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ENVIRONMENTAL ANALYSIS 550

CHIMIA 2003, 57, No. 9

Chimia 57 (2003) 550–555


© Schweizerische Chemische Gesellschaft
ISSN 0009–4293

Biogeochemistry of Aromatic
Surfactants in Microtidal Estuaries
Marijan Ahel* and Senka Terzic

Abstract: This paper summarizes several studies on input, distribution, and fate of two different types
of aromatic surfactants, the anionic linear alkylbenzene sulphonates (LAS) and nonionic alkylphenol
polyethoxylates (APnEO), in a karstic estuary characterized by sharp salinity gradients. A combination of
reversed-phase and normal-phase HPLC analysis followed by spectrofluorimetric detection allowed detailed
characterization of homologue and oligomer compositions of aromatic surfactants in wastewater and
estuarine waters. The distribution patterns of homologues and/or oligomers in the wastewater plume reveal
a significant alteration of the original composition of both surfactants by biotransformation and physico-
chemical partitioning. The vertical distribution of surfactant residues in the estuarine water column is
characterized by pronounced maxima at the air–brackish water and brackish water–sea water interface. The
brackish water–sea water interface is a very efficient barrier, which prevents spreading of surfactants into the
deeper layers. In addition, the interface seems to be a site of high biological activity, including biotrans-
formation of surfactant residues. As a consequence, this layer can contain enhanced levels of lipophilic
metabolites of APnEO. Biotransformation is the main mechanism for the removal of both surfactant classes
from the water column. However, our studies suggest that a significant percentage of surfactant residues
discharged into the stratified estuaries reaches the coastal sea due to the incomplete removal in the estuary.
This situation is a consequence of a rather fast flushing of the brackish layer and a very slow biotransfor-
mation kinetics in the saline layer, especially in the winter period.

Keywords: Alkylphenol polyethoxylates · Biotransformation · Estuaries ·


Linear alkylbenzene sulphonates (LAS) · Wastewater

Introduction is a great deal of structural similarity be- usually starts at the hydrophilic part of the
tween LAS and APnEO in the hydrophobic molecule, resulting in a rather unique meta-
Aromatic surfactants, including linear parts of their molecules, both containing bolic pathway, which is characterized by
alkylbenzene sulphonates (LAS) and branched long-chain alkylbenzenes, while the formation of various stable intermedi-
alkylphenol polyethoxylates (APnEO) with the hydrophilic parts are rather different ates [2]. Some of these metabolites are
estimated annual worldwide production (Fig. 1). The solubility of LAS in water is more lipophilic and therefore more toxic to
rates of about 3 × 106 and 6 × 105 tons, re- assured by a strongly polar sulphonic group aquatic life than the parent molecules [4]. In
spectively, belong to the most popular sur- substituted in para position, while the solu- the last decade, interest in ecotoxicological
factant classes. Due to their widespread use bility of APnEO depends on the length of effects of these lipophilic metabolites has
in such high volumes and considerable tox- the polyethoxylate chain. Such structural dramatically increased because of their
icity to aquatic life, LAS and APnEO features determine similarities and differ- proven endocrine-disrupting potential
should be considered potentially important ences in abiotic and biological processes, [5][6]. The most recent studies have shown
environmental contaminants [1][2]. There which govern the environmental behavior that APnEO intermediates with shorter EO-
and fate of LAS and APnEO. chains are further transformed by oxidation
It was shown in model laboratory ex- of the highly branched alkyl-chain, yielding
periments as well as in sewage treatment a suite of more polar metabolites, which al-
plants and various types of ambient waters so exhibit significant persistence [7][8].
that both LAS and APnEO exhibit a com- Owing to their hydrophobic moiety,
plex metabolic behavior, yielding a variety both LAS and APnEO show a significant
*Correspondence: Dr. M. Ahel of relatively stable metabolic products. The affinity for suspended particles, which re-
Center for Marine and Environmental Research
Rudjer Boskovic Institute biotransformation of LAS seems to be sim- sults in a widespread presence of surfactant
Bijenicka 54 pler, resulting in more polar intermediates residues in aquatic sediments and biota [9].
HR-10002 Zagreb, Croatia formed by successive β- and ω-oxidations The adsorption onto sediment and bio-
Tel.: + 385 1 4561 042
Fax: + 385 1 4680 242 of the alkyl chain [3]. In contrast, biotrans- accumulation are particularly pronounced
E-Mail: ahel@rudjer.irb.hr formation of APnEO is more complex and for the lipophilic degradation products of
ENVIRONMENTAL ANALYSIS 551
CHIMIA 2003, 57, No. 9

Fig. 1. Structures and acronyms of linear alkyl-


LINEAR ALKYLBENZENE ALKYLPHENOL benzene sulphonates and alkylphenol poly-
SULPHONATES POLYETHOXYLATES ethoxylates
(LAS) (APnEO)

SO3 O(CH2CH2O)nCH2CH2OH
Homologues: R = C9 – C14 R = C8 , C9
Isomers: 4–6 positional more than 10 differently branched
isomers/homologue isomers/oligomer
Oligomers: – n = 3–20
World production 3000 000 t/year 600 000 t/year

APnEO such as nonylphenol (NP), nonyl- environmental behavior of chemical con- which contains an organic film formed
phenol monoethoxylate (NP1EO), and no- stituents entering the system [25][26]. As a mainly by accumulation of plankton-de-
nylphenol diethoxylate (NP2EO). consequence, even rather small estuarine rived organic matter [26]. The depth of the
Coastal and estuarine waters receive sections usually cover wide ranges of the halocline fluctuates seasonally, depending
large quantities of aromatic surfactants, ei- key environmental variables and represent on the river flow, between 0.2 and 6 m.
ther directly from municipal wastewaters or therefore ideal natural laboratories to study It was shown that such stratified estuar-
indirectly from polluted rivers. In the past the physical chemistry and bioreactivity of ies are particularly suitable for studies of
decade, there have been an increasing num- pollutants under ambient conditions. environmental behavior of different con-
ber of reports dealing with the behavior and The studies presented in this paper were stituents since the entire range of estuarine
fate of LAS and APnEO in coastal and es- carried out in the Krka River estuary situat- master variables can be accessed at one sin-
tuarine environments [10–16]. In estuaries, ed in the middle part of the eastern Adriatic gle station, which significantly simplifies
most of the published data deal with well- coast. The total length of the estuary is the required sampling strategy. On the oth-
mixed macrotidal estuaries, while the stud- about 30 km and the depth varies from a er hand, the Krka River estuary shows a
ies in stratified estuaries, characteristic few meters, immediately below the water- conspicuous change of anthropogenic pres-
of the Mediterranean Sea, are relatively falls, to 40 meters at the sea-end of the es- sure along its longitudinal profile. The
scarce. There are two major motivations to tuary (Sibenik Harbor). Owing to its unique largest part of the estuary is a pristine envi-
study behavior and fate of surfactants in es- hydrographic features, the Krka River estu- ronment situated within the borders of a
tuarine environments. Many of the world ary belongs to the most intensively investi- National Park area with only few smaller
estuaries are densely populated and repre- gated estuaries of the Mediterranean Sea settlements and very limited industrial ac-
sent areas of intensive and often mutually with a special emphasis on the processes tivities, while the main source of anthro-
conflicting anthropogenic activities includ- that occur at the estuarine boundaries. The pogenic input are wastewaters of the city of
ing fishery, industry, navigation and Krka River estuary is a typical karstic estu- Sibenik (40,000 inhabitants), which enter
tourism. On the other hand, estuaries are ary characterized by low terrigenous input the estuary in its lower part, i.e. in the area
well known as important regions of biolog- of suspended materials and conspicuous of Sibenik Harbor. Municipal and industri-
ical diversity and as such are potentially vertical salinity gradients, resulting in a al wastewaters are discharged into the estu-
highly vulnerable to environmental stress very stable stratification throughout the ary without pretreatment through several
imposed by different human activities, in- year (Fig. 2). The upper, freshwater, and outlets along the northern shoreline of the
cluding those characterized by extensive lower, seawater layers are separated by a Sibenik Harbor basin.
introduction of man-made chemicals. visible interface situated at the halocline,
This paper summarizes our studies
[17–24] conducted in the estuary of the 0 10 20 30 40 0 10 20 30 40
0 0
Krka River, Croatia, and gives a compari-
son of environmental behavior and fate of
5 5
LAS and APnEO in this unique system
a) winter b) summer
characterized by sharp salinity gradients.
Depth [m]

Depth [m]

10 10

15 15
Stratified Estuaries as Natural
Laboratories
20 Temp. 20 Temp.
Sal Sal
One of the main features of estuarine 25 25
environments are pronounced gradients of
physicochemical properties, notably salini- Fig. 2. Typical vertical profiles of temperature [°C] and salinity [PSU] in the water column of the
ty and turbidity, which strongly influence Krka River estuary in winter and summer [27]
ENVIRONMENTAL ANALYSIS 552
CHIMIA 2003, 57, No. 9

Since 1989, several sampling cam- Characterization of Surfactant Input situation can be explained by decreased wa-
paigns were performed, comprising sam- ter solubilities [32] and, consequently, in-
pling of wastewaters and the estuarine wa- The input of aromatic surfactants into creased lipophilicities [33] of the lower
ter column. In order to determine the spread the Sibenik Harbor was determined by ana- oligomers. The observed change in the
of the wastewater plume into the Sibenik lyzing wastewaters from all major outlets oligomer distribution patterns depends on
Harbor, water samples were collected at of the city of Sibenik [22][23]. The homo- the concentration of suspended solids in the
different distances from the major sewage logue- and oligomer-compositions of LAS wastewater sample. The typical maximum
outlets at depths characteristic of brackish and APnEO (Fig. 3) found in wastewater of oligomer distribution in the dissolved
(0.5 m) and saline (6 m) layers. A more extracts revealed the presence of common phase displays a shift of the maximum
detailed sampling on the vertical profile of commercial mixtures of the target com- towards higher oligomers (NP11EO–
the water column, with special emphasis pounds, which have been partially changed NP12EO). It should be noted that the
on the brackish water–seawater interface, due to the physico-chemical partitioning oligomer distributions presented in Fig. 3
was performed at the station E4A, which is and biotransformation in the sewer system. show only the distribution of higher
situated in the middle part of the Sibenik It should be stressed that a significant per- oligomers (nEO> 3), which are considered
Harbor. centage of LAS (11–59%) and NPnEO parent compounds [34]. In addition to these
(6–60%) entering Sibenik Harbor via mu- parent oligomers, their lipophilic metabo-
nicipal wastewaters is bound to sewage par- lites, including NP, NP1EO and NP2EO,
Methods ticles. This fact markedly influences their were detected in all samples in lower but
fate in the estuary. The average chain length significant concentrations (typically below
LAS and NPnEO, including their stable of the total LAS in the wastewater samples 10 µg/l of the individual metabolite). Their
metabolic products, were determined using of the city of Sibenik was 11.47 ± 0.17. The over-proportional presence in the waste-
an approach based on HPLC separation fol- more lipophilic higher homologues were water extracts as compared to that in com-
lowed by spectrofluorimetric detection, enriched in the particulate- and depleted in mercial surfactant mixtures indicated an
which involved both reversed phase (sepa- the dissolved phase, as indicated by a sig- ongoing change of the original NPnEO
ration of homologues and isomers) and nor- nificantly altered corresponding chain composition by biotransformation. Due to a
mal phase (separation of oligomers) sys- lengths of 11.93 ± 0.14 and 11.2 ± 0.14. The rather short sewer system (residence time is
tems [28–31]. High-resolution gas chro- determination of aromatic nonionic surfac- estimated to be less than 1 h), only a minor
matography/mass spectrometry (GC/MS) tants in wastewater extracts by reversed- part of the parent compounds is biotrans-
and liquid chromatography/tandem mass phase HPLC [29] indicated a strong pre- formed and the contribution of the
spectrometry (LC/MS/MS) were used for dominance of nonyl homologues, while the lipophilic metabolites to the total concen-
identification and confirmation purposes. presence of octyl homologues was insignif- tration of nonylphenolic compounds does
In order to investigate the partitioning be- icant (<5%). The oligomer composition of not exceed 5%.
havior of surfactant residues, water samples NPnEO in the total wastewater samples dis- The characteristics of physicochemical
were previously filtered through glass fiber plays a great deal of similarity to those partitioning and biotransformation process-
filters (GF/F) and the dissolved and partic- commercial mixtures that are commonly es described above do not depend on the
ulate fractions were further processed sepa- used in detergent formulations, which are total concentration of LAS and NPnEO and
rately. Briefly, the dissolved fraction of characterized by an oligomer distribution are applicable as a general feature describ-
both classes of aromatic surfactants was en- maximum at NP10EO. ing the input composition of target com-
riched from wastewater and estuarine wa- The comparison of distribution patterns pounds. However, it is interesting to note
ters using C18 solid-phase extraction [10], in the dissolved and particulate phases that the concentration of aromatic sur-
while the particulate fraction was extracted shows a pronounced selectivity in the parti- factants varied significantly during the
using an ultrasonically enhanced extrac- tioning of individual oligomers. The period covered by these investigations
tion. Lipophilic metabolites of NPnEO (NP, oligomer composition in the particulate (1989–2003). In the late eighties, the
NP1EO and NP2EO) were determined by phase is characterized by an enhanced average levels of the total LAS and NPnEO
an alternative enrichment procedure, using abundance of lower oligomers, resulting in were rather similar (approximately
a continuous steam distillation/solvent ex- oligomer distributions that show typical 0.5 mg/l), suggesting an extensive usage of
traction in a special apparatus, followed by maxima between NP6EO–NP9EO. This NPnEO in that period. Assuming an aver-
a direct analysis of the cyclohexane extracts
by normal phase HPLC [28].
In addition to the determination of aro- 600 90
Dissolved Dissolved
matic surfactant residues in the estuary, the Total
80
Particulate
500
die-away biodegradation experiments were a) LAS
Particulate 70 Total
b) NPnEO
performed to assess the behavior of and fate 400 60
C / [mg/m3]
C / [mg/m3]

of the target compounds [18][24]. The ex- 50


300
periments were performed using autochtho- 40

nous microbial populations, which were 200 30

sampled in different estuarine compart- 100


20
ments as well as in different seasons. The 10
biodegradation media were always kept at 0 0
C10 C11 C12 C13
temperatures identical to those found in the Homologue
0 5 10 15 20
No. of EO units
ambient water at the time of sampling.
Fig. 3. Distribution of (a) homologues of linear alkylbenzene sulphonates (LAS) and (b) oligomers
of nonylphenol polyethoxylates (NPnEO) in dissolved and particulate fractions of municipal
wastewaters entering Sibenik Harbor
ENVIRONMENTAL ANALYSIS 553
CHIMIA 2003, 57, No. 9

age discharge of municipal wastewaters of likely since this process would tend to de- particulate LAS in the saline layer (salinity
about 0.3 m3/s, the inputs of LAS and crease the relative percentage of lipophilic 30–37 PSU) is therefore significantly high-
NPnEO were estimated at 5 tons per year metabolites. er than that in the brackish layer (salinities
each. As a consequence of risk reduction <20 PSU). A similar effect was reported by
measures, which were introduced in West- Rubio et al. [36], who studied partitioning
400
ern Europe, as well as reduced industrial ac- of LAS between water and estuarine sedi-
tivities during and after the war in Croatia ments.
(1991–1995), the usage pattern of aromatic
300 NPnEO
surfactants has changed dramatically. The
tot-LAS
concentration of NPnEO decreased below Distribution on the Vertical Profile

C / [mg/m 3 ]
0.1 mg/l, while the concentration of LAS in
200
wastewater increased to 5 mg/l. The most characteristic feature of the
surfactant distribution in a microtidal estu-
ary is the distribution pattern on the vertical
100
Distribution in the Wastewater profile of the water column (Fig. 7). The
Plume maximal concentrations of both LAS and
NPnEO are observed at estuarine phase
0
The spread of the wastewater plume in 0 50 100 150 200 250
boundaries, i.e. in the surface microlayer
the Sibenik Harbor was investigated by Distance from sew age outlet [m]
(air–brackish water interface) and at the
sampling at different distances from the brackish–seawater interface. The tendency
main outlet at two different depths charac- Fig. 4. Dilution of linear alkylbenzene sulpho- of aromatic surfactants to accumulate at the
teristic of the brackish compartment (0.5 m; nates (LAS) and nonylphenol polyethoxylates phase boundaries is in agreement with their
salinities <20 PSU) and marine compart- (NPnEO) in the wastewater plume near the amphiphilic nature. The enrichment factors
ment (6 m; salinities >37 PSU) of the estu- outlet in the Sibenik Harbor in the surface microlayer (sampled with the
ary. The results indicate that spreading of Garrett net) were in the range from
wastewaters occurs almost exclusively in 60,0 3.2–19.5, while the apparent enrichment at
NP0-2EO [% of total NPnEO]

the brackish layer, while the underlying the brackish water–seawater interface was
50,0
saline layer remains hardly affected. Fig. 4 smaller. However, comparatively lower en-
shows the distribution of LAS and NPnEO 40,0 richment factors at the brackish water–sea-
in the wastewater plume. As can be seen, water interface could be simply a conse-
30,0
there is a strong reduction (down to 1–10 quence of insufficient resolution of the pro-
µg/l) of the surfactant concentrations in the 20,0 cedure that was used for the sampling of
closest proximity (25 m) of the outlet. After organic films at the brackish water–sea wa-
a distance of only 100 m the concentration 10,0 ter interface (2 cm), as compared to the
of both LAS and NPnEO in the plume 0,0 well-known Garrett net technique. It should
dropped down below 2 µg/l. The observed 0 50 100 150 be noted that the concentrations of both
effect depends strongly on the wind condi- Distance from outlet [m] LAS and NPnEO in the underlying seawa-
tions, which can enhance the velocity and ter layer are very low, indicating that their
direction of surface currents as well as mix- Fig. 5. Relationship between the parent nonyl- transport through the brackish water–saline
ing of the brackish and saline layers [35]. phenol polyethoxylates (NPnEO) and their water interface is greatly reduced. The in-
lipophilic metabolites (NP0-2) in the waste-
Such a fast reduction of surfactant concen- terface prevents both the mixing of the two
water plume in the Sibenik Harbor
tration with an increasing distance from the layers as well as a vertical flux of suspend-
outlets can mainly be assigned to a very fast ed particles [26]. It is interesting to note that
dilution, however, differences in the distri- It is interesting to note that the parti- a similar vertical concentration profile of
bution patterns of individual LAS homo- tioning of LAS into the particulate phase NPnEO-derived compounds, characterized
logues suggests the importance of some can be enhanced at higher salinities due to by a pronounced maximum at the boundary
other mechanisms that lead to the elimina- stronger ionic interactions of LAS with the of two physically different water masses,
tion of parent compounds. The same con- cations present (Fig. 6). The percentage of was observed in Lake Geneva with the
clusion was reached from the changing dis-
tribution patterns of lipophilic metabolites
50
of NPnEO, which exhibit a much lower 40
45 brackish
concentration decrease than the parent 40 35
saline
Particulate LAS [%]

compounds. If the relative contribution of 35 30


C/ [mg/m3]

lipophilic metabolites in the total nonylphe- 30 25


nolic compounds is plotted versus distance 25
20
20
from the outlet (Fig. 5), one can see that 15
15
their percentage in the plume significantly 10 10
increases (up to 54%). This indicates the 5
5
possible importance of some oligomer-spe- 0
0 100 200 300 400 0
cific elimination processes in the plume, Outlet 50 m 100 m 300 m
most probably biotransformation of the Distance from outlet [m]
Sample location
parent NPnEO. An alternative mechanism,
i.e. fast sedimentation of surfactant mole- Fig. 6. Distribution of linear alkylbenzene sulphonates (LAS) in the brackish and saline layers
cules with sewage-derived particles, is less near the outlet in the Sibenik Harbor
ENVIRONMENTAL ANALYSIS 554
CHIMIA 2003, 57, No. 9

3
C / (mg/m )
the temperatures representative of summer
0 2 4 6 8 10 0 20 40 60 80
(23 °C) the transformation rate of LAS is
0 0 approximately 2 times faster than under
winter temperature (14 °C) conditions. This
5 5 effect is even more pronounced for NPnEO,
mainly because of its very slow biotrans-
NPnEO
10 LAS 10
formation under winter temperature condi-

Depth [m]
Depth [m]

tions. The biotransformation is particularly


Sal (PSU)
inhibited at low temperatures in the saline
15 15 NP0-2EO (%)
layer, resulting in very long half-lives in
that layer.
20 20

a) b)
25 25 Assessment of Elimination Mecha-
nisms and Residence Times
Fig. 7. Vertical profiles of surfactant residues in the water column of a stratified estuary: (a) dis-
tribution of linear alkylbenzene sulphonates (LAS) and nonylphenol polyethoxylates (NPnEO) To assess the elimination and residence
and (b) percentage of lipophilic metabolites in the total NPnEO time of the two surfactant classes, a simple
calculation has been performed assuming
maximum that was situated at the thermo- seasonally dependent transformation were that biodegradation and transport to the bot-
cline [37]. confirmed by controlled laboratory experi- tom sediment are the main elimination
The homologue and oligomer composi- ments, which were conducted using natural mechanisms. Taking into account the rather
tions of aromatic surfactants vary along the microbial populations, originating from low concentration of aromatic surfactants
vertical profile, suggesting that significant both brackish and saline estuarine compart- in the surface sediments (<5 mg/kg), the
changes occur during the passage through ments. The results presented in the Table transfer of surfactants to estuarine sedi-
the interface. As indicated in Fig. 7, the show the estimated biotransformation rates ments was calculated to be less than 1% of
concentration of lipophilic metabolites of of NPnEO and LAS under different tem- the total amount of 5 t/year that enters the
NPnEO shows a very sharp maximum at perature conditions. The biotransformation Sibenik Harbor [22][23]. Therefore, this
the halocline, reaching a high share of over rate constants for the total LAS ranged from mechanism is not expected to be dominant
60% of the total nonylphenolic compounds. 0.030 to 0.269 d–1, corresponding to half- for the removal of aromatic surfactants
This indicates a very efficient transforma- lives of 2.8 to 23 d. Estimated overall bio- from the water column. The reason is, most
tion of NPnEO at the brackish water–sea transformation rate constants for NPnEO probably, the hydrographic structure of the
water interface. (0.01 to 0.28 d–1) are generally in a similar stratified estuary, which prevents an effi-
range to those for LAS, however, a more cient transport of sediments to the bottom.
detailed analysis shows that NPnEO are Consequently, biotransformation should be
Biotransformation of Aromatic more resistant to biodegradation by micro- considered the most important removal
Surfactants bial populations from the saline layer mechanism. The efficiency of elimination
and/or under lower temperatures. In addi- of aromatic surfactants by biotransforma-
The biotransformation processes were tion, the model experiments have shown tion was estimated using the one-box
shown to be seasonally dependent and the that biotransformation of NPnEO results in steady-state estuarine model proposed by
seasonal differences are more clearly re- the formation of persistent metabolites, in- Morris [38]. The original expression was
flected in the oligomer composition than cluding NP1EO and NP2EO as well as cor- modified to suit an irreversible first-order
in the homologue patterns. It should be responding carboxylic acids [24]. Since reaction as follows:
stressed that it is difficult to decouple the both surfactant classes are biotransformed
effect of biotransformation on the LAS ho- several times faster by estuarine popula- Biodegradation (%) = kT / (1+kT)
mologue composition from the changes in- tions from the brackish layer than those
duced by physico-chemical partitioning, from the underlying saline layer, it was sug- where k and T represent the biotransforma-
since in both cases the aqueous phase is gested that the present surfactant-degrading tion rate constants and hydrodynamic resi-
preferentially depleted in higher oligomers. bacteria were predominately of wastewater dence time (flushing time), respectively.
To assess the effect of biotransformation on origin [19]. The average residence time of water in the
LAS composition one should look at the The effect of temperature on the bio- brackish layer of the Sibenik Harbor was
isomer composition, which shows prefer- transformation rate is rather pronounced. At estimated at 1.2 d, while the residence time
ential degradation of external isomers
[11][18]. For NPnEO oligomers, one could Table. Overall biotransformation rate constants for linear alkylbenzene sulphonates (LAS) and
clearly separate the effects of biotransfor- nonylphenol polyethoxylates (NPnEO) in brackish and saline compartments of the Sibenik Har-
mation and adsorption, since biotransfor- bour.
mation is more effective for the higher
oligomers, while the lower oligomers ex- Estuarine Temperature [°C] LAS NPnEO
hibit a stronger affinity for adsorption. The compartment Rate constant (d-1) Rate constant (d-1)
corresponding average number of EO units
Brackish 13–14 0.161 0.02–0.03
in summer and winter are typically found in 22.5–23 0.247 0.17–0.28
the ranges of 7 to 9 and 9 to 11, respective- Saline 13–14 0.020 0.01–0.02
ly, which indicates more efficient degrada- 22.5–23 0.156 0.02–0.05
tion during summer. Field observations on
ENVIRONMENTAL ANALYSIS 555
CHIMIA 2003, 57, No. 9

of the saline layer is much longer and varies biodegradation, especially in the saline [23] S. Terzic, M. Ahel, Mar. Poll. Bull. 1995,
from 6.2 d in winter to 18 d in summer [39]. compartment of the estuary. Therefore, the 28, 735.
Taking into account the overall biotransfor- residence time of surfactant residues in [24] R. Kvestak, M. Ahel, Arch. Environ. Con-
tam. Toxicol. 1995, 29, 551.
mation rates given in the Table, it was esti- stratified estuaries greatly depends on [25] A.W. Morris, R.F.C. Mantoura, A.J. Bale,
mated that the expected removal rate of flushing time of the brackish layer. R.J.M. Howland, Nature 1978, 274, 678.
LAS in the brackish layer ranges from [26] V. Zutic, T. Legovic, Nature 1987, 328,
16–23%. Such a relatively low removal is Acknowledgements 612.
mainly due to a very short residence time of This research was supported by the Ministry [27] Z. Grzetic, ‘Basic Hydrographic and
water in that layer. Removal rates in the of Science and Technology of the Republic of Chemical Properties of the Krka River Es-
Croatia (Project No. 0098120) and the Swiss tuary’, PhD Thesis, University of Zagreb,
saline layer range from 11% in winter and
National Science Foundation (SCOPES re- 1990.
74% in summer. For NPnEO, the estimated search project on ‘Aromatic Surfactants and [28] M. Ahel, W. Giger, Anal. Chem. 1985, 57,
elimination in the brackish layer varies be- Emerging Chemical Contaminants – Analyses, 1577.
tween 10% in winter and 25% in summer. Occurrence and Fate in the Aquatic Environ- [29] M. Ahel, W. Giger, Anal. Chem. 1985, 57,
In the saline layer, the elimination of ment (ASECCO)’) 2584.
NPnEO in winter is rather restricted (6%), Received: July 18, 2003 [30] A. Marcomini, W. Giger, Anal. Chem.
but reaches 47% in summer. Based on these 1987, 59, 1709.
estimates it is apparent that most of the sur- [31] M. Ahel, W. Giger, E. Molnar, S. Ibric,
Croat. Chem. Acta 2000, 73, 209.
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[32] M. Ahel, W. Giger, Chemosphere 1993,
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very dilute form. ronmental Chemistry’, vol. 3, part F, Ed. [33] M. Ahel, W. Giger, Chemosphere 1993,
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