N AT U R A L O R G A N I C M AT T E R

Soil and Hydrology:

their effect on NOM
Soil chemistry, hydrology, and source material
affect not only the amount of natural organic matter in an
aquatic system but its reactivity as well. They also help
water treatment plant operators anticipate problems.

George Aiken
and Evangelo Cotsaris

D uring the past 15 years, environ-

mental scientists have placed increasing emphasis
on understanding the geochemical and ecological
roles of organic matter in aquatic ecosystems. Organic
matter in aqueous systems often controls geochem-
ical processes by acting as proton donors–acceptors
and as pH buffers, by affecting the transport and
degradation of pollutants, and by participating in

Organic matter derived from different source materials has

mineral dissolution and
precipitation reactions.
Dissolved and particulate
distinctive chemical characteristics associated with those organic carbon may also
materials. Interactions among organic matter and the minerals control the depth of the
and inorganic constituents in soil can result in the removal and photic zone in surface
fractionation of organic matter, altering the composition and waters, influence the
reactivity of the dissolved organic carbon (DOC). Hydrologic availability of nutrients,
conditions define the flow path and control the rate of transport and serve as a carbon
of DOC within the system. The nature, distribution, and reactivity substrate for microbially
of organic matter in a given system is determined, to a large mediated reactions. Nu-
extent, by the strength and nature of interactions among the merous studies have rec-
various components of the environment. ognized the importance
of natural organic matter

(C) 1995 American Water Works Association

36 JOURNAL AWWA
 This flume on the Shingobee River
measures the stream’s discharge
or natural flow. The foam on the
surface of the water indicates the
presence of organics.

Variation in the amount and

nature of organic matter, espe-
cially with respect to changes in
the aromatic carbon content, are
significant factors for designing
strategies for water treatment.
For instance, in a study of the
chlorination of aquatic humic
substances, Reckhow et al1 noted
a strong correlation between
chlorine consumption and fac-
tors such as aromatic carbon and
phenolic carbon contents. The
generation of chlorination by-
products resulting from the reac-
tion of chlorine with DOC may
be a greater problem during peri-
ods when both the DOC con-
centrations and aromatic carbon
content are high. Understanding
the factors that control the
nature and transport of organic
matter in aquatic systems, there-
fore, may enable scientists and
engineers to devise effective
treatment strategies that mini-
mize the generation of undesir-
able by-products.
The complexity of the bios-
phere makes it difficult to study
the nature, chemical reactivity,
and ecological roles organic mat-
PHOTO: DON ROSENBERRY

ter plays in aquatic systems. The

lithosphere is not divided into
distinct environmental compart-
ments that can be understood
independently of neighboring
environments. For instance, it is
not possible to understand the
(NOM) in the mobilization of hydrophobic organic chemistry of a stream without considering the local
species; of metals such as lead (Pb), cadmium (Cd), soil and groundwater chemistry. It is also necessary to
copper (Cu), zinc (Zn), mercury (Hg), and chromium consider factors such as variations in hydrology, veg-
(Cr); and of radionuclides such as plutonium (Pu), etation patterns in the stream watershed, and air-
americium (Am), uranium (U), and cobalt (Co). borne contributions to the system. The chemical char-
Many contaminants that scientists view as virtually acteristics of the DOC are the net result of all the
immobile in aqueous systems can interact with dis- biogeochemical processes occurring within the system.
solved organic carbon (DOC) or colloidal organic Changes in soil composition or hydrology, for instance,
matter, resulting in migration of hydrophobic chem- can influence not only the amount of organic matter
icals far beyond distances predicted by structure and within a stream but its chemical nature as well. This
activity relationships. In addition, these reactive sub- article discusses the importance of source materials
stances are potential precursors for the formation of (i.e., precursor materials), soil chemistry, and hydrol-
disinfection by-products resulting from water treat- ogy on the amount and composition of DOC in
ment practices. aquatic systems.

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JANUARY 1995 37
 FIGURE 1 Comparison of the ratio of carbon to nitrogen with the graphic techniques: hydrophobic acids,
ratio of aromatic carbon to aliphatic carbon for a variety bases, and neutrals; and hydrophilic
of aquatic fulvic acids acids, bases, and neutrals.5 In natural
waters, organic acids comprise the most
100 abundant class of DOC. Only a small
fraction of these organic acids are low-
Suwannee River ■ molecular-weight compounds that can
be identified using current analytical
80 techniques. The major fractions of the
Ogeechee River ■ DOC pool of most natural waters are
Yakima River ■ refractory organic compounds that are
Coal Creek ■ operationally defined as aquatic fulvic
60
C-to-N Ratio

acids and hydrophilic acids.6 Aquatic ful-

Missouri River ■ vic acids are yellow, heterogeneous, bio-
Williams Lake Ohio River ■ logically refractory organic acids, with
40
▲ ● ■ Shingobee River number-average molecular weights of
Pacific Ocean 500–1,000 daltons. Aquatic fulvic acids
❍ usually constitute 20–80 percent of the
❍ ❍
❍ DOC. Their biogeochemistry has been
20 ❍ studied in numerous aquatic environ-
Lake Fryxell, Antarctica
ments. 7 Hydrophilic acids are more
hydrophilic than fulvic acids, primarily
0 as a result of a greater density of acidic
0.0 0.2 0.4 0.6 0.8 1.0 1.2 functional groups.6 They too are het-
Ar-C to Al 1-C erogeneous mixtures of organic acids.
Hydrophilic acids comprise 5–20 percent
of the DOC of the relatively few systems
in which they have been studied. The
higher-molecular-weight, more hydro-
Definitions phobic fraction, commonly refered to as aquatic hu-
One of the difficulties encountered in the study of mic acid, generally represents approximately 5 per-
organic matter in aquatic environments relates to ter- cent of the DOC.
minology. Given the analytical constraints in study- Although the fractionation approach is useful for
ing organic matter, most of the definitions in current evaluating the reactivity and chemical properties of
use are operational definitions. Historically, organic each fraction, these fractions are chemically complex
matter in natural waters has been arbitrarily divided mixtures. As such they lack the chemical definition
into dissolved and particulate organic carbon (POC), associated with other classes of natural products, e.g.,
based on filtration through a 0.45-µm filter. No natural proteins and polysaccharides. The terminology used
cutoff exists between these two fractions, and the dis- to describe aquatic humic substances, including ful-
tinction is operational. Overlapping the dissolved and vic acid, can be confusing.8 In referring to aquatic
particulate fractions is the col-
loidal fraction, which consists
of suspended solids that are TABLE 1 Soil properties (A horizon) and concentrations and loads of organic
operationally considered as carbon during storms in the Lawless and Retreat Valley catchments
solutes. Colloidal organic mat- in South Australia
ter in natural waters is com-
posed of living and senescent Parameter Lawless Valley Retreat Valley
organisms, cellular exudates, Soil properties
and partially to extensively Carbon content—percent 2.6 4.5
degraded detrital material, all DOC in 1:5 (g/mL) soil to water extracts—mg C/L 31.3 25
Adsorption capacity*—µg C/g 71 153
of which may be associated Specific surface area—m /g 2 2.0 12.6
with mineral phases.2 Gener- Average clay content—percent 7.5 21.5
ally, DOC is in greater abun- Stream properties
DOC concentration—mg C/L 21.9 ± 4 6.5 ± 1.4
dance than POC, accounting Annual carbon load†—kg/ha/year 60.4 19.2
for approximately 90 percent
*Adsorption capacity for a given soil was determined by measuring the amount of DOC adsorbed by the soil in a
of the total organic carbon of 1:5 (g/mL) soil-to-solution suspension. The initial solution contained a high DOC concentration (182 mg C/L) of
most waters. 3,4 throughfall, defined as water that passes through the canopy vegetation and undecomposed litter layer on the soil
surface. The amount of carbon adsorbed was calculated from the difference between DOC of the solution before
DOC can be further frac- and after mixing with the soil.
†Carbon loads were estimated by multiplying the mean DOC concentrations of samples, taken at proportional
tionated into six fractions intervals, by the total annual discharge.
according to chemical char-
acteristics using chromato-

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38 JOURNAL AWWA
 Water from the Suwannee River has
been studied internationally to increase
understanding of the structure and
reactivity of natural organic matter.

reactivity and speciation will be con-

trolled by thermodynamics and reac-
tion kinetics.
In aquatic ecosystems, the sources
of DOC can be categorized as (1)
allochthonous—entering the system
from a terrestrial watershed, and (2)
autochthonous—being derived from

PHOTO: GEORGE AIKEN

biota (e.g., algae, bacteria, macro-
phytes) growing in the water body. In
temperate systems, the allochthonous
sources are very important. Most of
the DOC originates from the degra-
dation and leaching of organic detritus
systems, humic substance is a general term encom- in the soils of the watershed and is transported by
passing humic acid and fulvic acid. The terms used to streams and shallow groundwater flow. The chemi-
describe humic substances originated in the field of soil cal characteristics of the DOC are influenced not only
science where they were used to describe fractions of by the source materials but also by the biogeochem-
soil organic matter extracted from soil by rather severe ical processes involved in carbon cycling within the
chemical treatment. These fractions are, therefore, terrestrial and aquatic systems. These processes include
operationally defined, based on the procedures allochthonous flow of organic carbon to the aquatic
employed. With the introduction of chromatographic system from the watershed, autochthonous carbon
techniques to concentrate

M
and fractionate DOC,
another set of completely
different operationally
defined fractions was intro- ost DOC originates from the degradation
duced. Similarly named and leaching of organic detritus in the
fractions isolated from soils
and water are not chemi- soils of the watershed and is transported
cally equivalent. Unfortu-
nately, the soil science ter-
by streams and shallow groundwater flow.
minology was carried over
into the aquatic field at an early stage of the study of fixation by algae and aquatic plants, transformation
DOC, and the terms are now commonly used. and degradation of both autochthonous and
allochthonous organic material by heterotrophic
Origins of DOC microbial activity, transport of particulate organic
Microbial degradation of organic matter results material to the sediments, remobilization of DOC
in the formation of many of the compounds that from the sediments, and photodegradation by incident
comprise DOC, especially nonvolatile organic acids UV light. Each of these processes is likely to affect
that dominate the DOC in most aquatic environ- the DOC chemistry in a different way.
ments. Many of these organic acids are considered Organic matter derived from different source mate-
refractory because the rates of subsequent biodegra- rials has distinctive chemical characteristics associ-
dation are slower than for other fractions or classes of ated with those source materials.9 Aquatic humic
organic matter. However, microbial processes con- substances derived from lignin, for instance, are found
tinue to slowly alter the structure and chemical reac- to have relatively large amounts of aromatic carbon,
tivity of these compounds. Once in the system, organic are high in phenolic content, and, because lignin does
compounds, whether they be anthropogenic or nat- not contain nitrogen (N), are low in N content. Micro-
urally derived, can be truly dissolved, associated with bially derived humic substances, on the other hand,
immobile particles, or associated with mobile particles have relatively high N contents and low aromatic-
(DOC, colloids). Each species is interrelated to the carbon (C) and phenolic content. The relative con-
others through equilibrium partitioning. The mag- tributions of allochthonous and autochthonous
nitude of the partitioning coefficients and the abun- sources of DOC vary among different water bodies,
dance of sorbents determine the mechanisms and but there is currently no way to quantify this varia-
enhancement of transport for a particular organic tion based on chemical characterization of DOC. The
compound. Regardless of environment, chemical problem of sorting out relative contributions to the

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JANUARY 1995 39
 FIGURE 2 Stream DOC concentrations and A-horizon clay content corner of the diagram. Fulvic acids inter-
in Mt. Lofty Ranges in South Austrialia mediate between these extremes repre-
sent a combination of source diversity and
geochemical interactions that can frac-
25
● tionate the organic matter.

● Lawless Valley Soil influences

20 Much of the DOC present in surface
●
Mean DOC Concentration—mg C/L

waters is allochthonous material origi-

nating in the soils of the watershed. The
● ● generation of organic matter in the soil
● ● environment that can be transported
15
●
●● by water moving through the soil
● depends on factors such as vegetation,
● ● microbial activity, and the physical and
10 ● Retreat Valley chemical properties of the soil itself.
● ● ● Although it is accepted that soil is a
major source of DOC,4 few researchers
5
have examined the important soil fac-
● tors influencing DOC concentrations in
2
y = 22.3 – 0.70x r = 0.44 streams.12,13 The importance of these
factors is demonstrated by recent stud-
0 ies of stream DOC in two small catch-
5 10 15 20 25 ments: the Retreat Valley catchment
Average Clay Content of A-Horizon (1.3 km2) and Lawless catchment (3.0
Soils in Each Catchment Area—percent km 2 ), both located in the Mt. Lofty
Ranges in South Australia.14 Despite
similar land uses and precipitation
(annual rainfall of 800 mm) in the two
DOC pool from different compartments of the envi- catchments, the DOC concentrations were signifi-
ronment is further complicated by the turnover and cantly different, being three times greater in the
mixing that takes place in surface waters. Lignin- Lawless (22 mg C/L) than in the Retreat Valley (6.5
derived compounds are generally refractory, and, at mg C/L). The results of a soil survey indicate that the
this point, certain aromatic moieties found in aquatic soils in the two catchments have different natures.
humic substances have been recognized as chemical The mean C content of the Retreat Valley (4.5 per-
characteristics of aquatic humic substances indica- cent) and Lawless Valley (2.6 percent) soils was not
tive of origin from lignin-containing plants.10,11 A related to the concentration of DOC in the streams
distinctive chemical characteristic of humic substances (Table 1). The concentration of water-extractable C
or other DOC fractions derived from microorganisms was higher for Lawless than for Retreat Valley but
has yet to be identified. not large enough to fully explain the differences in
Comparing elemental and structural characteris- concentrations of DOC in the streams.
tics obtained for samples of aquatic humic substances The ability of soils to retain added DOC was deter-
can provide an indication of the sources of DOC that mined by mixing soil samples with water containing
are present in a particular aquatic environment. Figure DOC and measuring the amount of DOC adsorbed.
1 shows a graph of the N-to-C
ratios for a variety of aquatic
fulvic acids and the ratio of the
TABLE 2 Soil horizons*
aromatic C content (Ar-C) to
the aliphatic C content (Al 1-
C) as determined by 13C-NMR. Horizon Characteristics
Samples of fulvic acid isolated O The organic or O horizon is the upper soil layer, which consists of undecomposed
from Antarctic lakes that are to partially decomposed organic matter.
A The A horizon is the eluvial zone of the soil. It is a leached mineral horizon
known to be derived exclu- with finely divided organic matter and dark color.
sively from microbial sources B The B horizon is the illuvial zone of the soil below the A horizon. It is characterized
are clustered at one end of the by the accumulation of one or more of the following: humus, silicate clay
minerals, iron, aluminum, sesquioxides.
range, having low values for C The C horizon is a mineral horizon of the soil that lies below the A and B horizons
both ratios. Samples from and consists of unconsolidated rock material that has been little affected
streams and lakes in water- by pedogenic processes.
sheds with lignin-rich sources, *In soil science, horizons are layers of soil approximately parallel to the land surface and differing from adjacent
such as the Suwannee River, layers in chemical, physical, and biological properties.

are positioned in the opposite

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40 JOURNAL AWWA
The adsorption capacities of
FIGURE 3 Mechanism of soil-water flushing under low-flow baseline conditions

;;;;;;;
the soils were related to the
and under high-flow conditions23
surface areas of the soils. Spe-
cific surface area was in turn
related to the clay content, so

;;;;;;;
;;;;;;;;;
that the soils with a low clay Litter layer
content and a low specific sur- Upper soil horizon

;;;;;;;;;
face area had a low adsorp-

;;;;;;;
Lower soil horizon
tion capacity (Lawless),

;;;;;;;;;
whereas the soils with a high
Soil water zone
clay content and high specific

;;;;;;;
;;;;;;;;;
surface area had a high ad-

;;;;
Water
sorption capacity (Retreat Val- movement
ley). Clay (particles less than 2

;;;;;;;;;
mm in diameter) is important Stream

;;;;
Water table
for adsorption reactions, first
A q u i f e r
because the small particle size
leads to large specific surface Groundwater
areas, and second because the Water
zone
minerals in the clay fraction movement
are generally more reactive Gravel in streambed
than those in the larger size
fractions. For example, clay Low-Flow Conditions
minerals and oxides that dom-

;;;;;;;
inate the clay-size fraction are

;;;;;;;;;
more reactive than quartz Litter layer
(which dominates the sand- Upper soil horizon

;;;;;;;
;;;;;;;;;
size fractions).15 Thus, soil clay Lower soil horizon
can be seen as a sink for or-
ganic matter. The higher the

;;;;;;;;;
clay content, the larger the Water table ridge

;;;;;;;
;;;;
storage capacity, and the more

;;;;;;;;;
Water
likely that organic matter will movement
be retained until it is decom-

;;;;;;;;;
;;;;
posed by microorganisms. Stream Water table
The soils of the Mt. Lofty
Ranges are predominantly A q u i f e r
duplex (i.e., the soils have a

;;;;
Groundwater
relatively impermeable B zone
Water
horizon), so the influence of movement
the A horizon (see Table 2 for
Gravel in streambed
a general description of soil
horizons) clay content on High-Flow Conditions
stream DOC concentrations
in this wider area was exam-
ined. All available DOC data
for streams in the Mt. Lofty Ranges were plotted nature of the underlying geology of a region. In these
against the average clay content of the A horizons in cases, it is therefore possible to identify and predict
the corresponding catchments (Figure 2). The regres- catchments that may give rise to water high in DOC.
sion was significant (P < 0.001), and the clay contents This hypothesis was tested in the Otway Ranges in
of the catchment A horizons accounted for 44 per- Victoria, Australia, where two adjacent streams named
cent of the variation in the mean stream DOC con- Clearwater Creek and Redwater Creek are known to
centrations, despite the many other nonsoil factors have very different DOC concentrations.16 Redwa-
that would be expected to influence the concentra- ter and Clearwater have DOC concentrations of 31.7
tions. For example, the nature of the clay is impor- mg C/L and 2.5 mg C/L, respectively. The climate,
tant for adsorption reactions, as are the total cation land use, vegetation, and topography of the catch-
exchange capacity, the types of cations involved in the ments are very similar. An examination of geology and
exchange, the density and origin of charge, and the soils revealed they were different. Redwater Creek
expansibility of the clay minerals. catchment contains areas of Tertiary sediments that
In some cases, within an area of similar climate, have coarse texture giving rise to sandy soils that are
the clay content of the soil can be predicted from the unable to retain organic matter against leaching,

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JANUARY 1995 41
 generalizations can therefore
FIGURE 4 DOC concentration and staff gauge height for the Ogeechee River
in Georgia—Nov. 22, 1981, to Jan. 17, 1982
be made concerning the role
of soils in the amount of DOC
found in surface waters:
14 14 • Wetlands and areas rich
● DOC in organic soils produce water
12 ❍❍ 12
❍ Gauge height ❍ ❍ with high DOC concentra-
❍❍

Gauge Height —ft

10 ❍ ❍ 10 tions. In these environments
❍
DOC—mg C/L

●❍
❍❍ ❍ the water moves directly from
8 ●●
●❍ ●❍ ●
● 8
●
❍ ●● ❍ being in intimate contact with
●● ● ● ●●●
6 ●
●❍ ❍ ● 6 vegetation and organic detri-
❍
● ●● ❍
❍
●❍ ❍❍ ●
● ●
● ● ●
●
❍ ● 4 tus into streams with little or
4 ● ● ●
❍ ❍
❍ no contact with adsorptive
❍ ❍❍ ❍ ❍
2 2 materials. 19 Wetlands are
0 0 important sources of organic
matter in many watersheds,
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particularly in areas with little
relief.
Date • Areas that are underlain
by sandy soils often produce
water with relatively high
concentrations of DOC. Al-
whereas Clearwater Creek catchment contains Cre- though water moves through the soil, the soil has
taceous siltstones that have a fine texture giving rise very low adsorption capacity for DOC.20,21
to clay soils of high DOC adsorption capacity. • Areas that have permeable soil horizons rich in
Geochemical interactions between organic mat- clay or oxides produce water with low DOC con-
ter and inorganic constituents not only influence centrations.22
the amount of DOC but also result in the chemical
fractionation of the organic matter, altering the com- Hydrologic influences
position and reactivity of the DOC. Aiken and Mal- The transport of allochthonous organic carbon
colm17 noted a correlation between the concentra- into streams and lakes largely depends on the hydro-
tions of Ca2+ and Mg2+ in river water and the radii logic conditions within the watershed. Concentra-
of gyration and molecular weights of the corre- tions of soluble humic substance are substantial in
sponding fulvic acids. It appears that the presence surface soil solutions and vary significantly between
of these divalent cations in
the soils of the watershed
and in the river water
decreases the solubility of
higher-molecular-weight
components of the humic
substances through charge
suppression. Similarly, Mc-
Knight et al 18 noted that
S
tream DOC concentrations appear to be
a function of the flow path of the water
through the soil as well as the adsorptive
fulvic acids enriched in Ar-
properties of the soil itself.
C were preferentially re-
moved by sorption on precipitating hydrous metal different soil and ecosystem strata, vegetation types,
oxides in an acidic, metal-enriched headwater stream and seasons. When the soil is undersaturated with
in the Rocky Mountains. It is worth noting that the water (Figure 3), precipitation can percolate through
removal of DOC by coagulation in water treatment the upper soil horizons and the vadose (unsaturated)
follows similar mechanisms to the ones that occur in zone, finally recharging the groundwater.23 Within the
surface waters and soils. Addition of chemical coag- upper soil horizons, DOC concentrations can be fairly
ulants typically results in the removal of the higher- high, but as the organic matter is transported through
molecular-weight, more hydrophobic fractions of the soil and vadose zones, it is subjected to several
the DOC. processes, including sorption and biodegradation,
Stream DOC concentrations, therefore, appear to that decrease DOC concentrations. For instance, Cro-
a large extent to be a function of the flow path of nan and Aiken24 noted that during the summer grow-
the water through the soil and the adsorptive prop- ing season, DOC concentrations in the interstitial
erties of the soil through which the water flows. The waters of podzol soils in the Adirondack Mountains
DOC concentration of soil interstitial water is reduced ranged from 21 to 32 mg C/L in the O–A horizon,
when the water comes in contact with adsorptive from 5 to 7 mg C/L in the B horizon, and from 2 to
materials such as clays and oxides. The following 4 mg C/L in groundwater solutions. Under low-flow

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42 JOURNAL AWWA
conditions, groundwater dis-
charge to the stream may be FIGURE 5 DOC concentration and UV absorbance for the Shingobee River
the major source of water in in Minnesota—January 1992 to July 1992
the stream, and the organic ● DOC ❍ UV abs 254
matter in the stream will be 11 ❍ 0.30
representative of that trans- 10 ●
❍
ported by the groundwater. ●● 0.25
9
During high-flow condi- ❍ ●
tions when the soil is saturated 8 ●

DOC—mg C/L

Absorbance
with water, the flow of water 7 ● ●
0.20
within the soil column shifts ❍●
❍● ●● ● ●
to a more horizontal direction. 6 ❍●●
●●
❍ ● ●●● ● ● ● 0.15
●● ● ●
Shallow subsurface and sur- 5 ● ● ● ❍ ❍ ●● ●●❍ ● ●
❍
❍❍❍ ❍ ❍ ●● ●
face runoff is common. The ❍❍❍❍❍ ❍ ❍ ❍ ❍
4 ❍ ❍ ❍❍❍ ❍ ❍❍
❍ ❍❍
❍
0.10
organic matter transported in ❍
these waters has a shorter res- 3
idence time in the subsurface 2 0.05
and is not subjected to the

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same processes as material
transported to the water table.
This shift in flow path results
in higher DOC concentrations
FIGURE 6 DOC data for Shingobee River and Shingobee Lake in Minnesota—
and compositional changes in
March 1990 to June 1992
the organic matter transported
to the stream. Storm events, 12
the onset of the rainy season, Shingobee River outlet Shingobee Lake surface
or the melting of winter snow- Shingobee River inlet
pack (spring flush) all can pro- 10
duce high-flow conditions.
Figure 4 illustrates the effect 8
of increased discharge from
DOC—mg C/L

storm events on the Ogeechee

6
River in Georgia. Both the
DOC concentrations and the
staff gauge height are given 4
for a series of storm events.
These data were collected at 2
the end of a drought, and the
DOC of 4 mg C/L is associated
with the base flow of the river. 0
The data show the sensitivity
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of this river to increased dis-

charge. DOC concentrations
rose along with the discharge Date
for the early storm events.
However, each event flushed
the soils of soluble organic
matter, and eventually, the DOC concentrations no Concentrations of DOC in percolating water decreased
longer responded to the increased discharge. through clay B horizons because of its adsorption on
The flow path of water also depends on the phys- sesquioxides (e.g., Fe2O3) and clays.21,24 However,
ical properties of the soil environment. For both Law- at another site where water drained laterally over
less and Retreat Valley, only the A-horizon soils were the top of the B horizon, DOC concentrations
important for adsorption reactions because mea- remained high.24 In a sandy coastal area of Queens-
surements of the hydraulic conductivity of the B hori- land, Australia, “black” (high-DOC) waters moved
zon was generally 20 times lower than that of the laterally through bleached sands along semipermeable
corresponding A horizon. It therefore appeared that B horizons, whereas adjacent “white” (low-DOC)
the B horizon acted as a barrier to downward flow and waters had been decolorized by contact with the C
that most water movement occurred laterally through horizon, in which the sands were coated with
the A horizon into the stream. Other workers have oxides.20
also shown the importance of the flow path of water Figure 5 charts the spring flush for the Shingobee
through soil in influencing DOC concentrations.21,24 River in northern Minnesota. This figure shows DOC

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JANUARY 1995 43
FIGURE 7 DOC data for the Missouri River at Sioux City, Iowa—January 1981
heavily impounded, such as
to September 1982 the Missouri River (Figure 7).
DOC samples were collected
on the Missouri River at Sioux
10 City, Iowa, 80 mi below a
major impoundment of the
river. These data fluctuated
8
little over an extended period
of time.
DOC —mg C/L

6
Summary
●● This article focuses on the
4 ● ● ● role of source materials, soil
● ● ●
●● ●● ● ●
● ● ● ●● ●● ● ● ● composition, and hydrologic
● ● ●● ●●●●●●● ●
●●●●● ●
● ●●●●● ●
● ●●●● ●● ●
● ●
● ●●
● ● ●● ●
● ●●
● ●
properties on the fate and
2
transport of DOC. Each of
these factors influences not
0 only the amount of organic
12/1/80 3/1/81 6/1/81 9/1/81 12/1/81 3/1/82 6/1/82 9/1/82 matter in a given system, but
Date its reactivity as well. An anal-
ogy can be made between
chromatography and the
movement of organic com-
concentrations and UV absorbance values collected pounds in a watershed. Chromatography is essen-
from January to June 1992. The UV absorbance mea- tially the transport of a chemical in a mobile fluid
surements at  = 254 nanometers are an estimate of phase through a column packed with a stationary
the aromaticity of the DOC in these samples. Each phase. A chemical introduced at the beginning of
spring the DOC concentrations rise in association this column moves at a rate proportional to the
with snowmelt. Not only does the amount of organic average velocity of the fluid and inversely propor-
matter in the river change, the character of this mate- tional to the strength and nature of sorptive inter-
rial changes as well. Although the DOC concentrations actions with the stationary phase. These interac-
increased to approximately twice the background tions include ionic and complexation interactions,
levels, the UV absorbance tripled. This indicates that hydrogen bonding, van der Waal’s interactions, and
the organic matter being removed from the soil is equilibrium partitioning. In a watershed, the soil or
more aromatic and likely of higher molecular weight geologic matrix represents the stationary phase. The
than material found in the stream under base-flow mobile phase is the water, which can contain sig-
conditions. nificant quantities of dissolved organic and inor-
Impounding of the streamwater, whether in a ganic chemicals. Organic compounds move through
lake or reservoir, averages out the variations in DOC the system as a function of the flow rate of water and
concentration associated with increased stream dis- the strength and nature of interactions with the sta-
charge. Most water bodies are subject to various tionary phase. The nature and distribution of organic
degrees of physical mixing. Within many lakes, for matter in the system are determined to a large extent
instance, physical mixing can result in spatially uni- by the interactions between the various phases in the
form DOC chemistry. The degree of mixing will environment.
depend on the stratification in the lake, the frequency From a water treatment point of view, variations
of turnover, the size of the lake, and the hydraulic in the amounts and reactivity of organic matter in
retention time. The net effect is to dampen out vari- water supplies pose some interesting problems.
ations in water chemistry associated with periodic Although DOC in itself is not a direct concern in
events such as the spring flush. This effect can be drinking water, it contributes to color and functions
observed by comparing the temporal variation in as a disinfectant by-product precursor in the pres-
DOC concentrations for the Shingobee River with ence of disinfectants such as chlorine. Reactivity of
the corresponding data for Shingobee Lake and for the DOC affects the performance of water treatment
stream draining the lake (Figure 6). Shingobee Lake processes designed to remove organic matter from
has a residence time of approximately seven months. the water supply, such as coagulation, adsorption,
Pulses of organic matter that enter the lake are aver- and membrane techniques. In addition, the charac-
aged with the existing organic matter. The lake is rel- ter of DOC will also affect the performance of sor-
atively unresponsive to event-driven changes in the bents such as granular activated carbon used to
amount of DOC. Rather, the DOC and UV absorbance remove anthropogenic organic compounds such as
data (not shown) for the lake and the outflow stream pesticides. By understanding the factors that control
resemble the base flow data for the inflow stream. A the amount and reactivity of organic matter in a
similar trend can be noted on major rivers that are water supply, alternative solutions to the problems

(C) 1995 American Water Works Association

44 JOURNAL AWWA
posed by its presence may be identified. Approaches 12. MCDOWELL, W.H. & WOOD, T. Podzilization: Soil
that might prove useful include analysis of the effects Processes Control DOC Concentrations in Stream
of water- and land-use practices on the export of Water. Soil Sci., 137:23 (1984).
reactive organic matter (e.g., the draining of wet- 13. MOORE, T.R. Dynamics of DOC in Forested and
lands might result in the mobilization of DOC origi- Disturbed Catchments, Westland, New Zealand,
nally stored in the soil), the implementation of water- 1 Maimai. Water Resources Res., 25:1321 (1989).
shed treatment practices that can reduce the export 14. NELSON, P.N. ET AL. Influence of Soil Clay Content
of organic matter from the watershed (e.g., treat- on Dissolved Organic Matter in Streams. Aust.
ment of soils with adsorption-enhancing materials Jour. Marine Freshwater Res., 41:761 (1990).
such as gypsum or lime), or the judicious choice of 15. MOTT, C.J.B. The Inorganic Components of the
water supply (e.g., stream, river, or reservoir water) Soil. Russell’s Soil Conditions and Plant Growth (A.
based on seasonal or hydrologic variations in the Wild, editor). Longman Sci. & Tech., Harlow
DOC content. (11th ed., 1988).
16. HART, B.T. & MCKELVIE, I.D. Chemical Limnol-
References ogy in Australia. Limnology in Australia (P.
1. RECKHOW, D.A.; SINGER, P.C.; & MALCOLM, R.L. DeDekker and W.D. Williams, editors). Junk
Chlorination of Humic Material: Byproduct For- Publ., Melbourne, Australia (1986).
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& Technol., 24:1655. (1990). of Aquatic Fulvic Acids by Vapor Pressure
2. RANVILLE, J.F.; HARNISH, R.A.; & MCKNIGHT, D.M. Osmometry. Geochim. et Cosmochim. Acta, 51:2177
Particulate and Colloidal Organic Material in (1987).
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Autochthonous Source on Chemical Composi- Organic Carbon by Hydrous Aluminum and Iron
tion. Organic Substances and Sediments in Water, Oxides Occurring at the Confluence of Deer
Vol. 1: Humics and Soils (R.A. Baker, editor). Lewis Creek With the Snake River, Summit County,
Publ., Chelsea, Mich. (1991). Colorado. Envir. Sci. & Technol., 26:1388 (1992).
3. OWEN, D.; AMY, G.; & CHOWDHURY, Z. Character- 19. GRIEVE, I.C. Concentrations and Annual Load-
ization of Natural Organic Matter and Its Rela- ing of Dissolved Organic Matter in a Small Moor-
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4. THURMAN, E.M. Organic Geochemistry of Natural and Their Possible Relationship to the Pod-
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Preparative Isolation and Fractionation of Dis- in Two Subtropical Blackwater Rivers. Archives fur
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(1981). sition and Flux of Dissolved Organic Carbon in
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Acids From Water Utilizing Macroporous Resins. 58:177 (1988).
Organic Geochem., 18:567 (1992). 23. HORNBERGER, G.M.; BENCALA, K.E.; & MCKNIGHT,
7. AIKEN, G.R. ET AL, editors. Humic Substances in Soil, D.M. Hydrologic Controls on DOC During Snow-
Sediment and Water. John Wiley & Sons, New melt in the Snake River near Montezuma, Col-
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Humic Substances. Humic Substances and Their Watersheds of the Adirondack Park, New York.
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York (1988). About the author: George Aiken
9. M C K NIGHT, D.M.; A IKEN , G.R.; & S MITH , R.L. is a hydrologist at the US Geological
Aquatic Fulvic Acids in Microbially Based Ecosys- Survey (USGS), Water Resources
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nol. & Oceanog., 36:998 (1991). ter, 3215 Marine St., Boulder, CO
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Signature of Aquatic Humic Substances. Science, rience studying natural organic mat-
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11. MCKNIGHT, D.M. ET AL. The Biogeochemistry of ing from the Suwannee River in Georgia to Antarctic Lakes.
Aquatic Humic Substances in Thoreau’s Bog, Evangelo Cotsaris is with the State Water Laboratory,
Concord, Massachusetts. Ecology, 66:1339 Engineering and Water Supply Department, Salisbury,
(1985). Australia 5108.

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JANUARY 1995 45