Toxic metals from munition
(A 2.3.5)
Grzegorz Siedlewicz Marine Chemistry and Biochemistry Department,
Institute of Oceanology Polish Academy of Sciences
Toxic metals in munition
(Hg, Pb, As)
• Conventional munition primers
• Mercury fulminate
• Lead azide
• Arsenic (CWA constituent)
• Clark I, Clark II, Lewisite, Adamsite
• Arsine oil
Conventional munition
Platinum wire, mercury fulminate
Mercury methylation
• Anoxic environment
• Ionic mercury as a
substrate
• SRB bacteria
• Organic matter
• No UV
methylation process conditions
Mercury analyses
Quantitative measurements of Hg:
-Cold Vapor Atomic Fluorescence Spectrophotometer (CVAFS)
Mercury Analysis System model 2600 (TEKRAN)
(Bełdowski and Pempkowiak 2003)
Quantitative measurements of MeHg:
-Cold Vapor Atomic Fluorescence Spectrophotometer (CVAFS)
Methylmercury Analysis System MAREX-M (BROOKS RAND)
(Bełdowski et al. 2014; EPA 1690; USGS Method 5 A-7)
www.iopan.gda.pl
Mercury species to be measured:
• Hgtot
• MeHg
www.brooksrandinc.com
Lead analyses
Quantitative measurements of Pb:
-Inductively Coupled Plasma – Mass Spectrometry (Perkin Elmer ELAN 9000).
(Zaborska 2014)
-Atomic Absorption Spectrophotometer AA-6800 Series (SHIMADZU)
(Vallius and Leivuory 1999)
www.iopan.gda.pl
www.iopan.gda.pl
Correlations
-1,00
-0,50
0,00
0,50
1,00
LOI Cd Fe Pb Zn Mn Hg
Hot Cold
GEOCHEMICAL BACKGROUND: 5-10µg∙g-1
As
Arsenic analyses
Quantitative measurements of As species in sample using ion-exchange chromatografic
column (CF-Kit-As35) combined with detection on Inductively Coupled Plasma –
Mass Spectrometry (Perkin Elmer ELAN 9000).
(Koch et al. 2002; Krysiak and Karczewska 2007; Simon et al. 2004)
Arsenic species to be measured:
• As(III)
• As (V)
• Arsenobetaine
• Monomethylarsine
• Dimehylarsine
www.iopan.gda.pl ww
w.icp
ms.c
om
Sample treatment
Wet
sediment
sample
370 g
Pore
water
360 ml
Freeze drying Granulometry
30g
LOI
4g
MeHg/Hg
180 ml
Pb
4g
As
5g
XRF
10g
Moisture
Pb
90 ml
As
90 ml
MeHg/Hg
12g
Toxic metals analyses workplan
START
16-02-08
END
19-06-05
3 quarter 1 quarter 3 quarter
Methylmercury
16-03-01 - 17-07-17
Procurement of
equipment
16-03-01 - 16-10-10
Arsenic speciation
16-03-01 - 17-07-17
Methods test
16-03-01 - 16-
07-18
Total Mercury 16-05-02 -17-02-03
Method test
16-05-02 - 16-
09-16
Lead 16-05-02 - 17-02-03
Methods test
16-05-02 - 16-
09-16
Optimization and validation of analytical
procedure
16-07-19 - 17-07-17
Optimization
and validation
of analytical
procedure
16-09-19 - 17-
02-03
Optimization
and validation
of analytical
procedure
16-09-19 - 17-
02-03
Methods
test
16-10-11 -
17-01-30
Optimization and
validation of
analytical
procedure 17-01-
31 17-07-17
Report
16-07-18
Report
16-09-16
Report
16-09-16
Report
17-01-30
Validation report
17-02-03
Validation raport
17-02-03
Validation report
17-07-17
Validation report,
17-07-17
O 2.3 Toolbox for measuring
warfare agents' pollution in
sediments 17-07-17
1 quarter 3 quarter 1 quarter
Thank you for attention
Bełdowski J. Pempkowiak J., 2003 Horizontal and vertical variabilities of mercury concentration and speciation in sediments of the Gdansk Basin, Southern Baltic Sea Chemosphere, 52 (2003), pp. 645–654
Bełdowski J. , Miotk M. , Bełdowska M. , Pempkowiak J. Total, methyl and organic mercury in Sediments of the Southern Baltic Sea Mar. Pollut. Bull., 87 (2014), pp. 388–395
EPA Method 1630 Methyl Mercury in Water by Distillation, Aqueous Ethylation, Purge and Trap, and CVAFS, EPA 821-R-01-020Koch et al. 2002‘Sample extraction for arsenic speciation’, Canadian Journal of Analytical Sciences and Spectroscopy
Krysiak & Karczewska 2007‘ Arsenic extractability in soils in the areas of former arsenic mining and smelting, SW Poland, Science of the Total Environment
Simon et al. 2004‘Simultaneous determination of twelve inorganic and organic arseni compounds by liquid chromatography-ultraviolet irradiation-hydride generation atomic fluorescence spectrometry, Journal of Chromatography A
USGS Method 5 A-7 Methods for the Preparation and Analysis of Solids and Suspended Solids for Methylmercury.
Vallius and Leivuory 1999, The distribution of heavy metals and arsenic in recent sediments in the Gulf of Finland Boreal Environ. Res. 4: 19–29
Zaborska A. 2014, Anthropogenic lead concentration and sources in Baltic Sea sediments based on lead isotopic composition. Marine Pollution Bulletin 85. 99-113
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