Keijo Mäntykoski

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.

Environmental history of an urban lake: a palaeolimnological study of Lake Jyväsjärvi, Finland

Sedimentary diatom frustules and chironomid remains, in addition to the chemical stratigraphy of 32 elements and organic pollutants such as resin acids, PCB, DDT and its metabolites, were studied from core samples taken from Lake Jyväsjärvi in Central Finland (64° 14′ N, 25° 47′ E). The sediment profile covered over 200 years, with the oldest samples representing a period of very low human interference. The town of Jyväskylä was established on the lake shore in 1837, and the lake received untreated municipal wastewater from the town up until, 1977. A paper mill started operations in 1872 and began discharging effluent into Lake Jyväsjärvi. In recent years this effluent loading has been reduced. Based on the biological and chemical properties of the sediment strata, five developmental phases were distinguished and named as follows: (1) a pre-industrial phase (approximately up until the 1860s); (2) a phase of early changes in the lake ecosystem (from the ∼1870s to ca. 1940s); (3) a phase of increasing eutrophication (from ca. 1950 to ca. 1965); (4) a phase of severe pollution (from ca. 1966 to the early-1990s); and (5) a phase of recovery, which proceeded more quickly during the late-1990s following long-term hypolimnetic aeration. It was estimated that the ecological status of the lake changed from good to moderate during the second phase. Due to the poor chemical status of the lake (including increased concentrations of harmful substances) and the pronounced changes in diatom and chironomid communities, the ecological status from 1950 to the early-1990s was classified as bad. The present ecological status, after a slow recovery of about 20 years, can be classified as moderate/poor. Chemical analysis of the sediment revealed that some elements (C, N, P, S, Ba, Cd, Cu, Fe, Pb, Ni and Zn) followed the known history of municipal waste water discharge into the lake, but Hg, Cr and persistent organic pollutants had different stratigraphies, and therefore mainly originated from other sources. Pronounced changes in profundal benthic communities (chironomids) started about 80 years later than those in diatoms, but later changes in chironomid assemblages were greater than those in diatoms.

Structure analyses of planar polychloroaromatic compounds in environment

Abstract Persistent planar or coplanar aromatic chlorocompounds (PLACs) with structures to fit in the dioxin receptor behave like PCDDs and PCDFs in their analytical clean up with carbon column - reversed elution. Structures of PLACs in emission and environmental samples are screened with GC/MS. IR and NMR spectrometry, GC/GC, model compound mixtures and pure model compounds are also used in structure-specific analysis methods under development. Some alkylated PCDF compounds are indicated in coffee filter paper and in pulp mill effluent. Comparison of levels in salmons and eagles in South-West Finland showed high enrichment rates of some PLACs.

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.

Gas-liquid chromatographic analyses. L: Retention, dispersion and selectivity indices of polychlorinated dibenzo-p-dioxins and dibenzofurans

Abstract The retention (I), dispersion (IM) and selectivity (I*) indices of sixteen polychlorinated dibenzo-p-dioxins and fourteen polychlorinated dibenzofurans were determined on a low-polarity HP-5 capillary column using a gas chromatograph connected with an ion-selective detector. IM and I* values were also calculated for all 73 dibenzo-p-dioxins from the di- to the octachloro isomer and for all possible 135 chlorinated dibenzofurans based on the predicted retention index data reported earlier. The effect of the position of chlorination is shown and the results are compared with those for several series of chlorinated aromatics.

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.

Combustion products of biosludge from pulp mill

Abstract Polychlorinated phenols (PCP), catechols (PCC), guaiacols (PCG), benzenes (PCBz), biphenyls (PCB), dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) were analysed in flue gas, fly ash, grate ash and biosludge samples. Samples were collected from a Finnish pulp mill, where biosludge is used in a power station for energy production.

PCB in recycled paper products

PCB mixtures occur in amounts of 5 to 6000 ppb in paper products made of recycled material. Contents in samples made from Central-European raw material were higher than those from Finnish material. However, the origin of some samples with high contents remained unknown.

Gas—liquid chromatographic analyses : XLIX. Polychlorinated dibenzo-p-dioxins and dibenzofurans on low-polarity NB-54 and NB-1701 capillary columns☆

Abstract The gas chromatographic retention behaviour of complex mixtures of sixteen polychlorinated dibenzo-p-dioxins and fourteen polychlorinated dibenzofurans, containing in addition to the most toxic 2,3,7,8-chloro isomers the so-called “window” isomers, was studied on low-polarity NB-54 and NB-1701 capillary columns under suitable temperature-programmed conditions. The retention data for the components are given and their separation is discussed. The results are compared with those of the related isomers reported previously on low-polarity and polar stationary phases.