dr. john ashworth senior soil scientist

Dr. John AshworthSenior Soil Scientist

Analytical and regulatory requirements for barium in soils and drilling wastes

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

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.

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.

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

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)

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

Axiom Environmental, 2004 (Miles Tindal)

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

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

Katanax auto fluxer

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

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

Province Confirm “barite

waste” by:

Analyze waste for Ba

by:

Alberta Weak calcium

chloride test

Total Ba method (XRF, or

fusion ICP)British

ColumbiaDocumentatio

nStrong calcium

chloride test

Strong calcium chloride (BC) = 1.0 M

Weak calcium chloride (AB) = 0.1 M