Xenobiotic Pollutants Research Articles

English

The accumulation of recalcitrant xenobiotic compounds is due to continuous efflux from population and industrial inputs that have created a serious impact on the pristine nature of our environment. Apart from this, these compounds are mostly carcinogenic, posing health hazards which persist over a long period of time. Metabolic pathways and specific operon systems have been found in diverse but limited groups of microbes that are responsible for the transformation of xenobiotic compounds. Distinct catabolic genes are either present on mobile genetic elements, such as transposons and plasmids, or the chromosome itself that facilitates horizontal gene transfer and enhances the rapid microbial transformation of toxic xenobiotic compounds. Biotransformation of xenobiotic compounds in natural environment has been studied to understand the microbial ecology, physiology and evolution for their potential in bioremediation. Recent advance in the molecular techniques including DNA fingerprinting, microarrays and metagenomics is being used to augment the transformation of xenobiotic compounds. The present day understandings of aerobic, anaerobic and reductive biotransformation by co-metabolic processes and an overview of latest developments in monitoring the catabolic genes of xenobiotic-degrading bacteria are discussed elaborately in this work. Till date, several reviews have come up, highlighting the problem of xenobiotic pollution, yet a comprehensive understanding of the microbial biodegradation of xenobiotics and its application is in nascent stage. Therefore, this is an attempt to understand the microbial role in biotransformation of xenobiotic compounds in context to the modern day biotechnology.

WASTE WATER REUSE PATHWAYS FOR PROCESSING TOMATO

Direct or indirect water reuse involves several aspects: contamination by faecal, inorganic and xenobiotic pollutants; high levels of suspended solids and salinity; rational use of the dissolved nutrients (particularly nitrogen). The challenge is to apply new strategies and technologies which allow for use of the lowest irrigation water quality without harming food safety, yield and fruit or derivatives of quality. The EU project SAFIR aims to help farmers solve problems with low quality water and decreased access to water. New water treatment devices (prototypes) are under development to allow a safe use of waste water produced by small communities/industries (≤2000 EI) or of treated water discharged into irrigation channels. Water treatment technologies are coupled with irrigation strategies and technologies to obtain flexible, easy to use, integrated management.

Hormone-activated estrogen receptors in annelid invertebrates: implications for evolution and endocrine disruption.

As the primary mediators of estrogen signaling in vertebrates, estrogen receptors (ERs) play crucial roles in reproduction, development, and behavior. They are also the major mediators of endocrine disruption by xenobiotic pollutants that mimic or block estrogen action. ERs that are sensitive to estrogen and endocrine disrupters have long been thought to be restricted to vertebrates: although there is evidence for estrogen signaling in invertebrates, the only ERs studied to date, from mollusks and cephalochordates, have been insensitive to estrogen and therefore incapable of mediating estrogen signaling or disruption. To determine whether estrogen sensitivity is ancestral or a unique characteristic of vertebrate ERs, we isolated and characterized ERs from two annelids, Platynereis dumerilii and Capitella capitata, because annelids are the sister phylum to mollusks and have been shown to produce and respond to estrogens. Functional assays show that annelid ERs specifically activate transcription in response to low estrogen concentrations and bind estrogen with high affinity. Furthermore, numerous known endocrine-disrupting chemicals activate or antagonize the annelid ER. This is the first report of a hormone-activated invertebrate ER. Our results indicate that estrogen signaling via the ER is as ancient as the ancestral bilaterian animal and corroborate the estrogen sensitivity of the ancestral steroid receptor. They suggest that the taxonomic scope of endocrine disruption by xenoestrogens may be very broad and reveal how functional diversity evolved in a gene family central to animal endocrinology.

On the fate of LAS, NPEOs and DEHP in municipal sewage sludge during composting

The fate of hydrophobic xenobiotic pollutants such as linear alkylbenzene sulfonates (LAS), nonylphenol ethoxylates (NPEO) and di-ethyl-hexyl phthalate (DEHP) during sewage sludge composting was addressed in this work. The experiments were conducted in a fully automated in-vessel autothermal composting system which was fed with a mixture of primary and secondary sludge and manure. The mixture composition was determined to achieve satisfactory humidity, C/N ratio and free air space (FAS). The effect of various parameters, such as the initial xenobiotic concentration, the presence of multiple xenobiotic compounds and the temperature of composting material sustained during the process on the xenobiotics biodegradation kinetics was investigated. It was generally established that significant xenobiotic reduction is achievable through composting under all conditions tested. According to the obtained results, the presence of LAS, NPEO and DEHP even at higher concentrations was not inhibitory to the bioprocess. However, the presence of multiple xenobiotic compounds such as NPEO, NP and DEHP in the sludge can influence LAS removal during LAS composting.

Ralstonia pickettiiin environmental biotechnology: potential and applications

Xenobiotic pollutants such as toluene and trichloroethylene are released into the environment by various industrial processes. Ralstonia pickettii possess significant biotechnological potential in the field of bioremediation and has demonstrated the ability to breakdown many of these toxic substances. Here, we provide a description of the major compounds that various strains of R. pickettii are capable of degrading and a brief review of their breakdown pathways and an argument for its use in bioremediation.

Widespread capacity to metabolize polychlorinated biphenyls by diverse microbial communities in soils with no significant exposure to PCB contamination

The purpose of this work was to determine the extent of microbial metabolic potential for polychlorinated biphenyls (PCBs) in soils that have had no previous exposure to this class of xenobiotic pollutants. Soil and sediment samples of distinct characteristics from six sites in Germany were used to inoculate PCB oil (Aroclor 1242) microdroplets. All samples yielded multispecies biofilms, as revealed by single-strand conformation polymorphism (SSCP) analyses of polymerase chain reaction (PCR) analysis of 16S rRNA genes, and sequence analysis of the main amplicons. Microbes representing 20 different operational taxonomic units (OTUs) were identified in the biofilms, but only a few were common to all biofilms, namely those closely related to Aquabacterium sp., Caulobacter sp., Imtechium assamiensis, Nevskia ramosa, Parvibaculum lavamentivorans and Burkholderia sp. The PCB biofilm communities were always distinct from control biofilms developing from the same samples in the absence of PCB. All PCB droplet-grown biofilms degraded multiple PCB congeners but differed in the congener spectra they degraded. These findings reveal that microbial potential to degrade PCBs is widespread in soils that have not been subjected to PCB contamination, and that this potential is characteristic of consortia of very diverse phylogenetic composition.

Molecular and histological evaluation of tributyltin toxicity on spermatogenesis in a marine fish, the mummichog ( Fundulus heteroclitus)

There is still concern about the effects of organotin compounds (OTs) on marine organisms, and especially on their reproductive systems. We investigated the toxicity of tributyltin oxide (TBTO) on spermatogenesis in a marine fish, mummichog, Fundulus heteroclitus. TBTO exposure caused serious histological damage to the testis, including reduction in counts of spermatids and spermatozoa and malformation of somatic cells around the seminal duct. Analysis of the incorporation of bromodeoxyuridine into spermatogenic cells revealed inhibition of the proliferation of germ cells. To find a biomarker for evaluation of the effects of TBTO on fish spermatogenesis, we cloned genes downregulated by TBTO exposure in the mummichog testis, and identified mummichog creatine kinase (mCK). The cDNA sequence of mCK contained an open reading frame encoding 387 amino acid residues ( M r = 43,344). The derived amino acid sequence of mCK was very similar to that of the testicular-type CK of the rainbow trout, Oncorhynchus mykiss. Furthermore, Northern blot analysis revealed that mCK was produced specifically in the testis. We therefore identified mCK in the mummichog as a testicular-type CK. Real-time PCR revealed that exposure of the fish to TBTO significantly reduced mCK expression in the testis. To some extent, this reduction was coincident with that of bromodeoxyuridine incorporation into spermatogenic cells. The mCK gene can therefore be used as a biomarker for evaluating the effects of TBTO on fish spermatogenesis. In addition, levels of expression of the mCK gene in control fish were well correlated with increments in the gonad somatic index (GSI) below 4%. Individuals that were thought to have testicular damage caused by TBTO could be discriminated from those considered normal. The results suggest that TBTO is involved in the suppression of fish spermatogenesis and that analysis of both GSI values and mCK gene expression is useful for evaluating the levels of xenobiotic pollution in coastal areas.

Analysis of Gene Expression in Poplar Trees (Populus Deltoides × Nigra, DN34) Exposed to the Toxic Explosive Hexahydro-1,3,5-Trinitro-1,3,5-Triazine (RDX)

Poplar plants (Populus deltoides × nigra, DN34) growing under hydroponic conditions were exposed to 50 mg L−1 of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) for 24 h. The expression of genes potentially involved in the metabolism of toxic explosives was analyzed by reverse-transcriptase (RT) real-time PCR. Genes under study were selected by reference to corresponding genes that were previously shown to be upregulated in the model plant Arabidopsis thaliana by exposure to 2,4,6-trinitrotoluene (TNT) (Ekman et al., 2003. Plant Physiol., 133, 1397–1406). The target genes investigated include several genes encoding for enzymes known to be involved in the detoxification of xenobiotic pollutants, such as glutathione S-transferases (GSTs), cytochrome P-450s (CYPs), NADPH-dependent reductases, and peroxidases. Starting from A. thaliana TNT-inducible genes, corresponding Populus sequences were retrieved from the JGI Poplar Genome Project database and were used to design gene-specific primers. 18S ribosomal DNA (rDNA) was used as an internal standard and recorded gene expression levels were normalized by reference to nonexposed plants. In three separate experiments, five genes were found to be significantly amplified in leaf tissues by exposure to RDX, including GST (9.7 fold), CYP (1.6 fold), reductases (1.6–1.7 fold), and peroxidase (1.7 fold). In root tissues, only a single GST gene was found to be significantly amplified by exposure to RDX (2.0 fold). These results show, for the first time, that the exposure of poplar plants to RDX results in the induction of several genes that are potentially involved in explosive detoxification.

Expanding networks: Signaling components in and a hypothesis for the evolution of metamorphosis

Metamorphosis is a substantial morphological transition between 2 multicellular phases in an organism's life cycle, often marking the passage from a prereproductive to a reproductive life stage. It generally involves major physiological changes and a shift in habitat and feeding mode, and can be subdivided into an extended phase of substantial morphological change and/or remodeling, and a shorter-term phase (for example, marine invertebrate "settlement," insect "adult eclosion," mushroom fruiting body emergence) where the actual habitat shift occurs. Disparate metamorphic taxa differ substantially with respect to when the habitat shift occurs relative to the timing of the major events of morphogenetic change. I will present comparative evidence across a broad taxonomic scope suggesting that longer-term processes (morphogenetic changes) are generally hormonally regulated, whereas nitric oxide (NO) repressive signaling often controls the habitat shift itself. Furthermore, new evidence from echinoids (sea urchins, sand dollars) indicates a direct connection between hormonal and NO signaling during metamorphosis. I incorporate 2 hypotheses for the evolution of metamorphosis-one involving heterochrony, the other involving phenotypic integration and evolutionarily stable configurations (ESCs)-into a network model for metamorphosis in echinoderms (sea urchins, starfish, and their kin). Early indications are that this core regulatory network can be acted upon by natural selection to suit the diverse ecological needs of disparate metamorphic organisms, resulting in evolutionary expansions and contractions in the core network. I briefly speculate on the ways that exposure to xenobiotic pollutants and other compounds might influence successful settlement of juveniles in the wild. Indeed, environmentally regulated life history transitions-such as settlement, metamorphosis, and reproductive maturation-may be developmental periods that are especially sensitive to such pollutants.

Biotechnological potential within the genus Burkholderia

Many species within the genus Burkholderia possess significant biotechnological potential in bioremediation and biological control. Here we provide a description of the Burkholderia strains being investigated for their ability to degrade major xenobiotic pollutants and update information on their taxonomy, metabolic capacity and genomes.

Evaluation of PAH bioaccumulation and DNA damage in mussels ( Mytilus galloprovincialis) exposed to spilled Prestige crude oil

We analyzed the hydrocarbon composition of the Prestige oil as it reached the shores, its solubility in sea water, its bioaccumulation, and the genotoxic damage associated to oil exposure, using Mytilus galloprovincialis as sentinel organism. Mussels were exposed to two oil volumetric ratios (1:500 and 2:500) for 12 days. Great concentrations of total polycyclic aromatic hydrocarbons (TPAH) have been obtained, being in general higher in the samples from the dose of 1:500, both in sea water (55.14 vs. 41.96 μg/l) and mussel tissue (16,993.80 vs. 17,033.00 μg/kg), probably due to the great tendency of these compounds to link to particles in water. Comet assay results reflected an increase in the DNA damage associated to oil exposure, higher in the mussels exposed to the higher aqueous TPAH content. In the view of our results, the importance of the evaluation of biodisponibility, bioaccumulation and DNA damage in the assessment of the effects of xenobiotic pollutants to marine environments could be highlighted.

A novel stress‐acclimation response in Spirodela punctata (Lemnaceae): 2,4,6‐trichlorophenol triggers an increase in the level of an extracellular peroxidase, capable of the oxidative dechlorination of this xenobiotic pollutant

ABSTRACTPeroxidases are haem‐containing enzymes capable of oxidizing a wide range of substrates. This article describes the presence of peroxidase activity in the growth medium of axenic Spirodela punctata (Lemnaceae) cultures. It was found that the release of extracellular peroxidase activity is specifically enhanced by phytotoxic, halogenated phenols but not by other abiotic stress‐factors, elicitors or plant metabolites. Based on the concentration dependence of 2,4,6‐trichlorophenol (TCP)‐enhanced peroxidase release, it is concluded that release is not simply a consequence of physiological damage, but rather requires metabolically healthy fronds. In vitro studies (UV/VIS spectroscopy and liquid chromatography/mass spectrometry) show that the extracellular duckweed peroxidase (SpEx), which was partially purified from Spirodela growth medium, is capable of catalysing the oxidative dechlorination of TCP with hydrogen peroxide as the electron acceptor. It is proposed that the ability of S. punctata to specifically sense environmentally persistent phytotoxic chlorophenols, and to respond by increasing extracellular levels of a peroxidase capable of catalysing their oxidative dechlorination, is part of the protection strategy of this aquatic plant against xenobiotic stress.

Investigation of organic xenobiotic transfers, partitioning and processing in air–soil–plant systems using a microcosm apparatus. Part II: comparing the fate of chlorobenzenes in grass planted soil

A microcosm system was used to investigate and compare transfers of 14C labeled-1,2-dichlorobenzene (DCB), 1,2,4-trichlorobenzene (TCB) and hexachlorobenzene (HCB) in an air–soil–plant system using single grass tillers planted into spiked soil. This study was the second phase of a development investigation for eventual study of a range of xenobiotic pollutants. Recoveries from the system were excellent at >90%. The predominant loss pathway for 14C labeled-1,2-DCB and 1,2,4-TCB was volatilisation with 85% and 76% volatilisation of parent compound and volatile metabolites over 5 weeks respectively. Most of the added label in the hexachlorobenzene spiked system remained in soil. Mineralisation was <1% for all compounds. 14C plant burdens expressed as μg parent compound/g plant fresh weight were significant and suggest that plant uptake of chlorobenzenes from soil may be an important exposure pathway for grazing herbivores. Both shoot and root uptake of 14C was detected, with foliar uptake of volatilised compounds dominating shoot uptake, and being greatest in TCB spiked systems. The microcosm is shown as potentially an ideal system with which to investigate organic xenobiotic partitioning in air–soil–plant systems to improve understanding of the equilibria and kinetics of exchanges. However, limitations imposed by the lab based conditions must be recognized and data should be compared with field based data sets as a consequence.

Liquid chromatography–electrospray mass spectrometry study of cysteine-10 S-glutathiolation in recombinant glutathione S-transferase of Ochrobactrum anthropi

Glutathione S-transferase of Ochrobactrum anthropi (OaGST), a bacterium isolated from soils contaminated by xenobiotic pollutants, was recently purified, cloned and characterised in our laboratories. The recombinant OaGST (rOaGST), highly expressed in Escherichia coli, when purified by glutathione-affinity chromatography and then analysed by electrospray ionisation mass spectrometry (ESI-MS), has evidenced a disulphide bond with glutathione ( S-glutathiolation), which was removable by reduction with 2-mercaptoethanol. Enzymatic digestion of rOaGST with endoproteinase Glu-C, followed by liquid chromatography (LC)–ESI-MS analyses of the peptide mixtures under both reducing and not reducing conditions, have shown that glutathione was covalently bound to the Cys10 residue of rOaGST. Furthermore, LC–ESI-MS analyses of overexpressed rOaGST in Escherichia coli crude extracts, with and without incubation with glutathione, have not shown any S-glutathiolation of the recombinant enzyme.

Xenobiotics in the environment: present and future strategies to obviate the problem of biological persistence

Sustainable chemistry aims at an improved efficiency of using natural resources which are used to meet human needs for chemical products. Chemists in science and industry, have become aware of the importance to design environmentally benign chemicals. One aspect is the biological persistence and the present paper reviews work in this field focussing on the degradation of xenobiotics in the environment. Different structural reasons for chemical and biological persistence are described and strategies to use single bacterial isolates or microbial communities for the elimination of xenobiotic pollutants in the environment are summarized. Perspectives and limitations to evolve and use this catabolic potential are critically discussed with respect to the complexity of mixtures of xenobiotics often found in practice. An interdisciplinary approach for the prospective design of environmentally benign substances is presented and examples for new commodity chemicals that better fit the naturally existing catabolic potential are included.

Aromatase inhibitors: past, present and future

For the cellular physiology of sex steroid sensitive cells, the androgen/estrogen ratio may be more important than only one hormone action per se, in both sexes. This ratio is controlled in vertebrates by aromatase; its gene expression can be inhibited in different ways, and this is crucial for the treatment of estrogen-dependent diseases such as breast cancer, or gynecomastia in males for instance. To reach this goal, new steroidal and non-steroidal inhibitors are continuously being developed, and some of them are used as first or second line agents. Aromatase inhibition is also an essential tool for studying the role of estrogens in the adult, or during development. Aromatase inhibitors have shown in particular that estrogens are essential also in males for skeletal maturation and bone mineralization, development of masculine dendritic morphology in male brain linked to mating behaviour, and testicular function. Testosterone is often the prohormone converted in situ in active estrogens, at these levels. Several strategies can be used for aromatase inhibition. The first ones employed were blind screening or deductions from in vivo observations, which led for instance to the discovery of the role of aminoglutethimide in aromatase inhibition. Subsequently, in the years 1975–1990, the molecular modeling of compounds to mimic the substrate shape of the enzyme constituted the major idea. Hundreds of chemicals were synthesized by numerous authors, ranging from the well-known and very efficient 4-OHA to complicated imidazole or indane derivatives tested by sophisticated comparative molecular field analyses. Reticulum-bound active aromatase has not as yet been X-ray analyzed. Thus, aromatase inhibitors were also used more recently to probe and understand the active site conformation of the enzyme and its modelization was obtained from comparisons with bacterial-related cytochromes. We developed a mammalian model considerably closer to human aromatase in order to study the active site shape with new potent aromatase non-steroidal inhibitors. This model is equine aromatase. This enzyme was biochemically characterized, purified, and cloned by our group. It allowed testing, by site-directed mutagenesis, predictive hypotheses in human aromatase which contributed to designing of new inhibitors. The understanding of the functioning of an essential member of the cytochrome P450 family, which is necessary for cellular detoxification, was also facilitated. Inhibition of aromatase activity has also been carried out with antibodies directed to the catalytic site and at the gene level by knock-out or by control of factor-specific promoters. This may result in different mRNA synthesized by alternative splicing. We have also obtained specific inhibition of aromatase activity in human cells with antisense stable phosphorothioate oligodeoxynucleotides directed against aromatase mRNA tertiary structures. Besides known steroidal and non-steroidal inhibitors, the antiaromatase effects of compounds found in our daily environment such as dietary flavonoids or xenobiotic pollutants have also been described. Finally, we underline that all these aromatase inhibitors, or methods of aromatase inhibition, can modulate the estrogenic balance essential not only for female, but also for male physiology, including gonadal function.

Photodegradation of the herbicides butachlor and ronstar using natural sunlight and diethylamine.

Deterioration of water quality by pesticide residues in rivers has raised environmental safety concerns. Butachlor and ronstar are the two most widely used herbicides in Taiwan. Due to their relatively high stability and retardation factors, butachlor and ronstar were persistent environmental pollutants in waters (Widmer and Spalding, 1995, 1996). Photodegradation with natural sunlight may be one of the most natural and economical degradation routes for environmental pollutants such as pesticides. The photodegradation pathways of pesticides include direct and indirect reactions. Direct photodegradation involves the process of the excitation of organics after exposure to natural sunlight and then release of the energy of radiation through molecular restructuring (i.e. isomerization, substitution, oxidation or reduction) usually broken down to smaller compounds. Photodegradation of xenobiotics could be inhibited if inorganic anions (i.e. SO4 , PO 4 3and NO;) exist and compete for the oxidation sites or react with free radicals such as ·OH (Kochany and Lipczynska, 1992). Under indirect photodegradation, the photoreaction could be enhanced by excited states of photosensitizers, free radicals, and short-lived reactive transients (Zepp, 1988). The light energy can be absorbed by photosensitizers and transferred to the organic contaminants indirectly. Various amine groups such as diethyamine, triethylamine, and diethyl phenylene diamine have been used as photosensitizers to enhance the photodegradation of xenobiotic pollutants (Freeman et al. 1986; Lin et al. 1995; 1996). This study was conducted to determine the effects of natural sunlight and diethylamine on the degradation of butachlor and ronstar in river water.

Transformation of 2,4,6-Trinitrotoluene (TNT) Reduction Products by Lignin Peroxidase (H8) from the White-Rot Basidiomycete Phanerochaete chrysosporium

White-rot fungi are known to degrade a wide range of xenobiotic environmental pollutants, including the nitroaromatic explosive 2,4,6-trinitrotoluene (TNT). TNT is first reduced by the fungal mycelium to aminodinitrotoluenes and diaminonitrotoluenes. In a second phase, reduced TNT metabolites are oxidatively transformed and mineralized. The extracellular oxidative enzyme of the ligninolytic system of these fungi includes the lignin peroxidases (LiP) and the manganese-dependent peroxidases (MnP). In the present study, we have shown that a cell-free enzymatic system containing fast protein liquid chromatography (FPLC)-purified LiP (H8) from the white-rot fungus Phanerochaete chrysosporium was able to completely transform 50 mg/L of 2,4-diamino-6-nitrotoluene (2,4-DA-6-NT) and 2-amino-4,6-dinitrotoluene (2-A-4,6-DNT) in 1 and 48 h, respectively. Veratryl alcohol (VA), often described as a mediator in the LiP-catalyzed oxidative depolymerization of lignin, was not required for the enzymatic transformation of 2,4-DA-6-NT or 2-A-4,6-DNT. 2,4-DA-6-NT was also shown to be a competitive inhibitor of the LiP activity measured through the oxidation of VA. Experiments using 14C-U-ring labeled compounds showed that 2-A-4,6-DNT was converted to 2,2′-azoxy-4,4′,6,6′-tetranitrotoluene. No significant mineralization, measured by the release of 14CO2, was observed over 5 d.

Gamete viability as an indicator of reproductive endocrine disruption in fish

Xenobiotic pollutants may disrupt reproductive endocrine function by acting at the hypothalamus, pituitary, gonad or liver. Disruption at any of these sites may result in either changes in the rate of gonadal development or in the viability of the gametes. Production of high quality gametes is dependent upon the correct hormonal milieu throughout their development, and any disruption of hormonal balance may result in abnormal sperm or eggs. Such effects may be apparent at levels of pollutant lower than that which causes arrest of gametogenesis or decreased gonadosomatic index. In this paper the use of sperm motility, morphology and fertilising ability in males, and egg numbers, size and hatching success in females as monitors of endocrine disruption will be discussed. Data are presented to show that exposure of adult zebra danios ( Danio rerio) to 5 ng l −1 ethynylestradiol leads to arrest in development of the eggs produced at the early blastula stage and induces vitellogenesis in exposed males.

Adsorption of Five Model Organic Compounds on a Peat at Different Stages of Drying

Acridine orange (AO), dinitrobenzoic acid (DNB), bromocresol green (BCG), bromophenol blue (BPB), and methylene blue (MB) were chosen as model aromatic compounds of different polarity, charge, and solubility in water to examine the effects of solute properties on hydrophobic adsorption. These compounds show strict structural similarities to some herbicides and other potential xenobiotic pollutants and exhibit distinct absorption maxima in the visible region, which allows for their easy determination. A well-decomposed peat (medisaprist) at four different stages of drying was used to determine compound adsorption/desorption influences based on the degree of hydrophobicity and charge density of an organic surface. Adsorption and desorption isotherms were investigated using the batch equilibration method and determining the concentration of free chemicals by UV-Vis spectrophotometry. AO had a high tendency of adsorption and was strongly sorbed on peat samples that had been air-dried for 12 months. The lower Freundlich coefficient values found for MB when compared with AO at all the drying stages of the peat indicated that electrostatic attraction has a secondary contribution to sorption. On the contrary, the higher energy that must be spent to break solute-solvent interactions in the case of charged or polar molecules is one of the main factors in determining the position of the equilibrium. For a given solute, Kf values varied with the degree of hydrophobicity and the charge density of the surface, but again solute-solvent interactions appear to be much more important in the overall energy balance of hydrophobic pollutants than the electrostatic sorbate-sorbent interactions. A change in the solution pH does not improve the adsorption of the relatively polar DNB molecule, but sorption increases strongly for BCG and BPB when these molecules are in non-dissociated forms. The larger increase in BPB sorption observed on H+ saturated peat suggests that the degree of interaction increases with the suppression of the negative charge, but charge repulsion has a small effect in preventing adsorption of molecules bearing hydrophobic groups such as BCG. Desorption results differed depending on the chemical structure of the compound examined. For example, with AO there was no desorption from the more hydrophobic peat surfaces. A negative hysteresis was observed for DNB; the magnitude of hysteresis, evaluated using the ratio of Freundlich coefficients for adsorption and desorption, increased with the drying stage of the sorbent and was larger on oven-dried samples.