Jaakko Paasivirta

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, lifetimes in each compartment, will be used as input parameters to the Baltic Sea model.

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.

Polychlorinated phenols, guaiacols and catechols in environment

Abstract Emissions, bioaccumulation and possible food chain enrichment of polychlorinated phenols, guaiacols and catechols have been studied by analyses of water, snow, ash, benthic animal, fish and bird samples in Finland. Seventeen individual compounds were analyzed using authentic reference model compounds and internal standard by GC/ECD. Although the enrichment potential of the studied compounds appeared to be lower than that of the chlorinated hydrocarbons, they proved to be very general pollutants and some of them showed specific bioaccumulation to certain species and high persistency thus forming environmental hazards.

Toxic significance of planar aromatic compounds in Baltic ecosystem — New studies on extremely toxic coplanar PCBs

Abstract Baltic salmon and white-tailed eagle samples have been analyzed for organochlorine compounds including polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, polychlorinated naphtalenes and toxic coplanar PCBs. In salmon, PCB and DDT residue contents were 0.2-0.3 ug/g in fresh muscle. Chlordanes, toxaphene, hexachlorobenzene, α-hexachlorocyclohexane and γ-hexachlorcyclohexane were found at 1 – 10 ng/g levels. Significant dioxin type of toxins found were only 2,3,7,8-tetrachlorodibenzofuran (45–81 pg/g) and 3,3′,4,4′-tetrachlorobiphenyl (638–1120 pg/g). Polychloronaphtalene contents in all salmon and eagle samples were of the same order of magnitude ranging from 4 to 85 ng/g. The highest chlorohydrocarbon contents in eagle samples were for PCB 462 ug/g, sum of the DDT residues 42 ug/g, chlordanes 5.7 ug/g and HCB 1.6 ug/g. In contrary, toxaphene, α-hexachlorocyclohexane and γ-hexachlorocyclohexane were not detected in eagles. Levels of polychlorodibenzo-p-dioxins, polychlorodibenzofurans and coplanar PCBs were highest ever reported in wildlife in adult eagle samples, in liver of a juvenile eagle and in eagle egg from South Finland ranging from 1 to 13 ng/g for PCDD/Fs and from 18 to 229 ng/g for coplanar PCBs. Calculation of the TCDD-equivalents of the contents gave that dioxin toxicity load comes in great excess from the coplanar PCBs, especially from 3,3′,4,4′,5-pentachlorobiphenyl.

Contamination of pike and sediment from the Kymijoki River by PCDEs, PCDDs, and PCDFs : contents and patterns compared to pike and sediment from the Bothnian Bay and seals from Lake Saimaa

Sediment and pike from Kymijoki River and Bothnian Bay were analyzed for contents of polychlorinated diphenyl ethers (PCDE), 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF), and non-ortho-substituted polychlorinated biphenyls (coplanar PCBs). Both sites are located in the vicinity of pulp mills. The same compounds were measured in a chlorophenol formulation Ky-5, which used to be used as a wood preservative, and in four ringed seals from Lake Saimaa and in one seal from Lake Baikal. Results of this preliminary study indicated that spills from the manufacture of Ky-5 in the past have contaminated Kymijoki River sediments with PCDEs, PCDDs, and PCDFs. The same PCDE congeners that dominated in these sediments were abundant in Ky-5, pikes from Kymijoki River, and seals from Lake Saimaa. The TEQs of PCDD/PCDFs in the Kymijoki River sediments varied from 0.04 to 59 ng/g dry weight. The contents of PCDE, PCDD, and PCDF compounds were low in sediments and pikes from the Bothnian Bay.

Transportation and enrichment of chlorinated phenolic compounds in different aquatic food chains

Abstract Food chain and sediment samples of three lake areas in Middle Finland have been analyzed for their chlorophenol contamination using twelve model compounds which are main residues of chlorobleaching and wood preservation. Six of these compounds were commonly found. Statistical treatment of the analysis results indicate that tetrachloroguaiacol is the most potent biocide of the compounds studied.

PCDEs, PCBs, PCDDs AND PCDFs in black guillemots and white-tailed sea eagles from the Baltic Sea

Abstract Concentrations and patterns of several chloro compounds including polychlorinated dibenzo p-dioxins (PCDD), dibenzofurans (PCDF), biphenyls (PCB) and diphenyl ethers (PCDE) were determined in black guillemots ( Cepphus grylle L.) and white-tailed sea-eagles ( Hallaeetus albicilla L.) from the Baltic Sea environment. Three breast muscles of eagles were analyzed and had different concentrations and patterns of the studied compounds, whereas the three guillemot eggs were found to have more similar levels and patterns. The concentrations of individual PCDE congeners varied from

Occurence and fate of polychlorinated aromatic ethers (PCDE, PCA, PCV, PCPA and PCBA) in environment

Abstract Analyses of aromatic chloroethers in salmon (Salmo salar), white-tailed eagle (Hailaetus albicilla) and fish liver oil have been performed by improved clean up method which separates polychlorinated diphenyl ethers (PCDEs), anisoles and veratroles (PCAs and PCVs), phenoxy anisoles and biphenyl anisoles (PCPAs and PCBAs), dioxins and dibenzofurans (PCDDs and PCDFs) to different fractions, respectively. Compounds from all these substance groups were detected and many of them identified with authentic model compounds.

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.

Polychlorinated diphenyl ethers, dibenzo-p-dioxins, dibenzofurans and biphenyls in seals and sediment from the gulf of finland

Polychlorinated diphenyl ethers (PCDEs), 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) were analyzed in seals from the Gulf of Finland and in sediments from the Gulf of Finland and near Gotland. The sediments included one surface core from both sampling sites. The seal material consisted of 14 ringed seals and 6 grey seals that all were found dead and examined for pathology. The main aims were to scrutinize levels and patterns of PCDEs for the first time in seals from the Baltic Sea and to estimate whether chlorinated compounds mentioned have an influence on an exceptional high mortality that occurred among ringed seals in the Gulf of Finland in late 1991. The concentrations of 50 congeners of tetra- through deca-CDEs analyzed ranged from < 0.3 to 62 ng/g lipid weight (lw) in seal blubber, but in the sediments PCDEs were non-detectable (tetra- through hepta-CDEs < 0.1 ng/g dry weight (dw)). In ringed seals with good nutritional status, the concentrations of almost all PCDE congeners were greater in two adult females than in specimens of younger age groups. The concentrations of PCDDs and PCDFs as TCDD-equivalents exceeded those of the coplanar (non-ortho) PCBs in sediments, whereas non- and monoortho PCBs constituted greater toxic loads as those calculated for PCDDs and PCDFs in seals. However, the levels revealed do not explain the high mortality of ringed seals.