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Blake International Limited Conventional Ammunition, Alternative Materials & Risk.

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1 Blake International Limited Conventional Ammunition, Alternative Materials & Risk

2 Lead Ammunition Leads density, malleability and casting characteristics make it an ideal material for use in the mass manufacture of projectiles and it has been used for this application since at least the time of the ancient Greeks. Today, lead still remains the primary material of choice for bullet and shot manufacture.

3 Pb-Sb Pb Bi Cu Cu-Sn Sn Zn Cu -Poly Steel W W-Poly W-Sn W-Steel (TNI) W-Bronze Relative Cost Density Projectile Materials The Alternatives to Lead-Antimony Alloys COST vs PERFORMANCE Pb-Zn

4 Lead is Durable Ely Cathedral: The central tower collapsed in the reign of Henry IV. It was replaced by a hexagonal lantern tower, constructed of oak clad with lead 1322 ~1342.

5 Lead is Durable Roman Baths at Bath, Somerset.: Built on a pre-roman pagan site, the Roman baths were constructed AD. The lead plumbing is still in place and in working condition after over 1,700 years! Original plumbing

6 Corrosion of Lead Corrosion of Lead in soil is linear in nature. Corrosion of Lead in soil is linear in nature. Antique lead corrodes at 4 to 6 x cm per year at pH >6.5 #. Antique lead corrodes at 4 to 6 x cm per year at pH >6.5 #. Equates to ~2,150- 3,250 years for shot (No.s 7-9) Equates to ~2,150- 3,250 years for shot (No.s 7-9) # Measurement of corrosion content of archaeological lead artifacts by their Meissner response in the superconducting state; a new dating method, S Reich, G Leitus and S Shalev, Deutsche Physikalische Gesellschaft. New J. Phys. 5 (July 2003) 99. © Copyright 2004 Cylenchar Limited

7 Development of Lead-Antimony Alloys © Copyright 2004 Cylenchar Limited Corrosion; electrolytic processes / redox effects. Corrosion; electrolytic processes / redox effects. Batteries are controlled redox corrosion systems. Batteries are controlled redox corrosion systems. Faure invention 1881 improved reliability of the redox corrosion process through; initiation (Pb0 / PbO 2 / PbSO 4 ) and improvedelectron yield of the plate (Pb-Sb alloy) Automotive Battery Faure invention 1881 improved reliability of the redox corrosion process through; initiation (Pb0 / PbO 2 / PbSO 4 ) and improvedelectron yield of the plate (Pb-Sb alloy) Automotive Battery Downside increased corrosion on +ve Plate. (ANODIC CORROSION) Downside increased corrosion on +ve Plate. (ANODIC CORROSION)

8 Construction of Lead-Acid Batteries Connecting stems and posts - 4% Sb. Negative Plates - 2% Sb Lead alloy. Positive Plates have 0% Sb or low Sb + other metals; Ca, Se, As, Ag, Al, Sn, etc. Recycled Battery Lead contains ~2% Sb. For positive plate production of limited use as its too corrosive ~1.4 M tonne p.a. surplus Pb-Sb alloy World wide ~300,000 tonnes p.a. Pb-Sb alloy used in projectile manufacture.

9 Comparative Corrosion of 2mm Pure Lead Shot vs US No.8 Lead- (1.25%w/w)Antimony Shot © Copyright 2004 Cylenchar Limited

10 Roman Lead Sling Shot Excavated from Roman sites on the Danube. May date from ~100BC, and are no older than Trajans Dacian campaign ~100AD. Slow corroding Pb-4%As alloy.

11 UK-No7.5 Shot; 4% Sb, >1%O Polished un-etched cross-sections © Copyright 2004 Cylenchar Limited

12 US-#8 Shot ~1.25% Sb, 2.2%O Polished un-etched cross- sections © Copyright 2004 Cylenchar Limited

13 The Contents and Structure of Commercial Lead Shot Lead-antimony alloy shot isnt homogeneous, its a heterogeneous material, made up of:- Lead-antimony alloy shot isnt homogeneous, its a heterogeneous material, made up of:- Lead-antimony poor alloy granules separated by lead- antimony rich (>10%Sb) brittle, porous dendritic eutectic alloy. (Pb-As / Pb-Sn alloys have lower redox potential, with coarser and tighter crystal structure) Lead-antimony poor alloy granules separated by lead- antimony rich (>10%Sb) brittle, porous dendritic eutectic alloy. (Pb-As / Pb-Sn alloys have lower redox potential, with coarser and tighter crystal structure) High levels of antimony at the surface. High levels of antimony at the surface. Other metals, (As, Ag, Al, Cu, Sn, Zn) in dendritic zone. Other metals, (As, Ag, Al, Cu, Sn, Zn) in dendritic zone. Contains ~6-12%w/w lead oxide and sulphate, from secondary lead (result of crudely melted old batteries!) Contains ~6-12%w/w lead oxide and sulphate, from secondary lead (result of crudely melted old batteries!)

14 Summary of Corrosion Rates for Shot Sample Linear Slope mg/Litre/day Approx. Corrosion Rate mg/m 2 /day Relative Corrosion Rate Pure Lead (~2mm dia) / 1.00 N o 8 Lead- Antimony Shot / 22.4 N o 6 Steel Shot / N o 8 Lead- Antimony Shot + Steel Shot / N o 8 Lead- Antimony Shot + 1% IFS / 0.018

15 © Copyright 2004 Cylenchar Limited Heavy Metals Released on Dilution of Steel Shot Corrosion Product

16 Electrochemical Series of Selected Ammunition Metals and their Contaminants - Thermodynamic issues Eq.N o Redox Reaction Redox Potential E o (volts) 1 Ag + (aq) + e- Ag (s) Bi 3+ (aq) + 3e- Bi (s) Cu 2+ (aq) + 2e- Cu (s) Sb 3+ (aq) + 3e- Sb (s) W 3+ (aq) + 3e- W (s) Pb 2+ (aq) + 2e- Pb (s) Sn 2+ (aq) + 2e- Sn (s) As 3+ (aq) + 3e- As (s) Fe 2+ (aq) + 2e- Fe (s) Ni 2+ (aq) + 2e- Ni (s) Zn 2+ (aq) + 2e- Zn (s) Mn 2+ (aq) + 2e- Mn (s)

17 Redox Corrosion Mechanism of Lead-Antimony Alloy – Kinetic Issues METAL-WATER INTERFACE METAL ANODIC REGION METAL CATHODIC REGION Pb(s) Pb 2+ (aq) + 2e - Anodic Region: Pb 2+ Pb(OH) 2 / PbOHCO 3 PbO / PbO 2 Cathodic Region: O 2 (g) + 2H 2 O + 4e - 4OH - (aq) H 2 CO 2 (aq) + 2OH - (aq) CO 3 - (aq) + H 2 O PbO 2 + H 2 O+ 2e- PbO +2OH - e - generated at anodic region released at the cathodic region Surface Area Increases due to porosity / frangibility Sb(s) Sb 3+ (aq) + 3e - Sb 3+ (aq) Sb(OH) 3 mildly acidic + High Redox potential ~2.0eV Fe Fe e- fast Fe 2+ + O 2 Fe 3+ fast, Acidic Aq ion + high redox potential ~2.5eV Sb3+(aq) + 3e- Sb(s) Fe e- Fe Fe 3+ (aq) + e - Fe 2+ (aq) CORROSION ACCERATED BY > ACIDITY, > SURFACE AREA & < PASSIVATION INITIAL CORROSION SLOWED BY PbO PASSIVATION IRON >> CORROSION

18 UK-5.56 Core; nominally 10% Sb, 3.8%O Polished un-etched cross-section © Copyright 2004 Cylenchar Limited

19 US-5.56 Core; 7-18%O Polished un-etched cross-section

20 Lead/Steel - Environmental Risk Factors Lead shot and bullets from secondary lead contain Toxic lead oxide / sulphate. Lead shot and bullets from secondary lead contain Toxic lead oxide / sulphate. Antimony and other impurities increase corrosion rates. Antimony and other impurities increase corrosion rates. Steel shot fired onto legacy lead High Redox material + lower pH increases Pb and Sb corrosion + Fe contaminants; e.g. Ni, Mn. Steel shot fired onto legacy lead High Redox material + lower pH increases Pb and Sb corrosion + Fe contaminants; e.g. Ni, Mn. Steel shot fast corroding Fe and Mn oxides transport metal for heavy metals; e.g. Pb, Sb, As, etc. Steel shot fast corroding Fe and Mn oxides transport metal for heavy metals; e.g. Pb, Sb, As, etc.

21 What should be the Risk status of Lead Projectiles, harmful irritant metal or Toxic oxide? ? Does Steel solve or compound the problem?

22 The Properties of Tungsten High density metal 19g/cc High density metal 19g/cc m.pt >3,400 o C W-Powder Technology m.pt >3,400 o C W-Powder Technology Inert, Insoluble and Non-toxic ??? Inert, Insoluble and Non-toxic ??? Noble metal High redox potential. Noble metal High redox potential. W readily oxidized in air at RT, rapid oxidation above 200 o C # W readily oxidized in air at RT, rapid oxidation above 200 o C # W powder is PYROPHORIC! W powder is PYROPHORIC! #" Tungsten, Properties, Chemistry, Technology of the element, Alloys, and Chemical Compounds" by Erik Lassner and Wolf-Dieter Schubert, Kluwer Academic/Plenum Publishers 1999 ISBN

23 Insoluble! – Low solubility in acids, soluble to alkali, and aqueous oxygenating environments: Anodic Oxidation; (i) W + 8OH - WO e - + 4H 2 O Cathodic reduction; (ii) O 2 + 2H 2 O + 4e - 4OH - Insoluble! – Low solubility in acids, soluble to alkali, and aqueous oxygenating environments: Anodic Oxidation; (i) W + 8OH - WO e - + 4H 2 O Cathodic reduction; (ii) O 2 + 2H 2 O + 4e - 4OH - Dissolution rate slow (30µm) pure W powder at 10%w/v in pure water ~10mgW/litre/day. Dissolution rate slow (30µm) pure W powder at 10%w/v in pure water ~10mgW/litre/day. Aqueous solubility of W metal 75mg/Litre at 38 o C equilibrium, i.e. pH 3.2. Passivates only below pH 4. Aqueous solubility of W metal 75mg/Litre at 38 o C equilibrium, i.e. pH 3.2. Passivates only below pH 4. H 2 WO 4.H 2 O - pKa 3.6 and very soluble and colloidal. H 2 WO 4.H 2 O - pKa 3.6 and very soluble and colloidal. Soil based electrolytes, Fe and Pb increase solubility and dissolution significantly! E.g. FeOH.WO 4 (5H 2 0) and PbWO 4 (Stolzite) sink effects. Soil based electrolytes, Fe and Pb increase solubility and dissolution significantly! E.g. FeOH.WO 4 (5H 2 0) and PbWO 4 (Stolzite) sink effects. #" Tungsten, Properties, Chemistry, Technology of the element, Alloys, and Chemical Compounds" by Erik Lassner and Wolf-Dieter Schubert, Kluwer Academic/Plenum Publishers 1999 ISBN The Properties of Tungsten #

24 The Properties of Tungsten SR Instrumentation Engineering Group Report, "Erosion/Corrosion of Machinable Tungsten in Water, Jeff T. Collins, Advanced Photon Source Experimental Facilities Division, SR Instrumentation Engineering Group, November 30, 2000 SR Instrumentation Engineering Group Report, "Erosion/Corrosion of Machinable Tungsten in Water, Jeff T. Collins, Advanced Photon Source Experimental Facilities Division, SR Instrumentation Engineering Group, November 30, 2000 Corrosion of machinable tungsten steel by oxygenated water Corrosion of machinable tungsten steel by oxygenated water

25 W W WWWWWWWWWWWWWWWWW WWWWWWWWWWWWWWWWWWW W Redox Corrosion of Tungsten Powder in Alloy

26 W W WWWWWWWWWWWWWWWWW WWWWWWWWWWWWWWWWWWW W M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+

27 W W0 3 W WWWWWWWWWWWWWWWW WWWWWWWWWWWWWWWWW M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ WO 3 Redox Corrosion of Tungsten Powder in Alloy

28 W W0 3 W WWWWWWWWWWWWWWWW WWWWWWWWWWWWWWWWW M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ WO 3 M+M+ M+M+ Redox Corrosion of Tungsten Powder in Alloy

29 W W0 3 W WWWWWWWWWWWWWWWW WWWWWWWWWWWWWWW M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ WO 3 M+M+ M+M+ Redox Corrosion of Tungsten Powder in Alloy

30 W W WWWWWWWWWWWWWWWW WWWWWWWWWWWWWWW M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ W0 3 WO 3 M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ H 2 W0 4 Redox Corrosion of Tungsten Powder in Alloy

31 W W WWWWWWWWWWWWW WWWWWWWWWWWWWW WO 3 M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ W0 3 WO 3 M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ W0 3 H 2 WO 4 H 2 W0 4 Redox Corrosion of Tungsten Powder in Alloy

32 W W WWWWWWWWWWWWW WWWWWWWWWWWWWW WO 3 M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ W0 3 WO 3 M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ W0 3 H 2 WO 4 H 2 W0 4 Redox Corrosion of Tungsten Powder in Alloy

33 W W WWWWWWWWWWW WWWWWWWWWWW WO 3 M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ M+M+ W0 3 WO 3 W0 3 H 2 WO 4 H 2 W0 4 Redox Corrosion of Tungsten Powder in Alloy

34 W W WWWWWWWWWWW WWWWWWWWWWW WO 3 W0 3 Base metal matrix dissolves via redox induced corrosion. Colloidal tungsten exposed and rendered soluble via oxidation. pH falls giving deposition of non- protective WO 3 and soluble isotungstates. If pH remains neutral or alkali, corrosion continues apace releasing tungstates. WO 4 2- salts formed with matrix corrosion products and soil contaminants. Redox Corrosion of Tungsten Powder in Alloy

35 Dissolution & Decay of Tungsten Polymer composite W W WWWWWWWWWWWWWWWWW WWWWWWWWWWWWWWWWWWW W

36 W W WWWWWWWWWWWWWWWW WWWWWWWWWWWWWWWWWW W0 3 WO 3 Dissolution & Decay of Tungsten Polymer composite

37 W W WWWWWWWWWWWWWWWW WWWWWWWWWWWWWWWWWW W0 3 WO 3 Dissolution & Decay of Tungsten Polymer composite

38 W W WWWWWWWWWWWWWWWW WWWWWWWWWWWWWWW W0 3 WO 3 Dissolution & Decay of Tungsten Polymer composite

39 W W WWWWWWWWWWWWW WWWWWWWWWWWWWW W0 3 WO 3 WWW W Dissolution & Decay of Tungsten Polymer composite

40 W W WWWWWWWWWWWWW WWWWWWWWWWWWWW W0 3 WO 3 Dissolution & Decay of Tungsten Polymer composite

41 W W WWWWWWWWWWWWW WWWWWWWWWWWWWW W0 3 WO 3 Dissolution & Decay of Tungsten Polymer composite

42 W W WWWWWWWWWW WWWWWWWWWWWWW W0 3 WO 3 H 2 WO 4 H 2 W0 4 Dissolution & Decay of Tungsten Polymer composite

43 W W WWWWWWWWWW WWWWWWWWWWWWW W0 3 H 2 W0 4 WO 3 H 2 WO 4 WO 3 H 2 WO 4 H 2 W0 4 Dissolution & Decay of Tungsten Polymer composite

44 W W WWWWWWWWW WWWWWWWWW W0 3 WO 3 H 2 W0 4 H 2 WO 4 Dissolution & Decay of Tungsten Polymer composite

45 W W WWWWWWWWW WWWWWWWWW W0 3 WO 3 Oxidation and dissolution of tungsten Assisted by physical rupture of matrix by reactive W oxides Coincidental with, or preceded by decay of the polymer matrix. Dissolution & Decay of Tungsten Polymer composite

46 W W WWWWWWWWW WWWWWWWWW W0 3 WO 3 R 1 -CH 2 -CO-NH-CH 2 -R 2 + H 3 O + R 1 -CH 2 -CO 2 H + H 2 N-CH 2 -R 2 R 1 -CH 2 -CO-NH-CH 2 -R 2 R 1 -CH 2 -CO-NH-*CH-R 2 + O 2 R 1 -CH 2 -CO-NH-CO-R 2 + H 2 O Acid Hydrolysis W / Cu free-radical induced oxidation (Plastics Cancer) Dissolution & Decay of Tungsten Polymer composite

47 Inherent Redox Instability of Tungsten Powder Technology – e.g. Chang et al (1998) When W was coupled to Fe #, CDA (Cu-Ni Bronze) and Invar (Ni-iron), significantly large current densities were measured. This suggest that corrosion protection schemes will need to be developed for W-alloys using these materials in the matrix. When W was coupled to Fe #, CDA (Cu-Ni Bronze) and Invar (Ni-iron), significantly large current densities were measured. This suggest that corrosion protection schemes will need to be developed for W-alloys using these materials in the matrix. Similar materials have been approved for sale in the US as NON-TOXIC under US Fish & Wildlife Department regulations. (Submissions cite limited duration in-vivo studies on waterfowl.) Similar materials have been approved for sale in the US as NON-TOXIC under US Fish & Wildlife Department regulations. (Submissions cite limited duration in-vivo studies on waterfowl.) Ref: Galvanic Corrosion of Tungsten Coupled With Several Metals/Alloys; Chang F.C., Beatty J.H., Kane M.J., Beck J; Army Research Lab, Aberdeen Proving Ground, MD

48 Inherent Redox Instability of Tungsten Powder Technology – e.g. Meijer et al (1998) W-Ni alloys with Fe, Cu, Co, Mn and Ta studied in relation to use at Elgin AFB. 10 year projection/assumption: Average 0.55% w/w W and 0.036% w/w Ni over surface area to a depth of 1cm, with average particle size 0.5cm. W-Ni alloys with Fe, Cu, Co, Mn and Ta studied in relation to use at Elgin AFB. 10 year projection/assumption: Average 0.55% w/w W and 0.036% w/w Ni over surface area to a depth of 1cm, with average particle size 0.5cm. Bare alloy (Stock Rod, not heat treated) discs, (26-33 mm dia) in rainfall event model drip tests over a ~6 hour period, yielded: Bare alloy (Stock Rod, not heat treated) discs, (26-33 mm dia) in rainfall event model drip tests over a ~6 hour period, yielded: W at mg/L (no soil) W at mg/L (no soil) Ni at mg/L (no soil) Ni at mg/L (no soil) Ni at mg/L (in soil) Ni at mg/L (in soil) Likely corrosion products include Cu-Ni and Ni Tungstates. Likely corrosion products include Cu-Ni and Ni Tungstates. Ref: Environmental Effects of Tungsten & Tantalum Alloys; Mejier A, Wroblicky G, Thrung S & Marcell MW; GCX Albuquerque NM; 1998

49 Inherent Redox Instability of Tungsten Powder Technology – e.g. Meijer et al (1998) W in Bonze alloy subject to sea water. Bronze matrix preferentially dissolves. W in Bonze alloy subject to ground water. Tungsten particles preferentially dissolve and give increased acidity. WO 3 W Grains Ref: Environmental Effects of Tungsten & Tantalum Alloys; Mejier A, Wroblicky G, Thrung S & Marcell MW; GCX Albuquerque NM; 1998

50 Inherent Redox Instability of Tungsten Powder Technology – e.g. Meijer et al (1998) W in Bonze alloy subject to ground water. Tungsten particles preferentially dissolve. With increasing acidity get formation of a Yellow scale NB: H 2 WO 4.H 2 O (Yellow), W0 3.2H 2 0 (white) WO 3 ? Ref: Environmental Effects of Tungsten & Tantalum Alloys; Mejier A, Wroblicky G, Thrung S & Marcell MW; GCX Albuquerque NM; 1998

51 Inherent Redox Instability of Tungsten Powder Technology – e.g. Meijer et al (1998) Tantalum and tungsten are strongly bound on mineral grains in the soil zone and will remain in this zone indefinitely Tantalum and tungsten are strongly bound on mineral grains in the soil zone and will remain in this zone indefinitely Unlikely to remain immobile, in our experience. Possibility of soil saturation and/or facilitated transport not considered. Dissolution tests done in absence of iron. Leach model sample seriously flawed! Unlikely to remain immobile, in our experience. Possibility of soil saturation and/or facilitated transport not considered. Dissolution tests done in absence of iron. Leach model sample seriously flawed! Tungsten and tantalum appear to have minimal human and ecological impact based on the current available data Tungsten and tantalum appear to have minimal human and ecological impact based on the current available data Scant evaluation of available tox. data! Scant evaluation of available tox. data! Analysis of potential ecological risks indicates no unacceptable risks will result from use of tantalum and / or tungsten alloys in the testing of penetrator munitions Analysis of potential ecological risks indicates no unacceptable risks will result from use of tantalum and / or tungsten alloys in the testing of penetrator munitions Independent comment: largely inconclusive with regards to the geochemical behaviour of tungsten and tungsten alloys Independent comment: largely inconclusive with regards to the geochemical behaviour of tungsten and tungsten alloys Ref: Environmental Effects of Tungsten & Tantalum Alloys; Mejier A, Wroblicky G, Thrung S & Marcell MW; GCX Albuquerque NM; 1998

52 Rapid dissolution of W from both W-Nylon an W-Tin bullet residues in sand column leaching studies: Rapid dissolution of W from both W-Nylon an W-Tin bullet residues in sand column leaching studies: deionised water, to 15.6 mg/L W. deionised water, to 15.6 mg/L W. simulated sea water, to 66 mg/L W. simulated sea water, to 66 mg/L W. simulated rain water, to 105 mg/L W. simulated rain water, to 105 mg/L W. On aging 130 o C, 48 days leach rates to 9,510 mg/L W. On aging 130 o C, 48 days leach rates to 9,510 mg/L W. W-Nylon residues with iron piercing tips faired least well. W-Nylon residues with iron piercing tips faired least well. Mixed W and WO 3 in rainwater, to 462 mg/L W. Mixed W and WO 3 in rainwater, to 462 mg/L W. Mixed W, WO 3 and H 2 WO 4 in rainwater, to 2,660mg/L W. Mixed W, WO 3 and H 2 WO 4 in rainwater, to 2,660mg/L W. It appeared that the tungsten powder oxidizes to form tungsten oxide, which is insoluble in water and thus relatively stable in the environment. It appeared that the tungsten powder oxidizes to form tungsten oxide, which is insoluble in water and thus relatively stable in the environment. Inherent Redox Instability of Tungsten Powder Technology – e.g. Middleton (1998) Ref: Elimination of Toxic Heavy Metals from Small Caliber Ammunition. Middleton J., SERDIP Report, ARDEC Picatinny 1998

53 Inherent Redox Instability of Tungsten Powder Technology – e.g. Middleton (1998) W uptake by Beans and Rye Grass, Growth stunted. Possibilities for phyto-remediation? W uptake by Beans and Rye Grass, Growth stunted. Possibilities for phyto-remediation? Earthworm toxicity study shows weight loss. W-Tin fared better than Pb - Worms on walls of the W test bin! Earthworms were not adversely affected Worm aversion test FAIL! Earthworm toxicity study shows weight loss. W-Tin fared better than Pb - Worms on walls of the W test bin! Earthworms were not adversely affected Worm aversion test FAIL! W-Nylon effect on earthworms not studied. Too acidic? W-Nylon effect on earthworms not studied. Too acidic? Earthworms in long term study contained 213ppm W:- Risk to food chain? Earthworms in long term study contained 213ppm W:- Risk to food chain? W binds strongly to soils/biomass. Twin edged sword. Other metals may bind strongly to colloidal W! W binds strongly to soils/biomass. Twin edged sword. Other metals may bind strongly to colloidal W! Ref: Elimination of Toxic Heavy Metals from Small Caliber Ammunition. Middleton J., SERDIP Report, ARDEC Picatinny 1998

54 Inherent Redox Instability of Tungsten Powder Technology Corroding W-Nylon round in situ. Massachusetts Military Reservation. Picture courtesy of Mark Begley Commonwealth of Massachusetts Environmental Management Commission

55 © Copyright 2004 Cylenchar Limited ECOMASS 10002D95, Tungsten in polyamide copolymer, 11g/cc Fresh Surface, injection moulded tile. Mole Ratio W:O 1:3.5

56 © Copyright 2004 Cylenchar Limited ECOMASS 10002D95 Aged Surface, Water 98 o C 3 hr. Mole Ratio W:O 1:4. Erosion & Oxidation. Carbon Matrix disappears. Ca detected

57 Tungsten – Toxicity Oral Toxicity: W – Irritant, LD 50 Rat 2-5g/Kg, WO 3 LD 50 Rat 840-1,050mg/Kg. - Mildly Toxic Oral Toxicity: W – Irritant, LD 50 Rat 2-5g/Kg, WO 3 LD 50 Rat 840-1,050mg/Kg. - Mildly Toxic Soluble W compounds are Toxic. Sub-acute effects include; weight loss, breathing problems, blood changes, decreased sperm motility with genetic changes, non-specific neurological disorders including tremors, adverse effects on the liver, spleen and kidneys, molybdenum deficiency, non-specific metabolic changes. (Lit. Rev. Haneke 2003) Soluble W compounds are Toxic. Sub-acute effects include; weight loss, breathing problems, blood changes, decreased sperm motility with genetic changes, non-specific neurological disorders including tremors, adverse effects on the liver, spleen and kidneys, molybdenum deficiency, non-specific metabolic changes. (Lit. Rev. Haneke 2003) Cancer: - Mildly Carcinogenic – Females at Greater Risk. 5ppm W in drinking water over lifetime produced tumours in 65% of female rats and 15% male rats. (Schroder & Mitchener 1975) Lung cancer mortality in tungsten miners has been attributed to silicosis. Recent studies indicate no link between the silicosis and lung cancer. (Chen et al 1994) Cancer: - Mildly Carcinogenic – Females at Greater Risk. 5ppm W in drinking water over lifetime produced tumours in 65% of female rats and 15% male rats. (Schroder & Mitchener 1975) Lung cancer mortality in tungsten miners has been attributed to silicosis. Recent studies indicate no link between the silicosis and lung cancer. (Chen et al 1994)

58 Tungsten – Toxicity Cancer promoter: Mammary cancer promoting effect of tungsten, an antagonist of molybdenum, noted in mice (Wei et al 1987). Mixed metal Tungsten ore increases the growth rate of leukemia cells (Witten et al 2005) Cancer promoter: Mammary cancer promoting effect of tungsten, an antagonist of molybdenum, noted in mice (Wei et al 1987). Mixed metal Tungsten ore increases the growth rate of leukemia cells (Witten et al 2005) Synergistic effects : The toxicity of Co is increased by the presence of WC. ( Roesems et al 1997) WC-Co is more genotoxic than Co and WC alone. (De Boeck et al 2003) Synergistic effects : The toxicity of Co is increased by the presence of WC. ( Roesems et al 1997) WC-Co is more genotoxic than Co and WC alone. (De Boeck et al 2003) DNA Affecter: Tungsten particle bombardment used to cleave DNA in creation of GM organisms. DNA Affecter: Tungsten particle bombardment used to cleave DNA in creation of GM organisms. Tungsten metal particles in suspension promote breakage of Cellular DNA, The rate of DNA self repair, not high enough to restore all genome functions. potential for adverse effects (Krysiak et al 1999). Tungsten metal particles in suspension promote breakage of Cellular DNA, The rate of DNA self repair, not high enough to restore all genome functions. potential for adverse effects (Krysiak et al 1999).

59 Tungsten – Toxicity Data Reproductive Affecter / Teratogen : Oral Rat, 1.2 mg/kg ( week prior to copulation and 1-2 weeks pregnant), Musculoskeletal defects and embryonic lethality. (Mezhdunarodnaya Kniga, 1936 and 1939 respectively) / Dangerous Properties of Industrial Materials, 7th Ed., by N. Irving Sax and Richard J. Lewis. Reproductive Affecter / Teratogen : Oral Rat, 1.2 mg/kg ( week prior to copulation and 1-2 weeks pregnant), Musculoskeletal defects and embryonic lethality. (Mezhdunarodnaya Kniga, 1936 and 1939 respectively) / Dangerous Properties of Industrial Materials, 7th Ed., by N. Irving Sax and Richard J. Lewis. There is anecdotal evidence of tungsten being a teratogen or a substance which causes deformities in developing fetus. However, other dietary and cultural factors could not be ignored in these studies. Thus tungsten is considered to be an experimental teratogen that has experimental reproductive effects There is anecdotal evidence of tungsten being a teratogen or a substance which causes deformities in developing fetus. However, other dietary and cultural factors could not be ignored in these studies. Thus tungsten is considered to be an experimental teratogen that has experimental reproductive effects Toxicity of tungsten, molybdenum and tantalum and the environmental and occupational laws associated with their manufacture, use and disposal. Kerwien S.C., ARDEC Picatinny Arsenal NJ, Management Engineering 1996

60 Tungsten Powder Technology Projectile Toxicity Miller et al (2005) Rats implanted with, high and low dose W-Ni alloy and Ni alloy. Noticeable changes in the animals blood and liver function after 1 month. Aggressive tumours around the implant within 5 months. 100% of test subjects developed tumours. Cancers metastasised to the lungs. High dose W alloy implants developed tumours faster than low dose, and faster than nickel, a known carcinogen. Kalinic FJ, Emond CA, Calton TK, Mog SR, Colemen GD, Kordell JE, Miller AC, McClain DE, Embedded Weapons-Grade Tungsten Alloy Shrapnel Rapidly Induces Metastatic High Grade Rhabdomyosarcomas in F344 Rats (2005)

61 Tungsten – Ecotoxicity Soluble W toxic to red worms, plants, microbes. 0.01μg/L in soil microbial yield reduce 8%. Volume of Toxic Influence. Tungsten particles had ability to affect microbial communities at >10 times the radius of the particle. (Strigul et al, 2003) Soluble W toxic to red worms, plants, microbes. 0.01μg/L in soil microbial yield reduce 8%. Volume of Toxic Influence. Tungsten particles had ability to affect microbial communities at >10 times the radius of the particle. (Strigul et al, 2003) 3% (NH 4 ) 2 WO 4 /WO 3 incubated in soil for 3 months, 95% death of soil microbe population. (Dermatas et al, 2004) 3% (NH 4 ) 2 WO 4 /WO 3 incubated in soil for 3 months, 95% death of soil microbe population. (Dermatas et al, 2004) 1% W incubated in soil for 1 year significant death of soil microbe population 68%. Toxic to nematodes, mites and ticks. (Braida et al, 2004) 1% W incubated in soil for 1 year significant death of soil microbe population 68%. Toxic to nematodes, mites and ticks. (Braida et al, 2004) NB:Tungstates - KNOWN PESTICIDES & BIOCIDES. NB:Tungstates - KNOWN PESTICIDES & BIOCIDES.

62 W - Environmental Risk Factors W-Powder technology potentially unstable. W-Powder technology potentially unstable. INSOLUBLE, irritant W powder readily oxidises to harmful and toxic SOLUBLE W oxides. INSOLUBLE, irritant W powder readily oxidises to harmful and toxic SOLUBLE W oxides. Current W-materials contaminated? Current W-materials contaminated? Frangible rounds maximise risk. Frangible rounds maximise risk. Redox effect corrosion of legacy metals. Redox effect corrosion of legacy metals. Lower pH faster corrosion and leaching. Lower pH faster corrosion and leaching. Colloidal W, a potential transport metal. Colloidal W, a potential transport metal.

63 W - Environmental Risk Factors W not fully toxicologically evaluated. However, significant data implicating W as a reproductive affecter and cancer promoter. W not fully toxicologically evaluated. However, significant data implicating W as a reproductive affecter and cancer promoter. Toxic to flora and fauna. Toxic to flora and fauna. Uptake by plants and invertebrates Food Chain. Uptake by plants and invertebrates Food Chain. Prior risk appraisals flawed and inconclusive. Probability and severity of risk understated Prior risk appraisals flawed and inconclusive. Probability and severity of risk understated Promotion of W as insoluble, inert and non-toxic has lead to inappropriate and widespread use. Promotion of W as insoluble, inert and non-toxic has lead to inappropriate and widespread use.

64 Tungsten, inert, insoluble and non-toxic or the New Asbestos? ?

65 For further information contact: Dr Peter J. Hurley Blake International Limited Tel: +44-(0) Fax: +44-(0)


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