Pollutants In Aquatic Environment Research Articles

Non-Linear Analyses of Fish Behaviours in Response to Aquatic Environmental Pollutants—A Review

Analysis of fish behaviour is an effective way to indirectly identify the presence of environmental pollutants that negatively affect fish life, its production and quality. Monitoring individual and collective behaviours produces large amounts of non-linear data that require tailor-suited computational methods to interpret and manage the information. Fractal dimension (FD) and entropy are two groups of such non-linear analysing methods that serve as indicators of the complexity (FD) and predictability (entropy) of the behaviours. Since behavioural complexity and predictability may be modulated by contaminants, the changes in its FD and entropy values have a clear potential to be embedded in a biological early warning system (BEWS), which may be particularly useful in Precision Fish Farming settings and to monitor wild populations. This work presents a review of the effects of a wide range of environmental contaminants, including toxic compounds, cleaning and disinfecting agents, stimulant (caffeine), anaesthetics and antibiotics, heavy metals (lead, cupper, and mercury), selenium, pesticides and persistent environmental pollutants, on the FD and entropy values of collective and individual behavioural responses of different fish species. All the revised studies demonstrate the usefulness of both FD and entropy to indicate the presence of pollutants and underline the need to consider early changes in the trend of the evolution of their values prior to them becoming significantly different from the control values, i.e., while it is still possible to identify the contaminant and preserve the health and integrity of the fish.

Fluchloralin induces developmental toxicity in heart, liver, and nervous system during early zebrafish embryogenesis

The zebrafish is a prominent vertebrate model popularly used for toxicity testing because of its rapid development and transparent embryos. Fluchloralin, a dinitroaniline herbicide used to control weeds, inhibits microtubule formation and cell division. The structurally homologous substances ethalfluralin and pendimethalin, which belong to the dinitroaniline family, were found to be genotoxic and to exert developmental toxicity via mitochondrial dysfunction in a zebrafish model. To date, developmental toxicity of fluchloralin in zebrafish has not been reported. In the present study, we identified morphological changes in developing zebrafish, including decreased survival rate and body length, and increased yolk sac edema. In dose-dependent response to fluchloralin exposure, inhibition of neurogenesis in the spinal cord and motor neuron defects were observed in transgenic zebrafish models (olig2:dsRed). Zebrafish exposed to fluchloralin also displayed organ dysfunction in the heart, liver, and pancreas in cmlc2:dsRed and lfabp:dsRed;elastase:GFP transgenic models. Fluchloralin increased cell death in the brain by promoting apoptosis, visualized via acridine orange staining, and by activating apoptosis signaling proteins, including cytochrome c1, zBax, and Bcl-XL. This study provides novel evidence supporting the necessity of controlling pollutants in aquatic environments.

Occurrence of extended-spectrum β-lactamases-producing Escherichia coli isolates over gradient pollution in an urban tropical estuary.

Bacterial resistance to antimicrobials is a global public health problem that surpasses the human context and can be increased by pollution. However, the lack of systematic monitoring of resistance in some aquatic matrices, such as tropical estuaries, makes it unknown whether its occurrence is associated with anthropogenic pollution in these environments. Therefore, we investigated the occurrence of extended-spectrum beta-lactamases (ESBLs) producing Escherichia coli as a resistance indicator for 12 consecutive months at three representative points of a pollution gradient in Guanabara Bay (GB), Brazil. Sixty-six E. coli strains were selected from 72 samples of GB waters in the presence of ceftriaxone (8 μg mL-1 ) and identified by MALDI-TOF MS. Of the 66, 55 (83.3%) strains were ESBL producers. They carried beta-lactamase/ESBL genes, with the predominance of blaCTX-M (54, 98.2%), especially the blaCTX-M-1,2 allele (49.1%). These strains were detected frequently (81.8%) from the point with the highest pollution levels. Furthermore, the marker for Class 1 integron, intI1 gene, was detected in 54.5% of ESBL producers. These data suggest an association between antimicrobial-resistant E. coli and sewage pollution in aquatic environments raising concerns about the possible risks of human exposure to these waters and fish consumption.

Plastic-associated metal(loid)s in the urban river environments of Mongolia

The widespread distribution of plastic debris in riverine environment is one of the major concerns of environmental pollution because of its potential impact on the aquatic ecosystem. In this study, we investigated the accumulation of metal(loid)s on polystyrene foam (PSF) plastics collected from the floodplain of the Tuul River of Mongolia. The metal(loid)s sorbed on plastics were extracted from the collected PSF via sonication after peroxide oxidation. The size-dependent association of metal(loid)s with plastics indicates that PSFs act as vectors for pollutants in the urban river environment. The mean concentrations of metal(loid)s (i.e., B, Cr, Cu, Na, and Pb) indicate a higher accumulation of the metal(loid)s on meso-sized PSFs compared with macro- and micro-sized PSFs. In addition, the images from scanning electron microscopy (SEM) indicated not only the degraded surface of plastics showing fractures, holes, and pits but also the adhered mineral particles and microorganisms on the PSFs. The interaction of metal(loid)s with plastics was probably facilitated by the physical and chemical properties of altered surface of plastics through photodegradation, followed by an increase in surface area by size reduction and/or biofilm development in the aquatic environment. The enrichment ratio (ER) of metals on PSF samples suggested the continuous accumulation of heavy metals on plastics. Our results demonstrate that the widespread plastic debris could be a carrier of hazardous chemicals in the environment. Considering that the negative impacts of plastic debris on environmental health are major concerns to be addressed, the fate and behavior of the plastics especially their interaction with pollutants in aquatic environments should be further studied.

The effect of lead (Pb) on the growth rates of two aquatic macrophyte species; Limnobium laevigatum (Humb & Bonpl. ex Willd) Heine and Egeria densa Planch. grown in different experimental media

Anthropogenic causes contribute to toxic pollutants in aquatic environments and heavy metal pollution. As a heavy metal, Lead (Pb), is one of the most common causes of pollution in water. Heavy metals must be removed from the aquatic environment because they adversely affect health and all living things in each environment. In this study we aimed to determine the effects of lead (Pb) exposure on the growth rates and biomass of two aquatic macrophyte species, E. densa and L. laevigatum. Plants grown in in two different experimental media. For this purpose, both plants were exposed to 3 different concentrations of lead (1 ppm, 5 ppm, 15 ppm). Samples were measured on the 1st, 4th and 7th days, and the first and last weights of the plants were compared. Bioexperiments were run in triplicate. Positive values were observed in the growth rates of both plants, except for the negative growth rates observed on the 1st day at 1 ppm and 5 ppm lead concentrations in the pond water environment. Both plants showed positive growth in 25% Hoagland medium at all concentrations and days, except for the 1 ppm lead concentration, being observed for E. densa. As a result of our study, lead exposure did not significantly alter the growth rates of E. densa and L. laevigatum in the experimental media used for short-term (up tp 7 days) durations.

Mechanisms of low susceptibility to the disinfectant benzalkonium chloride in a multidrug-resistant environmental isolate of Aeromonas hydrophila.

Excessive discharge of quaternary ammonium disinfectants such as benzalkonium chloride (BAC) into aquatic systems can trigger several physiological responses in environmental microorganisms. In this study, we isolated a less-susceptible strain of Aeromonas hydrophila to BAC, designated as INISA09, from a wastewater treatment plant in Costa Rica. We characterized its phenotypic response upon exposure to three different concentrations of BAC and characterized mechanisms related to its resistance using genomic and proteomic approaches. The genome of the strain, mapped against 52 different sequenced A. hydrophila strains, consists of approximately 4.6 Mb with 4,273 genes. We found a massive genome rearrangement and thousands of missense mutations compared to the reference strain A. hydrophila ATCC 7966. We identified 15,762 missense mutations mainly associated with transport, antimicrobial resistance, and outer membrane proteins. In addition, a quantitative proteomic analysis revealed a significant upregulation of several efflux pumps and the downregulation of porins when the strain was exposed to three BAC concentrations. Other genes related to membrane fatty acid metabolism and redox metabolic reactions also showed an altered expression. Our findings indicate that the response of A. hydrophila INISA09 to BAC primarily occurs at the envelop level, which is the primary target of BAC. Our study elucidates the mechanisms of antimicrobial susceptibility in aquatic environments against a widely used disinfectant and will help better understand how bacteria can adapt to biocide pollution. To our knowledge, this is the first study addressing the resistance to BAC in an environmental A. hydrophila isolate. We propose that this bacterial species could also serve as a new model to study antimicrobial pollution in aquatic environments.

Searching for a Reliable Viral Indicator of Faecal Pollution in Aquatic Environments.

The disposal of sewage in significant quantities poses a health hazard to aquatic ecosystems. These effluents can contain a wide range of pathogens, making faecal contamination a leading source of waterborne diseases around the world. Yet monitoring bacteria or viruses in aquatic environments is time consuming and expensive. The standard indicators of faecal pollution all have limitations, including difficulty in determining the source due to lack of host specificity, poor connection with the presence of non-bacterial pathogens, or low environmental persistence. Innovative monitoring techniques are sorely needed to provide more accurate and targeted solutions. Viruses are a promising alternative to faecal indicator bacteria for monitoring, as they are more persistent in ambient water, more abundant in faeces, and are extremely host-specific. Given the range of viruses found in diverse contexts, it is not easy to find one "ideal" viral indicator of faecal pollution; however, several are of interest. In parallel, the ongoing development of molecular techniques coupled with metagenomics and bioinformatics should enable improved ways to detect faecal contamination using viruses. This review examines the evolution of faecal contamination monitoring with the followingaims (i) to identify the characteristics of the main viral indicators of faecal contamination, including human enteric viruses, bacteriophages, CRESS and plant viruses, (ii) to assess how these have been used to monitor water pollution in recent years, (iii) to evaluate the reliability of recent detection methods of such viruses, and (iv) to tentatively determine which viruses may be most effective as markers of faecal pollution.

The Importance Of Seaweed As Bioremediation Natural Agent

Seaweed has emerged as a promising bioremediation agent for addressing heavy metal contamination in aquatic environments. This study presents a comprehensive review of ten selected references to explore the potential of seaweed-based bioremediation and its implications for environmental sustainability. The findings highlight the significant capacity of seaweed species to accumulate heavy metals, emphasizing the importance of species selection based on their metal uptake capabilities. Seaweed biomass and biochar demonstrate remarkable adsorption properties, providing efficient means of removing heavy metals from contaminated water through physical adsorption and ion exchange processes. Seaweed-based bioremediation techniques offer several advantages over traditional methods. The studies underscore the importance of considering environmental conditions and the presence of coexisting pollutants in designing seaweed-based bioremediation strategies. Optimal light availability, temperature, nutrient levels, and water quality parameters are critical for maximizing seaweed's metal removal efficiency. Overall, seaweed-based bioremediation offers a promising and sustainable approach for addressing heavy metal pollution in aquatic environments. Future research should focus on overcoming challenges related to biomass management, ecological impacts, and scaling up cultivation and processing methods to ensure the widespread implementation of this eco-friendly solution.

Distribution and potential ecological risks of microplastics in Zhushan Bay, China

The interaction between microplastics (MPs) and microorganisms may alter the distribution of antibiotic resistance genes (ARGs) in water and increase the ecological risk of drinking water sources. To investigate the characteristics of MPs geographical distribution and its potential ecological risk in typical urban water, this study was conducted in Zhushan Bay, and we carried out a combination of tests to analyze the distribution of MPs and the migration changes of their surface microbial community composition and ARGs in different media by 16S rRNA gene high-throughput sequencing, non-targeted metabolomics and qPCR genomics in the near-shore (I), middle area (Ⅱ) and near-lake (Ⅲ) of Zhushan Bay. The results showed that MPs in fibrous form were dominant in the aquatic environment of Zhushan Bay; Polyurethane (PU) and Silicone were the main MPs types in Zhushan Bay. The abundance of MPs in the water of Zhushan Bay was winter > summer > autumn > spring; and in the sediment was winter > summer > autumn > spring, respectively. The distribution results of MPs in geographical location are as follows: In the water I > Ⅱ > Ⅲ, sediment exhibited Ⅱ > Ⅲ > I. The results indicate that physicochemical factors will affect the geographical distribution of MPs and their surface microbial community composition in the aquatic environment of Zhushan Bay. More cooperative behaviors and increased metabolically important pathways occurred in the microbial network on water-MPs compared to sediment-MPs. However, the microbial community in the sediment-MPs was more stable and had higher abundance of mobile genetic elements (MGEs). A total of 362 differential metabolites were detected, of which 193 were up-regulated and 19 down-regulated differential metabolites. blaTEM, Sul, and inti1 were prevalent in both the water and sediments of Zhushan Bay. Sul1 was most contaminated in ARGs. This study provides the latest field data and insights into MPs pollution in key aquatic environments.

Multi biomarker approach to assess manganese and manganese nanoparticles toxicity in Pangasianodon hypophthalmus

Manganese (Mn) is an essential element for humans and animals including, fish. It is a still poorly studied in aquatic organisms, where it can be noticeably useful for dietary components and also found pollutant in aquatic environment at high concentrations. On the above information, an experiment was delineated to determine the lethal concentration of manganese (Mn) and manganese nanoparticles (Mn-NPs) alone and with high temperature (34 °C) and its effect on various biochemical markers in Pangasianodon hypophthalmus. The median lethal concentration (96-LC50) of Mn alone (111.75 mg L−1) and along with high temperature (110.76 mg L−1), Mn-NPs alone (93.81 mg L−1) and with high temperature (34 °C) (92.39 mg L−1) was determined in P. hypophthalmus. The length and weight of the fish were 6.32 ± 0.23 cm and 7.57 ± 1.35 g. The present investigation used five hundred forty-six fish, including range finding (216 fish) and definitive test (330 fish). The acute definitive doses were applied to assess the effect of oxidative stress, glycolytic biomarkers, protein biomarkers, fish immunity, neurotransmitter, energy level, stress hormone and histopathology. Oxidative stress (catalase, superoxide dismutase, glutathione-s-transferase and glutathione peroxidase), stress biomarkers (lipid peroxidation, cortisol, heat shock protein, and blood glucose), lactate and malate dehydrogenase, alanine and aspartate aminotransferase, a neurotransmitter, glucose-6-phosphate dehydrogenase (G6PDH), ATPase, immune system biomarkers (NBT, total protein, albumin, globulin and A:G ratio) were altered with exposure to Mn and Mn-NPs. The histopathology of the liver and gill were also changed due to exposure to Mn and Mn-NPs. The bioaccumulation of Mn in the liver, gill, kidney, brain and muscle tissues, and experimental water at different intervals of 24, 48, 72 and 96 h were determined. Based on the present results, it is strongly suggested that Mn and Mn-NPs exposure alone and with high temperature (34 °C) enhanced toxicity and altered biochemical and morphological attributes. This study also suggested that essential elements in both forms (inorganic and nano) at higher concentrations of Mn and Mn-NPs lead to pronounced deleterious alteration in cellular and metabolic activities and histopathology of P. hypophthalmus.

Recognition, possible source, and risk assessment of organic pollutants in surface water from the Yongding River Basin by non-target and target screening

Organic pollutants in aquatic environment could have important implications on pollution stress on aquatic organisms and even on the risk of human exposure. Thus, revealing their occurrence in aquatic environment is essential for water quality monitoring and ecological risk purposes. In this study, a comprehensive two-dimensional gas chromatography connected with time-of-flight mass spectrometry (GC × GC-TOF-MS) was applied, to enable non-target and target analysis of pollutants in the Yongding River Basin. Based on the isotopic patterns, accurate masses and standard substances, certain environmental contaminants were tentatively identified which including polycyclic aromatic hydrocarbon (PAHs), organochlorine pesticides (OCPs), phenols, amines, etc. The compounds with the highest concentration were naphthalene (109.0 ng/L), 2,3-benzofuran (51.5 ng/L) and 1,4-dichlorobenzene (35.9 ng/L) in Guishui River. Wastewater treatment plants (WWTPs) discharges were a main source of pollutants in Yongding River Basin, as the types of compounds screened in the downstream river were relatively similar to those from WWTPs. According to the target analysis, a number of pollutants were selected due to the acute toxicity and cumulative discharge from WWTPs and downstream rivers. Three PAHs (naphthalene, Benzo(b)fluoranthene and pyrene) homologues showed moderate risk to fish and H. Azteca in Yongding River Basin, while the rest of the measured chemicals showed low ecological impact across the entire study area based on the risk assessment. The results are helpful for understanding the necessity of high-throughput screening analysis for assessing water quality of rivers and the discharge emissions of pollutants from WWTPs to the river environment.

Algae-derived metal-free boron-doped biochar acts as a catalyst for the activation of peroxymonosulfate toward the degradation of diclofenac

In this study, plain seaweed biochar (SW) and boron-doped seaweed biochar (BSW) were prepared through a simple pyrolysis process using Undaria pinnatifida (algae biomass) and boric acid. The BSW catalyst was utilized to degrade organic pollutants in aqueous environments by activating peroxymonosulfate (PMS). Surface characterization of the BSW demonstrated successful doping of boron into the biochar materials. BSW600 exhibited greater catalytic activity than SW600, as evidenced by the former's maximum adsorption capacity of diclofenac (DCF) onto BSW600 (qmax = 30.01 mg g−1) and the activation of PMS. Complete degradation of DCF was achieved in 30 min using 100 mg L−1 BSW600, 0.5 mM PMS, and 6.5 initial solution pH as critical parameters. The pseudo-first-order kinetic model accurately described the DCF degradation kinetics. The scavenger experiment displayed that radical and non-radical reactive oxygen species (ROS) formed in the BSW600/PMS system. Furthermore, the generation of ROS in the BSW600/PMS system was confirmed by electron spin resonance spectroscopy (ESR). The percentage contribution of ROS was assessed to be 12.3, 45.0, and 42.7% for HO•, SO4•–, and 1O2, respectively. Additionally, the electron transfer pathway was also confirmed by electrochemical analysis. Moreover, the influence of water matrics on the BSW600/PMS system was demonstrated. The co-existence of anions and humic acid (HA) did not affect the catalytic activity of the BSW600/PMS system. The recyclability of BSW600 was assessed by DCF removal (86.3%) after three cycles. Ecological structure-activity relationships software was used to assess by-product toxicity. This study demonstrates the efficacy of non-metallic heteroatom-doped biochar materials as eco-friendly catalysts in groundwater applications.

Constructed Wetlands for the Wastewater Treatment: A Review of Italian Case Studies

Wastewater is one of the major sources of pollution in aquatic environments and its treatment is crucial to reduce risk and increase clean water availability. Constructed wetlands (CWs) are one of the most efficient, environmentally friendly, and less costly techniques for this purpose. This review aims to assess the state of the art on the use of CWs in removing environmental pollutants from wastewater in Italy in order to improve the current situation and provide background for future research and development work. To evaluate the CWs performances, 76 research works (2001–2023) were examined, and the parameters considered were the type of wastewater treated, pollutants removed, macrophytes, and the kinds of CWs utilized. The pollutant removal efficiencies of all CWs reviewed showed remarkable potential, even though there are biotic and abiotic factor-driven performance variations among them. The number of articles published showed an increasing trend over time, indicating the research progress of the application of CWs in wastewater treatment. This review highlighted that most of the investigated case studies referred to pilot CWs. This finding suggests that much more large-scale experiments should be conducted in the future to confirm the potential of CWs in eliminating pollutants from wastewater.

Analysis of Antibiotics in Bivalves by Ultra-High Performance Liquid Chromatography-Quadrupole Time-of-Flight Mass Spectrometry.

The presence of pharmaceuticals in aquatic ecosystems mostly originates from wastewater treatment plants (WWTPs) and such a situation can be responsible for significant negative impacts on natural ecosystems, such as estuarine and coastal areas. Bioaccumulation of pharmaceuticals, namely antibiotics, in exposed organisms is known to have remarkable effects on different trophic levels of non-target organisms such as algae, invertebrates and vertebrates, including the emergence of bacterial resistance. Bivalves are a highly appreciated seafood product, as they are fed by filtering water, and can bioconcentrate chemicals, being ideal for biomonitoring environmental health hazards in coastal and estuarine ecosystems. To use this sentinel species, an analytical strategy was developed to be used in accessing antibiotics, from human and veterinary medicine, and evaluate their occurrence as emerging pollutants in aquatic environments. The optimized analytical method was fully validated according to the European requirements defined by the Commission Implementing Regulation 2021/808. The validation comprised the following parameters: specificity, selectivity, precision, recovery, ruggedness, linearity, and the decision limit CCα, as well as the limit of detection (LoD) and limit of quantification (LoQ). The method was validated for 43 antibiotics to allow their quantification in both contexts, environmental biomonitoring and food safety.

A novel green solution to metal pollution in aquatic environment: Pyracantha coccinea M. J. Roemer

ABSTRACT Metal pollution today has reached the level of a great threat to humans and their environment. A novel green solution was presented for metal pollution in aquatic environment using Pyracantha coccinea M. J. Roemer in the current study. Due to its widespread industrial use, manganese pollution in water environment has become a serious issue in recent years, and for this reason, it was used as a model metal to determine the treatment potential of P. coccinea M. J. Roemer. The results showed that the pseudo-second-order kinetic model and Freundlich isotherm model agreed well with the experimental data, and the biosorption process had a physical, spontaneous and favourable nature. The maximum metal biosorption capacity was determined to be 59.867 mg g−1. This study showed that P. coccinea M. J. Roemer could present an environmentally friendly, cost-effective, effectual solution for the metal issue in aquatic environment.

Protective effect of quercetin on avermectin induced splenic toxicity in carp: Resistance to inflammatory response and oxidative damage

Avermectin pollution is an important problem that cannot be ignored in aquatic system in recent years. It has brought great trouble to freshwater aquaculture, especially fishery aquaculture. Plant-derived quercetin has anti-inflammatory and antioxidant properties and is widely used as a dietary additive, but its protective effect on immune damage induced by avermectin in freshwater carp remains unclear. This study evaluated the role of dietary additive quercetin supplementation in chronic avermectin exposure of carp spleen. Sixty carp were divided into 4 groups (n = 15/ group), including control group, avermectin treatment group, quercetin treatment group, quercetin and avermectin co-treatment group. Carp were exposed to a 1/10 96 h LC50 dose of avermectin for 30 d and fed a carp diet containing 400 mg/kg quercetin twice a day (3% body weigh/ carp). The results showed that chronic avermectin exposure caused the loose parenchymal structure of carp spleen tissue and the increase of inflammatory cells, accompanied by increased transcription levels of pro-inflammatory il-1β, il-6, tnf-α and decreased levels of anti-inflammatory factors il-10 and tgf-β1, ROS accumulation in spleen tissue. MDA content increased and T-AOC, CAT and GSH levels decreased. Quercetin down-regulates the NF-κB pathway by inhibiting the expression of iNOS and activating p38 MAPK, blocking the transcription of inflammatory factors, and alleviating the inflammation of carp spleen caused by chronic avermectin exposure. In addition, quercetin inhibits the over-activation of Nrf2/Keap-1 signaling axis, blocks ROS accumulation, and restores the spleen REDOX homeostasis. In conclusion, quercetin, as a dietary additive for carp feed, can effectively improve the immune damage caused by avermectin pollution in aquatic environment, resist spleen inflammation and oxidative stress, and provide a theoretical basis for clinical development of freshwater carp feed.

Efficient photodegradation of polystyrene microplastics integrated with hydrogen evolution: Uncovering degradation pathways

Photocatalytic microplastics (MPs) conversion into valuable products is a promising approach to alleviate MPs pollution in aquatic environments. Herein, we developed an amorphous alloy/photocatalyst composite (FeB/TiO2) that can successfully convert polystyrene (PS) MPs to clean H2 fuel and valuable organic compounds (92.3% particle size reduction of PS-MPs and 103.5μmol H2 production in 12h). FeB effectively enhanced the light-absorption and carrier separation of TiO2, thereby promoting more reactive oxygen species generation (especially ‧OH) and combination of photoelectrons with protons. The main products (e.g., benzaldehyde, benzoic acid, etc.) were identified. Additionally, the dominant PS-MPs photoconversion pathway was elucidated based on density functional theory calculations, by which the significant role of ‧OH was demonstrated in combination with radical quenching data. This study provides a prospective approach to mitigate MPs pollution in aquatic environments and reveals the synergistic mechanism governing the photocatalytic conversion of MPs and generation of H2 fuel.

Water-soluble anionic N-confused porphyrin for sensitive and selective detection of heavy metal pollutants in aqueous environment.

Efficient detection and quantification of metal ions in real time and in a cost-effective manner is a critical step in combating the increasing danger of heavy metal contamination of our biosphere. The potential of water-soluble anionic derivative of N-confused tetraphenylporphyrin (WS-NCTPP) has been investigated for quantitative detection of heavy metal ions. The results show that the photophysical properties of WS-NCTPP differ significantly in the presence of four metal ions, namely Hg(II), Zn(II), Co(II) and Cu(II). The variation in the spectral behaviour is driven by the formation of 1:1 complexes with all the four cations with varied degree of complexation. The selectivity of the sensing is studied through interference studies, indicating maximum selectivity for Hg(II) cations. Computational studies of the structural features of the metal complexes with WS-NCTPP help in establishing the geometry and binding interactions between the metal ions and the porphyrin nucleus. The results demonstrate the promising potential of the NCTPP probe which should be utilized for detection of heavy metal ions, especially mercury, in the near future.

Validation of an isotope dilution mass spectrometry (IDMS) measurement procedure for the reliable quantification of steroid hormones in waters.

Reliable data are compulsory to efficiently monitor pollutants in aquatic environments, particularly steroid hormones that can exert harmful effects at challenging analytical levels below the ng L-1. An isotope dilution two-step solid-phase extraction followed by an ultra-performance liquid chromatography separation coupled to tandem mass spectrometry (UPLC-MS/MS) detection method was validated for the quantification of 21 steroid hormones (androgens, estrogens, glucocorticoids, and progestogens) in whole waters. To achieve a realistic and robust assessment of the performances of this method, the validation procedure was conducted using several water samples representative of its intended application. These samples were characterized in terms of concentration of ionic constituents, suspended particulate matter (SPM), and dissolved organic carbon contents (DOC). For estrogens that are part of the European Water Framework Directive Watchlist (17beta-estradiol and estrone), the performances met the European requirements (decision 2015/495/EU) in terms of limit of quantification (LQ) and measurement uncertainty. For 17alpha-ethinylestradiol, the challenging LQ of 0.035ng L-1 was reached. More generally, for 15 compounds out of 21, the accuracy, evaluated in intermediate precision conditions at concentrations ranging between 0.1 and 10ng L-1, was found to be within a 35% tolerance. The evaluation of the measurement uncertainty was realized following the Guide to the expression of Uncertainty in Measurement. Finally, a water monitoring survey demonstrated the suitability of the method and pointed out the contamination of Belgium rivers by five estrogens (17alpha-ethinylestradiol, estriol, 17alpha-estradiol, 17beta-estradiol, and estrone) and three glucocorticoids (betamethasone, cortisol, and cortisone) which have been up to now poorly documented in European rivers.

New insights into arsenate removal during siderite oxidation by dissolved oxygen

Nowadays, arsenic (As) pollution in aquatic environments severely threatens the health of human beings. Although it has been known that siderite is capable of As adsorption and dissolved oxygen (DO) enhances the adsorption, effects of DO concentrations on As(V) adsorption onto siderite remain elusive. In this study, As(V) removal was investigated by synthesized siderite from aqueous solutions with different DO concentrations. Arsenic(V) adsorption kinetics were conformed to the pseudo-second-order model. As(V) adsorption onto siderite was enhanced in the presence of dissolved oxygen, but the excess DO concentration did not increase As(V) adsorption since Fe(III) oxides were coated onto the pristine siderite surface, preventing the mineral from further oxidation. With the increase in DO concentration, the rate of Fe(II) oxidation decreased, which was the kinetic-limited step during As(V) removal by siderite with the presence of DO. The theoretically generated Fe(III) was stoichiometrically proportional to the consumed oxygen. Microscopic characteristics by means of XRD, SEM, TEM, FTIR and XPS indicated that the adsorption was dominated by the chemical process via the As(V) complexation with siderite and co-precipitation with produced Fe(III) oxides. This study reveals the mechanisms of As(V) adsorption during siderite oxidation under different DO concentrations and emphasizes the importance of siderite oxidation in As(V) fate in aqueous systems.