Environmental transformation products of explosives
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Environmental transformation products of explosives Mateusz Szala Military University of Technology Warsaw, Poland DAIMON Kick-off Meeting Sopot, Poland, February 8-10, 2016
Transcript of Environmental transformation products of explosives
Environmental transformation
products of explosives
Mateusz Szala
Military University of Technology Warsaw, Poland
DAIMON Kick-off Meeting Sopot, Poland, February 8-10, 2016
Outline
My background
(synthesis, NMR analysis, blasting properties)
Explosives – modern and common
(TNT, RDX, HMX, NTO, DAAF, HNIW)
Transformation o explosives in environment (degradation products, metabilites)
Toxicity of explosives (acute LD50 and LC50 for fish and mammalia)
Summary
Area of interest
Modern explosives
1980 1905
1964 1998 1987
1999 1998 1983
NH
N
NH
N
O
O
O
N N
N N
NN
NO2
NO2
O2N
O2N
NO2O2N
C
C
NH2 NH2
O2N NO2N N
O
NH2N
N N
O
N NH2
O
NH+
NH
NH
NH2
NH2
NH2
NH+
NH
NH
NH2
NH2
NH2
N
N
N
N
N
N
N
N
N
N
N
N N
N
OO
O
OO
O
CCH2 CH2
CH2
CH3
OHO
ONO2
H
n
1983
NTO
DAAF HNIW
DADNE
TAGAZ
ONC
TNAZ pNIMMO
Common explosives
CH3
N
N
N
O
O
O O
O
O
N
N
N
N
N
N
O
O
O O
O
O
N
N
N
N
N
N
O
O
OO
O
O N
NO
O
O
O
O
O
N
N
N
N
OO
O
O
O O
O
O
O
O
O
N
N
N
O
O
O
O
O
O
Pb
N
N
N
N
N
N
1846 1863
1894
1899 1941
1891 1833
O
CH O
CH
CHCH
CH
O
CH2
ONO2
CH CH
CH
OCH
CH
O
CH2O2NO
ONO2
ONO2
ONO2
ONO2
n
TNT RDX
HMX NG
PETN
NC
LA
Physicochemical propetries of selected common explosives
Chemical Properties Database, Gunpowder Services Inc. http://www.gsi-net.com/usefultools/chempropdatabasehome.asp (July 2008) .
HSDB hazardous substances data bank, national Library of medcine, Bethesda, MD, http://toxnet.nlm.nih.gov/ (July 2008)
D. Rosenblatt , The handbook of Environmental Chemistry, vol. 3, part G, Springer, Heidelberg, 1991, 195.
F. Monteil-Rivera, Physico-chemical measurements of Cl-20 for environmental applications, Comparison with RDX and HMX, J. Chromatogr. A., 1025, 125, 2004.
Common
name/ Acronym
Melting
point, °C
Water
solubility, mg·dm-3
Octanol/wat
er partition coef., log
Ko/w
Vapour
pressure at 25 °C, mm
Hg
2,4-DNT 71.0 270 1.98 1.47·10-4
TNT 80.6 130 1.6 1.99·10-4
Tetryl 129.5 75 2.04 5.69·10-9
TATB 350.0 (dec.) 5 0.7 1.34·10-11
Picric acid 121.8 12800 1.33 7.5·10-7
NC 206.0 (dec.) Insoluble nd nd
PETN 143.3 43 3.71 5.38·10-9
NG 13.0 13 1.62 2·10-4
RDX 204.0 56 0.9 4.0·10-9
HMX 286.0 4 0.17 3.3·10-14
Environmental transformation of TNT
CH3
O2N
NO2
NO2 CH3
O2N
HN
NO2
OH
[H]
CH3
O2N
NH2
NO2
[H]
CH3
O2N
NO2
NH2
CH3
O2N
NO2
NH
OH
N
N
CH3
CH3 NO2
NO2
O2N
O2N
[H]
[H]
CH3
H2N
NO2
NH2
CH3
O2N
NH2
NH2
N
N
CH3 NO2
NO2
O2N
O2N
CH3
N
N
CH3
NO2
NO2
O2N
O2N
CH3
TNT
2,4’-Az
4,4’-Az 2,2’-Az
D. Kaplan, A. Kaplan, Reactivity of TNT and TNT-microbial reduction products with soil components, Technical raport , NATICK/TR-83/041, US Army 1983.
Munition wastewaters transformation of TNT
TNT
TNB
3,5-DNA
TN-Benzyl Alcohol
DNPhenol
DNBenzoic acid
CH3
O2N
NO2
NO2
C
O2N
NO2
NH2
O OH
CH2
O2N
NH2
NO2
OH
C
O2N
NO2
OH
O OH
CH3
O2N
NO2
NH2
CH3
O2N
NH2
NO2
+
O2N
NH2
NO2
C
O2N
NO2
O OH
O2N
NH2
NH2 O2N
NO2
OH
C
O2N
NO2
NO2
O OH
TNBA
ha
ha
T T
mic
Spanggord et al. Environmental fate studies on certain munition wastewater constituents, Phase IV – Lagoon model studies. Menlo Park, California: SRI Internationsl ADA 138550, 1983.
Abiotic transformations of TNT
TNT
TNBenzoic acid
CH3
NO2O2N
NO2
C
NO2O2N
NO2
O H
CH3
NH2O2N
NO2
CH3
NO2O2N
NH2
CH3
NO2O2N
NO2
OH
?
C
NO2O2N
NO2
O OH
CH3
NH2H2N
NO2
CH3
NH2O2N
NH2
CH3
NH2H2N
NH2
ha
Fe2+
base
TAT
D. Schmelling et al.. Photocalalytic transformation and mineralization of TNT i TiO2 slurries, Water Res. 29, 2651, 1995.
T. Hofstetter et al.., Complete reduction of TNT and other (poly)nitroaromatic compounds under iron-reducing subsurface conditions, Environ. Sci. Technol., 33, 1479, 1999.
A. Mills et al.., Alkaline hydrolysis of TNT, Phys. Chem. 5, 3921, 2003.
Aerobic transformations of TNT
T. Kalafut, Biotransformation pattern of TNT by aerobic bacteria, Current Microbiol., 36, 45, 1998.
C. French et al., Aerobic degradation of TNT by enterobacter cloace PB2 and PETN reductase, Appl. Environ. Microbiol., 64, 2864, 1998.
M. Pasty-Grigby et al. Transformation of TNT by actinomycetes isolated from TNT-contaminated and uncontaminated environments, Appl. Environ. Microbiol. 62, 1120, 1996.
Bacterial strain TNT,
mg·dm-3
Degradation
%
Degradation products
NO2- Denitrat.
Prod. Meisenheimer
cmplx ADNT
Bacillus sp. 100 95 + 2A4NT nd +
Enterobacter cloacae PB2 113 98 + — + Nd
Methylobacterium sp. 25 100 nd nd nd +
Pseudomonas sp. 50 100 + DNT + +
Mycobacterium vaccae 113 98 + — + +
Pseudomonas fluorescens nd nd + — + +
Streptomyces chromofuscus A11
25 100 — nd nd +
Staphylococus sp. 100 98 + 2A4NT nd +
Degradation of TNT with Fungi
T. Fernando et al. Biodegradation of TNT by Phanerochaete chrysosporium, All. Environ. Microbiol. 56, 1666, 1990.
K. Scheibner, Screening for fungi intensively mineralizing TNT, Appl. Microbiol. Biotechnol., 47, 452, 1997.
Fungal strain TNT, mg·dm-3 CO2, % Biotransformation, %
Phanerochaete chrysosporium ATCC 1767
100.7 13.7 100
Phanerochaete chrysosporium BKM-F-1767
100.0 18.0 100
Phanerochaete chrysosporium
BKM-F-1767 40.0 10.0 100
Fomes fomentarius MWF01-4 22.7 8.0 93
Clitocybe odora TM3 22.7 5.1 88
Alternaria TMRZ/WN2 22.7 0.4 74
Mucor mucedro DSM810 22.7 0.1 95
Neurospora crassa TM 22.7 0.6 100
Rhizoctonia solani MWi5 22.7 0.2 90
Abiotic transformations of RDX
RDX
denitration
ha Fe2+
N
N
N
NO2
NO2O2N
N
N
NNO2O2N
N
N
N
NO
NO2O2N
N
NH
NNO2O2N
OH C
NH
NH
NNO2O2N
O
H
NHNH
NO2O2N
NHNH
O2N
O
H
+
N2O
NH3
HCOOH
HCOH
NH2COH
N
N
N
NO
NOO2NN
N
N
NO
NOON
Catalyst: Me0
reduction
electrolysis
L. Hundal et al. Removal of TNT and RDX from water and soil using iron metal, Environ. Pollut., 97, 55, 1997.
J. Hawari et al.. Photodegradation of RDX in aqueous solution: a mechanistic probe for biodegradation with Rhodococcus sp., Environ. Sci. Technol., 36, 5117, 2002.
V. Balakrishnan et al.. The alkaline hydrolysis of the cyclic nitramine explosives RDX, HMX, CL-20: New insights into degradation pathways obtained by theobservation of novel intermediates, Environ. Sci. Technol. 37, 1838, 2003.
K. Gregory et al.., Abiotic transformation of RDX by Fe bound to magnetite. Environ. Sci. Technol. 38, 1408, 2004.
MEDINA
MEFNDA
Biotic transformations of RDX
RDX anaerobic aerobic
J. Zhao et al. Biodegradation of RDX and its mononitroso-derivative by Klebsiella peneumoniae strain SCZ-1 isolated from and anaerobic sludge, Appl. Environ. Microbiol. 68, 5336, 2002.
N. Coleman et al. Aerobic biodegradation of RDX as a nitrogen source by Rhodococcues sp. strain DN22, Soil. Biol. Biochem, 30, 1159, 1998.
http://www.fakt.pl/wydarzenia/odporna-na-antybiotyki-bakteria-klebsiella-pneumoniae-ndm-w-polsce,artykuly,488341.html
N
N
N
NO2
NO2O2N
N
N
NNO2O2N
N
N
NO2N
NHNH
NO2O2N
NHNH
O2N
O
H
N2O
NH3
HCOOH
HCOH
NH2COH
NH
NH
NO2N
OH
OH
N
NH
NO2N
OH
NO2
Klebsiella peneumoniae
Biotic transformations of HMX
denitrifiers
methanogens
reductase
Microbial degradation of RDX and HMX, SERDP Project CU1213, 2004.
NN
N N
NO2
NO2O2N
O2N
NN
N N
NO2
NOO2N
O2N
NN
N N
NO2
NOO2N
ON
NN
N N
NO2
NOON
O2N
+
CH2
NOH
CH2
N
H
NO2 NO2
3
NHCH2
NH
NO2 NO2
CH2
NOH
CH2
N
CH2
NO2 NO2
OH
CH2
N
CH2
NO2
OHOH
N
NH2
O O
N
NH
OH ON
NH2
O O
N2O N2
HCHO HCOOH CO2 CH4+
MEDINA
unidentified
products
Biotic transformations of PETN
PETN
Enterobacter cloacae
reductase
P. Binks et al.. Degradation of PETN by Enterobacter cloace PB2, Environmental Microbiology, 1996, p.1214.
C
CH2
CH2
CH2CH2
O
O
O
O
O2N
NO2
NO2
O2N
C
CH2
CH2
CH2CH2
O
OH
O
O
O2N
NO2
O2N
C
CH2
CH2
CH2CH2
O
OH
O
OH
O2N
NO2
C
CH2
CH2
CCH2
O
O
O
OH
O2N
NO2
HC
CH2
CH2
CC
O
O
O
O
O2N
NO2
H
H
C
CH2
CH2
CH2CH2
O
OH
O
OH
O2N
NO2
Biotic transformations of NG
NG
glycolysis
CO2
J. Husserl, Biodegradation of NG as a growth substrate, Thesis, Georgia Institure of Technology, 2011.
http://www.hkbs.co.kr/?m=bbs&bid=special15&uid=131292
a
CH2
CH
CH2
O
O
O
NO2
O2N
NO2
CH2
CH
CH2
O
OH
O
NO2
NO2
CH2
CH
CH2
O
O
OH
NO2
O2N
CH2
CH
CH2
OH
OH
O
NO2
CH2
CH
CH2
OH
O
OH
O2N
CH2
CH
CH2
OH
OH
OH
CH2
CH
CH2
OH
O
OH
O2NCH2
CH
CH2
OH
O
O
O2N
P
O
OHOH
H2O
Arthrobacter sp. Strain JBH1
Acute Oral Median Lethal Dose (LD50) to Western Fence Lizard
(Sceloporus occidentalis)
http://s202.photobucket.com/user/Zygote_photos/media/Ready_0199.jpg.html
C. McFarland et al. Toxicity of RDX in western fence lizards, Environ. Toxicol. Chem. 27, 1102, 2008.
J. Suski et al.. Dose-related effects following oral exposure of 2,4-DNT on the western fence lizard, Environ. Toxicol. Chem. 27, 352, 2008.
D. Liu et al. Toxicity of TNT wastewaters to aquatic organisms, Report DAMD 17-25-C-5056, 1983.
RDX,
mg·kg-1
DNT,
mg·kg-1
TNT,
mg·kg-1
Males 72 380 1038
Females 88 577 1579
Toxicological interactions of TNT and RDX
Fathead minnow
https://www.studyblue.com/notes/note/n/lab-practical-1/deck/1314004
http://blog.survivalsage.com/2013/04/when-shtf-find-these-fish-and-tarp.html
D. Liu et al. Toxicity of TNT wastewaters to aquatic organisms, Report DAMD 17-25-C-5056, 1983.
Explosive 96h LC50,
mg·dm-3
TNT 2.4
RDX 4.5
TNT/RDX (1:1) 5.4
TNT/RDX (1:3) 6.8
TNT/RDX (3:1) 1.9
Transformation
product
96h LC50,
mg·dm-3
TrinitroBenzene 1.1
TrinitroBenzAldehyde 1.0
TriNitroBenzoNitrile 2.0
DinitroAnthranil 0.16
Toxicological interactions of TNT and RDX
Daphnia Magna
http://www.evolution.unibas.ch/ebert/publications/parasitismdaphnia/ch2f12.htm
D. Liu et al. Toxicity of TNT wastewaters to aquatic organisms, Report DAMD 17-25-C-5056, 1983.
Explosive 48h LC50,
mg·dm-3
TNT 1.27
RDX 12.9
Transformation
product
48h LC50,
mg·dm-3
TrinitroBenzene 2.7
TrinitroBenzAldehyde 1.5
TriNitroBenzoNitrile 1.0
DinitroAnthranil 0.34
Acute toxicity of selected explosives
http://www.evolution.unibas.ch/ebert/publications/parasitismdaphnia/ch2f12.htm
http://cfb.unh.edu/phycokey/Choices/Anomalous_Items/invertebrates/Hydroids/HYDRA/Hydra_image_page.html
http://www.mountainanglers.com/Rainbow-Trout.html
D. Liu et al. Toxicity of TNT wastewaters to aquatic organisms, Report DAMD 17-25-C-5056, 1983.
Species
Explosive
Acute toxicity 96h LC50,
mg·dm-3
TNT RDX NG NQ
Invertebrates (D. Magna) 1.27 12.9 34.0 2.7
Hydra cladoceran n/a 17.0 17.8 2.1
Rainbow trout 2.6 12.7 1.9 1.5
Acute oral toxicities of explosives to rats
Mammalian toxicity of munition compounds: phase I. Acute oraz toxicity, primary skin and eye irritation, dermal sensitiaztion, and disposition and metabilism, Project No 3900-B, 1975.
http://sciencegraydon.blogspot.com/2012/10/journal-entry-7-typhoid-animal-model.html
Explosive LD50, mg·kg-1
Males Females
TNT 1010 820
RDX 71 70
Mustard gas 20* 20*
Nitrocellulose >5000 >5000
White phosphorus 4.85 4.82
Genotoxicity of Explosives
Mammalian toxicity of munition compounds: phase I. Acute oraz toxicity, primary skin and eye irritation, dermal sensitiaztion, and disposition and metabilism, Project No 3900-B, 1975.
http://sciencegraydon.blogspot.com/2012/10/journal-entry-7-typhoid-animal-model.html
TNT and it’s metabolites
Microorganism: Salmonella typhimurium Vibrio fischeri Escherichia coli Neurospora crassa Saccharomyces cerevisiae
Mammalia: Mouse P388 – lymphoma Chinese hamster – HGPRT locus
Mammalia:
Chinese hamster V79 CH3
NH2H2N
NH2
N
N
CH3
NO2
NO2
O2N
O2N
CH3
CH3
O2N
NO2
NH2
CH3
O2N
NH2
NO2
CH4
Summary (1) – potential markers
Summary (2) TNT (nitroaromatics) and nitroamines are susceptible to
environmental transformation. The main reaction paths
are recognized. For fast identification e.g. by using HPLC
methods is possible but standards are required.
Aqueous toxicity of common explosives is well known for
variety of freshwater and marine species. Especially RDX
and TNT is acutely toxic to fish and aquatic invertebrates.
Some of energetic compounds metabolites are more
toxic than starting compounds due to the solubility in
body fluids.
Common explosives and it’s metabolites are acutely
(chemical), genetically toxic to water and land species.
