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Organic Matter Mineralization and Decomposition

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 SE VEN
Carbon Dynamics and Ecosystem Processes
SCOT T D. BR IDGHAM
THE BASIC CARBON CYCLE: METRICS OF PRODUCTIVITY
AND CARBON BALANCE
BREAKDOWN AND DECOMPOSITION OF ORGANIC MATTER
Short-Term Breakdown and Decomposition
Litter Quality Controls over Decomposition
Exogenous Controls over Decomposition
Nutrient Mineralization-Immobilization during Decomposition
One of the primary functions of wetlands is their role in
the global carbon cycle. This topic has been of increas-
ing interest because of the potential for globally signifi-
cant feedbacks between various aspects of wetland carbon
dynamics and global change (Bridgham et al. 1995; Lim-
pens et al. 2008; Dise 2009; DeLaune and White 2011; Kir-
wan and Mudd 2012; Bridgham et al. 2013; see also Chap-
ter 10). Wetland carbon dynamics are also relevant at the
scale of watersheds because of their importance in the
export of dissolved organic matter to surface waters, with
its myriad effects on the chemistry and biology of surface
waters, which are discussed later in this chapter. Carbon
and nutrient cycles are intimately linked in all ecosystems,
so any understanding of nutrient cycling must entail a con-
sideration of associated aspects of carbon dynamics. Per-
haps most fundamentally, carbon dynamics are intimately
linked to the formation and development of wetlands;
this link is particularly dramatic in the hydrogeochemis-
try of peatlands (Moore and Bellamy 1974; Bridgham et al.
1996; Belyea and Baird 2006) and salt marshes (Kirwan and
Mudd 2012). This chapter primarily focuses on soil carbon
dynamics and the dissolved and gaseous exports that result
from those dynamics, although the basic carbon cycle and
overall net carbon accumulation or loss are also considered.
53488p151-286.indd 185
ANAEROBIC CARBON CYCLING
WHY DO WETLANDS ACCUMULATE SOIL CARBON?
DISSOLVED ORGANIC MATTER FLUXES FROM WETLANDS
THE BIG PICTURE
Methane Fluxes
Global Soil Carbon Pools and Accumulation
The Basic Carbon Cycle:
Metrics of Productivity and Carbon Balance
The basic carbon cycle is largely generic to any wetland
or terrestrial ecosystem, although the sizes of the various
pools and rates vary significantly among different types
of ecosystems (Fig. 7.1). Wetlands, in particular, vary dra-
matically in their degree of openness to the fluxes of dis-
solved inorganic carbon (DIC), dissolved organic matter (DOM),
and particulate organic matter (POM) that enter and leave an
ecosystem. DOM and POM are also often termed dissolved
organic carbon (DOC) and particulate organic carbon (POC),
depending on whether the carbon fraction is being empha-
sized or not.
A number of different carbon balance and productiv-
ity terms are used, and often misused. Net primary produc-
tivity (NPP) is the difference between plant carbon diox-
ide uptake in photosynthesis (or gross primary productivity,
GPP) and plant respiration; NPP can also be thought of as
the production of organic compounds by plants over some
period of time. This can be measured at the leaf level with
a portable photosynthesis analyzer, or at the whole plant or
plot level with destructive techniques such as peak stand-
ing biomass. Although many studies have measured NPP
185
8/19/14 9:06 AM
 Net Ecosystem Producvity or Net Ecosystem Exchange
CO2 + CH4 CO2
Respiraon
Consumers Herbivory
Predaon Death,
Excreon
DIC, DOM, POM
Decompo- Available Soil
Decomposers sion Organic
Maer
Detrivore
Death
Leaching of DIC and DOM
FIGURE 7.1. The basic carbon cycle in ecosystems.
in wetlands (see Chapter 5), the vast majority focus only
on determining the accumulation of new plant biomass
aboveground, although belowground NPP can be equal
to or greater than aboveground NPP (Weltzin et al. 2000).
This is because measuring belowground NPP is difficult,
can be very time consuming, and all methods have impor-
tant assumptions that are probably often not met (Lauen-
roth 2000). NPP may be underestimated by measuring just
peak standing crop because herbivory and mortality of
individual plant parts can remove plant biomass before it
is sampled, and not all NPP results in the production of
new plant tissue—​e.g., root exudates, carbon allocation to
mycorrhizae, and emissions of volatile organic compounds
(VOC) (Chapin III et al. 2011).
Net ecosystem production (NEP) is the difference between
gross primary productivity and ecosystem respiration (R E),
which is the sum of plant respiration and heterotrophic res-
piration (R H):
NEP = GPP –​R E = NPP –​R H. (7.1)
Actually measuring the various components of NEP is
someplace between very difficult and impossible, so it is
often approximated by net ecosystem exchange (NEE), which
is the net gaseous exchange of carbon between an ecosys-
tem and the atmosphere. NEE is measured with chamber
or eddy covariance techniques. NEE is often construed to
include only the net exchange of carbon dioxide, although
methane (CH4) fluxes can be a component of heterotrophic
respiration in wetlands. To add to the confusion, a net posi-
tive accumulation of carbon into an ecosystem is treated as
either a positive or a negative NEE flux, depending on the
study. In this chapter, a positive value for NEE indicates a
net flux of carbon into the ecosystem.
186  CHAP TER Seven
53488p151-286.indd 186
CO2 CO2 CO2, CO
Fire
Respiraon Photosynthesis
Harvesng
Plant NPP
Lier
DIC, DOM, POM
Preservaon
Unavailable
Processes
Soil Organic Maer
Δ C = Net Ecosystem Carbon Balance
The net ecosystem carbon balance (NECB) is the net gain or
loss of carbon by an ecosystem over time:
NECB = dC / dt = (gaseous inputs –​losses) + (dissolved
inputs –​losses) + (particulate inputs –​losses)
= (NEE + FCH4 + F VOC) + (FDOC + FDIC) + FPOC, (7.2)
where F refers to a flux. NECB includes all net fluxes of car-
bon in and out of an ecosystem, including those resulting
from disturbances such as fire and harvesting of trees.
Overall carbon dynamics at an ecosystem scale have been
most extensively studied in northern peatlands, so that is
used as an example of these concepts here. NECB in north-
ern peatlands averages between about 20 to 70 g C m–​2 yr–​1
in individual peatlands, based on multiple years of data (Fig.
7.2). The largest component of this is the net flux of carbon
dioxide in and out of the ecosystem (i.e., NEE), which, for
most northern peatlands, ranges between 20 and 60 g m–​2
yr–​1, with large interannual variability (Blodau 2002; Lim-
pens et al. 2008), which in turn causes large interannual
variability in NECB (Fig. 7.3). Leaching of DOC is a larger
loss term than methane emissions in these peatlands.
The net carbon balance (NCB) is derived from modeling
long-term carbon accumulation rates in peat and is compa-
rable to the NECB derived from the annual measurements
of the terms in Equation 7.2 (Yu 2012). The NCB in north-
ern peatlands averaged over the Holocene was 19 g m–​2 yr–​1,
but rates during the last millennium were only 10.4 g m–​2
yr–​1 (Fig. 7.3). Thus, carbon accumulation rates in north-
ern peatlands determined by NCB are somewhat lower than
NECB, but they are perhaps surprisingly close given the dif-
ferent methods employed, time frames examined, and lim-
ited number of sites in which NECB has been measured.
8/29/14 4:35 AM

FIGURE 7.3. (A) Interannual variability in the net ecosystem carbon balance from the sites in Figure 7.2. The box is the average + standard
error. (B) Average net ecosystem carbon balance over the Holocene in northern peatlands. Adapted from Yu (2012).
Breakdown and Decomposition of
Organic Matter
The breakdown of organic matter couples physical factors
and biological decomposition processes. For wetlands this
was recently reviewed by Bridgham and Lamberti (2009)—​
this portion of this chapter is an update of that review.
Methods used to determine rates of anaerobic carbon
cycling are described in Bridgham and Ye (2013). (Roles of
microbes in decomposition are covered in detail in Chap-
ter 4.)
Decomposition—​a lso referred to as mineralization—​is the
biological transformation of organic compounds into inor-
ganic forms of nutrients and carbon—​largely CO2 and CH4
gases—​and simpler organic compounds. As with many bio-
logical processes, this can be understood fundamentally
as an oxidation-reduction process in which organisms
release the energy stored in reduced organic compounds
53488p151-286.indd 187
FIGURE 7.2. Net ecosystem exchange (NEE), dissolved organic carbon
flux (DOC), and methane flux (CH4) in five peatlands averaged over
multiple years. The numbers above each bar are the net ecosystem
carbon balance (±1 standard deviation). Positive numbers indicate
carbon flux into the ecosystem, and negative numbers indicate
carbon flux from the ecosystem. Data are taken from Yu (2012),
but the original references are Roulet et al. (2007) for Mer Bleue, an
ombrotrophic bog in Canada with seven years of data; Nilsson et
al. (2008) for Degerö Stormyr, a minerotrophic fen in Sweden with
two years of data; Dinsmore et al. (2010) for Auchencorth Moss, an
ombrotrophic bog in Scotland with two years of data; Koehler et al.
(2011) for Glencar, a blanket bog in Ireland with six years of data;
and Olefeldt et al. (2012) for Stordalen, a permafrost palsa mire in
Sweden with two years of data. Auchencorth Moss includes other
fluxes such as stream evasion of carbon dioxide and methane, so the
components do not add up to the NECB.
by converting them into more oxidized forms—​ w ith
CO2 being the most oxidized endpoint—​a nd using that
energy for growth and maintenance requirements. Also,
as with many ecological processes, it can be understood
fundamentally as a stoichiometric process whereby organ-
isms obtain elements such as carbon, nitrogen, and phos-
phorus in relative proportion to the constraints imposed
by the elemental makeup of their tissues. Because of the
basic importance of decomposition and the relative ease
and low cost of many of the techniques used to quantify
it (Bridgham and Ye 2013), it has been widely studied in
wetlands and other ecosystems for many years. It was esti-
mated that, in the 20 years prior to 1997, over 1,000 papers
had been published on this topic (Heal et al. 1997). The
four aspects of this process that make decomposition in
wetlands different from other ecosystems are (1) the tissue
chemistry of Sphagnum spp. mosses of peatlands with their
Carbon Dy namics and Ecosystem Processes   187
8/19/14 9:06 AM
 A B

C D

FIGURE 7.4. Stages of leaf decomposition in aquatic ecosystems. Maple (Acer rubrum) leaf after (A) 1 week, (B) 2 weeks, (C) 4 weeks, and Fig. 4
(D) 6 weeks of decomposition in a Michigan, USA, stream. Note holes in leaf caused by detritivore feeding at 2 and 4 weeks, and residual
veins and ribs after 6 weeks. Photos courtesy of A. Bobeldyk (from Bridgham and Lamberti 2009).

very low rates of decomposition; (2) waterlogging and the
resultant anaerobiosis; (3) the imbalance between decom-
position and production in many wetlands, leading to the
buildup of large soil carbon stores; and (4) the low density
of mineral surfaces for organic matter to react with, at least
in peatlands.
Dead organic matter is termed detritus, and the input of
freshly senescent detritus is termed litterfall—​despite its
name, however, this should include belowground inputs.
The controls over rates of breakdown and decomposition
of relatively fresh litterfall and soil organic matter may be
quite different, and thus they are considered separately
below. The breakdown and decomposition of organic detri-
tus involves a number of basic processes that occur in a
foodweb cascade where detritus is repeatedly processed
by the decomposer community with the progressive loss
of mass; the loss of potential chemical energy in reduced
organic carbon bonds; the turnover of decomposer biomass
by death and predation; and ultimately the production of
carbon dioxide, methane, and inorganic nutrients. Leach-
ing is the abiotic removal of soluble compounds by water
and is particularly important in the initial stages of the
breakdown of fresh litterfall. Fragmentation is the physical
breakdown of detritus into smaller particles, largely by the
feeding activities of detritivorous invertebrates (Fig. 7.4).
Catabolism is the metabolic decomposition of detritus into
heat, metabolic energy, and simpler organic and inorganic
compounds. Soil organisms then use these compounds
and metabolic energy for their growth and reproduction in
the process of anabolism. Traditionally it has been thought
that the accumulation of soil organic matter is the result of
the process of humification wherein highly complex, recal-
citrant organic compounds that have very long turnover
times are formed in situ. This traditional concept has been
sharply challenged in recent years, as discussed further
below. Soil organic matter may also be stabilized by associ-
ations with mineral particles that appear to provide physi-
cal protection from microbial attack.

188  CHAP TER Seven

53488p151-286.indd 188 8/19/14 9:06 AM


Short-Term Breakdown and Decomposition
The short-term dynamics of breakdown and decomposi-
tion are normally defined over a number of years, when
the original plant litter is identifiable and, operationally,
within the timeframe of most research studies. The break-
down and decomposition of plant litter is most often quan-
tified by mass loss with the litter bag technique (Bridgham
and Ye 2013). The mass loss of litter over a period of years
often follows a simple exponential relationship:
Xt
= e –kt (7.3)
Xo
where Xt is the mass of litter remaining at time t, Xo is the
original mass of litter, and k is the decay rate—​usually with
units of year–​1. The mean residence time is then the inverse
of k. Much of the decomposition literature reports results in
terms of k, so it is important to be familiar with this simple
mathematical relationship. Alternatively, decomposition
rates can be determined over shorter periods by measuring
rates of the production of CO2 and CH4, but this approach
is more typically followed for soil organic matter (Bridgham
and Ye 2013).
Typical exponential decay relationships are shown in Fig-
ure 7.5. In general, decay rates follow the following pattern:
woody material < hummock Sphagnum species < hollow/
lawn Sphagnum species < tree leaves < shrub leaves < sedge
leaves, and evergreen leaves < deciduous leaves (Moore
and Basiliko 2006; Moore et al. 2007). A broader survey
53488p151-286.indd 189
FIGURE 7.5. Decomposition rates in Canadian
peatlands. Adapted from Moore and Basiliko (2006).
of decomposition studies shows more overlap in the decay
rates among vascular plant groups in wetlands, although
similar trends are evident (Table 7.1). However, aquatic spe-
cies have very high rates, and Sphagnum mosses, which are
a dominant component of many peatland plant communi-
ties, have very low rates. The few studies that have exam-
ined the decay of roots and rhizomes have indicated that
they decay at slower rates than corresponding leaf mass
(Bragazza et al. 2009). The reasons for these differences in
decay rates are explored in the next section.
Interestingly, with the exception of aquatic species and
Sphagnum mosses, wetland plants do not appear to have
lower average decay rates than vascular plants in terrestrial
ecosystems (Table 7.1). Similar results were found in a more
controlled comparison in Canadian peatlands and nearby
terrestrial ecosystems (Moore and Basiliko 2006; Moore et
al. 2008). Thus it appears that the short-term decay of plant
litter is a poor predictor of the ability of wetlands to seques-
ter soil carbon, with the exception of those containing
Sphagnum mosses. To put the difference in decay rates for
fresh plant litter and older soil organic matter in perspec-
tive, the time-averaged decay rate (k) of the catotelm—​t he
permanently waterlogged portion of a peat—​is 8.6 × 10 –​6
yr–​1 for northern peatlands and 2.4 × 10 –​4 yr–​1 for tropical
peatlands (Yu 2011). Thus long-term decay of soil organic
matter in wetlands is many orders of magnitude slower
than the decomposition of fresh plant litter (Table 7.1), and
it almost certainly has a different set of controls.
Carbon Dy namics and Ecosystem Processes   189
8/19/14 9:06 AM
 table 7.1
Decomposition Rates in Wetlands and Other Freshwater Aquatic Habitats

Mean k ± SD t50
Plant Type Na (yr-1) (yr) Reference

Wetlands
Emergent nonwoody aquatic 280 3.0 (7.8) 0.23 Chimney and Pietro (2006)
macrophytesb
Floating aquatic speciesb 80 13.9 (12.3) 0.05 Chimney and Pietro (2006)
Submerged aquatic speciesb 107 17.3 (19.2) 0.04 Chimney and Pietro (2006)
Peatland evergreen shrubs 18 0.30 (0.15) 2.3 Aerts et al. (1999)
and treesc
Peatland deciduous shrubs 4 0.39 (0.08) 1.8 Aerts et al. (1999)
and treesc
Peatland graminoidsc 32 0.40 (0.23) 1.7 Aerts et al. (1999)
Peatland vascular plantsd 69 0.23 (0.16) 3.8 Bragazza et al. (2009)
Peatland Sphagnum spp. mossesc 17 0.16 (0.07) 4.3 Aerts et al. (1999)
Peatland Sphagnum spp. mossesd 22 0.08 (0.05) 8.5 Bragazza et al. (2009)
Marsh plantsd 4 0.31 (0.06) 2.2 Bragazza et al. (2009)
Northern peatland catotelm NA 0.0000086 81,070 Yu (2011)
peate
Southern peatland catolelm NA 0.00024 2,937 Yu (2011)
peate

Terrestrial Ecosystems
Forestsd 34 0.42 (0.22) 1.6 Bragazza et al. (2009)
Mediterranean shrublandsd 20 0.29 (0.18) 2.4 Bragazza et al. (2009)
Grasslandsd 6 0.74 (0.18) 0.94 Bragazza et al. (2009)
Desertsd 2 0.30 (0.04) 2.4 Bragazza et al. (2009)
Tundrad 22 0.32 (0.20) 2.2 Bragazza et al. (2009)
a Number of published studies considered.
b Fields studies using a variety of techniques and duration (10 to 1052 d; median = 137 d) from tropics to arctic.
c Northern peatlands using litter bags based on first year of decomposition.

d Studies used litter bag technique for more than one year of field deployment (most 2–​5 yr).

e Time-averaged value for the entire catotelm.

Litter Quality Controls over Decomposition

The initial chemistry (often termed the “quality”) of plant
litter is one of the most important determinants of the rate
of short-term decomposition (Berg and Laskowski 2006).
Plant litter is actually a diverse assemblage of organic com-
pounds, each with its own characteristic decay rate under
a defined set of environmental conditions. Highly soluble
cell compounds such as some carbohydrates and polyphe-
nolics are leached from the plant litter in a matter of days
to weeks (Phase 1 in Fig. 7.6). Relatively simple compounds
such as many sugars, proteins, and some polysaccharides are
rapidly catabolized (Phase 2). Large macromolecules such as
cellulose and hemicellulose are entwined into strands or
fibers to form cell walls and require exoenzymes secreted by
microbes to cleave them into smaller subunits before they
can be taken into cells. However, these macromolecules still
decompose relatively quickly and are considered part of
Phase 2 here. Lignin is a complex, decay-resistant, hetero-
polymer with many aromatic rings that is a structural com-
pound in vascular plants and that occurs with particular
high concentrations in wood, although it is also often proxi-
mally characterized as an acid-insoluble fraction of detritus.
Lignin typically has a turnover time of many years (Phase
3). It can be closely bound with celluloses in cell walls and

190  CHAP TER Seven

53488p151-286.indd 190 8/19/14 9:06 AM

 Phase 1
100 Phase 2
Soluble cell products
Mass remaining (% of original)
Non-lignified cellulose &
hemicellulose
Microbial products
Lignified cellulose & hemicellulose
Lignin, other aromatic cell wall constituents (e.g.,
Sphagnum), fats and waxes
0 Berg and Laskowski (2006).
Time (years)
impede their decomposition. Fats and waxes, such as cutin
(which forms the outer waxy layer on leaves), also have very
slow decomposition rates. Mineral protection of soil organic
matter has been shown to be very important in terrestrial
ecosystems, and there is no reason to assume that it is not
equally important in wetlands with mineral soil. The forma-
tion of chemically recalcitrant humus compounds during
Phase 4 is currently under great debate (see below).
The relative proportion of these different plant com-
pounds are a primary determinant of the rate of decompo-
sition (Fig. 7.6). For typical non-woody plant biomass, dur-
ing the early stages of decomposition (Phase 2) there will
be abundant labile carbon compounds, so the microbes that
are responsible for decomposition will be primarily limited
by available nutrients, particularly nitrogen. During the later
stages of decomposition, most of the initial labile plant com-
pounds have been degraded so the remaining lignin concen-
tration becomes increasingly important (Taylor et al. 1989).
However, plant litter with very low initial concentrations of
labile compounds, as is often found in low-nutrient envi-
ronments, may forego any period of nutrient limitation of
decomposition and immediately enter into Phase 3 (Fig. 7.6).
The initial carbon:nitrogen and lignin:nitrogen ratios of
plant litter are often the best predictors of mass loss rates
over the first few years of decomposition within a particu-
lar study. The C:N ratio reflects the ratio of cytoplasm to
cell wall material, so it is a measure of carbon quality as
well as the availability of nitrogen for decomposition. Simi-
larly, the lignin:N ratio is an integrated measure of carbon
quality and nitrogen concentration. For example, a recent
summary of terrestrial decomposition studies in 110 sites,
including those in wetlands, indicated that the initial C:N
53488p151-286.indd 191
Phase 3 Phase 4
FIGURE 7.6. Representative time
course of decomposition of litter.
The time scale varies by climate,
pH, degree of waterlogging, etc.
Leaching predominates during Phase
1. During Phase 2, relatively labile
cell products are mineralized and
decomposition is regulated by the
amount of labile carbon and nutrients
in the substrate and exogenous soil
nutrient concentrations. During
Phase 3, decomposition is determined
Physically protected
soil organic matter by the amount of remaining lignin,
lignified carbohydrates, other
aromatic cell constituents, and fats
and waxes. Phase 4 represents long-
term soil stabilization mechanisms,
which are currently in great
Humus dispute. Extensively adapted from
ratio and total nitrogen content of litter were the primar-
ily controls over decomposition rates at the global level,
with climatic factors (temperature, precipitation, and lati-
tude) being of secondary importance through both direct
effects and indirect effects through litter quality (Zhang et
al. 2008). These explanatory variables described 87.5% of
the variance in k rates for this large global database.
Similar factors control decomposition in wetlands. For
example, in a review of numerous decomposition studies in
peatlands, Bragazza et al. (2009) found that decomposition
rates were best correlated with the acid insoluble reside (~
lignin):N ratio for both vascular peatland plant litter (r = –​
0.46, p <0.05, n = 27) and for Sphagnum litter (r = –​0.66, p <
0.05, n = 11). k values for peatland vascular plant litter were
also positively correlated with mean annual temperature (r
= 0.37, p <0.001) and mean total annual precipitation (r =
0.39, p <0.001), but k values for Sphagnum were not corre-
lated with climatic factors, suggesting that litter quality is
of paramount importance.
Sphagnum mosses have very low decomposition rates
(Table 7.1) and are responsible for a substantial fraction of
the world’s peat accumulation, but they lack true lignin in
their tissues (Williams et al. 1998). The acid-insoluble frac-
tion in Sphagnum is comprised of cell wall polymers domi-
nated by phenolic compounds, including “sphagnum acid”
(p-hydroxy-β[carboxymethyl]-cinnamic acid) (Williams et
al. 1998), as well as the cell wall polysaccharide sphagnan,
which acidifies the environment (Stalheim et al. 2009). The
fructose:pentose carbohydrate ratio was found to be a good
predictor of moss decomposition in peatlands, with fruc-
tosans being metabolic carbohydrates and pentoses being
structural carbohydrates (Turetsky et al. 2008). The former
Carbon Dy namics and Ecosystem Processes   191
8/19/14 9:06 AM
 are more common in Sphagnum species inhabiting hollows
and the latter in hummock-inhabiting species, potentially
explaining the slower decomposition of hummock species.
A number of other studies have also noted that C:P and C:N
ratios significantly explain Sphagnum decomposition rates.
Bragazza et al. (2009) suggested that increased atmospheric
nitrogen inputs into peatlands should increase Sphagnum
decomposition through an increase in both their tissue
nitrogen content and also a decrease in soluble phenolic con-
tent, as phenolics can inhibit microbial activity (see below).
Sphagnum has long been known to have important anti-
biotic and inhibitory properties (van Breemen 1995; Ver-
hoeven and Toth 1995; Stalheim et al. 2009). Sphagnum-
derived compounds may be particularly inhibitory to
methanogens, with important implications for the often
low methane fluxes observed from bogs and for the poten-
tial of these peatlands to become more dominated by vas-
cular species with climate change (Bridgham et al. 2013).
Exogenous Controls over Decomposition
Exogenous factors also control decomposition rates at a
local scale in wetlands; these factors include temperature
(determined both by climate and position in the soil pro-
file), soil moisture availability, anaerobiosis, pH, and soil
nutrient availability. The effects of temperature and precip-
itation on decomposition rates in litterbag studies at the
global scale in syntheses of the published literature were
described above. Decomposition of both fresh plant litter
and older soil organic matter typically have a Q10 (increase
in rate for a 10 °C increase in temperature) that ranges
from 2 to 4 (Brinson et al. 1981; Heal et al. 1981; Raich and
Schlesinger 1992).
High soil acidity (i.e., low pH) provides a strong environ-
mental constraint on many microbial groups (Fierer and
Jackson 2006). Numerous studies have shown that micro-
bial respiratory activity is inhibited at low pH in wetlands
(e.g., Benner et al. 1985; Kok et al. 1990; Ye et al. 2012).
However, studies that have manipulated pH in the field and
laboratory have not always found an inhibitory effect on
decomposition and nutrient cycling (Bridgham and Rich-
ardson 1992, 2003; Chapin et al. 2004), suggesting that
some microbial groups and associated processes are adapted
to low pH, or other controlling factors are more important
than pH in some circumstances.
Decomposition rates decrease with depth in the soil pro-
file because of greater duration of waterlogging, cooler tem-
peratures, and decreased carbon quality (Updegraff et al.
1995; Moore et al. 2007). Numerous studies have shown
that prolonged anaerobic conditions lead to substantially
reduced rates of decomposition (e.g., Godshalk and Wetzel
1978; Updegraff et al. 1995; Bridgham et al. 1998). The sub-
stantial oxidation of soil organic matter in peatlands upon
their drainage (Armentano and Menges 1986; Bridgham et
al. 2006) is compelling evidence of the importance of water-
logging in soil carbon sequestration in wetlands. However,
192  CHAP TER Seven
53488p151-286.indd 192
alternating flooded and drained conditions may enhance
decomposition because of factors such as increased leach-
ing, pulses of microbial activity, and amelioration of mois-
ture limitation under drier conditions (Lockaby et al. 1996a,
1996b; Moore et al. 2007; see also Chapter 4). Leaf litter typ-
ically falls on the surface of wetlands, which is often not
inundated; this may explain why decomposition rates are
similar in wetlands and uplands in general (Table 7.1).
If nutrients are limiting for decomposition, it is reason-
able to assume that fertilization would lead to faster decay
rates. However, fertilization studies have found contradic-
tory results regarding this hypothesis (see Bridgham and
Lamberti 2009). The phosphorus eutrophication gradient
from agricultural run-off in the Everglades is one of the few
clear examples of exogenous nutrient limitation of decom-
position in wetlands (DeBusk and Reddy 1998; Qualls and
Richardson 2000). Even in the Everglades, the positive
effect of eutrophication on NPP far outweighs its positive
effect on decomposition, so the net effect is a large increase
in peat accretion (Craft and Richardson 1993).
The effects of nutrients on decomposition are complex,
and understanding them requires taking a whole-ecosys-
tem approach. Figure 7.7 combines a number of lines of evi-
dence to propose very different sets of nutrient controls on
decomposition in high versus low nutrient environments.
Plants adapted to low nutrient environments have foliage
with low nutrient concentrations and low carbon quality
(i.e., high concentrations of the structural compounds lig-
nin and cellulose and inhibitory compounds such as phe-
nolics). These plants also have low inherent potential to
respond positively to nutrient additions. In contrast, plants
adapted to high nutrient environments have the opposite
set of traits. In initially low nutrient environments, fertil-
ization may cause an increase in nutrient uptake into plants
accompanied by increased growth (limiting nutrient), an
increase in nutrient uptake into plants with no increase in
growth (luxury uptake), or no increase in nutrient uptake
(non-limiting). In a fertilization study in a bog, interme-
diate fen, and rich fen, all three responses were observed
(Iversen et al. 2010). Because plants from low nutrient
environments have litter with low amounts of labile car-
bon, decomposition rates may be unaffected by either high
endogenous or exogenous nutrient availability until spe-
cies that are adapted to higher nutrient availability become
established. For these plants, fertilization will result in
both increased litter production and increased endogenous
nutrient concentrations, which should increase decomposi-
tion rates because their foliage has high carbon quality and,
thus, the initial stages of decomposition are nutrient rather
than carbon limited (Fig. 7.6).
Nutrient Mineralization-Immobilization
during Decomposition
Carbon and nutrient cycling are intimately linked dur-
ing decomposition. The heterotrophic microbes that are
8/19/14 9:06 AM
 availability

Nutrient
immobilization

A. Low Nutrient Net B. High Nutrient Net

Primary Primary
Environment production
Environment production
Increased Increased
0 (+) litter
0 (+) + litter
0 (+)
nutrient nutrient
content content
+ +
Increased Increased
Litter carbon Litter carbon
plant plant
quality (low) quality (high)
nutrient nutrient
(limiting or
content 0 (limiting content +
luxury uptake) — uptake)
+ (0) +
— +
Increasing Increasing
0 exogenous
+
exogenous Decomposition Decomposition
nutrient rate nutrient rate
availability availability

+ +

Nutrient Nutrient
immobilization immobilization

FIGURE 7.7. Conceptual model

Net of how changes in exogenous nutrient availability affect decomposition rates and nutrient immobilization in
B. High Nutrient
low-nutrient Primary
(A) and high-nutrient environments (B). Positive effects are shown by +, negative effects by −, and neutral effects by 0. Effects in
Environment production
parentheses indicate alternative possibilities based upon inconsistent results among previous studies. From Bridgham and Richardson (2003).
Increased
+ litter
0 (+)
nutrient
content
C:P
> 300 300 + 200 < 200
C:P > 300 300
Increased 200 < 200 Litter carbon
C:N > 30 plant 30 20 < 20 quality (high)
C:N > 30 30
nutrient 20 < 20
(limiting content +
uptake)
+
+ FIGURE 7.8. Time course of gross and

Increasing % Original N or P net immobilization and mineraliza-

exogenous
+ % Original N or P tion of nitrogen and phosphorus in lit-
Decomposition
nutrient Maximumrate net
Maximum net ter as a function of C:N and C:P ratios.
availability immobilization
immobilization ⇒

immobilization 100 If gross immobilization is greater than

Rate of gross immobilization ⇒

100
⇐ Percent of original C, N, or P
Maximum net gross mineralization, net immobi-
or gross mineralization

⇐ Percent of original C, N, or P
Maximum net
mineralization

+ mineralization lization occurs (area with horizon-

% Original C mineralization tal hatching); if gross mineralization
% Original C Nutrient is greater than gross immobiliza-
immobilization tion, gross mineralization occurs (area
with vertical hatching). The distance
of gross

Gross mineralization
Gross mineralization between the gross immobilization and
or gross

Net mineralization curves determines the

Net
immobilization Net mineralization relative magnitude of net immobiliza-
Rate

immobilization Net mineralization

tion or mineralization. The percentage
Gross immobilization of the original mass of nitrogen and
Gross immobilization
phosphorus in the litter reflects the
cumulative effect of these processes.
From Bridgham and Lamberti (2009).

Time ⇒
Time ⇒

responsible for decomposition are continually both min-
eralizing nutrients and carbon, i.e., converting them from
organic to inorganic forms, and immobilizing nutrients,
i.e., taking up nutrients as they build biomass (Fig. 7.8).
The gross rates of mineralization and immobilization are
the actual rates of both processes, but these rates are dif-
ficult to measure (requiring isotopic tracers) because both
are happening simultaneously. Thus, what is actually mea-
sured often is the net change in nutrient concentrations
over time in plant litter and soil organic matter, or net min-
eralization or immobilization. Net mineralization occurs if
the rate of gross mineralization is greater than the rate of
gross immobilization, and net immobilization occurs if the
opposite is true. Although both gross mineralization and
immobilization are always simultaneously occurring, their
relative proportions vary dramatically through the course
of decomposition, with important implications for nutrient
cycling and availability.
During decomposition, the microbial community
respires organic carbon to carbon dioxide and retains essen-
tial nutrients for growth, particularly nitrogen and phos-
phorus. Thus, the C:N and C:P ratios of detritus (which
operationally includes the plant material plus the associated
microbial biomass that cannot be easily separated) decrease
through time. However, all organisms have stoichiometric
constraints on the C:nutrient ratios that are imposed by the

Carbon Dy namics and Ecosystem Processes   193

53488p151-286.indd 193 8/19/14 9:39 AM

 cellular components of their biomass (Tezuka 1990; Elser
et al. 1996). Because of the large amount of holocellulose
and lignin in the cell walls of plant cells, the C:N and C:P
ratios of plant litter are initially much higher than they
are in microbial biomass (Swift et al. 1979). Consequently,
when plant litter with high initial amounts of labile car-
bon is decomposed, the microbial community actually
takes in nutrients from the surrounding environment (i.e.,
net immobilization occurs) and there is an increase in the
absolute amount of nutrients in the detritus (remember that,
operationally, it is the plant litter plus the associated micro-
bial biomass), and there is a decrease in soil nutrient avail-
ability (Fig. 7.8). A switch to net mineralization occurs when
the C:nutrient ratio of the detritus approaches that of the
microbes (i.e., the critical ratio). The critical ratios in bacte-
rial cultures are about 15:1 for C:N and 60:1 for C:P (Tezuka
1990), but substrates with more complex structural com-
pounds, such as plant litter, have higher effective ratios. Ste-
venson (1986) suggested critical ratios in soil organic matter
of 20:1 to 30:1 for C:N and 200:1 to 300:1 for C:P.
The immobilization phase of decomposition can be
thought of as a source-sink relationship between the lit-
ter-microbe complex (the sink) and external or exogenous
nutrient availability (the source). Litter that has lower ini-
tial endogenous concentrations of a limiting nutrient has
a higher sink capacity, whereas higher soil nutrient avail-
ability provides greater source strength (Fig. 7.7) (Bridgham
and Richardson 2003; Moore et al. 2008). Moreover, the net
mineralization dynamics of phosphorus are complicated
further by geochemical sorption of mineralized phospho-
rus, which varies dramatically among different soil types
(Bridgham et al. 1998).
In contrast to nitrogen and phosphorus, calcium and
magnesium are found in similar concentrations in micro-
bial biomass and litter (Swift et al. 1979), so these com-
pounds tend to be lost at approximately the same rate as
organic carbon (Day Jr 1983; Bridgham and Richardson
2003). In contrast to all four previously mentioned ele-
ments, potassium is quite soluble and is rapidly removed
through leaching.
Anaerobic Carbon Cycling
All wetlands experience periods of prolonged inundation
by definition, so anaerobic carbon cycling is a core wetland
function. The two end products of anaerobic carbon miner-
alization are carbon dioxide (CO2) and methane (CH4), both
of which are important greenhouse gases. Moreover, wet-
lands are the largest natural source of methane, and there
is great concern that with anthropogenic climate change,
wetlands may emit more methane in a positive feedback
cycle (see below and Chapter 10).
Organic carbon is broken down into its gaseous end prod-
ucts by a complicated series of steps that involve numerous
microbial functional groups that can be either competitive
or syntrophic (requiring each other for efficient growth)
194  CHAP TER Seven
53488p151-286.indd 194
(Megonigal et al. 2004; Bridgham et al. 2013). There are four
main processes in anaerobic heterotrophic carbon cycling:
the breakdown of complex biopolymers, fermentation, res-
piration, and acetoclastic methane production. There are
also three chemoautotrophic processes (i.e., processes that use
the energy from reduced inorganic chemical compounds to
fix carbon dioxide into biomass) that are an essential part
of anaerobic carbon cycling: methane production from car-
bon dioxide and hydrogen, homoacetogenesis, and meth-
ane oxidation.
The first step in anaerobic carbon cycling is the break-
down of complex biopolymers by microbial exoenzymes
into smaller compounds that can be transported across cell
membranes (Fig. 7.9). There is an extensive literature on
these exoenzymes that is not discussed further here. The
second step is a series of fermentation reactions that form
low-molecular-weight organic acids and alcohols, hydrogen
gas (H2), and carbon dioxide. The third step is heterotro-
phic microbial respiration, where various inorganic elec-
tron acceptors are coupled to the oxidation of organic car-
bon. The simplest way to understand the role of electron
acceptors in respiration is to realize that, at their essence,
all heterotrophic reactions involve the oxidation of reduced
organic carbon compounds and the accompanying release
of energy for microbial growth and maintenance (see Chap-
ter 4). However, all oxidation reactions must be coupled
to a reduction reaction to proceed because there must be
a sink for the electrons produced in oxidation reactions
(see Chapters 2 and 4). In the case of aerobic respiration,
the terminal electron acceptor is oxygen, forming carbon
dioxide, but oxygen is quickly consumed in the soil under
waterlogged conditions, and thus microbes must use other
electron acceptors (Fig. 7.9). In anaerobic respiration, the
organic carbon is oxidized to carbon dioxide using the fol-
lowing inorganic electron acceptors in order of thermody-
namic favorability: nitrate, Fe(III), manganese, and sulfate
(see Chapter 2, Table 2.5). There is also mounting evidence
that organic substances with aromatic structures can act as
electron acceptors, and these substances may be the domi-
nant acceptors in peatlands (Bridgham et al. 2013; Keller
and Takagi 2013). Because the pathways for these terminal
electron acceptors are more thermodynamically favorable
than pathways of methanogenesis, methane production
is usually low in wetlands with large abundances of these
acceptors (Fig. 7.9). The availabilities of electron acceptors in
wetland soils are controlled by a complex set of factors, but
particularly important are the degree of mineral content of
the soil, oxidation events in the soil caused by mechanisms
such as water table drawdown or oxygen leakage through
the rhizosphere, and the degree of oceanic influence. Sea-
water has high sulfate concentrations, so sulfate reduction
is the major pathway of anaerobic carbon mineralization in
many salt marshes and mangroves (Bartlett et al. 1987; Pof-
fenbarger et al. 2011). High rates of atmospheric deposition
of sulfate can also reduce methane production in freshwater
wetlands (Gauci et al. 2004).
8/19/14 9:06 AM
 CH4 Flux

Aerenchyma

Ebullition

Diffusion
Litter
Inputs
Aerobic Zone Aerobic Methane CO2
Production CH4 Methane
Biopolymers Oxidation
(e.g., soil organic matter,
Anaerobic Zone cellulose)

Exo-cellular
Enzymes CH4 CO2
Anaerobic Methane
Monomers Oxidation
(e.g., glucose and other
simple sugars)

Microbial
Fermentation Alternative Terminal Electron Acceptors (TEAs)
Denitrification
LMW Fatty Acids and TEA Respiration NO3- NH4+, N2
Alcohols
(e.g., ethanol, Manganese Reduction
Mn (III, IV) Mn (II)
Root propionate, acetate)
Iron Reduction
Exudates Secondary Fermentation / Fe(III) Fe(II)
Acetogenesis
Humic Reduction
HSox HSRED
TEA Respiration
Sulfate Reduction
Acetate H2 + CO2 SO42- S2-, S0
Homoacetogenesis

Acetoclastic
Hydrogenotrophic
Methanogenesis
Methanogenesis

CH4

FIGURE 7.9. Anaerobic cycling in wetland ecosystems. Pools of carbon are shown in white boxes and solid arrows show the progressive
mineralization of these carbon pools by the identified microbial processes . Dotted lines illustrate carbon inputs from the plant community.
Dashed lines represent the flux of the gaseous end products of these processes (CH4 and CO2) to the atmosphere. TEA = terminal electron
acceptor. Adapted from Bridgham et al. (2013).

Methane is produced through the acetoclastic pathway
where acetate is degraded into carbon dioxide and methane,
and also through the hydrogenotrophic pathway where car-
bon dioxide and hydrogen gas are converted into methane
(Fig. 7.9). The acetoclastic pathway is a heterotrophic reac-
tion, whereas the hydrogenotrophic pathway is a chemoau-
totrophic reaction. The acetoclastic pathway is dominant in
most freshwater environments, but the hydrogenotrophic
pathway is important in many peatlands (Bridgham et al.
2013). Under saline conditions, methanogens can also use
a variety of methylated compounds as substrates (Bridgham
et al. 2013).
Homoacetogenesis (i.e., the conversion of CO2 + H2  ace-
tate; Fig. 7.9) has not been well studied in wetlands because
it is thought to be thermodynamically unfavorable, but it
may be more important than previously thought (Drake
et al. 2009; Hädrich et al. 2012). Homoacetogens compete
with hydrogenotrophic methanogens for hydrogen but pro-
vide acetate for acetoclastic methanogens, which may cause
little net change in the total amount of methane produced
in wetlands. However, acetate pooling is often observed in
bogs (Ye et al. 2012; Bridgham et al. 2013), so homoace-
togenesis may provide a poorly understood limitation to
methane production in these wetlands.
Methane oxidation to carbon dioxide in aerobic envi-
ronments is not an anaerobic process, but given the impor-
tance of methane fluxes in wetlands, it has been extensively
studied. It has been estimated that methane oxidation con-
sumes between 40% and 70% of gross methane production
(Megonigal et al. 2004). The pathway of methane transport
from the soil to the atmosphere is very important in terms
of the proportion of methane that is oxidized. Methane is
transported by diffusion, ebullition (i.e., bubble release),
and plant-mediated transport. Diffusion results in maximal
methane oxidation, whereas ebullition results in almost no
methane oxidation. In plant-mediated transport, methane
can be oxidized in the rhizosphere, but once the methane
is in the aerenchyma of the plant, it undergoes little addi-
tional oxidation. Plant-mediated methane transport con-
tributes from about 30% to 100% of the methane flux in

Carbon Dy namics and Ecosystem Processes   195

53488p151-286.indd 195 8/19/14 9:06 AM

 wetlands (Bridgham et al. 2013). Consequently, important
controls over methane emissions from wetlands are the
abundance of vascular plant with aerenchyma, which con-
trols plant-mediated transport; and the water-table level,
which controls diffusive flux.
Anaerobic methane oxidation (AOM) has been docu-
mented for decades in marine systems and is thought to
consume greater than 90% of the methane produced in
these systems (Bridgham et al. 2013). Although the mech-
anisms for AOM in marine systems are still under debate,
electron acceptors other than oxygen—​particularly sul-
fate—​are involved. There is intriguing evidence that AOM
may also be important in freshwater wetlands, but it is very
poorly studied and the mechanisms are unclear (Smemo
and Yavitt 2011; Blazewicz et al. 2012).
Why Do Wetlands Accumulate Soil Carbon?
There are three potential, nonexclusive, reasons why many
wetlands, particularly peatlands, accumulate such large
amounts of soil organic matter. The first is that wetland
plants have inherently low carbon quality and thus form
low-quality soil organic matter. To understand this first
reason, it is instructive to compare wetland soils to terres-
trial soils because of the much greater body of research on
the latter. Humic substances are traditionally described as
a heterogeneous group of high-molecular-weight, aromatic,
refractory organic compounds of secondary origin in soils
(Sposito 2008). Humic substances in both the dissolved and
solid phases are considered to occur at very high concentra-
tions in wetlands (Kracht and Gleixner 2000; Collins and
Kuehl 2001). These substances have been thought to be fun-
damentally chemically recalcitrant to microbial attack and
to be responsible for much of the “old” soil carbon in ter-
restrial and wetland soils. However, the very existence of
humic substances as traditionally envisioned and the idea
of inherent chemical recalcitrance of soil organic matter
have been resoundingly attacked recently in the context of
terrestrial soils (e.g., Kleber and Johnson 2010; Schmidt et
al. 2011). Organic-mineral soil interactions increasingly are
being recognized as the primary mechanism of the stabili-
zation of soil organic matter in terrestrial soils. This may be
the case in wetlands with mineral soils, although it has yet
to be studied, but it cannot be the case for peatlands, which
by definition have very low amounts of mineral matter.
As discussed above, research on Sphagnum mosses shows
that they have a unique cell wall chemistry and suggests
that they form organic matter with a high degree of aro-
matic structures; they may also have direct inhibitory
effects on soil organisms. High amounts of phenolic com-
pounds in some wetland plants may also impede decom-
position of plant litter (see, e.g., Bridgham and Richardson
2003). Polyphenols inhibit carbon mineralization by inhib-
iting microorganisms, binding proteins and polysaccha-
rides, and inactivating enzymes (Harborne 1997; Freeman
et al. 2012). Moreover, some peatlands continue to accumu-
196  CHAP TER Seven
53488p151-286.indd 196
+ CO2
- CH4
Electron Plant
Acceptors Community
Oxygen + +
+ + +/-
C and N + Microbes
+ Phenol
Oxidase
- Phenolics,
Availability Quinones
- -
- + -
Low pH + Hydrolases
+
+
+
Inorganic
Nutrients -
CO2, CH4 DOM
Mineralization
FIGURE 7.10. Multiple roles of aromatic substances in carbon
cycling in wetlands. Phenol oxidase activity is thought to be an
“enzymatic latch” over carbon storage in peatlands because of the
widespread negative effects of polyphenols on decomposition and
microbial activity. This enzymatic latch mechanism is of unknown
importance in other types of wetlands. Other aromatic compounds,
e.g., quinones, are important organic terminal electron acceptors.
As with other electron acceptors, they cause preferential anaerobic
mineralization to carbon dioxide versus methane. Enzymatic latch
mechanisms are shown in green, organic terminal electron acceptor
mechanisms are shown in blue, controls over both mechanisms are
shown in pink, and generalized microbial controls are uncolored.
Extensively adapted from Freeman et al. (2012).
late soil carbon even though they experience long periods
with a water table far from the surface during the growing
season (e.g., Bridgham and Richardson 1992). Thus, there
is evidence that wetland soils may have unique properties
of their soil organic matter that promote carbon accumu-
lation, although almost all wetlands experience large oxi-
dative losses of soil carbon upon drainage, suggesting that
anaerobiosis is essential for them to maintain and grow
their soil carbon stores.
The second hypothesis to explain the large amounts of
soil organic matter accumulated in many wetlands is that
the low energy yields of the anaerobic pathways of carbon
mineralization reduce microbial activity enough to allow
for soil carbon accumulation. As discussed above, abundant
evidence shows that anaerobic carbon mineralization is
several-fold slower than aerobic carbon mineralization, but
this seems unlikely to be a large enough effect to account
for the large amounts of soil carbon accumulation seen in
many wetlands.
The third hypothesis is what has been termed the enzyme
latch mechanism (Fig. 7.10) (Freeman et al. 2001; Limpens
et al. 2008). As discussed above, polyphenols bind many
enzymes and make them inactive. Phenol oxidase and per-
oxidase exoenzymes are responsible for the degradation
of polyphenolic and aromatic compounds and are pro-
duced by a range of bacteria and fungi. However, the activ-
ity of these enzymes is constrained by low oxygen avail-
ability, low pH, and low temperature, all of which are very
8/19/14 9:06 AM
 common in many wetland soils. The basic premise of the
enzyme latch hypothesis is that the inactivity of phenol
oxidase in anaerobic wetland soils allows for the accumula-
tion of polyphenolic substances, which in turn make hydro-
lase exoenzymes inactive, thus reducing nutrient availabil-
ity and carbon availability. In turn, this reduces microbial
growth and activity, which spirals the system into a state of
very low carbon mineralization and high carbon sequestra-
tion capacity.
Dissolved Organic Matter Fluxes
from Wetlands
Dissolved organic matter (surface water DOM concentra-
tions) is an essential component of the carbon dynam-
ics of wetlands (Figs. 7.1, 7.2, and 7.10) and can reach very
high concentrations in wetland soils—​for example, ranging
between 20 to > 60 mg C L –​1 in northern peatlands (Blodau
2002). DOM is thought to be a heterogeneous mixture of
compounds that is typically dominated by high-molecular-
weight compounds (e.g., “humic” and “fulvic” acids) that
decompose very slowly (Docherty et al. 2006; Tfaily et al.
2013), although pooling of low-molecular-weight acetate
(CH3COOH) is sometimes observed in northern bogs for
reasons that are poorly understood (Bridgham et al. 2013).
High-molecular-weight DOM compounds have light-absorb-
ing (chromophoric) properties that give waters with high
concentrations of these compounds a tea-stained color.
Wetlands are a major source of DOM in surface waters,
and the proportion of wetlands in a catchment is often the
best landscape predictor of surface water DOM concentra-
tions (Xenopoulos et al. 2003; Johnston et al. 2008; Moore
2009). DOM in surface waters has myriad important effects,
including degradation of drinking water quality (Fenner
et al. 2009), mercury methylation and transport (Moore
2009), fueling of heterotrophic metabolism and control
over foodweb dynamics (Docherty et al. 2006; Frost et al.
2007), and attenuation of light and harmful ultraviolet
radiation (Frost et al. 2006).
Export of DOM ranges from <1 to 50 g C m –​2 yr–​1 in
northern peatlands (Blodau 2002); potentially, even higher
DOM export can occur in bottomland hardwood forests
(Trettin and Jurgensen 2003). However, emergent wet-
lands may be net sinks for DOM (Blodau 2002; Johnston
et al. 2008), and peatlands can be net sinks for DOM at
low rates of discharge (Pastor et al. 2003). The net trans-
port of DOM from wetlands is controlled by the interactive
effects of production, consumption, sorption, and trans-
port mechanisms (Fenner et al. 2009; Moore 2009). DOM is
produced through the decomposition of soil organic matter
and release of plant exudates. Even at great depth within
peatlands, DOM is of relatively recent origin compared
with the solid phase organic matter, demonstrating the
importance of plant sources of DOM (Chanton et al. 2008).
DOM is consumed through heterotrophic microbial respira-
tion, although, as discussed above, at least under anaerobic
53488p151-286.indd 197
conditions, its recalcitrant chemical nature slows this pro-
cess. DOM is also readily adsorbed to solid organic matter,
soil minerals, and even bacterial cells (Young et al. 2004;
Moore 2009). The rate of discharge from wetlands is par-
ticularly important in the dynamics of DOM export, with
high discharge rates causing rapid export of DOM, whereas
longer retention times result in the DOM being susceptible
to biodegradation and retention (Pastor et al. 2003; Moore
2009). There is often a strong relationship between DOM
transport from peatlands and water-table depth because of
the much lower hydraulic conductivity of deeply buried
peat (Moore 2009). Factors that increase rates of biodegra-
dation will tend to increase the ratio of the production of
carbon dioxide to DOM, such as higher temperatures, lon-
ger hydraulic residence times, and aerobic versus anaerobic
conditions (Moore 2009).
A long-term increase in surface water concentrations
has been observed in many boreal and sub-boreal regions
and that has been at least partly tied to wetland dynam-
ics (Fenner et al. 2009). Possible reasons for the increase
include greater DOM production due to warming, increased
drought frequency, and elevated atmospheric carbon diox-
ide concentrations. Decreasing atmospheric sulfate deposi-
tion may lead to both enhanced DOM production and solu-
bility. Melting permafrost may also cause increased release
of DOM (Moore 2009).
The Big Picture
Methane Fluxes
Methane (CH4) is a major product of anaerobic microbial
respiration in wetlands (Fig. 7.9), and its greenhouse gas
effects are about 25 times stronger than carbon dioxide on
a mass basis (Forster et al. 2007; see also Chapter 10). It is
also responsible for about 18% of anthropogenic warming
(Forster et al. 2007). Of the total global flux of 500 to 600
Tg CH4 yr–​1, wetlands are responsible for about 164 Tg CH4
yr–​1 (range from 80 to 280 depending on study and meth-
odology, Fig. 7.11). An estimated 73% of these emissions are
from tropical wetlands, with their large areal extent and
high flux rates (Bridgham et al. 2013). Open freshwater
aquatic ecosystems also emit 93 Tg CH4 yr–​1, with another
10 Tg CH4 yr–​1 coming from shallow littoral zones, but there
may be substantial overlap between freshwater aquatic eco-
systems and wetlands in these estimates. Rice fields are
responsible for about 53 Tg CH4 yr–​1, and these are essen-
tially agricultural wetlands with many of the same underly-
ing biogeochemical controls over methane fluxes.
There is substantial concern that wetlands may pro-
vide a positive feedback to future climate change for sev-
eral reasons. First, CH4 production is a temperature-limited
process—as are all microbially mediated biogeochemi-
cal pathways. Second, a large concentration of wetlands
exists at high northern latitudes where the largest tempera-
ture increases are predicted to occur, and the possibility of
Carbon Dy namics and Ecosystem Processes   197
8/19/14 9:06 AM

FIGURE 7.11. Dot density graph of global methane sources. Horizontal
lines are the median for each category. Anthropogenic sources
include rice fields and natural sources include freshwater aquatic
ecosystems and wetlands, but they are also presented separately.
Adapted from Bridgham et al. (2013).
widespread permafrost melting in the arctic is of special
concern. Third, the stimulatory effects of increased atmo-
spheric carbon dioxide concentrations on temperature may
also increase methane fluxes (Bridgham et al. 2013 and ref-
erences therein).
There is substantial evidence that methane emissions
from wetlands have affected climate and been at least par-
tially responsible as a feedback mechanism driving past
glacial-interglacial cycles (Loulergue et al. 2008). Moreover,
although longer-term recent trends in atmospheric concen-
trations of methane appear to be driven by anthropogenic
activities (Fig. 7.12), numerous studies suggest that much
of the large interannual variations in atmospheric meth-
ane concentrations, and potentially the large increases seen
since 2008, are due to climate effects on methane emissions
from wetlands (Bridgham et al. 2013).
Global Soil Carbon Pools and Accumulation
The soil carbon pool stored with in a particular ecosystem
depends on its area and the amount of soil carbon per unit
surface area, termed soil carbon density. Wetlands occupy
only about 6% of the global terrestrial surface, but some
wetland types have very high soil carbon densities (Table
7.2). Soil carbon density is particularly impressive in peat-
lands at 1,497 Mg C ha –​1 (I Mg = 106) and in mangroves
at 864 Mg C ha –​1, where the depth of the organic layer is
often many meters thick. These values are 6.3-fold and 3.6-
fold greater, respectively, than the highest value found in
any terrestrial ecosystem. However, carbon pools and fluxes
vary greatly among different types of wetlands. For exam-
ple, the soil carbon densities of freshwater mineral-soil wet-
lands and seagrass beds are in the range of other terrestrial
198  CHAP TER Seven
53488p151-286.indd 198
(a)
(b)
FIGURE 7.12. (A) Atmospheric growth rate of methane in dry air mole
fractions in blue and the de-seasonalized trend curve as a red, –​
dashed line. (B) The instantaneous growth rate of (A). The symbols
are the annual increase calculated from January 1 in one year to
January 1 in the next year, plotted in the middle of the year. Data
and graphic are from E. Dlugokencky (Dlugokencky et al. 2009).
ecosystems, whereas the value for salt marshes in Table 7.2
probably is an underestimate because it is calculated only
to 1 m depth. Also, the organic content of salt marsh soils
varies substantially (Chmura et al. 2003).
Wetlands contain 33% of the global soil organic pool to
2 m depth according to the calculations in Table 7.2. Peat-
lands alone contain 27% of the global soil carbon pool.
These estimates are based upon soil carbon densities by Job-
bagy and Jackson (2000) in which wetlands were included
within the vegetation categories used to define the vari-
ous global terrestrial ecosystem types. However, since most
peatlands occur in the boreal zone, and the total soil car-
bon estimated for the peatlands is substantially greater
than the total for boreal forests and shrub lands—​which
should be the categories that largely include peatlands, but
it appears that peatlands were not adequately represented
in the soil carbon densities determined by Jobbagy and
Jackson (2000). Thus, wetland soil carbon was added to the
terrestrial carbon pool to calculate a global total in Table
7.2, potentially underestimating the contribution of wet-
lands. For comparison, if one uses the global soil carbon
pool estimate of 2,416 Pg (1 Pg = 1015) by (Batjes 1996), then
wetlands contain about 25% of the soil carbon pool.
All wetland types apparently have much higher soil car-
bon accumulation rates than terrestrial ecosystems have
(Table 7.2), probably reflecting their prolonged water-
logged conditions and their anaerobic pathways of carbon
mineralization. Soil carbon accumulation rates in terres-
trial ecosystems decline exponentially with age (Zehet-
ner 2010), so that ecosystems older than several thousand
years have very low accumulation rates. Schlesinger (1990)
estimated that the overall rate of soil carbon accumulation
in deglaciated soils over the last 10,000 years is less than
8/19/14 9:06 AM
 table 7.2
Area and Soil Organic Carbon Pools and Accumulation in Global Wetlands and Other Ecosystems

Soil Carbon Global Soil Soil Carbon Soil Carbon

Area Density Organic Carbon Accumulation Rates Accumulation
Ecosystem Type (km2 × 1,000) (Mg C ha-1) Pool (Pg) (g C m-2 yr-1) (Tg C yr-1)

Wetlands
Peatlands 3,341a 1,497h 500n 11n 36h
Freshwater
mineral-soil 5,172b 199i 103h 17p 88p
Salt marsh 51c 162j 0.8h 151q 7.7h
Mangrove 138d 864k 12h 163r 23r
Seagrass beds 177e 140l 2.5h 101s 18h
Wetland total 8,879 618 173

Global Terrestrial
Ecosystems
Tropical forests 19,623f 238m 466h 4.0f 79f
Temperate forests 10,400f 196m 204h 5.1f 53f
Boreal forests 13,700f 117m 160h 4.6h 49f
Tropical savanna/
grasslands 15,000g 187m 280h
Temperate
grasslands 9,000g 159m 143h 2.2g 20h
Shrublands 8,500g 122m 104 h
Deserts 18,000g 91m 164h 0.8g 14h
Tundra 8,000g 166m 133h 1.2g 10h
Cropland 14,000g 150m 210h
Extreme desert, rock, ice 24,000g 1g 2.4h

Overall total 149,102 1,867o 400t

Wetland % of total 6.0 33o 43

From assessment of published values.

a o Wetlands are supposedly included in the terrestrial ecosystem classes

Wetland area from Lehner and Döll (2004) excluding coastal wet-
b for both area and soil carbon density, but a comparison of peatlands to
lands minus peatland area in table. boreal forest suggests that wetlands are poorly represented. Hence, wet-
c Pendleton et al. (2012). land soil carbon was added to the terrestrial soil carbon pool, potentially
d Giri et al. (2011). underestimating the wetland contribution. For comparison, Batjes (1996)
e Waycott et al. (2009). estimated the global soil carbon pool to 2 m depth to be 2,416 Pg, in
f McLeod et al. (2011). which case wetlands would represent 25.6% of the global total.
g Schlesinger (1997). p Using sedimentation rate of 2.2 Mg sediment ha-1 yr-1 and 7.7% C

h Calculated from other values in table. as in Bridgham et al. (2006), but the global rate is higher because of the
i Soil carbon density to 2 m depth from Batjes (1996). larger assumed area.
j Soil carbon density to 1 m depth from Pendleton et al. (2012). q Duarte et al. (2005).

k Soil carbon density from Donato et al. (2011). r Breithaupt et al. (2012).

l Soil carbon density from Fourqurean et al. (2012). s Average from Duarte et al. (2005) using sediment burial rates and

m Jobbagy and Jackson (2000) to 2 m depth. Duarte et al. (2010) using net ecosystem exchange.
n Yu (2012). t A maximum value from Schlesinger (1990).

53488p151-286.indd 199 8/19/14 9:06 AM

 FIGURE 7.13. (A) The current radiative balance and
(B) historical net radiative forcing for wetlands
in the conterminous United States as a result
of soil carbon sequestration, oxidation of soil
carbon from drained wetlands, methane flux,
and the sum of these fluxes. Units are Tg CO2 -C
equivalents yr-1. A warming effect is represented as
negative number, and a cooling effect as a positive
number. Data from Bridgham et al. (2006).
2.4 g m–​2 yr–​1. However, very young terrestrial soils (e.g.,
after volcanic eruptions) and those in abandoned agricul-
ture fields can have accumulation rates that rival those in
wetlands (Schlesinger 1997).
The size of the soil carbon pool within a wetland type
does not necessarily reflect its annual rate of soil carbon
accumulation. Peatlands have a comparatively small rate of
annual soil carbon sequestration, but that carbon has typ-
ically accumulated over several thousand years (Yu 2011)
and yields very large stores. The modest rates in freshwa-
ter mineral-soil wetlands may be substantially overesti-
mated for reasons discussed in Bridgham et al. (2006). It
appears that marine-associated wetlands have exception-
ally high soil carbon accumulation rates for reasons that are
not clear. Wetlands sequester 173 Tg C yr–​1 (1 Tg = 1012) in
their soils, which is 43% of the global total. Freshwater min-
eral-soil wetlands are particularly important in this regard
because of their large global areas. Wetlands can also store
substantial amounts of carbon in aboveground plant bio-
mass, particularly in those with early successional woody
vegetation (Trettin and Jurgensen 2003).
There is substantial recent interest in using the high car-
bon sequestration capacity of wetlands as justification for
200  CHAP TER Seven
53488p151-286.indd 200
their conservation, and even in selling carbon credits for
wetland restoration activities (Galatowitsch 2009; Irving et
al. 2011; Pendleton et al. 2012). However, caution is needed
when using carbon sequestration as a rationale for wetland
conservation and restoration activities. Two important
caveats must be weighed against the ability of wetlands to
sequester large amounts of carbon. First, the drainage of
wetlands leads to the eventual oxidation of the stored car-
bon back into the atmosphere as carbon dioxide. Second,
wetlands emit large amounts of the potent greenhouse gas
methane, as discussed above. An estimate of the current
radiative balance of wetlands in the conterminous United
States is shown in Figure 7.13, where methane fluxes have
been multiplied by their global warming potential on a
100-year timeframe (i.e., 6.3 on a mass C basis) into CO2 -C
equivalents (Bridgham et al. 2006). According to this anal-
ysis, peatlands, freshwater mineral-soil (FWMS) wetlands,
and estuarine wetlands have net global warming balances
of –​10.2, –​5.1, and 5.2 Tg CO2 -C equivalents yr–​1, respec-
tively, where a negative number indicates a net warming
effect. Thus, the carbon sequestration capacity of peatlands
and FWMS wetlands is more than offset by the oxidation of
peat in drained peatlands and methane fluxes in both wet-
8/19/14 9:06 AM
 land types. However, the low methane fluxes in estuarine
wetlands—​because of their high concentrations of porewa-
ter sulfate—​cause them to have a net cooling effect.
Another important caveat to consider is the differ-
ence between a radiative balance and a radiative forcing
(Bridgham et al. 2006). The radiative balance reflects the
static effect of a substance, whereas the radiative forcing
refers to an externally imposed perturbation on the Earth’s
radiative energy balance (Ramaswamy et al. 2001). Thus,
a change in the radiative balance leads to a radiative forc-
ing, which in turn causes a change in temperature. Wet-
lands have long emitted large amounts of methane to the
atmosphere, and it is only the change in methane flux that
causes a radiative forcing. Thus, increased methane fluxes
caused by climate change, or potentially even by resto-
ration activities, would have a warming effect, whereas
destruction of wetlands would have a cooling effect if the
decrease in methane fluxes outweighed the loss in their car-
bon sequestration rates. In peatlands in the conterminous
United States, the oxidation of soil carbon due to drainage
(a warming effect) has had a much larger effect on radia-
tive forcing than their loss in sequestration capacity (also
a warming effect) and the decrease in their methane fluxes
(a cooling effect) (Fig. 7.13). The drainage of peatlands has
had a net warming effect of 12.7 Tg CO2 -C equivalents yr–​1.
In contrast, the loss of FWMS wetlands in the contermi-
nous United States has dramatically reduced their meth-
ane fluxes, which more than offsets their loss in soil carbon
sequestration (oxidation is unimportant), so the net effect
is a cooling of 18.3 Tg CO2 -C equivalents yr–​1. The loss of
estuarine wetlands is estimated to have a small warming
effect of 0.5 TG CO2 -C equivalents yr–​1.
53488p151-286.indd 201
Even more caveats need to be considered here. Many
of these estimates have very low confidence in their mag-
nitudes (Bridgham et al. 2006), although the signs of the
net carbon balance and forcing for each wetland type
are probably correct. The role of wetlands in the carbon
balance and its subsequent effect on radiative forcing in
North America is relatively small compared with that of
other ecosystems (Pacala et al. 2007). Maybe most impor-
tantly, wetlands have many functions in the landscape
that far outweigh their effects on carbon cycles and trace
gas emissions. However, the analysis presented in Figure
7.13 indicates the unintended conundrums that can result
from narrow policy prescriptions based upon the carbon
dynamics and radiative forcing effects of wetlands. Much
more work needs to be done on these questions, particu-
larly in restored wetlands that almost certainly have vari-
able carbon balances dependent upon their hydrology,
vegetation, time since restoration, climate, etc. Because of
their low methane fluxes and large soil carbon sequestra-
tion potential, the restoration of marine-influenced wet-
lands such as salt marshes, mangroves, and seagrass beds
is likely to have a large net cooling effect (Bridgham et al.
2006; Fourqurean et al. 2012; Pendleton et al. 2012). This
may well be true of other wetlands such as young succes-
sional, forested, FWMS wetlands that experience only brief
periods with water tables close to the soil surface. Preserva-
tion of wetlands with large soil carbon accumulation, such
as peatlands and mangroves, will reduce the potential for
large soil oxidation losses due to drainage. Other types of
wetlands may have a minimal or warming effect because of
restoration activities, so other functions and values need to
be emphasized in these cases.
Carbon Dy namics and Ecosystem Processes   201
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