Enhancing Organic Micropollutants Removal in Wastewater with an Innovative Two-Stage Anaerobic Fixed-Film Bioreactor: Role of Acidogenic and Methanogenic Steps

The distinct stages of anaerobic digestion (AD) exhibit varying effects on the removal of diverse organic micropollutants present in wastewater. This study demonstrates the effectiveness of AD phase separation (acidogenesis and methanogenesis) in a two-stage anaerobic fixed-film bioreactor in the removal of pharmaceuticals and personal care products (PPCPs) from wastewater. The acidogenic–-methanogenic reactor achieved removal rates of over 95% for the chemicals sulfamethoxazole, methylparaben, propylparaben, naproxen, and acetaminophen and surpassed the single-stage methanogenic reactor in the removal of the more persistent compounds, ibuprofen, carbamazepine, metoprolol, ciprofloxacin, and diclofenac. The acidogenic step played a pivotal role in degrading persistent PPCPs, likely attributed to the selection of microbial enzymes involved in the production of volatile fatty acids from the oxidation of carbohydrates. The key candidate microbial genera for the PPCPs biodegradation were identified in the acidogenic reactor as Bacteroides, Clostridium, Williamwhitmania, Catenisphaera, and Erysipelothrix. In the methanogenic reactor, there was a predominance of Rectinema, Smithella, Syntrophus, and Syntrophorhabdus in coculture with hydrogen-using methanogens (Methanoregula and Methanolinea). This innovative two-stage reactor presents a promising solution for efficient organic micropollutant elimination in wastewater treatment plants

Reflection of Socioeconomic Changes in Wastewater: Licit and Illicit Drug Use Patterns

The economic crisis plaguing Greece was expected to impact consumption of pharmaceuticals and illicit drugs – <i>a priori</i> to an unknown extent. We quantified the change of use for various classes of licit and illicit drugs by monitoring Athens’ wastewater from 2010 to 2014. A high increase in the use of psychoactive drugs was detected between 2010 and 2014, especially for antipsychotics (35-fold), benzodiazepines (19-fold), and antidepressants (11-fold). This directly reflects the perceived increase of incidences associated with mental illnesses in the population, as a consequence of severe socioeconomic changes. Other therapeutic classes, like antiepileptics, hypertensives, and gastric and ulcer drugs also showed an increase in use (from 2-fold increase for antiepileptics to 13-fold for hypertensives). In contrast, the overall use of antibiotics and NSAIDs decreased. For mefenamic acid, an almost 28-fold decrease was observed. This finding is likely related to the reduction in drug expenditure applied in public health. A 2-fold increase of methamphetamine use was detected, associated with a cheap street drug called ″<i>sisa</i>″ (related to marginal conducts), which is a health concern. MDMA (5-fold) and methadone (7-fold) use showed also an increase, while cocaine and cannabis estimates did not show a clear trend

Exploring the Occurrence of Organic Contaminants in Human Semen through an Innovative LC-HRMS-Based Methodology Suitable for Target and Nontarget Analysis

Understanding the potential impact of organic contaminants on male fertility is crucial, yet limited studies have examined these chemicals in semen, with most focusing on urine and blood. To address this gap, we developed and validated a robust LC-HRMS methodology for semen analysis, with a focus on polar and semipolar chemicals. Our methodology enables the quantitative (or semiquantitative) analysis of >2000 chemicals being compatible with suspect and nontarget strategies and providing unprecedented insights into the occurrence and potential bioaccumulation of diverse contaminants in this matrix. We comprehensively analyzed exogenous organic chemicals and associated metabolites in ten semen samples from Spanish participants collected in an area with a large presence of the chemical industry included in the LED-FERTYL Spanish study cohort. This investigation revealed the presence of various contaminants in semen, including plastic additives, PFAS, flame retardants, surfactants, and insecticides. Notably, prevalent plastic additives such as phthalic acid esters and bisphenols were identified, indicating potential health risks. Additionally, we uncovered previously understudied chemicals like the tire additive 2-mercaptobenzothiazole and specific organophosphate flame retardants. This study showcases the potential of our methodology as a valuable tool for large-scale cohort studies, providing insights into the association between contaminant exposure and the risk of male fertility impairments

The Potential of Sewage Sludge to Predict and Evaluate the Human Chemical Exposome

Chemicals are part of our daily lives, and we are exposed to numerous chemicals through multiple pathways. Relevant scientific evidence contributing to the regulation of hazardous chemicals require a holistic approach to assess simultaneous exposure to multiple compounds. Biomonitoring provides an accurate estimation of exposure to chemicals through very complex and costly sampling campaigns. Finding efficient proxies to predict the risk of chemical exposure in humans is an urgent need to cover large areas and populations at a reasonable cost. We conducted an exploratory study to characterize the human chemical exposome in maternal blood and placenta samples of a population-based birth cohort in Barcelona (2018–2021). Ultimate HRMS-based approaches were applied including wide-scope target, suspect, and nontarget screening. Forty-two chemicals were identified including pesticides, personal care products, or industrial compounds, among others, in the range of ng/mL and ng/g. In parallel, sewage sludge from the wastewater treatment plants serving the residence areas of the studied population were also screened, showing correlations with the type and concentrations of chemicals found in humans. Our findings were suggestive for the potential use of sewage sludge as a proxy of the human exposure and its application in early warning systems to prevent bioaccumulation of hazardous chemicals

The Potential of Sewage Sludge to Predict and Evaluate the Human Chemical Exposome

Chemicals are part of our daily lives, and we are exposed to numerous chemicals through multiple pathways. Relevant scientific evidence contributing to the regulation of hazardous chemicals require a holistic approach to assess simultaneous exposure to multiple compounds. Biomonitoring provides an accurate estimation of exposure to chemicals through very complex and costly sampling campaigns. Finding efficient proxies to predict the risk of chemical exposure in humans is an urgent need to cover large areas and populations at a reasonable cost. We conducted an exploratory study to characterize the human chemical exposome in maternal blood and placenta samples of a population-based birth cohort in Barcelona (2018–2021). Ultimate HRMS-based approaches were applied including wide-scope target, suspect, and nontarget screening. Forty-two chemicals were identified including pesticides, personal care products, or industrial compounds, among others, in the range of ng/mL and ng/g. In parallel, sewage sludge from the wastewater treatment plants serving the residence areas of the studied population were also screened, showing correlations with the type and concentrations of chemicals found in humans. Our findings were suggestive for the potential use of sewage sludge as a proxy of the human exposure and its application in early warning systems to prevent bioaccumulation of hazardous chemicals

Development and Application of Liquid Chromatographic Retention Time Indices in HRMS-Based Suspect and Nontarget Screening

There is an increasing need for comparable and harmonized retention times (tR) in liquid chromatography (LC) among different laboratories, to provide supplementary evidence for the identity of compounds in high-resolution mass spectrometry (HRMS)-based suspect and nontarget screening investigations. In this study, a rigorously tested, flexible, and less system-dependent unified retention time index (RTI) approach for LC is presented, based on the calibration of the elution pattern. Two sets of 18 calibrants were selected for each of ESI+ and ESI-based on the maximum overlap with the retention times and chemical similarity indices from a total set of 2123 compounds. The resulting calibration set, with RTI set to range between 1 and 1000, was proposed as the most appropriate RTI system after rigorous evaluation, coordinated by the NORMAN network. The validation of the proposed RTI system was done externally on different instrumentation and LC conditions. The RTI can also be used to check the reproducibility and quality of LC conditions. Two quantitative structure–retention relationship (QSRR)-based models were built based on the developed RTI systems, which assist in the removal of false-positive annotations. The applicability domains of the QSRR models allowed completing the identification process with higher confidence for substances within the domain, while indicating those substances for which results should be treated with caution. The proposed RTI system was used to improve confidence in suspect and nontarget screening and increase the comparability between laboratories as demonstrated for two examples. All RTI-related calculations can be performed online at http://rti.chem.uoa.gr/