Paola A. Babay1
Raúl F. Itria2
Emiliano E. Romero Ale1
Elena T. Becquart 1
Eduardo A. Gautier 1
1Gerencia Química, Comisión
Nacional de Energía Atómica, San
Martín, Buenos Aires, Argentina
2Instituto Nacional de Tecnología
Industrial, San Martín, Buenos Aires,
Argentina
Research Article
Ubiquity of Endocrine Disruptors Nonylphenol
and Its Mono- and Di-Ethoxylates in Freshwater,
Sediments, and Biosolids Associated with High
and Low Density Populations of Buenos Aires,
Argentina
In Latin America, use of alkylphenol ethoxylates is unrestricted and widespread.
However, their environmental incidence is still little studied. In order to investigate the
occurrence, distribution and main sources of the endocrine disruptors nonylphenol
(NP), nonylphenol mono- and di-ethoxylate (NP1EO, NP2EO), we analyzed water and
sediments from thirteen sites in high and low population densities regions of Argentina.
Also ten biosolid samples from a municipal sewage treatment plant were analyzed.
Ranges for NP were 21–6359mg kg1 in sediments, 0.1–6.2mg L1 in water and
64–112 mg kg1 in sludge; for NP1EO were 7–3357mg kg1 in sediments, 0.1–9.2mg L1
in water and 8–140 mg kg1 in sludge and for NP2EO were 1–437mg kg1 in sediments,
0.1–5.2mg L1 in water and 2–23 mg kg1 in sludge. The highest levels were associated
with proximity to industry and sewage efuents discharge. In biosolids we found
predominantly NP, followed by NP1EO and NP2EO, consistently with the metabolic
potential of engineered systems. Our ndings are in agreement with historical reports
for Europe and North America, indicating an important incidence of the xenoestrogens
also in this important geographical region. Contrasted to guide values, they show a
potential threat to the water and terrestrial environments.
Keywords: Micro-pollutant; Nonylphenol polyethoxylate degradation products; Recalcitrant
metabolites; Sewage sludge; Surface water
Received: March 25, 2013; revised: May 3, 2013; accepted: May 19, 2013
DOI: 10.1002/clen.201300230
1 Introduction
Nonylphenol polyethoxylates (NPnEO) are among the most widely
employed non-ionic surfactants [1–3]. Their biotransformation leads
to the formation of recalcitrant metabolites, which are known to
have harmful effects on biota such as endocrine disruption in several
species [1–5]. NPnEO were early banned in Europe [6] and Canada [4];
however, the low cost and good performance for a broad number of
applications, added to the lack of regulations in most countries,
make these surfactants and their metabolites ever present in the
environment as an “eternal ame” [7]. Little is still known on their
fate and distribution in Latin America, where the use of these
surfactants is widespread and unrestricted [3]. A reduced number of
reports show the presence of the parent compounds and their bio-
refractory metabolites in sewage and freshwater systems of Mexico [8,
9] and Brazil [10–12]. In Argentina, a qualitative study showed their
presence among other micro-pollutants [13].
In previous works we reported the development and validation
of analytical methods for quantication of nonylphenol (NP),
nonylphenol mono- and di-ethoxylate (NP1EO, NP2EO) in natural
water [14] and sediments [15], nding environmentally relevant levels.
The above precedents indicate a potential problem in this
important geographical region, but there are still too scarce data
to attain the knowledge on how to deal with the problem. With
the aim of contributing to get a more comprehensive and
representative panorama, the objective of the current study was to
investigate the occurrence, main sources, and environmental
signicance of the endocrine disruptors NP, NP1EO, and NP2EO in
areas that comprise both high and low population densities.
2 Materials and methods
2.1 Reagents and standards
Technical grade NP (85% 4-NP, Fluka, Switzerland) and a NP1EO/
NP2EO technical mixture (Igepal CO-210, Aldrich, USA) were used
as analyte standards. For GC–MS analyses individual 4-NP1EO and
Correspondence: Dr. P. A. Babay, Gerencia Química, Comisión Nacional
de Energía Atómica, Av. General Paz 1499, San Martín, Buenos Aires,
Argentina.
E-mail: babay@cnea.gov.ar
Abbreviations: DCM, dichloromethane; dw, dry weight;NP, nonylphenol;
NP1EO, NP mono-ethoxylate; NP2EO, NP di-ethoxylate; NPnEO, NP
polyethoxylates; SPE, solid-phase extraction; STP, sewage treatment
plant; TEQ, toxic equivalent
1
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4-NP2EO standards (Promochem, Germany) were employed. All
solvents were HPLC grade and other chemicals were p.a. quality.
Glass-ber pre-lters were APFD 04700 from Millipore. For solid-phase
extraction (SPE), glass columns and PTFE frits from Merck were
employed; C-18 sorbent was CEC-18 (UCT, USA).
2.2 Sample collection and extraction procedures
2.2.1 Water and sediments
Water samples were collected in 1-L amber-glass bottles, added with
1% v/v formaldehyde and stored at 4°C until analysis. Grab sediment
samples, mostly clay (except for sample S3, sandy) were collected
from the water courses margins with a steel shovel, placed in 500 mL
glass asks with the addition of 2% v/v formaldehyde and stored at
20°C until analysis.
Since details on the extraction conditions are given elsewhere
[14, 15] only the outline of the procedures is described here. After
ltration through glass-ber pre-lters and addition of NaCl to the
acidied water samples, enrichment of the analytes was carried out
by SPE on C-18 and elution with ethyl acetate (EtAc). Following
addition of anhydrous Na2SO4 and evaporation of the SPE solvent, the
extracts were re-dissolved in HPLC mobile phase and analyzed.
Sediment samples were dried at 60°C until constant weight and
homogenized, obtaining a solid that passed through a 20 mesh sieve.
Extraction with EtAc was ultrasound assisted. The extracts were
dried under N2 and re-dissolved in the HPLC elution mixture for
measurement. No clean-up operations were performed.
Performance of the extraction procedures with real samples
was evaluated through recovery assays at different concentration
levels.
2.2.2 Sewage sludge
Biosolids were collected in 250 mL glass asks, immediately
preserved with 2% formaldehyde and stored at 20°C until analysis.
Method development experiments were carried out with a blank
material from a laboratory scale reactor operated as semi-continuous
activated sludge. The water phase was discarded after settlement and
the remaining solid was oven dried at 55–60°C for 2 h. The dried
sludge was treated with liquid N2 to allow mortar disintegration. A
stock solution of the three target compounds in hexane/2-propanol
(50:50) was spiked into the conditioned sludge and left at room
temperature in the dark for 48–72 h, in order to obtain a nal
concentration of 550mg NP, 534mg NP1EO, and 328mg NP2EO per
gram of sludge dry weight (dw). Ultrasonic-assisted extraction was
employed. Mixtures of dichloromethane (DCM), methanol (MeOH),
and ethyl acetate (EtAC) were assayed as extraction solvents. Three
sonication cycles of 5 min each were applied to 0.15 g of spiked blank
together with 0.45 mL of the corresponding extraction solvent. The
extracts were evaporated to dryness under N2 and re-dissolved in the
HPLC elution mixture for analysis.
A drying period of 50–60 h at 60°C was necessary to achieve
constant weight for the decanted solids of real sewage sludge samples
(water phase also discarded). Once dried, a homogeneous material (20
mesh) was obtained. Three sonication cycles of 5 min were applied to
0.15 g of dried sample with 0.45 mL of an extraction mixture of
MeOH/EtAc 25:75, selected during method development. Perfor-
mance of the extraction procedures with real samples was evaluated
through recovery assays.
2.3 Chromatographic analysis
Quantication of NP, NP1EO, and NP2EO extracted from water,
sediments and sludge was carried out by normal-phase HPLC with
uorescence detection (HPLC-FL), following our previous proce-
dures [14, 15]. A SpectraSERIES P200 binary pump (Thermo Separation
Products, USA) with a Linear LC-305 uorescence detector (Linear
Instruments, USA) was employed. Separations were performed on an
aminopropyl-silica column (5mm particle, 250 4.6 mm, APS-2
Hypersil, Thermo Scientic, USA) at 35°C, using isocratic elution
with 4% 2-propanol in hexane. Excitation and emission wavelengths
were 230 and 300 nm, respectively. Injection volume was 50mL, with
instrumental detection limits of 0.8mg L1 for NP1EO and NP2EO,
and 1.3mg L1 for NP. In all cases, the analytes were positively
identied by means of standard spiking.
Further conrmation of compounds identities was obtained by
GC–MS. For the real samples, every HPLC peak attributed to the
analytes was collected as eluted, evaporated to dryness and re-
dissolved in cyclohexane for GC–MS analysis. A Shimadzu GC-17A
split–splitless gas chromatograph coupled to a MS-QP5050A mass
spectrometer was used. A Zebron ZB-1 capillary column (60 m 0.32
mm id, 0.50 mm lm thickness, Phenomenex, USA) was employed.
Instrumental conditions for separate measurement of the three
analytes are described elsewhere [14].
Laboratory blanks were run among the samples, in order to verify
the absence of crossed contamination during the sample preparation
and analysis procedures.
2.4 Study area and sampling strategy
Water and sediment samples from 13 sites selected near potential
sources of NPnEO, as well as ten biosolid samples from a sewage
treatment plant (STP), were collected. Also, a number of locations
where no sources were anticipated were studied in order to establish
background levels, amounting to a total area of approximately
3000 km2.
In order to track the origin of NPnEO derived contamination and
detect hot spots, a survey of low, middle and high density population
areas was carried out. Sites were sampled along three selected natural
water courses (Fig. 1), whose main characteristics are summarized.
2.4.1 Luján River
It emerges from the conuence of Los Leones and El Durazno creeks
and runs 128 km through an area of 2690 km2. Three sections can be
distinguished: higher basin (40 km long from the source), with low
population density and agricultural and cattle activities; then
middle and lower basins, running through regions of increasingly
higher population densities and intense industrial activities,
receiving wastewater of both industrial and municipal origins.
The lower basin, running through the highest population density
area, receives the most signicant contamination charge, either
directly or by means of its tributaries, specially the Reconquista River
(www.atlasdebuenosaires.gov.ar) [13]. The higher basin was sampled
at El Durazno creek (point N1) and the middle basin was sampled in
the nearby of the municipal sewage treatment facility of Luján City (L-
STP), namely upstream (N2), directly from the end-pipe (N3), close to
the outlet (N4), and downstream the plant (N5).
Taking into account the potential use of biosolids for soil
amendment, a survey of the aforementioned pollutants was
performed. A new method of analysis was proposed for the study
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of biologic sludge. This method was applied in the analysis of the
biosolids resulting from a mesophilic anaerobic digestion of
secondary sludge (at 35–37°C with a retention time of 21 days)
from the main municipal STP of San Fernando district, at the lower
basin of Luján River (N-STP). This activated sludge facility serves a
population of 270 000 inhabitants, has a capacity of 0.9 m3 s1 and
discharges the liquid efuents into the highly polluted Reconquista
River at its conuence with Luján River.
2.4.2 Morón creek
It runs 16 km through one of the most densely urbanized and
industrialized zones in the Metropolitan Area of Buenos Aires. The
rst 4.5 km are piped and the open stream section receives the input
of a vast number of human activities. It belongs to the Reconquista
River basin and is recognized as one of the most highly polluted
ecosystems in the whole country (www.atlasdebuenosaires.gov.ar).
Sampling was focused on the nearby of a chemical industry (close to
the outlet (W1) and downstream the discharge (W2)) and a municipal
STP (W-STP; upstream (W3), close to the end-pipe (W4) and
downstream the plant (W5)).
2.4.3 Jiménez creek and its alleviator Jiménez channel
The creek rises as an intermittent water course and is one of the
several water courses that are recognized to be highly polluted due
the lack of control in efuent discharges. It ows into de la Plata River
estuary. Its basin covers an area of 80 km2 and runs through highly
urbanized and industrialized districts. All along its course, it receives
discharges from industrial and domestic efuents. The points
investigated, located at the city of Quilmes, are indicated as S1
(Jiménez creek), S2 (Jiménez channel), and S3 (irrigation channel).
3 Results and discussion
3.1 Water and sediments
3.1.1 Occurrence and distribution of NPnEO metabolites
The concentrations measured by HPLC-FL are shown in Tab. 1.
Recovery rates obtained after standard addition resulted always
>80% and therefore no correction factor was applied to the
quantitative results. As reported before [1, 16], concentrations of
the analytes in the solids were 1–3 orders of magnitude higher than
the aqueous levels, reecting accumulation due to their lipophilic
nature. Figure 2a and b shows their molar distribution in water and
sediments. Partitioning of organic compounds between these two
phases is usually controlled by physical, chemical, and biological
processes; fully de-ethoxylated NP and short-chain NP1EO and NP2EO
would display different behaviors because of their different physico-
chemical properties [17]. The less water soluble the metabolite the
higher the enrichment of the sediment that may be expected [16]. As
stems from the gure, there is not a clear tendency in terms of a
major compound in the water phase: NP, NP1EO, or NP2EO are
present at the highest molar fractions in the different sites, talking
about varying compositions of the discharges affecting the water
compartment. However, accumulation of NP in the sediments
becomes apparent; NP is always the major compound, with percent
molar fractions mostly >50%, followed by NP1EO and much smaller
amounts of NP2EO, except for point N1. In the latter site, a major
proportion of longer chain NP2EO is observed, probably due to the
presence of less adapted micro-biota in a slightly impacted site
(as this rural area is) in contrast with the metabolisms found in
engineered systems.
Figure 1. Sampling sites location at the Norwest (N1–N5), West (W1–W5), and South (S1–S3) of the city of Buenos Aires. L-STP, Luján sewage treatment
plant; N-STP, North sewage treatment plant; W-STP, West sewage treatment plant. Dashed line represents the piped section of Morón creek. Alleviator of
Jiménez creek is pointed by an arrow. Please note that only the water streams and cities or towns relevant for this work are shown in the map.
Endocrine Disruptors in Freshwater and Sewage Systems of Buenos Aires 3
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3.1.2 Sources and impact of NPnEO metabolites
Since NP, NP1EO, and NP2EO occur together, their combined impact
was assessed through calculation of NP-toxic equivalents (NP-TEQs),
as described in Canadian guidelines for water [18] and sediments [19].
Relative toxicity values, or NP-toxic equivalency factors (TEFs) are
as follows: NP is assigned a TEF value of 1 and the shorter NPnEO
oligomers (with n up to 8) have TEFs of 0.5. Then, the total
concentration of NP-TEQs was calculated as:
NP TEQs ¼ CNP þ 0:5 CNP1EO þ 0:5 CNP2EO
where CNP, CNP1EO, and CNP2EO are the concentrations of the
respective analytes in the sample. This was compared against the
corresponding guidelines (1mg L1 for freshwater and 1.4 mg kg1
dw for freshwater sediment, according to the aforementioned
Canadian documents).
The results are graphically depicted in Fig. 2a and b. In Tab. 2 we
gathered the sites characteristics and their related NP-TEQs. Not
surprisingly, the most impacted area was Morón creek (sites W1–W5),
a water body strongly inuenced by untreated municipal and
industrial wastewater, turning it into an “open sewer”. The highest
TEQs seem to be associated with proximity to industry and sewage
treatment efuents discharges; levels both in the aqueous and solid
phases reached maximum values at the point of the creek that
receives the STP efuent. All in all, the levels found are coherent with
a densely populated area, dominated by the continuous discharge of
industrial and domestic (many times untreated or deciently treated)
residual water.
The water samples of Quilmes (sites S1–S3) present higher TEQs
than those from the comparatively less urbanized Luján River zone
(sites N2 and N5); however, there is a clear disturbance caused by the
discharge of Luján City STP efuent into Luján River (sites N3 and N4).
The end-pipe water sample (N3) reached 13.2mg TEQs L1, affecting
the river water with 5.7mg TEQs L1 and also the sediments with
1516mg TEQs kg1 (N4). Those were the maximum values accounted
for these two areas. Finally, when comparing the results for Jiménez
creek and Jiménez channel, it is interesting to note the signicantly
higher values found in the alleviator channel (4.5mg TEQs L1 in
water and 378mg TEQs kg1in sediments), possibly due to surrepti-
tious discharges that could be happening into this water stream.
3.2 Sewage sludge
3.2.1 Extraction method
Published literature shows that the most widely employed extrac-
tants for this or similar purposes have been for a long time DCM,
MeOH, acetone, and hexane, either alone or in binary mixtures
[1, 17, 20–22]. Based on our previous experience with sediment
extraction [15], performance of MeOH, DCM, and EtAc, individually
and in mixtures, was comparatively evaluated, the latter thought as a
potentially suitable solvent in replacement of DCM (an environmen-
tally and toxicologically harmful solvent).
Similar extraction performances were achieved with DCM and EtAc
when mixed with MeOH, the latter showing to be an essential
component of the binary mixtures in order to obtain high recovery
rates. Therefore and in accordance with the idea of replacing DCM
with a more environmentally friendly and less toxic solvent, and also
reducing laboratory manipulation of toxic MeOH, the extraction
media selected was a mixture of MeOH/EtAc 25:75, for which
Table 1. Quantitative results for water, sediment, and biosolid samples
Sample
NP NP1EO NP2EO
Liquid (mg L1) Solida) Liquid (mg L1) Solida) Liquid (mg L1) Solida)
(S1) Jiménez creek – motorway 0.9 0.2 (2) 21 2 (2) 0.4 0.06 (2) 7 0.6 (2) 0.7 0.02 (2) 1 0.09 (2)
(S2) Jiménez channel – motorway 1.6 0.1 (5) 249 13 (8) 3.3 0.2 (5) 173 29 (8) 2.5 0.05 (5) 84 10 (8)
(S3) Irrigation channel – mouth 0.7 0.1 (5) 437 17 (3) 0.5 0.07 (5) 120 9 (3) 0.8 0.1 (5) 72 4 (3)
(W1) Morón creek – industry discharge 1.9 0.1 (3) 384 28 (4) 8.2 0.3 (3) 163 22 (4) 4.8 0.3 (3) 33 5 (4)
(W2) Morón creek – railway 2.3 0.2 (3) 2229 47 (2) 9.2 0.1 (3) 1372 34 (2) 5.2 0.02 (3) 217 5 (2)
(W3) Morón creek – cemetery 0.5 0.02 (2) 1436 107 (2) 5.1 0.06 (2) 642 89 (2) 3.8 0.1 (2) 350 72 (2)
(W4) Morón creek – STP discharge 6.2 0.6 (4) 6359 1058 (3) 7.0 0.3 (4) 3357 614 (3) 4.9 0.2 (4) 437 55 (3)
(W5) Morón creek – motorway 4.2 0.9 (3) – 8.6 0.2 (3) – 2.8 0.05 (3) –
(N1) El Durazno creek 0.1 0.005 (2) 21 2 (2) 0.1 0.002 (2) 11 3 (2) 0.2 0.008 (2) 22 3 (2)
(N2) Luján River – upstream STP 0.4 0.03 (4) 544 2 (2) 0.3 0.02 (4) 370 10 (2) 0.1 0.01 (4) 148 6 (2)
(N3) Discharge of Luján STP 7.0 0.3 (4) – 7.0 0.2 (4) – 5.4 0.7 (4) –
(N4) Luján River – Luján STP discharge 3.0 0.06 (2) 985 9 (2) 3.0 0.3 (2) 847 7 (2) 2.4 0.2 (2) 214 27 (2)
(N5) Luján River – downstream Luján STP 0.3 0.03 (5) 606 62 (3) 0.4 0.03 (5) 197 44 (3) 0.3 0.02 (5) 24 2 (3)
(B1) San Fernando STP biosolid – 112 10 (2) – 35 0.2 (2) – 7 0.6 (2)
(B2) San Fernando STP biosolid – 64 2 (2) – 8 0.1 (2) – 2 0.07 (2)
(B3) San Fernando STP biosolid – 69 7 (2) – 10 0.6 (2) – 2 0.07 (2)
(B4) San Fernando STP biosolid – 79 15 (2) – 24 4 (2) – 6 0.8 (2)
(B5) San Fernando STP biosolid – 71 (1) – 140 (1) – 3 (1)
(B6) San Fernando STP biosolid – 101 9 (4) – 30 3 (4) – 6 0.8 (4)
(B7) San Fernando STP biosolid – 91 3 (2) – 25 1 (2) – 4 0.1 (2)
(B8) San Fernando STP biosolid – 62 (1) – 38 (1) – 5 (1)
(B9) San Fernando STP biosolid – 97 (1) – 54 (1) – 13 (1)
(B10) San Fernando STP biosolid – 101 12 (2) – 107 7 (2) – 23 2 (2)
In brackets are given the number of replicate samples analyzed for each site (n). Blank space () indicates that no sample was analyzed.
a) Solid phase concentrations (dry basis) are expressed in mg kg1 for sediments and mg kg1 for biosolids.
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recoveries higher than 80% were obtained for the three analytes.
Percentage relative standard deviations for duplicate experiments
were always <10%. As no interfering signals were detected during
chromatographic analyses of blank extracts, no clean-up procedures
were included in the extraction protocol.
Recovery rates in real samples were assessed by spiking two
biosolids in the concentration range from 4000 to 55 000mg kg1
(dw), resulting always >85%.
3.2.2 Occurrence and distribution of NPnEO metabolites
Table 1 presents the concentrations found. In terms of molar ratios
(Fig. 2c), NP prevailed followed by NP1EO and minute amounts of
NP2EO, consistently with the metabolic potential generally found in
engineered systems. Output pathways of organic compounds from
STPs may be outlined as a sum of biodegradation processes,
adsorption on sludge and release via nal efuents. Nonylphenolic
substances are usually incompletely degraded, leaving relatively high
amounts adsorbed onto sludge ocks [17]. As generally observed, the
more hydrophobic a molecule the greater the amount that will be
retained by the particulate phase. The high proportion of NP,
followed by NP1EO and NP2EO found in the sludge samples can be
derived therefore from their partitioning to the particulate matter
during the earlier stages of wastewater treatment. Further removal of
residual oxyethylene groups takes place during anaerobic digestion,
making NP to persist in digested sludge [3, 23].
3.3 Environmental significance and literature
comparison
As previously pointed out, there are scarce data on micropollutants
concentrations in Latin America. Furthermore, there is a lack of
regulations related to the environmental hazard of NP and its
ethoxylates in the region. However, regarding the environmental
signicance of the levels measured in this work, we can say that in
most cases they are very close or surpass the guidelines for protection
Figure 2. Molar fractions of NP, NP1EO and NP2EO and NP-toxic
equivalents (TEQs) in: (a) sediments, (b) water and (c) biosolids. Solid lines
indicate the Canadian Water [18], Sediment [19], and Soil [26] Guidelines
(NP-TEQs of 1mg L1, 1.4mg kg1, and 5.7mg kg1, respectively).
Table 2. Summary of sites characteristics and their related NP-TEQs
Site Location characteristics/potential sources of high NP-TEQs
NP-TEQs
water
(mg L1)
NP-TEQs
sediment
(mg kg1)
(N1) El Durazno creek Low population density; mostly agricultural and cattle activities 0.2 0.04
(N2) Luján River Middle to high population density; industrial activities 0.7 0.8
(N3) Luján STP Middle to high population density; industrial activities/Luján City municipal STP
discharge (directly from the end-pipe)
13.2 –
(N4) Luján River Middle to high population density; industrial activities/Luján STP discharge 5.7 1.5
(N5) Luján River Middle population density; agricultural activities 0.7 0.7
(S1) Jiménez creek Highly urbanized and industrialized districts 1.5 0.03
(S2) Jiménez channel Highly urbanized and industrialized districts/surreptitious discharges 4.5 0.4
(S3) Irrigation channel Highly urbanized and industrialized districts 1.3 0.54
(W1) Morón creek Among the most densely urbanized and industrialized zones in the Metropolitan Area of
Buenos Aires (MABA)/industry discharge
8.4 0.5
(W2) Morón creek Among the most densely urbanized and industrialized zones in the MABA/downstream
industry discharge
9.5 3.0
(W3) Morón creek Among the most densely urbanized and industrialized zones in the MABA 5.0 1.9
(W4) Morón creek Among the most densely urbanized and industrialized zones in the MABA/municipal STP
discharge
12.2 8.3
(W5) Morón creek Among the most densely urbanized and industrialized zones in the Metropolitan Area of
Buenos Aires/downstream municipal STP
9.9 –
Blank space () indicates that no sample was analyzed.
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of freshwater ecosystems established in other countries. A graphical
comparison of measured NP-TEQs with the Canadian guidelines
(Fig. 2a and b), shows that water levels fairly approach or widely
surpass safe values in all but one sample; in the case of sediments,
this occurs in about 40% of the samples. When we contrast our results
for instance with the Dutch Environmental Risk Limits [16], they
cause even higher concern. We found that in all cases, with exception
of El Durazno creek (N1), NP levels widely exceed maximum
permissible concentrations (MPCs) for surface water (0.33mg L1), by a
factor of 10–20 in the worst cases, always related with the vicinity to
STP discharges. Also for NP1EO and NP2EO, a combined MPC of
0.12mg L1 is surpassed by all samples, with no exceptions. Talking
about the sediments, MPCs of 105mg kg1 (dw) for NP and 150mg kg1
(dw) for NP1EOþNP2EO were mostly widely exceeded, except for the
samples taken at Jiménez (S1) and El Durazno (N1) creeks.
Concentrations found in the current study are in accordance with
data published for water streams and sediments of highly urbanized
and/or industrialized countries (i.e., USA, Canada, Switzerland,
Germany, Korea, Spain), which have been extensively reviewed [3].
In those cases the higher values were associated with STP discharges,
as well as with urbanized and industrialized areas, a fact that was
also observed in our research. This is exalted in the case of Morón
creek, where the analytes show high values all throughout its course,
consistently with the high anthropogenic impact mentioned above.
Analyte concentrations in the biosolids ranged from 62 to
112 mg kg1 (dw) for NP, from 7.6 to 107 mg kg1 (dw) for NP1EO
and from 1.65 to 23 mg kg1 (dw) for NP2EO. Even when these levels
did not reach values as high as those eventually found in other
countries [3], sometimes one order of magnitude superiors [24], they
deserve enough attention because of the increasing, widely spread
use of nutrients and organic matter contained in sludge for
agricultural purposes [3, 17]. Application of dehydrated stabilized
sludge in agriculture is considered a potential input way of
alkyphenols into the terrestrial environment. These degradation
products have been encountered in soil and also in ground water as a
consequence of leaching of sludge fertilized elds [23]. In this regard,
the EU proposed a limit value of 50 mg kg1 (dw) for the sum of NP,
NP1EO and NP2EO in sludge intended for use in agriculture land [25].
The values measured in the present work certainly surpass this safe
limit, raising concern about the possible disposal or nal use of the
generated biosolids. Finally, when contrasted with the Canadian NP-
TEQ of 5.7 mg kg1 (dw) for agricultural use of soil, our results are at
least 10 orders of magnitude above safe limits (Fig. 2c) [26].
4 Concluding remarks
In the nearby of Buenos Aires City there exist a vast number of
industrial, municipal, and domestic facilities discharging their
wastewater into rivers and creeks. These efuents are in some cases
treated streams and many other times they correspond to direct
discharges of untreated water. Therefore, this area appeared as an
important environment to investigate the occurrence of degradation
products of NPnEO, given that this is one of the major classes of non-
ionic surfactants still employed in all kind of industrial and domestic
applications in the country. In addition, the use of NPnEO as a co-
adjuvant in several agricultural preparations increases the risk of
occurrence of these substances in theoretically slightly impacted
areas, such countryside zones. This kind of research had not been
carried out before in the country, what acquires even highest
relevance taking into account the small number of works of its type
for the whole Latin America, in a context of widespread and
unregulated use and disposal of NPnEO. We think that comprehen-
sive information on the occurrence and fate of pollutants should
serve for evaluation and management purposes. Concentrations and
behavior of NP, NP1EO, and NP2EO found in surface water and
sediments, as well as in sewage systems, are in agreement with those
reported for several sites of Europe and North America along the last
decades, and reect an important incidence of the target xenoes-
trogens also in this region. The metabolites of NPnEO were present in
all the sites and compartments sampled at concentration levels
which contrasted to guide values show a potential threat to the water
and terrestrial environments.
Acknowledgments
Special thanks are given to O. Schenone and the workers of COMACO,
to F. Meijide, F. de la Torre, J. Magallanes, and M. J. Fernández Sturla
for invaluable collaboration.
The authors have declared no conict of interest.
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