Evaluating slurry broadcasting and injection to ley for phosphorus losses and fecal microorganisms in surface runoff

The recent growth in the size of dairy cattle farms and the concentration of farms into smaller areas in Finland may increase local water pollution due to increased manure production and slurry application to grass. Therefore, a field study was conducted to monitor losses of total phosphorus (TP), dissolved reactive phosphorus (DRP), and fecal microorganisms in surface runoff from a perennial ley. Cattle slurry was added once a year in June 1996-1997 (Study I) and biannually in June and October 1998-2000 (Study II). The slurry was surface broadcast or injected into the clay soil. The field had a slope of 0.9 to 1.7%. Mineral fertilizer was applied on control plots. Biannual slurry broadcasting increased DRP (p < 0.001) and TP losses (p < 0.001) and numbers of fecal microorganisms in surface runoff waters. The highest losses of TP (2.7 kg ha(-1) yr(-1)) and DRP (2.2 kg ha(-1) yr(-1)) and the highest numbers of fecal coliforms (880 colony-forming units [CFU] per 100 mL) and somatic coliphages (2700 plaque-forming units [PFU] per 100 mL) were measured after broadcasting slurry to wet soil followed by rainfall in fall 1998. Injection reduced the TP and DRP losses in surface runoff by 79 and 86%, respectively, compared with broadcasting (17 Oct. 1998-27 Oct. 1999). Corresponding numbers for fecal coliforms were 350 CFU (100 mL)(-1) and for somatic coliphages were 110 PFU (100 mL)(-1) in surface runoff after injection in October 1998. Slurry injection should be favored when spreading slurry amendments to grassland to avoid losses of P and fecal microorganisms in runoff to surface waters.     

Dioxin concentrations in sediments of the Baltic Sea--a survey of existing data

Recent survey results for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, dioxins) in Baltic Sea sediments from Finland, Sweden and Denmark were merged with previously published Baltic Sea data. Regional distribution of concentration levels, differences in congener patterns, and temporal changes in sediment profiles were examined. One of the main objectives was to study if any major point sources for different PCDD/F congeners could be identified on a regional scale, based on sediment records. The survey confirmed the impact of chlorophenol production derived highly chlorinated PCDF-congeners on the total toxicity in sediments in the Gulf of Finland near the Kymijoki river estuary. Signatures of other point sources or combined point sources pertinent to specific industry branches or particular production processes (such as pulp bleaching, vinyl chloride production, thermal processes) may be discerned. However, the findings did not support any of the known point sources significantly influencing those congeners that are most abundant in Baltic herring and salmon. Instead, regional distributions in the Baltic Sea indicate that atmospheric deposition may act as a major source for those congeners and especially for 2,3,4,7,8-PeCDF. There were clear indications of declines in levels in sediment in some areas, but generally the levels of highly chlorinated PCDD/Fs on the northern coast of the Gulf of Finland were still high when compared with other areas of the Baltic Sea. Major areas with data gaps cover the south-eastern and eastern coastal regions of the Baltic Proper and the southern Gulf of Finland.     

Current levels of DDT,PCB and trace elements in the Baltic ringed seals (Phoca hispida baltica) and grey seals (Halichoerus grypus)

Residue levels of polychlorinated biphenyls (PCBs) and 1,1,1-trichloro-2,2-bis[p-chlorophenyl]ethane (DDT) were determined from liver samples of ringed seals (Phoca lispida) from the Baltic Sea and Svalbard, and of grey seals (Halichoerus grypus) from the Baltic Sea and Sable Island in Canada. Both Baltic seal populations showed clearly higher average sum PCB (SPCB) and sum DDT (SDDT) levels than the reference seal populations. Among the Baltic seals, SPCB levels were twice as high as SDDT levels, and both contaminants were higher in ringed seals than in grey seals. A difference in gender was observed only in the Sable Island grey seal population, in which males showed a higher level of contamination than females. A reduction of the SDDT levels, and to a lower extent of the SPCB levels can be observed in the Baltic seals since the peak contaminant levels during the 1970s. The decrease has been more rapid in the grey seals than in the ringed seals. The SPCB levels in the Baltic ringed seals are still high enough to cause a threat to their well being. Residue levels of the trace elements mercury, cadmium, lead and selenium were determined from liver, kidney and muscle samples of grey seals from the Baltic Sea and Sable Island. Only cadmium showed a geographic difference being higher in the seals from Sable Island than from the Baltic Sea. No clear reduction of the metal burden can be observed in the Baltic grey seal population since the 1970s.     

Formation of PFOA from 8:2 FTOH in closed-bottle experiments with brackish water

The formation of perfluorooctanoate (PFOA) from 1H,1H,2H,2H-perfluorodecanol (8:2 FTOH) was studied for the first time in laboratory experiments with brackish water. The water samples were collected from the Baltic Sea, which is one of the largest brackish water areas in the world and is polluted with PFOA and other perfluorinated compounds. The formation of PFOA was studied in closed-bottle experiments at different water temperatures. As a reference experiment, a modified OECD 310 test was conducted with sludge from a wastewater treatment plant and with brackish water. The PFOA and 8:2 FTOH were concentrated from water samples by solid-phase extraction (SPE) and were analysed using liquid chromatography–mass spectrometry. The effect of oxygen concentration on the formation of PFOA was studied using surface water samples with high and low oxygen contents. Other experiments were performed with oxygen-rich surface water and oxygen-deficient bottom water. The formation of PFOA was observed in all experiments; it was higher in the trial performed with brackish water than in the reference test carried out with sludge. Clear temperature dependence was observed in the formation of PFOA in brackish water tests; after a 30-day test period, a sixfold increase was observed in the amount of PFOA in surface water between the temperatures of 15 and 20 °C. Microbes were suggested as the major cause of the formation of PFOA, but other environmental characteristics, such as oxygen, could also affect the formation potential of PFOA.     

Organohalogen pollutants in herring from the northern Baltic Sea: concentrations, congener profiles and explanatory factors

Organohalogen contaminants were investigated in Baltic herring caught from three catchment areas in the Baltic Sea, off the coasts of Finland. Pools of both small and large herring were analysed for polychlorinated biphenyls (PCB), dibenzo-p-dioxins, dibenzofurans, naphthalenes, camphenes (toxaphene), polybrominated diphenyl ethers and the pesticide DDT and its metabolites. PCB concentrations per fresh weight in small herring were at the same level in all catchment areas, i.e. the Bothnian Bay, the Bothnian Sea and the Gulf of Finland, revealing no hot spots and reflecting most likely long term emissions and atmospheric deposition. Differences in the levels and/or congener profiles of other contaminants between catchment areas may be explained by point sources. Similar concentrations in small and large herring in the Gulf of Finland were possibly due to their common nutrition. In the other areas, differences between small and large herring most likely reflected their different food sources.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Comparison of SFE with Soxhlet in the analyses of PCDD/PCDFs and PCBs in sediment

The efficiency of supercritical fluid extraction (SFE) for the isolation of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) from sediments was investigated by comparing SFE with Soxhlet. Five sediments obtained from an international interlaboratory study were used as a test material. SFE was performed with an automatic system where extracted analytes were collected by solid-phase trapping using carbon mixed with Celite as an adsorbent. For the first time, SFE of the most toxic PCBs, coplanar PCBs, was studied with real sediment samples. The majority of PCBs investigated, a total of 38 congeners from tri- to decachlorinated, were quantitatively extracted from sediment by SFE with pure CO2 at pressure 400 atm and temperature 100 degrees C. Under these conditions a successful extraction was obtained also for PCDD/PCDFs except for hepta- and octachlorinated congeners. Copper powder added to the sediment efficiently prevented the transfer of sulfur from the sample during SFE. The TEQs of both PCDD/PCDFs and PCBs obtained by SFE corresponded well with those obtained by the Soxhlet-based method. The reproducibility of SFE was high for both groups.     

Bioaccumulation, bioavailability and environmental fate of chlorophenol impurities, polychlorinated hydroxydiphenylethers and their methoxy analogues

The bioaccumulation potential and environmental fate of polychlorinated hydroxydiphenyl ethers (HO-PCDEs; polychlorinated phenoxyphenols, PCPP), the major impurities of chlorophenol formulations and their methoxy analogues (MeO-PCDEs; polychlorinated methoxyanisoles, PCPAs) were investigated. Oligochaete worms (Lumbriculus variegatus) exposed to sediment spiked with a model substance of one HO-hexaCDE (4'-HO-PCDE 161) or its methoxy analogue (4'-MeO-PCDE 161) clearly accumulated the test compounds revealing the potential for environmental risk of HO-PCDEs and MeO-PCDEs. The HO-PCDE tested has earlier been reported as an abundant component in a Finnish chlorophenol formulation (Ky-5) and its methoxy analogue is recognized as an abundant MeO-PCDE in sawmill soil contaminated by the formulation. The occurrence of 4'-HO-PCDE 161 and its methoxy analogue among other HO-PCDEs and MeO-PCDEs in lake mussels (Anodonta piscinalis) incubated in a river contaminated via the manufacture of Ky-5 showed that these compounds are bioavailable and transported in the aquatic environment. Mussel comparison with sediment data pointed to a higher accumulation potential for MeO-PCDEs than for HO-PCDEs. The finding of HO-PCDEs in groundwater samples collected from a groundwater reservoir, which had been contaminated by chlorophenols, points to potential of HO-PCDEs for transport with water in soil.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls, naphthalenes and polybrominated diphenyl ethers in the edible fish caught from the Baltic Sea and lakes in Finland

A total of 156 fish composite samples were collected from five areas of the Baltic Sea and from three lakes and analysed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polybrominated diphenyl ethers (PBDEs). The European Union's maximum permissible level for PCDD/Fs, 4 pg WHO-TEQ/g fresh weight (fw), was exceeded in salmon, river lamprey and Baltic herring. In other species from the Baltic Sea, the 90th percentile was 3.42 pg WHO(PCDD/F)-TEQ/g fw. In the lake fish, the concentrations of PCDD/Fs, PCBs and PCNs were only 29-46% of those in the same species caught from the Baltic Sea, whereas the concentrations of PBDEs in the lake fish were as high as in the Baltic Sea fish. Dioxin-like PCBs contributed to the total dioxin-like toxicity of PCBs and PCDD/Fs by 49+/-12% in all the analysed samples.