Chemosphere 92 (2013) 247–257

Contents lists available at SciVerse ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Seasonal input of regulated and emerging organic pollutants through

surface watercourses to a Mediterranean coastal lagoon
R. Moreno-González ⇑, J.A. Campillo, V. García, V.M. León ⇑
Instituto Español de Oceanografía, Centro Oceanográfico de Murcia, Apdo. 22, C/Varadero 1, 30740 San Pedro del Pinatar, Murcia, Spain

h i g h l i g h t s

" Input of organic pollutants through watercourse to Mar Menor lagoon was determined.
" Surface waters were analyzed by SBSE/GC/MS.
" The predominance of insecticides in Summer and herbicides in Winter were observed.
" Heavy rain inputs of some pesticides represent over 70% of the total annual input.

a r t i c l e i n f o a b s t r a c t

Article history: Seasonal input of organic pollutants through El Albujón Watercourse to the Mar Menor lagoon was esti-
Received 19 October 2011 mated from Spring 2009 to Winter 2010, including regular periods and two flash flood events. 82 semi-
Received in revised form 22 November 2012 volatile organic pollutants (persistent organic pollutants, different groups of pesticides and others) were
Accepted 15 December 2012
determined by stir bar sorptive extraction and thermal desorption followed by capillary gas chromatog-
Available online 8 February 2013
raphy coupled to mass spectrometry from surface waters with quantification limits of a few ng L1. Pes-
ticide concentrations varied significantly along the watercourse due to the presence of different sources
Keywords:
(groundwaters, wastewater effluent, tributary contributions, brackish waters, etc.) and physicochemical/
Stir bar sorptive extraction
Semivolatile organic pollutants
biological processes that take place simultaneously. The most commonly detected analytes were propy-
Pesticides zamide, triazine compounds and chlorpyrifos. A clear seasonal pattern has been detected, with a predom-
Surface water input inance of insecticides during Summer and of herbicides during Winter. The input of pesticides through
Seasonal variations this watercourse is particularly relevant during periods of heavy rain, representing more than 70% of total
Flash flood event yearly input for many of them.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction several international monitoring programs for persistent pollutants

High volumes and a great variety of organic substances (pesti-
cides, hydrocarbons, surfactants, plasticizers, etc.) enter the envi-
ronment, as a result of the wide diversity of anthropogenic
activities (industrial, urban, agricultural, farming, etc.) and uses.
For this reason the coastal environment receives direct and indirect
(surface waters, rivers, air deposition, etc.) discharges and is, in
many cases, the ultimate ‘‘sink’’ for large volumes of many pollu-
tants. As a result, a wide variety of organic contaminants (organo-
chlorine pesticides (OCPs), polycyclic aromatic hydrocarbons
(PAHs), organophosphorus pesticides, etc.) are present in rivers
and watercourses, such as the Ebro River area (Hildebrandt et al.,
2007) and in coastal environments (Sánchez-Ávila et al., 2010). Their
potential effects on the ecosystem have led to the establishment of
⇑ Corresponding authors. Tel.: +34 968 180500; fax: +34 968 184441.
E-mail addresses: ruben.moreno@mu.ieo.es (R. Moreno-González), victor.leon@
mu.ieo.es (V.M. León).
(MED POL and OSPAR programmes in the Mediterranean and Atlan-
tic areas respectively). The protection of the environment is one of
the relevant regional interests in Europe, as shown by the introduc-
tion of international legislation such as the Water Framework Direc-
tive 2000/60/EC and Marine Strategy Framework Directive 2008/56/
EC. Environmental Quality Standards for priority substances have
also been established for waters, including pollutants of different
polarities and natures.
Many organic pollutants are present in the environment at very
low concentrations, and it is thus necessary to use a preconcentra-
tion step prior to their analysis, particularly for the determination
of hydrophobic pollutants in water samples, for which purpose mul-
tiresidue methods are the most useful tools. The stir bar sorptive
extraction (SBSE) technique is a solventless and sensitive prepara-
tion method that is now being used for biomedical, environmental
and food applications (Prieto et al., 2010). Many analytical proce-
dures of this multiresidue method have been developed for different
mixtures of apolar pollutants (log Kow > 2) in freshwater samples:

0045-6535/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2012.12.022