Comparative formation of chlorinated and brominated disinfection byproducts from chlorination and bromination of amino acids.

Amino acids are the main components of dissolved organic nitrogen in algal- and wastewater-impacted waters, which can react with chlorine to form toxic halogenated disinfection by-products (DBPs) in the disinfection process. In the presence of bromide, the reaction between amino acids and secondarily formed hypobromous acid can lead to the formation of brominated DBPs that are more toxic than chlorinated analogues. This study compares the formation of regulated and unregulated DBPs during chlorination and bromination of representative amino acids (AAs) (e.g., aspartic acid, asparagine, tryptophan, tyrosine, and histidine). In general, concentrations of brominated DBPs (trihalomethanes, haloacetonitriles, and haloacetamides, 24.9-5835.0 nM) during bromination were higher than their chlorinated analogues (9.3-3235.3 nM) during chlorination. This indicates the greater efficacy of bromine as a halogenating agent. However, the formation of chlorinated haloacetic acids during chlorination was higher than the corresponding brominated DBPs from bromination. It is likely that an oxidation pathway is required for the formation of haloacetic acids and chlorine is a stronger oxidant than bromine. Moreover, chlorine forms higher levels of haloacetaldehydes (74.4-1077.8 nM) from amino acids than bromine (1.0-480.2 nM) owing to the instability of brominated species. The DBP formation yields depend on the types of functional groups in the side chain of AAs. Eight intermediates resulting from chlorination/bromination of tyrosine were identified by triple quadrupole mass spectrometer, including N-chlorinated/brominated tyrosine, 3-chloro/bromo-tyrosine, and 3,5-dichloro/dibromo-tyrosine. These findings provided new insights into the DBP formation during the chlorination of algal- and wastewater-impacted waters with elevated bromide.

Efficiency and mechanism of micro- and nano-plastic removal with polymeric Al-Fe bimetallic coagulants: Role of Fe addition.

The occurrence of microplastics (MPs) and even nanoplastics (NPs) in tap water has raised considerable attention. As a pre-treatment and also the most important process in drinking water treatment plants, coagulation has been widely studied to remove MPs, but few studies focused on the removal pattern and mechanism of NPs, especially no study paid attention to the coagulation enhanced by prehydrolysed Al-Fe bimetallic coagulants. Therefore, in this study, polymeric species and coagulation behaviour of MPs and NPs influenced by Fe fraction in polymeric Al-Fe coagulants were investigated. Special attention was given to the residual Al and the floc formation mechanism. The results showed that asynchronous hydrolysis of Al and Fe sharply decreases the polymeric species in coagulants and that the increase of Fe proportion changes the sulfate sedimentation morphology from dendritic to layered structures. Fe weakened the electrostatic neutralization effect and inhibited the removal of NPs but enhanced that of MPs. Compared with monomeric coagulants, the residual Al decreased by 17.4 % and 53.2 % in the MP and NP systems (p < 0.01), respectively. With no new bonds detected in flocs, the interaction between micro/nanoplastics and Al/Fe was merely electrostatic adsorption. According to the mechanism analysis, sweep flocculation and electrostatic neutralization were the dominant removal pathways of MPs and NPs, respectively. This work provides a better coagulant option for removing micro/nanoplastics and minimizing Al residue, which has promising potential for application in water purification.

Effects of electrostatic neutralization of Keggin Fe13 on the removal of micro and nano plastic.

The successful preparation and identification of Keggin-structure Fe13 clusters in recent years further enriched the potential application scenarios of ferric coagulants. Comparing the coagulation efficiencies and mechanisms of Fe13 in the removal of nano/microplastics with conventional polymeric Al13 and monomeric Al/Fe, this work aimed to elucidate the coagulation behaviour of Fe13 compared with the traditional mono ferric coagulant, which has the coagulation applied bottleneck of quick and violet hydrolysis. The results showed that Fe13 has a similar electrostatic neutralization potential to Al13, which could keep a positively charged species, especially in acid conditions. The Fe13 species has a selective removal potential toward the microplastics with a polar functional group like ester. Moreover, Fe13 could hydrolyze to form active sol-gel hydroxides in neutral and alkalinity conditions, which is like the behaviour of traditional monomeric Fe coagulants but seldom restabilization. The electrostatic neutralization of Fe13 could enhance the removal of nano plastic from - 25-75% compared with monomeric Fe at pH 4. The higher floc density as a monomeric Fe coagulant and better electrostatic neutralization potential of Keggin Fe13 posed a good prospect for Fe13 to replace the monomeric Fe coagulants in conventional coagulation.

Microplastic bioaccumulation in estuary-caught fishery resource.

The environmental behavior of microplastics (MPs) in estuaries with saline and freshwater intersections is extremely complex. This increases the chance of MP ingestion by fishery resources, posing potentially tremendous health risks for humans. Herein, a total of 105 fishes from 14 different species, and 86 crustaceans (including shrimps and crabs) from five different species were sampled in the Yangtze River estuary and offshore, and MP bioaccumulation, accumulative organ, and the influencing factors were comprehensively studied. The results elucidated that MP accumulation in benthos was significantly higher than that in pelagic animals due to the lower acceptance threshold, assimilation efficiency and egestion rate for benthos. The MP content in crustaceans with the burrowing favoring the MP retention was significantly higher than that in fishes. MPs ingested by fish can accumulate in skin, gills and viscera rather than muscles. Most MPs accumulated in fishery resources were cellulose and polyethylene terephthalate characterized by black and gray fibrous and lengths ranging from 0.1 mm to 1 mm. The gill retention capacity of pelagic fish to smaller-size (<0.1 mm) MPs was pronouncedly stronger than that of benthic fish. It was more accurate to assess the ecological risk of MPs in terms of the maximum size of MPs accumulated in organisms. Compared with the offshore area, the incidence of MP uptake was higher in the estuary owing to anthropogenic impacts. This study helps understand the transfer of MPs in aquatic food webs and offers a foundation for assessing the risk of human exposure to MPs.

Nanoplastic-Induced Genotoxicity and Intestinal Damage in Freshwater Benthic Clams (Corbicula fluminea): Comparison with Microplastics.

With the wide application of plastics in daily life, nanoplastics (NPs) are ubiquitous in freshwater environments. However, to date, few studies have focused on the mechanism underlying the toxicity of NPs, and the differences between this mechanism and that governing the toxicity of MPs have also not been thoroughly characterized. In this study, the genotoxicity, intestinal damage, and intestinal flora in Corbicula fluminea exposed to micro/nanoplastics were investigated through RNA sequencing, histopathology, and 16S rRNA sequencing, respectively. Significant differences in differentially expressed genes (DEGs) were observed between MP and NP exposure groups. It was observed that NPs preferentially elicited the process related to cellular components and triggered the apoptosis through the mitochondrial pathway in various tissues, especially in indirectly contacted tissues, while MPs induced the innate immune response and activated the complement and coagulation cascades (complement system) pathway. Both MPs and NPs can induce an inflammatory response and cause epithelial damage in the intestines, and they can notably change the gut microbial community structure. However, the abundance of pathogenic bacteria (e.g., Mycoplasma) was observed to increase only in the MP-treated group, which exacerbated intestinal damage. Unlike MPs, the effect of NPs on the intestinal microflora was highly limited, while NPs elicited more severe damage to the intestinal mucosal barrier. The results of this study may help to elucidate the toxicity mechanisms governing the responses of bivalves to MPs and NPs and to evaluate the detriment of MPs and NPs to the benthic ecosystem.

The identification of Al nanoclusters by electrospray ionization mass spectrometry (ESI-MS).

Lacking consolidated qualitative and quantitative analysis methods of Al nanoclusters in aqueous, the distributions and concentrations of each Al species could not be revealed with single method before or after coagulation, which limited the development of environmental Al clusters control. As the ESI-MS applied in the inorganic cluster's identification tentatively, the deficient identification of Al species could be analyzed qualitatively and quantitatively with mass spectrum directly. Although many studies have applied the ESI-MS to analyze Al species in aqueous, the experimental conditions were not compared and not reached an agreement. Therefore, this work is the first study to review the methodology developments of ESI-MS in Al identification and to summarize the qualitative and quantitative analysis promoted by ESI-MS. The principle and rationality of quantitative ESI-MS method were inducted and discussed from the prospects of resolving mass spectrum assignment and transforming species in ionization. The qualitative ESI-MS results in previous studies were also analyzed by quantitative ESI-MS analysis in this work. The quantitative Al species results are accordant with the distribution results concluded via Al-Ferron and 27Al NMR methods. The identification principles and instrumental parameters were summarized and unified, which would give hints to further methodological applications and modifications. This study puts forward the further possibilities and prospects of ESI-MS applied in the transformation and in-situ identification of Al13 nanocluster in aqueous.

Impact of water source mixture and population changes on the Al residue in megalopolitan drinking water.

This study establishes a new understanding of the contributions of Al residue in a megalopolitan drinking water supply system with mixed water sources. The different influences and contributions of foreign water source, resident migration and season changing to Al residue in drinking water were investigated. Especially, the role of Southern water transferred over 1200 km via the South-to-North Water Diversion Project in the Al residue of drinking water supply system of a northern megalopolitan were revealed for the first time. Comparisons of big data on Al residue in the water supply system with sole and mixed water sources showed that the introduction of Southern water enhanced the Al residue in drinking water by over 35%. The world's largest annual residents' migration during Chinese Lunar New Year and the changes of season affect the water pipework hydrodynamics, which were embodied as the periodic changes of particulate aluminium and the relations with resident's temporal-spatial distribution in the megalopolitan. Because of the differences in water quality, Southern water promotes the release of historically deposited Al and facilitates the cleaning of old pipes.

Spatial distribution, source apportionment and risk assessment of antibiotics in the surface water and sediments of the Yangtze Estuary.

The "pseudo-durability" of antibiotics in estuaries is gaining increasing interest, especially in the Yangtze Estuary, a vital water supply source for the Shanghai city. To clearly describe the pollution level and risk of antibiotics in this estuary, the contents of 8 typical antibiotics in the surface water and the sediment along the nearshore zone and in the estuarine channel in the estuary were comprehensively analyzed. The results revealed that sulfonamides and tetracycline are the predominant antibiotics in the surface water, while tetracyclines and fluoroquinolones are the dominant ones in the sediments. The ranges of the eight antibiotic concentrations between the nearshore zone (not detected to 7.06 ng/L for water, below LOD to 10.94 ng/g for sediment) and the estuarine channel (not detected to 8.46 ng/L for water, not detected to 14.84 ng/g for sediment) showed no notable differences, but the degree of scatter was different for each antibiotic. The spatial distribution was different for each antibiotic in the north branch and the south branch; higher values for most of the target antibiotics were observed in the south branch of the estuary. The distribution and source analysis from a GIS map using the kriging method indicated that runoff input and the antibiotic residues from aquaculture were the two major sources of the antibiotic pollution in the Yangtze Estuary. A risk assessment of the individual antibiotic exposure in the surface water showed that sulfamethoxazole, ofloxacin and ciprofloxacin, tetracycline and oxytetracycline, and sulfadiazine, roxithromycin and erythromycin in this area exhibited a medium risk, low risk and almost no risk to the selected aquatic microorganisms, respectively.

A Simple and Rapid Fluorescent Probe for Detection of Cr3+ Based on a Coumarin Schiff Base in Aqueous Solution.

A new Cr3+ probe was synthesized using simple Schiff base reaction, which showed prominent fluorescence increasing switch before and after addition Cr3+. The probe proved to have excellent properties, based on both UV-vis absorption and fluorescence spectra. Those properties included high switching performance, good selectivity, and small interference with other metal ions. The fluorescent change mechanism of the probe was attributed to the combined action between the restricted C=N isomerization and the suppression of highly efficient photo-induced electron transfer (PET) process. Moreover, this fluorescence probe for Cr3+ detection also has great potential for bioimaging of cancer cells.

Enhanced adsorption of anionic toxic contaminant Congo Red by activated carbon with electropositive amine modification.

Anionic ionizable toxic organic contaminants, such as pesticides, herbicides, pharmaceuticals and dyestuffs, are widely detected in aqueous and can exert specific toxicity in organisms. They are hard removed by traditional adsorbents with negative surface charges and hydrophilic property. To solve that bottleneck problem, this study synthesized a carbon-based electropositive absorbent via surface activation and radical impregnation. The monolayer adsorption capacity and favorability of the novel adsorbent increased 4.2 and 16 times compared with activated carbon, evaluated by Congo Red. The adsorption kinetics could be described by pseudo-second-order equation, dominated by chemisorption and shortened 75% equilibrium time. The excellent adsorption behavior of synthesized material was attributed to created and bridged electropositive quaternary ammonium structure onto activated carbon, identified with XPS and FT-IR. Additionally, the abundant mesoporous structures of modified carbon provide more tunnels and facilitate adsorption of Congo Red, identified by AutoSorb-iQ. With the batch experiments of pH and ion strength influence, the absorbent behaved well in acidic low ion strength conditions and attenuated by coexisting cations. The study provides a high efficiency, large capacity and low cost materials to remove anionic ionizable organic contaminants in aqueous.

Heavy metal partitioning of suspended particulate matter-water and sediment-water in the Yangtze Estuary.

The partitioning of ten heavy metals (As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, and Zn) between the water, suspended particulate matter (SPM), and sediments in seven channel sections during three hydrologic seasons in the Yangtze Estuary was comprehensively investigated. Special attention was paid to the role of tides, influential factors (concentrations of SPM and dissolved organic carbon, and particle size), and heavy metal speciation. The SPM-water and sediment-water partition coefficients (Kp) of the heavy metals exhibited similar changes along the channel sections, though the former were larger throughout the estuary. Because of the higher salinity, the Kp values of most of the metals were higher in the north branch than in the south branch. The Kp values of Cd, Co, and As generally decreased from the wet season to the dry season. Both the diagonal line method and paired samples t-test showed that no specific phase transfer of heavy metals existed during the flood and ebb tides, but the sediment-water Kp was more concentrated for the diagonal line method, owing to the relatively smaller tidal influences on the sediment. The partition coefficients (especially the Kp for SPM-water) had negative correlations with the dissolved organic carbon (DOC) but positive correlations were noted with the particle size for most of the heavy metals in sediment. Two types of significant correlations were observed between Kp and metal speciation (i.e., exchangeable, carbonate, reducible, organic, and residual fractions), which can be used to identify the dominant phase-partition mechanisms (e.g., adsorption or desorption) of heavy metals.

Role of dams in the phase transfer of antibiotics in an urban river receiving wastewater treatment plant effluent.

Dams are universally constructed to change hydrodynamic forces and impound water in urban rivers, but few efforts have been made to expound the impact of dams on the transport of antibiotics in rivers. In this study, the main object and focus was to elucidate the intercept effect of rubber dam and the gate dam on the sediment-water phase redistribution of eight typical antibiotics along an urban river with the water replenished from wastewater treatment plants (WWTPs). The results show that the eight antibiotics were widely detected in the whole river segment, and the WWTPs were found to be the main sources. Among the eight antibiotics, fluoroquinolones had the highest concentrations in the surface water, while tetracyclines constituted the dominant composition in the sediments. Due to the retention effect, the rubber dam encouraged the enrichment and degradation of the antibiotics in the river. However, the role of gate dams depended mainly on the opening and closing of the sluice gate. For all eight antibiotics, each dam or WWTP exhibited a generally consistent impact on the changes (e.g., an increase or decrease) of the sediment-water partitioning coefficients, although obvious differences existed between effect degree. Moreover, the changes in the coefficients caused by the rubber dam were completely opposite to those affected by gate dams. Contrary to the other six antibiotics, the two sulfonamides showed significant relationships with the dissolved organic matter in the surface water but had no significant relationships with the organic matter in the sediments.

Relationship of metal enrichment with adverse biological effect in the Yangtze Estuary sediments: role of metal background values.

Exclusive pristine values of As, Cd, Cr, Cu, Fe, Mn, Pb, and Zn in the Yangtze Estuary are calculated using principal components analysis (PCA) to probe the relationship between degrees of metal enrichment and their adverse biological effects. The results show that obvious differences in the degrees of metal enrichment exist when the enrichment factors are analyzed with reference background values on global, national, and local scales. Based on the low variability of aluminum, the exclusive metal background values in the estuary are obtained with PCA and are more likely to reflect the pristine contents of the abovementioned metals in the Yangtze Estuary. For the six most common metals (As, Cd, Cr, Cu, Pb, and Zn), significant correlations exist between the enrichment factors and their adverse biological effects. Arsenic shows the highest potential to cause adverse effects despite its general lack of enrichment. However, Cd is the most conservative element and is not likely to cause biological effects in the estuary.