Chemical Geology 206 (2004) 163 – 165
www.elsevier.com/locate/chemgeo
Editorial
Geochemistry of organic-rich shales: new perspectives
Organic-rich shales may be deposited over a
wide range of depositional environments ranging
from terrestrial to marine, have wide geographic
distribution, and occur in sediments of all ages,
from modern to Precambrian. Over the past 25
years, there has been significant debate over the
environmental conditions necessary for such accu-
mulations and the primary controls on deposition.
The earlier debate of ‘‘productivity vs. preservation’’
has evolved in recent years to an understanding that
there are multiple tectonic, geographic, and eustatic
controls that influence sedimentation rate, redox
conditions, recycling of nutrients, and variations in
sources and types of organic materials. It has
become clear that there is probably no single model
that may be called upon to explain black-shale
deposition in marine basins, and whereas there
may be depositional similarities, each deposit will
likely possess its own nuances.
Geochemical variations within black shales may
reflect depositional conditions, including water-col-
umn conditions and those within the sediment, sedi-
ment provenance, variations in organic matter source,
diagenetic alteration including hydrothermal alter-
ation, and even weathering processes. It has become
increasingly evident that the geochemistry of these
units is the end result of an extremely complex set of
depositional and diagenetic processes. The history of
deciphering black-shale geochemistry has grown from
the interpretation of C/S ratios, through calculation of
degree of pyritization (DOP) as an indicator of bot-
tom-water oxygenation conditions, to the more recent
utilization of trace-element and biomarker paleoredox
proxies. In this issue, redox indicators are a common
theme, with studies utilizing redox-sensitive trace-
element abundances (e.g., Mo, V, U, and Zn) and
ratios (e.g., V/(V + Ni), V/Cr, and Ni/Co), trace-ele-
0009-2541/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemgeo.2003.12.004
ment Corg relationships (e.g., Mo – Corg), and C – S– Fe
relationships (e.g., S/TOC, DOP). Further evidence
for anoxic conditions may come from organic geo-
chemical data, e.g., the aryl isoprenoid ratio may be
used to assess photic-zone anoxia.
An earlier special issue of Chemical Geology
(1992, volume 99) focused on the geochemistry of
metalliferous black shales. Since that time, advance-
ments in technologies associated with the study of
black shales have led to a better understanding of
these deposits. One area in particular has been the
use of chemostratigraphy as a tool to enhance our
understanding of black shales and to recognize
patterns in vertical successions within the units. In
the technical session entitled Chemostratigraphy:
An Emphasis on Metal-Rich Black Shale Deposits
(held at the 2002 Annual Meeting of the Geological
Society of America, Denver, CO), speakers focused
on various applications of chemostratigraphic tech-
niques as applied to black shales. The concept of
chemostratigraphy, originally applied to isotopic
studies in connection with stratigraphic studies, is
used herein in a broader sense to include multiple
aspects of geochemical stratigraphy. More than half
of the papers presented at the theme session is
represented in this special issue. We broadened the
scope of the special issue to include a wider array
of geochemically oriented papers in recognition of
the breadth of black-shale geochemistry as a field
of study.
Twelve papers in this special issue address the
implementation of chemostratigraphy in the study of
black shales and the usefulness of the technique in our
understanding of these units. Geochemical parameters
and other factors including redox interactions, diage-
netic processes, presence/absence of organic matter,
interactions between metals and organic matter, and
164 Editorial
the role of rare earth elements (REEs) are all discussed
in the context of unraveling the depositional and
diagenetic history of black shales.
The papers in this issue are arranged ‘‘stratigraph-
ically’’ based on the age of the black shale sediments.
The first two papers utilize observations from the
Cariaco Basin as a means to understand ancient black
shale deposits. The paper by Wilde et al. considers
Mo/Al ratios as a proxy for original TOC content in
ancient sediments. These authors use regression anal-
ysis for data from the Cariaco Basin (on the conti-
nental shelf of Venezuela), the Carboniferous of Iowa,
and the Devonian of New York to estimate the
original TOC contents for Lower Ordovician black
shales. Piper and Perkins also consider the geochem-
istry of sediments in the Cariaco Basin, and model
accumulation rates for Cd, Cr, Cu, Mo, Ni, V, and Zn
on the sea floor. This model is applied to the Meade
Peak Phosphatic Shale Member of the Phosphoria
Formation (Permian, northwest USA). Trace-element
accumulation suggests that moderate primary produc-
tivity in the photic zone likely occurred in the Phos-
phoria Basin, comparable to primary productivity in
the Cariaco Basin.
Frimmel et al. and Schwark and Frimmel examine
the organic-rich mudrocks of the Posidonia Black
Shale (Toarcian, SW Germany). They present a
high-resolution, multi-proxy chemostratigraphic study
within a carefully constrained sequence stratigraphic
framework. Frimmel et al., using trends in Rock-Eval
data, elemental analyses of organic matter, and bio-
marker analysis of aliphatic hydrocarbon fractions,
suggest that changing sea level was the major control
on the composition of organic matter and on its redox-
controlled preservation. Establishment of episodic
anoxia was related to a monsoonal climate model.
This model calls for increased surface run-off during
the summer monsoon which provided increased
nutrients leading to high primary productivity. Winter
conditions were determined to be associated with
episodic establishment of dysoxic conditions.
Schwark and Frimmel assess the degree and persis-
tence of photic-zone anoxia experienced by these
sediments using the relative abundance of derivatives
of chlorobiaceae lipids, specifically an aryl isoprenoid
ratio (AIR) obtained by calculating the proportion of
short chain C13 – 17 versus intermediate chain C18 – 22
aryl isoprenoids.
The next set of papers deals with various geochem-
ical aspects of Carboniferous (Pennsylvanian) black
shales of the Midcontinent, USA. Doveton and Mer-
riam take a novel approach using petrophysical data as
a basis for chemostratigraphic analysis of units in the
subsurface. These authors use spectral gamma-ray
logs, photoelectric factor log measurements, and neu-
tron porosity curves to evaluate compositional varia-
tions in the black shales. Application of these methods
may extend traditional chemical analyses from spa-
tially restricted outcrop and core locations into a wider
areal coverage in the subsurface. Algeo et al. examine
the geochemistry of the Hushpuckney Shale (Missou-
rian Stage, eastern Kansas), a pivotal ‘‘core’’ shale of
a Kansas-type cyclothem. Using compositional data
including Corg, sulfides, phosphate, detrital siliciclas-
tics, organic macerals, and trace-element redox prox-
ies (Mo, U, V, and Zn), coupled with ichnofabric
features, these authors evaluate paleo-redox condi-
tions within the water column. Trends are interpreted
within a sequence stratigraphic framework for the
Kansas-type cyclothems, reflecting Gondwanan Ice
Age glacio-eustatic cycles. Algeo and Maynard focus
on the redox-sensitive trace elements within the gray
and black shale submembers of the core shales,
specifically evaluating trace-element enrichment fac-
tors and relationships with Corg. Within the black
shales, two patterns emerged within their data set,
representing different benthic redox conditions, one of
‘‘weak’’ and one of ‘‘strong euxinic affinity’’. These
relationships may allow differentiation of dysoxic,
non-sulfidic anoxic, and euxinic conditions during
accumulation of ancient sediments. Such a multi-
proxy approach may allow more reliable redox dif-
ferentiation than when a single-proxy approach is
taken (e.g., those based on a single trace element,
trace-element ratio, or on C – S –Fe systematics alone).
Cruse and Lyons also look at the Hushpuckney Shale
in Iowa, and compare it with its stratigraphic equiv-
alent in Oklahoma, the Coffeyville Formation. They
note that although C – S – Fe systematics and 34S-
isotope ratios suggest pervasive euxinic conditions
for these shales, there are regional variations in the
efficiency of Mo scavenging and in the rates of
siliciclastic sedimentation expressed in varying Fe/
Al ratios. These authors also point to differences in the
relative input of terrestrial versus marine organic
matter, and inputs of metals to bottom waters from
 Editorial
contemporaneous hydrothermal vents as additional
factors leading to geographic variations in metal
enrichments in ancient organic-rich sediments. The
final paper in this group by Schultz challenges the
previously suggested ‘‘exclusively anoxic’’ origin for
Midcontinent Carboniferous (Pennsylvanian) black
shales. Using extensive geochemical and statistical
analysis, he infers that deposition of the once thought
anoxic periods was likely punctuated by short-lived
dysaerobic or even near-oxic events. Microstrati-
graphic sampling intervals and geochemical analyses
support the notion that fluctuating, rather than exclu-
sively anoxic, geochemical settings prevailed.
The last group of papers focuses on the geochemis-
try of the Devonian black shales of the Appalachian
Basin. Rimmer evaluates redox conditions that pre-
vailed during accumulation of Upper Devonian – Low-
er Mississippian organic-rich shales of the central
Appalachians using C –S – Fe relationships, trace-ele-
ment enrichment factors, and trace-element ratios. This
study suggests that thresholds established for paleore-
dox indicators in previous studies should not be strictly
applied, but that relative differences collectively may
infer variations in the degree of anoxia (DOA). Data are
presented that suggest conditions for shale accumula-
tion were variable, ranging from anoxic or euxinic
conditions to periodic dysoxic or even marginally oxic
conditions. Lev and Filer suggest that Upper Devonian
Java and Huron shales from the southern Appalachian
Basin exhibit evidence for REE redistribution and the
resetting of the U – Pb isotopic system. This alteration
to the primary detrital signature of these shales is
indicative of black shale diagenetic/depositional pro-
cesses that in effect obscure paleo-environmental and
provenance information. The inference here is that the
once held notion that black shale diagenetic processes
could be unraveled by standard isotopic analyses alone
is challenged by the extremely complex post-diagenet-
ic history. Lastly, Lash and Blood describe carbonate
concretions within the Upper Devonian Rhinestreet
black shale of the western New York State Appalachian
Plateau. Sedimentological evidence suggests early dia-
165
genetic growth within unconsolidated sediment. Isoto-
pic data is consistent with a carbon source within the
zone of biogenic methanogenesis, diffusing upward to
the zone of anaerobic methane oxidation at the base of
the sulfate reduction zone where diagenetic carbonate
precipitated.
We hope this collection of papers illustrates the
wide-ranging interests of those involved in black shale
research and highlights some of the new approaches
to black shale geochemical research. We would like to
thank the Technical Program Committee of the 2002
Annual Meeting of the Geological Society of America
(Denver, CO) for their assistance in holding the
technical session ‘‘Chemostratigraphy: An Emphasis
on Metal-Rich Black Shale Deposits’’, and appreciate
co-sponsorship by the GSA Sedimentary Geology
Division and the SEPM Society for Sedimentary
Geology. Sincere thanks go to our many reviewers
for their insightful and timely comments, including
Ariel Anbar, Mike Arthur, Ray Coveney, John Dove-
ton, Joe Hatch, Pat Hatcher, Paul Howell, Matt
Joeckel, Mike Kruge, Dan Merriam, Barry Maynard,
Stan Paxton, Troy Rasbury, Ed Ripley, Joe Werne, and
several anonymous reviewers. It is through their
tireless efforts that the manuscripts were greatly
improved. We thank Patricia Massar of Elsevier for
helping us navigate the process of putting this issue
together, and Lynn M. Walter, Editor-In-Chief of
Chemical Geology, for the opportunity to publish this
special issue.
Richard B. Schultz
a
Department of Geography and Environmental
Planning, Elmhurst College,
Elmhurst, IL 60126-3296, USA
Susan M. Rimmer *
b
Department of Geological Sciences,
University of Kentucky,
Lexington, KY 40506-0053, USA
E-mail address: srimmer@uky.edu
* Corresponding author. Tel.: +1-859-257-4607; fax: +1-859-
323-1938.