Size-exclusion chromatographic study of ECF and TCF softwood kraft pulp bleaching liquors.

BACKGROUND, AIMS, AND SCOPE: Currently, elemental chlorine-free (ECF) and totally chlorine-free (TCF) bleaching systems are widely used for pulp production. Low and medium molecular weight lignin break-down products are known to have harmful effects on the environment. According to some recent results, also high molecular weight (HMW) material consisting mainly of lignin and carbohydrates may cause toxic effects to the environment. For these reasons, toxicity and structure studies of HMW materials are of great importance. This investigation is a part of a larger project to obtain more structure information of HMW materials and toxicity of ECF and TCF bleaching effluents. Size-exclusion chromatography (SEC) has been commonly used for the characterization of organic macromolecules such as lignin, but to our knowledge, no reports have appeared dealing with the comparison of SEC of ECF and TCF bleaching liquors. The aim of the present study was to get more information about the molecular weight distribution (MWD) of HMW fractions of waste liquors from ECF and TCF bleaching sequences by SEC. METHODS: The MWDs of organic materials dissolved during different stages of ECF bleaching (O-D-EOP-D-ED) and TCF bleaching (O-Z-Q-P-Z-Q-P-P) of softwood (Pinus sylvestris) kraft pulp were determined and compared by SEC. All effluent samples from the above bleaching stages were ultrafiltrated using a membrane with a cutoff value of 1,000 Da. SEC was performed on high and also low molecular weight fractions and non-fractionated effluents. In the SEC experiments, a Superdex 75 column was used with 0.1 M NaOH solution as the eluent. Standards used for calibrating the SEC system were albumin, carboanhydrase, cytochrome C, tannic acid, dehydrodiacetovanillone, and vanillin. RESULTS AND DISCUSSION: The chromatograms of liquors from TCF bleaching stages vary more than those from ECF bleaching. Peroxide and chelating stages contained mostly high molecular weight (HMW) matter whereas chlorine dioxide and ozone stages had more low molecular weight compounds. The lignin content in HMW matter was higher than in stages that consisted of low molecular matter. Bleaching effluents contained the highest amounts of HMW material, mainly lignin, in the beginning of the sequences; the amounts decreased towards the end of the bleaching sequence. CONCLUSION: Determinations of MWD by the SEC method showed that effluents from the TCF sequence contained more HMW material than those from the ECF stage. This might be due to peroxide stages (P) that dissolve HMW lignin effectively. However, the molecular weights of ozone stages (Z) were very low compared to other stages. Chlorine dioxide stages also dissolved mostly low molecular weight lignin. Ultrafiltration of bleaching liquors showed that high molecular weight fraction also included some low molecular weight compounds and vice versa. High polydispersity and high lignin content correlated with the amount of HMW material in ECF and TCF bleaching stages. RECOMMENDATION AND OUTLOOK: Our liquor samples were studied by using a UV detector commonly used for lignin preparations; in upcoming investigations, it will be interesting to determine carbohydrates such as hemicelluloses. The results are applicable in papermaking in order to improve commonly used bleaching procedures, to test new potential bleaching systems, and to study chemical behavior of HMW materials in various bleaching liquors. The present results also form a good basis for toxicity measurements of ECF and TCF bleaching effluents and for more comprehensive spectroscopic and chromatographic experiments with samples taken from various bleaching stages. From the behavior of liquors studied, it appears that our other structure investigations by spectroscopic and chromatographic (NMR, Py-GC/MS, etc.) methods mostly correlate well with the present results.

Biological effects of high molecular weight lignin derivatives.

A number of high molecular weight (HMW) lignin derivatives possessing varied chemical properties were screened for their biological effects in order to obtain more information on the possible structural features of HMW lignin-related effects. The studied compounds were both commercial and in-house extracted lignin derivatives. Bioassays used include reverse electron transport (RET), Vibrio fischeri, Daphnia magna, and juvenile rainbow trout (Oncorhynchus mykiss) hepatocytes. The studied lignin derivatives inhibited the in vitro systems and luminescence of V. fischeri bacteria to some extent-daphnids were not affected. It seems that, at least in the RET assay, certain pH-dependent functional groups in lignin may be of importance regarding the biological effects.

Long-range atmospheric transport of three toxaphene congeners across Europe. Modeling by chained single-box FATEMOD program.

BACKGROUND, AIMS, AND SCOPE: Since toxaphene (polychlorocamphene, polychloropinene, or strobane) mixtures were applied for massive insecticide use in the 1960s to replace the use of DDT, some of their congeners have been found at high latitudes far away from the usage areas. Especially polychlorinated bornanes have demonstrated dominating congeners transported by air up to the Arctic areas. Environmental fate modeling has been applied to monitor this phenomenon using parallel zones of atmosphere around the globe as interconnected environments. These zones, shown in many meteorological maps, however, may not be the best way to configure atmospheric transport in air trajectories. The latter could also be covered by connecting a chain of simple model boxes. We aim to study this alternative approach by modeling the trajectory chain using catchment boxes of our FATEMOD model. Polychlorobornanes analyzed in biota of the Barents Sea offered one case to study this modeling alternative, while toxaphene has been and partly still is used massively at southern East Europe and around rivers flowing to the Aral Sea. MATERIALS AND METHODS: Pure model substances of three polychlorobornanes (toxaphene congeners P26, P50, and P62) were synthesized, their environmentally important thermal properties measured by differential scanning calorimetry, as evaluated from literature data, and their temperature dependences estimated by the QSPR programs VPLEST, WATSOLU, and TDLKOW. The evaluated property parameters were used to model their atmospheric long-range transport from toxaphene heavy usage areas in Ukraine and Aral/SyrDarja/AmuDarja region areas, through East Europe and Northern Norway (Finnmarken) to the Barents Sea. The time period used for the emission model was June 1997. Usual weather conditions in June were applied in the model, which was constructed by chaining FATEMOD model boxes of the catchment's areas along assumed maximal air flow trajectories. Analysis of the three chlorobornanes in toxaphene mixtures function as a basis for the estimates of emission levels caused by its usage. High estimate (A) was taken from contents in a Western product chlorocamphene and low estimate (B) from mean contents in Russian polychloroterpene products to achieve modeled water concentrations. Bioaccumulation to analyzed lipid of aquatic biota at the target region was estimated by using statistical calculation for persistent organic pollutants in literature. RESULTS: The results from model runs A and B (high and low emission estimate) for levels in sea biota were compared to analysis results of samples taken in August 1997 at Barents Sea. The model results (ng g(-1) lw): 4-95 in lipid of planktovores and 7-150 in lipid of piscivores, were in fair agreement with the analysis results from August 1997: 21-31 in Themisto libellula (chatka), 26-42 in Boreocadus saida (Polar cod), and 5-27 in Gadus morhua (cod) liver. DISCUSSION: The modeling results indicate that the application of chained simple multimedia catchment boxes on predicted trajectory is a useful method for estimation of volatile airborne persistent chemical exposures to biota in remote areas. For hazard assessment of these pollutants, their properties, especially temperature dependences, must be estimated by a reasonable accuracy. That can be achieved by using measurements in laboratory with pure model compounds and estimation of properties by thermodynamic QSPR methods. The property parameters can be validated by comparing their values at an environmental temperature range with measured or QSPR-estimated values derived by independent methods. The chained box method used for long-range air transport modeling can be more suitable than global parallel zones modeling used earlier, provided that the main airflow trajectories and properties of transported pollutants are predictable enough. CONCLUSIONS: Long-range air transport modeling of persistent, especially photo-resistant organic compounds using a chain of joint simple boxes of catchment's environments is a feasible method to predict concentrations of pollutants at the target area. This is justified from model results compared with analytical measurements in Barents Sea biota in August 1997: three of six modeled values were high and the other three low compared to the analysis results. The order of magnitude level was similar in both modeled (planktovore and piscivore) and observed (chatka and polar cod) values of lipid samples. The obtained results were too limited to firm validation but are sufficient to justify feasibility of the method, which prompts one to perform more studies on this modeling system. RECOMMENDATIONS AND PERSPECTIVES: For assessment of the risk of environmental damages, chemical fate determination is an essential tool for chemical control, e.g., for EU following the REACH rules. The present conclusion of applicability of the chained single-box multimedia modeling can be validated by further studies using analyses of emissions and target biota in various other cases. To achieve useful results, fate models built with databases having automatic steps for most calculations and outputs accessible to all chemical control professionals are essential. Our FATEMOD program catchments at environments and compound properties listed in the database represent a feasible tool for local, regional, and, according our present test results, for global exposure predictions. As an extended use of model, emission estimates can be achieved by reversed modeling from analysis results of samples corresponding to the target area.

Sulfur organic compounds in bottom sediments of the eastern Gulf of Finland.

BACKGROUND, AIMS AND SCOPE: Despite the large number of studies on the forms of sulfur in marine deposits, investigations on sulfur organic compounds are still rare. It is known that the processes leading to formation of intermediate and final sulfur compounds (including organic ones) in modern deposits are the results of microbiological transformation of sulfur containing proteins, as well as the microbiological reduction of sulfate ions. The latter are finally reduced by anaerobic sulfate-reducing bacteria to H2S, HS- and S2-; the total sum of these is referred to as 'hydrogen sulfide' in chemical oceanography. Further, the formation of reduced sulfur organic derivatives (sulfides and polysulfides) is the result of interaction of the organic substance destruction products with the sulfide ions. In such cases, the main source of organic substances, as well as sulfates for the sulfur reducing processes, is the pore water in the sediments. The choice of the target of our study is based on the fact that the eastern part of the Gulf of Finland water area receives the bulk of the anthropogenic load of the St. Petersburg region. Low vertical intermixing of the water thickness is observed there (thus creating a deficiency of oxygen near the bottom), and the bottom sea current transfers the polluted salty water of the Baltic Sea into the Neva Bay. The whole of the above are the preconditions for the formation of sulfur-bearing organic compounds. A great number of bottom sediment samples for analytical surveys were collected in the Eastern Gulf of Finland during research expeditions in the years of 1997 and 2001. These were screened for structures of sulfur organic microcontaminants, including organic forms of sulfur, using advanced instrumentation and experienced personnel in our two, cooperating laboratories. This work is a part of the research being carried out on organic micro-admixtures present in bottom sediments, and is the summary of our findings on previously unstudied sulfur organic substances there. MATERIALS AND METHODS: A number of sulfur organic compounds present in nineteen bottom sediment samples from the Eastern Gulf of Finland (EGF) were characterized by high performance gas chromatography connected to low and high resolution mass spectrometers (GC/LRMS and GC/HRMS). The structure screening was carried out as compared with literature and library mass spectra, and taking the GC retention times into account. In the cases of an absence of mass spectra not in the literature, interpretation of the most probable structures was performed with the help of high resolution mass-spectrometric data, fragmentation rules for sulfur-bearing organic substances and ICLU simulation of spectra. These data were registered to form a conclusive 'fingerprint' for identification and confirmation of the structure of each novel compound found, e.g. by later syntheses of authentic model compounds. The relative contents of sulfur organic compounds were determined from MS response ratios of each compound to 2-fluorine naphthalene (internal standard). RESULTS: This paper is a completion of work, which has been published in part as three papers in the European Journal of Mass Spectrometry. As the total study result, 43 sulfur-bearing compounds were characterized. The mass spectra of 20 of them were found in the literature. The most probable structures for the 23 compounds whose mass-spectra were not available in the literature data were proposed. All of those 23 compounds were detected in bottom sediments for the first time, and 5 of them were described as originating from plants or being generated by chemical synthesis products, while the remaining 18 substances were previously unknown. The structures of these were deduced to be most probably the following (in order of their GC retention): dichloromethyl thiylsulfenylchloride, chloromethyl dichloromethyl disulfide, 3,4-dithiacyclohexene, 1,2,4-trithiacycloheptane, 1,2,3-trithiacyclohexane, tetrathiacyclopentane, 3,4,5-trithiacyclohexene, 1,2,4-trithiacyclohexane, cyclopropylhydrotrisulfide, 1,2-dithiane-3-thiol, 1,3-dithiane-2-thiol, bis(trichloromethyl)-tri-sulfide, 1,2,4,5-tetrathiacyclohexane, 1,2,3,4-tetrathiacycloheptane, 1,2,3,4-tetrathiacycloheptane, 1,2,3,4-tetrathia-cyclo-hexane, pentathiacyclohexane, and 1,2,4,6-tetrathiacyclooctane. The highest amounts of sulfur organic compounds were found in the deepest, bottom areas in the open part of the sea, where the salinity was highest, and oxygen deficiency occurred as well. Also, some coastal places with a high solid matter deposition rate had elevated contents of sulfur organic compounds. DISCUSSION: From the 43 sulfur organic compounds found, the HRMS data provided the atomic composition of the molecular ions for 16 compounds with a high confidence (see Table 3). The LRMS spectra could be identified with catalogue or literature spectra in 29 cases. The MS information obtained was insufficient in two cases: 1) The obvious molecular ion (at m/z 110) of compound 1 was not visible in LRMS. 2) For compound 43, the HRMS measurement, due to the low intensity (2%) of the molecular ion (m/z 210), could not exclude the presence of 2 oxygen atoms (instead of one sulfur atom) in the molecule. Major fragments, however, of our 43, certainly contained no oxygen atoms according to HRMS. The limited LRMS data in the literature, for an isomer of 43, had m/z values of all fragments different from those of the compound found by us. The retention times (RT) formed one more evidence for identity between compounds in different samples. The use of different non-polar columns in GC and similar, but not identical, temperature programs produced eluted peaks of novel and known compounds in each sample (mixture) in GC/HRMS and GC/LRMS. These gave sets of RTs which were in a very significant linear correlation (measured example R = 0.999866, p = 1.85E-06, N = 5). Therefore, the RTs in the HRMS analysis systems could be converted to values comparable with those from the LRMS device. The RT values, HRMS m/z values, LRMS spectra, and ICLU simulation results for each organic sulfur compound form an identification 'fingerprint'. The interpretation of these experimental data, with supporting use of fragmentation rules, allow the giving of a provisional name and structure to the 'suspect'. In this study and in environmental surveys of micropollutants in general, the compounds suspected of anthropogenic or natural origin occur at low levels in complex mixtures. Therefore, no bulk amount of an authentic, pure model substance for the suspect is available quite often. The most probable name and structure from the fingerprint data are very useful in guiding the preparation of the model substance for a conclusive identification. Similarly, the unknown criminal can be identified in advance by forensic science and his fingerprint, DNA, etc. as registered before the arrest. The analogy can be found in the literature and CAS register of organic polysulfides, which in great part consists of the results of sensitive mixture analysis methods. CONCLUSIONS: Sediment of the Eastern Gulf of Finland is over large areas anaerobic, as indicated by the existence of novel, non-oxygenated sulfur organic microcontaminants. These substances were most abundant in anoxic and saline, deep bottom regions, and, in addition, in one coastal area near industrial discharges. This occurrence, and also the limited information about sulfur organic compounds in scientific literature, is considered evidence for the dominantly natural processes in their formation. RECOMMENDATIONS AND PERSPECTIVES: The importance and necessity of investigating the sulfur organic compounds in the bottom sediments, result from the fact that their presence can be an indicator of stable anaerobic processes. Similarly, the oxygen disappearance (anoxia) in the marine water, due to a high concentration of the sulfate ions and relatively high content of organic matter, is practically always connected with the appearance of hydrogen sulfide and sulfides. The generation of sulfur organic compounds precedes the formation of the new, or expansion of the existing anaerobic ('hydrogen sulfide') zones, which lead to such environmental disasters as mass destruction of hydrobionts. Many organic compounds of sulfur, including sulfides and polysulfides, are toxic to the aquatic organisms. Therefore, in addition to the danger of mass wholesale deaths of marine fauna in the bottom sediments region, there exists a probability of secondary pollution of the water thickness as well, due to the entry of those substances from bottom sediments in the water when the environmental conditions are changed (stormy weather, floods, geological activity of the earth's crust, etc.).

POPs and organic polysufides in sediments of Lake Ladoga.

The study included one station close to a pollution source (depth 59 m) and another far from polluted areas (depth 40 m). Samples were analysed for organic chlorine, bromine and sulfur compounds. Samples taken with a corer were sliced to the layers of 0-1, 1-4, 4-7 cm etc. down to the depth of 34 cm. The dating was made with two independent methods, the 210Po method and with the soot particle counting method. The analyses were made with a multiresidue method. Gas chromatography was connected to low resolution mass spectrometry (LRMS) or to high resolution mass spectrometry (HRMS). A different extraction was applied to screen the possible occurrence of polysulfides. Typical chlorophenol and chlorohydrocarbon traces from chlorobleaching of pulp were non-detectable. Also PCDDs, PCDFs, PCBs and various organochloride pesticides, fire retardant residues PBDEs, PBDDs and PBDFs and polychlorinated phenyl salicylates were not detected. Instead, methylated dibenzothiophenes Me-DBTs and Di-Me-DBTs, typical traces of oil based defoamers used in e.g. paper mills were found in the surface layers of the polluted site. Polysulfides were analyzed from layers representing years 1955-1970 from the polluted site. The structures of five congeners were according to GC/MS dimethyl trisulfide, 1,2,3,4-tetrathiepane, pentathiane, 1,2,3,4-tetrathiane and 1,2,4,5-tetrathiepane. Many of the analyzed pollutants have not been reported earlier from Lake Ladoga. The only positive observations were from oil-based defoamers used in paper mills, and from polysulfides, which are either of natural origin or indicate a discharge in the 1950s and 1960s. Owing to the large spreadout and dilution, the concentrations are low even at moderate distances from the pollution centers.

Multivariate statistics of the pyrolysis products of high molecular components in pulping wastewaters to explain their toxicity.

BACKGROUND, AIM AND SCOPE: At present, large-scale paper manufacture involves delignification and bleaching by elemental chlorine free (ECF), or totally chlorine free (TCF) processes. The wastewater is purified by secondary treatment (mechanical, chemical and biological) which removes most of the toxic substances from the discharge. However, we found residual toxicity in the high molecular (> 1000 D) matter (HMWM) of the discharge by test of the RET (reverse electronic transfer) inhibition. This fraction consists mainly of polydispersed lignin (LIG) and carbohydrate (CH) macromolecules. Structural units in these molecules are studied by pyrolysis gas chromatography/mass spectrometry (Pyr-GC/MS). In the present work, our aim was to find out those structural units which could explain the RET toxicity of LIG or CH molecules. We compared statistically RET toxicity values of the HMWM samples from treated wastewaters of pilot pulping experiments and intensity variation of the pyrolysis product gas chromatograms of these samples. This application is a novel study procedure. METHODS: Pyrolysis products (Py-GC/MS results) and inhibition of RET (reverse electronic transport toxicity) as TU50 and TU20 of HMWM (High Molecular Weight Material; Mw > 1000 D) were compared by multivariate statistics. The samples were from laboratory pilot stages of TCF (Totally Chlorine Free) and ECF (Elemental Chlorine Free) manufacture of softwood pulp. Py-GC/MS was done without and with the addition of TMAH (Tetra Methyl Ammonium Hydroxide). The name and structure of each abundant fragment compound was identified from its retention time and mass spectrum compared to authentic reference compounds or literature. Four sets of Toxicity Units (TUs) and GC peak areas of the pyrolysis fragments were obtained. The data were normalized by division with LIG (lignin content of each sample). TU values were dependent and the fragment values independent (explanatory) variables in statistical treatments by SPSS system. Separate analyses of correlations, principal components (PCA) and stepwise multiple linear regression (SMLR) were performed from the four sample sets TCF and ECF with and without TMAH. RESULTS AND DISCUSSION: From the CH fragments, 2-furfural in TCF, and from the LIG fragments, styrene in ECF showed the highest probabilities of originating from source structures of toxicity. Other possible compounds in concern were indicated to be CH fragment 2-methyl-2-cyclopenten-1-one in ECF and LIG fragments 2-methoxy-4-methylphenol, 4,5-dimethoxy-2-methylphenol and 2-methylphenol in TCF.

A wood preservative metabolite in river water.

A previously unknown pollutant in river water was identified to be 2-mercaptobenzothiazole (2-MBT) by interpretation and simulation of its GC/LRMS spectrum. Further GC/HRMS measurement of the isotope composition of the molecular ion verified this structure. 2-MBT is a well-known agent for corrosion inhibition and a stable metabolite of several other benzothiazoles. The present 2-MBT trace was most probably a metabolite of the wood preservative TCMTB which leaked from an upstream sawmill. The metabolite had been detected earlier in urine of the sawmill workers, but now was identified in the recipient water environment for the first time.

Mass spectrometric identification of cyclic polysulfides in sediment of the Eastern Gulf of Finland. I.

Structures of six cyclic polysulfides, previously unknown as organic environmental pollutants, were analyzed from a sediment sample from the Eastern Gulf of Finland. The determinations were done by gas chromatography connected to mass spectrometry. High resolution (HRMS) measurements of the isotopic composition of four compounds could be done to confirm their molecular formulae. Total low resolution (LRMS) spectra were used to elucidate structures of all six compounds by thermochemical approach, application of fragmentation rules and by ICLU simulation of the spectra. The compounds were deduced to be (in the order of GC- retention) 1,2,4-trithiacycloheptane, tetrathiacyclopentane, 1,2,4,5-tetrathia-cyclohexane, 1,2,3,4- tetrathiacycloheptane, 1,2,3,4-tetrathiacyclohexane and 1,2,4,6-tetrathiacyclooctane.

Mass spectrometric identification of cyclic polysulfides in sediment of the Eastern Gulf of Finland. II.

Nine polysulfides, previously unknown as environmental organic pollutants, were analyzed from a sediment sample from the Eastern Gulf of Finland. The determinations were done by gas chromatography connected to low- and high-resolution mass spectrometers. The structure of the polysulfides was elucidated by determination of isotopic composition of abundant molecular and fragment ions by high-resolution mass spectrometry (HRMS), the interpretation of ion structures in low-resolution mass spectra (LMRS) using the thermochemical approach, the application of fragmentation rules and performing the ICLU simulation of abundance of ions in isotope clusters. Seven compounds were known in literature, but mass spectra were reported for only two of them, both recorded from mixture. Struture evaluation was successful for other substances, but not for the substance(s) in first eluting GC peak, where HRMS date were not obtained. Suggested structures of the cyclic compounds were (in the order of GC retention) 3,4-dithiacyclohexene, 1,2,3-trithiacyclohexane, 3,4,5- trithiacyclohexene, 1,2,4-trithiacyclohexane, cyclopropyl hydrodisulfide, 1,2-dithiole-3-thione and 1,2,3,4,5-penta- thiacyclo-octane. One acyclic congener identified was dimethyl tetrasulfide.

Polybrominated methoxy diphenyl ethers (MeO-PBDEs) in fish and guillemot of Baltic, Atlantic and Arctic environments.

Arctic cod liver samples from Vestertana Fjord at the Arctic coast of Norway, salmon and guillemot samples from the Baltic Sea and the Atlantic Ocean, and salmon and lamprey larva samples from Kymijoki River in southern Finland were analysed for the occurrence of tri-, tetra- and pentabromomethoxy diphenyl ethers and their concentration levels were estimated. These compounds have previously been identified by other research groups in salmon, seal and dolphin samples. The aim of this study was to find out a possible temporal trend in the concentrations of these compounds in the cod liver samples from years 1987-1998 and to investigate the possible spatial differences in the concentrations in biota samples from the Baltic Sea, Atlantic Ocean, Arctic Sea and contaminated freshwater river. Two most abundant methoxy-tetrabromo diphenyl ether congeners occurred in the same statistically significant ratio in 14 sea biota samples. Levels in lamprey larvae were below detection limit. The origin of these methoxylated bromodiphenyl ethers in biota samples remained unknown. They may be metabolites of polybrominated diphenyl ethers used as flame retardants or compounds of natural origin.

Screening of halogenated aromatic compounds in some raw material lots for an aluminium recycling plant.

Four samples of scrap raw materials for an aluminium recycling plant were screened for the occurrence of persistent halogenated aromatic compounds. The samples contained waste from handling of electric and electronic plastics, filter dust from electronic crusher, cyclone dust from electronic crusher and light fluff from car shredder. In our screening analyses, brominated flame retardants were observed in all samples. Polybrominated diphenyl ethers (PBDE) were identified in all samples in amounts of 245-67450 ng/g. The major PBDE congeners found were decabromo- and pentabromodiphenyl ethers. 1,1-bis(2,4,6-tribromophenoxy)ethane, hexabromobenzene, ethyl-pentabromobenzene, tetrabromobisphenol-A, pentabromotoluene and dimethyl tetrabromobenzene were observed in all scrap samples. The concentrations of PCBs, PCNs (polychlorinated naphthalenes) and nona- to undecachlorinated terphenyls in some of these scrap samples were remarkably high.

Isolation and identification of intermediates from biodegradation of low chlorinated biphenyls (Delor-103).

Microorganism Pseudomonas species P2 metabolizes polychlorinated biphenyls (PCBs) and biphenyl, producing the whole spectrum of intermediates, among them coloured intermediates, which are suitable for the monitoring of PCBs degradation by optical sensors. Knowledge of chemical structures and conditions of development of colour metabolites is necessary for application of optical analytical methods. The main goal of this work was the isolation and identification of intermediates from the biodegradation of the mixture of low chlorinated biphenyls (Delor-103), which is based on the solid phase extraction (SPE) of the whole mixture using LiChrolut EN cartridges, then silylation of the extract as one way to the identification of one part of intermediates by GC-MS, and acetylation of the extract as a way for the further concentration and analysis of more polar chlorobiphenylols and chlorobiphenyldiols. The combination of SPE and following acetylation allows to obtain chlorobiphenylols and chlorobiphenyldiols as an almost pure fraction. The acetylation method could be also used instead SPE procedure with the same final concentration effect. Using the simulation mass spectrometry program, two new compounds, dihydrodihydroxytrichloro- and tetrahydrodihydroxytrichlorobiphenyl, as silylderivatives, were identified.

Similarities in bioaccumulation patterns of polychlorinated dibenzo-p-dioxins and furans and polychlorinated diphenyl ethers in laboratory-exposed oligochaetes and semipermeable membrane devices and in field-collected chironomids.

Sediment and chironomid samples were collected from a river in the vicinity of and downstream from a closed chlorophenol production plant, and they were analyzed for polychlorinated dibenzo-p-dioxins and furans (PCDD/F) and polychlorinated diphenyl ethers (PCDE). Bioaccumulation of these compounds from the sediments by the oligochaeta, Lumbriculus variegatus, and semipermeable membrane devices (SPMDs) was studied in a 28-d bioaccumulation test. The sum concentrations of PCDD/Fs and PCDEs in sediments varied spatially, peaking at the site below the production plant, but the congener composition remained fairly constant throughout the river. The sum concentrations of chironomids, oligochaetes, and SPMDs all varied independently of sediment concentrations. Both invertebrates accumulated more PCDEs, whereas PCDD/Fs dominated in sediments and SPMDs. Despite the variable sum concentrations, similarities were observed in concentrations and compositions of individual congeners. A significant correlation was found between sediments and oligochaetes, and between oligochaetes and chironomids, for both PCDD/Fs and PCDEs. These results suggest that bioaccumulation of PCDD/Fs and PCDEs in invertebrates is nonselective. Furthermore, the laboratory bioaccumulation tests seem to yield relevant results. The SPMDs were found to give good predictions of the PCDD/F concentrations of sediments and oligochaetes. For PCDEs, the estimates were slightly poorer, but still useful for preliminary concentration assessments.

Bioavailability of sediment-associated PCDD/Fs and PCDEs: relative importance of contaminant and sediment characteristics and biological factors.

Factors that determine accumulation of sediment-associated polychlorinated dibenzo-p-dioxins and furans and polychlorinated diphenyl ethers into semipermeable membrane devices (SPMDs) and benthic oligochaete worms (Lumbriculus variegatus) were examined. These factors included both physical-chemical and structural characteristics of the contaminants (water solubility, lipophilicity, dipole moment, molecular size, and conformation) and sediment characteristics (organic carbon content, particle size, aromaticity, and polarity of organic carbon). The results of partial least squares regression analysis indicated that lipophilicity alone is not a sufficient predictor for contaminant bioaccumulation potential, even though it is a significant contributor. It was shown that contaminant molecular size and conformation (specifically planarity/nonplanarity) as well as sediment characteristics also have a significant role. The studied factors contributed up to 63-88% of the variation in accumulation data for SPMDs and 50-65% for oligochaetes. Comparison of (bio)accumulation factors (BAF28d for oligochaetes and AF28d for SPMDs) revealed that accumulation of contaminants in oligochaetes is largely influenced by biological factors (e.g., feeding habits), while the physical-chemical nature of the process is emphasized for SPMDs.

Analyses of known and new types of polyhalogenated aromatic substances in oven ash from recycled aluminium production.

Persistent aromatic bromine, chlorine and mixed chlorine-bromine compounds were analysed from recycled aluminium smelter (ALS) ashes to explore the impact of brominated flame retardants (BFR) on their formation. Polybrominated diphenyl ethers (PBDE) were the most abundant original BFRs found. Induction furnace ash contained tetra- to octa-BDEs about 2000ng g(-1) in similar congener ratios as the original scrap, but contents of nona- and deca-BDEs were only 25 and 5ng g(-1) indicating their significant degradation in ALS process. In the most non-polar fraction, PCB levels and profiles were similar as earlier ALS ash samples in 1990s. The highest PCB level measured was that of deca-CB (450ng g(-1)) in the induction furnace ash. In this fraction, bromo compounds were non-detectable (<5ng g(-1)). Fraction of the most polar compounds (from reversed toluene elution of carbon column ("dioxin fraction") contained PCDDs, PCDFs and polychlorinated dibenzothiophenes (PCDTs) in similar amounts and congener profiles as earlier investigated ALS ash samples. Bromine-containing dioxin and furan congeners were not detected. From individual PCDDs and PCDFs, octaCDF was the most abundant (205ng g(-1)) in induction furnace ash. In this fraction, the original BFR, tetrabromo-bisphenol-A, was identified. Its level in the induction furnace ash was approximated to be 388ng g(-1). In addition, 12 novel brominated and chlorinated compounds were found as abundant (8-441ng g(-1) in the induction furnace ash) contaminants from the fraction. Four of them were bisphenol derivatives, five biphenylols, then octachlorofluorenone (OCFL) and octachlorobiphenylene (OCBP). Their structures or structure types were deduced from total low-resolution EI mass spectra by theoretical isotope cluster simulation (ICLU) and through known fragmentation rules.

Temperature dependent properties of environmentally important synthetic musks.

Environmental fate determining physical properties including their temperature dependence for five nitro musks and for seven polycyclic musks were estimated. The properties evaluated were vapor pressure in a solid and liquid state (PS and PL), solubility in water (S), Henry's law coefficient (H = PL/S) and log octanol-water partition coefficient (log KOW). Gas chromatography for starting values of vapor pressure estimation and HPLC experiments at 5-20 degrees C for comparison of the theoretical versus experimental solubilities in water were performed. The values of temperature (T) dependence coefficients (Ai and Bi) in equations: log (Property)i = Ai - Bi/T were determined. Values of properties were compared with literature-based data, and an example of their use in environmental hazard estimation by fate modeling was given.