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

2004

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-…

Comparison of extraction methods for polycyclic aromatic hydrocarbon determination in sediments

1990

Different sample preparation methods for the determination of polycyclic aromatic hydrocarbons (PAHs) in lake and river sediments were compared and evaluated. Freeze‐dried sediment materials were e...

Chlorinated dioxins and dibenzothiophenes in fly ash samples from combustion of peat, wood chips, refuse derived fuels and liquid packaging boards

1995

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…

Bioaccumulation of dioxins, coplanar PCBs, PCDEs, HxCNs, R-PCNs, R-PCPHs and R-PCBBs in fish from a pulp-mill recipient watercourse

1993

Abstract Pike, perch and lake bream from the river Kymijoki were analyzed by gas chromatography/mass spectrometry (GC/MS) for toxic polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), hexachlorinated naphthalenes (HxCNs), non-ortho substituted polychlorinated biphenyls (coplanar PCBs) and alkylchloroaromatics of pulp mill origin. In most fish, the only congener of PCDD/PCDFs found was 2,3,7,8-TeCDF (

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant

1995

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…

Methods for the Identification of Tainting Terpenoids and other Compounds from Algae

1992

Off-flavour compounds produced by algae in freshwater ecosystems were studied for their structure using integrated sensory and spectroscopic methods: mass spectrometry (MS), nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR). Both solvent extraction and thermal desorption were used to isolate and to introduce the compounds into gas chromatography/mass spectrometry (GC/MS) and gas chromatography/Fourier transform infrared (GC/FTIR) systems. Ten ng of a terpenoid compound gave a readable IR spectrum. For 1H NMR studies the compounds were collected directly into NMR solvent by preparative gas chromatography. About 5 µg of a monoterpenoid compound was needed for a reliable 1…

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

2003

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…

Chlorinated and methylated dibenzothiophenes in sediment samples from a river contaminated by organochlorine wastes

2001

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…

Recent Development in Analytical Methods for Identification of Off-Flavour Compounds

1983

The best resolution of individual off-flavour compounds is achieved by glass or quartz capillary gas chromatography. A special two-column system was used by which simultaneous instrumental detection and sniffing (odour desorption) of odorous compounds could be done. The measuring detectors were flame ionization (FID), electron capture (ECD), flame photometric (FPD) and a mass spectrometer (MS). Structural assignments of the odorous substances were done from MS data and verified by model compounds. Before the GC run the sample was collected at the head of the double column using a cold trap device. The sample for analysis was injected in liquid form or, more efficiently, thermally desorbed f…

Gas chromatographic study of acetyl derivatives of chlorinated 4-hydroxybenzaldehydes

1982

The GC retention times of 4-hydroxybenzaldehyde and its chloro derivatives have been measured on three nonpolar capillary columns. Multiple linear regression analysis has been used to explain the mobility of chlorinated compounds relative to the reference compound 4-hydroxybenzaldehyde. The most important effects have shown to be due to the number of chlorine atoms and the substituents ortho to the formyl group. Other effects have also been observed but found to be unable to explain the GC data.

Gas chromatographic-mass spectrometric analysis of chlorinated phenoxyphenols in the technical chlorophenol formulation ky-5′

1984

Abstract The content of polychlorinated phenoxyphenol (PCPP) impurities in the technical chlorophenol formulation Ky-5 (wood preservative) was studied. The phenolic fraction was shown to contain predioxins and isopredioxins, the structures of the components being verified by gas chromatography mass spectrometry of non-derivatized, methylated and acetylated fractions. 2,6-Dichloro-4-(2,4,6-trichlorophenoxy)phenol and 2,6-dichloro-4-(2,3,4,6-tetrachlorophenoxy)phenol were identified by the comparison of their retention times and the mass spectra of their methyl and acetyl derivatives with those of authentic specimens. The amounts of the above components in Ky-5 were ca. 0.8 and 0.2%, respecti…

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

1997

Abstract Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo- p -dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between

Chlorinated acetic and propionic acids in pine needles from industrial areas

1998

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

1993

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…

Analytical Methods of Off-Flavours in the Aquatic Environment

1988

Mass spectra of methoxychlorobenzenes (chloroanisoles)

1988

Electron impact mass of all 19 ring-substituted chloroanisoles have been investigated. The fragmentation pathways were elucidated with the aid of the 1st field-free region metastable ions. The greatest disparity between the spectra of the positional isomers is shown with the [M−CH 3 ] + and [M−CH 2 O] +• ions, i.e., the ortho and para isomers preferentially lose • CH 3 , whereas the meta isomers generally show both loss of • CH 3 and elimination of formaldehyde, the latter process being more dominant with the meta-monochloro and di- and trichloro isomers having two meta-chlorine atoms. Characteristic for all isomers is also the abundant M +• and [M−CH 3 −CO] + ions, the other fragmentation …

Alkylated dibenzothiophenes in pine needles from pulp and paper mill environment

1998

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.

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

2004

Abstract 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 e…

A new potential toxaphene congener: synthesis, GC/EI-MS study, crystal structure, NMR analysis, and ab initio calculations of 3-endo,5-endo-dichloro-…

2001

Abstract A new potential toxaphene congener 3- endo ,5- endo -dichloro-7,7-bis-chloromethyl-4-dichloromethyl-tricyclo[2.2.1.0 2,6 ]heptane 2 has been isolated from reaction mixture obtained by the chlorination of 2- exo ,10,10-trichlorobornane 1 . The X-ray structural analysis of 2 revealed an unusual tricyclic structure, where the two chlorine atoms occupying endo -positions are in close spatial proximity with each other and near to the neighbouring CHCl 2 group. Further, it revealed that the symmetry of the molecule is distorted. The 1 H and 13 C NMR spectra of 2 have been assigned by means of 1 H, 1 H d ouble- q uantum f iltered co rrelation s pectroscop y (DQF COSY), PFG 1 H, 13 C HMQC …

Chlorinated short chain aliphatic hydrocarbons in pine needles by purge and trap gas chromatography/mass spectrometry

1995

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.

Potential Off-Flavour Compounds from Chloro-Bleaching of Pulp and Chlorodisinfection of Water

1983

Chlorobleaching of pulp is the most important source of organochlorine pollutants in the Finnish aquatic ecosystems. Similar types of pollutants are formed during chlorodisinfection of water. The model compound approach employed in our laboratory has revealed the structures and amounts of pollutants formed and has made the interpretation and assay of individual organochlorine compounds in the environment possible. Tainting of fish near chlorination plants is frequently observed. Especially chlorinated phenols and anisoles (microbial metabolites of the former) are chlorination products which are known to have a strong odour and taste at very low concentrations. Other chlorinated products, wh…

The effect of chlorine substituent(s) on the primary loss of a methyl radical from chlorinated veratroles (1,2-dimethoxybenzenes)

1989

Structure and Sensory Analyses of Tainting Substances in Finnish Freshwater Environments

1988

GC/MS/SNIFF/TASTE methods have been used in Finland to identify the causes of three tainting problems in water and one in fish nets. Structure determination was often verified by comparison with authentic compounds. Algal growth was implicated to be the source of geosmin and MIB in river water in Northern Finland and was associated with the appearance of tainting problems in raw water and reservoir water in Åland county. Terpenoids (e.g. camphor), degradation products of natural lipids (e.g. aldehydes, ketones and unsaturated aliphatic compounds) and volatile organohalogen compounds were frequently found in contaminated water but showed minor tainting effects compared to geosmin and MIB. Di…

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

2003

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…

Gas chromatographic and mass spectrometric analysis of chlorinated catechols occurring in pulp bleach liquors

1982

Chlorination step (C-step), spent bleach liquor from a kraft pulp mill and the product from the chlorination of guaiacol in aqueous solution have been investigated for their content of chlorinated catechols. After separation the samples were derivatized with diazoethane and analysed by glass capillary gas chromatography with an electron capture detector. The external standard mixture of all ethylated chlorocatechols was used in the measurements. The structures of the compounds identified were confirmed by gas chromatography/mass spectrometry. Eight chlorinated catechols were identified from a sample prepared by chlorination of guaiacol with Cl2 in aqueous solution. However, only four of the…

Chlorophenanthrenes, alkylchlorophenanthrenes and alkylchloronaphthalenes in kraft pulp mill products and discharges

1994

Abstract Chlorinated phenanthrenes (PCPHs; P=1–5), alkylphenanthrenes (C4-PCPHs; P=1–3), dimethylnaphthalenes (C2-PCNs; P=1–4) and trimethylnaphthalenes (C3-PCNs; P=1–2) were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) in pulp, effluent and biosludge of two kraft pulp mills (mills 1 and 2). These compounds were indicated to be formed in the manufacture of both bleached hardwood and softwood kraft pulp. Different compound groups dominated in mill 1 samples compared to mill 2 samples. Differences between birch and pine pulp from mill 1 were observed for all substance groups but in mill 2 pulp only for PCPHs. The highest concentrations of PCPHs …

POPs and organic polysufides in sediments of Lake Ladoga

2007

Abstract 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 chloroph…

Identification of lipophilic pollutants discharged from a Finnish pulp and paper mill.

1998

Lipophilic organic compounds originating from kraft pulping and papermaking were identified by straight gas chromatography/mass spectrometry (GC/MS) analyses. Samples analyzed included a primary clarifier effluent (PE) and a secondary clarifier effluent (SE) from the activated sludge treatment plant of a Finnish ECF-bleached (Elementally Chlorine Free) kraft pulp and paper mill. Liquid-liquid extraction composition of PE was compared with solid phase extraction (SPE) and dialysis of a semipermeable membrane device (SPMD) exposed to PE. Dichloromethane extracts of particulate material isolated from PE, sludges from both the primary and secondary clarifier, a sediment collected in the vicinit…