The use of a sequential leaching procedure for assessing the heavy metal leachability in lime waste from the lime kiln at a caustizicing process of a pulp mill

A five-stage sequential leaching procedure was used to fractionate 13 heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Al, Ni, Co, As, V, Ba) and sulphur (S) in lime waste from the lime kiln at the causticizing plant of Stora Enso Oyj Veitsiluoto Pulp Mills at Kemi, Northern Finland, into the following fractions: (1) water-soluble fraction (H₂O), (2) exchangeable fraction (CH₃COOH), (3) easily reduced fraction (HONH₃Cl), (4) oxidizable fraction (H₂O₂ + CH₃COONH₄), and (5) residual fraction (HF + HNO₃ + HCl). Although metals were leachable in all fractions, the highest concentrations for most of the metals were observed in the residual fraction (stage 5). It was also notable that the total heavy metal concentrations in lime waste did not exceed the maximal allowable heavy metal concentrations for soil conditioner agents set by the ministry of the Agricultural and Forestry in Finland. The heavy metals concentrations in lime waste were also lower than the maximal allowable heavy metals concentrations of the European Union Directive 86/278/EEC on the protection of environment, and in particular of the soil, when sewage sludge is used in agriculture. The Ca concentration (420 g kg⁻¹; d.w.) was about 262 times higher than the typical value of 1.6 g kg⁻¹ (d.w.) in arable land in Central Finland. However, the concentration Mg (0.2 g kg⁻¹; d.w.) in lime waste was equal to the Mg concentration in arable land in the Central Finland. The lime waste has strongly alkaline pH (12.8) and a neutralizing value (i.e. liming effect) of 47.9% expressed as Ca equivalents (d.w.). This indicates lime waste to be a potential soil conditioner and improvement as well as a pH buffer.     

The use of a sequential leaching procedure for heavy metal fractionation in green liquor dregs from a causticizing process at a pulp mill

A five-stage sequential leaching procedure was used to fractionate heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Ni, Co, As, V, Ba and Ti) in green liquor dregs into the following fractions: (1) water-soluble fraction (H2O), (2) exchangeable fraction (CH3COOH), (3) easily reduced fraction (HONH3Cl), (4) oxidizable fraction (H2O2 + CH3COONH4), and (5) residual fraction (HF + HNO3 + HCl). The green liquor dregs were derived from a causticizing process at a pulp mill at Kemi, Northern Finland. According to the leaching studies, the leachability of heavy metals in the water-soluble fraction varied between 0.5 and 2 mg kg(-1) expressed on a dry weight (d.w.) basis, indicating relatively low bioavailability of the metals. However, the concentration of Mn (2065 mg kg(-1); d.w.) showed a strong and of Zn (17.6 mg kg(-1); d.w.), Ni (39.7 mg kg(-1); d.w.) and Ba (32.0 mg kg(-1); d.w.) slightly tendency to be extracted in the exchangeable fraction. In addition, Zn, Mn, Ni, Co, V and Ba showed clear leachability in the easily reduced fraction, as well as Cd, Cu, Cr, Zn, Mn, As and Ba in the oxidizable fraction. For Cd, Cu, Cr, Zn, Mn, Ni, Co, Ba and Ti, the sum of leachable heavy metal concentrations in fractions 1-5 agreed relatively well with the "total" heavy metal concentrations. Recoveries of the sum of fractions 1-5 were 84-56% of those obtained by the US EPA method 3052 (i.e. concentrations obtained after microwave oven digestion with a mixture of HF and HNO3).     

Green liquor dregs as an alternative neutralizing agent at a pulp mill

Green liquor dregs is the biggest waste fraction at sulphate pulp mills. It is commonly landfilled. Here we demonstrate that the utilization of green liquor dregs as a neutralizing agent for acidic wastewaters is a potential alternative and an environmentally friendly method in contrast to its landfill disposal. The liming effect value of 39.6% for green liquor dregs, expressed as Ca equivalent, is similar to the liming effect value of 38% of a commercial limestone product. In addition, the pH value of 10.7 indicates a strong liming effect.     

Extractability of trace elements in precipitated calcium carbonate (PCC) waste from an integrated pulp and paper mill complex

From the utilization point of view, it is notable that the total element concentrations in the precipitated calcium carbonate (PCC) waste were significantly lower than the maximal allowable heavy metal concentrations for fertilizers used in agriculture and in forestry, set on the basis of the EU and Finnish legislation. The easily soluble Ca concentration of 168.5g kg(-1) (d.w.) in PCC waste was 105 times higher than the typical value of 1.6g kg(-1) (d.w.) in the coarse mineral soil in Finland indicates that the PCC waste is a potential agent for soil remediation and for improving soil fertility if it is used as fertilizer. According to a five-stage sequential extraction procedure, the highest concentrations of most of the elements occurred either in HF+HNO3+HCl or H2O2+CH3COONH4 fraction. This means that the major part of the elements retained in the PCC waste are not easy to extract (leach) under conditions normally found in nature. This is beneficial since, if inorganic materials and by-products are utilized in earth construction, the content of harmful compounds must be low and the harmful components must be tightly bound to the matrix.     

Use of sibling relationship reconstruction to complement traditional monitoring in fisheries management and conservation of brown trout

Declining trends in the abundance of many fish urgently call for more efficient and informative monitoring methods that would provide necessary demographic data for the evaluation of existing conservation, restoration, and management actions. We investigated how genetic sibship reconstruction from young‐of‐the‐year brown trout (Salmo trutta L.) juveniles provides valuable, complementary demographic information that allowed us to disentangle the effects of habitat quality and number of breeders on juvenile density. We studied restored (n = 15) and control (n = 15) spawning and nursery habitats in 16 brown trout rivers and streams over 2 consecutive years to evaluate the effectiveness of habitat restoration activities. Similar juvenile densities both in restored and control spawning and nursery grounds were observed. Similarly, no differences in the effective number of breeders, N_b(SA), were detected between habitats, indicating that brown trout readily used recently restored spawning grounds. Only a weak relationship between the N_b(SA) and juvenile density was observed, suggesting that multiple factors affect juvenile abundance. In some areas, very low estimates of N_b(SA) were found at sites with high juvenile density, indicating that a small number of breeders can produce a high number of progeny in favorable conditions. In other sites, high N_b(SA) estimates were associated with low juvenile density, suggesting low habitat quality or lack of suitable spawning substrate in relation to available breeders. Based on these results, we recommend the incorporation of genetic sibship reconstruction to ongoing and future fish evaluation and monitoring programs to gain novel insights into local demographic and evolutionary processes relevant for fisheries management, habitat restoration, and conservation.     

Chlorination of p-cymene by chlorine in carbon tetrachloride: Model compounds for environmental analyses

p-Cymene was chlorinated by chlorine in CCl₄. The products of the chlorination were separated by distillation and purified by preparative gas chromatography. The structures of chlorocompounds were confirmed by means of their NMR and mass spectra. The distillation gave as the main compounds: (2) 2-chloro-, (4) 2,3-dichloro-, (5) 2,5-dichloro-, (6) 2,3,6-trichloro-, (7) 2,3,5,6-tetrachloro-p-cymenes and as by-products: (8) 2,5,7-trichloro-p-cymene, (9) 2,6-dichloro-1-methyl-4-(1-methylethenyl)benzene (cymenene), and (10) 2,3,6-trichloro-1-methyl-4-(1-methylethenyl)benzene (cymenene).     

Chemical sequential extraction of heavy metals and sulphur in bottom ash and in fly ash from a pulp and paper mill complex

A five-stage sequential extraction procedure was used to determine the distribution of 11 metals (Cd, Cr, Cu, Mo, Pb, Zn, As, Co, V, Ni, Ba), and sulphur (S) in bottom ash and in fly ash from a fluidized bed co-combustion (i.e. wood and peat) boiler of Stora Enso Oyj Oulu Mill at Oulu, Northern Finland, into the following fractions: (1) water-soluble fraction (H2O); (2) exchangeable fraction (CH3COOH); (3) easily reduced fraction (NH2OH-HCl); (4) oxidizable fraction (H2O2 + CH3COONH4); and (5) residual fraction (HF + HNO3 + HCl). Although metals were extractable in all fractions, the highest concentrations of most of the metals occurred in the residual fraction. From the environmental point of view, this fraction is the non-mobile fraction and is potentially the least harmful. The Ca concentrations of 29.3 g kg(-1) (dry weight) in bottom ash and of 68.5 g kg(-1) (dry weight) in fly ash were correspondingly approximately 18 and 43 times higher than the average value of 1.6 g kg(-1) (dry weight) in arable land in Central Finland. The ashes were strongly alkaline pH (approximately 12) and had a liming effects of 9.3% (bottom ash) and 13% (fly ash) expressed as Ca equivalents (dry weight). The elevated Ca concentrations indicate that the ashes are potential agents for soil remediation and for improving soil fertility. The pH and liming effect values indicate that the ashes also have a pH buffering capacity. From the environmental point of view, it is notable that the heavy metal concentrations in both types of ash were lower than the Finnish criteria for ash utilization.     

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.