Contaminants of emerging concern fate and fluvial biofilm status as pollution markers in an urban river.

Contaminants of emerging concern (CEC) are still under research given the vast diversity of compounds reaching freshwater ecosystems and adverse effects they might cause. In this study, the environmental fate of 73 CEC, comprising sweeteners, stimulants and several pharmaceutical therapeutic classes, and changes in fluvial biofilm photosynthetic parameters were evaluated in a semi-arid urban river receiving diffuse and point sources of pollution (Suquía river, Argentina). Out of the 37 CEC detected, 30 were quantified in surface water (n.d. - 9826 ng/L), 10 in biofilm (n.d. - 204 ng/gd.w.) and 9 in the clay fraction of sediments (n.d. - 64 ng/gd.w.). CEC distribute differently among the 3 matrices: water phase presents the biggest diversity of compounds (14 CEC families), being analgesic/anti-inflammatories the most abundant family. Antibiotics largely predominated in biofilms (7 CEC families), while the stimulant caffeine and some antibiotics where the most abundant in sediments (6 CEC families). Different CEC accumulated in biofilms and sediments upstream and downstream the city, and big shifts of biofilm community occurred downstream WWTP. The shift of biofilm community upstream (F0 > 0) and downstream the WWTP (F0 = 0) shows a sensitive response of F0 to the impact of WWTP. Biofilm photosynthetic parameters responded in less impacted urban sites (sites 1, 2 and 3), where significant correlations were found between ketoprofen and some antibiotics and biofilm parameters. The diversity and amount of CEC found in the urban section of Suquía river alert to the magnitude of point and non-point sources of pollution.

Distribution of antibiotics in water, sediments and biofilm in an urban river (Córdoba, Argentina, LA).

In this study, we evaluated the distribution of up to forty-three antibiotics and 4 metabolites residues in different environmental compartments of an urban river receiving both diffuse and point sources of pollution. This is the first study to assess the fate of different antibiotic families in water, biofilms and sediments simultaneously under a real urban river scenario. Solid phase extraction, bead-beating disruption and pressurized liquid extraction were applied for sample preparation of water, biofilm and sediment respectively, followed by the quantification of target antibiotics by UPLC-ESI-MS/MS. Twelve antibiotics belonging to eight chemical families were detected in Suquía River samples (67% positive samples). Sites downstream the WWTP discharge were the most polluted ones. Concentrations of positive samples ranged 0.003-0.29 µg L-1 in water (max. cephalexin), 2-652 µg kg-1d.w. in biofilm (max. ciprofloxacin) and 2-34 µg kg-1d.w. in sediment (max. ofloxacin). Fluoroquinolones, macrolides and trimethoprim were the most frequently detected antibiotics in the three compartments. However cephalexin was the prevalent antibiotic in water. Antibiotics exhibited preference for their accumulation from water into biofilms rather than in sediments (bioaccumulation factors > 1,000 L kg-1d.w. in biofilms, while pseudo-partition coefficients in sediments < 1,000 L kg-1d.w.). Downstream the WWTP there was an association of antibiotics levels in biofilms with ash-free dry weight, opposite to chlorophyll-a (indicative of heterotrophic communities). Cephalexin and clarithromycin in river water were found to pose high risk for the aquatic ecosystem, while ciprofloxacin presented high risk for development of antimicrobial resistance. This study contributes to the understanding of the fate and distribution of antibiotic pollution in urban rivers, reveals biofilm accumulation as an important environmental fate, and calls for attention to government authorities to manage identified highly risk antibiotics.

Sublethal effects of carbendazim in Jenynsia multidentata detected by a battery of molecular, biochemical and genetic biomarkers.

The fungicide carbendazim (CBM) has been applied all around the world but its potential adverse effects other than its recognized activity as endocrine disruptor in non target organisms have been scarcely studied. The aims of this work were (1) to use a battery of biomarkers that can reflect potential negative effects such as oxidative stress, genotoxicity, neurotoxicity or altered immune response; and (2) to examine biomarkers of detoxification by analyzing the gene expression of cytochrome P4501A1 (CYP1A1) and the multi-xenobiotic resistance protein P-glycoprotein (P-gp) in the freshwater fish Jenynsia multidentata exposed to environmentally relevant concentrations of CBM during 24 h. Fish exposed to 5 µg/L showed inhibition of GST activity and an increase of TBARs contents in gills, the organ of direct contact with waterborne contaminants. Genotoxicity - measured in peripheral blood-was evidenced by the increases of micronuclei frequency when fish were exposed to 5, 10 and 100 µg/L CBM and of nuclear abnormalities (NA) frequency at 0.05, 0.5, 5, 10 and 100 µg/L CBM. The expression inhibition of interleukin (IL-1ß) and tumor necrosis factor a (TNF-α) at 10, and 5 and 10 µg/L CBM, respectively, indicated an altered immune response. The expression of CYP1A1 was down regulated in liver at 10 µg/L and of P-gp at 5 µg/L CBM, indicating a possible slow on CBM metabolization. On the other hand, in gills CYP1A1 decreased at 5 and 10 µg/L while P-gp was induced at 5 and 100 µg/L CBM. Overall, most of these significant effects were detected below 10 µg/L CBM, in a range of realistic concentrations in aquatic ecosystems worldwide.