0000000000016526
AUTHOR
Seija Sinkkonen
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-…
Polychlorinated organic compounds in the Arctic cod liver: trends and profiles
Polychlorinated organic compounds (POCs) have been measured in Arctic cod liver from Vestertana Fjord for a period of 1987-1998. Significant decrease was observed for DDD (p = 0.043), alpha-HCH (p = 0.001), and gamma-HCH (lindane; p = 0.001). Contents of DDE, 2,3,7,8-tetrachlorodibenzofuran, PCBs, chlordanes, chloronaphthalenes, hexachlorobenzene and polychlorodiphenyl ethers had no significant trend. Contents of three hexa- and two heptachlorodibenzofurans and octachlorodibenzofuran increased slightly from 1987 to 1994, but then at very high rate from 1994 to 1998. Trends of HCHs, profiles of PCBs and levels of chlordanes are in accordance with atmospheric long range transport. The hexa-, …
PCDDs, PCDFs, PCDTs, PCBs and some other organochlorine compounds in pine needles exposed to pulp and paper mill emissions and effects of waste combustion on the concentrations
Concentrations of semivolatile chlorinated organic compounds α-HCH, lindane, HCB, DDT, DDE, DDD, chlordanes and PCBs, and low-volatility compounds PCDDs, PCDFs and PCDTs in pine needles in a recipient area of the emissions from a pulp and paper mill where also waste combustion was done were measured. Mostly, the concentrations were found to be near the background levels. Elevated concentrations of HCB, some PCB congeners and some HxCDF isomers in samples from two sampling points were observed. Some other possible point sources of these compounds are situated in the vicinity of the pulp and paper mill.. Also the community of Pietarsaari is one possible source of the slightly elevated concent…
Chlorinated and methylated dibenzothiophenes: Preparation of the model compounds and their analysis from some environmental samples
Abstract Polychlorinated and polymethylated dibenzothiophenes if occuring in the environment can cause environmental hazards and problems like chlorinated dibenzodioxins and dibenzofurans. Some chlorinated and methylated dibenzothiophenes have been synthesized to serve as model compounds in environmental and toxicological analysis. The synthesis mixtures and some environmental samples have been analyzed by high resolution GC/low resolution MS. This investigation showed that the concentrations of these compounds in environmental samples were below ppb level but it did not exclude the occurence of these compounds in our environment. More investigation is needed.
Chlorinated dioxins and dibenzothiophenes in fly ash samples from combustion of peat, wood chips, refuse derived fuels and liquid packaging boards
Abstract Peat, wood chips, refuse derived fuel and liquid packaging board in different combinations were burned at a temperature of at least 850 °C. Fly ash samples from these combustions were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzothiophenes (PCDBTs) by high resolution GC/MS. The concentrations of tri- and tetrachlorodibenzothiophenes and tri-, tetra- and pentachlorodioxins were highest when mixtures of wood chips and refuse derived fuel (RDF) were burned. The fly ash from the combustion of pure peat pellets did not contain any polychlorinated dibenzothiophenes. When wood chips and RDF were burned the concentrations of chlorinated compounds in fly…
Chlorinated phenolic compounds in coniferous needles. Effects of metal and paper industry and incineration
Abstract Pine needles were analyzed for their contents of chlorinated phenolic compounds. Altogether about 30 samples from surroundings of a metal scrap plant, a pulp and paper mill, a hazardous waste incinerator and reference samples outside of the immediate influence of these were analyzed by GC/ECD and GC/MS. Most phenolic compounds in the needles were found to be bound to the plant material and were not extractable as such by organic solvents. The concentrations of some bound chlorinated phenolic compounds were on level of 1–300 ng/g in dried needle. For many compounds the concentrations were remarkably higher in the three years old needles compared to the concentrations in the one and …
Environmental analysis of chlorinated aromatic thioethers, sulphoxides and sulphones
Abstract Chlorinated aromatic thioethers discussed here are polychlorinated dibenzothiophenes, thianthrenes and diphenylsulphides. Relatively little is known about their occurrence, behaviour and fate in the environment. Polychlorinated dibenzothiophenes and diphenylsulphides have recently been found to be formed in waste combustion and analysed in pulp mill effluents. Chlorinated sulphoxides and sulphones are usually metabolites or oxidation products of different chlorinated aromatic compounds. Different gas chromatographic-mass spectrometric techniques are used in the analysis of the chlorinated thioethers. The sulphoxides and sulphones, because of their higher polarity, can be isolated f…
Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant
Abstract Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant were analyzed by GC/ECD and GC/MS. Wax and the rest of the needles were analyzed separately. As a rule the concentrations of α-HCH (0.5–13.6 ng/g), γ-HCH (0.4–7.3 ng/g), HCB (0.2–3.4 ng/g), PCB congeners (0.2–67 ng/g), PCDDs and PCDFs were higher in the older needles. The ratio of the concentration in the wax to the concentration in the rest of the needles was higher in the younger needles. The concentrations of PCB congeners, TeCDDs and TeCDFs were higher in the needles collected in the area nearest to the plant. The samples, obviously, co…
SULFUR ANALOGUES OF POLYCHLORINATED DIBENZO-p-DIOXINS, DIBENZOFURANS AND DIPHENYL ETHERS AS INDUCERS OF CYP1A1 IN MOUSE HEPATOMA CELL CULTURE AND STRUCTURE-ACTIVITY RELATIONSHIPS
Three sulfur-containing compounds, 2,3,7,8-tetrachlorothianthrene (TCTA), 2,3,7,8-tetrachlorodibenzothiophene (TCDT), and 3,3[prime],4,4[prime]-tetrachlorodiphenyl sulfide (TCDPS), were analyzed for their CYP1A1-inducing potencies--measured as aryl hydrocarbon hydroxylase (AHH) and 7-ethoxyresorufin O-deethylase (EROD) activities--in mouse hepatoma cell culture Hepa-1. Marked differences in the induction potencies were observed among the three compounds studied and between 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and its sulfur analogue. The estimated EC50 values for TCDD, TCTA, and TCDT were about 8 pM, 700 pM, and 7.5 nM, respectively. TCDPS did not elicit any AHH/EROD induction. Compar…
Estimation of vapor pressures, solubilities and Henry's law constants of selected persistent organic pollutants as functions of temperature
Abstract An internally consistent set of temperature dependent physical-chemical property data was derived for 73 persistent organic pollutants, including polychlorinated biphenyls, diphenylethers, dibenzo-p-dioxins, and dibenzofurans, organochlorinated pesticides and polycyclic aromatic hydrocarbons. Measured data reported in the literature were expanded by different estimation and regression methods. Temperature dependent vapor pressures were estimated from relative gas chromatographic retention times and by a modified Watson equation. Temperature dependent water solubilities were estimated by equations based on mobile order theory modified from Ruelle and Kesselring. The temperature depe…
Analyses of known and new types of polyhalogenated aromatic substances in oven ash from recycled aluminium production
Abstract 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 2000 ng g −1 in similar congener ratios as the original scrap, but contents of nona- and deca-BDEs were only 25 and 5 ng 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-C…
Substituted Dibenzothiophenes I: Synthesis, Chromatography, Mass Spectrometry and Structure Elucidation by1H NMR Spectroscopy
Abstract Some polychlorinated and polymethylated dibenzothiophenes have been synthesized to serve as model compounds in environmental analysis. In order to obtain pure isomers, the synthesis mixtures have been fractionated with reversed-phase high performance liquid chromatography. In spite of a high sensitivity, mass spectrometry does not provide any reliable way to determine the precise structures of different isomers. Therefore, 1H NMR spectroscopy has been utilized as an aid in their analysis. The structures for two isomeric tetramethyldibenzothiophenes could be suggested on the basis of their 1H NMR spectra. Also some proposals for possible structures of two isomeric trimethyldibenzoth…
Chlorinated and methylated dibenzothiophenes in sediment samples from a river contaminated by organochlorine wastes
Eleven sediment samples from the lower Kymijoki River were analyzed for the occurrence of polychlorinated and polymethylated dibenzothiophenes (PCDT and PMeDTs). The area was heavily polluted by wastes from a pulp chlorobleachery and by leakage from a factory producing wood preservative chlorophenol formulation Ky-5. Levels in the sediments were from <5 to 400, 200 and 50 pg g-1 dw for tetra, penta and hexa-CDT, respectively. The concentrations of mono, di, tri and tetra-MeDTs were in the range of 1–5, 5–85, 5–500 and 15–2300 ng g-1 dw, respectively. PCDT contents in surface sediment (0–3 cm layers) decreased by distance downstream from the bleachery and Ky-5 factory similar to those of the…
Tetra- and pentachlorodibenzothiophenes are formed in waste combustion
Abstract Two different waste combustion samples have been analyzed for tetra- and pentachlorodibenzothiophenes. HRGC/HRMS with a resolution of 20 000 was used for identification. By resolution of 10 000 chlorinated dibenzo-p-dioxins and some unknown compounds gave GC/SIM peaks at the exact masses of the chlorinated dibenzothiophenes. These peaks were no more present by resolution 20 000. Several tetra- and pentachlorodibenzothiophenes were found in both samples. In the other one of the samples the concentrations were seemingly high although exact quantitative determination could not be done.
Liquid chromatographic determination of planar aromatic sulphur compounds in crude oil
Oxydation des dibenzothiophenes en sulfones et analyse par chromatographie liquide haute performance
Environmentally Relevant Properties of All 209 Polychlorinated Biphenyl Congeners for Modeling Their Fate in Different Natural and Climatic Conditions
The temperature dependence of physical properties and degradation lifetimes in the environment of all polychlorinated biphenyl (PCB) congeners (N = 209) were determined. For physical properties, the coefficients A and B in equations log(property) = A(property) − B(property)/T(K) were determined by thermodynamic and QSPR methods and compared with the results of independent methods in the literature. The coefficients Apl and Bpl for liquid state vapor pressure PL, As and Bs for solubility in water SW, Ah and Bh for volatility kH (or kH = PL/SW), and Aow and Bow for lipophilicity (KOW), stored in the database of the fate model program, allowed automatic temperature corrections for realistic fa…
Chlorinated acetic and propionic acids in pine needles from industrial areas
Abstract Concentrations of chlorinated acetic and propionic acids in pine needles from the surroundings of a pulp and paper mill and a metal reclamation plant were measured. Different ways of extraction and chromatographic separation were tried. Ultrasonic extraction with water of the powdered needles was found to be efficient. The acids were analysed as their pentafluorobenzyl esters with GC-ECD. The ECD sensitivity of the pentafluorobenzyl derivatives was good. The detection limit was below 1 ng/g for the chlorinated acetic and propionic acids. The concentrations of dichloroacetic acid and 2,2-dichloropropionic acid in fresh needles were on the 0–4 ng/g level. Monochloroacetic acid, 2-chl…
High-resolution gas chromatographic-mass spectrometric determination of neutral chlorinated aromatic sulphur compounds in stack gas samples
Abstract Four stack gas samples from waste incineration were analysed by high-resolution GC-MS for neutral chlorinated aromatic sulphur compounds such as polychlorinated dibenzothiophenes, thianthrenes and diphenyl sulphides. Samples were analysed tentatively also for some methylated derivatives of these compounds. The stack gas samples had earlier been found to contain some tri- and tetrachlorodiphenyl sulphides. Two of the stack gas samples contained tetra- and pentachlorodibenzothiophenes. One sample was strongly suspected to contain some tri- and tetrachlorothianthrenes in low concentrations. No methylated derivatives of these compounds could be found. Polychlorothianthrenes, some polyc…
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 proper…
Alkylated dibenzothiophenes in pine needles from pulp and paper mill environment
Abstract Concentrations of alkylated dibenzothiophenes (C n DBTs) in pine needles in a recipient area of the emissions from a pulp and paper mill where also waste combustion was done were measured. The concentrations (ng/g dry weight) of C 1 DBTs were in the range of 2 DBTs in the range of 3 DBTs in the range of 3 DBTs] > [C 2 DBTs] > [C 1 DBTs]. The pulp mill could not be shown to be the source of C 1 C 3 DBTs in the pine needles. Other possible sources are situated in the vicinity of the pulp and paper mill. Long-range transport, either, cannot be excluded as a possible source.
Chlorinated short chain aliphatic hydrocarbons in pine needles by purge and trap gas chromatography/mass spectrometry
The concentrations of volatile chlorinated short chain aliphatic hydrocarbons in pine needles have been measured using purge and trap GC/MS. The concentrations of dichloromethane, chloroform, dichloroethene and tetrachloroethene in the needles were calculated. The concentrations of dichloromethane and tetrachloroethene were highest. As a rule the concentrations were higher in the older needles. The needle samples were collected from five sampling points in an area situated in the Southern Finland in the vicinity of a metal scrab plant. Reference needles were collected in the Central Finland. Needles originated from years 1991, 1992 and 1993.
PCDTs in the environment
Abstract Polychlorinated dibenzothiophenes (PCDTs) are sulfur analogues of polychlorinated dibenzofurans. Recently, PCDTs have been found in stack gas and fly ash samples, pulp mill effluents, sediments and in some aquatic organisms. PCDTs have been analyzed by high resolution GC/MS and by other GC-MS techniques. Combustion is until now the major known source of PCDTs in the environment. Tri-, tetra- and pentaCDTs in concentrations approaching those of PCDTs have been analyzed in some samples from waste incineration and metal reclamation. Concentrations of PCDTs in pulp mill effluents have been found to be quite low. 2378-TeCDT was found to be the major TeCDT isomer in some pulp mill efflue…
Structural organic chemistry in ecotoxicology
Abstract Role of the methods of structural chemistry in assessment of the ecotoxic effects of organic compounds is described as examples of fate modeling based on structural properties, screening analyses of the affected population, use of model substances and various structure-specific determination methods. Case examples from literature are given and, in addition, structure screening and verification for a contaminant in herring is described.
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…
Estimation of the environmental hazard of organochlorines in pulp mill biosludge used as soil fertilizer
Abstract Contents of total organic chlorine and polychlorinated phenols, guaiacols, catechols, benzenes, cymenes, cymenenes, naphthalenes, toxic dibenzodioxins, toxic dibenzofurans, toxic PCB congener 77, alkylated dibenzofurans, alkylated bibenzyls and alkylated phenanthrenes in spent biosludges from activated sludge treatment plants of chlorobleaching kraft pulp mills are reported. Some estimations of hazard caused by these organochlorines to humans and wildlife from the use of biosludge as soil fertilizer are constructed and discussed.
Polychlorinated Dibenzothiophenes (PCDTs), Thianthrenes (PCTAs) and Their Alkylated Derivatives
Polychlorinated dibenzothiophenes (PCDTs) and polychlorinated thianthrenes (PCTAs) are interesting compounds due to their structural similarity with polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs). PCDTs are sulfur analogues of PCDFs and PCTAs are sulfur analogues of PCDDs. PCDTs and PCTAs are probably formed by processes similar to the formation of PCDFs and PCDDs. PCDTs were first detected in the environment in 1986. Since then PCDTs have been analyzed in samples from combustion and metallurgy, sediments, pulp mill effluents, and in aquatic biota. Combustion and metallurgy seem to be the major sources of PCDTs in the environment. PCDTs and PCTAs are ana…
Isolation of chlorinated dibenzothiophenes by high-performance thin-layer chromatography
Abstract Chlorinated dibenzothiophenes can cause environmental problems analogous to chlorinated dibenzodioxins and dibenzofurans. In the analysis of chlorinated dibenzodioxins by gas chromatography—mass spectrometry some unknown chlorinated compounds have been found. The chlorinated dibenzothiophenes have the same m/z values as the corresponding dioxins in low-resolution mass spectrometry and they are found in same planar aromatic compound fraction in alumina and carbon column chromatography. Some chlorinated dibenzothiophenes were synthesized to serve as model compounds in analytical work. High-performance thin-layer chromatography (TLC) with different plates and several eluents was tried…
Degradation half-life times of PCDDs, PCDFs and PCBs for environmental fate modeling.
Literature search of the knowledge on the degradation of persistent organic pollutants (POPs) in environmental compartments air, water, soil and sediment was done in purpose to find properties of POPs of interest for modeling. One degradation process, hydrolysis (chemical degradation), was omitted as negligibly slow for POPs studied. The other two, photolysis and biodegradation processes, were considered separately in purpose to develop estimation procedures. The estimates can be given as pseudo first-order rate constants kP for photolysis and kB for biodegradation. For each compartment, an overall degradation rate is k(tot) = kP + kB and lifetime t(1/2) = ln 2/k(tot). The latter values, li…