Although pollutants pose environmental and human health risks, the majority are not routinely monitored and regulated. Organic pollutants emanate from a variety of sources, and can be classified depending on their chemistry and environmental fate. Classification of pollutants is important because it informs fate processes and apposite removal technologies. The occurrence of emerging contaminants (ECs) in water bodies is a source of environmental and human health concern globally. Despite being widely reported, data on the occurrence of ECs in South Africa are scarce. Specifically, ECS in wastewater in the Northern Cape in South Africa are understudied. In this study, various ECs were screened in water samples collected from three wastewater treatment plants (WWTPs) in the province. The ECs were detected using liquid chromatography coupled to high resolution Orbitrap mass spectrometry following Oasis HLB solid-phase extraction. The main findings were: (1) there is a wide variety of ECs in the WWTPs, (2) physico-chemical properties such as pH, total dissolved solids, conductivity, and dissolved organic content showed reduced values in the outlet compared to the inlet which confirms the presence of less contaminants in the treated wastewater, (3) specific ultraviolet absorbance of less than 2 was observed in the WWTPs samples, suggesting the presence of natural organic matter (NOM) that is predominantly non-humic in nature, (4) most of the ECs were recalcitrant to the treatment processes, (5) pesticides, recreational drugs, and analgesics constitute a significant proportion of pollutants in wastewater, and (6) NOM removal ranged between 35 and 90%. Consequently, a comprehensive database of ECs in wastewater in Sol Plaatje Municipality was created. Since the detected ECs pose ecotoxicological risks, there is a need to monitor and quantify ECs in WWTPs. These data are useful in selecting suitable monitoring and control strategies at WWTPs.

PM₂.₅ (particulate matter having aerodynamic diameter ≤2.5 μm) samples were collected during wintertime from two polluted urban sites (Allahabad and Kanpur) in the central Indo-Gangetic Plain (IGP) to comprehend the sources and atmospheric transformations of light-absorbing water-soluble organic aerosol (WSOA). The aqueous extract of each filter was atomized and analyzed in a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Water-soluble organic carbon (WSOC) and WSOA concentrations at Kanpur were ∼1.2 and ∼1.5 times higher than that at Allahabad. The fractions of WSOC and secondary organic carbon (SOC) to total organic carbon (OC) were also significantly higher ∼53% and 38%, respectively at Kanpur compared to Allahabad. This indicates a higher abundance of oxidized WSOA at Kanpur. The absorption coefficient (bₐbₛ₋₃₆₅) of light-absorbing WSOA measured at 365 nm was 46.5 ± 15.5 Mm⁻¹ and 73.2 ± 21.6 Mm⁻¹ in Allahabad and Kanpur, respectively, indicating the dominance of more light-absorbing fractions in WSOC at Kanpur. The absorption properties such as mass absorption efficiency (MAE₃₆₅) and imaginary component of refractive index (kₐbₛ₋₃₆₅) at 365 nm at Kanpur were also comparatively higher than Allahabad. The absorption forcing efficiency (Abs SFE; indicates warming effect) of WSOA at Kanpur was ∼1.4 times higher than Allahabad. Enhancement in light absorption capacity was observed with the increase in f44/f43 (fraction of m/z 44 (f44) to 43 (f43) in organic mass spectra) and O/C (oxygen to carbon) ratio of WSOA at Kanpur while no such trend was observed for the Allahabad site. Moreover, the correlation between carbon fractions and light absorption properties suggested the influence of low-volatile organic compounds (OC3 + OC4 fraction obtained from thermal/optical carbon analyzer) in increasing the light absorption capacity of WSOA in Kanpur.

As an emerging brominated flame retardant (BFR), tetrabromobisphenol S (TBBPS) has been frequently detected in the environmental media and organisms. Knowledges on the transformation and fate of TBBPS in both environment and engineering systems are essential to its ecological risk assessment. Herein, we reported the photochemical decomposition of TBBPS in aqueous solution upon 254 nm ultraviolet irradiation (UV₂₅₄). Results show that TBBPS was highly photoreactive, most likely due to the presence of four ortho-bromine substituents. The molar absorption coefficient and quantum yield of TBBPS were found to be pH-dependent, with the monoanionic form being most photoreactive. A series of photoproducts were identified by solid phase extraction (SPE) combined with liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI(+)-MS/MS. The photolysis of TBBPS likely proceeded through photonucleophilic substitution, photoreductive debromination, and β-scission reactions. A ketocarbene, possibly derived from the lower lying excited triplet state, was proposed to be involved in the photolysis of TBBPS. Ion chromatography analysis revealed that debromination occurred quickly, and the yield of bromide (Br⁻) approached 100% after 90 min irradiation. The presence of SRNOM and MRNOM inhibited the photodegradation rate of TBBPS, which is likely due to the light-screening and physical quenching effects of natural organic matter (NOM). Our results reveal that photolysis is an important process for the attenuation of TBBPS in aquatic system; however, naturally occurring species such as NOM can appreciably retard the decay of TBBPS.

Chromophoric dissolved organic matter (CDOM) in rivers is mainly affected by natural conditions and human activities and can reflect the watershed pollution status to a certain extent. The Yellow River is one of the largest contributors to the global riverine sediment flux from the land to ocean, and there is a paucity of information on how the optical properties of CDOM have the potential to serve as an indicator of water quality for the sediment-laden Yellow River. In this study, a three-dimensional fluorescence parallel factor (PARAFAC) analysis method was applied to investigate the seasonal and spatial variations in CDOM fluorescence components and spectral characteristics from the source region to the estuary in the mainstream of Yellow River. The relationships of CDOM with water quality indicators and trophic state were also analyzed. Six PARAFAC components (C1–C6) were identified and grouped into two categories: humic-like components (C1–C4), which accounted for 85.8 %, and protein-like components (C5 and C6), which accounted for only 14.2 %. The CDOM components, spectral parameters, and their clear correlations with the main ions (Na⁺ and Cl⁻) all indicated that the humic-like components may be primarily derived from nonpoint source erosion, and the protein-like components were mainly derived from point source discharges in the watershed. The combination of the CDOM absorption coefficient at 254 nm (a(254)), spectral slope ratio (SR), specific UV absorbance SUVA₂₅₄, and fluorescence index (FI) had a good predictive ability for the key water quality indicators (total nitrogen (TN), dissolved total nitrogen (DTN), total phosphorus (TP), dissolved total phosphorus (DTP), and chlorophyll a (Chl a)) and trophic state index (TSI). Therefore, some fluorophores and UV spectral parameters of CDOM in the Yellow River can be used for rapid water quality monitoring and pollution source indication, especially pollutants related to nitrogen and phosphorus nutrients in the basin.

Samples from two reservoirs with eutrophication problems, located in Pontevedra and Ourense (Northwestern Spain), were cultured, along with a third crop from a reservoir with no problems detected in Ourense (Northwestern Spain). The samples were grown under the same conditions (with an average temperature of 21 ± 2 °C, and a 3000 lux light intensity) in triplicate, and their growth, absorbance and pH were studied. High correlation values were obtained for pH and cellular growth (R² ≥ 95%). The water from Salas showed the greatest microalgal growth (0.15 × 10⁶ cells/ml to 31.70 × 10⁶ cells/ml of Microcystis sp. for the last day of culturing) and the greatest increase in pH (5.72–9.02). In all the cultures studied here, the main species that reproduced was Microcystis sp., which can produce neurotoxins and hepatotoxins. In addition, water samples were cultured with sediments of their own reservoir and with others to observe their evolution. The sediments studied in this case were rich in biotites, which can lead phosphate to be a limiting factor for phytoplankton due to the formation and sedimentation of insoluble salts of ferric phosphate. In crops grown with sediments from the Salas reservoir, actinobacteria developed which can inhibit microalgal growth. The study of the growth of cyanobacteria and possible methods of inhibiting them directly concerns the quality of water and its ecosystems, avoiding pollution and impact on ecosystems.

An increasing number of findings from epidemiological studies support associations between exposure to air pollution and the onset of several diseases, including pulmonary, cardiovascular and neurodegenerative diseases, and malignancies. However, intermediate, and potentially mediating, biological mechanisms associated with exposure to air pollutants are largely unknown. Previous studies on the human exposome have shown that the expression of certain circulating microRNAs (miRNAs), regulators of gene expression, are altered upon exposure to traffic-related air pollutants. In the present study, we investigated the relationship between particulate matter (PM) smaller than 2.5 μm (PM₂.₅), PM₂.₅ absorbance (as a proxy of black carbon and soot), and ultrafine-particles (UFP, smaller than 0.1 μm), measured in healthy volunteers by 24 h personal monitoring (PEM) sessions and global expression levels of peripheral blood miRNAs. The PEM sessions were conducted in four European countries, namely Switzerland (Basel), United Kingdom (Norwich), Italy (Turin), and The Netherlands (Utrecht). miRNAs expression levels were analysed using microarray technology on blood samples from 143 participants. Seven miRNAs, hsa-miR-24-3p, hsa-miR-4454, hsa-miR-4763-3p, hsa-miR-425-5p, hsa-let-7d-5p, hsa-miR-502-5p, and hsa-miR-505-3p were significantly (FDR corrected) expressed in association with PM₂.₅ personal exposure, while no significant association was found between miRNA expression and the other pollutants. The results obtained from this investigation suggest that personal exposure to PM₂.₅ is associated with miRNA expression levels, showing the potential for these circulating miRNAs as novel biomarkers for air pollution health risk assessment.

Fulvic acid (FA) significantly influences the bioavailability and fate of heavy metals in environments, while its acid-base characters and metal binding processes are still unclear. Here, spectroscopic techniques combined with multiple models (e.g., NICA-Donnan model) and two-dimensional correlation spectroscopy (2D COS) were applied to explore the proton and copper binding properties of FA sub-fractions (FA3-FA13). The charge densities, average contents of carboxylic and phenolic groups, average dissociation constants pKa1 and pKa2 of sub-fractions ranged 0–16 meq∙g∙C−1, 5.03–9.58 meq∙g∙C−1, 2.52–4.67 meq∙g∙C−1, 4.15–4.33 and 8.52–9.72, respectively. FA sub-fractions had a relatively narrow distribution of carboxyl group and a broad distribution of phenolic group. FA sub-fractions also exhibited roughly two phenolic hydroxyl groups per every 1–3 phenyl rings. Differential absorbance spectra (DAS) derived Gaussian bands were associated to the inter-chromophore interactions, the changes of molecular conformations and functional groups with copper addition. Differential spectra slopes (DSlope275-295&325-375) were more significant with higher copper concentration and copper amounts bonded to carboxylic groups. UV–Vis and fluorescence spectra with 2D heterospectral COS revealed the copper binding heterogeneities and sequential orders of chromophores and fluorophores, quantitatively confirming by the order of conditional stability constants (log KCu: 4.64–5.56). Salicylic-/polyhydroxyphenolic, hydroxyl and amino groups were strongly associated to the basic units for fluorophores. Sequential changes followed the order of humic-like→fulvic-like materials for FA3/FA5, humic-like→fulvic-like→tryptophan-like materials for FA7, and humic-like→tryptophan-like→fulvic-like→tyrosine-like materials for FA9/FA13. Spectroscopic techniques combined with various models (especially for 2D COS) are beneficial to elucidate the binding heterogeneity and sensitivity for metal-organic matters at the functional group level.

The hexafluoropropylene-oxide-dimer-acid (GenX) is a short-chain perfluoroalkyl substance that was recently introduced following the phase out of PFOA, as an alternative for the process of polymerization. GenX was detected at high concentrations in rivers, drinking water and in sera of exposed workers and recent findings suggested its potential dangerousness for human health.Aim of the study was to assess the consequences of GenX exposure on in vitro thyroid cells with particular attention to the effects on cell-viability, proliferation, DNA-damage and in the thyroid-related genes expression.FRTL-5 rat-thyroid cell line were incubated with increasing concentrations of GenX for 24 h, 48 h and 72 h to assess cell viability by WST-1. DNA-damage was assessed by comet assay and further confirmed by micronucleus assay. The proliferation of survived cells was measured by staining with crystal violet and evaluation of its optical density after incubation with SDS. Changes in TTF-1, Pax8, Tg, TSH-R, NIS and TPO genes expression were evaluated by RT-PCR.GenX exposure reduced FRTL-5 viability in a time and dose-dependent manner (24 h: ANOVA F = 22.286; p < 0.001; 48 h: F = 43.253, p < 0.001; 72 h: F = 49.708, p < 0.001). Moreover, GenX exerted a genotoxic effect, as assessed by comet assay (significant increase in tail-length, olive-tail-moment and percentage of tail-DNA) and micronucleus assay, both at cytotoxic and non-cytotoxic concentrations. Exposure to GenX at concentrations non-cytotoxic exerted a significant lowering of the expression of the regulatory gene TTF-1 (p < 0.05 versus untreated) and higher expression of Pax-8 (p < 0.05 versus untreated) and a down-regulation of NIS (p < 0.05 versus untreated). In addition, cells survived to GenX exposure showed a reduced re-proliferation ability (24 h: ANOVA F = 11,941; p < 0,001; 48 h: F = 93.11; p < 0.001; 72 h F = 21.65; p < 0.001).The exposure to GenX produces several toxic effects on thyroid cells in vitro. GenX is able to promote DNA-damage and to affect the expression of thyroid transcription-factor genes.

This work investigates the absorption properties of soluble brown carbon (BrC), extracted in methanol and water, from ambient aerosol (PM₁₀) samples, collected over an urban background site in Mumbai, India. The diurnal variability was investigated in samples collected in the morning (7–11 a.m.) and afternoon (12–4 p.m.) periods. Absorption properties of BrC (in the 300–600-nm wavelength range) were measured in filter extracts of water-soluble organic carbon (WSOC) and methanol-soluble organic carbon (MSOC). WSOC and MSOC accounted for on average 52% and 77%, respectively, of the measured OC, potentially indicating unextracted BrC and rendering these values the lower bound. Compared with afternoon samples, the morning samples of MSOC and WSOC had increased BrC concentrations and absorption coefficients (bₐbₛ365; 40%–65%). The correlation between bₐbₛ365 and EC, ns-K⁺, and NO₃⁻ in the morning samples indicated contributions from primary sources, including both biomass and vehicular sources. The decreased bₐbₛ365 in the afternoon samples was partly explained by mixing layer dilution, accompanied by a reduction in the concentrations of primary aerosol constituents. Furthermore, in the afternoon samples, ¹HNMR spectroscopy revealed the presence of more oxidized functional groups and significantly higher OC/EC and WSOC/OC ratios, indicating the greater aging of afternoon aerosol. The MAC₃₆₅ (m²gC⁻¹) for both WSOC and MSOC extracts decreased significantly by 20%–34% in the afternoon samples compared with the morning samples, indicating degradation in the absorption properties of the particles and potentially a change in the constituent BrC chromophores.

Studies on Fe uptake by phytoplankton have been often conducted using artificial culture media. However, Fe chemistry in freshwater can be influenced by riverine anthropogenic impacts and other factors causing water quality changes. In this study, therefore, Fe uptake in natural (river and reservoir) and effluent waters was investigated for the notorious bloom-forming freshwater cyanobacterium Microcystis aeruginosa. To investigate the Fe uptake mechanism, a short-term incubational assay was conducted in the presence of light, Fe(II) ligand and Fe(III) reductant, with results consistently indicating that unchelated Fe(III) is the major substrate for Fe uptake by M. aeruginosa. Further assays using various freshwater samples indicated that Fe uptake is lower in natural waters compared to that of effluent waters and, interestingly, Fe uptake was found to be limited in natural waters. These results suggest that Fe limitation can be alleviated by the inflow of effluent waters. Statistical analysis with various water quality variables indicated that Fe availability is significantly influenced by concentrations of dissolved Fe and organic matter as well as specific UV absorbance (an index of aromaticity). Overall, findings of this study highlight that watershed anthropogenic activities exert important roles in Fe uptake by freshwater cyanobacteria via alteration of Fe speciation.