Monitoring of pharmaceutically active compounds on the Guadalquivir River basin (Spain): occurrence and risk assessment

Guadalquivir River (South of Spain) is among the major freshwater sources of the European Atlantic basin. Until now scientific efforts have been focused on contamination by heavy metals and some priority pollutants in Guadalquivir River. However, the presence of "emerging contaminants", such as pharmaceutically active compounds, has not yet been studied. In this work the occurrence and risk assessment of sixteen pharmaceutically active compounds, belonging to different therapeutic groups, in Guadalquivir River during its course through Seville city are reported. Wastewater effluents from four wastewater treatment plants discharging into Guadalquivir River and river water samples were analyzed. All studied pharmaceutically active compounds, except sulfamethoxazole, trimethoprim, estrone and clofibric acid, were detected in effluent wastewaters at concentration levels up to 28.9 μg L(-1). Among the pharmaceutically active compounds found in effluent wastewater, seven were present in Guadalquivir River samples at concentration levels up to 0.75 μg L(-1), which indicated an important dilution from effluent discharge. Environmental risk assessment reveals that potential ecotoxicological risk cannot be expected on Guadalquivir River at measured concentration levels. Only, the lipid regulator gemfibrozil showed a medium risk for the environment. The risk for acute toxic effects in the environment with the current use of active pharmaceutical ingredients is unlikely. However, the results do not rule out the potential for chronic environmental effects.     

Tracking sewage derived contamination in riverine settings by analysis of synthetic surfactants

A study has been made of the presence and reactivity of the most commonly used surfactants, both anionic (linear alkylbenzene sulfonates, LAS, and alkyl ethoxysulfates, AES) and non-ionic (alcohol polyethoxylates, AEOs, and nonylphenol polyethoxylates, NPEOs), in water and surface sediments from the middle stretch of the Guadalete River in SW Spain (12 stations). Average values were between 0.1 and 3.7 mg kg(-1) in sediment, and between 0.2 and 37 μg L(-1) in water. The sorption of surfactants was dominated by hydrophobic mechanisms, so those homologues having longer alkyl chains (e.g. C(18)AEO) showed higher relative percentages and concentrations in sediments compared with water. Local and sharply higher concentrations of these compounds were observed at three sampling stations (7, 9 and 12), indicating the occurrence of wastewater discharges into the river. By analysing the distributions of different surfactant homologues and their metabolites we were able to distinguish between sewage contamination from sources discharging treated and untreated wastewaters. Upstream (stations 1-2), LAS concentrations were below 30 μg L(-1) and the composition of their degradation intermediates (sulfophenyl carboxylic acids, SPCs) (160 μg L(-1)) was dominated by short-chain homologues (C(6)-C(9)SPCs), indicating that the degradation of this surfactant is at an advanced stage. The highest concentration (487 μg L(-1)) of SPCs was detected near the effluent outlet of a sewage treatment plant (STP) (station 12). Sampling stations (7 and 9) affected by untreated wastewater discharges were the only ones showing the presence of the most reactive and biodegradable SPC isomers and homologues (e.g. C(11)SPC). Here, LAS reached the highest concentration values measured (>2 mg L(-1)), and showed a homologue distribution closer to that of commercial mixtures than LAS found at the other stations.     

Distribution and availability of trace elements in municipal solid waste composts

Trace element contamination is one of the main problems linked to the quality of compost, especially when it is produced from urban wastes, which can lead to high levels of some potentially toxic elements such as Cu, Pb or Zn. In this work, the distribution and bioavailability of five elements (Cu, Zn, Pb, Cr and Ni) were studied in five Spanish composts obtained from different feedstocks (municipal solid waste, garden trimmings, sewage sludge and mixed manure). The five composts showed high total concentrations of these elements, which in some cases limited their commercialization due to legal imperatives. First, a physical fractionation of the composts was performed, and the five elements were determined in each size fraction. Their availability was assessed by several methods of extraction (water, CaCl(2)-DTPA, the PBET extract, the TCLP extract, and sodium pyrophosphate), and their chemical distribution was assessed using the BCR sequential extraction procedure. The results showed that the finer fractions were enriched with the elements studied, and that Cu, Pb and Zn were the most potentially problematic ones, due to both their high total concentrations and availability. The partition into the BCR fractions was different for each element, but the differences between composts were scarce. Pb was evenly distributed among the four fractions defined in the BCR (soluble, oxidizable, reducible and residual); Cu was mainly found in the oxidizable fraction, linked to organic matter, and Zn was mainly associated to the reducible fraction (iron oxides), while Ni and Cr were mainly present almost exclusively in the residual fraction. It was not possible to establish a univocal relation between trace elements availability and their BCR fractionation. Given the differences existing for the availability and distribution of these elements, which not always were related to their total concentrations, we think that legal limits should consider availability, in order to achieve a more realistic assessment of the risks linked to compost use.     

Land degradation assessment by geo-spatially modeling different soil erodibility equations in a semi-arid catchment

Land degradation by soil erosion is one of the most serious problems and environmental issues in many ecosystems of arid and semi-arid regions. Especially, the disturbed areas have greater soil detachability and transportability capacity. Evaluation of land degradation in terms of soil erodibility, by using geostatistical modeling, is vital to protect and reclaim susceptible areas. Soil erodibility, described as the ability of soils to resist erosion, can be measured either directly under natural or simulated rainfall conditions, or indirectly estimated by empirical regression models. This study compares three empirical equations used to determine the soil erodibility factor of revised universal soil loss equation prediction technology based on their geospatial performances in the semi-arid catchment of the Saraykoy II Irrigation Dam located in Cankiri, Turkey. A total of 311 geo-referenced soil samples were collected with irregular intervals from the top soil layer (0-10?cm). Geostatistical analysis was performed with the point values of each equation to determine its spatial pattern. Results showed that equations that used soil organic matter in combination with the soil particle size better agreed with the variations in land use and topography of the catchment than the one using only the particle size distribution. It is recommended that the equations which dynamically integrate soil intrinsic properties with land use, topography, and its influences on the local microclimates, could be successfully used to geospatially determine sites highly susceptible to water erosion, and therefore, to select the agricultural and bio-engineering control measures needed.     

Characterization of PM10-bound polycyclic aromatic hydrocarbons in the ambient air of Spanish urban and rural areas

Urban areas constitute major pollution sources due to anthropogenic activities located in these areas. Among the legislated air pollutants, the particulate matter with an aerodynamic diameter less than or equal to 10 microns (PM10) and polycyclic aromatic hydrocarbons (PAH) are controlled under Directive 2008/50/EC and Directive 2004/107/EC, respectively due to their adverse health effects. A study was carried out at four urban and rural Spanish areas during the warm and cold seasons in 2008-2009 to quantify 19 PAH associated with the atmospheric PM10 by gas chromatography-mass spectrometry-mass spectrometry detection (GC-MS-MS) with the internal standard method. The particle-bound composition of the analysed PAH was 5 and 10 times greater in industrial and urban areas, respectively when compared to those measured in rural areas. The highest PAH concentrations during the cold period were possibly due to the additional contribution of domestic heating sources and meteorological conditions such as low temperature and solar irradiation. The use of molecular diagnostic ratios indicated that the possible, major PAH pollution sources in the most polluted areas were pyrogenic sources, mainly attributed to petroleum combustion sources (motor vehicle emissions and crude oil combustion). Petrogenic sources related to evaporative emissions also seemed to contribute in the most polluted area during the warm period. Those dates with high carcinogenic character according to the benzo(a)pyrene equivalent (BaP-eq) were also possibly attributed to petroleum combustion sources.     

Environmental monitoring of alcohol sulfates and alcohol ethoxysulfates in marine sediments

The study describes the environmental monitoring of anionic surfactants―alcohol sulfates (AS) and alcohol ethoxysulfates (AES)—in marine sediments. Concentration values were obtained after pressurised liquid extraction (PLE) and liquid chromatography–tandem mass spectrometry analysis (LC–MS/MS). Samples were collected from a range of wastewater discharge points along the coast of the provinces of Huelva, Málaga, Granada and Almería. Urban, agricultural and industrial wastewaters are discharged at the selected 38 sampling sites. Principal component analysis was carried out in order to evaluate the distribution and behaviour of these compounds in these coastal environments. Evaluation of the data revealed that the behaviour and sources of AS and AES in marine sediments are different, and that the distribution of AES depends on the length of the alkyl chain, while the number of ethoxylated units is not relevant. Additionally, the 38 sampling sites can be grouped into only two types of outfalls according to their AS distribution. The concentration of compounds in sediment samples ranged from 7.52 to 13.50 mg kg^?1 for AS, from 3.04 to 10.68 mg kg^?1 for AES–C₁₂E_x and from 3.83 to 11.56 mg kg^?1 for AES–C₁₄E_x.     

Effect of ibuprofen exposure on blood,gill, liver,and brain on common carp (Cyprinus carpio) using oxidative stress biomarkers

Although trace concentrations of ibuprofen (IBP) have been detected in diverse water bodies, there is currently insufficient information on the potentially deleterious effects of this xenobiotic. The present study aimed to determine whether IBP induces oxidative stress in brain, liver, gill, and blood of the common carp Cyprinus carpio. To this end, the median lethal concentration at 96 h (96-h LC₅₀) was determined and the lowest observed adverse effect level was established. Carp were exposed to the latter concentration (17.6 mg L^?1) for 12, 24, 48, 72, and 96 h, and the following biomarkers were evaluated: lipid peroxidation (LPX) and activity of the antioxidant enzymes superoxide dismutase, catalase, and glutathione peroxidase. Results indicated that LPX and antioxidant enzymes’ activity increased significantly (p?<?0.05) with respect to the control group in liver, gill, and blood, while no significant differences occurred in brain. In conclusion, IBP induced oxidative stress on C. carpio, the liver being the organ most affected by this damage.     

Frequency of micronuclei and of other nuclear abnormalities in erythrocytes of the grey mullet from the Mondego,Douro and Ave estuaries—Portugal

Fish are bioindicators of water pollution, and an increased rate of their erythrocyte nuclear morphological abnormalities (ENMAs)—and particularly of erythrocyte micronuclei (EMN)—is used as a genotoxicity biomarker. Despite the potential value of ENMAs and MN, there is scarce information about fish captured in Iberian estuaries. This is the case of the Portuguese estuaries of the Mondego, Douro and Ave, suffering from different levels of environmental stress and where chemical surveys have been disclosing significant amounts of certain pollutants. So, the aim of this study was to evaluate genotoxicants impacts and infer about the exposure at those ecosystems, using the grey mullet (Mugil cephalus) as bioindicator and considering the type and frequency of nuclear abnormalities of erythrocytes as proxies of genotoxicity. Sampling of mullets was done throughout the year in the important Mondego, Douro and Ave River estuaries (centre and north-western Portugal). The fish (total n?=?242) were caught in campaigns made in spring–summer and autumn–winter, using nets or fishing rods. The sampled mullets were comparable between locations in terms of the basic biometric parameters. Blood smears were stained with Diff-Quik to assess the frequencies of six types of ENMAs and MN (given per 1,000 erythrocytes). Some basic water physicochemical parameters were recorded to search for fluctuations matching the ENMAs. Overall, the most frequent nucleus abnormality was the polymorphic type, sequentially followed by the blebbed/lobed/notched, segmented, kidney shaped, vacuolated, MN and binucleated. The total average frequency of the ENMAs ranged from 73?‰ in the Mondego to 108?‰ in the Ave. The polymorphic type was typically ≥50 % of the total ENMAs, averaging about 51?‰, when considering all three estuaries. The most serious lesion—the MN—in fish from Mondego and Douro had a similar frequency (≈0.38?‰), which was significantly lower than that in the Ave (0.75?‰). No significant seasonal differences existed as to the MN rates and seasonal differences existed almost only in the Douro, with the higher values in AW. In general, the pattern of ENMAs frequencies was unrelated with the water physicochemical parameters. Considering the data for both the total ENMAs and for each specific abnormality, and bearing in mind that values of MN in fish erythrocytes >0.3?‰ usually reflect pollution by genotoxicants, it is suggested that mullets were likely being chronically exposed to such compounds, even in the allegedly less polluted ecosystem (Mondego). Moreover, data supported the following pollution exposure gradient: Mondego?<?Douro?<?Ave. The scenario and inferences nicely agree with the published data from chemical monitoring.     

Atrazine and Alachlor Inputs to Surface and Ground Waters in Irrigated Corn Cultivation Areas of Castilla-Leon Region, Spain

The inputs of atrazine and alachlor herbicides to surface and ground waters from irrigated areas dedicated to corn cultivation in the Castilla-León (C-L) region (Spain) as related to the application of both herbicides were studied. Enzyme-linked immunosorbent assays (ELISA) were used for monitoring the atrazine and alachlor concentrations in 98 water samples taken from these areas. Seventy-nine of the samples were of ground waters and 19 were of surface waters. The concentration ranges of the herbicides detected in the study period (October 1997–October 1998) were 0.04–25.3 g L^–1 in the surface waters and 0.04–3.45 g L^–1 in the ground waters for atrazine, and 0.06–31.9 g L^–1 in the surface waters and 0.05–4.85 g L^–1 in the ground waters in the case of alachlor. The highly significant correlation observed between the concentrations of both herbicides in the surface waters (r = 0.89, p < 0.001) pointed to a parallel transport of atrazine and alachlor to these waters. A study was made of the temporal evolution of the concentrations of both herbicides, and it was found a maximum recharge of atrazine in the ground waters for April 1998 and of alachlor in October 1997 and October 1998. The temporal evolution of the concentrations of both herbicides in surface waters was parallel. The highly significant correlations observed between atrazine concentrations determined by ELISA and by HPLC (r = 0.92, p < 0.001) and between alachlor concentrations also determined by both methods (r = 0.96, p < 0.001) confirmed the usefulness of ELISA for monitoring both herbicides in an elevated number of samples. Using HPLC, the presence in some waters of the alachlor ethanesulfonate (ESA) metabolite was found at a concentration range of 0.52–4.01 g L^–1. However the interference of ESA in the determination of alachlor by ELISA was negligible. The inputs of atrazine and alachlor to waters found in this study, especially the inputs to ground waters, could pose a risk for human health considering that some waters, though sporadically, are even used for human consumption.