Dr. John Ashworth Senior Soil Scientist Analytical and regulatory requirements for barium in soils...
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Dr. John Ashworth
Senior Soil Scientist
Analytical and regulatory requirements for barium in soils and drilling wastes
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2012 D-50Trace Element Guideline Value (mg/kg)
AgriculturalLand Use
Natural Area Land Use ParklandLand Use
Antimony 20 20 20
Arsenic (inorganic) 17 17 17
Barium 750 750 500
Barite-barium 10,000 10,000 10,000
Beryllium 5 5 5
Boron (hot water soluble) 2 2 2
Cadmium 1.4 3.8 10
Chromium (total) 64 64 64
Chromium (hexavalent) 0.4 0.4 0.4
Cobalt 20 20 20
Copper 63 63 63
Lead 70 70 140
Mercury (inorganic) 6.6 12 6.6
Molybdenum 4 4 4
Nickel 50 50 50
Selenium 1 1 1
Silver 20 20 20
Thallium 1 1 1
Tin 5 5 5
Vanadium 130 130 130
Zinc 200 200 200
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Typically a mixture of water and clay, drilling fluids (mud) may contain other additives. Barite is a commonly added weighting agent, used to improve the viscosity and density of the fluid, to counterbalance the formation pressure as well as carry cuttings to the surface.
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![Page 5: Dr. John Ashworth Senior Soil Scientist Analytical and regulatory requirements for barium in soils and drilling wastes.](https://reader030.fdocuments.net/reader030/viewer/2022033105/56649c925503460f9494d04e/html5/thumbnails/5.jpg)
Typically a mixture of water and clay, drilling fluids (mud) may contain other additives. Barite is a commonly added weighting agent, used to improve the viscosity and density of the fluid, to counterbalance the formation pressure as well as carry cuttings to the surface.
![Page 6: Dr. John Ashworth Senior Soil Scientist Analytical and regulatory requirements for barium in soils and drilling wastes.](https://reader030.fdocuments.net/reader030/viewer/2022033105/56649c925503460f9494d04e/html5/thumbnails/6.jpg)
L488407 Sample ID
Description SALM Ba mg/kg
- 4 Pit D solids 620
- 5 Clay soil 580
- 15 3:1 mix 2,600
- 16 5:1 mix 2,500
- 17 7:1 mix 2,600
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Society of Petroleum Engineers and International Association of Drilling Contractors (SPE/IADC)
Paper by Deuel and Freeman, read at SPE/IADC Conference in New Orleans, Louisiana
“Efforts to close existing pits within on-site criteria have been frustrated by unexpected problems with Ba. Treatment often included dilution techniques whereby waste materials are incorporated into the native soil. Operators have observed, in many cases, higher Ba levels following treatment than initially.”
“It was suggested from the experiments and surveys in this study that the strong acid digest Ba level is not a reliable index for regulatory purposes. It is recommended that Ba be regulated from a “true” total metal analysis perspective.”
(Feb. 1989)
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L488407 Sample ID Description SALM Ba mg/kg XRF (total Ba) data - 4 Pit D solids 620 (mg/kg)
- 5 Clay soil 580
- 15 3:1 mix (R=3) 2,600
- 16 5:1 mix (R=5) 2,500
- 17 7:1 mix (R=7) 2,600
99,000
1,400
19,000
12,500
9,700
Bamix = [ Bawaste x DBD + Basoil x R x 1540 ] / [ DBD + R x 1540 ]
For this waste, DBD was approx. 1,000 g/L, based on SG = 1.6
All total Ba results (XRF data) in the Table agree with values predicted by the D-50 weighted-average formula
R = mix ratio. DBD = waste dry bulk density. Typical soil density = 1540 g/L
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Axiom Environmental, 2004 (Miles Tindal)
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Province Confirm “barite
waste” by:
Analyze waste for Ba
by:
Alberta Weak calcium
chloride test
Total Ba method (XRF, or
fusion ICP)
Weak calcium chloride (AB) = 0.1 M
ALS Innovation
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Read-out
Total Ba
Non-destructive Instantaneous
X-rays
Ba BaBa
Ba Ba
Detector
XRF method
Ba
Fusion-ICP method
Agitate crucible + flux with acid
2
Ba Ba Ba
ICP spectrometer3
Ba BaBa
Muffle furnace, 1000 C
1
Solid sample + Li borate in graphite crucible
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Katanax auto fluxer
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Fusion procedure (soil + 250,000 ppm barite)
Oxidizer Ba recovery
Pt crucible + Li borate in auto-fluxer at 1000 ⁰C(followed by dissolution in acid)
Li nitrate 10 %Tungsten oxide 9 %V2O5 4 %
Graphite crucible + Li borate in muffle at 1000 ⁰C
None 97-100 %
Pt crucible + Li borate in muffle None 60 %Pt crucible + Li borate in auto-fluxer
Charcoal 33 %
BaSO4 = BaO + SO3BaO + 2HNO3 = Ba(NO3)2 + H2O
BaSO4 + 4C = BaS + 4COBaS + 2HNO3 = Ba(NO3)2 + H2S
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Crucibles are arranged in a listed order
Placed in same order in muffle furnace
0.20 g soil + 0.45 g each of Li metaborate & tetraborate (Note: no oxidizing agent)
2BaSO4 + C + 2H2O = 2Ba(OH)2 + CO2 + 2SO2
Ba(OH)2 + 2HNO3 = Ba(NO3)2 + 2H2O
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Province Confirm “barite
waste” by:
Analyze waste for Ba
by:
Alberta Weak calcium
chloride test
Total Ba method (XRF, or
fusion ICP)
British Columbia
Documentation
Strong calcium
chloride test
Strong calcium chloride (BC) = 1.0 M
Weak calcium chloride (AB) = 0.1 M