Organic chlorine compounds in lake sediments. V. Bottom of Baikal near a pulp mill

Organically bound chlorine (OCl) together with inorganic chloride (Cl⁻) was measured from bottom surface samples of the Lake Baikal near a pulp mill and compared to organic matter contents (OM). Although total contents of OCl, Cl⁻ and OM were much lower than, the ratio of OCl to OM was of the same order of magnitude as in pulp mill recipients of Finland.     

Trends of organochlorine compounds in Finnish inland waters

Caged common lake mussels (Anodonta piscinalis) have been used in the monitoring of organochlorine compounds in pulp and paper mill recipient watercourses of Finland annually from 1984 to 1998. Statistically significant decreasing trends of chlorophenols and chloroguaiacols originating from chlorobleaching were observed in all recipients in parallel with the decreasing discharges from the mills. Metabolites of chlorophenols, chloroanisoles and chloroveratroles had no or slightly increasing trends. Elevated PCB concentrations were measured in four watercourses. In two areas, PCBs were found to be significantly increasing, in two other cases they showed no trend. A mill producing recycled paper was apparently responsible for an increase of PCBs and DDE in recipient watercourses. Overall decreases were observed for other chlorohydrocarbons except for DDT. Material flows of chlorohydrocarbons were positively correlated with waterflows (Q) in some cases.     

Rainy River water quality in the vicinity of bleached kraft mills

Water and suspended solids samples were collected at four river stations and from two pulp and paper mill final effluents and analysed for a variety of organic contaminants. Juvenile fish were collected upstream and downstream of the mill discharges. Results showed significant mill inputs of PCBs, PAHs, chlorophenols, dioxins and furans which impacted downstream stations. Juvenile fish analysed downstream of the effluents indicated uptake of PCBs and chlorinated phenols.     

Organochlorine compounds in Baltic salmon and trout. I. Chlorinated hydrocarbons and chlorophenols 1982

Polychlorinated hydrocarbons and chlorophenol compounds were analyzed in three populations of Baltic salmon (Salmo salar) and one population of Bothnian Bay trout (Salmo trutta). Muscles, livers and unfertilized eggs were studied and the analysis results treated by standard statistical methods. PCB, DDT residues, HCB and lindan were detected in most, 2,3,6-t-richlorocymene in some samples at levels which are near to the global baseline. Ten chlorophenol compounds were detected, 34DCC at 0–1000 ug/kg the others 0–100 ug/kg (fresh weight) levels. Chlorohydrocarbons showed some significant positive correlations with weight, and fat contents of the fish. Significances of the differences between populations and tissues were low or neglible except that the chlorophenols in liver were at clearly higher level than in muscle or eggs.     

Isomer specific syntheses of chlorinated catechols and guaiacols relevant to pulp bleaching

A variety of chlorinated catechols and guaiacols relevant to pulp bleaching were synthesized by employing fundamental differences in the acidities of phenolic hydroxyl groups in chlorinated catechols, and directive effects in guaiacols.     

Conifer aphids in an air-polluted environment. II. Host plant quality

Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L.) Karst.) seedlings were transported to five forest sites at increasing distances from a pulp mill emitting mainly SO(2). Levels of compounds which may have nutritional or defensive value for aphids on pine and spruce seedlings were studied. Glucose and fructose concentrations were significantly increased in pine and spruce needles near the pulp mill. There were no changes in sucrose and starch concentrations. In pine shoots, total free amino acid concentration and the concentrations of ornithine, lysine, histidine and arginine were significantly negatively correlated with the distance from the pulp mill, while in spruce only the individual amino acids glycine, ornithine, lysine and histidine showed a significant negative correlation with distance. There were no changes in total phenolic, catechin, total monoterpene and total resin acid concentrations. However, in pine seedlings monoterpenes beta-pinene and sabinene and in spruce seedlings resin acid palustric acid were significantly correlated with the distance from the pulp mill. The results indicate that SO(2) disturbs carbohydrate metabolism in spruce and pine seedlings. The elevated concentrations of arginine may be the result of the combinations of SO(2), NO(3) and NH(3) emissions of the pulp mill. The emissions did not have any impact on total amounts of defensive substances in trees. Thus, the possible susceptibility of conifers to herbivores appears to be due to changes in nutritive value rather than to reduced chemical resistance.     

Study of organochlorine pollutants in snow at North Pole and comparison to the snow at north, central and south Finland

Organic pollutants, especially polychlorinated hydrocarbons, phenols, guaiacols and catechols have been studied by analyses of snow samples from North Pole, May 1984. All of these pollutants were below the limit of determination which was estimated to be as fallout 0.1–0.05 μg/m² for individual compounds. For comparison, snow samples from Central Finland and South Finland 1983–1985 also showed non-detectable levels of chlorinated hydrocarbons but well measurable levels of chlorophenol compounds which were significantly higher at urban (heavy traffic) than rural and higher at South than Central Finnish places, respectively. One sample from Lapland, North Finland 1985, however, had no measurable amounts of chlorophenols like the North Pole sample.     

Food chain enrichment of organochlorine compounds and mercury in clean and polluted lakes of Finland

Lakes polluted by pulp mill and urban wastes including chlorobleaching of pulp, semipolluted lakes and reference lakes in nearly natural condition in Central Finland were studied for contents of mercury, methyl mercury and organochlorine compounds in sediment, plankton, roach and pike. Chlorobleaching had caused a 30-fold concentration of Hg in bottom sediment related to that of the purest reference lake. This was not reflected to the mercury levels in fish which were highest at one natural condition (humic) lake and rather high also at semipolluted lake Päijänne. Mercury in fish was shown to be mostly methylated but not completely and its time trends could be estimated. Chloroform showed no but carbon tetrachloride, tetrachloroethylene and chlorinated cymenes significant bioaccumulation in fish. Levels of chlorophenols from bleaching had strongly decreased but pentachlorophenol and 2,3,4,6-tetrachlorphenol levels remained related to earlier results. Using fat basis attenuated the power of estimation of food chain enrichment by a three throphic level model for lipohilic biocides and a strong proof was obtained of the enrichment of hexachlorobenzene. The time trends at Päijänne were decreasing for mercury and DDE but increasing for PCB.     

Environmental fate and bioavailability of wood preservatives in freshwater sediments near an old sawmill site.

Impacts of an old contaminated sawmill site located in Eastern Finland were studied, with emphasis on transportation and bioaccumulation of wood preservatives in the surrounding water system. To assess the transportation of chlorophenols and chromated copper arsenate (CCA) from the sawmill to the nearby lake, the concentrations of these compounds in selected sediment samples were analyzed. To assess the contribution of a pulp mill further upstream, the concentration of extractable organic halogens (EOX) was analyzed. Bioaccumulation of wood preservatives from sediments was examined using Lumbriculus variegatus as test organism. In sediments collected from the sawmill area, concentrations of chlorophenols, arsenic, chromium and copper were high. In the surrounding area the concentrations of these compounds were slightly elevated at some sampling points but were mostly within the natural range of variation. Thus, it can be concluded that transportation of wood preservatives from the sawmill area to its surroundings is fairly low. However, 60 microg/l of arsenic and 50 microg/l of copper were found in water taken from a brook that runs through a landfill area of the sawmill to the nearby river, and the concentration of arsenic in the surface sediment at one sampling point in the lake was slightly elevated. The total amount of organohalogens in sediment was higher in the river and the lake than in the sawmill area. Of all the wood preservatives studied, only arsenic was found to bioaccumulate in present conditions, reaching a tissue concentration of 362 microg/g dw in organisms exposed for 28 days to sediment from the brook. High concentration of arsenic in oligochaeta tissue was related to high concentration of arsenic in the pore water.     

Effects of nitrogen and phosphorus limitation on the activated sludge biomass in a kraft mill biotreatment system.

Unlike wastewater, pulp and paper mill effluents are generally severely deficient in bioavailable nitrogen and phosphorus. The influence of nitrogen and phosphorus limitations on steady-state or typical pulp and paper mill activated sludge floc properties and performance was studied using a bioreactor-fed synthetic raw mill effluent and seeded with mill activated sludge. Limitation of either nitrogen or phosphorus decreased growth, five-day biochemical oxygen demand, and suspended solids removal. Nitrogen limitation greatly enhanced activated sludge floc poly-beta3-hydroxybutyrate (PHB), but not carbohydrate or extracellular polymeric substances (EPS). In contrast, phosphorus limitation increased total floc carbohydrate and EPS, but not PHB. The flocs showed little ability to store either nitrogen or phosphorus. Nitrogen limitation, but not phosphorus limitation, produced much more negative net floc surface charge, increasing fines, while phosphorus limitation, but not nitrogen limitation, increased the floc bound water content and surface hydrophobicity and decreased fines.     

The distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans in Jackfish Bay, Lake Superior, in relation to a kraft pulp mill effluent

Samples of whole effluent and effluent suspended solids from a kraft pulp mill and sediments and biota from Jackfish Bay, Lake Superior were analyzed for polychlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs). Tetra-CDFs (4CDF) were consistently detected in whole effluent at levels ranging between 0.3 and 1.3 ng/L. Effluent suspended solids also contained 4CDFs as well as traces of 4CDD, 5CDF, 8CDF and 8CDD. The horizontal sediment distribution suggests that the effluent was the only active source of 4CDF in the area but that 8CDD originated from a more general source such as the atmosphere. An abrupt appearance of 4CDF in the more recent sections of a core profile taken in the bay suggests that an operational change at the pulp mill resulted in the formation of 4CDFs in the mill effluent some time after 1973. Moderate values of 4CDF and low values of 4CDD were found in samples of the shrimp confirming the presence of an active source of 4CDF in Jackfish Bay.     

Reproductive success and chlorinated hydrocarbon contamination in tree swallows (Tachycineta bicolor) nesting along rivers receiving pulp and paper mill effluent discharges

The insectivorous tree swallow was chosen as an indicator species to investigate the uptake of pulp mill-related chlorinated hydrocarbons from emergent aquatic insects. Nest box populations were monitored for reproductive success at locations upstream and downstream of pulp mills on two river systems in British Columbia, Canada. Also, 16-day-old nestlings were collected and analysed for polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), pesticides, chlorophenols and chloroguaiacols. Most reproductive parameters were not different between populations at upstream and downstream locations, and were equivalent to or greater than those recorded for other tree swallow populations. Chlorinated hydrocarbon contamination of nestlings was low at all sites. The highest tissue concentrations were detected downstream of pulp mills on the Fraser River, where PCDD and PCDF patterns along with the presence of pentachlorophenol (PCP) suggested that the primary source of contaminants was past use of PCP for timber preservation. Although the absolute tissue concentration of contaminants was less, the toxic concentration (as estimated with I-TEQs) was greatest in nestlings downstream of a pulp mill on the Thompson River. The proportionately larger contributions from 2,3,7,8-TCDF and PCB-77 elevated these TEQs in comparison to other populations. Nest success was the one reproductive measure that showed substantial reductions in downstream populations on both rivers; however, there was little indication that nest failures were the direct result of contamination. Failures were largely due to parental abandonment, and, while poor parental attentiveness and nest abandonment have been associated with chlorinated hydrocarbon tissue concentrations in other studies, our 1-year assessment was insufficient to establish any link with pulp mill effluent exposure. Nestling growth models showed some subtle differences in growth patterns between nest box populations on the two rivers, but an association with pulp mill effects on aquatic insect prey availability was not established.     

Investigation of pathogenic Escherichia coli and microbial pathogens in pulp and paper mill biosolids.

Biosolids produced from pulp and paper mill wastewater treatment have excellent properties as soil conditioners, but often contain high levels of Escherichia coli. E. coli are commonly used as indicators of fecal contamination and health hazard; therefore, their presence in biosolids causes concern and has lead to restrictions in land-spreading. The objectives of this study were to determine the following: (1) if E. coli from the biosolids of a wastewater-free pulp and paper mill were enteric pathogens, and (2) if other waterborne microbial pathogens were present. E. coli were screened for heat-labile and heat-stable enterotoxin and verocytotoxin virulence genes using a polymerase chain reaction. Ten isolates were also screened for invasion-associated locus and invasion plasmid antigen H genes. None of the 120 isolates carried these genes. Tests for seven other microbial pathogens were negative. Effluents and biosolids from this mill do not contain common microbial pathogens and are unlikely to pose a health hazard.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Characterization of the humic material formed by composting of domestic and industrial biowastes Part 1. HPLC of the cupric oxide oxidation products from humic acids

The changes induced by humification of anaerobically digested sewage sludge, source separated biowaste, and pulp mill biosludge were determined by extracting the fractions of bitumen and humic and fulvic acids from the samples of fresh and humified composts. In all cases, a distinct decrease in the amount of bitumen could be detected during humification. The amount of humic acids increased in sewage sludge and biowaste samples, but decreased in pulp mill biosludge sample during humification. The humic acids were degraded by CuO oxidation and the phenolic degradation products were analysed by reversed-phase high-performance liquid chromatography. The yield of these aromatic degradation products was in the range 0.9–2.0 % for each sample. The main phenolic degradation products were 4-hydroxybenzoic acid, vanillic acid, 4-hydroxybenzaldehyde, vanillin, syringaldehyde, and acetovanillone. Two lignin dimers, dehydrodivanillin and dehydrodiacetovanillone, were also identified.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Organic chlorine compounds in lake sediments. IV. Dioxins, furans and related chloroaromatic compounds

Polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), polychloronaphthalenes (PCNs) and coplanar PCBs were measured in surface sediments from 18 lake areas in Central Finland. Toxic 2, 3, 7, 8-substituted PCDD and PCDF congeners occurred at low levels (<20 − 230 pg/g dw). PCNs appeared at few ng/g (total PCNs) levels. Pulp mills or any other local sources could not be associated with the sedimented PCDDs, PCDFs and PCNs. Coplanar PCB congeners 77 and 105 (IUPAC Nr) were generally found at 20–550 pg/g levels. The most toxic congener 126 was measured (110 pg/g) only at one area near a local PCB leakage. Pulp mill originated aromatic chlorocompounds which coelute with PCDDs and PCDFs in clean up, probably alkyl polychlorobibenzyls (R-PCBBs) appeared at ng/g levels and showed a clear gradient dowstreams from pulp mill effluent points.     

Exposure assessment at a PCDD/F contaminated site in Sweden—field measurements of exposure media and blood serum analysis

Background, aim, and scope  

The main pathway for human exposure to the highly toxic polychlorinated-p-dioxins and polychlorinated furans [polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)] is via dietary intake. Other exposure pathways may, however, be important in close proximity to point sources, such as wood preservation sites, where PCDD/F contaminated chlorophenols (CP) were previously used. In this study, a heavily PCDD/F contaminated CP saw mill site in Sweden was investigated. Human exposure through a broad spectrum of exposure pathways was assessed. Such studies are in demand since the question whether contaminated sites represent a current or future risk can only be answered by detailed site-specific risk assessments.     

Determination of partition coefficients of chlorinated phenols,guaiacols and catechols by shake-flask GC and HPLC

The logarithm of the partition coefficients in the n-octanol-water system, log P, of 21 chlorinated phenols, guaiacols and catechols are determined, by both shake-flask gas chromatography (GC) and high pressure liquid chromatography (HPLC). In the shake-flask GC method, the water phase, after equilibration with spiked octanol, was analysed by glass capillary GC with electron capture detection. The relative responses of individual phenols were compared with those from before partition, and the partition coefficients were calculated. In the HPLC method, the capacity factors were used for calculating the log P values by calibration using four chlorophenols with known log P values. The use of short columns with 3 μm packing materials, combined with amperometric detection, offers fast and sensitive determinations.The results from both these methods have high precision, and agree well with the values calculated according to Hansch (1). The small deviations between the results obtained by shake-flask GC and HPLC for the compounds which have high dipole moments can be explained by the influence of different dipole moments and hydrogen bonding affinities in the solute-solvent and solute-stationary phase interactions. Compared with these interactions, the salt effect for concentrations lower than 1 M sodium chloride is negligible.     

Bleached kraft pulp mill discharged organic matter in recipient lake sediment

Environmental properties of organic matter contained halogen and sulfur were studied in sediments of bleached kraft pulp mill effluent (BKME) recipient lakes and 2 m³ outdoor enclosures (mesocosms). The BKME contributed to 1% (v/v) of the total water flow in the lake downstream of the pulp mill where the sediments contained 1.7 to 4 mg of tetrahydrofuran extractable organic halogen (EOX-Cl) and 0.6 to 0.8 mg of tetrahydrofuran extractable organic sulfur (EOS-S) g⁻¹ of organic matter. Upstream sediment contained 0.03 mg of EOXCl and 0.7 mg of EOS-S g⁻¹ of organic matter. EOX was a better indicator for the influence of BKME in the recipient sediment than EOS. The polarity of BKME contained EOX corresponded to log K^ow of < 1, and that of the downstream sediment contained EOX to > 4.5. HP-SEC analysis of the molecular weight distribution (MWD) of the EOX showed a peak between 300 to 600 g mol⁻¹ for the BKME and between 1000 to 2000 g mol⁻¹ for the downstream sediment. The MWD of the BKME contained EOS peaked at 300 to 1000 g mol⁻¹, and that of the downstream sediment contained EOS at 1000 to 5000 g mol⁻¹. These results indicate that BKME contained organic halogen and sulfur undergo major structural transformations when incorporated into sediment. The biota-to-sediment accumulation factor (BSAF) of EOX from sediments formed downstream of the mill and in the mesocosms to the lipids ofLumbriculus variegatus was 0.4 to 0.7. This is of a similar order of magnitude to the BSAF reported for 2,3,7,8-tetrachlorodibenzop-dioxin and 2,3,7,8-tetrachlorodibenzofuran.