Carmen Corada-Fernández

Occurrence and spatial distribution of emerging contaminants in the unsaturated zone. Case study: Guadalete River basin (Cadiz, Spain)

Irrigation with reclaimed water is becoming a common practice in arid- and semi-arid regions as a consequence of structural water resource scarcity. This practice can lead to contamination of the vadose zone if sewage-derived contaminants are not removed properly. In the current work, we have characterized soils from the Guadalete River basin (SW Spain), which are often irrigated with reclaimed water from a nearby wastewater treatment plant and amended using sludge. Physico-chemical, mineralogical and hydraulic properties were measured in soil samples from this area (from surface up to 2 m depth). Emerging contaminants (synthetic surfactants and pharmaceutically active compounds, or PhACs) were also determined. Synthetic surfactants, widely used in personal care products (PCPs), were found in a wide range of concentrations: 73-1300 μg kg(-1) for linear alkylbenzene sulfonates (LAS), 120-496 μg kg(-1) for alkyl ethoxysulfates (AES), 19-1090 μg kg(-1) for alcohol polyethoxylates (AEOs), and 155-280 μg kg(-1) for nonylphenol polyethoxylates (NPEOs). The presence of surfactant homologues with longer alkyl chains was predominant due to their sorption capacity. A positive correlation was found between LAS and AEOs and soil organic carbon and clay content, respectively. Out of 64 PhACs analyzed, only 7 were detected occasionally (diclofenac, metoprolol, fenofibrate, carbamazepine, clarithromycin, famotidine and hydrochlorothiazide), always at very low concentrations (from 0.1 to 1.3 μg kg(-1)).

Occurrence, distribution and environmental risk of pharmaceutically active compounds (PhACs) in coastal and ocean waters from the Gulf of Cadiz (SW Spain)

In this study, we have evaluated the occurrence and distribution of 78 pharmaceuticals in different aquatic marine environments from the Gulf of Cadiz (SW Spain) for the first time. The obtained results revealed that pharmaceuticals were present in seawater at total concentrations ranging 61-2133 and 16-189ngL-1 in coastal and oceanic transects, respectively. Potential marine pollution hotspots were observed in enclosed or semi-enclosed water bodies (Cadiz Bay), showing concentrations that were one or two orders of magnitude higher than in the open ocean. The presence of these chemicals in local sewage treatment plants (STPs), one of the main contamination sources, was also assessed, revealing total concentrations of up to 23μgL-1 in effluents. PhACs with the highest detection frequencies and concentrations in the sampling region were analgesics and anti-inflammatories followed by antibiotics in the case of samples from Cadiz Bay or caffeine in oceanic seawater samples. Risk quotients, expressed as ratios between the measured environmental concentration (MEC) and the predicted no-effect concentrations (PNEC) were higher than 1 for two compounds (gemfibrozil and ofloxacin) in effluent of Jerez de la Frontera sewage treatment plant (STP). No high environmental risk was detected in both coastal and oceanic sampling areas, although the information available about the effects of these chemicals on marine biota is still very limited and negative effects on non-target species cannot be discarded.

Vertical distribution profiles and diagenetic fate of synthetic surfactants in marine and freshwater sediments

This manuscript deals with the presence and degradation of the most commonly-used surfactants, including anionic (linear alkylbenzene sulfonates, LAS, and alkyl ethoxysulfates, AES) and non-ionic (alcohol polyethoxylates, AEOs, and nonylphenol polyethoxylates, NPEOs) compounds, in sediments and pore water from several aquatic environments (Southwest, Spain). Different vertical distributions were observed according to the respective sources, uses, production volumes and physicochemical properties of each surfactant. Levels of nonionics (up to 10 mg kg(-1)) were twice as high as anionics in industrial areas and harbors, whereas the opposite was found near urban wastewater discharge outlets. Sulfophenyl carboxylic acids (SPCs), LAS degradation products, were identified at anoxic depths at some sampling stations. Their presence was related to in situ anaerobic degradation of LAS in marine sediments, whereas the occurrence of these metabolites in freshwater sediments was attributed to the existence of wastewater sources nearby. No significant changes in the average length of AEO and NPEO ethoxylated chains were observed along the sediment cores, suggesting that their biodegradation was very limited in the sampling area. This may be directly related to their lower bioavailability, as their calculated sediment-pore water distribution coefficients (log K(sw)), which showed that non-ionic surfactants examined in this study had greater sorption affinity than the anionic surfactants (e.g., 2.3±0.3 for NPEOs).

Effects of extreme rainfall events on the distribution of selected emerging contaminants in surface and groundwater: The Guadalete River basin (SW, Spain)

This study is focused on the Guadalete River basin (SW, Spain), where extreme weather conditions have become common, with and alternation between periods of drought and extreme rainfall events. Combined sewer overflows (CSOs) occur when heavy rainfall events exceed the capacity of the wastewater treatment plants (WWTP), as well as pollution episodes in parts of the basin due to uncontrolled sewage spills and the use of reclaimed water and sludge from the local WWTP. The sampling was carried out along two seasons and three campaigns during dry (March 2007) and extreme rainfall (April and December 2010) in the Guadalete River, alluvial aquifer and Jerez de la Frontera aquifer. Results showed minimum concentrations for synthetic surfactants in groundwater (<37.4μg·L-1) during the first campaign (dry weather conditions), whereas groundwater contaminants increased in December 2010 as the heavy rainfall caused the river to overflow. In surface water, surfactant concentrations showed similar trends to groundwater observations. In addition to surfactants, pharmaceuticals and personal care products (PPCPs) were analyzed in the third campaign, 22 of which were detected in surface waters. Two fragrances (OTNE and galaxolide) and one analgesic/anti-inflammatory (ibuprofen) were the most abundant PPCPs (up to 6540, 2748 and 1747ng·L-1, respectively). Regarding groundwater, most PPCPs were detected in Jerez de la Frontera aquifer, where a synthetic fragrance (OTNE) was predominant (up to 1285ng·L-1).

Monitoring the occurrence of pharmaceuticals in soils irrigated with reclaimed wastewater

The use of reclaimed wastewater for irrigation is foreseen as a possible strategy to mitigate the pressure on water resources in dry regions. However, there is the risk of potential accumulation of contaminants of emerging concern (CECs) in the edaphic environment, their percolation and consequently contamination of aquifers. In the present study, we measured the levels of a wide range of commonly used pharmaceutically active compounds (PhACs) in sewage from a local wastewater treatment plant (WWTP) and in soils irrigated with treated wastewater. Analysis of target compounds showed total concentrations between 73 and 372 μg L-1 in WWTP influents, and from 3 to 41 μg L-1 in effluents. The total concentrations of PhACs detected in surface soil samples were in the range of 2 and 15 ng g-1, with predominance of analgesics and anti-inflammatories (maximum concentration = 10.05 ng g-1), followed by antibiotics and psychiatric drugs (maximum concentration = 5.45 ng g-1 and 3.78 ng g-1, respectively). Both effluent samples and irrigated soils shared similar compositional patterns, with compounds such as hydrochlorothiazide and diclofenac being predominant. Additionally, PhACs were also detected in soil samples at a depth of 150 cm, indicating that these chemical undergo leaching associated with heavy-rain episodes. Their occurrence in soils was affected by temperature too, as maximum concentrations were measured in colder months (up to 14 ng g-1), indicating higher persistence at lower temperatures. Finally, the ecotoxicological risk of PhACs in soil was evaluated by calculating their risk quotients (RQs). The risk was very low as RQ values ranged between <0.01 and 0.07. However, this initial assessment could be improved by future works on toxicity using specific terrestrial organisms.

Effects of exposure to pharmaceuticals (diclofenac and carbamazepine) spiked sediments in the midge, Chironomus riparius (Diptera, Chironomidae)

Human and veterinary pharmaceuticals and degradation products are continuously introduced into the environment. To date, there is a lack of information about the effects of pharmaceuticals in spiked toxicity tests with non-target organisms. In this study, we have evaluated the effects of exposure to two common pharmaceuticals in the midge Chironomus riparius in spiked sediment experiments. The selected pharmaceuticals are the nonsteroidal anti-inflammatory drug (NSAID): diclofenac (DF) and the anti-depressant drug carbamazepine (CBZ). In order to assess the effects of the pharmaceuticals, a chronic toxicity test with the midge was carried out. The endpoints survival, growth and developmental stage by means of biomass, were measured after 10days, and emergence rates and sex-ratio (male/female) were measured after 21days of exposure. Significant mortality was observed in organisms at day 10 with a 40% of larvae surviving in the highest exposure concentration of CBZ. DF decreased the emergence ratio with respect to the controls in organisms exposed at concentrations of 34.0μg·g-1 whereas CBZ reduced the growth of the midges (30,6% with respect to the control) and induced a significant change in sex-ratio at concentrations of 31.4μg·g-1. The results obtained in the present study indicate possible adverse effects on aquatic invertebrates, which should be taken into account for environmental risk assessment of pharmaceutical compounds in sediments.

Evaluation of the anaerobic biodegradation of linear alkylbenzene sulfonates (LAS) using OECD 308 water/sediment systems

Linear alkylbenzene sulfonates (LAS) are the most widely used anionic surfactants in household detergents and cleaning products. We have evaluated LAS anaerobic degradation in sediments following OECD 308 guidelines. Four different classes of sediments were collected from non-polluted areas and tested to check the influence of: fine and coarse texture, low and high organic carbon content, and freshwater and marine origin. The concentrations of LAS and possible degradation metabolites in sediment and water phases were monitored by high resolution mass spectrometry over an incubation period of 160 days. LAS removal was between 0 and 63%, depending on the sediment used, and it was accompanied by formation of sulfophenyl carboxylic acids (SPCs). The best results were observed for marine sediments having low organic carbon and silt + clay contents (0.5% and 13%, respectively), whereas degradation was negligible in freshwater sediments. The large differences in degradation observed across the sediments tested were attributed to their physicochemical properties influencing LAS bioavailability and the heterogeneity of microbial communities. Further research is also needed to address some shortcomings observed during the application of the OECD 308 and to ensure that test results obtained with these guidelines model anaerobic biodegradation under realistic environmental conditions.