Pollutants in Buildings, Water and Living Organisms

Materials on the built environment are exposed to several agents that promote alteration processes resulting in features that might be considered detrimental of its value. Here we review the main issues related to the struggle against these alteration processes, from the consideration of the intervention criteria, including the non-intervention option, to strategic considerations on the organisation of the intervention that must consider the temporal and spatial features of the alteration processes, as well as possible interventions on the surroundings of the materials, e.g. atmosphere, terrain and structure, and in relation to treatments of materials, including its replacement. It is highlighted the problem of testing using small clean specimens aggravated by comparative studies based on one specimen by case. Assessment of short-term an effects is discussed in relation to intrinsic aspects of the interventions. The long-term effectiveness is linked with the global strategy namely in relation to the conditions that promote the alteration processes. Some sustainability questions related to the intervention operations are also considered such the use of toxic substances and the consumption of resources.

Industrialization and excessive use of pesticides for boosting agricultural production has adversely affected the ecosystem, thus polluting natural water reserves. Remediation of contaminated water has been an area of concern with numerous techniques being applied to improve the quality of naturally available water to the level suitable for human consumption. Most of these methods however generate byproducts that are sometimes toxic. Heterogenous photocatalysis using metal oxide nanostructures for water purification is an attractive option because no harmful byproducts are created. A discussion on possible methods to engineer metal oxides for visible light photocatalysis is included to highlight the use of solar energy for water purification. Multifunctional photocatalytic membranes are considered advantageous over freely suspended nanoparticles due to the ease of its removal from the purified water. An overview of water remediation techniques is presented highlighting innovations through nanotechnology for possible addressing of problems associated with current techniques.

Major methods for the biodegradation of organophosphate and pyrethroid pesticides are reviewed in this chapter. Although these methods are very promising, it is not easy to avoid fully the release of metabolites into the environment. Therefore, serious problems of soil, water and even foods contamination still exist. Despite the great benefits of pesticides to agricultural productivity, they also cause serious problems of contamination and increasingly need studies, especially in the search of compounds that are less harmful to the environment. Knowledge of the biodegradation route of pesticides and the development of new techniques that allow the improvement of these degradation pathways are essential, therefore, this chapter presents studies about the biodegradation of organophosphate and pyrethroid pesticides by biological processes, focussing on the development of new enzymatic methods, especially those using bacteria and fungi. Other methods of biological degradation of organophosphate and pyrethroid pesticides are also described.

Contamination of water resources is one of the major problems to be faced for environment preservation and sustainability. Although anti-pollution strategies taken in the last half-century have consistently reduced in surface water the amount and the presence of many recognised contaminants, other potentially hazardous chemicals are being released into the environment, together with new substances that are continuously synthesized and whose dangerous properties are not well known. Water-pollutant monitoring makes typically use of methods developed for target analysis, focused on priority pollutants. The monitoring of target-compounds based on mass spectrometry (MS) and selected reaction monitoring (SRM) mode is often insufficient to definitely assess the quality of surface water, just because the presence of only a limited number of potential pollutants is considered. Also potentially harmful non-target pollutants simultaneously present must be taken into account.

In the determination of semi-polar and polar pollutants, liquid chromatography coupled with tandem MS is generally the technique of choice. To obtain a complete information on water composition, full-spectrum acquisition techniques, better if with the possibility to obtain information about MS/MS spectra, are required. For this purpose, hybrid mass spectrometers like triple quadrupole/linear ion trap (QqLIT), hybrid quadrupole/time-of-flight (QqTOF) MS and linear ion trap/orbitrap analyzer must be used. The last two instruments are the masters of the non-target approach, because their can offer the advantage of high resolution MS, that combined with a good MS accuracy allows to identify the unknown species. In addition, the hybrid nature of such instruments allows to acquire during a single chromatographic run also information about high resolution MS/MS spectra, that are fundamental in order to attribute to each unknown species a probable chemical structure. An interesting advantage associated with high resolution MS based methodologies consists in the possibility of performing retrospective analysis, since it allows the identification of organic contaminants included in the first screening: this investigation can be done at any time, without the need of new analysis or new sample injection.

In addition, the elevated acquisition speed of TOF makes it compatible with ultra high performance liquid chromatography (UHPLC). UHPLC and high resolution MS provide potent analysis rich in information on sample composition. During a non-target screening analysis, all the compounds eluted from the analytical column can be detected without any kind of selection, a part the obvious limitations derived from chromatography and ionization process in the LC-MS interface. A genuine non-target analysis involves the automated component detection from the total ion current and the use of deconvolution software to detect the presence of multiple species and to produce pure spectra for each individual component. An important limitation to this approach is the lack of availability of large compound libraries similar to those used in gas chromatography-mass spectrometry (GC-MS), making the identification of unknown species very complex and time-consuming. At the moment, spectral libraries for LC-MS are home-made and quite limited. This review presents an overview of published UHPLC-MS methods developed for post-target and non-target screening analysis of water emerging contaminants, such as pesticides and their degradation products, pharmaceuticals and drug side-reaction products, surfactants and illicit drugs. The different aspects of the current MS instrumentations, using tandem, hybrid and high resolution MS systems, are compared and discussed.

Polycyclic aromatic hydrocarbons (PAHs) are broad environmental contaminants which due to their lipophilic profile tend to be absorbed on particles and finally accumulate in marine environments. Analysis of PAHs is conducted in various commodities, such as water, sediment and in organisms, with bivalves possessing a predominant role due to their cumulative for organic contaminants and PAHs profile. Substantial research has been performed on the effects of PAHs pollution on the bioindicator itself, the marine bivalve, in matters of subcellular, cellular, tissue or organ alterations. Taking into account the persistence of these compounds, their ubiquity and the variety of health effects they may elicit to invertebrates, it is imperative to focus on biomarkers assessment after acute or subchronic exposure to PAHs. Nowadays, a tiered approach in Mussel Watch Programs is followed with chemical analysis of PAHs in mussel tissues being accompanied by detection of effects at subcellular, cellular, tissue, organ or organism level. This combined methodology serves on a number of levels-it measures with precision current PAHs pollution status and it links this pollution to possible health effects on bivalve populations

This review aspires to consolidate knowledge on PAHs analysis and the biological effects that they elicit in bivalves. In this context, it is provided an overview on PAHs pollution as monitored with the use of bivalves. Specific focus is given on: (1) PAHs analytical methodologies and their performance (2) levels of marine PAHs as measured through bivalves within the last decade; current pollution status and (3) health effects of PAHs on bivalves as shown from field studies and laboratory experiments.

Selenium (Se) is a naturally occurring metalloid element which occurs nearly in all environments in the universe. The common sources of Se in earth crust occurs in association with sulfide minerals as metal selenide whereas, it is rarely seen in elemental form (Se⁰). Furthermore, Se is considered a finite and non-renewable resource on earth, and has been found to be an essential element for humans, animals, micro-organisms and some other eukaryotes; but as yet its essentiality to plants is in dispute. Thus, plants vary considerably in their physiological and biochemical response to Se. Therefore, this review focuses on of the physiological importance of Se for higher plants, especially plant growth, uptake, transport, metabolism and interaction of selenium with other minerals. Biogeochemistry of Se, its relationship with S, application of Se-containing fertilizers, Se in edible plants and finally, red elemental Se nanoparticles in higher plants will be highlighted.

Aromatic amines are widely used industrial chemicals as their major sources in the environment include several chemical industry sectors such as oil refining, synthetic polymers, dyes, adhesives, rubbers, perfume, pharmaceuticals, pesticides and explosives. They result also from diesel exhaust, combustion of wood chips and rubber and tobacco smoke. Some types of aromatic amines are generated during cooking, special grilled meat and fish, as well. The intensive use and production of these compounds explains its occurrence in the environment such as in air, water and soil, thereby creating a potential for human exposure. Since aromatic amines are potential carcinogenic and toxic agents, they constitute an important class of environmental pollutants of enormous concern, which efficient removal is a crucial task for researchers, so several methods have been investigated and applied.

In this chapter the types and general properties of aromatic amine compounds are reviewed. As aromatic amines are continuously entering the environment from various sources and have been designated as high priority pollutants, their presence in the environment must be monitored at concentration levels lower than 30 mg L⁻¹, compatible with the limits allowed by the regulations. Consequently, most relevant analytical methods to detect the aromatic amines composition in environmental matrices, and for monitoring their degradation, are essential and will be presented. Those include Spectroscopy, namely UV/visible and Fourier Transform Infrared Spectroscopy (FTIR); Chromatography, in particular Thin Layer (TLC), High Performance Liquid (HPLC) and Gas chromatography (GC); Capillary electrophoresis (CE); Mass spectrometry (MS) and combination of different methods including GC-MS, HPLC-MS and CE-MS. Choosing the best methods depend on their availability, costs, detection limit and sample concentration, which sometimes need to be concentrate or pretreated. However, combined methods may give more complete results based on the complementary information. The environmental impact, toxicity and carcinogenicity of many aromatic amines have been reported and are emphasized in this chapter too.

Lately, the conventional aromatic amines degradation and the alternative biodegradation processes are highlighted. Parameters affecting biodegradation, role of different electron acceptors in aerobic and anaerobic biodegradation and kinetics are discussed. Conventional processes including extraction, adsorption onto activated carbon, chemical oxidation, advanced oxidation, electrochemical techniques and irradiation suffer from drawbacks including high costs, formation of hazardous by-products and low efficiency. Biological processes, taking advantage of the naturally processes occurring in environment, have been developed and tested, proved as an economic, energy efficient and environmentally feasible alternative. Aerobic biodegradation is one of the most promising techniques for aromatic amines remediation, but has the drawback of aromatic amines autooxidation once they are exposed to oxygen, instead of their degradation. Higher costs, especially due to power consumption for aeration, can also limit its application. Anaerobic degradation technology is the novel path for treatment of a wide variety of aromatic amines, including industrial wastewater, and will be discussed. However, some are difficult to degrade under anaerobic conditions and, thus, other electron acceptors such as nitrate, iron, sulphate, manganese and carbonate have, alternatively, been tested.