Search

In this study, stir-bar sorptive extraction and thermal desorption followed by gas chromatography coupled with high resolution mass spectrometry was applied for determination of halo-organic compounds (bromodichloromethane, dibromochloromethane, bromoform, and tetrachloroethylene) in water and human urine samples. Time of extraction and stirring speed were optimized. The results show that the optimum extraction time is 30 min with 600 rpm of stirring speed with Twister of 20 mm in length and 1.0-mm film thickness of PDMS (126 microL). The calibration curves, limits of detection and quantification for all compounds were calculated. This procedure is characterized by very low limits of detection and quantitation: lower than 0.0017 microg/L and good repeatability for all four volatile compounds. This new analytical procedure was identified to be easy, reliable, sensitive, and requires only small amounts of sample. It can constitute a good alternative to well-known procedures based on application of head space and gas chromatography coupled with electron capture detection.

Human breast milk offers the optimal nutrition for all infants and have been widely used in biomonitoring programs to assess human exposure to lipophylic environmental contaminants such as polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB). There are no previous reports from Turkey on chemically determined levels of PCDDs, PCDFs, and PCBs in human breast milk expressed as World Health Organization (WHO) toxic equivalents (TEQ). To get an overview of the levels of these contaminants in Turkish human milk, samples from 51 Turkish women living in the Ankara, Istanbul, Antalya, Kahramanmaraş, and Afyon provinces were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) throughout 2007. The mean concentrations of WHO(PCDD/F-)TEQ and WHO(PCB-)TEQ of all samples from the five regions were 7.5 and 3.1 pg g(-1) on a lipid basis, respectively. PCDD/F concentrations ranged between 0.78 and 29.3 pg WHO-TEQ g(-1) fat (1.7 and 36.2 pg WHO-TEQ g(-1) fat, respectively, including PCB). Of the five studied locations, the lowest levels of sigmaTEQs (PCDD/F+PCB) were found in the Afyon (6.8 pg WHO-TEQ g(-1) fat) and the highest in the Antalya (15.6 pg WHO-TEQ g(-1) fat) province. The results have been discussed in terms of regions and PCDD/F and PCBs for which analyses had been made. The mean levels of PCDD/Fs and PCBs in Turkish human milk are comparable to that found in other countries.

Sediment and mussel samples collected along the coasts of the Istanbul strait and an island in Marmara Sea (Turkey) were analyzed for six indicator polychlorinated biphenyl (PCB), 12 dioxin-like PCB (dl-PCB) and 17 polychlorinated dibenzo-p-dioxin/furan (PCDD/F) congeners. Samples contained different concentrations of PCBs and among these, congeners 153, 75, 105 and 118 in sediments and congeners 153, 138 and 118 in mussels were most abundant. The concentration levels of total PCBs and PCDD/Fs in sediments ranged from 17.9 to 539746 pg g(-1)dm and 2.04 to 60.5 pg g(-1)dm, respectively. The total WHO-TEQ values ranged between 0.01 and 17.8 pg g(-1)dm in sediments, and 0.98 and 1.01 pg g(-1)ww in mussels. None of the sediment and mussel samples analyzed exceeded the limits suggested in the sediment quality guideline and safe values set by the European Community for seafood intended for human consumption, respectively.

The objectives of this work were to study the emissions of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyl (PCB) during the combustion of wood, wood and hospital waste as well as wood, hospital waste and (NH(4))(2)SO(4) in a pilot plant and to determine the relation of the toxic emissions to the fuel properties. The presence of PVC (experiments b and c) increases PCDD/F and PCB formation compared to burning only eco-farm wood (a). However, analysis and quantification of PCDD/F and PCB showed that the amount of 5% of (NH(4))(2)SO(4) in the fuel mixture significantly impacted the dioxins emissions and suppressed it by approximately 50%. In addition, longer duration of the combustion experiment by using (NH(4))SO(4) resulted in a stronger inhibition of the toxic emissions. Overall, the lowest values were observed during the combustion of the fuel blends containing wood only. Relationships of PCDD/F (WHO-TEQ) and individual congeners of WHO-PCDD/F, WHO-PCB and six PCB indicator congeners were also found. As a result, all single PCB congeners were identified as PCDD/F (WHO-TEQ) surrogates in the flue gas. Furthermore, the correlation between PCDD/F and PCB congeners was examined by statistical methods such as cluster analysis (CA). Closely neighboured pairs on the dendrogram were additionally confirmed by a high linear coefficient of determination (R(2)). (NH(4))(2)SO(4)-containing samples did not affect the correlations between PCDD/F and PCB at the concentrations given.

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) were measured in the water column from Three Gorges Reservoir (TGR) collected in May 2008 using semipermeable membrane devices (SPMDs). The sampling sites spanned the whole reservoir from the upstream Chongqing to the great dam covering more than 600 km long distance with water flow velocities ranging from <0.05 to 1.5 ms(-1). This is the first experience of SPMD application in the biggest reservoir in the world. The results of water sampling rates based on performance reference compounds (PRC) were tested to be significantly correlated with water flow velocities in the big river. Results of back-calculated aqueous concentrations based on PRC showed obvious regional variations of PAH, PCB and OCP levels in the reservoir. Total PAH ranged from 13.8 to 97.2 ngL(-1), with the higher concentrations occurring in the region of upstream and near the dam. Phenanthrene, fluoranthene, pyrene and chrysene were the predominant PAH compounds in TGR water. Total PCB ranged from 0.08 to 0.51 ngL(-1), with the highest one occurring in the region near the dam. PCB 28, 52, 101, 138, 153, 180, 118 were the most abundant PCB congeners in the water. The total OCP ranged from 2.33 to 3.60 ngL(-1) and the levels showed homogenous distribution in the whole reservoir. HCH, DDT and HCB, PeCB were the major compounds of OCP fingerprints. Based on water quality criteria, the TGR water could be designated as being polluted by HCB and PAH. Data on PAH, PCB and OCP concentrations found in this survey can be used as reference levels for future POP monitoring programmes in TGR.

The present study investigated the distribution, transportation, and biodegradation of the selected chiral persistent organochlorine pesticides (OCP) in the Alps. In the complex environment, we found the movement and fate of OCP could be defined by many factors. Taking HCE as an example, below the timberline its accumulation from air into SPMD increased with altitude and seasonally changed, but the trends reversed above the timberline. In soil, the tendency of HCE concentrations vs organic materials followed a sigmoid curve, and HCE concentration-altitude correlations are positive in central Alps but negative in southern Alps. The HCE enantiomeric ratios (ERs) in soil correlated to HCE isomers concentrations, the humus pH values, and the sampling site altitudes. HCE shift from humus to mineral soil can also be traced by ERs. The altitudinal and longitudinal trends in needles suggested that alpha-HCH has a more complex movementthan HCE in Alps. In conclusion, altitude conducted condensation, plant canopies, organic material in soil, and geographic specific precipitations may affect OCP distributions and transportation, whereas altitude conducted temperature and soil pH could dictate their fate in the environment.

An inter-laboratory exercise was performed with a yeast estrogen bioassay, based on the expression of yeast enhanced green fluorescent protein (yEGFP), for the determination of estrogenic activity in extracts of calf urine samples. Urine samples were spiked with 1 and 5 ngmL(-1) 17beta-estradiol and 17alpha-ethynylestradiol, 10 and 50 ngmL(-1) mestranol, and 100 ngmL(-1) testosterone and progesterone. Sample extracts of blank and spiked urine samples were prepared at our laboratory and sent to seven laboratories together with a reagent blank, a DMSO blank, and eight 17beta-estradiol stock solutions in DMSO ranging in concentration from 0 to 545 ngmL(-1). Sample extracts and standards were coded and tested blindly. A decision limit (CCalpha) was determined based on the response of seven blank urine samples. Signals of the negative controls, e.g. urine samples spiked with 100 ngmL(-1) testosterone or progesterone, were all below the determined CCalpha and were thus screened as compliant. Positive controls, i.e. the urine samples spiked at two levels with 17beta-estradiol, 17alpha-ethynylestradiol and mestranol, were almost all screened as suspect, i.e. gave signals above the determined CCalpha. Determined EC(50) values calculated from the 17beta-estradiol dose-response curves obtained by the seven laboratories ranged from 0.59 to 0.95 nM.

Surficial sediments and mussels (Mytilus galloprovincialis) from the Istanbul Strait and Marmara Sea were analysed for sixteen parent polycyclic aromatic hydrocarbon (PAH) contents by gas chromatography-mass spectrometry (GC-MS) employing isotope dilution technique. Microalgae toxicity testing was applied to sediment elutriates and biological responses in terms of filtration rate and lysosomal stability were measured in mussels. Total PAH concentrations ranged from 2.1 to 3152 ng g(-1) dry wt in sediments and from 43-601 ng g(-1) wet weight in mussels. Molecular indices of phenanthrene/ anthracene, fluoranthene/pyrene and benzo(a)anthracene/chrysene were used to differentiate between pyrolytic and petroleum origin. Results showed that most of the contamination originates from high temperature pyrolytic inputs with some slight contribution of petrogenic PAH. PAH in sediments were frequently lower than the National Oceanic and Atmospheric Administration (NOAA)-ERM (Effects Range Medium) index. Results of sediment elutriate toxicity testing and biomarkers indicate that the cause of negative effects in sediments may result from different classes of pollutants and does not only relate with PAH contamination. Mussels from most of the stations showed both reduced lysosomal membrane stability and filtration rate indicating disturbed health although the two biomarker results did not always complement each other. The effect studies showed that the pollutants in the strait ecosystem have more pronounced effects in the middle parts than those at the Black Sea entrance.

Environmental health sciences focus on the link between the presence of contaminants in the environment and their relation with possible adverse health effects. Within this context, human biomonitoring (HBM) data have proven to be a valuable addition to, or have even surpassed, estimates of exposure based on environmental measures. Probably the main achievement of HBM data is that it provides an integrated overview of the pollutant dose any constituent is exposed to and incorporates bioaccumulation, excretion, half-life, and other potentially critical toxicokinetic parameters. In an integrated environmental health impact assessment framework, HBM serves as a pivotal point between environment and health, on the one hand leaning on environmental data to provide information on sources and pathways of exposure, and on the other hand clarifying hypotheses on the relationship between internal dose and prevalence of disease clusters. This study reflects the work performed in the INTARESE project (Integrated Assessment of Health Risk of Environmental Stressors in Europe). Because it was perceived that there was an overall lack of knowledge on the general methodology and potential application of HBM data in integrated environmental health impact assessment, an extensive review of literature was performed on past and current developments, potential, and applicability of HBM within the context of integrated environmental health impact assessment. This study covers three main topics that provide guidance for improved interpretation and application of HBM data: (1) sample collection and storage, (2) sample measurement, and (3) data interpretation. These main issues were discussed for 15 of the most common or relevant (classes of) chemicals. For more detailed information, the reader is pointed to the unabridged review (INTARESE, 2007), and consultation is available through the INTARESE web site (www.intarese.org).

In this study, the distribution and sources of inputs of trace metals including Cd, Cu, Zn and Pb from various sources as well as Fe which is widely used in the construction industry, into Winam Gulf of Lake Victoria were investigated. The sampling sites were located up streams and down streams of four rivers (Sio, Nyamasaria, Nyando and Sondu-Miriu), in four beaches along the lake (Port Victoria, Kisumu Car Wash, Dunga and Hippo point beaches) and in three estates (Nyamasaria, Migosi and Nyawita) in Kisumu city, covering potential agrochemical and industrial sources and drinking water points, respectively. The concentrations (in microg/L) of trace metals analysed in the lake and river waters ranged from <1.79 (Cd), <3.83 (Pb), <1.53-3.86 (Cu), 4.37-11.6 (Zn), 11.8-2,440 (Fe). The sediment concentrations (in microg/kg x 10(3)) ranged from 0.19 to 1.91 (Cd), 6.86-138 (Pb), 18-100 (Cu), 36.2-443 (Zn) and 960-73,200 (Fe), with highest concentrations of all metals being recorded at Kisumu Car Wash area. The study confirmed that the concentrations of the metals accumulate downstream in the rivers both in water and sediment and these rivers are major sources of the heavy metal load into Winam Gulf of Lake Victoria.

The aim of the present study was to assess the total daily energy intake of infants (aged 0-4 months) exclusively fed with infant formulae available on the European Union market. All of the products were identified from the European market share data of the year 2007 covering 22 countries. The calculated daily energy intake based on the instructions labelled on these products was compared with the energy requirements based on World Health Organization recommendations, considering the standard body weight established by the Food and Agriculture Organization. In addition, the daily energy intake was also calculated based on direct measurements of the amount of formulae contained in the spoon provided by the supplier. It was found that the kcal/day intakes provided by the supplier were higher than the values recommended by international organizations. The energy intake values calculated based on the direct spoon measurements were even higher.

A 96-well plate culture methodology for the unicellular eukaryote Tetrahymena pyriformis, strain GL was used for the determination of toxicity and metabolism of catecholamines. Catecholamines exhibited moderate acute toxicity to Tetrahymena cells where dopamine and L-DOPA showed higher toxic potential at EC(10) (0.39 ppm and 0.63 ppm, respectively) and EC(20) (1.1 ppm and 1.0 ppm respectively) after 48 h exposure. All tested catecholamines were highly degradable in the PPY-medium due to the oxidizing environment during incubation. Also the catecholamines were naturally synthesized and released by Tetrahymena cells into the culture medium and increasingly accumulated with time where noradrenalin exhibited the highest degree of accumulation. However, the exogenous exposure of catecholamines to the cells caused the depletion of natural noradrenalin synthesis even with the addition of very low physiological concentration (0.12 ppm). Dopamine caused the higher effect on inhibiting noradrenalin synthesis. Treatment with a higher concentration (8.0 ppm) of dopamine in 96-well plates caused strong excitation of the cells and ascertained a new metabolite in vivo while the other representative catecholamines were not responsible for the production of this metabolite. This dopamine metabolite is relatively non-polar as compared to noradrenalin, adrenaline and dopamine and eluting later through the reverse phase C-18 column.

Gaseous emissions of combusted electronic scrap, PVC, carpet and wood were monitored for polycyclic aromatic hydrocarbons (PAHs) by simultaneous use of semipermeable membrane devices (SPMDs) and shoots of spruce needles (Picea abies). It was found that phenanthrene, acenaphthylene and fluorene were the dominating PAHs in all samples. SPMDs and needles mainly sequestered PAH associated with the vapor phase. Particle-bound PAHs were only detected in small amounts, at which the needles tended to uptake more of these compounds in comparison to the SPMDs. Nevertheless, the logarithm of the concentrations of PAHs analyzed in both passive samplers after the same sampling period exhibited a significant linear correlation with correlation coefficients larger than 0.8073. SPMDs and spruce needles can complement each other in passive air sampling for compounds with a preference to the gas phase rather than aerosols.

In this study, the use of recombinant estrogen receptor alpha (ERalpha)-based affinity columns was reported, for the isolation and the identification of estrogenic substances present in complex matrices, focusing on bioactive compounds present in foodstuff. The capability of affinity columns to trap high, but also low-affinity radio-labelled ligands (17beta-estradiol, genistein and bisphenol A) was demonstrated. Three pooled samples of infant formulas (milk-based, hypoallergenic and soy-based formulas for infants aged 0-4 months) from a EU market basket were prepared by the CASCADE Network of Excellence. After determining the estrogenic activity of these food samples, human recombinant ERalpha ligand binding domain (LBD) based affinity columns combined with suitable analytical methods (high resolution LC-MS/MS) were used to identify the bioactive compounds present in the soy-based formula extract, namely phytoestrogens (genistein and daidzein) involved in the agonistic activity measured. Incubations of genistein with liver microsomes were carried out and the extracts analysed following the same protocol, demonstrating that hERalpha affinity columns can also be used for trapping active metabolites. This approach combining bioluminescent cell lines with this useful tool based on hERalpha-LBD affinity columns thus allowed the purification and the concentration of both known and unknown estrogenic ligands prior to investigation of their structure using LC-MS.

Some epidemiological studies suggested the occurrence of an alteration in the male reproductive function in the past 50 years, particularly a decrease in the sperm count and quality, an increase in the malformations frequency of the reproductive apparatus (cryptorchidism and hypospadias) and of testicular cancers. Especially according the laboratory animals studies, polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) have been suspected to play a crucial and deleterious role in the alteration of human fertility. For this reason, we measured adipose tissue concentrations of PCDDs/Fs and dioxin-like PCBs in 23 fertile and 22 infertile men living in Ankara, Turkey. Adipose tissue samples were analyzed for PCDD/F and 12 dioxin-like PCB congeners using high-resolution gas chromatography/high-resolution mass spectrometry. For the fertile and infertile groups, the World Health Organization (WHO)(PCDD/F)-TEQ concentrations ranged from 3.0 to 15.8 pg/g fat and from 2.8 to 17.2 pg/g fat, respectively (4.4-31.5 and 4.7-22.3 WHO-TEQs/g fat, respectively, including dioxin-like PCBs) (p > 0.05). The mean concentrations of WHO(PCDD/F)-TEQ and WHO(PCB)-TEQ have been calculated as 7.2 and 12.5 pg/g (on a lipid basis) for the fertile group and 7.0 and 9.4 pg/g for the infertile group, respectively. Concentrations of each of the PCDD/F and dioxin-like PCB congeners were compared in fertile and infertile groups among themselves, and no statistical significance was obtained (p > 0.05), except 2,3,7,8-tetrachlorodibenzofuran (p = 0.0029) and 1,2,3,4,6,7,8,9-octachlorodibenzofuran (p = 0.01).

This report reviews past research on hair analysis development for organic contaminants from the point of view of analytical procedures, successful applications and their limitations. For the past 20 years, hair analysis for organic pollutants has received more and more attention, since it is non-invasive, easily available and ethically not prioritized. New methods such as SFE, SPME and INAA have been developed to make the analysis more accurate and reliable. Furthermore, the correlation of contamination levels between hair samples and ambient air or internal tissues has been found by hair analysis and short-term and long-term exposure assessment in combination. However, there are still some limitations of hair analysis to be a validated risk assessment tool for many compounds. Some limitations had been of the past, some have not been fully investigated and need still further study. In this way, hair analysis can be the key to successfully biomonitor organic contaminations.

Concentrations of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB) in Baltic Sea fish like herring (Clupea harengus membras), sprat (Sprattus sprattus balticus), perch (Perca fluviatilis), pikeperch (Sander lucioperca) and flounder (Platichthys flesus trachurus) collected from four areas of the Estonian coastal waters are reported. All samples are studied for their relationship between the length (cm) and wet weight (g); length (cm) and age (years); lipid content and dry matter. The level of PCDD/F and PCB concentrations in younger 1-5 years old Baltic herring and sprat collected in 2002-2005 from the eastern and central parts of the Gulf of Finland, Gulf of Riga and Open Baltic Sea (Central Baltic) is related to the fish age and compared with those found in the 1990s. In addition, PCDD/F and PCB concentrations of different age groups herring, sprat, perch, pikeperch and flounder collected in 2003-2004 from the Lake Peipsi, Gulf of Finland, Gulf of Riga and Open Baltic Sea are related also to their age. Consequently, it was manifested that in older Baltic fish the concentrations of PCDD/F and PCB were higher than in the younger age groups. By the help of principle component analysis (PCA) the effect of gender on the concentrations of PCDD/F for the juvenile Baltic herring and sprat collected in 2004-2005 is investigated for the first time. It was summarized that the biological factor age plays a large role for the contamination of the fish with important toxic organohalogenated compounds such as PCDD/F.

We investigated effects of 17alpha-ethinylestradiol (EE) in vertebrate free 230 L still water microcosms. Zooplankton composition and physico-chemical variables were observed during 4 weeks of pre-application, 6 weeks of dosing via controlled release, and a 12 weeks post-treatment period. In the treated microcosms, time-weighted averages of EE concentration ranged between 7 and 220 ng/L during the dosing period, with concentration maxima up to 724 ng/L. EE exposure resulted in a decrease of species numbers and diversity (Shannon-Wiener, Simpson). Abundances of cladocerans, copepods, and, less unambiguously, rotifers declined. Strongest affected groups were the offspring of cladocerans and copepods and, on species level, the cladoceran species Daphnia longispina and Chydorus sphaericus as well as the rotifer species Keratella quadrata and Polyarthra sp. EE apparently affected the phosphate cycle as indicated by increased phosphate concentrations in the water. During post-treatment period, the treated microcosms recovered, but especially the highest treated microcosms did not fully re-approximate to the controls. Whereas EE affected cladocerans and copepods directly, shifts of rotifers may (partly) be caused indirectly, e.g. by competition with crustaceae. Although not providing an absolute proof, the traits of direct and indirect effects on different taxonomic groups and larval stages as well as the time course of the effects indicate that effects primarily resulted from endocrine activity of EE.

Effects of 17alpha-ethinylestradiol (EE) on phytoplankton were investigated in a lentic freshwater microcosm study. Treatment with EE caused a shift in the species composition as shown by a principle response curve. Whereas densities of Cyanophyceae, Dinophyceae, and Chrysophyceae increased, those of Conjugatophyceae and Cryptophyceae decreased. Furthermore, relative density of Chlorophyceae declined after EE treatment. The changes showed taxa-specific time dependencies. Some species, especially the cyanobacterium Cyanobium parvum, bloomed after the treatment. EE treatment promoted total abundance and biomass of phytoplankton. Although the number of species per microcosm increased, the diversity indices (Shannon-Wiener, Simpson) tended to lower values. The ecosystem only partly recovered during the investigated post-treatment period of 6 weeks. Probably at least the main effects were caused indirectly, i.e. via decrease of grazing zooplankton (crustaceans). The relation of EE to variation of phytoplankton composition was closer than those of other abiotic factors, indicating the relevance of its impact. EE also probably affected nutrients of the phytoplankton.

Background: A significantly reduced male reproductive health status, including a higher prevalence of cryptorchidism and hypospadias, has been documented in Danish men compared with Finnish men. Exposure to environmental pollutants with endocrine disrupting activities has been suggested as a possible contributing factor. In this study, we investigated whether there was a difference in milk and placental concentrations of persistent organohalogen compounds, between the two countries., Methods: Organohalogens were analysed by high-resolution gas chromatography-high-resolution mass spectrometry in human milk samples from Finland (n = 65) and Denmark (n = 65) and in placentas from Finland (n = 112) and Denmark (n = 168)., Results: 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (p,p'-DDE) was the dominant pollutant. beta-Hexa-chloro-cyclohexane (beta-HCH), hexachlorobenzene (HCB), endosulfan-I, dieldrin, oxychlordane (OXC), cis-heptachloroepoxide (c-HE) and 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (p,p'-DDT) were the other main organochlorines detected. Danish samples had significantly higher concentrations of p,p'-DDE, p,p'-DDT, beta-HCH, HCB, dieldrin, c-HE and OXC than did the Finnish samples. Levels of organobrominated compounds were very low and most were undetectable in the majority of samples. BB-153 and BB-155 were the most abundant polybromobiphenyl congeners. BB-153 was more abundant in Danish milk samples compared with Finnish samples, whereas BB-155 was more abundant in the Finnish milk., Conclusions: The organochlorine levels were higher in Danish, than in Finnish, samples, suggesting a higher exposure for Danish infants.

Co-combustion of coal-solid waste mixtures in pilot and laboratory-scale combustors with emphasis on monitoring of toxic chlorinated hydrocarbon emissions such as polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) and polychlorinated biphenyls (PCB) is elaborated. The objective of the work is to investigate the so-called primary measures technique. Twenty different thermally resistant inorganic compounds were added directly to the fuel as inhibitors of PCDD/F formation. The fuel-types used in this study included lignite coal, pre-treated municipal solid waste and polyvinyl chloride (PVC). Principle component analysis (PCA) provides the basis for a feasible discussion about the efficiency of 20 inhibitors on PCDD/F and PCB formation. The study showed that the metal oxides group investigated had no inhibitory effect. Although the single N- and S-containing compounds, used as additives for the type of lignite coal, solid waste and PVC fuel, are not very effective as inhibitors, all other N- and S-containing substances are capable to strongly reduce PCDD/F and PCB flue gas emission. The most effective inhibitors are (NH(4))(2)SO(4) and (NH(4))(2)S(2)O(3). (NH(4))(2)SO(4) present at 3% of the fuel can reduce the PCDD/F emissions to 90%. Its low cost and high efficiency favour them as useful for full-scale combustion units.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) are sampled and investigated in a forested area in Middle-Europe. The campaigns, consisting in active and passive samplings, were conducted in the Bavarian and Bohemian Forest at four sites chosen for their similar soil and forest stand characteristics. Passive sampling was conducted using both semi-permeable membrane devices (SPMDs) and needles of well-exposed dominant spruce trees. Active air sampling was also performed at one site with a low volume air sampler. Correlations were performed to identify relationships and trends of PCDD/F. Lower chlorinated PCDD/F are accumulated in SPMDs, needles collected all compounds among homologues and their PCDD/F pattern is close to that of active sampling. Results of the analysed compounds obtained with the different sampling methods served as a basis for the establishment of advantages and disadvantages of the sampling tools applied and their possible optimisation.

Reported herein are semi-empirical calculations of the molecular geometry of TCDD, TCPT, TCPT-sulfoxide (TCPT-O), TCPT-sulfone (TCPT-O(2)), N-methyl-TCPT (Me-TCPT), N-methyl-TCPT-sulfoxide (Me-TCPT-O), and N-methyl-TCPT-sulfone (Me-TCPT-O(2)), the characterization of their AhR binding affinity in rat hepatic cytosol, and their ability to induce EROD activity in a rat hepatoma cell line in vitro. Semi-empirical calculations yielded detailed information about the stereochemistry and the preferred conformation of each of these compounds. These results in combination with observations reported in this paper were used to determine structure-activity relationships. In vitro displacement of (3)H-TCDD was measured by increasing concentrations of the respective ligands. This assay revealed a strong binding affinity of TCPT to the AhR with a K(i) value of 1.08 nM. TCDD had a K(i) value of 0.54 nM. The affinity of TCPT derivatives for the AhR decreased with increasing degree of oxidation. Moreover, N-methylation further lowered the affinity, so that the N-methyl sulfone derivative of TCPT displayed the highest K(i) at approximately 1200 nM (=460.4 ng/ml). A corresponding trend was observed regarding the potency of TCPT and derivatives to induce EROD activity in vitro. However, the potencies were considerably lower than that of TCDD. Enzyme induction was measured in a rat hepatoma cell line H4IIEC/T3 by quantification of ethoxyresorufin-O-deethylase (EROD) activity. Induction was measured at 12, 24, 48 and 72 h to determine time dependence. Sulfoxidated and N-methylated phenothiazines displayed a lower potency than their respective parent compounds. TCPT and all derivatives induced enzyme activity at an efficacy similar to TCDD at all time points measured. The reported findings clearly separate the induction of EROD activity by TCPT and derivatives from their binding affinities to the AhR. In contrast, a direct correlation between the two is generally assumed in drug development, leading to - in our view - unwarranted termination of drug candidates. Therefore, a lack of such a correlation for TCPT and derivatives in fact supports their further development as possible drug leads.

The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.

The levels of organohalogenated contaminants, i.e. PCBs, PCDDs and PCDFs were determined in sediment and fish samples collected from different locations in the River Nile, Egypt. Thirty-six sediment and eighteen fish samples were carried out during a period of 12 months from February 2003 to February 2004. Determination of PCBs and dioxins was carried out using a high resolution GC mass spectrometer. The results indicated that the PCB and PCDD/F mean concentrations in sediment samples ranged from 1461 to 2244 and from 240 to 775pgg(-1) dry wt basis, respectively. The mean concentration of PCBs and PCDD/Fs in fish samples were found to be in the range from 695 to 853pgg(-1) fresh wt for PCB congeners and from 27.7 to 121pgg(-1) lipid for total PCDD/Fs. Moreover, the concentrations of both PCBs and PCDD/Fs were found to be different at different locations along the River Nile. It could be concluded that the contamination of the River Nile is within the permissible limits set by the FDA and the Egyptian Standards for fish and shellfish.

Polychlorinated dibenzo-p-dioxins are persistent environmental pollutants. The most potent congener, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), causes a wasting syndrome and is a potent carcinogen and immunosuppressant in the rat at high doses. However, low doses cause opposite effects to some of those observed at higher doses, resulting in chemoprevention, stimulation of the immune system, and longevity in experimental animals. The new TCDD analogue, 2,3,7,8-tetrachlorophenothiazine (TCPT), was developed to take advantage of the low-dose effects of dioxins that have potential application as therapeutics. Its development marked a deviation from the traditional scope of phenothiazine drug design by deriving biological effects from aryl substituents. TCPT was synthesized in three steps. The key ring-closing step was performed utilizing a Buchwald-Hartwig amination to provide TCPT in 37% yield. Its potency to induce CYP1A1 activity over 24 h was 370 times lower than that of TCDD in vitro. The elimination half-life of the parent compound in serum was 5.4 h in the rat and 2.7 h in the guinea pig, compared to 11 and 30 days, respectively, for TCDD. These initial findings clearly differentiate TCPT from TCDD and provide the basis for further studies of its potential as a drug lead.

The exposure levels of placenta and paired breast milk samples to selected organochlorine compounds and pesticides from Danish and Finnish samples have been investigated. p,p'-DDE is the dominant pollutant, beta-HCH, hexachlorobenzene, endosulfan-I, dieldrin, oxychlordane, cis-heptachlor epoxide and p,p'-DDT being the other major constituents. Their concentrations are linearly correlated between milk and placenta in similar patterns for Danish and Finnish samples. Milk samples have higher levels of these pollutants than placenta on lipid base. However, the apparently not correlated compounds, such as alpha-HCH, pentachlorobenzene, pentachloroanisole and methoxychlor, are generally accumulated more in placenta, which may suggest a tissue specific metabolic activity. Thus, depending on the compound of interest, biomonitoring may be done in placenta only or in both matrices.

The tertiary branched alkyl-chain isomers of p-nonylphenol (NP) are perceived to have more estrogenic potency than its constituent secondary and primary straight alkyl-chain isomers. Investigations with single tertiary branched isomers of NP can therefore contribute toward the elucidation of the mechanisms of toxicity and estrogenicity of NP. A single tertiary branched alkyl-chain isomer (4(3',6'-dimethyl-3'-heptyl)-phenol) was used in studies to determine its effects on embryonic growth and mortality in Lymnaea stagnalis L. Egg masses were exposed to the test compound for 20 days in a static waterborne-exposure regime with an average NP concentration of 105 microg/L and water temperature range of 18-20 degrees C. Observations were made under a microscope and pictures were taken with a digital camera to determine the various developmental stages of growth, the duration of growth in each stage, embryo hatchability, and embryo mortality. The isomer was found to cause significant delay in all stages of growth and more significantly in the Morula and Veliger stages. An increase in embryo mortality, from the third day until the end of the experiment, was observed in exposed egg masses compared to controls. The hatching success of embryos was also significantly reduced by exposure, with 81% hatchability in exposed egg masses compared to 93% in the controls, after 18 days of continuous exposure. The encapsulating jelly strand that completely covers the rows of egg masses may have prevented the isomer residues from effectively penetrating into the embryos as shown by the observed low bioconcentration factors of the isomer in egg masses during exposure, resulting in unexpectedly lower observed estrogenic effects. However, this factor was not investigated. In vivo biotransformation of some of the residues of the isomer into catechol metabolites by the embryos during exposure could also result in the reduction of its estrogenic potential. To understand more fully the extent of toxicity and estrogenicity of this isomer, in vitro estrogenic assays are recommended. It would also be necessary to investigate its estrogenic effects on embryo development after in vivo maternal exposure.

There is no previous report from Turkey on chemically determined polychlorinated dibenzo-para-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) in human tissues expressed as World Health Organization (WHO) toxic equivalents (TEQs). The objective of this study was to determine the occurrence of PCDDs/Fs, and dioxin-like PCBs in the general adult Turkish population. For this reason we measured adipose tissue concentrations of PCDDs/Fs and dioxin-like PCBs in 23 Turkish men living in Ankara,Turkey in 2004. PCDD/F concentrations ranged between 3.2 and 19.7 pg WHO-TEQ/g fat (5.34 and 42.7 WHO-TEQ/g fat, respectively, including dioxin-like PCBs). The mean concentrations of WHO(PCDD/F)-TEQ and WHO(PCB)-TEQ were 9.2 and 6.67 pg/g on a lipid basis , respectively. Samples were analyzed for PCDD/F and twelve dioxin-like PCB congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). This study is very important since it is the first report on PCDDs/Fs and dioxin-like PCB contamination in human adipose tissue from Turkey.

The concentrations and congeners pattern of the polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in sprat collected by the commercial catches in the Gulf of Finland, Baltic Sea. Based on the toxic equivalent concentrations 2,3,4,7,8-PeCDF prevailed among the congeners of PCDD/Fs. The significance of age- and season-specific relationship between the concentration of lipids and dioxins was demonstrated. On lipid weight basis the concentration of PCDDs was significantly higher in spring than in autumn. This difference was not statistically significant for PCDFs. On lipid weight basis the concentration of dioxins decreased with rising content of lipids. PCDD/Fs toxic equivalent concentration increased with the age of sprat exceeding the EU maximum limit value at more than 5-year-old fish.

Dalian is a seaside city situated in the northeastern monsoon area of China. For the first time, levels of PCDD/F and PCB congeners in pine (Cedrus deodara) needles of Dalian urban areas were investigated. Two sampling campaigns with 17 sampling points were performed in 2002. The summation of tetra- to octachlorinated PCDD/Fs and summation of 209 PCB congeners in Dalian pine needles averaged 127+/-40 ng/kg (dry) and 4389+/-1575 ng/kg (dry), respectively. Average toxic equivalence (TEQ) for PCDD/Fs and PCBs are 2.1 and 0.4 ng/kg (dry), respectively. The pine needles can differentiate spatial variation of the pollutants. The PCDD/F and PCB levels in Dalian pine needles are low or comparable with other international regions that were not impacted by evident point sources. The data can serve as a base for long-term spatial and temporal studies of PCDD/Fs and PCBs in China.

Izmit Bay and its coastal environment was strongly affected by the August 17th, 1999 Izmit Earthquake. The changes in the Bay ecosystem and its chemical oceanography have been studied in detail previously [Okay, O.S., Tolun, L, Telli-Karakoç, F., Tüfekçi, V., Tüfekçi, H. And Morkoç, E. 2001. Yzmit Bay ecosystem after Marmara earthquake and subsequent fire: The long-term data. Marine Pollution Bulletin 42, 361-369; Balkýs, N. 2003. The effect of Marmara (Izmit ) Earthquake on the chemical oceanography of Izmit Bay, Turkey. Marine Pollution Bulletin 46, 865-878.]. In this study surface sediments collected from the Izmit Bay before and after the earthquake have been analysed for total and individual (14 compounds) polycyclic aromatic hydrocarbons (PAH). Analyses have been performed by high performance liquid chromatography with fluorescence detection (HPLC/FD). Before the earthquake, total PAH concentrations in the Bay sediments ranged from 120 to 8900 ng/g while after the earthquake PAH concentrations varied between 240 and 11,400 ng/g. Molecular indices based on isomeric PAH ratios used to differentiate the pollution sources, clearly indicate the differences in molecular distribution of PAHs before and after the earthquake. Sediment data obtained before the earthquake shows that most of the contamination originated from high temperature pyrolytic inputs while after the earthquake it originated from petrogenic sources. This difference emphasises the environmental impact of uncontrolled discharges from petroleum industries after the earthquake. The LMW/HMW ratio (sum of the low molecular weight PAHs / the sum of higher molecular weight PAHs) predominance also changed after the earthquake as a result of the strong water movements. According to the characteristics of aromatic rings distributed in the bay sediments, the soluble parts of the total PAH were probably transferred to the water column after the earthquake as a result of resuspension process. The TEL/PEL (Threshold Effect Level / Probable Effect Level) analysis suggests that the Izmit Bay sediments were likely contaminated by acutely toxic PAH compounds.

Introduction: Prenatal exposure to some pesticides can adversely affect male reproductive health in animals. We investigated a possible human association between maternal exposure to 27 organochlorine compounds used as pesticides and cryptorchidism among male children., Design: Within a prospective birth cohort, we performed a case-control study; 62 milk samples from mothers of cryptorchid boys and 68 from mothers of healthy boys were selected. Milk was collected as individual pools between 1 and 3 months postpartum and analyzed for 27 organochlorine pesticides., Results: Eight organochlorine pesticides were measurable in all samples (medians; nanograms per gram lipid) for cases/controls: 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (p,p -DDE) : 97.3/83.8; beta-hexachlorocyclohexane (beta-HCH) : 13.6/12.3; hexachlorobenzene (HCB) : 10.6/8.8; alpha-endosulfan: 7.0/6.7; oxychlordane: 4.5/4.1; 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (p,p -DDT) : 4.6/4.0; dieldrin: 4.1/3.1 ; cis-heptachloroepoxide (cis-HE) : 2.5/2.2. Five compounds [octachlorostyrene (OCS); pentachlorobenzene, 1,1-dichloro-2,2-bis(4-chlorophenyl) ethane(p,p -DDD) ; o,p -DDT ; mirex] were measurable in most samples (detection rates 90.8-99.2%) but in lower concentrations. For methoxychlor, cis-chlordane, pentachloroanisole (PCA), gamma-HCH, 1,1-dichloro-2-(2-chlorophenyl) -2,2(4-chlorophenyl) ethane, trans-chlordane, alpha-HCH, and o,p -DDE, both concentrations and detection rates were low (26.5-71.5%). Heptachlor, HCH (lc delta, epsilon), aldrin, beta-endosulfan and trans-heptachloroepoxide were detected at negligible concentrations and low detection rates and were not analyzed further. Seventeen of 21 organochlorine pesticides [p,p -DDT, p,p-DDE, p,p-DDD, o,p-DDT, HCH (alpha, beta, gamma), HCB, PCA, alpha-endosulfan, cis-HE, chlordane (cis-, trans-) oxychlordane, methoxychlor, OCS, and dieldrin] were measured in higher median concentrations in case milk than in control milk. Apart from trans-chlordane (p = 0.012), there were no significant differences between cryptorchid and healthy boys for individual chemicals. However, combined statistical analysis of the eight most abundant persistent pesticides showed that pesticide levels in breast milk were significantly higher in boys with cryptorchidism (p = 0.032)., Conclusion: The association between congenital cryptorchidism and some persistent pesticides in breast milk as a proxy for maternal exposure suggests that testicular descent in the fetus may be adversely affected.

In the flue gas of co-combustion of solid waste and coal in a laboratory scale furnace high concentrations of polychlorinated dibenzo-p-dioxin and furans (PCDD/F), polychlorinated biphenyls (PCB) and polychlorinated benzenes (PCBz) have been detected. These toxic emissions have been reduced by the help of various inhibitors added to fuel before incineration. Knowledge of the congener pattern and homologue profiles of PCDD/F, PCB and PCBz is important to elaborate the mechanism of formation and inhibition of the toxic compounds formed during co-combustion of solid waste and coal. Principle component analysis (PCA) is used in order to find the similarity between the samples and separate them according their toxicity. By the help of the component analysis (CA) the best correlated congeners are effectively detected. Using linear regression between the independent variables and the indicator parameters various good correlated pairs between PCDD/F, PCB and PCBz have been elaborated. Generally it was found that the samples with higher toxicity show a good correlation between tetra- and pentachlorinated benzenes and tetra- and pentachlorinated dibenzo-p-furans. The best indicator parameter for PCDD/F World Health Organization toxic equivalent (WHO-TEQ) among the PCBz congeners investigated is 1,2,4,5-TCBz. This isomer is also significantly correlated with PCDD/F WHO-TEQ and with the sum of PCDD/F WHO-TEQ and PCB WHO-TEQ. However for samples with higher percentage of inhibitors the above mentioned relationship between the surrogate and WHO-TEQ disappeared. The PCB homologues and congeners show no correlation with PCBz and PCDD/F homologues and congeners.

The aim of this project was to assess the concentration ranges of persistent organic pollutants (POPs) in air by means of active and passive sampling devices located in remote areas along the southern part of the German-Czech border. During the measuring program we also used spruce needles of different ages as biomonitors. The first results, which are restricted to PCDD/F measurements, indicate that the concentrations in both air and needles measured at four sites in the Bavarian Forest and Sumava crest region are lower than in many other regions of Bavaria and lower than during former measuring campaigns in adjacent regions of Austria and Bohemia. There is no apparent reason for the higher contamination by dioxins and furans in South Bohemia ecosystems, which are far from emission centers in central and northern Czech Republic. Other POPs will be investigated in the future.

The enantiomeric ratios (ER) of alpha-HCH and o,p'-DDT ((+)-isomer concentration/(-)-isomer concentration) and o,p'-DDD (first eluting enantiomer/second enantiomer) were investigated in 112 human placentas from Finnish boys collected 1997-2001. Both o,p'-DDD and alpha-HCH showed changes in their ER depending on the total concentration of the compound in the sample. Their ERs are approaching a value close to racemic mixture (ER=1) at high concentrations. At low concentrations they often differ from 1. The relationship between concentration and ER is clearly identified and it has been shown that it is not affected by analytical uncertainty. This relationship appears to be important for assessing tissue- and species-specific exposure and risk and it may indicate whether net uptake or metabolic activity is dominant in exposure for the resulting exposure of the enantiomers.

Numerous environmental pollutants have been detected for estrogenic activity by interacting with the estrogen receptor, but little information is available about their interactions with the progesterone receptor. In this study, emission samples generated by fossil fuel combustion (FFC) and air particulate material (APM) collected from an urban location near a traffic line in a big city of China were evaluated to interact with the human progesterone receptor (hPR) signaling pathway by examining their ability to interact with the activity of hPR expressed in yeast. The results showed that the soot of a petroleum-fired vehicle possessed the most potent anti-progesteronic activity, that of coal-fired stove and diesel fired agrimotor emissions took the second place, and soot samples of coal-fired heating work and electric power station had lesser progesterone inhibition activity. The anti-progesteronic activity of APM was between that of soot from petroleum-fired vehicle and soot from coal-fired establishments and diesel fired agrimotor. Since there was no other large pollution source near the APM sampling sites, the endocrine disrupters were most likely from vehicle emissions, tire attrition and house heating sources. The correlation analysis showed that a strong relationship existed between estrogenic activity and anti-progesteronic activity in emissions of fossil fuel combustion. The discoveries that some environmental pollutants with estrogenic activity can also inhibit hPR activity indicate that further studies are required to investigate potential mechanisms for the reported estrogenic activities of these pollutants.

Microcosm studies unveil relevant information in ecotoxicology. However, statistical evaluation of data gained from the different parts of the ecosystem often remain on unsatisfying, discretely level, e.g. separately for different species communities. A combination of different multivariate statistical methods enables an ecological interpretation of the found changes in zoo- and phytoplankton abundances in connection with the physico-chemical variables. To investigate the effects of nonylphenol (NP) on plankton communities, NP was continuously applicated in microcosms by controlled release. Plankton taxa were identified and quantified, various physico-chemical variables were measured. Maximum NP concentration ranged between 29 and 129 microg/L. The most important abiotic variable explaining both zoo- and phytoplankton abundances was NP concentration. NP primarily inhibited Crustaceae, especially juveniles. Cladocera and Copepoda abundances decreased. Rotatoria tend to increase, probably due to a decline of competition and predator pressure. Shifts in phytoplankton structure occurred with a time lag. Aggregating phytoplankton on class level did not show NP effects, whereas aggregating them according to feeding protection strategies did. Thus NP influences phytoplankton at least prevailingly indirectly via zooplankton. Zooplankton shifts led to species composition with different feeding preferences and strategies. Thereby the feeding pressure on phytoplankton changed. NP reorganized the plankton interrelation. Whereas without NP phytoplankton composition was dominated by Rotatoria, in the NP treated microcosms the Crustaceae unveiled highest explanatory power. The found effects were reversible in all but the highest treated microcosm. There are indications that the found effects were caused by endocrine activity of the chemical. Iteratively combining multivariate statistical methods with ecological and toxicological knowledge proved to provide a deeper insight into the mode of ecosystem disturbance by toxic substances.

Co-combustion of coal and waste in power plants poses both environmental and economic challenges, especially because of the high polychlorinated dibenzo-p-dioxin and furan (PCDD/F) emissions from solid waste. In this study, we performed a series of experiments focusing on the prevention of PCDD/F formation by the use of various inhibitors added to the fuel before combustion. A mixture of lignite coal, solid waste, and poly(vinyl chloride) (PVC) was thermally treated in a laboratory-scale furnace at 400 degrees C. Twenty different additives were investigated at a level of 10 wt% of the total fuel during the experiments. We have divided them into four general groups according to their chemical nature: metal oxides, N-containing compounds, S-containing compounds, and N- and S-containing compounds. The resulting values showed a significant reduction of PCDD/F levels when N- and S-containing compounds were used as additives to the fuel. Principle component analysis (PCA) was used to illustrate the effect of the 20 different inhibitors on the congener patterns emitted. As a result, the most effective inhibitors for PCDD/F formation in flue gases were determined to be (NH4)2SO4 and (NH4)2S2O3; they are inexpensive and nontoxic materials. Both compounds can suppress the formation of toxic compounds such as PCDD/Fs by more than 98-99%, and the most toxic PCDD/F congeners were not detectable in most of the samples. Thus, these compounds were also studied as a lower percentage of the fuel. (NH4)2SO4 resulted in a greater than 90% reduction of PCDD/F even when composing only 3% of the fuel combusted. However, less than 5% (NH4)2S2O3 resulted in far weaker inhibition. The PCDD/F homologue distribution ratio for samples with varying percentages of (NH4)2SO4 and (NH4)2S2O3 was also investigated. Higher percentages of the inhibitors produced a lower percentage of lower chlorinated PCDDs. The opposite effect was found for PCDFs.

2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) affects glycemia due to reduced gluconeogenesis; when combined with a reduction in feed intake, this culminates in decreased body weight. We investigated the effects of steady-state levels of TCDD (loading dose rates of 0.0125, 0.05, 0.2, 0.8, and 3.2 microg/kg) or approximately isoeffective dose rates of 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin (HxCDD) (loading dose rates of 0.3125, 1.25, 5, 20, and 80 microg/kg) on body weight, phosphoenolpyruvate carboxykinase (PEPCK) mRNA expression and activity, and circulating concentrations of insulin, glucose, and insulin-like growth factor-I (IGF-I), and expression of hepatic phosphorylated AMP kinase-alpha (p-AMPK) protein in female Sprague-Dawley rats (approximately 250 gm) at 2, 4, 8, 16, 32, 64, and 128 days after commencement of treatment. At the 0.05 and 1.25 microg/kg loading dose rates of TCDD and HxCDD, respectively, there was a slight increase in body weight as compared to controls, whereas at the 3.2 and 80 microg/kg loading dose rates of TCDD and HxCDD, respectively, body weight of the rats was significantly decreased. TCDD and HxCDD also inhibited PEPCK activity in a dose-dependent fashion, as demonstrated by reductions in PEPCK mRNA and protein. Serum IGF-I levels of rats treated initially with 3.2 microg/kg TCDD or 80 microg/kg HxCDD started to decline at day 4 and decreased to about 40% of levels seen in controls after day 16, remaining low for the duration of the study. Eight days after initial dosing, hepatic p-AMPK protein was increased in a dose-dependent manner with higher doses of TCDD and HxCDD. There was no effect with any dose of TCDD or HxCDD on circulating insulin or glucose levels. In conclusion, doses of TCDD or HxCDD that began to inhibit body weight in female rats also started to inhibit PEPCK, inhibited IGF-I, while at the same time inducing p-AMPK.

Cytochrome P450 1A1 (CYP1A1) is among the cytochrome P450 classes known to convert xenobiotics and endogenous compounds to toxic and/or carcinogenic metabolites. Suppression of CYP1A1 over expression by certain compounds is implicated in prevention of cancer caused by chemical carcinogens. Chemopreventive agents containing high levels of flavonoids and steroids-like compounds are known to suppress CYP1A1. This study was carried out for assessment of the genomic and proteomic effects of caraway (Carum carvi) extracts containing high levels of both flavonoids and steroid-like substances on ethoxy resorufin dealkylation (EROD) activity and CYP1A1 at mRNA levels. Rat hepatoma cells co-treated with a CYP1A1 inducer i.e. TCDD (2, 3, 7, 8-tetrachlorodibenzo-p-dioxin) and different preparations of caraway extracts at concentrations of 0, 0.13, 1.3, and 13 microM in culture medium. After incubation (37 degrees C and 7% CO2 for 20 h), changes in EROD specific activity recorded and compared in cells under different treatments. The results show that caraway seed extract prepared in three different organic solvents suppressed the enzyme activity in hepatoma cells in a dose-dependent manner. The extracts added above 0.13 microM could significantly inhibit EROD activity and higher levels of each extract (1.3 and 13 microM) caused approximately 10-fold suppression in the enzyme activity. Accordingly, data obtained from the RT-PCR (TaqMan) clearly showed the suppressive effects of plant extract on CYP1A1-related mRNA expression. These data clearly show that substances in caraway seeds extractable in organic solvents can potentially reverse the TCDD-dependent induction in cytochrome P450 1A1.

Exposure to indoor air pollution (IAP) from the combustion of biomass fuels is an important cause of morbidity and mortality in developing countries. In the work discussed in this paper we evaluated the endocrine activity of soot particles from biomass fuels by using yeast bioassay. These pollutants could have beta-galactosidase activity with a relative potency (RP) about 10(-7)-10(-9) that of estradiol. Soot particles from wood and straw combustion only partially induced beta-galactosidase activity whereas others produced fully inductive activity in the yeast assay system. These pollutants did not have estrogen antagonist and progesterone agonist activity within the defined concentration range. However, these pollutants require 2-4 orders of magnitude higher IC50 to inhibit the activity of progesterone in a similar dose-response manner to mifepristone. We therefore propose that the endocrine activity of some environmental pollutants may be because of inhibition of the progesterone receptor (hPR). GC-MS results showed that substituted polycyclic aromatic hydrocarbon (PAH) compounds, substituted phenolic compounds and derivatives, aromatic carbonyl compounds, and phytosteroids in these soot particles may be mimicking endogenous hormones.

By partial least squares (PLS) regression, quantitative structure-property relationship (QSPR) models were developed for photolysis half-life (t1/2) of PCDD/Fs and PAHs sorbed to spruce (Picea abies (L.) Karst.) needle surfaces and irradiated by sunlight. Quantum chemical descriptors computed by PM3 Hamiltonian were used predictor variables. PLS analysis for the PCDDs and PAHs respectively resulted in no correlation by our statistical methods. The cross-validated Qcum2 value for the optimal QSPR model of PCDFs is 0.722, indicating a good predictive ability for logt1/2 of PCDFs adsorbed to spruce needle surfaces. The QSPR results show that the number of chlorine atoms bonded to the parent structure and (E(LUMO)-E(HOMO))2 has a dominant effect on t1/2 values of PCDFs. Increasing the number of chlorine atoms and (E(LUMO)-E(HOMO))2 values leads to increase of logt1/2 values of PCDFs.

Physicochemical parameters (vapor pressure, water solubility, Henry's law constant) and biological activities of two halogenated natural products frequently detected in marine samples and food were determined. Synthetic 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) and 2,4,6-tribromoanisole (TBA) were available in pure form. The physicochemical parameters were in the range of anthropogenic chlorinated compounds of concern. The aqueous solubilities at 25 degrees C (S(w,25)) of Q1 and TBA were 4.6 microg/L and 12,200 microg/L, respectively, whereas subcooled liquid vapor pressures were 0.00168 Pa (Q1) and 0.06562 Pa (TBA) as measured by the gas chromatographic-retention time technique. Q1 was negative by established test systems for the determination of ethoxyresorufin-O-deethylase (EROD) induction and by sulforhodamine B assay. EROD induction potency was at least 10(-7) times lower than that of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). At a relatively high concentration (20 microM), Q1 inhibited specific binding of 2 nM [(3)H]TCDD to the in vitro-expressed human aryl hydrocarbon receptor (AHR) by 18%; lower concentrations showed no effect. Molecular modeling showed that Q1 is nonplanar, consistent with its relatively modest affinity as an AHR ligand. When tested for cell-growth inhibitory/cytocidal activity in human tumor cells, Q1 was only marginally, if at all, active with an IC(50) value >50 microM compared with five to ten times lower IC(50) values for potent cytotoxins tested in the test system used. Furthermore, standard pesticide tests on insecticidal, herbicidal, and fungicidal activity did not provide any significant activity at highest concentrations. For TBA, the results in all tests were comparable with Q1. The SRB assay was also applied to the halogenated natural product 4,6-dibromo-2-(2',4'-dibromo)phenoxyanisole, but no toxic response was found. Although it was apparent that Q1 and TBA had been proven to have relatively low biological activity in all tests performed, further research is necessary to clarify whether metabolites of the compounds eventually may possess a risk to humans or other living organisms. Nevertheless, the role of Q1 in nature remains uncertain.

A simple and rapid high-performance liquid chromatography method with ultraviolet detection was developed for the determination of the thyreostatic compound methimazole (1-methyl-2-mercaptoimidazole, MET) and metabolites 2-mercaptoimidazol (SHMET), N-methylthiourea (MTU) and N-methylhydantoin (MEH) from zebrafish (D. rerio) whole body homogenates using mixed mode solid phase extraction technique for sample pre-treatment. The highly polar compounds were separated on a difunctionally bonded silica based reverse phase column using gradient elution. Retention factors ranged between 1.53 and 5.66. The method was linear between 0.1 and 30 microg/ml, the detection limits were 0.4 ng for MET and SHMET, 0.6 ng for MTU and 2.6 ng for MEH. Extraction method was exhibited average recovery rates of 85.2-97.6%.

Estonia still has no waste incineration facilities, which would act as substantial sources of dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) pollution. As landfill fires may serve as sources of dioxins, we focused on the concentrations of PCDD and PCDF in soil samples taken in the vicinity of the landfill located at south-east Estonia in the course of our inventory. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in five soil samples taken in the vicinity of the Laguja landfill in south-east Estonia. The four soil samples were taken in southern, eastern, western and northern parts not further than 300 m from the landfill, and one sample was taken at the distance of 3 km from the landfill. The PCDD/F concentrations in all soil samples were at background level (0.64-2.33 pg I-TEQ WHO/g dry weight). To maintain this situation, the administrator of the landfill must avoid landfill fires, which are one of the reasons for the generation of dioxins and furans.

Owing to the importance of octanol-air partition coefficients (KOA) in describing the partition of organic pollutants from air to environmental organic phases, the paucity of KOA data at different environmental temperatures, and the difficulty or high expenditures involved in experimental determination, the development of predictive models for KOA is necessary. Approaches such as this are greatly needed to evaluate the environmental fate of the ever-increasing list of production chemicals. Partial least squares (PLS) regression with 18 molecular structural descriptors was used to develop predictive models based on directly measured KOA values of selected chlorobenzenes, polychlorinated biphenyls (PCBs), polychlorinated naphthalenes, polychlorinated dibenzo-p-dioxins/dibenzofurans, polybrominated diphenyl ethers, polycyclic aromatic hydrocarbons, and organochlorine pesticides (OPs). An optimization procedure resulted in two temperature-dependent universal predictive models that explained at least 91 % of the variance of log KOA. Model 1 was the more general of the two models that could be used for all the persistent organic pollutant (POP) classes investigated. Although model 1 performed poorly for select OPs, this was attributed to wide variability in structural types within this subset of POPs and their diversity compared to the other POP classes that were investigated. The exclusion of the structurally complex OP subset resulted in a more precise model, model 5. Intermolecular dispersive interactions (induced dipole-induced dipole forces) between octanol and solute molecules play a decisive role in governing KOA and its temperature dependence. Further investigations are needed to better characterize the steric structures of the POPs under study, especially of OPs.

Fly ash samples containing polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were generated by combustion of polyvinyl chloride, wood, high-density polyethylene and styrene. By partial least-squares (PLS) regression, quantitative structure-property relationship (QSPR) models were developed for photolysis half-lives (t(1/2)) of PCDD/Fs adsorbed on fly ash surfaces and irradiated by UV-B of simulated sunlight. Quantum chemical descriptors computed by PM3 hamiltonian were used as predictor variables. The cross validated value for the optimal QSPR model was 0.678, indicating robustness and good predictive abilities of the model. The QSPR results showed that the stability of the PCDD/F molecules increased with the increase of chlorine atoms in the parent molecules. Increasing the energy of the highest occupied molecular orbital (E(HOMO)), the energy of the lowest unoccupied molecular orbital (E(LUMO)), E(LUMO)+E(HOMO) and E(LUMO)-E(HOMO) values of the PCDD/Fs led to decrease of log t(1/2) values. Increasing the most negative atomic charge on the oxygen atom of PCDD/Fs led to elevated log t(1/2) values. The log t(1/2) values of PCDD/Fs increased with the decrease of the largest negative atomic charge on a carbon atom.