-
Biljana Balabanova, Trajče Stafilov, Robert Šajn
LONGTIME GEOCHEMICAL EVALUATION OF ANTHROPOGENIC ELEMENT’S
DISTRIBUTION IN THE AIR USING DEPOSITED ATTIC DUST
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
1Faculty of Agriculture, University “Goce Delčev”, Štip,
Republic of Macedonia2Institute of Chemistry, Faculty of Science,
Ss. Cyril and Methodius University, Skopje, Republic of
Macedonia
3Geological Survey of Slovenia, Ljubljana, Slovenia
-
CHEMICAL ELEMENTS IN ENVIRONMENT
Biologically effective elements:
Na, Mg, Si, P, S, Cl, Ca, Ti, V, Mn, Fe,
Co, Mo
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
Biologically hazardous elements:
Bi, Be, Al, Cr, Ni, As, Nb, Ag, Cd, Sb, Ba, Hg, Pb, Zn
1. municipal wastewater-treatment plants2. manufacturing
industries,3. mining,4. transportation5. agricultural cultivation
& fertilization…….
-
ENVIRONMENTAL POLLUTION WITH HEAVY
METALS IN REPUBLIC OF MACEDONIA
Dominant geochemical association
In areas with anthropogenic
introducing of heavy metals
Stafilov T. (2014). Environmental pollution with heavy metals in
the Republic of Macedonia. Contributions, Sect. Nat. Math. Biotech.
Sci., MASA, 35, 81–119.
Barandovski L., Frontasyeva M.V., Stafilov T., Šajn R.,
Ostrovnaya T. (2015). Atmospheric deposition of trace elements in
Macedonia studied by the moss
biomonitoring technique. Environ. Sci. Pollut. Res. 22,
16077-16097.
(Cd-Cu-Pb-Zn)
-
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
Atmospheric
distribution/deposition of
elements
Case studies (2010-2012)
-
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
CASE STUDY:
BREGALNICA RIVER BASIN
R. MACEDONIA (2012-2014)
Bregalnica River basinN: 41°27'-42°09'
E: 22°55'-23°01'
-
Potentially emission sources
Copper mine “Bučim” Pb-Zn mine “Sasa”
Pb-Zn mine “Zletovo”
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
-
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
DATASET BUILDING
SAMPLING STRATEGY AND
ANALYTICAL METHODS
-
ICP-MS SCIEX Perkin Elmer Elan DRC II (Canada)
INCDO-INOE 2000 Research Institute
for Analytical Instrumentation (ICIA),
Cluj-Napoca, Romania
Chemical preparation of samples according to
ISO 14869-1:2001
ATTIC DUST
LONG-TIME DEPOSITION
-
DATA PROCESSING
BOX-COX TRANSFORMATION
For a data set (x1, x2 … xn), the parameter λ is
estimated based on the assumption that the
transformed values (y1, y2 … yn) are normally
distributed
FIRST STEP……………DATA NORMALISATION!!!!
Balabanova, B., Stafilov, T., Sajn, R., Tănăselia, C. (2016).
Multivariate factor assessment for lithogenic and anthropogenic
distribution of macro and trace
elements in surface water. Case study: basin of the Bregalnica
river, Republic of Macedonia. Maced. J. Chem. Chem. Eng., 35,
1-16.
Balabanova, B., Stafilov, T., Sajn, R., Tănăselia, C. (2016).
Multivariate extraction of dominant geochemical markers for
deposition of 69 elements in the
Bregalnica River basin, Republic of Macedonia (moss
biomonitoring). Environ. Sci. Pollut. Res., 23, 22852-22870.
MULTIVARIATE STATISTICS METHODS
(CLUSTER AND R-MODE FACTOR
ANALYSES)
http://eprints.ugd.edu.mk/16750/http://eprints.ugd.edu.mk/16648/
-
ATTIC DUST - can reveal the longtime
depositions of emitted dust?
Factor 3 (Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn)
OLIGOCENE AND
NEOGENE VOLCANISM
Total 69 elements: Ag, As, Al, Au, B, Ba, Be, Bi, Br, Ca,
Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf,
Hg, Ho, I, In, Ir, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd,
Ni, Os, P, Pb, Pd, Pr, Pt, Rb, Re, Rh, Ru, Sb, Sc, Se, Sm,
Sn, Sr, Ta, Tb, Te, Ti, Th, Tl, Tm, V, W, Y, Yb, Zn and Zr
Multivariate
EXTRACTION
ANTHROPOGENIC ANOMALIES!!!
Balabanova, B., Stafilov, T., Šajn, R., Tanaselia C. (2017).
Long-term geochemical evolution of lithogenic vs. anthropogenic
distribution of macro and trace
elements in household attic dust, Arch. Environ. Contam.
Toxicol. 72, 88.
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomena
Allu
viu
m (
Q)
Terr
ace (
Q)
Sedim
ent
(Ng)
Pyro
cla
stite
(N
g)
Fly
sch (
Pg)
Schis
t (R
)
Schis
t (P
t)
Gneis
s (
Pt)
Gra
nite (
Pt)
Attic dust
0.4
0.6
0.8
1.0
1.2
1.4
Ag (
mg/k
g)
Allu
viu
m (
Q)
Te
rrace
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
0.35
0.40
0.45
0.50
0.55
0.60
Ag (
mg/k
g)
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomena
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Attic dust
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Bi (m
g/k
g)
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
0.12
0.14
0.16
0.18
0.20
0.22
0.24
0.26
0.28
Bi (m
g/k
g)
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomena
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Attic dust
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Cd
(m
g/k
g)
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Cd
(m
g/k
g)
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomenaA
lluviu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Attic dust
20
25
30
35
40
45
50
Cu
(m
g/k
g)
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
10
12
14
16
18
20
22
24
Cu
(m
g/k
g)
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomenaA
lluviu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Attic dust
30
40
50
60
70
80
90
In (
µg
/kg
)
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
20
25
30
35
40
45
In (
µg
/kg
)
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomenaA
lluviu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Attic dust
300
400
500
600
700
800
900
Mn
(m
g/k
g)
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
300
400
500
600
700
800
900
Mn
(m
g/k
g)
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomena
Allu
viu
m (
Q)
Terr
ace (
Q)
Sedim
ent
(Ng)
Pyro
cla
stite
(N
g)
Fly
sch (
Pg)
Schis
t (R
)
Schis
t (P
t)
Gneis
s (
Pt)
Gra
nite (
Pt)
Attic dust
20
40
60
80
100
120
Pb (
mg/k
g)
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
0
10
20
30
40
50
60
70
80
90
Pb
(m
g/k
g)
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomena
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Attic dust
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
Sb
(m
g/k
g)
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Sb
(m
g/k
g)
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomenaA
lluviu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Attic dust
10
20
30
40
50
60
70
Te
(µ
g/k
g)
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
8
10
12
14
16
18
20
22
24
26
28
Te
(µ
g/k
g)
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomenaA
lluviu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Attic dust
0.8
1.0
1.2
1.4
1.6
1.8
2.0
W (
mg
/kg
)
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
0.80
0.85
0.90
0.95
1.00
1.05
1.10
1.15
W (
mg
/kg
)
-
Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn
lithogenic vs. anthropogenic phenomenaA
lluviu
m (
Q)
Te
rra
ce
(Q
)
Sed
ime
nt
(Ng
)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gne
iss (
Pt)
Gra
nite
(P
t)
Attic dust
60
80
100
120
140
160
180
200
220
Zn (
mg/k
g)
Allu
viu
m (
Q)
Te
rra
ce
(Q
)
Se
dim
en
t (N
g)
Pyro
cla
stite
(N
g)
Fly
sch
(P
g)
Sch
ist
(R)
Sch
ist
(Pt)
Gn
eis
s (
Pt)
Gra
nite
(P
t)
Top soil
30
40
50
60
70
80
90
Zn
(m
g/k
g)
-
Areas with dominantly presence of
the Oligocene and Neogene
volcanism
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
-
Spotting effect!!!! Kriging anomaly?
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
-
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
PERSPECTIVES…..
-
Artificial neural networks
Biological neuron and mathematical model of McCulloch and Pitts
neuron
Artificial Neural Network - A computer simulation of human
neurons. A
system (implemented in software or hardware) that is intended to
emulate
the computing structure of neurons in the human
brain-MODELLING
SYSTEM THAT CAN HANDLE A LARGE NUMBER OF INPUT AND
OUTPUT PARAMETERS.
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
-
Multilayer perceptron architecture
REASONS FOR
APPLICATION
They can model extremely complex
systems, which cannot be modeled
by methods based on linear
algebra.
No problems with the dimensionality
- it can be arbitrary.
Due to well developed learning
algorithms they are easy to use.
MULTILAYER PERCEPTRON
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
-
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
-
Copper distribution
Universal Kriging
Sasa – Toranica
Pb minesZletovo
Pb mines
Bučim
Cu open pit
(ANN-MLP)
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
-
GREDIT2018, 22nd March – 25th of March 2018, SKOPJE, St. Cyril
and Methodius University, Technical Campus
CONLUSIONSSpatial patterns show intensive deposition in the area
of poly-metallic
hydrothermal exploitations, Sasa, Zletovo and Bučim
The analyzed elements can explain and mark the anthropogenic
affects on
air pollution
These anthropogenic anomalies have an HISTORICAL RECORD for
decades
continuously introduction of significant emission of dust
particle with
enriched contents of Cd, Pb and Zn.
This investigation fortifies an extended anthropogenic
association
(Ag, Bi, In and Mn)
secondary affection from mine poly-metallic
pollutionagricultural activities (use of urban sludge, manure and
phosphate fertilizers)
-
THANK YOU FOR YOUR ATTENTION!
