192
cal occurrence can be used as a poly-metallic marker for anthropogenic emissions.
This geochemical association unite some “not very common” elements for air pollution (argentum, indium and tellurium). Generally, most of the trace element distribution is characterized mainly in terms of the different lithological units, as in the
case of In (42 μg/kg), Bi (0.30 mg/kg) and Ag (0.54 mg/kg) distribution differs from
the rest of the trace elements, due to the dominance of the atmospheric deposition
(with median of 31 μg/kg and max. Value of 1300 μg/kg) vs. soil distribution
(median of 17 μg/kg and max value of 280 μg/kg). Copper contents in air- distributed
dust range from 6.7 to 880 mg/kg, while in the topsoil layer, an extended distribution has occurred to 1200 mg/kg. Enriched values for the Cu content in attic dust
were obtained from houses located very close to Cu mine Bučim. Cadmium contents also have an enrichment trend in air-distributed dust (0.054–25 mg/kg); but
cadmium content in the topsoil layer does not indicate any significant enrichment
(0.005–9 mg/kg). The distribution of lead and zinc is similar to that of copper and
cadmium in the investigated area. Lead content ranges from 0.005 to 3900 mg/kg,
while Zn contents show lower enrichments from 26 to 3200 mg/kg. Lithogenic distribution in soil reaches 1200 mg/kg and 590 mg/kg, respectively, for Pb and Zn.
According to the dominant lithological units, Rifeous shales are mostly enriched
with Pb and Zn, where the median values for Pb and Zn contents are 110–220 mg/
kg, respectively. For the spatial distribution of the factor scores, universal kriging
with the linear variogram interpolation method was applied for the construction of
maps showing the spatial distribution of elemental distribution. The significance is
given on those areas where the content of the elements exceeds the 75th percentile
of the data distribution for the element content. Attic dust’s element distribution is
marked with number 1 at each figure for element distribution. In order to distinguish
the lithogenic impact on the element distribution, the topsoil layer was also investigated for the content of the elements (marked with number 2 at each figure for element distribution). Also, this investigation fortifies an extended anthropogenic
association (Ag, Bi, In and Mn) that implement some other anthropogenic activities
such as agricultural activities (use of urban sludge, manure and phosphate fertilizers) and their occurrence can be a secondary affection from mine poly-metallic
pollution (Balabanova et al. 2019). Affiliation of tellurium and wolfram to this
group spread up an elemental anomaly in the Berovo region. For all elements that
associate in this group, enriched value deposition occurs in this mentioned area.
Almost 20 years ago, Arsovski (1997) points to a poly-metallic enrichment in this
area, so-called Vladimirovo-Berovo, during the tectonic investigation. The present
investigation also interpolates this area as a metallic−/metalloid-enriched zone,
with emphasis on the anthropogenic elements. This occurrence was also determined
for the geochemical marker (As-Co-Ge-V) established by Balabanova et al. (2019).
Spatial mappings for each element are presented in Figs. 6.4, 6.5, 6.6, 6.7, 6.8, 6.9,
6.10, 6.11, 6.12, 6.13, and 6.14.
Geochemical association given as Factor 5 (Balabanova et al. 2019) associates
the following elements, As, Co, Ge and V, with predominant occurrence on Rifeous
shales (Table 6.2). This kind of geochemical fingerprinting occurs along the whole
course of the Bregalnica river. Accordingly, the resulting areal distribution map used
R. Šajn et al.
cal occurrence can be used as a poly-metallic marker for anthropogenic emissions.
This geochemical association unite some “not very common” elements for air pollution (argentum, indium and tellurium). Generally, most of the trace element distribution is characterized mainly in terms of the different lithological units, as in the
case of In (42 μg/kg), Bi (0.30 mg/kg) and Ag (0.54 mg/kg) distribution differs from
the rest of the trace elements, due to the dominance of the atmospheric deposition
(with median of 31 μg/kg and max. Value of 1300 μg/kg) vs. soil distribution
(median of 17 μg/kg and max value of 280 μg/kg). Copper contents in air- distributed
dust range from 6.7 to 880 mg/kg, while in the topsoil layer, an extended distribution has occurred to 1200 mg/kg. Enriched values for the Cu content in attic dust
were obtained from houses located very close to Cu mine Bučim. Cadmium contents also have an enrichment trend in air-distributed dust (0.054–25 mg/kg); but
cadmium content in the topsoil layer does not indicate any significant enrichment
(0.005–9 mg/kg). The distribution of lead and zinc is similar to that of copper and
cadmium in the investigated area. Lead content ranges from 0.005 to 3900 mg/kg,
while Zn contents show lower enrichments from 26 to 3200 mg/kg. Lithogenic distribution in soil reaches 1200 mg/kg and 590 mg/kg, respectively, for Pb and Zn.
According to the dominant lithological units, Rifeous shales are mostly enriched
with Pb and Zn, where the median values for Pb and Zn contents are 110–220 mg/
kg, respectively. For the spatial distribution of the factor scores, universal kriging
with the linear variogram interpolation method was applied for the construction of
maps showing the spatial distribution of elemental distribution. The significance is
given on those areas where the content of the elements exceeds the 75th percentile
of the data distribution for the element content. Attic dust’s element distribution is
marked with number 1 at each figure for element distribution. In order to distinguish
the lithogenic impact on the element distribution, the topsoil layer was also investigated for the content of the elements (marked with number 2 at each figure for element distribution). Also, this investigation fortifies an extended anthropogenic
association (Ag, Bi, In and Mn) that implement some other anthropogenic activities
such as agricultural activities (use of urban sludge, manure and phosphate fertilizers) and their occurrence can be a secondary affection from mine poly-metallic
pollution (Balabanova et al. 2019). Affiliation of tellurium and wolfram to this
group spread up an elemental anomaly in the Berovo region. For all elements that
associate in this group, enriched value deposition occurs in this mentioned area.
Almost 20 years ago, Arsovski (1997) points to a poly-metallic enrichment in this
area, so-called Vladimirovo-Berovo, during the tectonic investigation. The present
investigation also interpolates this area as a metallic−/metalloid-enriched zone,
with emphasis on the anthropogenic elements. This occurrence was also determined
for the geochemical marker (As-Co-Ge-V) established by Balabanova et al. (2019).
Spatial mappings for each element are presented in Figs. 6.4, 6.5, 6.6, 6.7, 6.8, 6.9,
6.10, 6.11, 6.12, 6.13, and 6.14.
Geochemical association given as Factor 5 (Balabanova et al. 2019) associates
the following elements, As, Co, Ge and V, with predominant occurrence on Rifeous
shales (Table 6.2). This kind of geochemical fingerprinting occurs along the whole
course of the Bregalnica river. Accordingly, the resulting areal distribution map used
R. Šajn et al.