Simulated Drinking Water Research Articles

Effects of ozone dose on brominated DBPs in subsequent chlor(am)ination: A comprehensive study of aliphatic, alicyclic and aromatic DBPs

Ozone‒chlor(am)ine is a commonly used combination of disinfectants in drinking water treatment. Although there are quite a few studies on the formation of some individual DBPs in the ozone‒chlor(am)ine disinfection, an overall picture of the DBP formation in the combined disinfection is largely unavailable. In this study, the effects of ozone dose on the formation and speciation of organic brominated disinfection byproducts (DBPs) in subsequent chlorination, chloramination, or chlorination‒chloramination of simulated drinking water were investigated. High-molecular-weight, aliphatic, alicyclic and aromatic brominated DBPs were selectively detected and studied using a powerful precursor ion scan method with ultra performance liquid chromatography/electrospray ionization triple quadrupole mass spectrometry (UPLC/ESI-tqMS). Two groups of unregulated yet relatively toxic DBPs, dihalonitromethanes and dihaloacetaldehydes, were detected by the UPLC/ESI-tqMS for the first time. With increasing ozone dose, the levels of high-molecular-weight (m/z 300–500) and alicyclic and aromatic brominated DBPs generally decreased, the levels of brominated aliphatic acids were slightly affected, and the levels of dihalonitromethanes and dihaloacetaldehydes generally increased in the subsequent disinfection processes. Despite different molecular compositions of the detected DBPs, increasing ozone dose generally shifted the formation of DBPs from chlorinated ones to brominated analogues in the subsequent disinfection processes. This study provided a comprehensive analysis of the impact of ozone dose on the DBP formation and speciation in subsequent chlor(am)ine disinfection.

Production of reactive species during UV photolysis of chlorite for the transformation of micropollutants in simulated drinking water

Chlorite (ClO2−) is a dominant product during chlorine dioxide (ClO2) disinfection. This study investigated the mechanism for UV photolysis of ClO2− and the production of reactive species. The apparent quantum yield of ClO2− is 1.21 ∼ 1.29 mol einstein−1 by UV photolysis at 254 nm at pH 7. UV photolysis primarily transforms ClO2− to ClO2, and then to HOCl/OCl−, ClO3− and Cl−. Both ClO2 and HOCl/OCl− are major reactive chlorine species, which maximum concentrations are 8.4 and 11.0 μM, respectively, at 50 μM ClO2− and pH 7. Meanwhile, hydroxyl radical (HO) and chlorine atom (Cl) are also formed with the concentrations of 3.1 × 10−14 and 7.8 × 10−15 M, respectively. The abatement of structurally diverse pharmaceuticals and personal care products (PPCPs) by UV/ClO2− is compound specific, depending on their reactivity toward ClO2, HOCl/OCl− and HO. The first-order rate constants of PPCPs primarily relying on ClO2 and HOCl/OCl− range from 0.043 to 1.533 min−1 and from 0.240 to 2.071 min−1, respectively, while those relying on HO range from 0.012 to 0.020 min−1. As for phenolics, phenol and bisphenol A (BPA) are completely removed within 15 min and ClO2 plays a dominant role. Natural organic matter (NOM) inhibits the degradation of phenol and BPA in UV/ClO2−, while chloride and bicarbonate shows slight impacts. The transformation pathways of BPA in the UV/ClO2− system initiate with electron transfer, and then hydroxylation, carbonylation, chlorination, and coupling reactions. The formation of disinfection byproducts (DBPs) and total organic chlorine (TOCl) is not significant during UV/ClO2− treatment, and over 90% TOCl are unknown DBPs. This study improves the understanding of the water chemistry of UV photolysis of ClO2−.

Effects of phosphate and silicate on stiffness and viscoelasticity of mature biofilms developed with simulated drinking water

Biofilms, a porous matrix of cells aggregated with extracellular polymeric substances under the influence of chemical constituents in the feed water, can develop a viscoelastic response to mechanical stresses. In this study, the roles of phosphate and silicate, common additives in corrosion control and meat processing, on the stiffness, viscoelasticity, porous structure networks, and chemical properties of biofilm were investigated. Three-year biofilms on PVC coupons were grown from sand-filtered groundwater with or without one of the non-nutrient (silicate) or nutrient additives (phosphate or phosphate blends). Compared with non-nutrient additives, the phosphate and phosphate-blend additives led to a biofilm with the lowest stiffness, most viscoelastic, and more porous structure, including more connecting throats with greater equivalent radii. The phosphate-based additives also led to more organic species in the biofilm matrix than the silicate additive did. This work demonstrated that nutrient additives could promote biomass accumulation but also reduce mechanical stability.

Critical Parameters and Mechanisms of Chromium Removal from Water by Copper-Based Nanoparticles

This research aims to explore the chromium removal from water using copper-based nanoparticles. The nanoparticles were synthesized by hydrothermal method and characterized by X-ray diffraction, scanning electron microscopy, infrared spectroscopy, and X-ray photoelectron spectroscopy as well as determination of the specific surface area (SBET) and point of zero charge (PZC). The size and composition of nanoparticles are influenced by the reaction time, organic coating, and oxidizing atmosphere. Sorption experiments were carried out in aqueous solutions as well as simulated drinking water at various initial concentration, time, and temperature. Cu nanoparticles had a significant Cr uptake capacity of 3.4 mg·g−1 for Cin 1.0 mg·L−1 lowering the Cr concentration below the provisional guideline value of 50 μg·L−1. Sorption isotherms were fitted to Henry, Langmuir, and Freundlich models, whereas kinetic data were reproduced by different kinetic models. Iodide sorption experiments were carried out to explore the sorption mechanism onto Cu-NPs. Considering the biocompatibility, stability, good uptake capacity, and reusability, Cu nanoparticles could be considered as promising agents for applications in water purification.

What determines accuracy of chemical identification when using microspectroscopy for the analysis of microplastics?

Fourier transform infrared (FTIR) and Raman microspectroscopy are methods applied in microplastics research to determine the chemical identity of microplastics. These techniques enable quantification of microplastic particles across various matrices. Previous work has highlighted the benefits and limitations of each method and found these to be complimentary. Within this work, metadata collected within an interlaboratory method validation study was used to determine which variables most influenced successful chemical identification of un-weathered microplastics in simulated drinking water samples using FTIR and Raman microspectroscopy. No variables tested had a strong correlation with the accuracy of chemical identification (r = ≤0.63). The variables most correlated with accuracy differed between the two methods, and include both physical characteristics of particles (color, morphology, size, polymer type), and instrumental parameters (spectral collection mode, spectral range). Based on these results, we provide technical recommendations to improve capabilities of both methods for measuring microplastics in drinking water and highlight priorities for further research. For FTIR microspectroscopy, recommendations include considering the type of particle in question to inform sample presentation and spectral collection mode for sample analysis. Instrumental parameters should be adjusted for certain particle types when using Raman microspectroscopy. For both instruments, the study highlighted the need for harmonization of spectral reference libraries among research groups, including the use of libraries containing reference materials of both weathered plastic and natural materials that are commonly found in environmental samples.

Effect of Pipe Materials on Bacterial Community, Redox Reaction, and Functional Genes

In the present study, the effect of pipe materials on water quality as well as the microbial community was researched with static devices as well as dynamic ones. Five kinds of pipe materials (SP: steel plastic composite pipe, SS: stainless steel pipe, DI: ductile iron pipe, CI: cast iron pipe, GS: galvanized steel pipe) were chosen, and the soaking experiment was carried out with bench-scale devices. To further investigate the performance of pipe materials over a long term, a pilot-scale simulated drinking water distribution system was constructed, and the water quality parameters were monitored for six months. The pipe materials were ranked as SP, DI, and CI by the order of increasing turbidity, CODMn, and NH3-N. Furthermore, the biofilm samples were analyzed via pyrosequencing and COG functional categories. The DI biofilm possessed the highest bacterial diversity with a Shannon index of 3.56, followed by SP (3.14) and CI (0.77). The presence of nitrate-reducing bacteria (NRB), iron-oxidizing bacteria (IOB), iron-reducing bacteria (IRB), and sulfate-reducing bacteria (SRB)was identified, and NRB composed the largest share in all pipe materials (13.0%–17.2%), with other redox bacteria making up a minor proportion (0.02%–1.52%). NRB and IRB inhibited the corrosion process while IOB and SRB enhanced it. Most dominant genera present in samples were derived firstly from soil or active sludge, indicating a turbidity problem due to soil contamination in the distribution network.

Nitrophenolic byproducts formation during sulfate radical oxidation and their fate in simulated drinking water treatment processes

Nitrite can be transformed to nitrophenolic byproducts in sulfate radical oxidation processes (SR-AOPs). These nitrophenols are highly mobile in subsurface and can potentially contaminate drinking water sources. However, their fate in a drinking water treatment remains ambiguous. Herein, the removal and transformation of four nitrophenolic byproducts formed during a heat activated peroxydisulfate oxidation process, i.e., 4-nitrophenol, 2,4-dinitrophenol, 5-nitrosalicylic acid, and 3,5-dinitrosalicylic acid, in a simulated drinking water treatment train were comprehensively examined. The removal of these nitrophenolic compounds in coagulation by either aluminum sulfate or ferric chloride ranged from 3.8% to 13.4%. In the chlorination process, 4-nitrophenol was removed only by 45.4% in 24 h at a chlorine dose of 5.0 mg/L. The removal of the other three nitrophenolic byproducts were less than 20%. Reaction between nitrophenolic byproducts and chlorine via electrophilic substitution gave rise to their chlorinated derivatives. Chlorinated nitrophenolic byproducts were more recalcitrant and toxic than their parent compounds, but still a tiny fraction of them could undergo further oxidation to form trichloronitromethane. This work implied that once nitrophenolic byproducts enter water source, they can penetrate the drinking water treatment train and react with the residual chlorine in distribution pipelines to form more hazardous byproducts. The findings raised additional concerns to the potential risk of the nitrophenolic byproducts formed in SR-AOPs.

Floatable graphitic carbon nitride/alginate beads for the photodegradation of organic pollutants under solar light irradiation

Graphitic carbon nitride, both as powder and alginate floating beads, was synthesized by an easy and cheap approach using two different precursors (melamine and urea) and properly characterized by several techniques. The effect of the type of precursor on the photoactive properties of the final materials was investigated. Their activity towards the photodegradation of different pollutants (dyes, drugs, and herbicides) both in ultrapure water and simulated drinking water under solar light irradiation was investigated, reaching extraordinarily high photodegradation results (99% for diclofenac and rhodamine B and 90% for isoproturon) compared to the literature. The floating photocatalysts showed good stability during recycling maintaining high performances after 5-time usage without post-treatment. Finally, liquid chromatography equipped with mass spectrometry (UPLC/MS) was used to identify the main by-products formed during the photodegradation tests, and a plausible transformation pathway has been proposed.

Sustainable Solar Light Photodegradation of Diclofenac by Nano- and Micro-Sized SrTiO3

Currently, photocatalytic reactions under solar illumination have attracted worldwide attention due to the tremendous set of associated environmental problems. Taking sunlight into account, it is indispensable to develop highly effective photocatalysts. Strontium titanate, SrTiO3 (STO), is a cubic perovskite-type semiconductor, an inexpensive material with high thermal stability and corrosion resistance that exhibits a similar energy bandgap to TiO2 and can represent an interesting alternative in photocatalytic applications. Particle size can significantly affect both photocatalytic and photoelectrochemical properties of a photocatalyst, thus altering the photooxidation of organic pollutants in air or water. In this context, this research aims at investigating the photocatalytic features of nano- and micro-sized commercial STO powders towards the photodegradation of diclofenac (DFC), a non-steroidal, anti-inflammatory drug, widely used as analgesic, antiarthritic, and antirheumatic. Both nano- and micro-STO photocatalysts exhibited remarkable photocatalytic efficiency towards DCF, reaching photodegradation efficiency higher than 90% within one hour. Results obtained in simulated drinking water were also compared to those obtained in ultrapure water. Both STOs showed good stability during recycling tests, maintaining high performances after three cycles. Eventually, active species were identified using various scavengers by trapping holes and radicals generated during the photocatalytic degradation process.

Quantitative identification of halo-methyl-benzoquinones as disinfection byproducts in drinking water using a pseudo-targeted LC-MS/MS method

Halobenzoquinones (HBQs) as disinfection byproducts (DBPs) in drinking water is prioritized for research due to their prevalent occurrence and high toxicity. However, only fifteen HBQs can be identified among a high diversity using targeted LC-MS/MS analysis in previous studies due to the lack of chemical standards. In this study, we developed a pseudo-targeted LC-MS/MS method for detecting and quantifying diverse HBQs. Distinct fragment characteristics of HBQs was observed according to the halogen substituent effects, and extended to the development of a multiple-reaction-monitoring (MRM) method for the quantification of the 46 HBQs that were observed in simulated drinking water using non-targeted analysis. The fragmentation mechanism was supported by the changes of Gibbs free energy (ΔG), and a linear relationship between the ΔG and the ionization efficiency of analytes was developed accordingly for quantification of these 46 HBQs, 30 of which were lack of chemical standards. It is noted that 29 of the 30 newly-identified HBQs were halo-methyl-benzoquinones (HMBQs), which were predicted to be carcinogens related with drinking-water bladder cancer risk and be more toxic than non-methyl HBQs. Using the new method, twelve HMBQs were detected in actual drinking water samples with concentrations up to 100.4 ng/L, 3 times higher than that reported previously. The cytotoxicity in CHO cells of HMBQs was over 1-fold higher than that of non-methyl-HBQs. Therefore, HMBQs are an essential, highly toxic group of HBQs in drinking water, which deserve particular monitoring and control.

Compromised Effectiveness of Thermal Inactivation of Legionella pneumophila in Water Heater Sediments and Water, and Influence of the Presence of Vermamoeba vermiformis.

Intermittent reduction of temperature set-points and periodic shutdowns of water heaters have been proposed to reduce energy consumption in buildings. However, the consequences of such measures on the occurrence and proliferation of Legionella pneumophila (Lp) in hot water systems have not been documented. The impact of single and repeated heat shocks was investigated using an environmental strain of L. pneumophila and a reference strain of V. vermiformis. Heat shocks at temperatures ranging from 50 °C to 70 °C were applied for 1 h and 4 h in water and water heaters loose deposits (sludge). The regrowth potential of heat-treated culturable L. pneumophila in presence of V. vermiformis in water heaters sludges was evaluated. A 2.5-log loss of culturability of L. pneumophila was observed in simulated drinking water at 60 °C while a 4-log reduction was reached in water heaters loose deposits. Persistence of Lp after 4 h at 55 °C was shown and the presence of V. vermiformis in water heater’s loose deposits resulted in a drastic amplification (5-log). Results show that thermal inactivation by heat shock is only efficient at elevated temperatures (50 °C) in both water and loose deposits. The few remaining organisms can rapidly proliferate during storage at lower temperature in the presence of hosts.

Chlorine decay and disinfection by-products formation during chlorination of biofilms formed with simulated drinking water containing corrosion inhibitors

Corrosion inhibitors used to reduce pipe corrosion can alter the physical structure and biochemical components of the biofilm in premise plumbing systems. We studied the effects of corrosion inhibitors on chlorine decay and associated disinfection by-products (DBPs) formation by biofilms grown with simulated drinking water amended with silicate, phosphate, and the phosphate blends. Experiments were conducted with either intact biofilms or biofilm materials dispersed in solution during sonication (referred to as biomass). While there was no significant difference in chlorine decay among biomass from different biofilms, biomass from the phosphate blend biofilm showed the lowest trihalomethane (THMs) and haloacetic acids (HAAs) formation. The chlorine decay rate constants from the biofilm experiment were ranked as: phosphate blends > phosphate ≈ groundwater (GW) > silicate. The kinetics of chlorine decay and formation of DBPs were successfully described by pseudo-first-order kinetics. These fitting parameters were used to predict the DBPs formation in a realistic premise plumbing system. The results showed that biofilm-derived THMs and HAAs increased with increasing chlorine concentration, while THMs and HAAs first increased and then stabilized to a maximum with increasing biofilm total organic carbon (TOC) concentration. In general, the biofilms grown with phosphate-based corrosion inhibitors resulted in lower DBPs formation yield but higher bacterial release, which could potentially increase the risk of user exposure to opportunistic pathogens in drinking water. The silicate biofilms showed the largest yield coefficient of DBPs formation but had the least biomass and lower bacterial release.

Corrosion Behavior and Susceptibility to Stress Corrosion Cracking of Leaded and Lead-Free Brasses in Simulated Drinking Water.

Duplex α + β’ brasses are widely used in drinking water distribution systems for tube fittings, valves, and ancillaries because they are low cost, easy to fabricate, and exhibit high mechanical strength. However, depending on application conditions and alloy composition, they may undergo dealloying and stress corrosion cracking. In this research, three different brass types, two leaded (CW617N and CW602N) alloys and one lead-free brass (CW724R), were investigated to assess their corrosion behavior and susceptibility to stress corrosion cracking (SCC) in simulated drinking water (SDW) solutions containing different chloride concentrations, compatible with drinking water composition requirements according to Moroccan standard NM 03.7.001. The corrosion behavior was assessed by electrochemical tests such as polarization curve recording and electrochemical impedance spectroscopy (EIS) monitoring, coupled to SEM-EDS surface observations. The susceptibility to SCC was investigated by slow strain rate tests (SSRT). The tests showed that corrosion was mainly under diffusion control and chlorides slightly accelerated corrosion rates. All alloys, and particularly CW617N, were affected by SCC under the testing conditions adopted and in general the SCC susceptibility increased at increasing chloride concentration.

Inhibiting the increase of antibiotic resistance genes during drinking water distribution by superior microbial interface using Fe modified granular activated carbon

The effects of biological activated carbon treatment using Fe2O3-modified granular activated carbon in inhibiting antibiotic resistance genes in simulated drinking water distribution systems was compared with unmodified granular activated carbon as a reference. Fe2O3-modified biofiltration resulted in a sustained inhibition of resistance genes during drinking water chlorination and distribution (relative abundance in simulated tap water after the modified and unmodified filtration was 1.31% and 9.40%, respectively). A new electron transfer pathway occurring in attached biofilms on Fe2O3-modified granular activated carbon surface, which was identified using X-ray photoelectron spectroscopy and the phenanthroline spectrophotometric method, enhanced the extracellular electron transfer rate and weakened the pressure of organic micropollutants on microorganisms. Hence, the relative abundance of resistance genes (36.32%) and integron (8.79%) on modified carbon was considerably lower than that on unmodified carbon (115.59% and 13.85%, respectively). Meanwhile, the secreted extracellular polymeric substances on modified carbon presented higher flocculating efficiency and better mechanical stability, resulting in the suspended extracellular polymeric substances in downstream water exhibiting stronger electrostatic repulsion. The particle-attached biofilms in downstream distribution systems consistently failed to form larger aggregates, inhibiting horizontal gene transfer, and overall microbial metabolism. Based on network analysis, 11 OTUs in the water samples from raw water to simulated tap water formed an extremely interrelated module with no links to target resistance genes and integron. Therefore, a range of microbial variations triggered by the microbial interface on modified carbon successfully controlled the transfer of antibiotic resistance genes-associated risk from biological activated carbon effluent to tap water. Our findings revealed that enhancing the microbial interface using Fe2O3-modified granular activated carbon is a promising option for inhibiting the antibiotic resistance genes increase in tap water.

Novel chlorinated disinfection byproducts from tannic acid: nontargeted identification, formation pathways, and computationally predicted toxicity

Tannic acid is ubiquitously present in various simulated and real water sources and in wastewater. Various chlorinated disinfection byproducts (Cl-DBPs) are generated via reactions with tannic acid during disinfection with chlorine. We used high-resolution mass spectrometry in combination with our self-developed halogen extraction code to selectively identify Cl-DBPs. Our strategy enabled successful detection of 35 Cl-DBP formulas formed by chlorination of tannic acid, and we identified 26 of these structures. The structures of 17 novel Cl-DBPs are firstly reported here. The reaction pathways of these Cl-DBPs were tentatively proposed. These Cl-DBPs are likely to be generated during chlorination at various chlorine doses, from 0.0 to 10.0 mg-Cl2/L, and 14 of the 26 Cl-DBPs were detected in simulated drinking water, which implies a relatively high probability of incidence. Quantitative structure-activity relationship toxicity analyses predicted that most of these Cl-DBPs would exhibit much higher acute toxicity than the common DBPs trichloromethane and monochloroacetic acid and that some of these compounds would induce developmental toxicity and be mutagenic, which further emphasizes that these Cl-DBPs should raise concerns. This study broadens our understanding of the Cl-DBPs formed from tannic acid and should prompt wider application of our analytical strategy in environmental matrices.

Effect of disinfectant exposure and starvation treatment on the detachment of simulated drinking water biofilms

Biofilms were one of the main habitats of microbes in the drinking water distribution system. The variation of environmental conditions can lead to the detachment of biofilms and the deterioration of water quality. In this study, the effects of disinfectant exposure and starvation treatment on the detachment of biofilms were investigated. The results showed that detaching rate increased with the concentration of chloramine in the inlet water and 1.0 mg/L of chloramine led to the largest detached biomass. The starvation treatment resulted in less biofilm biomass but the detaching rates of treated biofilms were higher than those without starvation. The 16S rRNA sequencing results showed that detached and stubborn biofilms had a significant difference in microbial diversity and richness. The microbial community composition of the two types of biofilm showed the difference in the abundance of Nitrospira, Bryobacter, Hyphomicrobium, and Pedomicrobium. Chloramine exposure did not have a significant impact on the microbial community while the starvation treatment led to a higher abundance of chemolithotrophs bacteria. Metagenomic results indicated that detached biofilms had higher abundances of ARGs and starvation treatment could enrich the ARGs. The results of this research could provide the knowledge of biofilm sloughing and help understand the health risk of antibiotic resistance in drinking water.

Mechanistic and kinetic understanding of micropollutant degradation by the UV/NH2Cl process in simulated drinking water

The UV/monochloramine (UV/NH2Cl) process has attracted increasing attention in water treatment, in which hydroxyl radicals (HO•), reactive chlorine species (RCS) and reactive nitrogen species (RNS) are produced. This study investigated the effects of water matrices including halides, natural organic matter (NOM), alkalinity and pH, on the degradation kinetic of a variety of micropollutants and radical chemistry in the UV/NH2Cl process. The presence of chloride blunted HO• and Cl• impacts, but enhanced Cl2•- effect on micropollutants reactive toward Cl2•-. The presence of 30 μM bromide led to an 82% decrease in the specific pseudo-first-order rate constants (k') by HO• (kHO•'), and significantly diminished RCS efficacy. Reactive bromine species (RBS) were formed in the presence of bromide, while the contribution could not compensate for the decrease of HO• and RCS due to their lower reactivity toward micropollutants. Iodide rapidly transformed to HOI via reacting with NH2Cl, which resulted in a 59% decrease of kHO•' and 12% ∼ 100% decreases of k' by reactive halogen species (RHS) and RNS (kRHS+RNS') for most micropollutants. Nevertheless, k' of phenolic compounds, such as paracetamol, bisphenol A and salbutamol, increased in the presence of iodide by 78%, 360% and 130%, respectively, due to the roles of HOI and reactive iodine species (RIS). Bicarbonate decreased the contributions of HO• and RCS, but enhanced that of CO3•- for micropollutants reactive toward CO3•-. The presence of 1 mg/L NOM scavenged over half the amount of HO•, and also consumed RCS and RNS, resulting in significantly decreased removal of micropollutants. High pH value witnessed enhanced degradation for those micropollutants reactive toward RCS and RNS through deprotonation. The degradation of most micropollutants was inhibited in real drinking water and in the coexistence of halides. This study provides a better understanding of radical chemistry in the UV/NH2Cl process under a practical water treatment condition.

Efficient removal of a low concentration of Pb(II), Fe(III) and Cu(II) from simulated drinking water by co-immobilization between low-dosages of metal-resistant/adapted fungus Penicillium janthinillum and graphene oxide and activated carbon

Drinking water safety cannot be overemphasized. Filamentous fungi have many excellent features for metal removal. Both graphene oxide (GO) and activated carbon (AC) are conventional metal adsorbents, but they are not suitable for large-scale use due to high cost. In this study, a low dosage of conidia (2.0 × 104 conidia/mL) of metal-resistant/adapted filamentous fungus Penicillium janthinillum strain GXCR were co-immobilized with a low dosage of 0.5 mg/L GO or 0.5 mg/L AC by embedding in 2% polyvinyl alcohol (PVA)-3% sodium alginate (SA), generating six types of microbead adsorbents (MBAs) to remove metals from a low concentration of either single metal (100 mg/L) or mixed metals (100 mg/L each) of Pb (II), Fe (III) and Cu (II) in drinking water. Fungus GXCR-containing MBAs had higher specific surface areas (SSAs), better mesoporous structures, and a higher removal rate (85–98.99%) of single or mixed metals. Singl-metal adsorptions of MBAs were almost unaffected by temperature changes. MBAs showed a stable removal rate of 87–94% during four cycles of adsorption-desorption of single metal. Single-metal adsorptions were well described by multiple models of Freundlich isotherm with constant values of 0.21–0.432, Langmuir isotherm with constant values of 0.037–0.17, Pseudo-fist-order, Pseudo-second-order, and intra-particle diffusion (IPD). In conclusion, co-immobilization between GXCR, GO and AC can make metal removal more efficient. Adsorption capacity is increased with SSAs but not in the same proportion. Single-metal adsorptions involve multiple mechanisms of monolayer and multilayer adsorptions, external mass transfer, and IPD. IPD is important but not the only one rate-controlling step for single-metal adsorptions.

Impacts of antibiotics on biofilm bacterial community and disinfection performance on simulated drinking water supply pipe wall

Overuse of antibiotics is accelerating the spread of resistance risk in the environment. In drinking water supply systems, the effect of antibiotics on the resistance of biofilm is unclear, and there have been few studies in disinfectant-containing systems. Here, we designed a series of drinking water supply reactors to investigate the effects of antibiotics on biofilm and bacteria in the water. At low concentrations, antibiotics could promote the growth of bacteria in biofilm; among the tested antibiotics (tetracycline, sulfadiazine and chloramphenicol), tetracycline had the strongest ability to promote this. And the antibiotic resistant bacteria (ARB) could inhibit the growth of bacteria in drinking water. Results have shown that antibiotics enhanced the bacterial chlorine resistance in the effluent, but reduced that in the biofilm. Furthermore, metagenomic analysis showed that antibiotics reduced the richness of biofilm communities. The dominant phyla in the biofilm were Proteobacteria, Planctomycetes, and Firmicutes. In tetracycline-treated biofilm, the dominant phylum was Planctomycetes. In sulfadiazine- and chloramphenicol-treated groups, bacteria with complex cell structures preferentially accumulated. The dominant class in biofilm in the ARB-added group was Gammaproteobacteria. The abundance of antibiotic resistant genes (ARGs) was correlated with biofilm community structure. This study shows that antibiotics make the biofilm community structure of drinking water more resistant to chlorine. ARGs may be selective for certain bacteria in the process, and there may ultimately be enhanced chlorine and antibiotic resistance of effluent bacteria in drinking water.

A New Group of Heterocyclic Nitrogenous Disinfection Byproducts (DBPs) in Drinking Water: Role of Extraction pH in Unknown DBP Exploration.

pH adjustment prior to extraction is an important step in water sample pretreatment processes for exploration of new/unknown disinfection byproducts (DBPs) in drinking water. To achieve a better extraction efficiency, the pH of a water sample is usually adjusted to a low level (e.g., < 0.5) to ensure that target DBPs are in their neutral forms. However, such a practice may elude some amphoteric DBPs (especially those nitrogenous DBPs with multiple functional groups), which can accept protons at a low pH and lose protons at a high pH. In this study, with careful extraction pH selection and optimization, we first report the detection and identification of a new group of heterocyclic nitrogenous DBPs, halogenated pyridinols, in simulated drinking water using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry and time-of-flight mass spectrometry, including 5-chloro-3-pyridinol, 2-bromo-3-pyridinol, 2,6-dichloro-4-pyridinol, 2,6-dibromo-3-pyridinol, 3-bromo-2-chloro-5-pyridinol, 5-bromo-2-chloro-3-pyridinol, 3,5,6-trichloro-2-pyridinol, and 2,4,6-tribromo-3-pyridinol. On the basis of the speciation of dissociated chemical species and recovery tests at different extraction pH values, it was found that, only at a pH of 3.0, all the eight new DBPs could achieve recoveries of >50%. With subsequent instrumental parameter optimization, the method detection and quantitation limits of the eight new DBPs were determined to be 0.04-1.58 and 0.15-4.11 ng/L, respectively. The optimized method enabled an accurate detection of the eight new DBPs in two real drinking water samples. Further aided with in vivo developmental and acute toxicity assays using zebrafish embryos, the developmental and acute toxicity of the new DBPs were found to be slightly lower than those of halogenated benzoquinones but dozens of times higher than those of commonly known DBPs such as tribromomethane and iodoacetic acid.