A decision framework for possible remediation of contaminated sediments in the River Kymijoki, Finland

Background, aim, and scope  The paper describes the spatial contamination of the River Kymijoki, South-Eastern Finland, and the coastal region of the Gulf of Finland with PCDD/Fs and mercury. The findings of ecotoxicologial and human health studies are also reported, including environmental and human risk assessments. Sediments from the River Kymijoki, draining into the Gulf of Finland, have been heavily polluted by the pulp and paper industry and by chemical industries. A wood preservative, known as Ky-5, was manufactured in the upper reaches of the river between 1940 and 1984 causing severe pollution of river sediments with polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). Moreover, the sediments have been polluted with mercury (Hg) from chlor-alkali production and the use of Hg as a slimicide in pulp and paper manufacturing. Materials and methods  An extensive sediment survey was conducted as well as sediment transport modeling, toxicity screening of sediment invertebrates, and a survey of contaminant bioaccumulation in invertebrates and fish. Studies on human exposure to PCDD/Fs and the possible effects on hypermineralization of teeth as well as an epidemiological study to reveal increased cancer risk were also conducted. An assessment of the ecological and human health risks with a null hypothesis (no remediation) was undertaken. Results  The sediment survey revealed severe contamination of river and coastal sediments with PCDD/Fs and Hg. The total volume of contaminated sediments was estimated to reach 5 × 10⁶ m³ and hot spots with extremely high concentrations (max 292,000 ng g⁻¹ or 1,060 ng I-TEQ g⁻¹ d.w.) were located immediately downstream from the pollution source (approximately 90,000 m³). Sediment contamination was accompanied by changes in benthic assemblages, but direct effects were masked by many factors. The fish showed only slightly elevated PCDD/F levels in muscle, but orders of magnitude higher in the liver compared with reference freshwater sites and the Baltic Sea. The concentrations in human fat did not reveal high human exposure in the Kymijoki area in general and was lower than in sea fishermen. The relative risk for total cancer among farmers was marginally higher (RR = 1.13) among those living close to the river, compared with farmers living further away, and the possibility of increased cancer risk cannot be ruled out. A conservative risk assessment revealed that the present probability of exceeding the WHO upper exposure limit of 4 pg WHO-TEQ kg⁻¹ d⁻¹ for PCDD/Fs and DL-PCBs was 6%. The probability of exceeding the WHO limit value of 0.23 μg kg⁻¹ d⁻¹ for methyl mercury was estimated to be notably higher at 62%. Based on these studies and the estimated risks connected with different remediation techniques a general remediation plan with cost benefit analysis was generated for several sub-regions in the river. Dredging, on-site treatment, and a close disposal of the most contaminated sediments (90,000 m³) was suggested as the first phase of the remediation. The decision regarding the start of remediation will be made during autumn 2008. Conclusions  The sediments in the River Kymijoki are heavily polluted with PCDD/Fs and mercury from earlier chlorophenol, chlor-alkali, and pulp and paper manufacturing. A continuous transport of contaminants is taking place to the Gulf of Finland in the Baltic Sea. The highly increased PCDD/F and Hg levels in river sediments pose an ecotoxicological risk to benthic fauna, to fish-eating predators and probably to human health. The risks posed by mercury exceed those from PCDD/Fs and need to be evaluated for (former) chlor-alkali sites and other mercury releasing industries as one basis for remediation decision making. Recommendations and perspectives  The studies form the basis of a risk management strategy and a plan for possible remediation of contaminated sediments currently under consideration in the Southeast Finland Regional Environment Centre. It is recommended that a detailed restoration plan for the most seriously contaminated areas should be undertaken. Based on current knowledge, the restoration of the whole river is not feasible, considering the current risk caused by the contaminated sediment in the river and the costs of an extensive restoration project. The experiences gained in the present case should be utilized in the evaluation of PCDD/F- and mercury-contaminated sites in other countries. The case demonstrates that the historic reservoirs are of contemporary relevance and should be addressed, e.g., in the national implementation plans of the Stockholm Convention. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Expression of alkane monooxygenase (alkB) genes by plant-associated bacteria in the rhizosphere and endosphere of Italian ryegrass (Lolium multiflorum L.) grown in diesel contaminated soil

For phytoremediation of organic contaminants, plants have to host an efficiently degrading microflora. To assess the role of endophytes in alkane degradation, Italian ryegrass was grown in sterile soil with 0, 1 or 2% diesel and inoculated either with an alkane degrading bacterial strain originally derived from the rhizosphere of Italian ryegrass or with an endophyte. We studied plant colonization of these strains as well as the abundance and expression of alkane monooxygenase (alkB) genes in the rhizosphere, shoot and root interior. Results showed that the endophyte strain better colonized the plant, particularly the plant interior, and also showed higher expression of alkB genes suggesting a more efficient degradation of the pollutant. Furthermore, plants inoculated with the endophyte were better able to grow in the presence of diesel. The rhizosphere strain colonized primarily the rhizosphere and showed low alkB gene expression in the plant interior.     

Reproductive parameters and disturbances of embryonic development in the fieldfare (<Emphasis Type="Italic">Turdus pilaris</Emphasis> L.) in the zone of impact from the nuclear fuel industry

The impact of emissions from the Siberian Chemical Plant (Tomsk oblast) on reproduction and embryonic development of the fieldfare was studied. Bird abundance, clutch size, and egg volume in the impact and background (control) zones were similar, but partial brood mortality in the impact zone proved to be significantly higher, and the frequency of embryonic pathologies (including developmental abnormalities) was also several times higher than in the control.     

Chromium speciation in river sediment pore water contaminated by tannery effluent

Cr(VI) is far more soluble and toxic than Cr(III). Sediment pore water was investigated in a river adjacent to the property of a large former tannery, into which Cr-contaminated effluent was discharged over a 55-year period, and where extremely high Cr concentrations have been found in the sediments. Dialysis cells, or peepers, were used to generate depth profiles of Cr concentration in sediment pore water. Samples were analyzed for total Cr using inductively coupled plasma-mass spectrometry (ICP-MS) and for Cr species using high performance liquid chromatography (HPLC)-ICP-MS. The results show an absence of Cr(VI) in all samples. Furthermore, incomplete recovery of Cr(VI) added to the samples collected at the locations with highest sediment Cr concentrations indicate strong reducing conditions at those locations, which are not conducive to the presence of Cr(VI).     

Measurements of surface contamination of spray equipment with pesticides after various methods of application

Abstract

A traditional method to determine operator dermal exposure is to quantify the amount of pesticide coming into contact with specific body regions and then to integrate the deposition density values with the total body surface. It is known that extremely high deposition values may occur in the hand region; however, the source of contamination is generally assumed to be direct splash or contact with the pesticide container. One of the parameters affecting operator/pilot exposure could be the transfer of pesticide residue, particularly in the case of pesticides with a longer half‐life, from contaminated surfaces of spray equipment by direct contact over extended periods. If the rate of skin absorption of pesticide is readily known, the expected values of daily dose for an operator or pilot may significantly rise due to the extended contact period. This study produced field data on the surface contamination of spray equipment used for ground and aerial applications. If field data on precise work practice (time‐motion) observations are incorporated, it may be possible to estimate the potential exposure of operator/pilot due to hand contact with contaminated surfaces.     

Sorption of PAHs and PCBs to activated carbon: coal versus biomass-based quality

The addition of activated carbon (AC) is an increasingly popular method for pollutant immobilization, and the AC material can be made of biomass or coal/fossil feedstock. The aim of the present study was to investigate whether there are differences between pollutant sorption to biomass and coal-based AC in the presence and absence of sediment. Through N₂ and CO₂ adsorption to probe surface area and pore size it was shown that the biomass-based AC had a stronger dominance of narrow pores in the size range 3.5-15 Å than the anthracite-based material. In the absence of sediment, sorption isotherms for the probe compounds pyrene and PCB-101 showed stronger sorption for the biomass-based AC (logarithmic Freundlich coefficients 8.15 for pyrene; 9.91 for PCB-101) than for the anthracite-based one (logarithmic Freundlich coefficients 7.20 and 9.70, respectively). In the presence of sediment, the opposite trend was observed, with the stronger sorption for anthracite-based AC. Thus, the presence of competing and/or pore-blocking sediment constituents reduces sorption to a larger extent for biomass-derived AC (factor of 5 for pyrene to almost 100 for PCB-101) than for anthracite-based AC (no reduction for pyrene to factor of 5 for PCB-101). This difference is tentatively attributed to the difference in pore size distribution, narrow pores being more prone to clogging, and could have implications for remediation feasibility with AC from different sources.     

有机农药对土壤的污染及生物修复技术研究

农药的大量使用污染了大气、水体及生态系统。有机农药以直接施用、拌种、喷撒、随降水落入等方式进入土壤。农药在土壤中会以吸附、扩散稀释和降解等几种方式发生转化，并改变土壤结构、对土壤中生物的生存及酶的活性产生影响。生物修复技术可以通过动植物、微生物及根际环境对农药污染的降解来治理土壤中的农药，是治理农药污染的一种推荐方法。     

Phytoavailability and geospeciation of cadmium in contaminated soil remediated by Rhodobacter sphaeroides

A microorganism was isolated from oil field injection water and identified as Rhodobacter sphaeroides. It was used for the remediation of simulated cadmium-contaminated soil. The phytoavailability of Cd was investigated through wheat seedling method to determine the efficiency of remediation. It was found that after remediation, the accumulation of Cd in wheat roots and leaves decreased by 67% and 53%, respectively. The Cd speciation in soil was determined with Tessier extraction procedure. It was found that the total Cd content in soil did not change during the experiments, but the geo-speciation of Cd changed remarkably. Among the five fractions, the concentration of exchangeable phases decreased by 27-46% and that of the phases bound to Fe-Mn oxides increased by 22-44%. The decrease of Cd accumulation in wheat showed significant positive correlation with the decrease of exchangeable phases. It could be concluded that the remediation of R. sphaeroides was carried out through the conversion of Cd to more stable forms. The decrease of sulfate concentration in supernatant indicated that the R. sphaeroides consumed sulfate.     

Uptake of 14C-atropine and/or its transformation products from soil by wheat (Triticum aestivum var Kronjet) and their translocation to shoots

Plant uptake of toxins and their translocation to edible plant parts are important processes in the transfer of contaminants into the food chain. Atropine, a highly toxic muscarine receptor antagonist produced by Solanacea species, is found in all plant tissues and can enter the soil and hence be available for uptake by crops. The absorption of atropine and/or its transformation products from soil by wheat (Triticum aestivum var Kronjet) and its distribution to shoots was investigated by growing wheat in soil spiked with unlabeled or ¹⁴C-labeled atropine. Radioactivity attributable to ¹⁴C-atropine and its transformation products was measurable in plants sampled at 15 d after sowing (DAS) and thereafter until the end of experiment. The highest accumulation of ¹⁴C-atropine and/or its transformation products by plants was detected in leaves (between 73 and 90% of the total accumulated) with lower amounts in stems, roots, and seeds (approximately 14%, 9%, and 3%, respectively). ¹⁴C-Atropine and/or its transformation products were detected in soil leachate at 30, 60, and 90 DAS and were strongly adsorbed to soil, with 60% of the applied dose adsorbed at 30 DAS, plateauing at 70% from 60 DAS. Unlabeled atropine was detected in shoots 30 DAS at a concentration of 3.9 ± 0.1 μg kg^?1 (mean ± SD). The observed bioconcentration factor was 2.3 ± 0.04. The results suggest a potential risk of atropine toxicity to consumers.