Journal of Hazardous Materials 263P (2013) 95–104
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Journal of Hazardous Materials
jou rn al hom epage: www.elsevier.com/locate/jhazmat
Screening of currently used pesticides in water, sediments and biota
of the Guadalquivir River Basin (Spain)
Ana Masiá
∗
, Julián Campo, Pablo Vázquez-Roig, Cristina Blasco, Yolanda Picó
Food and Environmental Safety Research Group, Department of Medicine Preventive, Faculty of Pharmacy, University of Valencia, Av. Vicent Andrés Estellés
s/n, 46100 Burjassot, Valencia, Spain
h i g h l i g h t s
•
Spatial and temporal distribution of currently used pesticides in the Guadalquivir River Basin.
•
Organophosphorus > triazines > carbamates are the most commonly detected.
•
Transformation products were found at higher concentrations than parent pesticides.
•
WWTP are an important source of pesticide to the environment.
•
Low accumulation levels in sediments and biota.
a r t i c l e i n f o
Article history:
Received 20 May 2013
Received in revised form
11 September 2013
Accepted 17 September 2013
Available online 21 September 2013
Keywords:
Pesticides
Water
Sediment
Fish
Spatial distribution
Temporal distribution
a b s t r a c t
The occurrence of 50 currently used pesticides and their transformation products in surface and waste
waters, sediment and fish in the Guadalquivir River Basin was determined in 2010 and 2011. After selec-
tive sample extraction, pesticides were identified and quantified by liquid chromatography coupled to
tandem mass spectrometry (LC–MS/MS). The contamination profile in water and sediments is marked
by the presence of organophosphorus and triazines. Transformation products were even at higher con-
centrations than parent pesticides. A wider range of pesticides was present in water than in sediments
but none of them were detected in fish. The mean concentrations ranged from 0.2 to 13.0 ng/L in water
and from 0.1 to 13.2 ng/g d.w. in sediment. The spatial distribution of most pesticides was consistent
with the agricultural activities of the area or their urban applications. The waste water treatment plant
effluents that impact the river are minor sources for few pesticides but for most of them run-off would be
the most important contribution. The temporal distribution showed differences between both sampling
campaigns related to the river flow. The low-flow produced a pesticide concentration effect, generating
higher levels in water and accumulation in sediments. This forecasts a hazard in future scenarios if the
current situation of the climate change and water scarcity evolves to more critical conditions highlighting
the need of these monitoring studies.
© 2013 Elsevier B.V. All rights reserved.
1. Introduction
Water is the primary pathway of pesticides dissemination from
their application areas to other parcels of the environment [1,2].
As a result, the presence of pesticides - especially those polar and
highly soluble- in surface, waste and groundwaters, typically in the
lower ng L
-1
concentration ranges, have been reported [3–7]. Some
of these pesticides are bioaccumulative and due to their vertebrate
and non-vertebrate toxicity can affect non-target organisms [8].
In Europe, there are few studies that determine the occurrence
of currently used pesticides in environmental compartments other
∗
Corresponding author. Tel.: +34 963544118; fax: +34 963544954.
E-mail address: Ana.Masia@uv.es (A. Masiá).
than water and most of them are erratic samplings performed to
demonstrate the reliability of an analytical method but not system-
atic studies evaluating pesticide occurrence and levels in a River
Basin [2,9–11]. These studies, without being many, are more preva-
lent in the United States (US) [12–19].
The Guadalquivir River, chosen as study case, is among the major
freshwater sources of the European Basins and the Spain’s second
longest river. Its natural environment is one of the most varied in
Europe, with half of the continent’s plant species and nearly all
those of the North African region [20]. Thus, maintain a good qual-
ity of these ecosystems is of crucial interest. Because of its favorable
climate and fertile soils, a wide range of crops are cultivated along
the basin and more important, irrigated with its water. Despite its
importance and to our knowledge, only few studies have been car-
ried out in this River Basin. These reported the concentrations of
0304-3894/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2013.09.035