Analytical and regulatory requirements
for barium in soils and drilling wastes
Dr. John Ashworth
Senior Soil Scientist
2012 D-50
Trace Element
Guideline Value (mg/kg)
Agricultural
Land Use
Natural Area Land Use
Parkland
Land Use
Antimony
20
20
20
Arsenic (inorganic)
17
17
17
750
750
500
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
4
4
4
50
50
50
1
1
1
20
20
20
Thallium
1
1
1
Tin
5
5
5
Vanadium
130
130
130
Zinc
200
200
200
Barium
Barite-barium
Molybdenum
Nickel
Selenium
Silver
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 (Feb. 1989)
“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.”
L488407 Sample
ID
Description
SALM Ba mg/kg
XRF (total Ba) data
-4
Pit D solids
620
99,000
-5
Clay soil
580
1,400
- 15
3:1 mix
(R=3)
2,600
19,000
- 16
5:1 mix
(R=5)
2,500
12,500
- 17
7:1 mix
(R=7)
2,600
(mg/kg)
9,700
Bamix = [ Bawaste x DBD + Basoil x R x 1540 ] / [ DBD + R x 1540 ]
R = mix ratio. DBD = waste dry bulk density. Typical soil density = 1540 g/L
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
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
Fusion-ICP method
3
ICP spectrometer
2
1
Agitate crucible
+ flux with acid
Muffle furnace, 1000 C
Ba
Ba
Ba
Ba Ba Ba
Solid sample + Li borate
in graphite crucible
XRF method
X-rays
Detector
Read-out
Total Ba
Ba
Ba
Ba
Ba
Ba
Ba
Non-destructive
Instantaneous
Katanax auto fluxer
Fusion procedure
(soil + 250,000 ppm barite)
Pt crucible + Li borate in autofluxer at 1000 ⁰C
(followed by dissolution in acid)
Oxidizer
Graphite crucible + Li borate in
muffle at 1000 ⁰C
Pt crucible + Li borate in muffle
Pt crucible + Li borate in autofluxer
BaSO4 = BaO + SO3
Ba recovery
Li nitrate
Tungsten oxide
V2O5
10 %
9%
4%
None
97-100 %
None
Charcoal
60 %
33 %
BaO + 2HNO3 = Ba(NO3)2 + H2O
BaSO4 + 4C = BaS + 4CO
BaS + 2HNO3 = Ba(NO3)2 + H2S
Crucibles are arranged in a listed order
0.20 g soil + 0.45 g each of
Li metaborate & tetraborate
(Note: no oxidizing agent)
Placed in same order in muffle furnace
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
Columbia
Documentation
Strong calcium
chloride test
Strong calcium chloride (BC) = 1.0 M
Weak calcium chloride (AB) = 0.1 M