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

Risto Pöykiö

Department of Chemistry, University of Oulu

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.

Dedication

 

“How little I know of this world

Deeds of men, cities, rivers,

Mountains, arid wastes,

Unknown creatures, unacquainted trees!

The great Earth teems

And I know merely a niche.”

 
--Rabindranath Tagore, 1913 
Table of Contents
Acknowledgements
Abbreviations and definitions
List of original papers
1. Introduction
1.1. Legislative basis for preventing pollution threats
1.2. The use of plant bioindicators for determining the distribution pattern of aerial emissions
1.2.1. Pine needles as a bioindicator
1.2.2. Mosses as a bioindicator
1.3. Physical characterization of airborne matter is important
1.3.1. Inhalable and respirable particulates
1.3.2. Collection of airborne particles
1.3.3. The bioavailability of airborne particles
1.3.4. The particle size distribution
1.4. Methods for the dissolution and analysis of environmental samples
1.4.1. Dissolution
1.4.2. Determination of metals and sulphur
1.4.3. Determination of sulphur
1.5. Leaching and other techniques for the physico-chemical characterization of airborne particulate matter
1.5.1. Leaching
1.5.2. Sequential leaching
1.5.3. Speciation
1.5.4. Morphological characterisation
2. The study area and sources of pollutants
2.1. The study area (I–VI)
2.2. Sources of pollutants (I–VI)
3. Aims of the study
4. Analytical procedures for sampling and trace element determination in environmental samples
4.1. Sampling and analysis of plant materials for the comparison of dissolution methods (I)
4.2. Sampling and analysis of pine needles for sulphur determination (II)
4.3. Sampling and analysis of mosses for heavy metal determination (III)
4.4. Sampling and determination of total suspended particulate (TSP) material (IV)
4.5. Sampling and analytical procedure for Cr, Ni and Pb determination in TSP material (IV)
4.6. Sampling and sequential leaching procedure for heavy metal determination in TSP material (V)
4.7. Sampling and analysis of TSP filters for the homogeneity study (VI)
5. Results and discussion
5.1. Biological samples (I–III)
5.1.1. Comparison of dissolution methods for sulphur and heavy metals analysis in plant materials (I)
5.1.2. Sulphur concentrations in pine needles (II)
5.1.3. Concentrations of Fe, Zn, Ca, V and Pb in pine needles (II)
5.1.4. Accumulation of Cr, Ni and Zn in mosses (III)
5.2. Airborne particulates and filters (IV–VI)
5.2.1. Concentrations of TSP, Cr, Ni and Pb in the ambient air in the mine area (IV)
5.2.2. Estimation of the bioavailability and environmental mobility of heavy metals in TSP material (V)
5.2.3. The homogeneity of heavy metal deposition on TSP filters (VI)
6. Conclusions
7. Future research work
References and notes
List of Tables
1. Major air pollutants (t/a) emitted from the ferrochrome and stainless steel works of AvestaPolarit Stainless Oy, and from the opencast chromium mining complex of AvestaPolarit Chrome Oy Kemi Mine at Kemi during 1990–1999. (III)
2. Results (mg/kg) for sulphur (S) determination in certified samples BCR CRM 100, BCR CRM 101, HUMH2 and "Kemi" and "Tornio" pine needle samples using different digestion procedures. (n=3, except (*) for “Kemi” and “Tornio” pine needles where n=1). Analysis by ICP-AES (a) or Leco (IR combustion) method (b).(I)
3. Results (mg/kg) for chromium (Cr) determination in certified sample HUMH2 and "Tornio" pine needle samples using different digestion methods. (n=3, expect (*) and for “Tornio” pine needles where n=1). Analysis by ICP-AES (a) or ICP-MS (b). (I)
4. Sulphur dispersion area (km2) in Kemi during 1979–1999. (II)
5. The Kendall´s coefficients for the correlation between S, Fe, Zn, Ca, V and Pb in (C+1) pine needles in 1999, (n=29).
6. The Kendall´s cofficients for the correlation between Cr, Ni and Zn in the mosses in 2000, (n=52).(III)
List of Figures
1. Total sulphur (SO2 + TRS) emissions in Kemi during 1980–1998 (t S). (II)
2. The dispersion pattern of sulphur in the (C) needles (left) and in the (C+1) needles (right) in 1999 at Kemi. (II)
3. Heavy metal (Cr, Ni, Zn) concentrations (g/g) in mosses at distances of 0.6–44.5 km (along the same straight line) to the north of the ferrochrome and stainless steel works of AvestaPolarit Stainless Oy in 2000. (III)
4. The 3-D scatterplots for Cr, Ni and Zn in 2000. (III)
5. The correlation between TSP (g/m3) and wind direction at monitoring stations MA1 (Porasydänvarasto), MA2 (Konttori) and MA3 (Selkeytysallas) in 2000. (Mean = the annual mean). (IV)
6. The ambient air concentration of Cr (g/m3) at monitoring station MA2 (Konttori) during January–December in 2000. (IV)
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