Assessing the Fate of Benzophenone-Type UV Filters and Transformation Products during Soil Aquifer Treatment: The Biofilm Compartment as Bioaccumulator and Biodegrader in Porous Media.

The fate of selected UV filters (UVFs) was investigated in two soil aquifer treatment (SAT) systems, one supplemented with a reactive barrier containing clay and vegetable compost and the other as a traditional SAT reference system. We monitored benzophenone-3 (BP-3) and its transformation products (TPs), including benzophenone-1 (BP-1), 4,4'-dihydroxybenzophenone (4DHB), 4-hydroxybenzophenone (4HB), and 2,2'-dihydroxy-4-methoxybenzophenone (DHMB), along with benzophenone-4 (BP-4) and avobenzone (AVO) in all involved compartments (water, aquifer sediments, and biofilm). The reactive barrier, which enhances biochemical activity and biofilm development, improved the removal of all detected UVFs in water samples. Among monitored UVFs, only 4HB, BP-4, and AVO were detected in sediment and biofilm samples. But the overall retained amounts were several orders of magnitude larger than those dissolved. These amounts were quantitatively reproduced with a specifically developed simple analytical model that consists of a mobile compartment and an immobile compartment. Retention and degradation are restricted to the immobile water compartment, where biofilm absorption was simulated with well-known compound-specific Kow values. The fact that the model reproduced observations, including metabolites detected in the biofilm but not in the (mobile) water samples, supports its validity. The results imply that accumulation ensures significant biodegradation even if the degradation rates are very low and suggest that our experimental findings for UVFs and TPs can be extended to other hydrophobic compounds. Biofilms act as accumulators and biodegraders of hydrophobic compounds.

Comparative study of emerging pollutants of interest in the groundwater of the volcanic islands of La Palma and El Hierro (Canary Islands).

Emerging pollutants (EPs) include a wide array of chemical compounds, as well as some microorganisms, which presence was unknown or unmeasurable until recently, or have recently started to be considered a threat towards the environment or animal and human health. No clear or homogeneous regulations exist for their measurement or control, and efforts should be made to assess their presence and offer solutions for their safe management, as well as to achieve an optimal protection of water resources. A previous study performed by our research group thoroughly studied a wide profile of EPs in El Hierro Island (Canary Islands) for the first time. Now, we present the study of the same panel of 70 EPs in La Palma Island (Canary Islands). 14 samples were collected in 2021, at different locations in La Palma island, representing seven municipalities (Los Llanos de Aridane, Santa Cruz de la Palma, El Paso, Breña Baja, Tazacorte, Barlovento and Fuencaliente) and four installation types (Piezometers/Wells, Wastewater Treatment Plant (WWTP), Water Gallery and Water Springs). High performance liquid chromatography-mass spectrometry (HPLC-MS) was performed to analyse the EP array, which included five chemical families: UV filters, UV blockers/stabilizers, parabens, Pharmaceutical Active Compounds (PhACs) and pesticides. Subsequently, a comprehensive descriptive and statistical analysis, including different tests was performed on the data obtained. Heterogeneous concentration levels of the EPs studied were found based on municipality and installation type among the island, with some of the PhACs and UV blockers/stabilizers showing very high levels, especially at Breña Baja and wastewater treatment plants (WWTPs). It is worth noting that some of the samples comprised within the WWTPs category were collected outside the treatment plant, after water has been treated, so they should not bear dangerous concentrations of any hazardous compound. The high presence of two pesticides, imidacloprid (ranging from 68.7 to 24,896.5 ng⋅L-1) and acetamiprid (ranging from 1010.7 to 5168.1 ng⋅L-1) was worth highlighting too. In addition, three EP concentration clusters were found to virtually divide the island based on mathematical percentiles of EP mean concentrations, which can help gain more insight into the contamination status of the island and measures that could be taken for their management. Finally, a comparison between La Palma results and the profile observed at El Hierro by our research group was presented. Altogether, the study performed calls for a need to take actions towards avoiding entrance of EPs in the water cycle, and not just focusing on remediation strategies once they have reached the groundwater, freshwater or soil.

Occurrence and ecological risk assessment of organic UV filters in coastal waters of the Iberian Peninsula.

This study aimed to assess the presence of 21 UVFs and metabolites in coastal regions of the Iberian Peninsula, to evaluate their environmental risk, and identify possible influential factors affecting their measured concentrations. Sampling was carried out in spring and summer to assess possible seasonal variations. UVFs were detected in 43 of the 46 sampling sites. Only 5 were found above LOD: BP4, OC, BP3 and metabolites BP1 and BP8. Samples collected in Mar Menor had the greatest variety of compounds per sample and the highest cumulative concentrations. The risk was characterized using Risk Quotients (RQ). BP1 showed a Low environmental Risk in 2 sites while for OC the RQ indicated a Moderate Risk in 22 points. The variables that contribute most to the variation are population density, sampling season, whether it was an open bay or not, and level of urbanization. The presence of WWTPs had a lower influence.

Factors driving PPCPs uptake by crops after wastewater irrigation and human health implications.

Currently, water scarcity affects more than three billion people. Nevertheless, the volume of treated wastewater discharged into the environment is estimated to exceed 100 m3 per inhabitant/year. These water resources are regularly used in agriculture worldwide to overcome water shortages. Such a practice, however, entails the uptake of waterborne pollutants, such as pharmaceuticals and personal care products (PPCPs), by crops and their further access to the food web, constituting an additional route of human exposure to PPCPs, with potential health outcomes. In this study, the occurrence of 56 PPCPs in tomatoes, lettuce, and carrot, together with soil and irrigation water, was evaluated using a QuEChERS-based methodology for extraction and LC-MS/MS for analysis. The influence of the selected cultivation conditions on the plant uptake levels of PPCPs was assessed. Two irrigation water qualities (secondary and tertiary treatment effluents), two soil compositions (sandy and clayey), two irrigation systems (dripping and sprinkling), and three crop types (lettuce, tomato, and carrot) were tested. Carrots showed the highest load of PPCPs (7787 ng/g dw), followed by tomatoes (1692 ng/g dw) and lettuces (1248 ng/g dw). The most translocated PPCPs were norfluoxetine (fluoxetine antidepressant main metabolite) (521 ng/g dw), and the anti-inflammatory diclofenac (360 ng/g dw). Nine PPCPs, are reported to be accumulated in crops for the first time. Water quality was the most important factor for reducing PPCPs' plant uptake. Overall, the best conditions for reducing PPCP uptake by crops were irrigation with reclaimed water by sprinkling in soils with higher clay content. The risk assessment performed revealed that the crops' consumption posed no risk to human health. This study serves as the first comprehensive assessment of the relevance of diverse cultivation factors on PPCPs' plant uptake under field agricultural practices.

First emerging pollutants profile in groundwater of the volcanic active island of El Hierro (Canary Islands).

Emerging pollutants (EPs) are substances present in wastewater that have not been studied, previously, leading to ambiguity in regulations for their presence in water resources. Territories that are highly dependent on groundwater resources are at a high risk of suffering the consequences of EP contamination due to their dependence on good quality groundwater for agriculture, drinking, and other uses. A relevant example is El Hierro (Canary Islands), which was declared a biosphere reserve by the UNESCO in 2000 and is almost completely powered by renewable energies. Using high performance liquid chromatography-mass spectrometry, the concentrations of 70 EPs were assessed at 19 sampling points on El Hierro. The results indicated that no pesticides were present in groundwater; however, varied concentration levels of ultraviolet (UV) filters, UV stabilizers/blockers and pharmaceutically active compounds (PhACs) were found, with La Frontera being the most contaminated municipality. With regard to the different installation types, piezometers and wells were the ones showing the highest concentrations for most EPs. Interestingly, the depth of sampling correlated positively with EP concentration, and four different clusters virtually dividing the island into two areas could be identified based on the presence of each EP. More studies should be performed to ascertain why a few of the EPs showed considerably high concentrations at different depths. The results obtained highlight the need to, not only implement remediation measures once EPs have reached the soil and aquifers, but also to avoid their incorporation into the water cycle via homes, animal husbandry, agriculture, industry, and wastewater treatment plants (WWTPs).