Hydrogeochemistry

Dissolved metals and trace elements in

natural surface and groundwater can serve as
vectors to mineralization deep under cover,
while the isotopic composition of certain
metals can further delineate anomalies
originating from mineralization.

ALS Minerals now offers analysis of natural water by High-

Resolution ICP-MS (HR-ICP-MS) for use in exploration
geochemistry. Deeply-circulating groundwater and surface
water discharging from depth can carry a geochemical
fingerprint of buried deposits through dissolved metals, major
anions and trace elements. The regional nature of water
surveys makes hydrogeochemistry a large-scale, effective
exploration technique in areas covered with glacial till and has Figure 1: Near-neutral pH pond in the Pebble East area.
(Eppinger et al. 2011)[3]
the added benefit of functioning as baseline environmental
data when projects progress into feasibility assessment.
Reliable measurement of background concentrations and The HR-ICP-MS solves many of the mass interference issues
detection of anomalies in the sub-parts per billion or parts that limit detection sensitivity on the quadrupole ICP-MS
per trillion range is key to the use of hydrogeochemistry in and allows for valuable data collection from water samples.
exploration. Knowledge of mobile and immobile elements In addition, the Multi-Collector HR-ICP-MS can accurately
typical to various mineralization and alteration systems can be measure isotopic ratios of elements such as lead and zinc
applied to results from hydrogeochemical studies to identify to aid in differentiating anomalies resulting from barren and
hidden deposits at depth.[1] mineralized systems.

Deposit Type Primary pathfinders Secondary pathfinders Isotopes

VMS Zn Low pH, Pb, sulphate Zn, Pb
Porphyry Cu, Au, Mo Cu, Mo, Se, Re, As Pb, Zn
SEDEX / MVT Zn, Pb Au, Ag, Ba, Cd Zn, Pb
Vein Gold Au Se, As, Sb
Kimberlite Low Mg, high pH Ni, Co, Cr
Cu-Ni-PGE Ni, Cu, Pd As, Cr, Co, S, PGEs
2012-10e

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A recent study by the USGS over the undisturbed Pebble Cu-Au-Mo
deposit in southwest Alaska[2] showcased the ability of Considerations for surface water sampling:
surface water to present anomalies below the detection limit
• Eh, pH, temperature, and other physical and chemical
of quadrupole ICP-MS. The Pebble West zone is overlain by
controls on aqueous geochemistry
50m of glacial cover, and the Pebble East zone is additionally
• Drainage patterns and points of discharge from/recharge
covered by 300-600m of barren volcano-sedimentary rocks. into groundwater
In the West area where mineralization is relatively close to • Flow rate and seasonal variation including input from rain
the surface, a significant number of anomalies in surface run-off and snow melt
waters identified the deposit including Cu, Ni, K, Zn, REEs, F • Total dissolved solids; Fe, Mn, Al-oxyhydroxides in
and SO4. Many of these are detectable by quadrupole ICP-MS, suspension adsorb and concentrate metals
although they are close to the detection capabilities of the
method. The elements Tl and Re further identify the Pebble
West zone and Mo, V, W and Sb all identify both the Pebble Stream or spring water sampling is an attractive option for
West and more deeply buried Pebble East zones, at detection reconnaissance geochemical surveys due to the relative
limits only achievable by HR-ICP-MS. ease of sample collection and lack of sample preparation
required before analysis. Understanding the redox and pH
conditions of sample sites is crucial to correct interpretation
of results, so field measurement with an ORP (Eh)-pH meter
and thermometer is recommended. Standard water sampling
protocol includes duplicate sampling and filtering, followed
by acidification with high purity nitric acid of one sample.
Strict quality control must be maintained in the field due to
the risk of contamination at the parts per trillion level, and a
clean collection environment including removal of jewelry and
disposable gloves is imperative. Finally, quick delivery to the
lab in a cool environment will preserve the integrity of your
water samples prior to analysis.[1]
Sampling packs are available for pickup from ALS Minerals
Vancouver lab which include labeled sample bottle pairs, high
purity nitric acid, disposable 45μm filters with syringes for field
filtration, and disposable powderless nitrile gloves. Results are
reported for anions, F-Cl-Br, and either standard or HR–ICP-MS.
Please note that samples with high salts or TDS can only be
Figure 2: Surface water anomalies in Tl (ppt) by HR-ICP-MS at analyzed by ICP-AES.
the Pebble Deposit, Alaska (Eppinger et al, 2011)[3]

Method ALS Method Code

REFERENCES: High Resolution ICP-MS for Natural Waters ME-MS14HR

[1] Leybourne, M.I., 2007, Aqueous geochemistry in mineral exploration, in Standard ICP-MS for Water ME-MS14
Goodfellow,W.D., ed., Mineral Deposits of Canada: A Synthesis of Major Saline water analysis by ICP-AES ME- ICP15
Deposit-Types, District Metallogeny, the Evolution of Geological Provinces, F-Cl-Br Anion Determination (F-Cl-Br) IC881
and Exploration Methods: Geological Association of Canada, Mineral
pH, Conductivity, Sulphate, Alkalinity WAN-PKG
Deposits Division, Special Publication No. 5, p.1007-1033.
Pb, Zn Isotopes in Water PbZn-ISPw
[2] Anderson, E.D., Smith, S.M., Giles, S.A., Granitto, Matthew, Eppinger,
R.G., Bedrosian, P.A., Shah, A.K., Kelley, K.D., Fey, D.L., Minsley, B.J., and
Brown, P.J., 2011, Geophysical and geochemical data from the area of the Please contact an ALS Minerals laboratory
Pebble Cu-Au-Mo porphyry deposit, southwestern Alaska: Contributions to
assessment techniques for concealed mineral resources: U.S. Geological in your area to discuss how we can help
Survey Data Series 608.
with your exploration project. For contact
[3] Eppinger, R.G., Kelley, K.D., Fey, D.L., Giles, S.A., Minsley, B.J., and Smith,
S.M., 2010, USGS exploration geochemistry studies at the Pebble porphyry information for our laboratories around
Cu-Au-Mo deposit, Alaska—pdf of presentation: U.S. Geological Survey
Open-File Report 2010–1225. the world, visit our website.

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