sugimoto et al. [18] applied plasmapolymerized polypyrrole films on QCM devices for detection of volatile organics in an environment. The interesting concept is taking into consideration the dynamic response behaviour of the differently coated sensors towards the different volatile organic compounds and using these data for calibration. The variations in this case result from the fact that any sensor layer is covered with two to three layers of water under atmospheric conditions. Depending on the different affinities of each volatile organic compound with water and the sensor surface, respectively, each compound produces a distinct time-dependent response pattern. Selective sensor materials: Molecular imprinting Electronic noses have the advantage of relying exclusively on robust devices and achieving selectivity by data processing. However, often it is preferable to operate only a single sensor rather than an array, because this inherently reduces electronic complexity. A straightforward example for this is amperometry owing to the selectivity resulting from the various redox potentials of different analytes, as could recently be shown by the detection of allergens [19]. However, a main goal of chemistry is mimicking nature and its recognition ability in a robust, man-made system. In principle, biological selectivity also can be implemented in artificial sensors via immobilizing natural antibodies on the sensor surface.

While being an outstandingly successful tool for sensing [20, 21], most natural antibodies are not robust enough for environments strongly differing from physiological conditions. One way to overcome this problem is to use molecularly imprinted polymers (MIP) [22, 23], where cavities in a highly cross-linked polymer are generated by self-organization of the polymer chains forming around a template compound such as the analyte-to-be (Fig. 3). During polymerization, non-covalent interaction networks are generated between the material and the template species based mainly on hydrogen bonds and dipolar, and hydrophobic interactions. After the template has been removed, these interaction networks are retained within the material, which hence leads to ideally adapted geometry and functionality of the resulting cavities. Being man-made, they can usually withstand harsh conditions, e.g. as present during process control [24]. This results in highly selective, stable matrices covering analytes ranging from molecules to entire cells. Two examples for environmental sensing are the detection of sodium dodecyl sulfate [25] as a model compound of detergent contamination and of trichloroacetic acid (TCAA) [26] as a remnant of hypochlorite disinfectants in water. In both cases the authors developed the necessary selective sensor materials, coated them on QCM devices and after calibration exposed them to real-life water samples, namely river waters in the first case and treated tap waters in the second case. Both sensors led to highly appreciable sensor responses with detection limits in the low micrograms per litre range. Compared with their template, the sodium dodecyl sulfate sensors showed substantially lower responses towards sodium dodecanoate, but similar effects towards sodium dodecyl benzyl sulfonate; therefore, the sulfonate group in this case plays the key role in recognition. In the other case, i.e. the TCAA sensor, the authors observed very appreciable selectivity towards related compounds, such

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Polymerization

Template Removal

Analyte Re-Uptake

Fig. 3 Principle of molecular imprinting: a highly cross-linked polymer is generated in the presence of a template compound leaving behind selective recognition sites

as the dichloroacetic and monochloroacetic esters and the respective brominated analogues as well as acetic acid and malonic acid. Tribromoacetic acid and dichloroacetic acid, respectively, yielded around 40% of the TCAA sensor signal. The selectivity for the other compounds was even better than that. The tribromo-substituted compound is obviously slightly too large for the cavities and in the case of the dichloro acid the one missing CCl bond obviously leads to substantially reduced incorporation. Therefore, generally both functionality and steric properties of the template are important in molecular imprinting. For instance a polymer optimized to incorporate the pesticide carbaryl from natural waters [27] shows only minimal cross-sensitivity: when bendiocarb and carbofuran are added in up to sevenfold excess, the sensor signals remain unaltered. We could observe similar selectivity for other volatile organics, which enabled us to combine six selective, mostly MIP-based materials to form a sensor array responding to aliphatic alcohols, acetic esters, limonene and humidity to monitor composting processes
Fig. 4 Principal quartz crystal microbalance array setup for monitoring composting processes online. The inset shows an actual array comprising six electrodes

[28] on-line via the basic setup shown in Fig. 4. Chemometric data analysis resulted in quantitative data in good accordance with gas chromatographymass spectrometry. A very interesting point in this case is the duration of the individual composting runs monitored: they lasted for up to almost 2 months without any signal stability problems. Furthermore, MIP materials also show very appreciable selective results in much harsher environments, such as engine oils: titanium dioxide nanoparticles templated with a mid-chain carbonic acid readily incorporate oxidized lubricant compounds [29] and thus are excellently suitable for designing a chemical sensor for the oxidation of engine oil. The nanoparticle approach furthermore allows for substantially increased sensitivity owing to improved accessibility of the individual cavities as a consequence of increased porosity. Again, the sensor layers can be subjected to a harsh medium at elevated temperatures (around 100 C), which would not be possible with other highly selective systems such as natural antibodies. Furthermore, titanium oxide layers also showed another advantage for sensing in real-life matrices: after coating, they lead to hardly any increase of damping [30], i.e. the layer behaves ideally rigidly and thus does not impair the electronic quality of the QCM device, leading to appreciably low noise.

Outlook Currently, one can observe the first steps on the way to selective, chemical sensor systems being developed from excellent laboratory tools into real-life applications. On the way, the main challenges are simplicity and ease of operation of the devices, long-term stability, energy consumption, recalibration and drift stability. Though they are still at an early stage of development, the first successful applications have already been reported; however, these are predominantly based on straightforward measurements of physical parameters, such as conductivity or capacity of the respective matrix. The issue of sensor drift and long-term signal stability is currently mainly addressed by inventive
c(EtAc) c(ROH) c(terpenes) rH

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P.A. Lieberzeit, F.L. Dickert 7. Lee JH, Jang A, Bhadri PR, Myers RR, Timmons W, Beyette FR Jr, Bishop PL, Papautsky I (2006) Sens Actuators B 115:220226 8. Je CH, Stone R, Oberg G (2007) Sci Total Environ 382:364374 9. Runkle RC, Brodzinski RL, Jordan DV, Hartman JS, Hensley WK, Maynard MA, Sliger WA, Smart JE, Todd LC (2005) Sensors 5:5160 10. Tsujita W, Yoshino A, Ishida H, Moriizumi T (2005) Sens Actuators B 110:304311 11. Feng J, Qu G, Potknojak M (2006) IEEE Sens J 6:15711579 12. Bourgeois W, Romain AC, Nicolas J, Stuetz RM (2003) J Environ Monit 5:852860 13. Nake A, Dubreuil B, Raynaud C, Talou T (2005) Sens Actuators B 106:3639 14. Nix MB, Homer ML, Kisor AK, Soler J, Torres J, Manatt K, Jewell A, Ryan MA (2007) IEEE Potentials 26:1824 15. Palacios MA, Nishiyabu R, Marquez M, Anzenbacher P Jr (2007) 129:75387544 16. Fraga C, Melville AM, Wright BW (2007) Analyst 132:230236 17. Nicolas J, Romain AC (2004) Sens Actuators B 99:384392 18. Sugimoto I, Nagaoka T, Seyama M, Nakamura M, Takahashi K (2007) Sens Actuators B 124:5361 19. Sarkar P, Ghosh D, Bhattacharya D, Kataky R, Setford SJ, White SF, Turner APF (2005) J Chem Technol Biotechnol 80:1389 1395 20. Sapsford KE, Bradburne C, Delehanty JB, Mednitz IL (2008) Mater Today 11:3849 21. Borisov SM, Wolbeis OS (2008) Chem Rev (2008) 108:423461 22. Ye L, Haupt K (2004) Anal Bioanal Chem 378:18871897 23. Hall AJ, Emgenbroich M, Sellergren B (2005) Top Curr Chem 249:317349 24. Lieberzeit PA, Afzal A, Podlipna D, Krassnig S, Blumenstock H, Dickert FL (2007) Sens Actuators B 126:153158 25. Albano DR, Sevilla F III (2007) Sens Actuators B 121:129134 26. Suedee R, Intakong W, Lieberzeit PA, Wanichapichart P, Chooto P, Dickert FL (2007) J Appl Polym Sci 106:38613871 27. Snchez-Barragn I, Karim K, Costa-Fernndez JM, Piletsky SA, Sanz-Medel A (2007) Sens Actuators B 123:798804 28. Lieberzeit PA, Rehman A, Najafi B, Dickert FL (2008) Anal Bioanal Chem 391:28972903 29. Lieberzeit PA, Afzal A, Glanznig G, Dickert FL (2007) Anal Bioanal Chem 389:441446 30. Lieberzeit PA, Afzal A, Rehman A, Dickert FL (2007) Sens Actuators B 127:132136 31. Willner I, Zayats M (2007) Angew Chem Int Ed 46:64086418 32. Estevez MC, Galve R, Sanchez-Baeza F, Pilar FM (2008) Chem Eur J 14:19061917 33. Wang H, Meng S, Guo K, Liu Y, Yang P, Zhong W, Liu B (2008) Electrochem Commun 10:447450

recalibration routines making use either of internal stimuli or of suitable environmental conditions determined by the sensor network itself. Despite the wide variety of powerful selective materials, still only little work can be found on successfully operating them in natural environments outside standardized laboratory conditions. One exception is molecularly imprinted layers that have been successfully applied in widely varying matrices, as they provide one possible way of how to combine both high sensitivity and selectivity in a single, robust sensor. Sensitivity in the short term may be achieved, e.g., by including preconcentration units into a sensor device, whose drawback of course is the increased energy consumption resulting from desorption steps. In the long term, highly sensitive devices, such as nanostructured semiconductor devices or novel bulk resonators, seem promising. For selectivity, aside from MIP materials, also other approaches such as aptamers [31] and modified, i.e. stabilized antibodies [32, 33], seem promising. Though currently not yet applied in real-life environments, they also follow the strategy of retaining biological selectivity within a matrix rugged enough for operation in non-physiological conditions over an extended period of time. A further, more technical yet fundamentally important problem awaiting solution is sensor packaging to avoid biofouling especially when deploying a system in an aquatic environment over an extended period of time.

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