Direct in situ Dating of Carbonates by LA-ICP-(MC)-MS and its Applications to Chronostratigraphy*

Randy Parrish1 and Troy Rasbury2

Search and Discovery Article #41269 (2014)**

Posted February 11, 2014

*Adapted from oral presentation given at AAPG 2013 Annual Convention and Exhibition, Pittsburgh, Pennsylvania, May 19-22, 2013
**AAPG©2013 Serial rights given by author. For all other rights contact author directly.

1
University of Leicester & NIGL, British Geological Survey, Leicester, United Kingdom (rrp@nigl.nerc.ac.uk)
2
SUNY at Stony Brook, Stony Brook, New York (troy.rasbury@stonybrook.edu)

Abstract

A viable method to provide absolute age constraints in carbonate strata has proven elusive. Direct dating of primary carbonate deposits,
and/or early marine cements would constrain rates of carbonate platform growth, allowing refinement of models of sea level and climate
change that might have influenced the carbonate depositional environment. Absolute age constraints on later diagenetic elements such as
meteoric and burial cements and tectonic veins is very important to a wide range of problems in both the hydrocarbon industry (such as burial
history and timing of fluid migration) and earth science more generally. U-Pb dating of carbonate has been shown to be viable but so far has
been restricted in application due to use of time consuming ID-TIMS methods that involve dissolution and processing of a sample of
carbonate. A major hurdle is that there is currently no a priori way to know if a sample has a viable U/Pb ratio, and many carbonates are not
datable.

We have successfully adapted LA-ICP-(MC)-MS methods (used routinely in zircon U-Pb dating) by using a well characterized 254+/-6 Ma
calcite standard (dated by ID-TIMS at NIGL and Stony Brook) to correct the U/Pb ratio for matrix effects. This approach allows in situ U-Pb
dating with uncertainties as little as ±4% at 95% confidence with minimal sample consumption. We have applied this method to the dating of
samples with average uranium concentrations (0.4-5 ppm) such as speleothems, paleosols, lacustrine carbonates, tufa, early marine cements
(in ammonite chambers), calcite veins from fractures in MORB and marine fossils. The age of dated materials so far ranges from Permian to
late Quaternary, as young as 250ky. Laser ablation allows us to quickly assess the U/Pb ratios of the variety of carbonate phases in a sample
to determine if the sample has potential for dating. Carbonate components with favorable U/Pb are subjected to in situ dating using textural
petrography and SEM/fluorescence imaging to guide the analysis of coherent zones of growth. Examples of these applications will be
presented.

The wealth of applications to explore in the future include structural geology and the dating of structural veins, post-depositional
cementation, and direct dating of biogenic aragonite (biogenic calcite usually being too low in uranium to be suitable). The future scope of
applicability of this method to earth science, sedimentary geology, and hydrocarbon exploration is very exciting.
Direct in situ
Direct in situ Dating of Carbonates by LA
Dating of Carbonates by LA‐ICP‐(MC)‐
ICP (MC)
MS and its Applications to Chronostratigraphy
Randy Parrish
University of Leicester & NIGL, British Geological Survey

Troy Rasbury
SUNY, Stony Brook
 Wouldn’tt we like to …
Wouldn we like to
• Date calcite cement in carbonate rocks
l b k
g p
• Determine when diagenesis took place,  ,
• Directly date fossils and other carbonate 
deposits speleothems paleosols etc
deposits, speleothems, paleosols, etc.
• Date calcite in structural settings – tension 
veins stretched belemnites calcite in fault
veins, stretched belemnites, calcite in fault 
rocks, slickenfibers, etc.

These applications have been nearly 
intractable, but there is real progress…..
Laser ablation high sensitivity
ICP-(MC)-MS

methods borrowed from U-Pb

U Pb
LA-ICP-MC-MS techniques
A vital ingredient
g to an efficient method is …
standardisation during analysis –
usingg reference materials that are appropriate
pp p
U-Pb calcite standard: about 4ppm U, 251 Ma old
 data-point error ellipses are 2
This material is  Tera-Wasserburg diagram
fantastic: almost  0.6 Y-intercept = Intercept
p at
no initial lead  initial ‘common lead 0.4623±0.0065 Ma
MSWD = 3.5
(<1ppb), ~100ppm  0.5
uranium and not
uranium, and not  462 7k
ky
altered, meaning 
0.4
little if any  Pb/2066Pb
recrystallisation/
recrystallisation/ 
replacement  0.3
207

during subsequent 
precipitation of 
i i i f
0.2
younger calcite; 
the age via U‐Pb 
agrees with the U‐ 0.1
series (U‐Th) date 1.6
^ ^
1.0
0.8 ^ ^
0.0
0 0
1.4 Ma 0.6 0.4
3000 5000 7000 9000 11000 13000 15000 17000

Data from high uranium Flowstone from  238
U/206Pb
Nahanni Park Yukon Territory
Nahanni Park, Yukon Territory ‘Concordia’
Concordia intercept =
Data courtesy of Chris Smith, University of  pure radiogenic lead,
Bristol 2012 ratio a function of age
Early diagenetic calcite 
y g
cements (photos: Q Li, 2011)
Large amount of calcite  Early diagenetic calcite
cements, less open deposit 
environment

Regions
<100μm can
be targeted
and dated to
± 2-3% in
calcite
Septum
p

Hildoceras spp 1.  Late diagenetic calcite
Somerset, Bifrons Zone
LA‐ICP‐MC‐MS U‐Pb data on early 
diagenetic cements

Ages of earliest
cements are 10-15 Ma
younger
y g than
chronostratigraphic
ages
Data courtesy of
Qiong Li, 2011
 data-point error ellipses are 2

0.8 Intercepts at
4800 101.08±0.98
101 08±0 98 [±0.99]
[±0 99] & 4708±13 [±16] M
Ma
MSWD = 1.2

0.6
4400 DSDP 51-417D
51 417D 274R core
Pb/206Pb

basalt host
4000
04
0.4
207P

3600

0.2 2800

1200 400 300 200 150

101
0.0
0 20 40 60 80
238U/206Pb

Fragments of calcite in vein hosted MORB, oceanic crust known to

be ~115 Ma old; this data demonstrates hydrothermal deposition of
calcite off the ridge axis for millions of years following generation
of oceanic crust
Data: L Coogan U of Victoria 2012
 Pilot study
Palaeolake Olduvai
ca lcite crysta Is

La ke
margin
sediments

sodiments

t --
N 10km
Lake carbonates
100 μm Detrital nodular calcite in
l
lacustrine-derived
t i d i d sediments,
di t
Olduvai Gorge, E Africa
((E Rushworth 2010 data))

data-point error ellipses are 2s

0.8
0 8

Age: 1.89±0.10
Intercepts at Ma
2.39±0.12 & 4853±42 [±43] Ma
(±5%MSWD2σ)= 0.38
06
0.6
MSWD
S 0.38
Pb/206Pb

In favourable 04
0.4
samples, calcite is
207

datable by U-Pb LA-

ICP MS h
ICP-MS; here, li
linear 0.2

arrays of data allow

a precise date with 0.0
very small 0 1000 2000 3000 4000
238 206
uncertainties U/ Pb
 Test the potential resolution by dating crystals in
older and younger parts of the sequence

40Ar/39Ar ages' Calcite crystal ages

-1.5 - 1.48 ± 0.05 1.623±0.033

1.89 ± 0.10
1.873 ± 0.086
1.79* -1.72 ± 0.003
1.85 ± 0.11
1.89 ± 0.12

RHC 1.917±0.037
1.839 ± 0.005 - 1. 79
1.900±0.059

RHC
1.98 ± 0.06 - 1.87 ± 0.01 2.022±0.033

Mean deviation of 0.103Ma with a 2-6% uncertainty

‘excess’ age attributable to high initial Uranium activity;
This excess activity is common in terrestrial waters• •
Age (Ma)
Primary aragonite and some calcite suitable for 87Sr/86Sr may
be datable for U-Pb
U Pb, depending upon degree of alteration
alteration,
common Pb content, and initial uranium content.
How widely applicable is this method?
How widely applicable is this method?
• C
Calcite cement in ammonite/fossil chambers
l it ti it /f il h b
• Calcite in veins in basalt, ophiolites 
• Carbonate lake sediments, and oolite‐like 
C b t l k di t d lit lik
concretionary grains
• Speleothems and flowstones 0.26‐>4 Ma
Speleothems and flowstones 0 26‐>4 Ma
• Fracture‐filled veins
• Tufas and paleosols, crusts on boulders
Tufas and paleosols crusts on boulders
• The above have been demonstrated
However it is early days of exploiting this method and
However, it is early days of exploiting this method and 
its application to sedimentary geology and 
chronostratigraphic applications
 Structural Geology applications

Stretched belemnites, calcite infill

Tension gashes

brecciation with
calcite deposition

Cross-cutting veins
Other Applications …. 
• Structural veins in foldbelts and 
Structural veins in foldbelts and
thrusting
• Stretched belemnites and other 
extensional structural features
• C o o ogy a d t esca es o po os ty
Chronology and timescales of porosity 
occlusion in carbonate reservoir rocks 
• gy
Better chronology in strata with non‐
diagnostic biostratigraphy
• Molar tooth structure in Precambrian
• Applications to strata of unknown age, 
(p
in Precambrian (potentially)y)
Thank you for your interest in this work
rrp@nigl nerc ac uk (Parrish)
rrp@nigl.nerc.ac.uk
troy.rasbury@stonybrook.edu (Rasbury)