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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