Assessing industrial pollution by means of environmental samples in the Kemi-Tornio region

Abstract The results of the comparison of various dissolution methods for sulphur showed, that HNO3 together with H2O2 gave more complete decomposition of organic components than HNO3 alone. The acid procedure with a mixture of HNO3+H2O2 slightly underestimated the S concentrations of plant material. The losses of sulphur were the highest in the dry ashing digestion procedure (HF(DAC)). The Leco combustion technique with infrared (IR) detection gave good precision and accuracy for sulphur. For the determination of heavy metals in plant materials, both the HNO3 and HNO3+H2O2 procedures were especially effective for determining Cr. However, the HNO3+HClO4 procedure gave lower results, and HF and HF(DAC) procedures greater values for Cr. Sulphur accumulation in pine needles around the pulp and paper mills was clearly higher than other points in the Kemi area. For example, within a radius of about 1-1.5 km around the mills of Oy Metsä-Botnia Ab Kemi Mills, the sulphur concentrations for (C) and (C+1) needles were 28 % and 26 % higher than those in the corresponding background samples collected in Kuivaniemi at a distance about 25 km from Kemi. Pine needles do not appeared to be appropriate a method for monitoring the accumulation of Fe, Zn, V and Pb emitted from pulp and paper mills. However, the Ca concentrations in (C+1) needles in the vicinity of the Oy Metsä-Botnia Ab Kemi Mills was 48 % higher than the average Ca concentration calculated from all (C+1) needles; thus it is likely that part of the Ca in the needles is derived from the mills. The regional distribution pattern of Cr and Ni in mosses in the Kemi-Tornio area in 2000 showed clearly that the most polluted area (Cr > 200 μg/g and Ni > 20 μg/g) appeared to lie within a few kilometres of the ferrochrome and stainless steel works of AvestaPolarit Stainless Oy. Within this area, the Cr concentrations in mosses were 4-13 times higher than those outside the urban area of Tornio. The area most polluted by the opencast chromium mining complex (Cr > 200 μg/g and Ni < 20 μg/g) appeared to be in the immediate vicinity of complex. All the 95th percentile values for TSP (total suspended particles) in the mine area of AvestaPolarit Chrome Oy Kemi Mine were below the current Finnish air quality limit value of 300 μg/m3. However, the 98th percentile value exceeded the Finnish air quality guideline value of 120 μg/m3 at one monitoring site. According to leaching studies, the sum of calculated annual airborne pollution impact of water-soluble fraction (H2O) and environmentally mobile (CH3COONH4) fraction from the AvestaPolarit Chrome Oy Kemi Mine was Cr 1.2 kg, Fe 29 kg, Cu 63 kg, Ni 2.5 kg and Cd < 100 mg. According to the homogeneity studies of heavy metal deposition on TSP filters, Cr, Ni, Cu and Fe were non-uniformly distributed over the glass fibre filters. The rsd values varied between 5.4-33.9 % for Cr, between 7.5-35.0 % for Ni, between 3.6-25.9 % for Cu, and between 6.6-19.9 % for Fe

Earth Construction and Landfill Disposal Options for Slaker Grits

Abstract: Slaker grits, an industrial residue originating from the chemical recovery process at sulfate (kraft) pulp mills, are typically disposed of to landfill in Finland. However, due to the relatively low total heavy metal and low leachable heavy metal, chloride, fluoride, sulfate, Dissolved Organic Carbon (DOC) and Total Dissolved Solids (TDS) concentrations, the residue is a potential earth construction material. This paper gives an overview of the relevant Finnish legislation on the use of industrial waste as an earth construction agent, the classification of waste into one of three classes: hazardous waste, non-hazardous waste and inert waste, as well as the broad waste policy goals under EU law that affects their management

Evaluation of trace element availability from secondary metallurgical slag generated in steelmaking by sequential chemical extraction

During carbon steel manufacture, slag residues are generated to remove material impurities from liquid metal and thus control the quality of carbon steel. As the utilization of secondary metallurgical slags is not as effi- cient as those of primary slags, a comprehensive charac- terization of steel ladle slag was performed. Pseudo-total concentrations of a wide range of elements were deter- mined during a 6-week sampling period with relevant physical and chemical properties, sequential extraction of trace elements, and parallel mineralogical characterization of extraction residues from a representative combined sample. According to the results, only Cr and V occurred in elevated concentrations with respective 6-week mean val- ues of 198 and 310 mg kg -1 (d.w.). The residual standard deviation of the weekly pseudo-total concentration values of the aforementioned elements (24 and 31 %, respec- tively) indicated that significant variation in the concen- tration of trace elements can occur due to fluctuation in process conditions and/or slag characteristics. The sequential extraction procedure suggested potential phyto- availability of V (123 mg kg -1 , d.w., amounting to 41 % of the respective pseudo-total concentration) through, e.g., changes in prevailing redox conditions. Although the analytical approach was validated by the analysis of a certified reference material and the calculation of extrac- tion recoveries, the mineralogical characterization of par- allel extraction residues indicated non-selectivity of the procedure coupled with potential redistribution phenomena during extraction with hydrogen peroxide and ammonium acetate

Comparison of dissolution methods for multi-element analysis of some plant materials used as bioindicator of sulphur and heavy metal deposition determined

Most analytical methods for trace element determination in plant material require decomposition of the sample. Sample decomposition procedures play an important role in ensuring that chemical analysis gives correct results. This is especially important in the determination of trace elements in plant material for environmental studies because, as a rule, plant material is not homogeneous and usually contains variable matrices. In this paper microwave digestion procedures using HNO$_3$, HNO$_3$+H$_2$O$_2$, HNO$_3$+HClO$_4$, HF mixtures and dry ashing + HF were investigated for the analysis of Al, Ca, Cr, K, Mg, Mn, Zn, S, Pb, V, Cu, Cd, Co and Ni by ICP-AES or ICP-MS from pine needle samples. Reference samples BCR CRM 100 (Spruce Needles), BCR CRM 101 (Beech Leaves) and HUMH2 (Organic surface soil) were used to test the dissolution methods. The results showed that the sample digestion procedure is critical step for obtaining accurate results. Losses of volatile metals were notable in many cases when dry ashing was used

Particle size distribution and dissolution properties of metals in cyclone fly ash

The particles in the examined cyclone fly ash were all smaller than 0.25 mm. in diameter, and particles smaller than 0.075 mm. in diameter accounted for 88.4 % of the ash weight. This result indicates that cyclone fly ash consists of particles with a small diameter. The metals in the cyclone fly ash were enriched in small particles. The highest concentrations for zinc, copper, lead, cadmium and molybdenum in the cyclone fly ash were found in the smallest particle size fraction (< 0.075 mm.) and for Barium, chromium, nickel, Vanadium and Cobalt in the second to smallest particle size fraction (0.0750.125 mm.). From an environmental and toxicological standpoint, the smallest particles are of the greatest concern when ash is handed at landfill disposal sites (transport and disposal especially in stormy weather conditions), and some studies have reported risks to workers from prolonged exposure to ash. The results of the comparison of various dissolution methods for metals showed that the digestion procedures with nitric acid alone (USEPA 3051) or with a mixture of nitric acid + hydrogen peroxide (USEPA 3050B) slightly underestimated the metal concentrations in the cyclone fly ash. Although the use of hydrofluoric acid is often necessary for the determination of a number of elements associated with siliceous minerals, its use can result in loss of trace elements during dissolution

Characterisation of used traction sand for utilization aspects in earth construction based on the requirements of Finnish environmental legislation

Abstract Finland launched a new Government Decree, the so-called MARA-regulation, on the utilization of certain wastes in earth construction on 1.1.2018. This statutory regulation sets limit values for the solubility of heavy metals (Sb, As, Ba, Cd, Cr, Cu, Pb, Mo, Ni, Se, Zn, V, Hg), chloride, sulphate, fluoride and dissolved organic carbon, as well as for organic substance (petroleum hydrocarbons, benzene, naphthalene, TEX (toluene, ethylbenzene and xylene), PAH-, phenolic- and PCB-compounds). In this case study, the concentrations of these harmful substances in the used traction sand collected in the city of Kemi, Northern Finland, were lower than their limit values set in the MARA-regulation. Therefore, this residue is a potential material to be used at earth construction sites such as in roads and roadways, in field and embankment structures, as well as in floor structures of industrial or storage buildings. However, if the used traction sand is to be utilized for these kinds of civil engineering purposes, an environmental permit is still needed because this material is not yet included in the scope of the MARA-regulation. This paper also gives an overview of the relevant Finnish environmental legislation on the utilization of wastes as an earth construction material