nang ¥efefred mechanisits fet ot gE San toma effects species ir EES cranes frequently -o C@llS ASO =-xenob ioties= biodegradationsmrgnmert sre po ar ow high Ler EHO DIOTICI AY degradation” it. environmenta OunNC betaine “eve nd levels DACCE Fi Aya ee “nes toxicology *yametabolites rgani Nd: Ort HracesSEs us rwichycrarte organic organi 9 yi Sr aa Uat a geanan TOCeSSES Seicneean mime Concentrations anne et SOUFCE. bacterial Oxford transporters concentiations | sissies fsa tse amotoney REE" aromaticCOMPoUNd, enna's from Human Impacts ‘Magali Soléand Dietmar Schlosser Overview Xenobiotics are either artificial organic compounds not present in nature without prior synthesis by humans or at least not present at worryingly high concentrations without human activities. Such xenobiotic compounds have been known for a long time to contaminate envi- ronmental compartments, In addition to the more “clas- sical” environmental mass pollutants mainly arising from {industrial and agricultural activities in the past and fre- quently found in contaminated environmental media in high concentrations, a multitude of xenobioties with tions, structures, and properties waa Xenobiotics from Emission to Cellular Uptake waa Emission, Dispersal, Fate Processes, and Bioaval Xenobiotics bility of ‘The production of a multitude of chemicals, pesticides, and pharmaceuticals and their use and discharge were fre quently associated with heavy environmental pollution in the past. Inaddition, accidents and wars have contributed to the contamination of environmental compartments, Promi- nent examples ae serious contaminations of aquatic as well as terrestrial environments with various hydrocarbons from crude oil spills and leaks related to the production, storage, ‘conveyance, use, and further processing of fuels and diverse oil products, and contamination of soils with explosives such as 2,4,6-trinitrotoluene (TNT) from military activities. “Classical” mass pollutants of xenobiotic nature can be characterized by their release into the environment in high quantities, often leading to very high environmental concentrations as exemplified for polycyclic aromatic hydrocarbons (PAHs) and TNT where soil concentrations ‘of up to the gram per kilogram range can be found at par ticularly contaminated sites. Point source pollutions can be traced back to single, identifiable sources or origins such as, for example, municipal wastewater treatment plants (WWTPs) or industrial effluents, Well-known examples for recalcitrant point source mass pollutant mixtures altogether referred to as emerging or micro-pollutants has increasingly attracted attention during the past decade. ‘Micro-pollutants contaminate enviconmental media in only minute concentrations. In this chapter, xenobiotic ‘compounds are tracked from the respective sources of ‘emission to the organisms where they cause biological effects and responses. The biochemical determinants of the interactions between organisms and xenobiotics are illustrated, along with their interplay with environmental factors outside the cells of organisms. contaminating wastewaters of the respective industries at igh concentrations are toxic phenols and lipids contained in acidic olive oil mill wastewaters; structurally diverse, often toxic, and potentially carcinogenic dyes and pigments arising from the textile and dyestuff industries; melanoidin- type high molecular weight compounds contained in highly. toxic molasses based wastewaters, and various toxic pheno- lic, chlorinated, and colored compounds of pulp and paper bleach plant effluents. Nonpoint source pollutions arise from diffuse sources, with major contributions from runoff, spray drift, and drainage in agricultural areas and imper- vious surfaces. PAHs from anthropogenic combustion of fossil fuels are released by smokestacks or ear tailpipes, and according to the definition given earlier, they may be considered as point source pollutants, However, because of the existence of multiple point sources and long-range atmospheric transport processes, PAHs are increasingly ecoming ubiquitous, nonpoint source pollutants. Xeno: biotics representing environmental mass pollutants can be contrasted with the so-called emerging contaminants (or ‘micro-pollutants) mainly on the basis of the respective amounts released and the resulting environmental con- centrations. Following the fact that minute environmental concentrations of many micro-pollutants have become amenable to analysis only with the improvement of mainly. mass spectroscopy-based analytical techniques during the past 10-15 years (which is one reason for referring to them as emerging contaminants), scientific, public, and {© 3s Wiey VCH Vero Gb Co, KGAA, Pabahed 2015 by Wlky-VCH Verlag GmbH & Ca Gah Companion Website hsp! wor weycom gorau Nis eaagealiocbemisry 259260 12 Xenobiatics rom Haman Impacts legal awareness of micro-pollutants has increased during the past decade, There is neither a general definition nor a ‘complete list of xenobioties representing micro-pollutants, and the most common characteristic of this group of ‘compounds is a concentration in the aquatic environment in the lower microgram per liter range or even lower, Emerging or micro-pollutants include both hydrophobic and polar compounds with quite diverse chemical strue- tures and applications. They arise from, for example, urban, industrial, and agricultural activities, involve nonpoint source as well as point source emissions, and are frequently neither sulliciently degraded nor retained in municipal WWTPs, Examples of xenobiotics representing “classical” ‘mass pollutants, and of those that may be referred to as ‘micro-pollutants, are compiled in Table 13.1. Following considerable variation among dispersal routes involving the aquatic, atmospheric, and terrestrial envi- ronment, xenobiotics can be found almost everywhere (Figure 13.1). Aquatic environments and soils act as pre ferred sinks. Xenobiotics not only contaminate the technical systems and facilities used for their production, further processing, and disposal together with the corresponding. proximities and thelr areas of application, but also more distant environmental matrices (surface and groundwater and the related sediments; sols). Living organisms could, therefore, be faced with xenobiotics in nearly any envi ronment where they ate active, Workers employed in the production or processing of chemicals, plants influenced by pesticide treatment of agricultural areas, microorganisms contributing to activated sludge flocs of WWTPs, and anaerobic bacteria in aquifers contaminated with, for ‘example, benzene-toluene-ethylbenzene-xylenes (BTEXs) ‘compounds represent only a few places where organisms may get in contact with xenobiotics. ‘The environmental fate of xenobiotics and hence their ‘concentrations in a given environmental matrix are influ- ‘enced by various physicochemical and biological processes. Photolysis, hydrolysis, sorption onto sediments and soil par ticles, and biodegras (see Sections 13.3) represent prominent though incomplete ‘examples (Figure 13.1). Together with the properties of a compound (eg., its hydrophobicity or susceptibility to photo- or hydrolysis) and its surroundings (eg., properties ‘of soil particles, presence of water, climate conditions, exposure to light) such processes determine the amount of a xenobiotic that may get in contact with an organism. The term bioavailability integrates several dynamic processes influencing the fate of a chemical in a given environment. In this context, the amount of a substance that can cross an organisms cellular membrane at a given point in time is considered bioavailable. The bioavailability concept ‘can be applied to any environmental compartment, but is most important when applied to xenobiotics in soils and sediments, where processes such as sorption and sequestration influence bioavailability largely. In fact, the bioavailability of an organic contaminant is considered ion or biotransformation reactions an important factor controlling the rate of its microbial degradation in soils, Bioavailability may be distinguished from bioaccessibility, which is defined as the amount of substance that is not immediately bioavailable but may ‘become bioavailable in the future (eg., via desorption from soil or sediment particles). A third fraction of a xenobiotic _may be nonbioaccessible, because of very strong binding to particles, which practically eliminates the flux to organisms (Figure 13.2) (Katayama et al, 2010; Semple et al, 2007) naz Cellular Uptake of Xenobiotics Despite the existence of possible signaling pathways act vated on recognition of xenobioties at the cel surface, the uptake of xenobioties by cells is frequently a prerequisite for their biological effects and corresponding cellular responses. As most xenobiotic compounds axe uncharged, lipophilic organic chemicals, passive diffusion is the most important mechanism for cellular uptake by any ‘organism, including those of particular relevance for the environmental fate of xenobiotics in natural terrestrial and aquatic ecosystems (microorganisms, plants, soil fauna) In addition, import into the cells occurs by facilitated diffusion, primary active transport catalyzed by ATP- binding cassette (ABC) transporters, or secondary active transport by proteins of the solute carrier (SLC) protein family (see Chapter 1, Section 1.2 for more details ‘Active transport proteins are universally distributed in both pro- and eukaryotes and can be found in, for example, bacteria, yeasts, plants, parasites, and mammals. There are transporters facilitating the cellular uptake of solutes (influx transporters), as well as transporters removing substances from the cytosol of cells (efflux transporters) A proportion of mammal members of the SLC transporter superfamily, an important group of membrane transport proteins involved in the uptake of many xenobiotics, are facilitative influx transporters. In contrast, ABC trans porters are concerned mainly with the efflux of xenobioties from cells. Apart from solute transport, solid particles may also be imported into amoeba by phagocytosis and into plant root cells by endocytosis. Bacterial, fungal, and plant cells are surrounded by cell walls. Bacteria and fungi are major contributors to the biodegradation of xenobiotics in terrestrial and aquatic environments. The cytoplasmic membranes of these groups of organisms are covered with cell walls composed mainly of peptidoglycan (bacteria) and chitin-glucan (fungi), which are permeable to nutrients and other chemicals and enable « concentration gradient-driven transport of compounds to the cytoplasmic membrane where the uptake mechanisms described before become operative. Whereas gram-positive bacteria have a thick cell wall composed of peptidoglycan, the cell walls of gram-negative bacteria are rather thin and, besides peptidoglycan, contain an outer membrane (lipid bilayer) of lipopolysaccharides. Porins, which