Organic Micropollutants Research Articles

Potential of Laccase as a Tool for Biodegradation of Wastewater Micropollutants

In the 21st century, humans are facing a high risk of exposure to emerging pollutants. Water contamination has become a major threat due to its devastating impacts on the entire ecosystem. Relatively great danger for aquatic microorganisms is posed by organic micropollutants, which are a consequence of progressing urbanization and industrialization. This review focuses on laccase of mainly fungal and bacterial origin, which provides an eco-friendly strategy for the transformation of these harmful pollutants to less or non-toxic compounds, as it acts oxidatively on the aromatic ring of a wide range of compounds, releasing water as the only by-product. Laccase alone or with the use of mediators has been used successfully to remove micropollutants from wastewater, including pharmaceuticals and personal care products, biocides, endocrine disrupting agents, steroid hormones, and microplastics. Even though the potential of an LMS (laccase–mediator system) is tremendous, the selection of an appropriate mediator and the persistent monitoring of toxicity after treatment are critical and should be performed routinely. Hence, further research is still needed for the optimization of degradation processes to improve our understanding of the different interactions of laccase with the substrate and to develop sustainable advanced water treatment systems.

What is in the fish? Collaborative trial in suspect and non-target screening of organic micropollutants using LC- and GC-HRMS

A collaborative trial involving 16 participants from nine European countries was conducted within the NORMAN network in efforts to harmonise suspect and non-target screening of environmental contaminants in whole fish samples of bream (Abramis brama). Participants were provided with freeze-dried, homogenised fish samples from a contaminated and a reference site, extracts (spiked and non-spiked) and reference sample preparation protocols for liquid chromatography (LC) and gas chromatography (GC) coupled to high resolution mass spectrometry (HRMS). Participants extracted fish samples using their in-house sample preparation method and/or the protocol provided. Participants correctly identified 9–69 % of spiked compounds using LC-HRMS and 20–60 % of spiked compounds using GC-HRMS. From the contaminated site, suspect screening with participants’ own suspect lists led to putative identification of on average ∼145 and ∼20 unique features per participant using LC-HRMS and GC-HRMS, respectively, while non-target screening identified on average ∼42 and ∼56 unique features per participant using LC-HRMS and GC-HRMS, respectively. Within the same sub-group of sample preparation method, only a few features were identified by at least two participants in suspect screening (16 features using LC-HRMS, 0 features using GC-HRMS) and non-target screening (0 features using LC-HRMS, 2 features using GC-HRMS). The compounds identified had log octanol/water partition coefficient (KOW) values from −9.9 to 16 and mass-to-charge ratios (m/z) of 68 to 761 (LC-HRMS and GC-HRMS). A significant linear trend was found between log KOW and m/z for the GC-HRMS data. Overall, these findings indicate that differences in screening results are mainly due to the data analysis workflows used by different participants. Further work is needed to harmonise the results obtained when applying suspect and non-target screening approaches to environmental biota samples.

Mechanisms of iopamidol transformation catalyzed by a copper corrosion product (c-Cu2O) during peroxymonosulfate disinfection

Peroxymonosulfate (PMS) is an alternative disinfectant for drinking water. This study aimed to investigate the transformation of iopamidol (IPM) catalyzed by a main copper corrosion product (c-Cu2O) with PMS as a disinfectant. The observed pseudo-first-order constant (kobs) for the IPM degradation in the c-Cu2O/PMS system (0.033 min−1) was 3 times that in the CuO/PMS system (0.011 min−1). The quenching tests and the electron paramagnetic resonance (EPR) experiments indicate that O2•− and 1O2 contributed to IPM degradation in the c-Cu2O/ PMS system. The complexation of metastable Cu(II) with a PMS molecule polarized the OO bond and then facilitated the electron transfer from the PMS molecule to other PMS and O2 molecules, which directly and indirectly promoted the yield of O2•− and 1O2. The iodine balance indicated that 26.0% of initial TOI was converted to IO3−, and CHI3 only accounted for 0.6% of the residual TOI. In the c-Cu2O/PMS system, IPM conversion was started with amide C−N bond breakage, deiodination reaction and hydrogen abstraction. This study helps to better understand the conversion mechanisms of iodine-containing organic micropollutants when PMS is deployed as a disinfectant in copper pipes.

Promoted micropollutant degradation and structural evolution of natural organic matter by a novel S(IV)-based water treatment strategy

The ubiquity of various organic micropollutants in global water and wastewater has raised considerable concern about their cost-efficient elimination. This study reported that the novel UV365/FeTiOX/S(IV) system could accomplish superior abatement of different micropollutants (e.g., carbamazepine, CMZ) in 30–45 min with excellent reusability and stability of FeTiOX. In addition, this system functioned effectively to remove roxarsone and As(III)/As(V) by catalytic oxidation and adsorption, respectively. Mechanistic investigations suggested the dual roles of S(IV) in enhancing pollutant oxidation, i.e., promoted Fe(II)/Fe(III) cycle and photocatalysis. These processes facilitated the continuous generation of multiple oxidizing intermediates (e.g., hydroxyl radicals, sulfate radicals, and singlet oxygen), in which the last one was first proposed as the main contributor in iron-mediated S(IV)-based oxidation processes. Based on the product identification, the transformation pathways of four different micropollutants were tentatively unraveled. The in silico prediction suggested the lower environmental risks of the final reaction products than the precursors. Particularly, the structural alteration of humic acid was analyzed, indicating an increased O/C ratio after oxidative treatment. Overall, this study has implications for developing an efficient oxidation technique for removing multiple micropollutants in water and facilitating the mechanistic reactivity modulation of the S(IV)-based oxidation strategies in water treatment.

Rainwater Quality Analysis for Its Potential Recovery: A Case Study on Its Usage for Swimming Pools in Poland

This paper describes the possibility of using rainwater for filling artificial swimming pools in Poland. The overall purpose of this study is to understand whether the quality of rainwater collected from roofs would be suitable for use in the swimming pools without any additional treatment. The rainwater samples were collected from five areas in the Silesian region and analysed for a number of physico-chemical parameters. The results show that the content of nitrates met Polish standards, whereas the standards set for pH and turbidity would only be met after the water had undergone the treatment process which takes place in every swimming pool installation. The paper further compares rainwater data from this study with the corresponding data for drinking water and groundwater. It shows that the content of ammonia, some metals (Ni, Cr and Mn) and a semimetal are in line with the parameters used for drinking water and are a lot lower compared to those set for groundwater. However, the results indicated some possible consequences which might be harmful for swimming pool users. These include the adverse effects of zinc and other organic micropollutants which are classified as contaminants of emerging concern (CECs). These may form dangerous byproducts in the presence of the chlorine, the use of which is required by the standards to be applied for swimming pool disinfection purposes.

Effects on the food-web structure and bioaccumulation patterns of organic contaminants in a climate-altered Bothnian Sea mesocosms

Climate change is expected to alter global temperature and precipitation patterns resulting in complex environmental impacts. The proposed higher precipitation in northern Scandinavia would increase runoff from land, hence increase the inflow of terrestrial dissolved organic matter (tDOM) in coastal regions. This could promote heterotrophic bacterial production and shift the food web structure, by favoring the microbial food web. The altered climate is also expected to affect transport and availability of organic micropollutants (MPs), with downstream effects on exposure and accumulation in biota. This study aimed to assess climate-induced changes in a Bothnian Sea food web structure as well as bioaccumulation patterns of MPs. We performed a mesocosms-study, focusing on aquatic food webs with fish as top predator. Alongside increased temperature, mesocosm treatments included tDOM and MP addition. The tDOM addition affected nutrient availability and boosted both phytoplankton and heterotrophic bacteria in our fairly shallow mesocosms. The increased tDOM further benefitted flagellates, ciliates and mesozooplankton, while the temperature increase and MP addition had minor effect on those organism groups. Temperature, on the other hand, had a negative impact on fish growth and survival, whereas tDOM and MP addition only had minor impact on fish. Moreover, there were indications that bioaccumulation of MPs in fish either increased with tDOM addition or decreased at higher temperatures. If there was an impact on bioaccumulation, moderately lipophilic MPs (log Kow 3.6 – 4.6) were generally affected by tDOM addition and more lipophilic MPs (log Kow 3.8 to 6.4) were generally affected by increased temperature. This study suggest that both increased temperatures and addition of tDOM likely will affect bioaccumulation patterns of MPs in shallow coastal regions, albeit with counteracting effects.

Thioether-functionalized porous β-cyclodextrin polymer for efficient removal of heavy metal ions and organic micropollutants from water

Herein, a thioether-functionalized porous β-cyclodextrin polymer (P(Bn-S-CD)) was prepared for efficient removal of heavy metal ions and organic micropollutants (OMPs) from water. P(Bn-S-CD) showed a surface area of 763 m2/g and a sulfur content 5.83 wt%. Based on screening studies, Hg2+ and diclofenac sodium (DS) were selected as model pollutants. P(Bn-S-CD) could adsorb Hg2+ and DS simultaneously, while the adsorbed Hg2+ afforded positive charges to the primary rims of CDs, greatly enhancing the adsorption rate and adsorption capacity of DS. Although the adsorbed DS showed no obvious effect on Hg2+ adsorption, it improved the affinity of Hg2+ upon P(Bn-S-CD). Adsorption mechanism studies confirmed the essential role of electrostatic interactions for these results. P(Bn-S-CD) also showed good selectivity towards heavy metal ions, excellent adsorption performance in real water at environmental levels and good reusability, implying great promise for water treatment.

Enhancing pharmaceutical removal in a full-scale constructed wetland with effluent recirculation

Emerging organic micropollutants pose a threat to aquatic environments even at trace levels. Among the many different groups of emerging pollutants, pharmaceutical residues are of special concern because of their toxicity and long-term effects on biota. Natural wastewater treatment systems are effective at eliminating pharmaceuticals, but removals are usually incomplete. In this regard, effluent recirculation can help to improve the removal of pharmaceuticals in natural wastewater treatment systems with the goal of producing a better-quality effluent for reuse. This is particularly interesting for water-scarce regions such as semi-arid islands of this study. The obtained results provide evidence that effluent recirculation can significantly improve the removal of pharmaceuticals in natural wastewater treatment systems. Of the 11 compounds studied, the highest concentrations and detection frequencies (in decreasing order) were those of caffeine, paraxanthine, nicotine, ibuprofen, naproxen and atenolol. The average removals increased from 87.5% (no recirculation) to 97% (100% recirculation ratio), and these results are associated with an improved ammonium and total N removal with 100% recirculation. To the knowledge of the authors, this is the first study showing the positive effect of effluent recirculation on the removal of pharmaceuticals in a full-scale natural wastewater treatment system.

ADSORPTION WATER TREATMENT WITH ADSORBENTS BASED ON VEGETABLE RAW MATERIALS

Currently, the world of environmental protection through the disposal of industrial waste and their rational processing is one of the main problems at the global level, aimed at improving the well-being of the population. However, the rapid development of industrial enterprises is accompanied by the formation of a significant amount of various wastes, including wastewater. Wastewater treatment from various pollutants is important from an environmental and economic point of view. At the same time, the accumulation of plant waste is an unimportant problem. One of the solutions to this problem is the production of environmentally friendly adsorbents based on plant materials. Recent years The recovery of biomass and waste biomass in the last decade has attracted the attention of an increasing number of scientists. Activated carbon (AC), used to remove organic micro-pollutants in the world's wastewater treatment plants, is usually produced from non-renewable resources such as peat, lignite, coal, anthracite, wood materials, waste paper, leather industry and animal products that needs to be transported over long distances. The use of biomass as feedstock can be beneficial in terms of sustainability. The review is devoted to the analysis of publications in this field in recent years. The main areas of application of adsorbents based on pine cones are considered. Examples of the implementation of the production of an adsorbent based on plant wastes and their use for water purification from various chemicals are given.

Assessment of full-scale 4th treatment step for micro pollutant removal in Sweden: Sand and GAC filter combo

This study focuses on the 4th treatment step in Degeberga WWTP treatment plant, the first full scale GAC filter in Sweden installed in April 2020 for removal of micropollutants. The two GAC filters, containing two different carbon types, has operated flawlessly for three years (30,000 bed volumes) without requiring backwashing. The results indicate that the sand filter provides effective protection to the carbon filters, preventing solids from reaching the carbon and reducing the growth of organic matter. Additionally substantial biodegradation was observed for several substances.During the first year of operation, the two filters (at 8500 and 5700 bed volumes respectively) achieved >98 % removal of 24 substances. By the end of the second year (at 19,000 and 12,600 bed volumes respectively), fluconazole and sulfamethoxazole broke through completely, and the number of compounds below 80 % removal increased. The average removal of micro pollutants decreased over time. Compounds with positive charges generally exhibited higher adsorption capacities, while negatively charged compounds had lower removals. On average the investigated 24 compounds was removed by 89 % in the 4th treatment step over three years. The study suggests that biodegradation may contribute to the removal of some micropollutants in GAC filters, similar to observations made in the sand filter.Both Swiss and suggested EU regulations aim for at least an 80 % removal in micropollutant concentration. The study evaluated the performance of the filters based on this guideline and the presented technique is after a total of eight years of investigation and evaluation a proven performer.Overall, the 4th treatment combination of sand and GAC filters in WWTPs has shown promising results in removing organic micropollutants, addressing the need for efficient treatment strategies targeting these emerging pollutants. Degeberga WWTP serves as an example of successful implementation of advanced treatment for improving water quality and protecting human and aquatic health.

Status quo on identified transformation products of organic ultraviolet filters and their persistence.

Organic micropollutants of concern - including organic UV filters (UVF) - are getting increasing attention. Personal care products such as sun screens or cosmetic articles often contain large quantities of UVF. These substances enter the environment either directly (during outdoor activities) or indirectly (via sewages from households). Therefore, the removal or degradation of UVF by natural or technical treatment processes is important to understand. UVF are often incompletely removed and transformed to side products of incomplete mineralization by abiotic and biotic processes. An extensive overview on transformation products (TPs) is essential to systematically identify knowledge gaps and to derive research needs. Whilst there are many reviews on the UVF themselves, the number of reviews which focus on their TPs is limited. Consequently, this review gives an overview on the latest findings regarding TPs of UVF. In this publication, known TPs of UVF, which were formed during abiotic and biotic processes, are reviewed. Target substances were defined and a literature database was reviewed for studies on TPs of the target substances. The first list of studies was shortened stepwise, thus generating a final list of studies which contained only the relevant studies. Since biodegradation is one of the most important pathways for removal of organic compounds from the environment, this review presents an overview on known TPs of organic UVF and their biodegradability, which determines their environmental fate. In this way, all identified TPs of UVF were listed and checked for information on their biodegradability. 2,731 records of studies were assessed. 42 studies, which assessed 46 processes that lead to the formation of identified TPs, were included in this review. 177 different TPs resulting from eleven different UVF were identified. Little to no data on the biodegradability was found for TPs. This indicates a severe lack of data on the biodegradability of TPs of organic UVF substances. Since most TPs lack information on biodegradability, further research should provide information on both - identity and biodegradability - of formed TPs to be able to assess their hazardousness for the environment.

Ecological risk assessment of pharmaceuticals and endocrine disrupting compounds in Brazilian surface waters

Pharmaceuticals and endocrine disrupting compounds are organic micropollutants that can cause adverse effects at low concentrations. Their occurrence in surface waters has been reported in several countries, including Brazil, at concentrations on the order of ngL−1, while the concentrations at which toxic effects are observed are often in the range of mg.L−1 to μg.L −1, however few studies have been undertaken to characterize risks they represent in Brazilian surface waters. Thus, the objective of this study was to evaluate the ecological risk to Brazilian surface waters caused by the presence of pharmaceuticals and natural and environmental estrogens. Twenty-nine pharmaceuticals, hormones and environmental estrogens were included in the risk assessment while twelve were discarded due to insufficient data availability. The endocrine disrupting compounds were the most frequently detected (39.8% of the reported concentrations), followed by non-steroidal anti-inflammatory drugs (16.3%), antibiotics (6.6%), antiseptics (5.1%), analgesics (5.1%), antihypertensives (4.6%), and to a lesser extent, lipid controllers, anticonvulsants, antidepressants, antihistamines, antivirals and corticosteroids. Bisphenol-A was the most frequently detected compound, followed by diclofenac, 17-β-estradiol, 17-α-ethynilestradiol, naproxen, triclosan and 4-n-nonylphenol. Acute ecological risk was predicted in two thirds and chronic risk in one third of the water bodies surveyed. The presence of diclofenac or triclosan was determinant for acute risk while estrogenic hormones proved to be decisive for chronic risk. In addition to natural and synthetic endocrine disruptors, the pharmacological groups estimated to have the highest average associated risks were non-steroidal anti-inflammatory drugs, followed by anticonvulsants. No discharge limits exist for most of the compounds found to contribute to ecological risks, indicating the need for regulatory action by the proper Brazilian authorities.

Selective Adsorption of Organic Micro-Pollutants by Smectite Clays Revealed from Atomistic Simulations.

In this study, atomistic simulations were carried out to study the difference in the adsorption process between two similar molecules, diazepam and oxazepam, on Na+-montmorillonite. Kinetic and XRD measurements showed a contrasting adsorption mechanism of these two molecules, differing only by the presence/absence of methyl and hydroxyl groups, with a larger adsorption amount and intercalation for the oxazepam. The structural characterization of these molecules was investigated through DFT calculations and showed the vicinity of hydroxyl and carbonyl groups for only the chair conformation of oxazepam compared to the boat conformation. Classical molecular dynamics simulations of diazepam and the two forms of oxazepam on the external surface of Na+-montmorillonite highlighted the better coordination of the oxazepam-chair conformation, compared to its boat counterpart and diazepam. This has been confirmed through DFT calculations, from which a coordination energy that is greater by 10 kcal·mol-1 is observed. This strongly suggests that the experimentally observed intercalation of oxazepam occurs only in the chair form because of the strong coordination with the Na+ cation present in the Na-Mt interlayer. Classical MD simulations of the intercalated oxazepam chair molecule in the Na-Mt interlayer allowed the evaluation of the interlayer spacing d001, which was in very good agreement with the experimental XRD measurement.

Novel positively-charged polyamine nanofiltration membrane prepared by oligomer triggered interfacial polymerization for molecular separation

Nanofiltration (NF) has the potential to achieve the efficient effluent separation. However, conventional polyamide-based NF membranes face several challenging issues, including negatively charged surface, insufficient water permeance and low selectivity of organic micropollutants. Herein, we designed a novel polyamine membrane generated from the nucleophilic substitution reaction between 1,4,7,10-tetraazacyclododecane (Cyclen) and 1,3,5-tris(bromomethyl)benzene (TBB), and proposed its fabrication via oligomer triggered interfacial polymerization (OT-IP). As the crucial component of the polyamine membrane, the amine-linked Cyclen-TBB selective layer was assembled onto a porous substrate through interfacial polymerization between alkaline aqueous solution and organic solution consisting of Cyclen and TBB premixed in n-hexane. The resultant Cyclen-TBB composite membrane possessed an effective pore size of ∼1.6 nm and strongly positively charged surface with a zeta potential of +18.4 mV in a neutral solution. Owing to these characteristics, the Cyclen-TBB composite membrane exhibited a high water permeance of 77.0 L·m−2·h−1·bar−1, and high rejections to positively charged dyes and drugs with molecular weights above 500 Da. Moreover, the composite membrane possessed splendid chemical resistance under both acidic or alkaline conditions, and operational stability during continuous filtration. These results demonstrate that novel highly permeable and positively-charged polyamine NF membranes are potential candidates for selective separation of molecules, and provide a feasible alternative for application in the treatment of industrial and pharmaceutical effluents.

SONOCHEMICAL PROCESSES IN THE DECOMPOSITION OF ORGANIC MICROPOLLUTANTS FROM RAINWATER

A wide range of aquatic systems, drinking water, groundwater and surface water is known to includeseveral dangerous organic micropollutants (OMPs). Additionally, a lot of the OMPs that have beenfound are resistant to biodegradation, allowing the possibility of persistence and accumulationin the ecosystem. Although they are present in small amounts, they have the potential to causemajor health issues, such as cancer. Recent studies showed that ultrasonication is very successful inremoving numerous hazardous OMPs from water. However, there is a tendency of combining thismethod with other advanced oxidation processes because of some of this technology’s limitations.This study provided additional evidence that ultrasonication is a highly effective approach forremoving micropollutants from rainwater. The efficiency of this technique can even be higher than80%. Moreover, the addition of ozone and hydrogen peroxide during ultrasonication increased theremoval ratio significantly, which was proportional to the oxidant dosage.

Efficient charge carrier separation over carbon-rich graphitic carbon nitride for remarkably improved photocatalytic performance in emerging organic micropollutant degradation and H2 production

Graphitic carbon nitride (g-C3N4) shows great potentials in visible-light-driven catalytic oxidation of organic micropollutants to harmless products and reduction of water to H2 but suffers from drawback of sluggish charge carrier separation and transfer dynamics. To overcome this drawback, here a novel point defect engineering strategy, by a nicotinic acid or barbituric acid-assisted supramolecule self-assembly of dicyandiamide followed by thermal polymerization, is designed to prepare pyridine unit-incorporated g-C3N4 (CPyr-CNx) and carbon atom self-doped g-C3N4 (C-CNx). The strategy leads to well-regulated chemical structures of CPyr-CNx and C-CNx and thus the precisely controlled electronic structures. The CPyr-CNx and C-CNx both exhibit remarkably improved visible-light photocatalytic activity in degradation of emerging organic micropollutants (methylparaben, acetaminophen and bisphenol A) and water-splitting to H2 production in comparison of bulk g-C3N4 and carbon-rich g-C3N4 prepared by a direct thermal copolymerization of nicotinic acid or barbituric acid with dicyandiamide, and their photocatalytic redox activity depends on carbon doping level. Experimental results combined with theoretical simulations reveal that the superior photocatalytic redox performance of CPyr-CNx and C-CNx is mainly dominated by the significantly boosted charge carrier separation and transfer dynamics driven by carbon doping induced-local electric field and -midgap states, which finally generates abundant reactive oxidation species including •O2− anion radicals, •OH radicals and 1O2 for the deep oxidation of target organic micropollutants to significantly reduce their ecotoxicity; additionally, such efficient charge carrier separation and transfer also favors high mobility for free electron-involved photocatalytic H2 evolution reaction.

Advanced steam-explosion pretreatment mediated anaerobic digestion of municipal sludge: Effects on methane yield, emerging contaminants removal, and microbial community

Advanced steam explosion pretreatment, i.e., the Thermal hydrolysis process (THP) is applied mainly to improve the sludge solubilization and subsequent methane yield in the downstream anaerobic digestion (AD) process. However, the potential of THP in pretreating the high solids retention time (SRT) sludges, mitigating the risk of emerging organic micropollutants and effects on anaerobic microbiome in digester remains unclear. In this study, sludge from a sequencing batch reactor (SBR) system operating at a SRT of 40 days was subjected to THP using a 5 L pilot plant at the temperature ranges of 120–180 °C for 30–120 min. The effect of THP on organics solubilization, methane yield, organic micropollutant removal, and microbial community dynamics was studied. The highest methane yield of 507 mL CH4/g VSadded and volatile solids (VS) removal of 54% were observed at 160°C- 30min THP condition, i.e., 4.1 and 2.6 times higher than the control (123 mL CH4/gVSadded, 20.7%), respectively. The experimental values of hydrolysis coefficient and methane yield have been predicted using Modified Gompertz, First order, and Logistics models. The observed values fitted well with all three models showing an R2 value between 0.96 and 1.0. THP pretreated sludges showed >80% removal of Trimethoprim, Enrofloxacin, Ciprofloxacin, and Bezafibrate. However, Carbamazepine, 17α-ethinylestradiol, and Progesterone showed recalcitrant behavior, resulting in less than 50% removal. Microbial diversity analysis showed the dominance of Proteobacteria, Firmicutes, Chloroflexi, and Bacteroidetes, collectively accounting for >70–80% of bacterial reads. They are mainly responsible for the fermentation of complex biomolecules like polysaccharides, proteins, and lipids. The THP-mediated anaerobic digestion of sludge shows better performance than the control digestion, improved methane yield, higher VS and micropollutants removal, and a diverse microbiome in the digester.

Role of imperfections in transfer of organic micro-pollutants through RO/NF membranes: Numerical study

Due to relatively low diffusivities, the rejection of organic micro-pollutants in pressure-driven membrane processes is more affected by Concentration Polarization (CP) than that of typical inorganic ions. On the other hand, it can be more sensitive to various membrane imperfections because the rejection of these solutes by intact membranes can be expected to be quite high. This makes necessary simultaneous accounting for membrane imperfections and Concentration Polarization in Reverse Osmosis and/or Nanofiltration of organic micro-pollutants. This study, for the first time, explores this problem numerically for the model of a single circular opening in a selective layer (the porous support is assumed to remain undamaged). The solute accumulated due to the CP close to the surrounding intact active layer “spills over” to the imperfection, which leads to an enhanced transmembrane solute passage as compared to the classical solution-diffusion-imperfection model assuming this passage to be controlled by the feed concentration. Our analysis reveals that the extent of this “spill-over” depends primarily on the size of imperfection (we studied the range between 0.2 μm and 20 μm) as well as on the ratio of hydraulic resistances of selective and support layers. Smaller imperfections in active layers of membranes with less permeable porous supports have larger impact. The extent of CP away from the imperfection is also important. Contrary to the trend expected for imperfection-free membranes (a better rejection of larger solutes due to a stronger steric exclusion and hindrance), the solute passage through imperfections is demonstrated to be larger for solutes with smaller diffusion coefficients, so in future experiments this can be considered a signature feature of a noticeable impact of imperfections. Quantifying their impact is important for understanding membrane aging, rational selection of membrane cleaning procedures as well as development of better membranes.

Benchmarking the Persistence of Active Pharmaceutical Ingredients in River Systems.

Assessing the persistence of organic micropollutants from field data has been notoriously laborious, requiring extensive data including emissions and chemical properties, and the application of detailed mass-balance models, which often contain parameters that are impossible to measure. To overcome some of these obstacles, we developed the concept of persistence benchmarking for large rivers that receive numerous emissions and provide enough residence time to observe the dissipation of compounds. We estimated the dissipation rate constants of 41 compounds (mostly active pharmaceutical ingredients) from five measurement campaigns in the Rhine and Danube rivers using concentration rate profiles with respect to carbamazepine. Dissipation rates clearly distinguished between known fast- and slow-degrading compounds, and campaign-specific boundary conditions had an influence on a minor subset of compounds only. Benchmarking provided reasonable estimates on summer total system half-lives in the Rhine compared to previous laboratory experiments and a mass-balance modeling study. Consequently, benchmarking can be a straightforward persistence assessment method of continuously emitted organic micropollutants in large river systems, especially when it is supported by field monitoring campaigns of proper analytical quality and spatial resolution.

Implications on freshwater lake-river ecosystem protection suggested by organic micropollutant (OMP) priority list

Lake-river complex systems represent interconnected ecosystems wherein inflow rivers significantly influence the migration of terrigenous contaminants, particularly organic micropollutants (OMPs), into lakes. Given the extensive array of OMPs, screening for those with the highest potential hazard is crucial for safeguarding freshwater lake-river ecosystems. In this study, an optimized multi-criteria scoring method was applied to prioritize OMPs. Flux estimation was then performed to identify the contamination load contributed by the Le’an River to Poyang Lake. Higher concentrations of phthalate esters (PAEs) were detected in the lake-river system, ranging from 1154.5 to 22,732.8 ng/L, followed by antibiotics and polycyclic aromatic hydrocarbons (PAHs), while historical pollutant residues were comparably lower. Based on the prioritization methodology, 27 compounds, encompassing eight PAEs, six organochlorine pesticides (OCPs), six polychlorinated biphenyls (PCBs), five PAHs and two antibiotics, emerged as priority pollutants. Multiple risk assessments revealed that priority PAEs posed relatively high ecological and human health risks; concurrently, the annual fluxes of individual priority PAEs into the lake all exceeded 1000 kg, with DBP, DEHP and BBP fluxes reaching 18,352, 10,429, and 7825 kg, respectively. This research offers valuable insights stemming from OMP prioritization to aid in the conservation of freshwater lake ecosystems, particularly concerning lake-river system integrity.