Tiina Rantio

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 dependence of Henrys law constants was estimated from the temperature dependence of both the vapor pressure and water solubility. The results are presented as intercepts A and slopes B of log-linear relationships of the type log property = A - B / T. Octanol-water partition coefficients of the same compounds at 25°C were also compiled and estimated. A comparison of the estimated data with literature values showed fair agreement. The estimated property values may serve as interim input values to models of the fate of persistent organic pollutants under variable climatic conditions.

The M74 syndrome of baltic salmon (Salmo salar) and organochlorine concentrations in the muscle of female salmon

Abstract Organochlorine concentrations in the muscle of female Baltic salmon (Salmo salar), ascending for spawning in the Simojoki River on the north-eastern coast of the Gulf of Bothnia from 1988 to 1992 are given in this paper in relation to reproduction success, monitored as viability of offspring. In spring 1992 and 1993 all the yolk-sac fry of 52 % and 75 % of the females, sampled in autumns 1991 and 1992 respectively, died due to the M74 syndrome, i.e., heavy mortality of yolk-sac fry (YSM). The TEOs of the most frequently detected polychlorinated dibenzofurans (PCDFs: 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF and 2,3,7,8-TeCDF) and those of coplanar PCBs (CB77, CB126 and CB169) were about twice as high in 1991 and 1992 than before; these substances either showed a significantly increasing time trend or then none at all. The principal component analysis (PCA) showed a strong connection between YSM and the contents of these toxic congeners. PCA also indicated a strong negative connection with YSM and the orange colour intensity of eggs and a weak positive connection with YSM and oxychlordane, hexachlorobenzene and 2,3′,4,4′5-pentachlorodiphenyl ether. The PCA results were supported by the observed significant negative Pearson correlations between egg colour and the contents of toxic PCBs and PCDFs as well as between egg colour and YSM. These compounds seemed not to have any connection to early embryonal mortality, whereas total PCB and DDT concentrations did show an association to that.

Chloroterpenes and other organochlorines in Baltic, Finnish and Arctic wildlife

Abstract Chloroterpene mixtures were analyzed as toxaphene (TOX) in Baltic, Finnish and Arctic fish, seal and bird samples together with DDT residues, hexachlorocyclohexanes (HCH), hexachlorobenzene (HCBz), chlordanes, hexachloronaphthalenes (HxCN), PCBs, PCDDs and PCDFs. TOX was found to be the most globally (evenly) distributed organochlorine compound in Scandinavia, thus far. TOX seemed to bioaccumulate significantly in fish but not in predatory birds in Finland.

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, contained tri- and tetrachlorodibenzothiophenes but these were not determined quantitatively due to interfering peaks in GC/MS.

Concentrations of persistent organochlorine compounds in spruce needles from Western Finland

Abstract Persistent organochlorine compounds in spruce needles from Western Finland, altogether 60 samples, were analyzed by GC/ECD and GC/MS. The distribution of α-HCH, lindane and hexachlorobenzene in the spruce needles was found to be uniform all over the area investigated. The concentrations of α-HCH were higher than the concentrations of lindane. In the PCB profiles, PCB-153 and PCB-138 dominated in all samples, the concentration of PCB-153 being remarkably higher than that of PCB-138. As a rule, the needles from the year 1991 contained these compounds in larger amounts than the needles from the year 1992. TeCDFs, PeCDFs, HexaCDFs, TeCDDs and PeCDDs in very low (pg/g) concentrations were detected in the pooled samples. The concentrations of the PCDFs were higher than the concentrations of PCDDs. The effect of the tree age on the concentrations of organochlorine compounds was riot observed.

Organic chlorine compounds in lake sediments. VI. Two bottom sites of Lake Ladoga near pulp mills

Abstract Chloride, total and extractable organically bound chlorine, chlorohydrocarbons, polychlorodibenzo-p-dioxins (PCDD) and polychlorodibenzofurans (PCDF) were measured in dated bottom sediment layers of two sites of the northern Lake Ladoga near pulp mills. Concentrations and annual depositions of pulp chlorobleaching products in Ladoga sediments were significantly lower than those in pulp mill recipient bottoms in Central Finland. However, typical chlorobleaching traces bound chlorophenolics, chlorocymenes and chlororetenes were readily identified. HCBz, HCHs and chlordanes occurred at low background levels like in Central Finland. In contrary, depositions of the DDT residues (4–16 μg m −2 a −1 ) and PCBs (7–19 μg m −2 a −1 ) at Ladoga were higher than the background levels in Finland (1 and 2 μg m −2 a −1 , respectively). PCB isomer pattern in Ladoga indicated a Russian origin. PCDD and PCDF were at low background levels. Their isomer patterns deviated from those of pulp mill effluent or common background. ECOTOXICITY of the sediments studied can be only very preliminarly estimated from the TEQ values (Tables 2 and 3). Bioaccumulation ratio from sediment to (zoobenthos) mussels (dw/fw) have been observed to be about one for PCDD/Fs and about ten for PCBs /21/. Consequently, the maximal TEQ level in exposed mussels from the surface sediment could be 37 and 35 pg/g (fresh weight). These levels have not been observed to cause any toxic effects to the animals, but they are of concern in food due to biomagnification. PCDDs and PCDFs are not, but PCBs are significant contributors to this concern.

Studies on toxaphene in the environment. II. PCCs in Baltic and Arctic Sea and lake fish

Abstract Chloroterpene mixtures identified with toxaphene (PCC) were analyzed in Baltic and Arctic salmon, trout and cod samples and compared with hexachlorocyclohexane (HCH), chlordane (SCHLOR), DDT and PCB residues. The highest PCC levels in fish were found in some samples from East Finland. Contents of PCCs in Arctic fish were at the same order as in Baltic fish. In contrary, HCH, SCHLOR, DDT and PCB levels were significantly higher in Baltic fish.

Chlorocymenes, cymenenes and other chlorohydrocarbons in pulp mill effluents, sludges and exposed biota

Abstract Polychlorinated cymenes (PCYMS) and cymenenes (PCYMD) were analyzed by GC/LRMS/SIM in effluents and sludges of three different pulp mills and in fish and mussels exposed to pulp mill effluents. The levels of PCYMS+PCYMD were 0.3–4.8 μg/l in total effluents,

Fate of pulp mill effluent compounds in a finnish watercourse

Chloroorganic chemicals emitted from the pulp and paper mill at nekoski in central Finland were monitored for several years. Concentration time series are used for evaluating the environmental fate and the applicability and validity of an exposure models. Fitted elimination rates of 3,4,5-Tri-, 4,5,6-Tri-, Tetrachloroguaiacol and 2,4,6-Trichlorophenol are approx. 0.22 d-1, or rather the half-lives are approx. 3 days. The elimination is most likely by biodegradation and transport-controlled. For 2,3,6-trichloro-p-cymene, fate simulations indicate significant volatilization and sedimentation. Good agreement is achieved with a one-dimensional steady-state box model, except for concentrations in fish. For a reliable assessment of environmental damage, laboratory experiments, monitoring and simulations need to be in tune.

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-chloropropionic acid and 2,3-dichloropropionic acid were not detected. Trichloroacetic acid could not be analyzed by this method.