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2015 | Book

Environmental Analysis by Electrochemical Sensors and Biosensors


Editors: Ligia Maria Moretto, Kurt Kalcher

Publisher: Springer New York

Book Series : Nanostructure Science and Technology


About this book

This book discusses in detail the analysis and monitoring of the most important analytes in the environmental field. It also reviews the implementation, realization and application of sensor designs mentioned in the first volume of this set, dividing the coverage into global parameters, sensors of organics and sensors of inorganics.

Table of Contents


Sensors for Measurement of Global Parameters

Chapter 1. Chemical Oxygen Demand
Organic pollution in water can be monitored by measuring an important index called chemical oxygen demand (COD).
In some countries this parameter is a national standard to investigate the organic pollution in water. The conventional method to measure the COD is the determination of excess oxidizing agent such as dichromate or permanganate left in the sample. Thus, COD is defined as the number of oxygen equivalents required to oxidize organic materials in water. The conventional method presents some drawbacks associated with the procedure, particularly for the long time required and toxic reagents used. The possible methods for the determination of COD using electrochemical sensors are presented in this chapter. The different electrode materials and procedures are commented.
Usman Latif, Franz L. Dickert
Chapter 2. Biochemical Oxygen Demand (BOD)
Biochemical oxygen demand (BOD) is a widely used parameter to assess the organic pollution in water systems. This parameter can be detected by the amount of oxygen consumed via microorganisms in aerobic metabolism of organic matter present in the water. The authorized test to analyze biodegradable organic compounds is given by the American Public Health Association Standard Method Committee that is called a 5-day biochemical oxygen demand (BOD5) test. This conventional procedure produces good results; however, it is time consuming and cannot be used for rapid analysis such as environmental monitoring and/or process control. In this chapter the electrochemical sensors for BOD determination proposed in the literature are presented and critically commented.
Usman Latif, Franz L. Dickert
Chapter 3. Dissolved Oxygen
Dissolved oxygen (DO) plays a vital role in many industrial, physiological, and environmental processes. The electrochemistry is greatly influenced by the amount of dissolved oxygen because of the reduction of molecular oxygen.
A number of chemical and biological reactions in water also depend on the amount of dissolved oxygen. Monitoring the oxygen in ground or wastewater is an important test in water quality and waste treatment. In this chapter we present the electrochemical sensors for measurement of oxygen from the first Clark electrode to the more modern proposal of modified, miniaturized, and solid-state electrodes.
Usman Latif, Franz L. Dickert
Chapter 4. pH Measurements
The pH is an important parameter when we deal with environmental pollution, analyzing the quality of water, and even in clinical diagnosis. This vital parameter contributed a lot and still is contributing in advancing different fields such as pharmacy, chemistry, biology, medicine, industry, agriculture, biochemistry, and environment. The glass electrode is a most successful electrochemical sensor which is used to determine the activity of hydrogen ions in solution. This chapter focuses on the pH sensors developed since the glass electrode from one century ago up to the modern metallic, modified, nanostructured electrodes.
Usman Latif, Franz L. Dickert

Sensors and Biosensors for Inorganic Compounds of Environmental Importance

Chapter 5. Metals
Metals (toxic, nontoxic, essential) are an important issue in environmental analysis. A detailed overview is given on the measurement and sensor characteristics for the determination of the concentration of metals including choice of procedures and analytical techniques, pre-concentration approaches, and electroanalytical assays accompanied by numerous examples.
Ivan Švancara, Zuzana Navrátilová
Chapter 6. Non-metal Inorganic Ions and Molecules
In this chapter, electrochemical sensors and biosensors for the analysis of inorganic nonmetallic analytes, comprising selected inorganic anions, such as nitrate, nitrite, sulfate, cyanide, and hydroxyl, cations (H+, NH4 +, N2H5 +), and inorganic molecules (O2, H2O2, and common toxic gases like H2S, SO2, NOX, and Cl2) of environmental importance are presented. Additionally, some other species from the individual categories will be shortly presented throughout the text in an effort to cover briefly most analytes which deserve some attention with respect to their environmental occurrence and possible impact on the biosphere.
Ivan Švancara, Zuzana Navrátilová
Chapter 7. Electroanalysis and Chemical Speciation
The greatest concern for speciation of the elements relates to their impact on biological systems depending on their physical and chemical form, occurrence, behavior, and actual circulation in the environment, toxicological profile, and bioactivity and bioavailability. In combination with electrochemical principles, speciation has a long tradition and at least since the last third of the twentieth century this special area skillfully utilizes the ability of electroanalysis to indicate the changes in chemical equilibrium and redox state of various substances, which allows—together with determinations of their total content—the identification and quantification of the individual forms and their actual distribution—a problematic deal for many other instrumental techniques. In this respect, specialized teams have elaborated to a remarkable extent mainly the electrochemistry of natural aquatic systems, covering for two decades the dominant part of chemical speciation in environmental electroanalysis. In this chapter we the most convenient electrochemical techniques for speciation analysis, there is (equilibrium) potentiometry and, mainly, stripping techniques with the effective pre-concentration step for accumulating many species at a high concentration level, are presented and discussed.
Zuzana Navrátilová, Ivan Švancara
Chapter 8. Nanoparticles-Emerging Contaminants
The chemical nature of the different nanoparticles present in the environment, both naturally and through human activity, along with their estimated levels of release and likely toxicity is overviewed. The use of recently developed voltammetric methods for the identification of nanoparticles along with the measurement of their state of aggregation and their concentration is discussed in depth. Future directions in the field are evaluated.
Emma J. E. Stuart, Richard G. Compton

Sensors and Biosensors for Organic Compounds of Environmental Importance

Chapter 9. Pharmaceuticals and Personal Care Products
The world population was estimated as one billion of peoples in 1800 and from this data almost 130 years was necessary to attain two billion. This period coincides with the development of penicillin (1928) and after 1930, only 30 years was necessary to attain three billion. In the following decades, this number raised to seven billion. Development of synthetic fertilizers, of pesticides and of a myriad of pharmaceutical compounds is pointed as the most responsible for this spectacular increase of the number of peoples in the planet. Parallel to the ever-growing use of fertilizers, pesticides and pharmaceuticals, the generation of residual materials emerges as a critical problem, affecting soil, plants, water and animals and by extension, the humans. In this chapter we focus on development of sensors and biosensors for the analysis of pharmaceuticals in different medium (water, sludge, soils, etc.) with emphasis to voltammetric techniques, in batch or coupled to FIA and BIA techniques. Strategies for pre-concentration and elimination of interfering species and to obtain selectivity in different samples are discussed.
Lúcio Angnes
Chapter 10. Surfactants
Surfactants are the active ingredients in personal hygiene products, and detergents for industrial and household cleaning. There are four classes (cationic, anionic, amphoteric and nonionic) based on the ionic charge (if present) of the hydrophilic portion of the surfactant in an aqueous solution. The annual global production of surfactants was 13 million metric tons in 2008; about 70 % represent the anionic ones. Surfactants are among the most important components in the group of highly toxic substances that affect environmental conditions in marine ecosystems.
Analysis of surfactants in the environment is important not only because they are toxic, but also for their biodegradation products and metabolites that are more persistent. The routine procedure for surfactant analysis is based on two-phase titration methods. While this method was sensitive, it had many disadvantages such as limitation of application to strongly colored and turbid samples, time consumption, toxicity of organic chlorinated solvent used and formation of emulsion during titration which could disturb visual end-point detection. In view of its disadvantages, other alternative analytical techniques have been developed such as spectrophotometry, thin-layer chromatography and capillary electrophoresis.
However, increasing environmental concerns have fostered the development of automated analytical systems for environmental monitoring with added features for in situ, real-time and remote operation. The use of electrochemical sensors as detectors integrated in automated flow systems has proved to achieve simple, robust and automatic analyzers for environmental monitoring.
This chapter presents an overview of electrochemical techniques applied for the determination of surfactants. Special focusing on both potentiometric and amperometric sensors and biosensors is considered.
Elmorsy Khaled, Hassan Y. Aboul-Enein
Chapter 11. Determination of Aromatic Hydrocarbons and Their Derivatives
Aromatic hydrocarbons and their derivatives are important environmental pollutants. This chapter is devoted to their detection using either boron-doped diamond film electrodes or carbon paste electrodes. Boron-doped diamond is a fascinating new electrode material with extremely broad potential window, low noise and high resistance to passivation that make it very useful for environmental applications, based both on anodic oxidations and cathodic reductions depending on the functional groups present in target analyte. This is illustrated by numerous examples.
Easy surface renewal, chemical modification, user friendliness and a broad spectrum of described applications make carbon paste electrodes very popular sensors in environmental detection of aromatic hydrocarbons and their derivatives which is documented in this chapter.
K. Peckova-Schwarzova, J. Zima, J. Barek
Chapter 12. Explosives
Explosives produced both for military and civilian use are important pollutants of soils and aquatic systems in the vicinity of places where they are produced, stored or used. Many of them are classified as toxic by the US-EPA and other environmental agencies. Because of the easy electrochemical reducibility of nitro group, voltammetric and amperometric methods are frequently used for their determination which are discussed in this chapter. The various electrode materials in use for the determination of explosives as well as the analytical approaches including microfluidic devices are reviewed.
Jiri Barek, Jan Fischer, Joseph Wang
Chapter 13. Pesticides
The toxicity of modern pesticides justifies the crucial need of accurate and reliable methods to monitor the level of pesticides for safety considerations. Moreover, the area of biodefense is also interesting in this field of research, since several organophosphate compounds can be used as nerve agents (i.e., sarin and soman). The development and continual improvement of analytical methods for the determination of this large group of compounds, mostly at trace level, is a great challenge for analysts, and constitutes the subject of research and development for contemporary analytical chemistry. The current tendency to carry out field monitoring has driven the development of biosensors as new analytical tools able to provide fast, reliable, and sensitive measurements with lower cost, many of them aimed at on-site analysis.
Electrochemical biosensors combine the selectivity of biological recognition with the sensitivity of electroanalytical methods. In addition, the new approaches in terms of nanomaterials have allowed the development of an improved generation of biosensors with increased sensitivity, miniaturized systems, and the ability of on-site analysis and real-time responses. In this chapter new trends on electrochemical biosensing for pesticide residue detection and quantification are presented. We first address the basic principles of electroanalytical measurement and the merger of electrochemistry and biology into a biosensing system.
Elmorsy Khaled, Hassan Y. Aboul-Enein

Electrochemical Sensors for Gases of Environmental Importance

Chapter 14. Volatile Organic Compounds
Detection and quantification of volatile organic compounds (VOCs) are basic and necessary requirements for many applications, including environmental monitoring, occupational safety, and healthcare. Many toxic and/or carcinogenic VOCs are used as solvents and base raw materials in chemical process industries. For example, ketones (acetone and methylethyl ketone), alkanes (hexane), alcohols (ethanol), and aromatics (benzene and toluene) are widely used as a solvent, and formaldehyde is used as a base raw material for the resin industry. Benzene, toluene, ethylbenzene, and xylenes (commonly known as BTEX compounds) are released in automobile exhaust gas. Further, some VOCs have been identified as potential biomarkers of diseases in exhaled breath, such as alkanes and benzene derivatives for lung cancer and acetone for diabetes. Hence accurate identification and quantification of these VOCs is a must to protect the human health at work place, environment, and disease diagnosis.
We start the chapter with a brief introduction about the importance of VOC sensing, their major sources, OSHA regulations and conventional detection techniques. We discuss the importance of use of sensors in modern context. While discussing about the sensor, we discuss about the successes and limitations of the sensors developed using various kinds of transduction mechanism and materials. Further, we discuss about the various electrochemical sensor configurations and sensing materials and highlight the material properties that make them attractive for electrochemical sensors. We then continue to discuss the functionalization strategy and the selection criterions of the functional materials for the improvement of sensor selectivity and sensitivity. Finally, we conclude by highlighting some of the challenges that need to be addressed in the VOC sensor research arena and also predicting the possible future direction in this area.
Tapan Sarkar, Ashok Mulchandani
Chapter 15. Sulphur Compounds
This chapter presents a review of electrochemical sensors applied to the detection of sulphur compounds in the atmosphere, with a focus on environmental analysis of volcanic emissions of H2S and SO2. It describes the application to environmental monitoring of low-cost, low-power, miniature electrochemical sensors, originally developed for use in gas leak alarm systems within industry and for occupational health and safety monitoring systems. Over the last decade, such miniature electrochemical sensors have begun to be applied to real-time environmental monitoring of pollutants, including the characterization of volcanic sulphurous emissions. This review outlines the principles of electrochemical sensor detection of volcanic gases, and highlights recent advances made in volcano hazard monitoring by using electrochemical sensors within multi-gas in situ measurement systems. A critical view on sources of measurement error in the characterization of pollution plumes by electrochemical (and other) in situ sensors is presented, including the challenges imposed by sensor cross-sensitivities and finite sensor response within complex plume environments. Finally, future directions in this field are outlined, including the application of miniature electrochemical sensors to the monitoring of urban pollution, and sensor deployment on novel platforms such as balloon or unmanned aerial vehicle.
Tjarda J. Roberts
Chapter 16. Nitrogen Compounds: Ammonia, Amines and NOx
This chapter overviews the use of electrochemical sensors for the sensing of nitrogen compounds in respect of their potential use in gas sensing. The roles of electrode material, electrolyte, configurations and overall design of current electrochemical gas sensors for nitrogen compounds sensing are considered and critiqued. The use of electrochemical sensors in medical diagnosis for the measurement of compounds in breath is also briefly overviewed.
Jonathan P. Metters, Craig E. Banks
Chapter 17. Carbon Oxides
In the late twentieth century, the generation of oxide gases such as CO2, NOx, and SO2 through human activities became recognized as an extremely serious environmental problem. In 1997, at COP3, carbon dioxide (CO2) was also identified as a major greenhouse effect gas and the goal of reducing CO2 emissions was declared an international priority. The development of smart gas-sensing tools is an important step in effectively suppressing CO2 emissions into the atmosphere. Up to now, however, although many different CO2 sensors have been extensively studied, most have not been commercialized, with the exception of devices incorporating IR detection. Even these are expensive and bulky and require pretreatment of the sample gas, and so are difficult to install at the various sites where CO2 gas may be emitted. As a result, it is necessary to develop a compact CO2 gas sensor which can readily be positioned for on-site monitoring.
In this chapter, we describe the compact gas sensors which can detect the carbon oxides. Since such compact gas sensors can realize comfortable lives with high safety, they will contribute greatly to our daily lives.
Nobuhito Imanaka, Shinji Tamura

Data Treatment of Electrochemical Sensors and Biosensors

Chapter 18. Data Treatment of Electrochemical Sensors and Biosensors
The ultimate aim of developing electrochemical sensors or biosensors, EBs, is proposing to the scientific community devices suitable for real sample analysis. It follows that sensor performances should be concretized by proper figures of merit, FM, estimated according to agreed protocols, and reported according to unambiguous formats. As far as we know the most frequently reported FM are those usually estimated in validation studies, e.g., linear range, limits of detection and quantification, precision, trueness, uncertainty, selectivity, and recovery. Of course, developing and testing new EBs seldom need a complete validation study. Most frequently, papers are mainly aimed at reporting details of the method used to prepare the sensor, of experiments used for characterizing its chemical/biochemical/electrochemical/morphological features, and of its potential applications. But, if some analytical performances of the proposed sensor are presented to the reader, then they should be estimated by reliable approaches and allow a reasonably appropriate interpretation. However, while preparing a recent review paper dealing with glassy carbon electrode surface modified by acidic functionalities, it was noticed that quite often some of the reported FM were ill defined or reported in an inadequate format. In such a situation, reconsidering how to estimate and report them might be valuable to any experimentalist involved in developing EBs.
Elio Desimoni, Barbara Brunetti
Environmental Analysis by Electrochemical Sensors and Biosensors
Ligia Maria Moretto
Kurt Kalcher
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Springer New York
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