2724 Ecological Processes | Photolysis
from eutrophication. This is because the complex inter-
relations between the amount of aquatic biomass and the
phosphorus load are affected by a number of hydrological,
meteorological, and biochemical factors that remain
unclear under current knowledge. Further improvement
of our current understanding of phosphorus movement
and transformation within aquatic and territorial ecology,
across socioeconomic and ecological boundaries, is
desired.
Regulating the Societal Phosphorus Flows
Phosphorus (P), intensively extracted from the natural
sink in the lithosphere and processed through various
production–consumption cycles, ultimately deposits in
soil or reaches the water body by different pathways.
The societal P flows are characterized by complicated
physical interconnections in high intensities among a
number of production and consumption sectors. Hence,
it is vitally important to connect the P flows with envi-
ronmental regulations introduced to intervene in social
practices and human behaviors.
Instead of continuously trying to limit the growth of P
(like the bans of detergent P), there is a great need to
reconstruct the physical structure of P flows, in particular
by redirecting the crucial P flows with highly negative
environmental impacts. The ecological restructuring of
the current one-through mode of societal P metabolism is
thus desired, leading to a structural shift in the societal
production and consumption of P flows. The ecologically
rational switch can contribute to a substantial decline of P
outflows by minimizing P input and maximizing P recy-
cling. Since ecologizing the P flows only succeeds when
measures are institutionalized into the economy and
society as a whole, this process will most likely be a
gradual one rather than a radical revolution.
Photolysis
C E W Steinberg and A Paul, Humboldt University at Berlin, Berlin, Germany
ª 2008 Elsevier B.V. All rights reserved.
Introduction
Basic Processes
Effects of Photolysis
Introduction
This article presents an overview of the basic principles of
photolysis in the environment from an ecological point of
view. Photolysis refers to any chemical process in which a
See also: Nitrogen Cycle.
Further Reading
Compton JS, Mallinson DJ, Glenn CR, et al. (2000) Variations in the
global phosphorus cycle. In: Glenn CR (ed.) Marine Authigenesis:
From Global to Microbial, pp. 21–33. Tulsa, OK: Society for
Sedimentary Geology (SEPM).
Driver J (1998) Phosphates recovery for recycling from sewage and
animal wastes. Phosphorus and Potassium 216: 17–21.
EEA (2005) Source Apportionment of Nitrogen and Phosphorus Inputs
into the Aquatic Environment,No.7/2005. Copenhagen: European
Environment Agency.
Emsley J (1980) The phosphorus cycle. In: Hutzinger O (ed.) The
Handbook of Environmental Chemistry: The Natural Environment
and the Biogeochemical Cycles, pp. 147–167. Heidelberg: Springer.
FAO (2006) FAOSTAT. Statistics Division, Food and Agriculture
Organization of the United Nations.
Filippelli GM (2002) The global phosphorus cycle. Reviews in Mineralogy
and Geochemistry 48: 391–425.
Grove TL (1992) Phosphorus, biogeochemistry. In: Nierenberg WA (ed.)
Encyclopedia of Earth System Science, pp. 579–587. London:
Academic Press.
Hart MR, Quin BF, and Nguyen ML (2004) Phosphorus runoff from
agricultural land and direct fertilizer effects: A review. Journal of
Environ Quality 33(6): 1954–1972.
Litke DW (1999) Review of phosphorus control measures in the United
States and their effects on water quality. Water-Resources
Investigations Report 99-4007. Denver, CO: US Geological Survey.
Liu Y (2005) Phosphorus Flows in China: Physical Profiles and
Environmental Regulation. PhD Thesis, Environmental Policy Group,
Wageningen University, Wageningen, The Netherlands.
Pimentel D (2006) Soil erosion: A food and environmental threat.
Environment, Development and Sustainability (8): 119–137.
Richey JE (1983) The phosphorus cycle. In: Bolin B and Cook RB (eds.)
The Major Biogeochemical Cycles and Their Interactions, pp. 51–56.
New York: Wiley.
Schlesinger WH (1991) Biogeochemistry: An Analysis of Global Change.
San Diego, CA: Academic Press.
Smil V (2000) Phosphorus in the environment: Natural flows and human
interferences. Annual Review of Energy and the Environment
25: 53–88.
Turner BL, Frossard E, and Baldwin DS (eds.) (2005) Organic
Phosphorus in the Environment. Wallingford, UK: CABI Publishing.
Valsami-Jones E (ed.) (2004) Integrated Environmental Technology
Series: Phosphorus in Environmental Technology: Principles and
Applications. Cornwall, UK: IWA Publishing.
Conclusion
Further Reading
compound is directly or indirectly broken down by light.
It may take place wherever light is absorbed by chromo-
phores. Photolysis may occur directly by the light-
absorbing chromophores or indirectly following the
release of reactive species, which are formed via

photosensitization. In the terrestrial environment (soil
surface, leaf surfaces, or translucent leaves), but particu-
larly in the aquatic habitats these processes are of major
ecological significance and subject to many studies.
Photolysis is an important determinant of nutrient cycling
and trace gas production. In addition to this, photolysis of
water is a central process of photosynthesis, but will be
considered elsewhere in this encyclopedia.
Basic Processes
In natural systems, the majority of chromophoric sub-
stances are comprised of humic substances (HS). These
are the brownish materials, which mainly derive from
plant debris, are leached into freshwater systems, and,
ultimately, into the oceans. Wherever they interact with
light, a series of chemical reactions occur. They absorb
both ultraviolet (UV) and visible light (VIS) in the wave-
length range (290) 300–600 nm. These chromophores are
activated many times a day. One calculation says that, for
instance, on a sunny day in Lake Greifensee (Switzerland),
each chromophore in the lake’s epilimnion is activated
270 times, that is, ten times or more per hour. The light-
absorption capacity is, in most cases, linked to the presence
of n-electrons and delocalized -electron systems
which are available from heteroatoms, aromatic rings,
or conjugated double bonds. These are the so-called
‘chromophores’. By energy absorption, the outermost elec-
tron orbitals gain energy, and electrons are elevated
from their lowest energy state (ground state, S0) to a
e– S1 FC
ISC
Electron ejection
T1
hν F IC
P IC
IC
S0
Figure 1 Energy-level diagram to illustrate processes after light absorption (h) in a chromophore: S0, ground state; S1, first-excited
singlet state; T1, first-excited triplet state. Relaxation processes of S1, Franck Condon relaxation (FC), fluorescence (F); internal
conversion (IC) (black), and intersystem crossing (ISC) to T1 which deactivates by phosphorescence (P), and internal conversion (IC)
(red). Photochemistry may occur both from S1 and T1 via electron transfer to suitable acceptors R and energy transfer to molecular
oxygen resulting in the formation of singlet oxygen (1O2).
Ecological Processes | Photolysis 2725
higher energy state (the excited state, denoted S1 or S).
Molecules in excited states are more reactive than their
ground states (S0).
In order to understand the principles of photolysis, an
energy-level diagram (Figure 1) can be used to illustrate
basic processes after light absorption in chromophores. In
organic molecules, two types of excited states following
absorption of UV/VIS-light (symbolized as h) are
known: short-lived singlet (S1) and long-lived triplet
states (T1). The latter cannot be populated directly.
Immediately after light absorption, excited singlet states
(S1) are formed, which are usually short-lived (nanose-
conds, 1010 s). Excited singlet states can deactivate
radiationless by internal conversion (IC), by a radiant
process called fluorescence (F), or can contribute to the
formation of triplet states (T1) via intersystem crossing
(ISC). Furthermore, electron transfer to suitable accep-
tors (R) may occur or even the ejection of free dissolved
electrons (eaqu). As a result, free radicals of chromophores
are formed which undergo further reactions.
Because of their comparably long lifetimes (micro- to
milliseconds, 106–103 s), triplet states account for the
majority of photochemical reactions. In addition to the
radiation-less (IC) and radiant deactivation to the ground
state, which is called phosphorescence (P), reactions like
electron and proton transfer may occur. These reactions
mainly depend on the redox potentials of the involved
redox pairs. When electrons are transferred to molecular
oxygen, the super oxide anion (O 2 ) is formed. In addition
to electron transfer reactions, energy transfer from T1 to
molecular oxygen is an important pathway, which is
1O
2
Energy transfer,
ΔE = 94 kJ mol–1
O2
R R–
Electron transfer
2726 Ecological Processes | Photolysis

followed by the formation of singlet oxygen (1O2) that is Table 1 Examples for production pathways and steady-state
considered as one of the most reactive species in nature. concentrations of ROS in natural waters
‘Direct photochemical’ reactions are immediate chemi- Reactive Steady-state
cal changes to the chromophore such as isomerization, bond oxygen concentration
cleavage, or degradation of larger into smaller molecules as species (ROS) (M) Production
a consequence of electron transfer reactions. In the presence 1
O2 2  1015–1012 Energy transfer
of oxygen, photochemical decarboxylation and formation of 
OH 1.5  1018–1016 Photolysis of HS
CO2 are observed inHS, which are usually enhanced by the 
OH 4  1017– Photolysis of NO3 from
presence of iron in HS complexes. 2  1016 H2O2 (photo-Fenton-
The different reaction products in Figure 2 are summar- reaction)

OH –103
ized as ‘reactive oxygen species’ (ROS). Super oxide anions, eaqu 1017 Charge transfer
for example, may lead to the formation of a whole cascade of 
O
2 1011–1010 Charge transfer via eaqu
other ROS (Figure 2). The individual ROS have very H2O2 102–3  107 From disproportion
different half-lives, from only a few microseconds, as for of?O2
1
O2, to well over 1 h as for H2O2. Depending on production
rates and lifetimes, average steady-state concentrations for
ROS from 1018 to 102 M are found in natural waters
(Table 1). oxygen consumption studies. Oxygen plays a pivotal role
Production and particularly gross ecological effects are as the initial scavenger of radicals that are produced during
summarized in Figure 3. The light-induced formation of irradiation of water. This leads to the generation of alkoxy
ROS is called sensitization, and the photoexcited molecule and peroxy radicals that decay to stable oxygenated
itself the sensitizer. Although the sensitizer molecule species.
returns without modification to the ground state, the In the following section, the environmental relevant
photogenerated reactive species can attack any suitable formation pathways of OH-radicals will be discussed
target in their neighborhood, including the sensitizer in more detail. Besides natural chromophoric organic com-
itself. Photolysis by ROS or other photosensitizers pounds, inorganic chromophores play a major role in
(TiO2) is referred to as ‘indirect photolysis’. In fact, photochemistry. This applies for nitrate-rich freshwaters
ROS account for the majority of photodegradation and for first-year sea ice with its algal flora, which may
reactions observed with HS. Any photosensitized reac- account for as much as 25% of the primary production in
tion involves the transfer of energy, hydrogen atoms, ice-covered Antarctic waters.
protons, or electrons. The importance of oxygen in the
hv
photooxidation of natural organic matter is evident from 2NO3– ! 2NO2 þ 2½O – 

1O
NOx– Humics 2 + Humics ?

hν hν

Humics + •OH ?
? Humics* O2 O2

O2 Humics+•

O2– + Humics ?

2H+ Men+

? Humics + H2O2 + Me(n – 1) + Men+ + •OH + OH–

Enzymatic decay

Figure 2 Summary of ecochemical sources and removal pathways of ROS (red) in natural waters including singlet oxygen (1O2),
superoxide anion (O 
2 ), hydrogen peroxide (H2O2), and hydroxyl radicals ( OH). M
nþ
and Me(n  1) denote metals in the nþ or n(1)þ
oxidation state, NOx the nitrate or nitrite anion, and ‘?’ unknown pathways. ‘humics’ ¼ (dissolved) chromophoric organic carbon.
These processes are put into a more ecological framework in Figure 3. Modified from Kieber DJ, Peake BM, Scully NM (2003) Reactive
oxygen species in aquatic ecosystems. In: Helbling EW and Zagarese H (eds.) UV Effects in Aquatic Organisms and Ecosystems, pp.
251–288. Cambridge: Royal Society of Chemistry – Reproduced by permission of The Royal Society of Chemistry (RSC) on behalf of the
European Society for Photobiology.

hν
NO3–
Aquatic
organisms
Reactive oxygen
species:
1O , •OH, H O
2 2 2
Ph oto
ph
ot ble
oo a
xy ch
da ing
tio
n,
Humics
Figure 3 Schematic presentation of photolytic production of reactive oxygen species (ROS) in an aquatic ecosystem. The major
process is their release from illuminated dissolved chromophoric organic carbon. The ROS may interact with a great variety of water
constituents, including organisms and dissolved organic compounds. The interaction of ROS with dissolved organic compounds leads
to the well-known process of photobleaching.
The produced oxygen radical anion may react with water
to generate the reactive OH radical:
½O –  þ H2 O ! OH þ OH –
The production of OH-radicals transforms the habitats into
(strongly) oxidizing media, and the organisms there must
have developed an effective mechanism to protect them-
selves from this external oxidative stress. Furthermore, OH
may be also formed via direct photolysis of HS through an
oxygen-independent mechanism which probably involves
quinones as potential sources. OH-radicals are probably the
most important driving force for the oxidation of organic
compounds in sunlit ice, snow, and water.
Another important pathway of OH-radical formation
is the classical Fenton reaction in which H2O2 is reduced
and OH produced:
FeðIIÞ þ H2 O2 ! FeðIIIÞ þ OH – þ OH
When this reaction runs with light energy, where
H2O2 comes from the photolysis of chromophoric organic
substances, it is known as a photo-Fenton reaction.
Simultaneous OH formation along with the production
of H2O2 and Fe(II) provide evidence of photo-Fenton-
produced OH. This is often the case in natural,
Ecological Processes | Photolysis 2727
NO + OH– + •OH
NO2–
n,
tio
da hing
y
x c
oo a
ot ble
Ph oto
ph
particularly highly colored, iron-rich, acidic waters and
may lead to carbon limitation (see below). Once formed,
OH-radicals are unstable and react with many organic or
inorganic species at rates near diffusion limit, either
through an addition or H-abstraction pathway.
The impact of environmental factors on the ROS-
formation by humic matter will be demonstrated with 1O2.
Like OH-radicals, 1O2 is very reactive towards a wide
range of electron-rich organic compounds such as alkenes,
sulfides, phenols, or HS (photobleaching). With 1O2-
formation, several interesting differences between terres-
trial and aquatic chromophoric dissolved organic
compounds emerge: Terrestrial isolates tend to possess
higher quantum yields of 1O2-formation than those from
freshwater, meaning that terrestrial material is more
reactive. Furthermore, there is seasonality in the photoreac-
tivity, since spring samples from freshwater habitats release
more 1O2 than autumn samples do (Figure 4). For the
special case of 1O2, we know that aquatic samples collected
in spring apparently suffered less from the impact of solar
irradiation than samples collected in the fall because they are
exposed as long as they remain in the photic water column.
In contrast, chromophoric organic carbon compounds in
soils and peats, become photolyzed only at the surface.
2728 Ecological Processes | Photolysis
1.2
1.0
0.8
ΦΔ (%)
0.6
0.4
0.2
0 0
Bir Skj Val Svart Hiet
Figure 4 Seasonal variations in singlet oxygen quantum yields
(
, mean  accuracy 12.5%) upon excitation at 480 nm of humic
substances from five Scandinavian sampling sites. Gray color
indicates autumn 1999, and black indicates spring 2000. Bir,
Birkenes; Skj, Skjervatsjern; Val, Valkea–Kotinen; Svart,
Svartberget; Hiet, Hietajärvi. Reproduced from Paul A, Hackbarth S,
Vogt RD, et al. (2004) Photogeneration of singlet oxygen by humic
substances: Comparison of humic substances of aquatic and
terrestrial origin. Photochemical and Photobiological Sciences
3: 273–280 – Reproduced by permission of The Royal Society of
Chemistry (RSC) on behalf of The European Society for
Photobiology.
Combining the availability of underwater light quali-
ties and quantities with absorption coefficients and
quantum yields of 1O2 production (
), it becomes evi-
dent (Figure 5) that particularly the blue light in the
water column is responsible for the production of 1O2.
Although UV irradiation possesses higher 
values, it is
absorbed in the top layers of the water column and does
not significantly contribute to the photolytic capacity of
the whole water column.
Effects of Photolysis
Photochemical processes with ecological relevance are
well documented for marine and freshwater systems.
They can influence many aspects of carbon cycling in
these systems and
• decrease the average molecular weight of the chromo-
phoric organic substances;
• change the optical properties of the water as a result of
the changes in chromophoric organic substances;
• release a complex mixture of ROS, which can hurt organ-
isms and initiate indirect phototransformation reactions;
• produce oxidized C compounds such as CO, CO , or
short-chain fatty acids, which provide energy and car-
2 aquatic systems is probably decreasing worldwide. As a
bon to heterotrophic processes;
• release P- and N-rich products: phosphate ions, amino
acids, dissolved primary amines, and finally ammonia,
NHþ 4.
(mol cm–2 s–1 nm–1) per mg l–1 HS
3
1O production rate × 1011
2
1
2
350 400 450 500 550
λ (nm)
Figure 5 Wavelength dependence 1O2 production rates for
chromophoric dissolved organic carbon compounds in a whole
water column, exemplified for a midday, summer, sunlight at
latitude 40 N. &, Hietajärvi fall natural organic matter; , 
Suwannee River natural organic matter; N , Suwannee River
humic acid; &, Birkenes spring natural organic matter; , 
Birkenes fall natural organic matter; $, Svartberget spring
natural organic matter; *, peat humic acid; &, soil fulvic acid.
Reproduced from Paul A, Hackbarth S, Vogt RD, et al. (2004)
Photogeneration of singlet oxygen by humic substances:
Comparison of humic substances of aquatic and terrestrial origin.
Photochemical and Photobiological Sciences 3: 273–280 –
Reproduced by permission of The Royal Society of Chemistry
(RSC) on behalf of the European Society for Photobiology.
Photobleaching and Photomineralization of
Chromophoric Dissolved Organic Carbon
During summer months, photolysis may lead to a decrease
in the dissolved and colloidal chromophoric substances
(photobleaching) particularly of stagnant systems with no
significant influx from the terrestrial surrounding. Humic-
rich lakes and bogs lose much of their visible brown color.
Photobleaching produces a large proportion of no longer
chromophoric substances, but aliphatic carbon (and to a
lesser degree CO2); the aromatic ring structures are opened.
Photobleaching is accompanied with oxygen consump-
tion. Several balance studies show that the photolytic
H2O2 production is linearly related to the photobleaching
and may account for about half of the observed O2 uptake.
The other half may be ascribed to organically mediated
oxygen reductions. These may include formation of
organic peroxides and their decomposition products.
Due to the degradation of the global ozone layer in the
troposphere, and the consequent increase in UV-B radia-
tion, the proportion of chromophoric organic carbon in
consequence, one natural UV shield declines, the subse-
quent UV-penetration depth increases exponentially, and
energy transmission changes drastically. The most vul-
nerable systems are high mountain lakes above the tree
line, particularly those with catchments dominated by
 Ecological Processes | Photolysis 2729

bare rock and without higher vegetation. In these lakes,
photobleaching is a serious problem, particularly in shal-
low systems in which the plankton cannot avoid UV
radiation through vertical migration.
Effects on Nutrient Cycles, Such as Phosphorus,
Iron, and Nitrogen
In humic-rich freshwaters, phosphorus is absorbed by
high-molecular-weight HS fractions. Photolysis of these
complexes leads to a slow release of P as one major
regeneration mechanism of phosphorus within the illu-
minated water column (Figure 6). This release is based
on the photoreduction of Fe(III) in the presence of dis-
solved chromophoric organic carbon compounds
(Figure 7). The few available budget calculations demon-
strate that the photolytic regeneration pathway of
bioavailable P supports a medium production.
For a long time, it has been considered unlikely that
chromophoric organic substances can be N sources for the
microbial web. However, recent studies show that expo-
sure of chromophoric organic substances to sunlight forces
the release of nitrogen-rich compounds of high bioavail-
ability. These compounds include NHþ 4 , which is the most
effectively released, and amino acids (Figure 6).
The photoproduction of NHþ 4 and organic N-com-
pounds depends on dissolved organic N contents, rather
than aromaticity of the organic carbon. At least 20 organic
N-compounds were identified upon radiation of water sam-
ples containing HS. Among the amino acids identified are
alanine, asparagine, citrulline, glutamic acid, histidine, nor-
valine, and serine. Free amino acids are subsequently
subjected to further breakdown to NHþ 4 due to strong UV
radiation and long-term exposure – which may be one
mechanistic reason for the frequently observed low concen-
trations of free amino acids. Terrestrial chromophoric
organic carbon and its photolytic degradation products,
including N compounds, are also subject to long-range
transport; they can not only be found in freshwater systems,
but also far off the shore in oceans and support phytoplank-
ton growth up to several hundred kilometers from the river
delta.
Effect on Carbon Cycle
Organic carbon
Classical Swedish studies some 70 years ago, already
noticed that oxygen is undersaturated in the epilimnion
of humic-rich lakes. Approximately 40 years later, it has
been suggested that an increased degradation of dissolved

hν

Photosynthesis

Photoreduction of Fe(III),
release of P;
Primary
photolyt. release of NH4+, producers

Mixotrophy

Release of organic acids,

amines, amino acids
Humics

Bacteria

Figure 6 Photolysis of chromophoric organic substances as source of inorganic nutrients in aquatic ecosystems (particularly
phosphorus and nitrogen) and organic substrates (small organic acids, amino acids, amines), which sustain net-heterotrophy in
noneutrophicated systems. Heterotrophic production is indicated by black, and photoautotrophic by gray arrows. h is solar energy.
2730 Ecological Processes | Photolysis
Photoreduction Fe(III)
Photooxidation Humics
Figure 7 In the epilimnion of very acidic lakes, a major source of Fe(II) is photoreduction, which requires dissolved organic carbon and
simultaneously oxidizes it. This photooxidation is the main reason for very low concentrations of dissolved organic carbon in the very
acidic Lausatian postmining lakes (Germany). h is solar energy. The ecological consequences are outlined in the text.
organic substances is the potential cause for this under-
saturation. This increased degradation may be facilitated,
when chromophoric organic substances are split by UV
radiation and the photodegradation products become
more easily available to microorganisms.
The increased bioavailability is associated with signifi-
cant increases of bacterial numbers and biovolume of the
bacteria. In humic lakes, the direct coupling of photoche-
mical production to biological use of organic C accounts for
the comparatively constant activity of bacteria that is inde-
pendent of phytoplankton primary production. The
following fatty acids and further organic compounds are
released from sunlit chromophoric organic substances: acet-
aldehyde, acetate, acetone, citrate, formaldehyde, formiate,
glyoxal, glyoxalate, levulinate, malonate, methylglyoxal,
oxalate, propanal, and pyruvate. Many, but not all (such as
oxalate), of these compounds are valuable substrates for
microbial growth.
In nutrient-poor waters, the contribution of bacteria
to total planktonic respiration ranges up to as much as
90%. This applies even to some regions of the oceans.
These systems are net heterotrophic, where planktonic
communities respire more organic C than they pro-
duce by photosynthesis. The organic carbon derives
from the surrounding terrestrial environment and con-
tinents. Photolysis of chromophoric organic carbon is
the process which makes the autochthonous carbon
available to microorganisms, which form one major
basis of the aquatic food webs. For boreal freshwater
systems, there is an estimate that only 2% of terrestrial
hν
Fe(II)
(H+)
Humics + CO2
oxidized
production suffices to sustain net-heterotrophy in the
lakes.
A graphical summary of photolytic pathways for the
provision of inorganic and organic nutrients is given in
Figure 6.
Inorganic carbon
Photolytic processes also release inorganic carbon from
chromophoric organic substances as mentioned above. In
iron-rich, acidic lakes, the photo-Fenton pathway of CO2
and CO release prevails over the release of short-chained
organic compounds. This efficient shunting of bioavail-
able organic photoproducts to dissolved inorganic carbon
is most expressed in postmining lakes, which are strongly
acidified from pyrite (FeS2) weathering. In these lakes, for
instance in Lusatia, Germany, with pH-values between
2.0 and 3.0 and high iron contents, organic carbon com-
pounds are oxidized (eventually to carbon dioxide, CO2)
via the photo-Fenton reduction of Fe(III). Due to the very
low pH, CO2 escapes from the water column, leading to
limitation of inorganic carbon for primary production.
The processes are summarized in Figure 7. Primary
producers have developed interesting strategies to over-
come this limitation (see Acidification).
Effects on Organisms
Photolysis of various chromophoric dissolved compounds
results in the production of ROS, of which H2O2 is long-
lived and may attack organisms. It easily penetrates

biomembranes and, hence, contributes to the internal oxi-
dative stress, which, in general, may be adverse to the
exposed organisms. For instance, those leachates from aqua-
tic macrophytes, which release the highest concentrations
of H2O2, support microbial growth least. In addition to this
information, the predominantly adverse effect of internal
oxidative stresses, for instance from UV-irradiation or pro-
cessing of xenobiotic chemicals, is well documented and
comprises induction and modulation of stress response pro-
teins and enzymes, reduction of photosynthetic activity, and
increased membrane (lipid) peroxidation. However, the
oxidative stress as a potential ecological driving force has
not yet gained the attention it deserves.
Photolysis as Ecological Elimination Pathway
of (Algal) Toxins and Xenobiotics
Photolysis as ecological elimination (‘photofate’ of a chemi-
cal compound) may occur in water columns, on the surfaces
of moist soils and plants, and in translucent plant tissues
(‘phytophotolysis’). Interestingly, photolysis is the only
effective elimination pathway for many superlipophilic,
most troublesome chemicals, such as polychlorinated diox-
ins, furans, or biphenyls, which are well known to resist
microbial degradation.
In general, there are two pathways of degradation
of a xenobiotic or allelochemical compound: direct and
indirect photolysis. If a compound itself may be subject
to direct photolysis, naturally occurring chromophores
may compete with this compound for photons, thus,
reducing the efficiency of direct photolytic degradation.
Furthermore, the removal efficiency of xenobiotics in
soils, sediments, and water columns may be significantly
accelerated in the presence of Fe(III) and elevated chromo-
phoric organic carbon (HS) contents, due to photo-
Fenton-type processes described above. Generally, the
photodegradation process in soil is faster than in water,
because the concentrations of all reactants are much
higher than in the aquatic systems.
Algal toxins
Several studies show that algal toxins, such as domoic acids
(DAs) or cyanotoxins (particularly microcystins), may be
subject to photolysis. In the marine environment, the plank-
tonic diatom Pseudo-nitzschia spp. is a known producer of
DA, a tricarboxylic amino acid with neurotoxic properties;
its occurrence has been linked to fish kills, poisoning of
marine mammals and birds, and human poisoning through
ingestion of contaminated shellfish and finfish. DA may be
photodegraded directly as well as indirectly. The direct
photolysis degrades this potent toxin on a timescale of
days. However, Fe(III) and dissolved organic matter are
significant promoters of DA photodegradation – indicating
that photo-Fenton reactions are involved.
Ecological Processes | Photolysis 2731
Microcystins, potent freshwater toxins, are stable in
deionized water when exposed to natural sunlight.
However, they can indirectly be photodegraded, when
extracted algal pigments or humic material, serving as
photosensitizers, are added to the irradiation solutions.
With HS, the aromaticity was the most powerful mole-
cular predictor of the indirect photodegradation. Since its
rates are yet comparably low, this purification process
alone cannot explain the frequently observed low persis-
tence – neither does the microbial decomposition alone.
Hence, the combination of photolytic cleavage and
microbial decomposition is possibly the way that micro-
cystins disappear from open water. It means that indirect
photolysis may lead to products which microorganisms
can rapidly decompose and utilize the energy content.
Xenobiotics in water and soil surfaces
In many, but not all cases, even the xenobiotic com-
pounds, which have the potential to undergo direct
photolysis because they absorb solar light, are degraded
faster, when sensitizers are present in the system. One of
many examples is given in Table 1. Although the direct
photolysis experiments were carried out with monochro-
matic UV-B light (300 nm), Table 2 shows that the direct
plus indirect photolysis with solar light (low UV-B pro-
portion) in water with natural chromophoric substances
is as efficient as or even more efficient than the direct
UV-B-induced photolysis. In general, direct photolysis
may be slow, because either the pollutants poorly absorb
solar light (ethiofencarb, thiobencarb, propiconazole,
4-chloro-2methylphenol) or they are poorly photoreac-
tive (acifluorfen, nitrobenzene).
When studies on photolytic degradation were com-
bined with toxicity evaluations of both the educts and
products, it has often been shown that the photolytic
products were of higher toxicity than the educts. One
prominent example is the common fungicide vinclozo-
lin, from which three major photodegradation products
Table 2 Half-lives of selected pollutants at 300 nm in pure and
natural water (with natural concentrations of chromophoric
dissolved compounds), when exposed to solar light
Half-lives 1=2 (h)
Pure water Natural water
Propiconazole 85  10 60  10
Nitrobenzene 120  15 100  15
Acifluorfen 133  15 88  10
Ethiofencarb 320  30 40  5
Thiobencarb 320  30 320  30
4-Chloro-2-methylphenol 320  30 18  4
From Vialaton D and Richard C (2002) Phototransformation of aromatic
pollutants in solar light: Photolysis versus photosensitized reactions under
natural water conditions. Aquatic Sciences 64: 207–215.
2732 Ecological Processes | Photolysis
are significantly more toxic than the parent fungicide
itself.
In aquatic, mainly marine systems, photolysis plays
also a fundamental role after oil spills. The fate and effects
of the oil constituents after a spill are affected by solar
radiation through the action of photooxidation and so-
called phototoxicity. Photooxidation is the important pro-
cess in the weathering of oil and produces a variety of
oxidized compounds, including aliphatic and aromatic
ketones, aldehydes, carboxylic acids, fatty acids, esters,
epoxides, sulfoxides, sulfones, phenols, anhydrides, qui-
nones, and aliphatic and aromatic alcohols. Some of these
compounds contribute to the toxicity toward marine biota
observed after an oil spill. Similar to the vinclozolin
example, many photolytic products may exhibit elevated
toxicities to the marine biota as compared to the educts.
However in oil spills, an additional major pathway of
toxicity has been found, the phototoxicity. This term
comprises that the toxicity of, for instance, certain poly-
cyclic aromatic hydrocarbons (PAHs) greatly enhances
when the organisms are exposed to both PAHs and sun-
light. The mechanisms behind this include absorbance of
solar radiation by the PAH which produces a free radical,
and this, in turn, reacts with oxygen to produce ROS.
Petroleum constituents, particularly anthracene, fluor-
anthene, pyrene, and dibenzothiophene, have been
shown to be phototoxic to a variety of vertebrate and
invertebrate aquatic life in both sediment and water.
Conclusion
Photolysis is an important process for the turnover of
colored, photolabile compounds in ecosystems. In aquatic
systems, this has a major impact on the penetration depth
of damaging UV-A and UV-B irradiation and on the other
hand, on the penetration of photosynthetic active radia-
tion and control the vertical distribution of planktonic
primary producers.
Due to photosensitization processes (indirect photoly-
sis) also compounds which do not absorb solar energy
themselves are subject to photolytic degradation. This is
partly important for the degradation of xenobiotic com-
pounds of both anthropogenic and natural origin such as
oil spills and algal toxins like microcystins. Although
photolysis does not lead to complete mineralization of
most organic compounds, in many cases products are
formed, which are substrates for heterotrophic bacteria.
Photolysis, therefore, must be considered as the initial
step of cleavage.
Furthermore, photolysis of dissolved organic matter
plays an important role in the global cycle of carbon,
and is involved in the binding and release of nutrients
such as P and N. Photolysis of humic matter can alter the
mode of organic complexion, for example, elemental
toxicity of heavy metals can be modulated. Due to the
low quantum yields and short lifetimes of ROS formed by
humic matter in aquatic ecosystems, adverse effects on
organisms are restricted to the upper photic layer and,
probably more important, to the very proximity of the
organism.
See also: Acidification; Biodegradation.
Further Reading
Andrews SS, Caron S, and Zafiriou OC (2000) Photochemical oxygen
consumption in marine waters: A major sink for colored dissolved
organic matter? Limnology and Oceanography 45: 267–277.
Bouillon RC, Knierim TL, Kieber RJ, Skrabal SA, and Wright JLC (2006)
Photodegradation of the algal toxin domoic acid in natural water
matrices. Limnology and Oceanography 51: 321–330.
Jones RI (2005) Limnology of humic waters: Special theme or universal
framework? Verhandlungen der Internationalen Vereinigung für
theoretische und angewandte Limnologie 29: 51–60.
Just CL and Schnoor JL (2004) Phytophotolysis of hexahydro-1,3,5-
trinitro-1,3,5-triazine (RDX) in leaves of reed canary grass.
Environmental Science and Technology 38: 290–295.
Kieber DJ, Peake BM, and Scully NM (2003) Reactive oxygen species in
aquatic ecosystems. In: Helbling EW and Zagarese H (eds.) UV
Effects in Aquatic Organisms and Ecosystems, pp. 251–288.
Cambridge: Royal Society of Chemistry.
Lam MW, Tantuco K, and Mabury SA (2003) Photofate: A new approach
in accounting for the contribution of indirect photolysis of pesticides
and pharmaceuticals in surface waters. Environmental Science and
Technology 37: 899–907.
Lee RF (2003) Photooxidation and phototoxicity of crude and refined
oils. Spill Science and Technology Bulletin 8: 157–162.
Paul A, Hackbarth S, Vogt RD, et al. (2004) Photogeneration of singlet
oxygen by humic substances: Comparison of humic substances of
aquatic and terrestrial origin. Photochemical and Photobiological
Sciences 3: 273–280.
Schwarzenbach RP, Gschwend PM, and Imboden DM (1993).
Environmental Organic Chemistry. New York: Wiley.
Scully NM, Cooper WJ, and Tranvik LJ (2003) Photochemical effects on
microbial activity in natural waters: The interaction of reactive oxygen
species and dissolved organic carbon. FEMS Microbiology Ecology
46: 353–357.
Steinberg CEW (2003) Ecology of Humic Substances in Freshwaters.
Determinants from Geochemistry to Ecological Niches. Berlin:
Springer.
Tranvik LJ (1990) Bacterioplankton growth on fractions of dissolved
organic carbon of different molecular weights from humic and clear
waters. Applied and Environmental Microbiology 56: 1672–1677.
Vialaton D and Richard C (2002) Phototransformation of aromatic
pollutants in solar light: Photolysis versus photosensitized reactions
under natural water conditions. Aquatic Sciences 64: 207–215.
Voelker BM, Morel FMM, and Sulzberger B (1997) Iron redox cycling in
surface waters: Effects of humic substances and light. Environmental
Science and Technology 31: 1004–1011.
Welker M and Steinberg CEW (2000) Rates of humic substances
photosensitized degradation of microcystin-LR in natural waters.
Environmental Science and Technology 34: 3415–3419.
Zepp RG, Hoigné J, and Bader H (1987). Nitrate-induced
photooxidation of trace organic chemicals in water. Environmental
Science and Technology 21: 443–450.
Zepp RGW, Lee N, Baughman GL, and Hollis RC (1977). Singlet oxygen
in natural waters. Nature 267: 421–423.