from bedrock to burial: the evolution of particulate organic carbon across coupled...
TRANSCRIPT
www.elsevier.com/locate/marchem
Marine Chemistry 92
From bedrock to burial: the evolution of particulate organic carbon
across coupled watershed-continental margin systems
Neal E. Blaira,*, Elana L. Leitholda, Robert C. Allerb
aDepartment of Marine, Earth and Atmospheric Sciences, North Carolina State University, P.O. Box 8208 Raleigh,
NC 27695-8208, United StatesbMarine Sciences Research Center, Stony Brook University, Stony Brook, NY 11794-5000, United States
Received 3 December 2003; received in revised form 12 April 2004; accepted 30 June 2004
Available online 3 October 2004
Abstract
Deltas sequester nearly half of the organic carbon (OC) buried in the marine environment. The composition of the
buried organic matter reflects both watershed and seabed processes. A conceptual model is presented that describes the
evolution of particulate organic carbon (POC) as it travels from its terrestrial source to its burial at sea. Alterations to the
POC occur primarily in bioactive reservoirs, such as soils and the surface mixed layer (SML) of the seabed, where new
organic matter can be added and older material degraded. Bypassing or rapid passage through the reservoirs is a key
parameter because it avoids change.
The Eel River of northern California and the Amazon River systems illustrate the importance of reservoir transit time
and storage in determining the character of POC delivered to the continental margin. The Eel exemplifies a bypass
system. Mass-wasting processes on land deliver unaltered bedrock along with OC derived from extant vegetation directly
to the river channel without significant storage in soils. Rapid burial on the shelf occurs as a result of flood events. As a
consequence, the buried material appears to be a simple mixture of carbon derived from kerogen (bedrock C), and modern
terrestrial and marine sources. This is predicted to be a characteristic of the many similar short rivers on active margins
that supply N40% of the fluvial sediment to the world’s ocean.
Extensive storage and processing of OC in lowland soils is a characteristic of the large Amazon watershed. Upland
POC compositions are either overprinted or replaced by lowland sources. Upon delivery to the shelf, over half of the
riverine POC is lost as a result of residence in sediment layers that are periodically reworked over time scales of days to
months. The addition of fresh reactive marine OC, exposure to oxygen, and the regeneration of metal oxidants during
resuspension events fuel the oxidation of the riverine organic matter. The nature of the watershed-shelf processes likely
produce a complex mixture of organics possessing a continuum of ages and reactivities.
The model illustrates the need to develop tools to measure residence times of particles in the various reservoirs so that
the behavior of POC can be calibrated as it moves through a sedimentary system. The ultimate goal is to be able to use
0304-4203/$ - s
doi:10.1016/j.m
* Correspon
E-mail addr
(2004) 141–156
ee front matter D 2004 Elsevier B.V. All rights reserved.
archem.2004.06.023
ding author.
ess: [email protected] (N.E. Blair).
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156142
the organic geochemistry of soils and sediments to quantitatively infer the history of processes that determine both the
composition and amount of POC present in different depositional environments.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Organic carbon; Carbon isotopes; River; Continental margin; Soil; Kerogen; Delta
1. Introduction
Continental margins play a pivotal role in modu-
lating Earth’s atmospheric chemistry and global
climate over geological time scales (Berner, 1982,
1989; Hedges and Keil, 1995). Approximately 90% of
the organic carbon (OC) buried globally in the ocean
has been sequestered in shelf and slope sediments
(Hedges and Keil, 1995). Slow, continuous removal of
OC from the biosphere and storage in margin
sediments has contributed to the accumulation of O2
and depletion of CO2 in the atmosphere over the
Earth’s history (Berner, 1982, 1989). Uplift, weath-
ering and oxidation of sedimentary OC counterbal-
ance the burial process.
The mechanisms that govern OC burial in margins
are controversial and have historically focused on the
importance of marine processes. Productivity, bottom
water oxygen level, sediment accumulation rate, and
organic matter composition can all influence OC
preservation in sediments (see Hedges and Keil, 1995
for review). The protection of OC by association with
terrestrially derived, clay-sized particles has been
implicated as at least one of the key controls on such
seemingly disparate features as the OC content of
sedimentary rocks (Kennedy et al., 2002) and burial
efficiency in deltaic and continental shelf and slope
sediments (Mayer, 1994a,b; Keil et al., 1997; Hedges
and Keil, 1995). The nature of the apparent protective
process is poorly understood, although recycling of C
by particle-bound microbes and incorporation of
microscopic biogenic debris into the particle matrix
via organic glues may be important (Ransom et al.,
1997, 1999; Arnarson and Keil, 2001; Blair et al.,
2003). Sorption of dissolved OC by clays has also
been invoked as a potentially important mechanism;
however, modeling exercises, isotopic, and other
studies suggest that this is not the dominant process
in shallow water settings (Henrichs, 1995; Blair et al.,
2003; Arnarson and Keil, 2001).
Nearly half of margin OC burial occurs in deltaic
regions (Berner, 1989; Hedges and Keil, 1995). The
clay fraction of river suspensions is typically loaded
with terrestrial organic matter to a nearly uniform OC
to particle surface area ratio (OC/SA; Keil et al.,
1997). In some coupled river/delta systems, such as
the Amazon and Fly, riverine particles appear to
rapidly lose as much as 70% of their loads of
terrestrial OC upon discharge, demonstrating the
dynamic nature of the OC–clay association (Aller et
al., 1996; Keil et al., 1997). In contrast, little
detectable loss of riverine OC from the clay fraction
occurs on particles discharged to the Eel shelf offshore
of northern California (Blair et al., 2003). Watershed
and seabed processes may both contribute to the
differences.
There are literally thousands of rivers delivering
sediment and the associated OC to the ocean (Milli-
man and Syvitski, 1992). 40–70% of the sediment is
transported by the smaller, more numerous rivers
(Milliman and Syvitski, 1992; Milliman, personal
communication). Only a subset of rivers can be
studied, and, to-date, preference has been given to
those with either high fluvial sediment outputs, which
provide an easily recognizable signal on the shelf, or
to logistically convenient rivers. Important C-cycling
processes may go unappreciated if other selection
criteria are not considered. In addition, although the
sources and fates of terrestrial inputs to the seabed
have received attention in marine organic geochem-
istry (Hedges and Keil, 1995; Hedges et al., 1997),
terrestrial physical processes, such as those involved
in landscape evolution, have largely escaped scrutiny
as factors that might influence the OC signatures
buried on continental margins. Existing riverine OC
models, such as those based on the River Continuum
and Flood Pulse concepts, were developed primarily
to relate watershed C-dynamics to riverine food webs
(Vannote et al., 1980; Robertson et al., 1999) and do
not consider the nature of the OC exported from the
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156 143
river or its fate in the seabed. A conceptual model is
presented here that links the terrestrial and marine
portions of a river dispersal system and describes the
evolution of particulate OC (POC) as it passes through
the coupled watershed–seabed system. The model is
sufficiently general to be used as a template by which
to compare different river-margin systems and plan
future studies.
Fig. 1. Coupled watershed–seabed model describing the evolution
of POC. Changes in POC content occur primarily in boxes
however, transport between reservoirs can result in hydrodynamic
sorting and desorption of OC.
2. Model description
The preservation of OC requires its survival over
the time required to bury it beneath the biologically
active surface environment. This is accomplished
primarily when the kinetics of decomposition are
slowed relative to the burial rate via several mecha-
nisms: some organic materials are transported into
environments, typically anoxic, in which they are less
reactive; others are rendered unrecognizable to
enzymes by geochemical side reactions; and still
others are sequestered in protective matrices (Hedges
and Keil, 1995). In addition, certain biopolymers are
synthesized with an intrinsic resistance to degradation
(de Leeuw and Largeau, 1993). An underlying
premise of the model is that the protective mecha-
nisms may change as material moves through space
and time. History is important.
The model is composed of a series of intercon-
nected bioactive reservoirs representing locations
where the dominant changes in POC composition
occur (Fig. 1). The primary inputs into each reservoir
are the POC from an upstream reservoir, OC produced
within the reservoir, oxidants to support OC break-
down, and nutrients to support the in situ synthesis.
The OC produced in situ, while potentially possessing
a wide range of reactivities (de Leeuw and Largeau,
1993), will tend to be more susceptible to turnover
because it is younger and less degraded than that
arriving from upstream. It may add to the POC pool
entering from upstream, replace a portion of the older
pool, or act as a co-metabolic primer to facilitate the
oxidation of the older POC (Canfield, 1994; Aller,
1998). The primary oxidants are higher order in
energy, i.e., O2, NO3�, Mn+4 and Fe+3. Relatively
minor bulk compositional changes are expected in
sulfate reducing and methanogenic environments
based on the apparent stabilization of POC content
;
in anoxic sediments (Hartnett et al., 1998; Hedges
et al., 1999a).
There are numerous factors that can influence POC
and oxidant inputs that will, in turn, drive POC
turnover and/or preservation. These include climate,
hydrology, geology, and biota. Variations in these
environmental parameters lead to changes in POC
composition and preservation mechanisms as one
moves through the entire system. For instance,
terrestrial soils are primarily subaerial and are subject
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156144
to downward percolation of interstitial water, whereas
the bulk of marine sediments are subaqueous and have
relatively reduced advective flow of porewater and
solutes (Hedges and Oades, 1997). O2 transport is
thus more facile in soils while anaerobic conditions
dominate marine sediments millimeters to several
centimeters below the sediment–water interface. The
oxidation of recalcitrant biochemicals, such as spor-
opollenins, might be favored in aerobic soils (Hedges
and Keil, 1995). The cross-linking of olefinic species
by sulfides (vulcanization), which may reduce the
bioreactivity of the organic compounds, is more likely
to occur in sulfate-reducing marine sediments (Koh-
nen et al., 1991; Hedges and Oades, 1997).
The relative fluxes of material through and around
reservoirs, and the residence time within reservoirs are
key controls on OC character. An extreme example
would be bypassing a reservoir completely; it avoids
change altogether. Transport between reservoirs itself
can also influence the bulk composition of the POC.
Insofar as composition typically varies with particle
grain size (Hedges and Oades, 1997; examples to
follow), processes such as selective winnowing of
fine-grained particles from hillslopes (Rosenbloom et
al., 2001) and the hydrodynamic sorting of coarse and
fine particles can alter bulk POC characteristics
(Vannote et al., 1980; Goni et al., 1997).
Approximately 80–90% of recent sediment is
derived from the erosion of uplifted sedimentary rock
(Veizer and Jansen, 1985; Wold and Hay, 1990); thus,
the starting material in the model is ancient sedimen-
tary OC (Fig. 1A). Typically, this OC will contain a
significant fossil marine component that has experi-
enced extensive diagenesis and some catagenesis. The
characteristics of the rock OC are primarily functions
of the original depositional environment and thermal
history (Tissot and Welte, 1978).
Having survived diagenesis and likely some
thermal modification, the rock OC is relatively
unreactive. Even so, upon exposure in the regolith
(Fig. 1B) some of the rock OC may be removed if
time is sufficient (Petsch et al., 2000, 2001). In
unvegetated exposures, the time scale of kerogen
oxidation appears to be thousands of years. The time
required for significant rock OC loss in vegetated soils
is unknown but may be considerably less due to the
addition of reactive OC that could fuel co-metabolism
and the subsurface injection of O2 by plant roots.
Modern C is added to soils primarily as vascular
plant debris and transformed to heterotrophically
recycled material (Baldock and Skjemstad, 2000).
Aggregates of POC with inorganic minerals create a
hierarchy of stability (Golchin et al., 1997a). Macro-
aggregates (N250 Am) consist of plant fragments
encrusted with mineral particles. Mucilaginous glues
produced by microbes and plant roots provide
cohesion (Golchin et al., 1997a). The macroaggregate
disintegrates upon the decomposition of the core plant
fragment producing remnant microaggregate POC
that is of lower reactivity and more heterotrophic in
nature (Golchin et al., 1997a). The decomposition of
rock OC may occur simultaneously, resulting in a
partial blending of the modern and ancient C sources
via microbial processing (Petsch, 2001; Agnelli et al.,
2002). Turnover times of the various OC pools range
from seasonal to millennial (Admunson, 2001; Qui-
deau et al., 2001a).
Soil mineralogy, vegetative cover, exposure to
oxidants (which is dependent on regolith permeabil-
ity), water availability, temperature, and land use will
influence the evolution of soil organics (Connin et al.,
1997; Kay, 1997; Quideau et al., 2001b). Vegetative
cover in particular represents a nexus of controlling
processes. Climate, hydrology, and anthropogenic
activities, as examples, influence the composition of
the plant community. In turn, vegetative type can
affect the composition and timing of the organics
delivered to the soil (Quideau et al., 2001b), slope
stability, and soil residence time (Gabet and Dunne,
2002).
Lithology, hydrology, relief, climate (storm events),
and land use direct mass-wasting processes such as
shallow or deep landsliding, gully formation, and
sheet wash (Kelsey, 1980; DeRose et al., 1998;
Dymond et al., 1999; Page et al., 1999; Trustrum et
al., 1999; Hicks et al., 2000; Iverson et al., 2000).
These, in turn, influence the balance between bedrock,
soil, and vegetation delivered to waterways. Material
may go directly to the river (D) or to intermediate
storage locations such as slide tailings, channel infills,
and the floodplain (C; Page et al., 1994; DeRose et al.,
1998; Gomez et al., 1998; Marutani et al., 1999;
Trustrum et al., 1999). Modification of the OC is
predicted to occur during storage with the extent of
change controlled by time and exposure to biota,
oxidants, and possibly UV light. The extent of
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156 145
vegetative colonization of the stored soil/sediment and
the type of vegetative cover are predicted to signifi-
cantly influence the turnover and replacement of the
POC in a manner similar to that resulting from a
succession of plant communities caused by either
climate or land-use changes (Buyanovsky et al., 1997;
Connin et al., 1997; Golchin et al., 1997b; Quideau et
al., 2001b).
Further evolution of the POC can occur in the river
channel due to production from photosynthesis or
consumption via respiration (Richey et al., 1990;
Robertson et al., 1999; Bianchi et al., 2004). Little
change in suspended OC composition is expected to
occur within the channels of small, steep-sloped rivers
because of their short lengths and often high
turbidities (Blair et al., 2003).
Upon delivery to the shelf (E) and during transport
to the slope (F), sediment resides in the surface mixed
layer (SML) where it is subjected to repeated
resuspension–deposition cycles. SML residence time
will depend on wave, current, and tidal energy, the
slope and width of the continental shelf, bioturbation
depth, episodicity of erosion and deposition during
both floods and wave events, and the input flux of
sediment (Wright et al., 2001; Harris and Wiberg,
2002; Sherwood et al., 2002; Scully et al., 2003).
Residence time, along with water column productivity
and the intensity/frequency of reworking, are pre-
dicted to be factors controlling the extent of replace-
ment of rock and terrestrial plant-derived OC by
marine OM.
The replacement of terrestrial OC by marine-
derived material is likely facilitated, and perhaps
limited, by the disaggregation of soil particles in the
river or the marine SML. The newly exposed
terrestrial OC is thus vulnerable to enzymatic attack,
photolytic oxidation, and desorption. This is analo-
gous to the loss of POC from soils as a result of
agricultural tillage (Angers and Chenu, 1997). The
introduction of marine C proceeds via the incorpo-
ration of debris from the water column into the
sediment matrix followed by its partial reprocessing
by infauna and microbes (Blair et al., 1996, 2003;
Ransom et al., 1997, 1999; Arnarson and Keil, 2001;
Thomas and Blair, 2002). Sequestration in micro-
aggregates and mineral mesopores is hypothesized to
significantly slow the degradation kinetics of the OC,
particularly if coupled with cross-linking and con-
densation-style chemical reactions, and the production
of microbial glues (Hedges and Oades, 1997; Zimmer-
man et al., 2004).
2.1. The Eel River end-member: an example of
reservoir bypass
The Eel River drains a small watershed (~9000
km2) in northern California characterized by season-
ally heavy precipitation, steep slopes, rapid rates of
mass wasting, and the highest sediment yield for any
river in the contiguous U.S. (Fig. 2; Brown and Ritter,
1971; Sommerfield et al., 2002). The basin is under-
lain by the Jurassic to Tertiary Franciscan Complex, a
heterogeneous, tectonically sheared body of rock
composed primarily of easily eroded, shale-rich
melange and secondarily of more coherent sandstone
blocks (Kelsey, 1980; Blake et al., 1988). The
melange appears to be the primary source of fine-
grained sediment to the river based on its measured
contribution (70–94%) to the suspended load of the
Van Duzen River, a major tributary of the Eel (Kelsey,
1980). The melange OC (0.5–0.9% by weight) is
predominantly a Type III kerogen (Blair et al., 2003).
Gully wall erosion, earthflows, and landslides deliver
unweathered melange and plant debris-rich surface
soils to the river. Although some sediment is depo-
sited to form alluvial terraces and floodplain soils
during overbank events and then slowly eroded, the
bulk of the suspended riverine load appears to have
bypassed intermediate storage (Kelsey, 1980; Som-
merfield and Nittrouer, 1999).
The POC transported by the Eel is heterogeneous
in composition as a function of grain size (Fig. 3).
Plant debris, principally wood, is visually evident in
the coarse (N25 Am) fraction. The y13C value
(~�26.5x) and atomic C/N ratio (N20) are consistent
with a terrestrial C3 plant source (Leithold and Blair,
2001). Wood fragments collected from post-1960
shelf sediments have 14C-contents of ~108 pMC (%
modern 14C content; Blair et al., 2003).
The finer fractions contain OC from a mixture of
sources. The b4 Am OC in soils and riverine
suspended load is derived nearly equally from the
melange (0 pMC) and modern vegetation (~110 pMC)
as indicated by isotopic mass balances of 12C, 13C and14C (Figs. 3 and 4; Blair et al., 2003). Aged (N1000
years) soil C does not appear to be a major component
Fig. 2. Maps of the Eel watershed and margin (top panels) and Amazon shelf (bottom panel). Sampling locations are shown on each. The Eel
shelf was sampled 2 weeks after a flood event in 1997. River samples were collected at Cock Robin Island (CR) and the Scotia bridge (S).
Sampling details are provided in Blair et al. (2003). Amazon shelf sampling stations are from Blair and Aller (1995) (�) and Sommerfield et al.
(1996) (o). Approximate distances to Amazon River from each station are measured to X on the map.
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156146
Fig. 3. y13C and C/N ratios of riverine POC. Isotopic compositions
suggest that fine-grained POC is derived from plant debris in the
Amazon watershed (Hedges et al., 1986a,b). The shift in y13C from
coarse to fine POC may reflect a greater compositional complexity
for the fine-grained material as a result of its age. Alteration of the
C/N ratio is apparently the result of microbial processes in soils. The
same trend is seen in the Eel watershed except that the POC is
derived from a combination of kerogen and plant debris (Blair et al.,
2003).
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156 147
of the fluvial POC. The residence time of the
vegetation-derived OC in the eroding soils must be
on the order of several decades or less based on 14C-
content. The steep slopes of crushed bedrock in the
Eel watershed generates a weathering-limited situa-
tion (sensu Stallard, 1995), whereby the soil OC that
feeds the riverine suspended load has not had the
opportunity to age greatly. The POC is thus largely a
bimodal mixture of ancient and modern OC. C/N
ratios suggest microbial reprocessing of the two
sources (Fig. 3).
Greater than 80% of the sediment delivery to the
~25-km-wide shelf is associated with annual winter
storms (Sommerfield and Nittrouer, 1999; Sommer-
field et al., 1999). Sediment plumes from the river
initially travel northward and stay inshore of the 40-m
isobath (Geyer et al., 2000). Wave-induced gravity-
driven processes then transport thin fluid mud layers
to the mid-shelf depocenter within days (Ogston et al.,
2000; Traykovski et al., 2000; Scully et al., 2003).
20–25% of the fine sediment from floods accumulates
on the mid-shelf; the remainder is either trapped in
inner shelf sands or dispersed across and along shelf,
and downslope (Wheatcroft et al., 1997; Sommerfield
and Nittrouer, 1999; Mullenbach and Nittrouer, 2000;
Scully et al., 2002, 2003; Puig et al., 2003). Flood
layers are preserved on the mid-shelf as a result of
rapid burial through the surface mixed layer (Wheat-
croft and Drake, 2003).
The POC buried in the depocenter reflects the
short time spent in the surface mixed layer (Blair et
al., 2003). Portions of the flood layer may be buried
below the mixed layer nearly instantaneously (within
days) because of the volume of sediment deposited.
As a result, flood layer OC has essentially retained
the isotopic composition of riverine material (Fig. 4).
Muds not directly associated with preserved flood
layers have incorporated marine OC as result of their
longer residence in the SML and exposure to local
productivity (Leithold and Hope, 1999; Fig. 4).
Given the return frequency of major floods and the
average sediment accumulation, the residence time of
non-flood sediment in the SML is on the order of a
decade. The difference in the loading of marine OC
in the clay fraction between flood and non-flood
deposits is recorded in the seabed as each is buried
(Fig. 5). Significant loss of either modern terrestrial
C or the kerogen is not observed presumably
because the intensity and duration of surface mixing
processes are insufficient, even in the non-flood
intervals (Fig. 6).
2.2. The Amazon end-member: an example of
extensive storage in bioactive reservoirs
Whereas the bulk of the sediment buried on the Eel
shelf by a flood event can literally travel from bedrock
source to marine burial in a matter of days, suspended
sediment in the Amazon follows a more protracted
journey. The Amazon River drains nearly half of
South America or approximately 7.05�106 km2
(Hoorn, 1994). 80–90% of the suspended load
originates in the Andes (Gibbs, 1967; Meade et al.,
1985), which are composed of uplifted marine and
continental sediments, and igneous and metamorphic
rocks (Potter, 1997; Bevins et al., 2003). Large-scale
sedimentation has occurred in the adjoining foreland
basin due to the Andean uplift and erosion (Rasanen
et al., 1995; Irion et al., 1995; Potter, 1997), leading to
long-term storage of materials spanning millions of
years. Weathering of sedimentary cover and shield
bedrock has formed soils in the upper lowlands (the
terra firme) that may be tens of millions of years old
(Stallard, 1995; Irion et al., 1995). However, the low
Fig. 4. The evolution of POC on the continental margin. Both the Eel and Amazon display the same y13C trend towards more 13C-enriched
contents as one moves offshore but the underlying processes differ. On the Eel shelf and slope, marine C is added to particles with little loss of
kerogen or modern terrestrial OC. 14C ages decrease due to the addition of the marine OC (Blair et al., 2003). Shelf and slope analyses were
done on the b4 Am fraction of the 0–1-cm depth intervals of box cores. In contrast, particle age increases on the Amazon shelf as young
terrestrial OC is selectively lost. The particles are not completely reloaded with marine OC. Amazon River data are from Hedges et al. (1986a,b)
and Keil et al. (1997). Amazon shelf 14C data are from piston core tops (Sommerfield et al., 1996); the OC/SA and y13C measurements are from
the 3- to 13-cm depth interval of piston cores (Blair and Aller, unpublished data) and surface samples (Showers and Angle, 1986; see citation for
sampling locations). All samples should be representative of the surface mixed layer. The measurements were made on bulk samples, which
exhibit the same general OC/SA and y13C trends as clay fractions (Keil et al., 1997). Methods for the Blair and Aller’s unpublished data are
reported in Blair et al. (2003).
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156148
erosion rates that permit the formation of such ancient
soils also contribute little to the riverine sediment load
(Stallard, 1995).
50,000 km2 of the Amazon basin are occupied by
the floodplain (varsea), an area N5 times that of the
entire Eel watershed (Richey et al., 1990). An average
of 1.7 billion tons of sediment are deposited on the
floodplain and 1.6 billion tons are returned to the
mainstem via bank erosion per annum (Dunne et al.,
1998). Given that approximately 1.2 billion tons/year
of sediment are transported by the river to the delta
plain, where 0.3–0.4 billion tons/year are intercepted,
it is likely that much of the sediment discharged to the
ocean has resided in the floodplain for some period of
time (Dunne et al., 1998).
The coarse (N63 Am) POC fraction of the
Amazon’s suspended load is dominated by leaf
(70–80%) and woody (15–25%) debris (Hedges et
al., 1986a, 2000). Varsea C4 grasses contribute
V10%. Breakdown of the coarse POC and incorpo-
ration into soils appears to be the primary source of
the fine (b63 Am) POC (Fig. 3; Hedges et al.,
1986a, 1994). The respective 14C contents of the
coarse and fine pools, 123 and 102 pMC, are
consistent with the diagenetic flow of coarseYfine
(Hedges et al., 1986b). Neither POC fraction
undergoes extensive changes within the river chan-
nel in part because of low primary production rates
there (Richey et al., 1990). In-channel respiration
rates seem to be preferentially fueled by a reactive
Fig. 5. y13C and OC/surface area of Eel shelf b4 Am sediment.
Samples are from a core collected at the 70-m depocenter of the
shelf (K70 station). Flood layers were identified by their higher clay
content (Leithold and Blair, 2001). Marine OC is added to the b4
Am fraction as particles reside in the surface mixed layer. Non-flood
sediment spends more time in the mixed layer and thus has a more
marine signature.
Fig. 6. POC sources downcore on the Eel shelf. 13C/12C and 14C/12C
abundances were used to resolve kerogen, modern terrestrial, and
marine OC sources at the K70 site using an isotopic mass balance
approach (Blair et al., 2003). Deposition is post-1964. y13C end-
member values were �24.3x, �26.5x and �21x for the kerogen,
terrestrial and marine sources. D14C values were �1000x for the
kerogen and +100x for the terrestrial and marine OC. The
terrestrial isotopic end-member values were verified using wood
isolates from the core. Those of the kerogen and marine sources
were assumed to be the same as at present (Blair et al., 2003). Data
are from Perkey (2003) and Leithold et al. (2004).
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156 149
subset of dissolved OC and POC that turns over
rapidly.
Downstream y13C gradients of the fine POC argue
for an overprinting or replacement of Andean-derived
OC by that from the lowlands (Quay et al., 1992).
This is analogous to the overprinting of the original
tectonic (upland) signature of quartz sands (and
presumably many other inorganic minerals) by long-
term storage and intense chemical weathering in the
alluvial sediments and soils of the Orinoco drainage
basin (Johnsson et al., 1988). Much of the OC
transformation may occur during storage in the
floodplain (Richey et al., 1991). Deposition on varsea
surfaces and erosion of banks creates a slowly moving
solid bed reactor for the processing of the OC. Given
that the length and speed of the reactor will vary
throughout the floodplain, a continuum of ages is
predicted for the fine POC. In addition, the age
distribution should be skewed toward younger mate-
rial because in general the slower erosion rates that
would allow the OC to age would also contribute less
to the total sediment budget (Fig. 7). The exceptions
would be if the slower cycling region were suffi-
ciently large in area to compensate for the lower
sediment flux, or non-steady-state processes such
land-use perturbations greatly accelerated erosion of
previously stable soils. The mean residence time in
the watershed estimated for the suspended fine POC,
b600 years based on 14C age (Hedges et al., 1986b;
Richey et al., 1990), may thus reflect the preferential
delivery of younger, more rapidly eroded material to
the river. Residence times for the material remaining
in the varsea deposits must be longer, particularly
given that sediment deposition in the floodplains is
controlled in part by sea-level changes (Irion et al.,
1995). This is an important consideration when
comparing residence times of OC retained within soil
profiles to those of the soil C that escaped to the river.
A suite of physical processes act on the Amazon
sediment discharged to the ocean to create z1-m-thick
suspensions of fluid mud (N10 g l�1) that cover large
Fig. 7. Hypothetical 14C age distributions of riverine POC before and after deposition on the shelf. Short, mountainous rivers, such as the Eel,
are predicted to discharge POC predominantly composed of modern OC and kerogen. If deposition is sufficiently rapid, the POC will be largely
recalcitrant in the shelf environment. The modern component is augmented by the addition of marine OC on the shelf. Extensive storage, as
exhibited in the Amazon watershed, is predicted to lead to a more continuous range of POC ages that is skewed to the modern. Total OC
decreases and modern OC will be preferentially lost in the energetic regions of wide shelves. Reloading of particles with modern OC can occur
in deeper, more quiescent margin zones, provided that a source of fresh marine organic matter is present. The predicted age distribution may be
more like that of the river, except that the modern component will have a marine source.
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156150
areas of the shelf adjacent the river mouth (Kineke
and Sternberg, 1995; Kuehl et al., 1995). These fluid
muds overlie and exchange with a more consolidated
but still highly mobile zone of the seabed. During
neap tides, water column salinity is stratified and
resuspended sediment is trapped in turbidity max-
imum regions to form fluid muds (Kineke and
Sternberg, 1995). These fluid muds are dispersed
during the more energetic spring tides and become
temporarily incorporated into the underlying seabed.
The tidal excursion of the front is ~30 km.
Seasonal fluctuations in river discharge cause the
turbidity maximum-sediment mobilization zone to be
displaced either landward or seaward (Kineke and
Sternberg, 1995; Nittrouer et al., 1995). A combina-
tion of surface waves, tidal currents, and riverine
supply influence the thickness and expanse of the
fluid mud; winds tend to accentuate across-shelf
transport in both seaward and shoreward directions
(Kineke and Sternberg, 1995).
Mobilized sediment is transported northward
along-shelf, forming a reworked surface layer in the
relatively consolidated seabed that is as much as 1.5 m
thick between the 10- and 30-m isobaths (Kuehl et al.,
1995). Portions of the seabed are exhumed and
resuspended into overlying fluid muds during periods
when intense surface waves are superimposed upon
tidal currents (Cacchione et al., 1995; Kuehl et al.,
1995). Overall, ~31�109 tons of sediment are
reworked annually on daily to seasonal time scales
(Aller, 1998). Given the riverine discharge of
0.8�109–0.9�109 tons/year, the mean residence time
of material in the physically reworked zone is ~30–40
years.
More than 50% of the fluvial OC disappears on the
Amazon shelf (Aller et al., 1996; Keil et al., 1997).
Normalization of OC content to particle surface area
(OC/SA) indicates that this is not a result of hydro-
dynamic sorting, but instead that of desorption and/or
oxidation (Keil et al., 1997; Aller, 1998; Fig. 4). y13Cvalues indicate a seaward trend toward increasing
proportions of marine OC (Showers and Angle, 1986;
Keil et al., 1997; Fig. 4). Isotopic mass balance
calculations, assuming terrestrial and marine y13Cend-members of �28x and �20x, respectively
(Showers and Angle, 1986; Hedges et al., 1986a;
Sommerfield et al., 1996), indicate a nearly constant
marine loading but a net loss of terrestrial material
(Fig. 4). 14C ages of the POC increase with distance
from the river mouth, which is consistent with the
preferential loss of a younger, more reactive fraction
(Fig. 4; Sommerfield et al., 1996). Porewater dis-
solved inorganic y13C values converge over much of
the delta topset region to near �23x, reflecting an
oxidized mixture of ~40% terrestrial and ~60% ma-
rine C (Fig. 8). A trend towards a greater marine
contribution is seen as one moves seaward and
downdrift of the river mouth (Fig. 8). Modeling
indicates that the average y13C values of DIC added to
the porewater over the upper 5 m at these sites are
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156 151
�23.4F0.1 (RMT-2), �23.5F0.4 (OST-2), and
�22.0F0.7x (OST-3). A similar, albeit better re-
solved pattern is observed in the mobile deltaic topset
muds on the Fly River shelf offshore of Papua New
Guinea, where the 13C, 14C contents of porewater DIC
and the POC clearly indicate selective oxidation of
younger marine OC over the riverine input both with
distance from the river mouth and downcore within
the seabed (Aller and Blair, 2004).
Periodic regeneration of oxidants coupled with the
admixing of reactive marine OC likely fuels the loss of
the otherwise recalcitrant terrestrial material in a
manner analogous to what occurs during sewage
treatment (Graf, 1992; Canfield, 1994; Aller, 1998).
Although a large flux of marine carbon enters the
seabed, little is preserved in the highly dynamic
environment. Not until sediment moves out to the
more physically stable foreset region of the subaqu-
eous delta does the organic content increase with the
addition of marine carbon (Showers and Angle, 1986).
2.3. Implications and conclusions
The Eel is an example wherein the original
upland-generated organic carbon signal is transmitted
with some fidelity to the seabed. Modification of the
Fig. 8. Profiles of porewater dissolved inorganic carbon y13C (filled
symbols) and POC y13C (open symbols) on the Amazon shelf. POC
y13C values reflect the dominance of the terrestrial OC in the buried
solid phase. DIC y13C profiles record not only the co-oxidation of
terrestrial and marine OC but also the preferential oxidation of the
more reactive marine component. DIC y13C values at depthsz6 m
are impacted by anaerobic methane oxidation and are not shown
(Blair and Aller, 1995).
signal is accomplished by simple additions of
modern OC. In contrast, upstream signals from the
Amazon are erased and overprinted by successive
downstream reservoirs, primarily the floodplain soils
and the shelf surface muds. These two riverine
systems represent end-members in a continuum of
behaviors, yet their characteristics are far from
atypical. For instance, a number of highly turbid
rivers in addition to the Eel, including the Santa
Clara of southern California, the Lanyang Hsi of
Taiwan, and the Waipaoa of New Zealand, transport
kerogen loads on the order of 0.5% by weight
(Meybeck, 1993; Masiello and Druffel, 2001; Kao
and Liu, 1996; Gomez et al., 2003). This concen-
tration is the same as the mean OC content of
sedimentary rocks (Ronov, 1976), which may
explain the uniformity in fluvial kerogen load and
argues for an even greater and more widespread
occurrence than what has been reported to date. The
bimodal age distribution of POC (modern and
ancient) exported by the Eel is predicted to be
typical for short, steep, high sediment yield systems
(Fig. 7).
As on the Amazon shelf, distinctively low OC/
surface area ratios exist in the deltaic sediments of
other rivers, such as the Fly, Johnstone, and Mis-
sissippi, when compared to the riverine output or other
continental margin locations (Keil et al., 1997; Aller,
1998; Aller and Blair, 2004). The intensity (depth
within seabed), frequency and duration of physical
mixing coupled with sediment accumulation rate are
hypothesized to be factors in controlling the extent of
OC loss (Aller, 1998). Duration will be controlled in
part by shelf width and morphology. Narrow shelves,
such as those characteristic of the Eel and other small,
active margin rivers, facilitate sediment bypass to the
slope (Sommerfield and Nittrouer, 1999; Nittrouer et
al., 2001); thus, the material buried on them will have
spent relatively less time in the surface mixed layer
than on wider margins, particularly if sediment
accumulation rates are high. Partially enclosed coastal
embayments, such as the Columbia and Gironde
estuaries, would facilitate the exchange of marine for
terrestrial OC because of the retention of particles in an
environment subject to repeated deposition–resuspen-
sion cycles and the supply of reactive marine
production (Keil et al., 1997; Abril et al., 1999; Crump
and Baross, 2000). Given the complex resuspension–
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156152
deposition histories that are likely experienced by
sediment in deltas, determining the total residence time
of POC in the mixed layer and its frequency of
resuspension is a crude exercise at best. This lack of
constraint has limited our ability to evaluate quantita-
tively the relationship between OC preservation and
sediment transport processes. Determining the resi-
dence time of POC in its various reservoirs, especially
in the seabed mixed layer, poses a significant challenge
for the future.
Understanding the dynamics of both the watershed
and shelf processes is key to interpreting the preserved
OC record. For example, soil C can appear older
(more 14C-depleted) than co-buried marine material as
a result of various processes as illustrated by the
model. In short Eel-like systems, OC sources differing
in age by millions of years are mixed producing a
material with an apparent intermediate age. Where
sources of OC are lowland-dominated as in the
Amazon system, terrestrial OC is aged by storage in
soils. Further 14C-loss occurs via the preferential loss
of the younger, more reactive terrestrial component
during diagenesis (Raymond and Bauer, 2001; Aller
and Blair, 2004; Fig. 7). Not considering these factors
may lead to erroneous interpretations of 14C-sedimen-
tary profiles (Sommerfield et al., 1996; Aller and
Blair, 2004).
The global CO2 and O2 cycles are linked by a
tectonically driven, mineral conveyor belt that both
buries and exhumes sedimentary OC (Hedges et al.,
1999b). The present-day burial flux of OC in marine
sediments has been estimated to be 12–13 Tmol C/
year (Hedges and Keil, 1995; Schlunz and
Schneider, 2000). The oxidation rate of the exhumed
rock OC is assumed to equal the burial flux so as to
maintain near constant O2 levels (Berner, 1989;
Hedges, 1992). If 40–70% of the global fluvial
sediment flux to the ocean (~20,000 Tg/year) is
delivered by small, mountainous rivers (Milliman
and Syvitski, 1992; Milliman, personal communica-
tion), and those rivers transport material that is on
average 0.5% kerogen C by weight, then 40–70 Tg
kerogen C/year (3.3–5.8 Tmol C/year) escape imme-
diate oxidation and may be reburied. This calculation
does not include export of kerogen from larger
drainage basins where it is more likely to be
oxidized during long-term storage. The riverine
kerogen flux is ~25–50% of the presumed kerogen
oxidation rate and total OC burial term. The net
effect of widespread kerogen reburial would be to
buffer the atmosphere against dramatic changes in
pO2 (Hedges, 1992). However, comparisons of OC
burial fluxes with kerogen oxidation rates must be
done with the acknowledgment that they have been
impacted anthropogenically and not equally. Human
activities have accelerated mass-wasting rates (Milli-
man and Syvitski, 1992; Foster and Carter, 1997;
Sommerfield et al., 2002), which should increase
kerogen export and OC burial fluxes while decreasing
kerogen oxidation or at least displacing it from the
continents to the deep-sea. As a result, a steady-state
balance between OC burial and kerogen oxidation
should not be assumed for the present.
Acknowledgements
This article was written to commemorate John
Hedges for his substantial contributions and leader-
ship in the field of organic geochemistry. John opened
many doors for us and his impact on the field will be
felt for many years. In addition, we wish to thank the
many individuals involved in the AmasSeds and
STRATAFORM projects who made the marine
sample collection and analyses possible. Special
thanks go to C.A. Nittrouer for his leadership on both
projects. An early version of this model was prepared
for a research proposal and the co-PIs, J. Bauer, E.
Canuel, C. Harris, and S. Kuehl, are acknowledged for
their assistance in its development. Funding has been
provided by NSF grants OCE-8812907, OCE-
9115709, OCE-9809553, OCE-0219919, and EAR-
0222584, the American Chemical Society Petroleum
Research Fund (33207-AC2), and the Office of Naval
Research. The comments offered by P. Raymond and
an anonymous reviewer were appreciated, as were the
efforts of R. Benner, C. Lee, and S. Wakeham in the
organization of the symposium and editorial handling
of the manuscripts.
References
Abril, G., Etcheber, H., Le Hir, P., Bassoullet, P., Boutier, B.,
Frankignoulle, M., 1999. Oxic/anoxic oscillations and organic
carbon mineralization in an estuarine maximum turbidity zone
(the Gironde, France). Limnol. Oceanogr. 44, 1304–1315.
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156 153
Admunson, R., 2001. The carbon budget of soils. Annu. Rev. Earth
Planet. Sci. 29, 535–562.
Agnelli, A., Trumbore, S.E., Corti, G., Ugolini, F.C., 2002. The
dynamics of organic matter in rock fragments in soil inves-
tigated by 14C dating and measurements of 13C. Eur. J. Soil Sci.
53, 147–159.
Aller, R.C., 1998. Mobile deltaic and continental shelf muds as
suboxic, fluidized bed reactors. Mar. Chem. 61, 143–155.
Aller, R.C., Blair, N.E., 2004. Early diagenetic remineralization of
sedimentary organic C in the Gulf of Papua deltaic complex
(Papua New Guinea): net loss of terrestrial C and diagenetic
fractionation of C isotopes. Geochim. Cosmochim. Acta 68,
1815–1825.
Aller, R.C., Blair, N.E., Xia, Q., Rude, P.D., 1996. Remineralization
rates, recycling, and storage of Corg in Amazon Shelf sedi-
ments. Cont. Shelf Res. 16, 753–786.
Angers, D.A., Chenu, C., 1997. Dynamics of soil aggregation and C
sequestration. In: Lal, R., Kimble, J.M., Follett, R.F., Stewart,
B.A. (Eds.), Soil Processes and the Carbon Cycle. CRC Press,
NY, pp. 199–206.
Arnarson, T., Keil, R.G., 2001. Organic–mineral interactions in
marine sediments studied using density fractionation and X-ray
photoelectron spectroscopy. Org. Geochem. 32, 1401–1415.
Baldock, J.A., Skjemstad, J.O., 2000. Role of the soil matrix and
minerals in protecting natural organic materials against bio-
logical attack. Org. Geochem. 31, 697–710.
Berner, R.A., 1982. Burial of organic carbon and pyrite sulfur in the
modern ocean: its geochemical and environmental significance.
Am. J. Sci. 282, 451–473.
Berner, R.A., 1989. Biogeochemical cycles of carbon and sulfur and
their effect on atmospheric oxygen over Phanerozoic time.
Palaeogeogr. Palaeoclimatol. Palaeoecol. 75, 97–122.
Bevins, R.E., Robinson, D., Aguirre, L., Vergara, M., 2003.
Episodic burial metamorphism in the Andes—a viable model?
Geology 31, 705–708.
Bianchi, T.S., Filley, T., Dria, K., Hatcher, P.G., 2004. Temporal
variability in sources of dissolved organic carbon in the lower
Mississippi River. Geochim. Cosmochim. Acta 68, 959–967.
Blair, N.E., Aller, R.C., 1995. Anaerobic methane oxidation on the
Amazon shelf. Geochim. Cosmochim. Acta 59, 3707–3715.
Blair, N.E., Levin, L.A., DeMaster, D.J., Plaia, G., 1996. The short-
term fate of fresh algal carbon in continental slope sediments.
Limnol. Oceanogr. 41, 1208–1219.
Blair, N., Leithold, E., Ford, S., Peeler, K., Holmes, J., Perkey, D.,
2003. The persistence of memory: the fate of ancient sedimen-
tary organic carbon in a modern sedimentary system. Geochim.
Cosmochim. Acta 67, 63–73.
Blake Jr., M.C., Jayko, A.S., McLaughlin, R.J., Underwood, M.B.,
1988. Metamorphic and tectonic evolution of the Franciscan
Complex, northern California. In: Ernst, W.G. (Ed.), Meta-
morphism and Crustal Evolution of the Western United States.
Prentice-Hall, Upper Saddle River, NJ, pp. 1036–1060.
Brown, W.M. III, Ritter, J.M., 1971. Sediment Transport and
Turbidity in the Eel River basin, California. Water Supplemental
Paper No. 1986. U.S. Geological Survey.
Buyanovsky, G.A., Brown, J.R., Wagner, G.H., 1997. Sanborn
field: effect of 100 years of cropping on soil parameters
influencing productivity. In: Paul, E.A., Elliott, E.T., Paustian,
K., Cole, C.V. (Eds.), Soil Organic Matter in Temperate
Agroecosystems. CRC Press, NY, pp. 205–225.
Cacchione, D.A., Drake, D.E., Kayen, R.W., Sternberg, R.W.,
Kineke, G.C., Tate, G.B., 1995. Measurements in the bottom
boundary layer on the Amazon subaqueous delta. Mar. Geol.
125, 235–257.
Canfield, D.E., 1994. Factors influencing organic carbon preserva-
tion in marine sediments. Chem. Geol. 114, 315–329.
Connin, S.L., Virginia, R.A., Chamberlain, C.P., 1997. Carbon
isotopes reveal soil organic matter dynamics following arid land
shrub expansion. Oecologia 110, 374–386.
Crump, B.C., Baross, J.A., 2000. Characterization of the bacterially-
active particle fraction in the Columbia River estuary. Mar.
Ecol., Progr. Ser. 206, 13–22.
de Leeuw, J.W., Largeau, C., 1993. A review of macromolecular
organic compounds that comprise living organisms and their
role in kerogen, coal, and petroleum formation. In: Engel, M.H.,
Macko, S.A. (Eds.), Organic Geochemistry Principles and
Applications. Plenum, New York, pp. 23–72.
DeRose, R.C., Gomez, B., Marden, M., Trustrum, N.A., 1998.
Gully erosion in Mangatu Forest, New Zealand, estimated
from digital elevation models. Earth Surf. Process. Landf. 23,
1045–1053.
Dunne, T., Mertes, L.A.K., Meade, R.H., Richey, J.E., Forsberg,
B.R., 1998. Exchanges of sediment between the floodplain
and channel of the Amazon River in Brazil. GSA Bull. 110,
450–467.
Dymond, J.R., Jessen, M.R., Lovell, L.R., 1999. Computer
simulation of shallow landsliding in New Zealand hill country.
JAG 1, 122–131.
Foster, G., Carter, L., 1997. Mud sedimentation on the continental
shelf at an accretionary margin—Poverty Bay, New Zealand.
N.Z. J. Geol. Geophys. 40, 157–173.
Gabet, E.J., Dunne, T., 2002. Landslides on coastal sage-scrub and
grassland hillslopes in a severe El Nino winter: the effects of
vegetation conversion on sediment delivery. Geol. Soc. Amer.
Bull. 114, 983–990.
Geyer, W.R., Hill, P.S., Milligan, T.G., Traykovski, P., 2000. The
structure of the Eel River plume during floods. Cont. Shelf Res.
20, 2067–2093.
Gibbs, R.J., 1967. Amazon River: environmental factors that control
its dissolved and suspended load. Science 156, 1734–1737.
Golchin, A., Baldock, J.A., Oades, J.M., 1997a. A model linking
organic matter decomposition, chemistry, and aggregation
dynamics. In: Lal, R., Kimble, J.M., Follett, R.F., Stewart,
B.A. (Eds.), Soil Processes and the Carbon Cycle. CRC Press,
pp. 245–266.
Golchin, A., Clarke, P., Baldock, J.A., Higashi, T., Skjemstad, J.O.,
Oades, J.M., 1997b. The effects of vegetation and burning on
the chemical composition of soil organic matter in a volcanic
ash soil as shown by 13C NMR spectroscopy. I: whole soil and
humic fraction. Geoderma 76, 155–174.
Gomez, B., Eden, D.E., Peacock, D.H., Pinkney, E.J., 1998.
Floodplain construction by recent, rapid vertical accretion:
Waipaoa River, New Zealand. Earth Surf. Process. Landf. 23,
405–413.
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156154
Gomez, B., Trustrum, N.A., Hicks, D.M., Rogers, K.M., Page, M.J.,
Tate, K.R., 2003. Production, storage and output of particulate
organic carbon: Waipaoa River basin, New Zealand. Water
Resour. Res. 39, ESG 2-1–ESG 2-8.
Goni, M.A., Ruttenberg, K.C., Eglinton, T.I., 1997. Sources and
contribution of terrigenous organic carbon to surface sediments
in the Gulf of Mexico. Nature 389, 275–278.
Graf, G., 1992. Benthic–pelagic coupling: a benthic view. Ocean-
ogr. Mar. Biol. Annu. Rev. 30, 149–190.
Harris, C.K., Wiberg, P.L., 2002. Across-shelf sediment transport:
interactions between suspended sediment and bed sediment.
J. Geophys. Res. 107 (C1), 8-1–8-12.
Hartnett, H.E., Keil, R.G., Hedges, J.I., Devol, A.H., 1998.
Influence of oxygen exposure time on organic carbon
preservation in continental margin sediments. Nature 391,
572–574.
Hedges, J.I., 1992. Global biogeochemical cycles: progress and
problems. Mar. Chem. 39, 67–93.
Hedges, J.I., Keil, R.G., 1995. Sedimentary organic matter
preservation: an assessment and speculative synthesis. Mar.
Chem. 49, 81–115.
Hedges, J.I., Oades, J.M., 1997. Comparative organic geochemistries
of soils and marine sediments. Org. Geochem. 27, 319–361.
Hedges, J.I., Clark, W.A., Quay, P.D., Richey, J.E., Devol, A.H.,
Santos, U. de M., 1986a. Compositions and fluxes of particulate
organic material in the Amazon River. Limnol. Oceanogr. 31,
717–738.
Hedges, J.I., Ertel, J.R., Quay, P.D., Grootes, P.M., Richey, J.E.,
Devol, A.H., Farwell, G.W., Schmidt, F.W., Salati, E., 1986b.
Organic Carbon-14 in the Amazon River System. Science 231,
1129–1131.
Hedges, J.I., Cowie, G.L., Richey, J.E., Quay, P.D., 1994. Origins
and processing of organic matter in the Amazon River as
indicated by carbohydrates and amino acids. Limnol. Oceanogr.
39, 743–761.
Hedges, J.I., Keil, R.G., Benner, R., 1997.What happens to terrestrial
organic matter in the ocean? Org. Geochem. 27, 195–212.
Hedges, J.I., Hu, F.S., Devol, A.H., Hartnett, H.E., Tsamakis, E.,
Keil, R.G., 1999a. Sedimentary organic matter preservation: a
test for selective degradation under oxic conditions. Am. J. Sci.
299, 529–555.
Hedges, J.I., Keil, R.G., Lee, C., Wakeham, S.G., 1999b. Atmos-
pheric O2 control by a dmineral conveyor beltT linking the
continents and ocean. In: Armannsson, H. (Ed.), Geochemistry
of the Earth’s Surface. A.A. Balkema, Rotterdam, pp. 241–244.
Hedges, J.I., Mayorga, E., Tsamakis, E., McClain, M.E.,
Aufdenkampe, A., Quay, P., Richey, J.E., Benner, R., Opsahl,
S., Black, B., Pimental, T., Quintanilla, J., Maurice, L., 2000.
Organic matter in Bolivian tributaries of the Amazon River: a
comparison to the lower mainstream. Limnol. Oceanogr. 45,
1449–1466.
Henrichs, S.M., 1995. Sedimentary organic matter preservation—an
assessment and speculative synthesis—a comment. Mar. Chem.
49, 127–136.
Hicks, D.M., Gomez, B., Trustrum, N.A., 2000. Erosion thresholds
and suspended sediment yields, Waipaoa River basin, New
Zealand. Water Resour. Res. 36, 1129–1142.
Hoorn, C., 1994. An environmental reconstruction of the palaeo-
Amazon River system (middle–late Miocene, NW Amazonia).
Palaeogeogr. Palaeoclimatol. Palaeoecol. 112, 187–238.
Irion, G., Mqller, J., deMello, J.N., Junk, W.J., 1995.
Quaternary geology of the Amazonian lowland. Geo Mar.
Lett. 15, 172–178.
Iverson, R.M., Reid, M.E., Iverson, N.R., LaHusen, R.G., Logan,
M., Mann, J.E., Brien, D.L., 2000. Acute sensitivity of landslide
rates to initial soil porosity. Science 290, 513–516.
Johnsson, M.J., Stallard, R.F., Meade, R.H., 1988. First-cycle
quartz arenites in the Orinoco River basin, Venezuela and
Columbia. J. Geol. 96, 263–277.
Kao, S.J., Liu, K.K., 1996. Particulate organic carbon export from a
subtropical mountainous river (Lanyang Hsi) in Taiwan.
Limnol. Oceanogr. 41, 1749–1757.
Kay, B.D., 1997. Soil structure and organic carbon: a review. In:
Lal, R., Kimble, J.M., Follett, R.F., Stewart, B.A. (Eds.), Soil
Processes and the Carbon Cycle. CRC Press, NY, pp. 169–197.
Keil, R.G., Mayer, L.M., Quay, P.D., Richey, J.E., Hedges, J.I.,
1997. Loss of organic matter from riverine particles in deltas.
Geochim. Cosmochim. Acta 61, 1507–1511.
Kelsey, H.M., 1980. A sediment budget and an analysis of
geomorphic process in the Van Duzen River basin, north coastal
California, 1941–1975: summary. Geol. Soc. Amer. Bull. 91,
190–195.
Kennedy, M.J., Pevear, D.R., Hill, R.J., 2002. Mineral surface
control of organic carbon in black shale. Science 295, 657–660.
Kineke, G.C., Sternberg, R.W., 1995. Distribution of fluid muds on
the Amazon continental shelf. Mar. Geol. 125, 193–233.
Kohnen, M.E.L., Sinninghe Damste, J.S., Kock-van Dalen, A.C.,
de Leeuw, J.W., 1991. Di- or polysulphide-bound biomarkers in
sulphur-rich geomacromolecules as revealed by selective
chemolysis. Geochim. Cosmochim. Acta 55, 1375–1394.
Kuehl, S.A., Pacioni, T.D., Rine, J.M., 1995. Seabed dynamics of
the inner Amazon continental shelf: temporal and spatial
variability of surficial strata. Mar. Geol. 125, 283–302.
Leithold, E., Blair, N., 2001. Watershed control on the carbon
loading of marine sedimentary particles. Geochim. Cosmochim.
Acta 65, 2231–2240.
Leithold, E.L., Hope, R.S., 1999. Deposition and modification of a
flood layer on the northern California shelf: lessons from and
about the fate of terrestrial particulate organic carbon. Mar.
Geol. 154, 183–195.
Leithold, E., Perkey, D.W., Blair, N.E., Creamer, T.N., 2004.
Sedimentation and carbon burial on the northern California
continental shelf: the signatures of land-use change. Cont. Shelf
Res, in press.
Marutani, T., Kasai, M., Reid, L.M., Trustrum, N.A., 1999.
Influence of storm-related sediment storage on the sediment
delivery from tributary catchments in the upper Waipaoa River,
New Zealand. Earth Surf. Process. Landf. 24, 881–896.
Masiello, C.A., Druffel, E.R.M., 2001. Carbon isotope geochemis-
try of the Santa Clara River. Glob. Biogeochem. Cycles 15,
407–416.
Mayer, L.M., 1994a. Surface area control of organic carbon
accumulation in continental shelf sediments. Geochim. Cosmo-
chim. Acta 58, 1271–1284.
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156 155
Mayer, L.M., 1994b. Relationships between mineral surfaces and
organic carbon concentrations in soils and sediments. Chem.
Geol. 114, 347–364.
Meade, R.H., Dunne, T., Richey, J.E., Santos, U. de M., Salati, E.,
1985. Storage and remobilization of suspended sediment in the
lower Amazon River of Brazil. Science 228, 488–490.
Meybeck, M., 1993. C, N, P and S in rivers: from sources to global
inputs. In: Wollast, R., Mackensie, F.T., Chou, L. (Eds.),
Interactions of C, N, P and S Biogeochemical Cycles and
Global Change. Springer-Verlag, Berlin, pp. 163–193.
Milliman, J.D., Syvitski, J.P.M., 1992. Geomorphic/tectonic control
of sediment discharge to the ocean: the importance of small
mountainous rivers. J. Geol. 100, 525–544.
Mullenbach, B.L., Nittrouer, C.A., 2000. Rapid deposition of fluvial
sediment in the Eel canyon, northern California. Cont. Shelf
Res. 20, 2191–2212.
Nittrouer, C.A., Kuehl, S.A., Sternberg, R.W., Figueiredo Jr., A.G.,
Faria, L.E.C., 1995. Mar. Geol. 125, 177–192.
Nittrouer, C.A., Mullenbach, B.L., Walsh, J.P., Puig, P., Ogston,
A.S., Kuehl, S.A., Kineke, G.C., 2001. Mechanisms for
substantial sediment and associated carbon to escape seaward
from present continental shelves. 2001 Aquatic Sciences Meet-
ing Abstracts, Am. Soc. Limnol. Oceanogr., pp. 104.
Ogston, A.S., Cacchione, D.A., Sternberg, R.W., Kineke, G.C.,
2000. Observations of storm and river flood-driven sediment
transport on the northern California continental shelf. Cont.
Shelf Res. 20, 2141–2162.
Page, M.J., Trustrum, N.A., Dymond, J.R., 1994. Sediment budget
to assess the geomorphic effect of a cyclonic storm, New
Zealand. Geomorphology 9, 169–188.
Page, M.J., Reid, L.M., Lynn, I.H., 1999. Sediment production from
Cyclone Bola landslides, Waipaoa catchment. J. Hydrol., N.Z.
38, 289–308.
Perkey, D.W., 2003. Long-term sediment accumulation rates and
organic carbon burial on the middle Eel shelf, northern
California. MS thesis, North Carolina State University, Raleigh.
Petsch, S.T., Berner, R.A., Eglinton, T.I., 2000. A field study of the
chemical weathering of ancient sedimentary organic matter. Org.
Geochem. 31, 475–487.
Petsch, S.T., Eglinton, T.I., Edwards, K.J., 2001. 14C-dead living
biomass: evidence for microbial assimilation of ancient organic
carbon during shale weathering. Science 292, 1127–1131.
Potter, P.E., 1997. The Mesozoic and Cenozoic paleodrainage of
South America: a natural history. J. South Am. Earth Sci. 10,
331–344.
Puig, P., Ogston, A.S., Mullenbach, B.L., Nittrouer, C.A.,
Sternberg, R.W., 2003. Shelf-to-canyon sediment transport
processes on the Eel continental margin. Mar. Geol. 193,
129–149.
Quay, P.D., Wilbur, D.O., Richey, J.E., Hedges, J.I., Devol, A.H.,
1992. Carbon cycling in the Amazon River: implications from
the 13C compositions of particles and solutes. Limnol. Ocean-
ogr. 37, 857–871.
Quideau, S.A., Chadwick, O.A., Benesi, A., Graham, R.C.,
Anderson, M.A., 2001a. A direct link between forest
vegetation type and soil organic matter composition. Geo-
derma 104, 41–60.
Quideau, S.A., Chadwick, O.A., Trumbore, S.E., Johnson-May-
nard, J.L., Graham, R.C., Anderson, M.A., 2001b. Vegetation
control on soil organic matter dynamics. Org. Geochem. 32,
247–252.
Ransom, B., Bennett, R.H., Baerwald, R., Shea, K., 1997. TEM
study of in situ organic matter on continental margins:
occurrence and the bmonolayerQ hypothesis. Mar. Geol. 138,
1–9.
Ransom, B., Bennett, R.H., Baerwald, R., Hulbert, M.H., Burkett,
P.J., 1999. In situ conditions and interactions between microbes
and minerals in fine-grained marine sediments: a TEM micro-
fabric perspective. Am. Mineral. 84, 183–192.
R7s7nen, M.E., Linna, A.M., Santos, J.C.R., Negri, F.R., 1995. Late
Miocene tidal deposits in the Amazonian foreland basin.
Science 269, 386–390.
Raymond, P.A., Bauer, J.E., 2001. Riverine export of aged
terrestrial organic matter to the North Atlantic Ocean. Nature
409, 497–500.
Richey, J.E., Hedges, J.I., Devol, A.H., Quay, P.D., Victoria, R.,
Martinelli, L., Forsberg, B., 1990. Biogeochemistry of carbon in
the Amazon River. Limnol. Oceanogr. 35, 352–371.
Richey, J.E., Victoria, R.L., Salati, E., Forsberg, B.R., 1991. The
biogeochemistry of a major river system: the Amazon case
study. In: Degens, E.T., Kempe, S., Richey, J.E. (Eds.),
Biogeochemistry of Major World Rivers, SCOPE. J. Wiley
and Sons, pp. 57–74. Ch 3.
Robertson, A.I., Bunn, S.E., Boon, P.I., Walker, K.F., 1999.
Sources, sinks and transformations of organic carbon in
Australian floodplain rivers. Mar. Freshw. Res. 50, 813–829.
Ronov, A.B., 1976. Global carbon geochemistry, volcanism,
carbonate accumulation, and life. Geochem. Int. 13, 172–195.
(translation of Geokhimiya).
Rosenbloom, N.A., Doney, S.C., Schimel, D.S., 2001. Geomorphic
evolution of soil texture and organic matter in eroding
landscapes. Glob. Biogeochem. Cycles 15, 365–381.
Schlqnz, B., Schneider, R.R., 2000. Transport of terrestrial organiccarbon to the oceans by rivers: re-estimating flux- and burial
rates. Int. J. Earth Sci. 88, 599–606.
Scully, M.E., Friedrichs, C.T., Wright, L.D., 2002. Application of an
analytical model of critically stratified gravity-driven sediment
transport and deposition to observations from the Eel River
continental shelf, Northern California. Cont. Shelf Res. 22,
1951–1974.
Scully, M.E., Friedrichs, C.T., Wright, L.D., 2003. Numerical
modeling of gravity-driven sediment transport and deposition on
an energetic continental shelf: Eel River, northern California.
J. Geophys. Res. 108 (C4), 3120.
Sherwood, C.R., Drake, D.E., Wiberg, P.L., Wheatcroft, R.A.,
2002. Prediction of the fate of p,pV-DDE in sediment on the
Palos Verdes shelf, California, USA. Cont. Shelf Res. 22,
1025–1058.
Showers, W.J., Angle, D.G., 1986. Stable isotopic characterization
of organic carbon accumulation on the Amazon continental
shelf. Cont. Shelf Res. 6, 227–244.
Sommerfield, C.K., Nittrouer, C.A., 1999. Modern accumulation
rates and a sediment budget for the Eel shelf: a flood-dominated
depositional environment. Mar. Geol. 154, 227–241.
N.E. Blair et al. / Marine Chemistry 92 (2004) 141–156156
Sommerfield, C.K., Nittrouer, C.A., DeMaster, D.J., 1996. Sedi-
mentary carbon-isotope systematics on the Amazon shelf. Geo
Mar. Lett. 16, 17–23.
Sommerfield, C.K., Nittrouer, C.A., Alexander, C.R., 1999. 7Be as a
tracer of flood sedimentation on the northern California
continental margin. Cont. Shelf Res. 19, 335–361.
Sommerfield, C.K., Drake, D.E., Wheatcroft, R.A., 2002. Shelf
record of climatic changes in flood magnitude and frequency,
north-coastal California. Geology 30, 395–398.
Stallard, R.F., 1995. Relating chemical and physical erosion. Rev.
Miner. 31, 543–564.
Thomas, C.J., Blair, N.E., 2002. Transport and digestive alteration
of uniformly 13C-labeled diatoms in mudflat sediments. J. Mar.
Res. 60, 517–535.
Tissot, B.P., Welte, D.H., 1978. Petroleum Formation and Occur-
rence. Springer-Verlag, New York. 538 pp.
Traykovski, P., Geyer, W.R., Irish, J.D., Lynch, J.F., 2000. The role
of wave-induced density-driven fluid mud flows for cross-shelf
transport on the Eel River continental shelf. Cont. Shelf Res. 20,
2113–2140.
Trustrum, N.A., Gomez, B., Page, M.J., Reid, L.M., Hicks, D.M.,
1999. Sediment production, storage and output: the relative role
of large magnitude events in steepland catchment. Z. Geomorph.
N.F. 115, 71–86.
Vannote, R.L., Minshall, G.W., Cummins, K.W., Sedell, J.R.,
Cushing, C.E., 1980. The river continuum concept. Can. J.
Fish. Aquat. Sci. 37, 130–137.
Veizer, J., Jansen, S.L., 1985. Basement and sedimentary recycling:
2. Time dimension to global tectonics. J. Geol. 93, 625–664.
Wheatcroft, R.A., Drake, D.E., 2003. Post-depositional alteration
and preservation of sedimentary event layers on continental
margins: I. The role of episodic sedimentation. Mar. Geol. 199,
123–137.
Wheatcroft, R.A., Sommerfield, C.K., Drake, D.E., Borgeld, J.C.,
Nittrouer, C.A., 1997. Rapid and widespread dispersal of
flood sediment on the northern California margin. Geology 25,
163–166.
Wold, C.N., Hay, W.W., 1990. Estimating ancient sediment fluxes.
Am. J. Sci. 290, 1069–1089.
Wright, L.D., Friedrichs, C.D., Kim, S.C., Scully, M.E., 2001.
Effects of ambient currents and waves on gravity-driven
sediment transport on continental shelves. Mar. Geol. 175,
25–45.
Zimmerman, A.R., Goyne, K.W., Chorover, J., Komarneni, S.,
Brantley, S.L., 2004. Mineral mesopore effects on nitrogenous
organic matter adsorption. Org. Geochem. 35, 355–375.
Further reading
Wheatcroft, R.A., Borgeld, J.C., 2000. Oceanic flood deposits on
the northern California shelf: large scale distribution and small-
scale physical properties. Cont. Shelf Res. 20, 2163–2190.