Emerging Organic Compounds Research Articles

Synthesis and characterization of nanocomposite based polymeric membrane (PES/PVP/GO-TiO2) and performance evaluation for the removal of various antibiotics (amoxicillin, azithromycin & ciprofloxacin) from aqueous solution

The escalating global concern regarding antibiotic pollution necessitates the development of advanced water treatment strategies. This study presents an innovative approach through the fabrication and evaluation of a Polyethersulfone (PES) membrane adorned with GO-TiO2 nanocomposites. The objective is to enhance the removal efficiency of various antibiotics, addressing the challenge of emerging organic compounds (EOCs) in water systems. The nanocomposite membranes, synthesized via the phase inversion method, incorporate hydrophilic agents, specifically GO-TiO2 nanocomposites and Polyvinylpyrrolidone (PVP). The resultant membranes underwent comprehensive characterization employing AFM, EDS, tensile strength testing, water contact angle measurements, and FESEM to elucidate their properties. Analysis revealed a substantial improvement in the hydrophilicity of the modified membranes attributed to the presence of hydroxyl groups within the GO-TiO2 structure. AFM images demonstrated an augmentation in surface roughness with increasing nanocomposite content. FESEM images unveiled structural modifications, leading to enhanced porosity and augmented water flux. The pure water flux elevated from 0.980 L/m2.h−1 for unmodified membranes to approximately 6.85 L/m2.h−1 for membranes modified with 2 wt% nanocomposites. Membrane performance analysis indicated a direct correlation between nanocomposite content and antibiotic removal efficiency, ranging from 66.52% to 89.81% with 4 wt% nanocomposite content. Furthermore, the nanocomposite-modified membrane exhibited heightened resistance to fouling. The efficacy of the membrane extended to displaying potent antibacterial properties against microbial strains, including S. aureus, E. coli, and Candida. This study underscores the immense potential of GO-TiO2 decorated PES membranes as a sustainable and efficient solution for mitigating antibiotic contamination in water systems. The utilization of nanocomposite membranes emerges as a promising technique to combat the presence of EOC pollutants, particularly antibiotics, in water bodies, thus addressing a critical environmental concern.

ELECTRA: electricity-driven low energy and chemical input technology for accelerated bioremediation

The international cooperation project "electricity-driven low energy and chemical input technology for accelerated bioremediation" (abridged as "ELECTRA") is jointly supported by National Nature Science Foundation of China (NSFC) and European Commission (EC). The ELECTRA consortium consists of 5 research institutions and universities from China and 17 European research institutions and universities, as well as high-tech companies of EC countries. ELECTRA focuses on researches of biodegradation of emerging organic compounds (EOCs) and novel environmental biotechnologies of low-energy and low-chemical inputs. The project has been successfully operated for 2 years, and has made important progresses in obtaining EOCs-degrading microbes, developing weak-electricity-accelerated bioremediation, and 3D-printing techniques for microbial consortium. The ELECTRA has promoted collaborations among the Chinese and European scientists. In the future, ELECTRA will overcome the negative impact of the COVID-19 pandemic and fulfill the scientific objectives through strengthening the international collaboration.

Emerging organic compounds in European groundwater.

In Europe, emerging organic compounds (EOCs) in groundwater is a growing research area. Prioritisation for monitoring EOCs in Europe was formalised in 2019 through the development of the first voluntary groundwater watch list (GWWL). Despite this, groundwater occurrence data in the peer reviewed literature for Europe has not been reviewed to date. Questions surrounding the effect, toxicity, movement in the subsurface and unsaturated zone make the process of regulating EOC use difficult. The aim in Europe is to develop a unified strategy for the classification, and prioritisation of EOCs to be monitored in groundwater. This paper compiles evidence from the recent published studies from across Europe, since 2012, when the last major literature global review of EOCs in groundwater took place. A total of 39 studies were identified for review based on specific selection criteria (geography, publication date, sample size>10, inclusion of EOCs data). Data on specific compounds, and associated meta-data, are compiled and reviewed. The two most frequently detected EOCs, carbamazepine and caffeine, occurred in groundwater at concentrations of up to 2.3 and 14.8μg/L, respectively. The most frequently reported category of compounds were 'Pharmaceuticals'; a highly studied group with 135 compounds identified within 31 of the 39 studies. In Europe, the majority of reviewed studies (23) were at a regional scale, looking specifically at EOCs in a specific city or aquifer. The use of analytical methods is not uniform across Europe, and this inevitably influences the current assessment of EOCs in groundwater. A correlation between the number of compounds analysed for, and the number detected in groundwater highlights the need for further studies, especially larger-scale studies throughout Europe. For the development of EU and national regulation, further work is required to understand the occurrence and impacts of EOCs in groundwater throughout Europe and elsewhere.

Coupling isotope hydrology, geochemical tracers and emerging compounds to evaluate mixing processes and groundwater dependence of a highly anthropized coastal hydrosystem

Coastal aquifers can be considered as an important socio-economic and ecological component worldwide. The implementation of sustainable groundwater management is made difficult by complex hydrological behaviors due to many interactions between groundwater and fresh, brackish and salt surface water. This study proposes an original multi-tracer approach including physico-chemical parameters, trace elements, 18O, 2H, 3H of the water molecule and emerging organic compounds (EOCs) in order to improve the understanding of strongly urbanized coastal aquifers. This methodology was applied to a Mediterranean coastal aquifer in northern Corsica (France). Firstly, the isotopic data allow highlighting the complex recharge of groundwater, provided by both allochthonous rainfall from the mountain and autochthonous rainfall on the Marana-Casinca alluvial plain. Secondly, geochemical data coupled with isotopic signatures allow the identification of the different contributors and the quantification of the mixing processes into the aquifer. The residence time of groundwater were estimated with 3H. In addition, to display inertial areas with long residence time, 3H also highlights areas subject to infiltration of recent water. A better understanding of short-time hydrological processes was improved by EOCs. The study of the fate of EOCs in the environment provided a higher level of resolution than geochemical and isotopic tracers alone. Thus, the multi-tracing approach using isotopic and geochemical data, coupled with the study of the fate of EOCs, made possible to specify the conceptual model in highly anthropized hydrosystems, and particularly fast hydrological processes.

Dynamics of emerging organic contaminant removal in conventional and intensified subsurface flow treatment wetlands

Six pilot-scale treatment wetlands treating municipal wastewater were monitored for classical wastewater parameters and selected Emerging Organic Compounds (EOCs): caffeine (CAF), ibuprofen (IBU), naproxen (NPX), benzotriazole (BTZ), diclofenac (DCL), acesulfame (ACE) and carbamazepine (CBZ) on a weekly basis over the course of one year. Treatment efficacy of the wetland systems was compared to that of a municipal wastewater treatment plant adjacent to the research site (activated sludge technology). The aerated wetlands VAp and HAp, and the two-stage vertical flow system VGp + VSp showed the highest treatment efficacy (>70% removal on a mass basis) and comparable treatment efficacy to the conventional WWTP for removal of CAF, IBU, NPX, BTZ, and DCL. Annual mass removal of ACE in the WWTP was 50% and varied in the wetlands (depending on system design) from zero to 62%. On a mean monthly basis, ACE removal in the treatment wetlands VGp + VSp, VAp, HAp, R was high (> 90%) for six months of the year. Monthly mean mass removal of CBZ was negligible for the WWTP and all treatment wetland systems except H50p, which showed up to 49% mass removal in June. Monthly mean mass removals of classical wastewater parameters and readily biodegradable EOCs (represented by CAF, IBU, NPX) were most stable in the intensified wetland designs VAp, HAp, and R. A statistical analysis confirms that system complexity, aerobic conditions, and temperature have the highest correlation to overall pollutant removal in the treatment wetland systems, including EOCs of high to moderate biodegradability. First-order removal rate coefficents and temperature correction factors for EOCs are reported for the first time in the treatment wetland literature. Limitations on the use of these values in engineering design are discussed.

The uncertainty of biodegradation rate constants of emerging organic compounds in soil and groundwater – A compilation of literature values for 82 substances

The present study reports on biodegradation rate constants of emerging organic compounds (EOCs) in soil and groundwater available in the literature. The major aim of this compilation was to provide an assessment of the uncertainty of hydrological models with respect to the fate of EOCs. The literature search identified a total number of 82 EOCs for which 1st-order rate constants could be derived. It was found that for the majority of compounds degradation rate constants vary over more than three orders of magnitude. Correlation to factors that are well known to affect the degradation rate, such as temperature or redox condition was weak. No correlation at all was found with results from available quantitative structure-activity relationship models. This suggests that many unknown site specific or experimentally specific factors influence the degradation behavior of EOCs in the environment. Thus, local and catchment scale predictive models to estimate EOC concentration at receptors, e.g., receiving waters or drinking water wells, need to consider the large uncertainty in 1st-order rate constants. As a consequence, applying rate constants that were derived from one experiment or field site investigation to other experiments or field sites should be done with extreme caution.

Evaluation of EOC removal processes during artificial recharge through a reactive barrier

A reactive barrier that consisted of vegetable compost, iron oxide and clay was installed in an infiltration basin to enhance the removal of emerging organic compounds (EOCs) in the recharge water. First-order degradation rates and retardation factors were jointly estimated for 10 compounds using a multilayer reactive transport model, whose flow and conservative transport parameters were previously estimated using hydraulic head values and conservative tracer tests. Reactive transport parameters were automatically calibrated against the concentration of EOCs measured at nine monitoring points. The degradation rate of each compound was estimated for three zones defined according to the redox state, and retardation coefficients were estimated in two zones defined according to the organic matter content. The fastest degradation rates were obtained for the reactive barrier, and the estimated values were similar to or higher than those estimated in column and/or field experiments for most of the compounds (8/10). Estimated retardation coefficients in the reactive barrier were higher than in the rest of the aquifer in most cases (8/10) and higher than those values estimated in previous studies. Based on the results obtained in this study the reactive barrier seems to be able to enhance the removal of EOCs.

Effect of design and operational conditions on the performance of subsurface flow treatment wetlands: Emerging organic contaminants as indicators

Six pilot-scale subsurface flow treatment wetlands loaded with primary treated municipal wastewater were monitored over one year for classical wastewater parameters and a set of emerging organic compounds (EOCs) serving as process indicators for biodegradation: caffeine, ibuprofen, naproxen, benzotriazole, diclofenac, acesulfame, and carbamazepine. The wetland technologies investigated included conventional horizontal flow, unsaturated vertical flow (single and two-stage), horizontal flow with aeration, vertical flow with aeration, and reciprocating. Treatment efficiency for classical wastewater parameters and EOCs generally increased with increasing design complexity and dissolved oxygen concentrations. The two aerated wetlands and the two-stage vertical flow system showed the highest EOC removal, and the best performance in warm season and most robust performance in the cold season. These three systems performed better than the adjacent conventional WWTP with respect to EOC removal. Acesulfame was observed to be removed (>90%) by intensified wetland systems and with use of a tertiary treatment sand filter during the warm season. Elevated temperature and high oxygen content (aerobic conditions) proved beneficial for EOC removal. For EOCs of moderate to low biodegradability, the co-occurrence of aerobic conditions and low content of readily available carbon appears essential for efficient removal. Such conditions occurred in the aerated systems and with use of a tertiary treatment sand filter.

Improving degradation of emerging organic compounds by applying chaotic advection in Managed Aquifer Recharge in randomly heterogeneous porous media

AbstractImproving degradation rates of emerging organic compounds (EOCs) in groundwater is still a challenge. Although their degradation is not fully understood, it has been observed that some substances are preferably degraded under specific redox conditions. The coupling of Managed Aquifer Recharge with soil aquifer remediation treatment, by placing a reactive layer containing organic matter at the bottom of the infiltration pond, is a promising technology to improve the rate of degradation of EOCs. Its success is based on assuming that recharged water and groundwater get well mixed, which is not always true. It has been demonstrated that mixing can be enhanced by inducing chaotic advection through extraction‐injection‐engineering. In this work, we analyze how chaotic advection might enhance the spreading of redox conditions with the final aim of improving degradation of a mix of benzotriazoles: benzotriazole, 5‐methyl‐benzotriazole, and 5‐chloro‐benzotriazole. The degradation of the first two compounds was fastest under aerobic conditions whereas the third compound was best degraded under denitrification conditions. We developed a reactive transport model that describes how a recharged water rich in organic matter mixes with groundwater, how this organic matter is oxidized by different electron acceptors, and how the benzotriazoles are degraded attending for the redox state. The model was tested in different scenarios of recharge, both in homogenous and in heterogenous media. It was found that chaotic flow increases the spreading of the plume of recharged water. Consequently, different redox conditions coexist at a given time, facilitating the degradation of EOCs.

Monitoring the Behavior of Emerging Contaminants in Wastewater-Impacted Rivers Based on the Use of Fluorescence Excitation Emission Matrixes (EEM).

This study investigated the applicability of fluorescence indexes based on the interpretation of excitation emission matrices (EEMs) by PARAFAC analysis and by selecting fluorescence intensities at a priori defined excitation/emission pairs as surrogates for monitoring the behavior of emerging organic compounds (EOCs) in two catchment basins impacted by wastewater discharges. Relevant EOC and EEM data were obtained for a 90 km stretch of the Simeto River, the main river in Sicily, and the smaller San Leonardo River, which was investigated for a 17 km stretch. The use of fluorescence indexes developed by these two different approaches resulted in similar observations. Changes of the fluorescence indexes that correspond to a group of humic-like fluorescing species were determined to be highly correlated with the concentrations of recalcitrant contaminants such as sucralose, sulfamethoxazole and carbamazepine, which are typical wastewater markers in river water. Changes of the fluorescence indexes related to tyrosine-like substances were well correlated with the concentrations of ibuprofen and caffeine, anthropogenic indicators of untreated wastewater discharges. Chemical oxygen demand and dissolved organic carbon concentrations were correlated with humic-like fluorescence indexes. The observed correlations were site-specific and characterized by different regression parameters for every collection event. Caffeine and carbamazepine showed correlations with florescence indexes in the San Leonardo River and in the alluvial plain stretch of the Simeto River, whereas sucralose, sulfamethoxazole and ibuprofen have always been well correlated in all the investigated river stretches. However, when data of different collection events from river stretches where correlations were observed were combined, good linear correlations were obtained for data sets generated via the normalization of the measured concentrations by the average value for the corresponding collection event. These results show that fluorescence based indexes can be used to monitor the behavior of some trace organic contaminants in wastewater impacted rivers and to track wastewater discharges in streams and rivers.

Selected emerging organic contaminants in the Yangtze Estuary, China: A comprehensive treatment of their association with aquatic colloids

Contaminants that are becoming detected in the environment but are not yet generally regulated or monitored are known collectively as emerging contaminants. In the present study, the occurrence and distribution of 42 emerging organic compounds (EOCs) were investigated in the Yangtze River Estuary and adjacent East China Sea coastal areas. Study compounds were mainly pharmaceuticals, including antibiotics, hormones and sterols, and also included two industrial endocrine disruptors. Samples were analyzed using cross-flow ultrafiltration (CFUF) and ultra-performance liquid chromatograph–tandem mass spectrometry (UPLC–MS/MS). Results revealed that chloramphenicols, sulfonamides and non-steroidal anti-inflammatory drugs were the dominant compounds in filtered samples with relatively high concentrations and detection frequencies. EOC levels varied with location, with the highest concentrations being observed around rivers discharging into the estuary, and near sewage outfalls. Colloids that were separated by CFUF tended to be a sink for EOCs with up to 60% being colloid-associated in the water phase. In addition, colloidal properties, including hydrodynamic size, zeta-potential and organic carbon composition, were found to be the main factors controlling the association of EOCs with aquatic colloids. Moreover, these colloidal properties were all significantly related to salinity, indicating the critical role played by increasing salinity in EOCs–colloids interaction in an estuarine system.