Cover illustration
Front Cover Story (see: Feng Zhu, Zhijian Yao, Wenliang Ji, Deye Liu, Hao Zhang, Aimin Li, Zongli Huo, Qing Zhou, 2020, 14(3): 51)
Solid-phase extraction (SPE) is one of the most commonly used technique for aqueous sample preconcentration, especially for tracing organic pollutants (e.g. pharmaceuticals and personal care products, PPCPs). However, the diversity of PPCPs proposes high demand for the compatibility of hydrophilicity and hydrophobicity of the SPE adsorbents.
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• Comprehensive mitigation of gas emissions from swine manure was investigated. • Additives addition for mitigation of gas from the manure has been developed. • Sargassum horneri, seaweed masking strategy controlled gas by 90%-100%. • Immediate reduction in emitted gas and improving air quality has been determined. • Microbial consortium with seaweed completely controlled gas emissions by 100%.
Gas emissions from swine farms have an impact on air quality in the Republic of Korea. Swine manure stored in deep pits for a long time is a major source of harmful gas emissions. Therefore, we evaluated the mitigation of emissions of ammonia (NH3), hydrogen sulfide (H2S) and amine gases from swine manure with biological products such as seaweed (Sargassum horneri) and a microbial consortium (Bacillus subtilis (1.2 × 109 CFU/mL), Thiobacillus sp. (1.0 × 1010 CFU/mL) and Saccharomyces cerevisiae (2.0 × 109 CFU/mL)) used as additives due to their promising benefits for nutrient cycling. Overall, seaweed powder masking over two days provided notable control of over 98%-100% of the gas emissions. Furthermore, significant control of gas emissions was especially pronounced when seaweed powder masking along with a microbial consortium was applied, resulting in a gas reduction rate of 100% for NH3, amines and H2S over 10 days of treatment. The results also suggested that seaweed powder masking and a microbial consortium used in combination to reduce the gas emissions from swine manure reduced odour compared with that observed when the two additives were used alone. Without the consortium, seaweed decreased total volatile fatty acid (VFA) production. The proposed novel method of masking with a microbial consortium is promising for mitigating hazardous gases, simple, and environmentally beneficial. More research is warranted to determine the mechanisms underlying the seaweed and substrate interactions.
• Functional groups of AM and EDTA in composite increased removal of Cr(VI) and CR. • Removal process reached equilibrium within 30 min and was minimally affected by pH. • Elimination of Cr(VI) was promoted by coexisting CR. • Adsorption process of CR was less influenced by the presence of Cr(VI). • Mechanisms were electrostatic attraction, surface complexation and anion exchange.
We prepared ethylenediaminetetraacetic acid (EDTA)-intercalated MgAl-layered double hydroxide (LDH-EDTA), then grafted acrylamide (AM) to the LDH-EDTA by a cross-linking method to yield a LDH-EDTA-AM composite; we then evaluated its adsorptive ability for Congo red (CR) and hexavalent chromium (Cr(VI)) in single and binary adsorption systems. The adsorption process on LDH-EDTA-AM for CR and Cr(VI) achieved equilibrium quickly, and the removal efficiencies were minimally affected by initial pH. The maximum uptake quantities of CR and Cr(VI) on LDH-EDTA-AM were 632.9 and 48.47 mg/g, respectively. In mixed systems, chromate removal was stimulated by the presence of CR, while the adsorption efficiency of CR was almost not influenced by coexisting Cr(VI). The mechanisms involved electrostatic attraction, surface complexation, and anion exchange for the adsorption of both hazardous pollutants. In the Cr(VI) adsorption process, reduction also took place. The removal efficiencies in real contaminated water were all higher than those in the laboratory solutions.
• A hydrophilic resin (GCHM) was facile synthesis and characterized. • Average absolute recovery of GCHM (75.6%) performs better than Oasis® HLB. • Detection limits of method (SPE-UPLC-MS/MS) ranged between 0.03 and 0.6 ng/L. • 22 PPCPs were determined in environmental waters ranging from 0.5 to 1590 ng/L.
In this study, a hydrophilic resin named GCHM was fabricated based on poly(N-vinyl pyrrolidone-co-divinylbenzene), characterized, and applied as a solid-phase extraction (SPE) material. Up to 44 pharmaceuticals and personal care products (PPCPs) belonging to 10 classes were recovered in environmental water samples. Different variables affecting extraction, such as adsorbent amount, sample pH, and loading speed, were optimized. Under optimal conditions, the average absolute recovery of 44 PPCPs was 75.6% using GCHM, indicating a better performance than the commercial Oasis® HLB. SPE with home-made hydrophilic polymeric sorbent followed by ultra-performance liquid chromatography and tandem mass spectrometry was validated, and the method achieved good linearity (r2>0.991, for all analytes). In addition, the method detection limits of target compounds ranged from 0.03 to 0.6 ng/L. The developed method was applied to determine PPCPs in 10 environmental water samples taken from the Yangtze River, Huaihe River, and Taihu Lake, 1 groundwater sample from Changzhou in Jiangsu Province, 1 wastewater sample from Xiamen and 2 seawater samples from the Jiulong River in Fujian Province, China. In these samples, 22 compounds were determined at levels ranging from 0.5 to 1590 ng/L.
• The three simulation factors caused various changes in both water and sediment. • Responses to simulations differed with the reported natural lakes and wetlands. • Al has dominant effects on sediment P release control among the three factors. • Adding sediment Al can be effective and safe under the simulated conditions. • Polyphosphates were not generated, while added phytate was rather stable.
The effects of sediment aluminum (Al), organic carbon (OC), and dissolved oxygen (DO) on phosphorus (P) transformation, at the water-sediment interface of a eutrophic constructed lake, were investigated via a series of simulative experiments. The above three factors had various influences on dissolved P concentration, water pH, water and surface sediment appearance, and P fractions. Additions of Al had the greatest effect on suppressing P release, and the water pH remained alkaline in the water-sediment system under various OC and DO conditions. No dissolution of the added Al was detected. 31P-NMR characterization suggested that OC addition did not promote biological P uptake to polyphosphates under oxic conditions. The simulation result on the added phytate indicated the absence of phytate in the original lake sediment. As compared to the reported natural lakes and wetland, the water-sediment system of the constructed lake responded differently to some simulative conditions. Since Al, OC, and DO can be controlled with engineering methods, the results of this study provide insights for the practical site restorations.
• Penetration depth and substrate characters affect AGS formation and performance. • The relationship between substrate gradient and particle size affects AGS stability. • The fermentation process is proposed as a pretreatment to improve AGS stability.
The influences of flow patterns (mixed-flow and plug-flow) and fermentation pretreatment on aerobic granular sludge (AGS) formation with various substrate availability levels were investigated by running four identical laboratory-scale sequencing batch reactors (R1–R4), comparing two anaerobic feeding strategies and three kinds of substrates. R1 achieved faster granulation with a fast influent fill step followed by a modified anaerobic mixed-flow phase, but the AGS showed poorer stability with a cracked structure and a high suspended solids concentration in the effluent. The anaerobic plug-flow feeding mode (with influent fed slowly from the bottom) in R2 provided deeper penetration depth for the substance to reach the core of AGS and accordingly strengthen AGS stability. An acidogenic up-flow sludge bed reactor was introduced as a pretreatment to improve the AGS performance by enhancing glucose pre-fermentation (R4). AGS fed with mixed volatile fatty acids (VFA) after glucose fermentation showed similar performance compared with the reactor fed with acetate in the aspects of stability, structure, size distribution and nitrogen removal efficiency, and 74% similarity in the microbial community. For actual wastewater with low VFA concentrations, fermentation treatment was suggested as a promising pretreatment for stable AGS granulation and operation.
• Orange tree residuals biochar had a better ability to adsorb ammonia. • Modified tea tree residuals biochar had a stronger ability to remove phosphorus. • Partially-modified biochar could remove ammonia and phosphorus at the same time. • The real runoff experiment showed an ammonia nitrogen removal rate of about 80%. • The removal rate of total phosphorus in real runoff experiment was about 95%.
Adsorption of biochars (BC) produced from cash crop residuals is an economical and practical technology for removing nutrients from agricultural runoff. In this study, BC made of orange tree trunks and tea tree twigs from the Laoguanhe Basin were produced and modified by aluminum chloride (Al-modified) and ferric sulfate solutions (Fe-modified) under various pyrolysis temperatures (200°C–600°C) and residence times (2–5 h). All produced and modified BC were further analyzed for their abilities to adsorb ammonia and phosphorus with initial concentrations of 10–40 mg/L and 4–12 mg/L, respectively. Fe-modified Tea Tree BC 2h/400°C showed the highest phosphorus adsorption capacity of 0.56 mg/g. Al-modified Orange Tree BC 3h/500°C showed the best performance for ammonia removal with an adsorption capacity of 1.72 mg/g. FTIR characterization showed that P = O bonds were formed after the adsorption of phosphorus by modified BC, N-H bonds were formed after ammonia adsorption. XPS analysis revealed that the key process of ammonia adsorption was the ion exchange between K+ and NH4+. Phosphorus adsorption was related to oxidation and interaction between PO43– and Fe3+. According to XRD results, ammonia was found in the form of potassium amide, while phosphorus was found in the form of iron hydrogen phosphates. The sorption isotherms showed that the Freundlich equation fits better for phosphorus adsorption, while the Langmuir equation fits better for ammonia adsorption. The simulated runoff infiltration experiment showed that 97.3% of ammonia was removed by Al-modified Orange tree BC 3h/500°C, and 92.9% of phosphorus was removed by Fe-modified Tea tree BC 2h/400°C.
• Highly efficient debromination of BDE-47 was achieved in the ZVZ/AA system. • BDE-47 debromination by the ZVZ/AA can be applied to a wide range of pH. • AA inhibits the formation of (hydr)oxide and accelerates the corrosion of ZVZ. • Reduction mechanism of BDE-47 debromination by the ZVZ/AA system was proposed.
A new technique of zero-valent zinc coupled with ascorbic acid (ZVZ/AA) was developed and applied to debrominate the 2,2′,4,4′-Tetrabromodiphenyl ether (BDE-47), which achieved high conversion and rapid debromination of BDE-47 to less- or non-toxic forms. The reaction conditions were optimized by the addition of 100 mg/L ZVZ particles and 3 mmol/L AA at original solution pH= 4.00 using the solvent of methanol/H2O (v:v= 4:6), which could convert approximately 94% of 5 mg/L BDE-47 into lower-brominated diphenyl ethers within a 90 min at the ZVZ/AA system. The high debromination of BDE-47 was mainly attributed to the effect of AA that inhibits the formation of Zn(II)(hydr)oxide passivation layers and promotes the corrosion of ZVZ, which leads to increase the reactivity of ZVZ. Additionally, ion chromatography and gas chromatography mass spectrometry analyses revealed that bromine ion and lower-debromination diphenyl ethers formed during the reduction of BDE-47. Furthermore, based on the generation of the intermediates products, and its concentration changes over time, it was proposed that the dominant pathway for conversion of BDE-47 was sequential debromination and the final products were diphenyl ethers. These results suggested that the ZVZ/AA system has the potential for highly efficient debromination of BDE-47 from wastewater.
• A new algorithm of two-dimensional water quantity and the quality model was built. • The migration and diffusion of TP was simulated. • The emergency measures for sudden water pollution accidents was proposed.
In recent years, sudden water pollution accidents in China’s rivers have become more frequent, resulting in considerable effects on environmental safety. Therefore, it is necessary to simulate and predict pollution accidents. Simulation and prediction provide strong support for emergency disposal and disaster reduction. This paper describes a new two-dimensional water quantity and the quality model that incorporates a digital elevation model into the geographic information system. The model is used to simulate sudden water pollution accidents in the main stream of the Yangtze River and Jialing River in the Chongqing section of the Three Gorges Reservoir area. The sectional velocity distribution and concentration change of total phosphorus are then analyzed under four hydrological situations. The results show that the proposed model accurately simulates and predicts the concentration change and migration process of total phosphorus under sudden water pollution accidents. The speed of migration and diffusion of pollutants is found to be greatest in the flood season, followed by the water storage period, drawdown season, and dry season, in that order. The selection of an appropriate water scheduling scheme can reduce the peak concentration of river pollutants. This study enables the impact of pollutants on the ecological environment of river water to be alleviated, and provides a scientific basis for the emergency response to sudden water pollution accidents in the Three Gorges Reservoir area.
• A model-free sewer-WWTP integrated control was proposed. • A dynamic discrete control based on the water level was developed. • The approach could improve the sewer operation against flow fluctuation. • The approach could increase transport capacity and enhance pump efficiency.
This study aims to propose a multi-point integrated real-time control method based on discrete dynamic water level variations, which can be realized only based on the programmable logic controller (PLC) system without using a complex mathematical model. A discretized water level control model was developed to conduct the real-time control based on data-automation. It combines the upstream pumping stations and the downstream influent pumping systems of wastewater treatment plant (WWTP). The discretized water level control method can regulate dynamic wastewater pumping flow of pumps following the dynamic water level variation in the sewer system. This control method has been successfully applied in practical integrated operations of sewer-WWTP following the sensitive flow disturbances of the sewer system. The operational results showed that the control method could provide a more stabilized regulate pumping flow for treatment process; it can also reduce the occurrence risk of combined sewer overflow (CSO) during heavy rainfall events by increasing transport capacity of pumping station and influent flow in WWTP, which takes full advantage of storage space in the sewer system.
• PyLUR comprises four modules for developing and applying a LUR model. • It considers both conventional and novel potential predictor variables. • GDAL/OGR libraries are used to do spatial analysis in the modeling and prediction. • Developed on Python platform, PyLUR is rather efficient in data processing.
Land use regression (LUR) models have been widely used in air pollution modeling. This regression-based approach estimates the ambient pollutant concentrations at un-sampled points of interest by considering the relationship between ambient concentrations and several predictor variables selected from the surrounding environment. Although conceptually quite simple, its successful implementation requires detailed knowledge of the area, expertise in GIS, statistics, and programming skills, which makes this modeling approach relatively inaccessible to novice users. In this contribution, we present a LUR modeling and pollution-mapping software named PyLUR. It uses GDAL/OGR libraries based on the Python platform and can build a LUR model and generate pollutant concentration maps efficiently. This self-developed software comprises four modules: a potential predictor variable generation module, a regression modeling module, a model validation module, and a prediction and mapping module. The performance of the newly developed PyLUR is compared to an existing LUR modeling software called RLUR (with similar functions implemented on R language platform) in terms of model accuracy, processing efficiency and software stability. The results show that PyLUR out-performs RLUR for modeling in the Bradford and Auckland case studies examined. Furthermore, PyLUR is much more efficient in data processing and it has a capability to handle detailed GIS input data.
• TPhP showed faster and higher sorption on biochars than TPPO. • Pyrochars had higher sorption capacity for TPPO than hydrochar. • Hydrophobic interactions dominated TPhP sorption by biochars. • The π-π EDA and electrostatic interactions are involved in sorption.
Aromatic organophosphate flame retardant (OPFR) pollutants and biochars are commonly present and continually released into soils due to their increasingly wide applications. In this study, for the first time, the sorption of OPFRs on biochars was investigated. Although triphenyl phosphate (TPhP) and triphenylphosphine oxide (TPPO) have similar molecular structures and sizes, TPhP exhibited much faster and higher sorption than TPPO due to its stronger hydrophobicity, suggesting the dominant role of hydrophobic interactions in TPhP sorption. The π-π electron donor–acceptor (EDA) interactions also contributed to the sorption process, as suggested by the negative correlation between the sorption capacity of the aromatic OPFRs and the aromatic index (H/C atomic ratios) of biochar. Density functional theory calculations further showed that one benzene ring of aromatic OPFRs has no electrons, which may interact with biochar via π-π EDA interactions. The electrostatic attraction between the protonated P = O in OPFRs and the negatively charged biochar was found to occur at pH below 7. This work provides insights into the sorption behaviors and mechanisms of aromatic OPFRs by biochars.
• The fluorescence peak location of 14 compounds interpreted at protein-like region. • The p-electron system inside aromatic ring contributes to the fluorophore region. • Functional group variation effects the emission spectra. • Decrease in quantum yield and increase in DE is due to atomic weight F>Cl>Br>I. • Theoretically results are in line with experimental ones.
Various single-ring aromatic compounds in water sources are of great concern due to its hazardous impact on the environment and human health. The fluorescence excitation-emission matrix (EEMs) spectrophotometry is a useful method to identify organic pollutants in water. This study provides a detailed insight into the fluorescence properties of the 14 selected toxic single-ring aromatic compounds by experimental and theoretical analysis. The theoretical analysis were done with Time-Dependent Density Functional Theory (TD-DFT) and B3LYP/6-31G (d,p) basis set, whereas, Polarizable Continuum Model (PCM) was used to consider water as solvent. The selected compounds displayed their own specific excitation-emission (Ex/Em) wavelengths region, at Ex<280 nm and Em<340 nm, respectively. Whereas the theoretical Ex/Em was observed as, Ex at 240 nm–260 nm and Em at 255 nm–300 nm. Aniline as a strong aromatic base has longer Em (340 nm) than alkyl, carbonyl, and halogens substituted benzenes. The lone pair of electrons at amide substituent serves as a p-electron contributor into the aromatic ring, hence increasing the stability and transition energy, which results in longer emission and low quantum yield for the aniline. The fluorescence of halogenated benzenes illustrates an increase in the HOMO-LUMO energy gap and a decrease in quantum yield associated with atomic size (F>Cl>Br>I). In this study the theoretical results are in line with experimental ones. The understanding of fluorescence and photophysical properties are of great importance in the identification of these compounds in the water.
• The g-MoS2 coated composites (g-MoS2-BC) were synthesized. • The coated g-MoS2 greatly increased the adsorption ability of biochar. • The synergistic effect was observed for CIP adsorption on g-MoS2-RC700. • The adsorption mechanisms of CIP on g-MoS2-BC were proposed.
The g-MoS2 coated biochar (g-MoS2-BC) composites were synthesized by coating original biochar with g-MoS2 nanosheets at 300°C(BC300)/700°C (BC700). The adsorption properties of the g-MoS2-BC composites for ciprofloxacin (CIP) were investigated with an aim to exploit its high efficiency toward soil amendment. The specific surface area and the pore structures of biochar coated g-MoS2 nanosheets were significantly increased. The g-MoS2-BC composites provided more π electrons, which was favorable in enhancing the π-π electron donor-acceptor (EDA) interactions between CIP and biochar. As a result, the g-MoS2-BC composites showed faster adsorption rate and greater adsorption capacity for CIP than the original biochar. The coated g-MoS2 nanosheets contributed more to CIP adsorption on the g-MoS2-BC composites due to their greater CIP adsorption capacity than the original biochar. Moreover, the synergistic effect was observed for CIP adsorption on g-MoS2-BC700, and suppression effect on g-MoS2-BC300. In addition, the adsorption of CIP onto g-MoS2-BC composites also exhibited strong dependence on the solution pH, since it can affect both the adsorbent surface charge and the speciation of contaminants. It was reasonably suggested that the mechanisms of CIP adsorption on g-MoS2-BC composites involved pore-filling effects, π-π EDA interaction, electrostatic interaction, and ion exchange interaction. These results are useful for the modification of biochar in exploiting the novel amendment for contaminated soils.
• EC modified with BPEs enhances pollutant removal and reduce energy consumption. • Increasing BPE number cannot increase flocculants yield exponentially. • Simulations help to predict the distribution of electrochemical reactions on BPEs.
The design of electrodes is crucial to electrocoagulation process (EC), specifically, with respect to pollutant removal and energy consumption. During EC, the mechanisms for interaction between different electrode arrangement and electrode reactions remain unclear. This work presents an integrated EC process based on horizontal bipolar electrodes (BPEs). In the electrochemical cell, the graphite plates are used as driving cathode while either Fe or Al plates serves as driving anode and BPEs. The BPEs are placed horizontally between the driving electrodes. For municipal wastewater treatment, the pollutant removal efficiency and energy consumption in different configurations of two-dimension electrocoagulation (2D-EC) system with horizontal BPEs were investigated. The removal efficiency of turbidity, total phosphorus and total organic carbon increased significantly with the number of BPEs. Noted that the energy consumption for TP removal decreased by 75.2% with Fe driving anode and 81.5% with Al driving anode than those of 2D-EC, respectively. In addition, the physical field simulation suggested the distributions of potential and current in electrolyte and that of induced charge density on BPE surface. This work provides a visual theoretical guidance to predict the distribution of reactions on BPEs for enhanced pollutant removal and energy saving based on electrocoagulation process for municipal wastewater treatment.
• Genotoxicity of substances is unknown in the water after treatment processes. • Genotoxicity decreased by activated carbon treatment but increased by chlorination. • Halogenated hydrocarbons and aromatic compounds contribute to genotoxicity. • Genotoxicity was assessed by umu test; acute and chronic toxicity by ECOSAR. • Inconsistent results confirmed that genotoxicity cannot be assessed by ECOSAR.
Advanced water treatment is commonly used to remove micropollutants such as pesticides, endocrine disrupting chemicals, and disinfection byproducts in modern drinking water treatment plants. However, little attention has been paid to the changes in the genotoxicity of substances remaining in the water following the different water treatment processes. In this study, samples were collected from three drinking water treatment plants with different treatment processes. The treated water from each process was analyzed and compared for genotoxicity and the formation of organic compounds. The genotoxicity was evaluated by an umu test, and the acute and chronic toxicity was analyzed through Ecological Structure- Activity Relationship (ECOSAR). The results of the umu test indicated that biological activated carbon reduced the genotoxicity by 38%, 77%, and 46% in the three drinking water treatment plants, respectively, while chlorination increased the genotoxicity. Gas chromatograph-mass spectrometry analysis revealed that halogenated hydrocarbons and aromatic compounds were major contributors to genotoxicity. The results of ECOSAR were not consistent with those of the umu test. Therefore, we conclude that genotoxicity cannot be determined using ECOSAR .
• The SRAO phenomena tended to occur only under certain conditions. • High amount of biomass and non-anaerobic condition is requirement for SRAO. • Anammox bacteria cannot oxidize ammonium with sulfate as electron acceptor. • AOB and AnAOB are mainly responsible for ammonium conversion. • Heterotrophic sulfate reduction mainly contributed to sulfate conversion.
For over two decades, sulfate reduction with ammonium oxidation (SRAO) had been reported from laboratory experiments. SRAO was considered an autotrophic process mediated by anammox bacteria, in which ammonium as electron donor was oxidized by the electron acceptor sulfate. This process had been attributed to observed transformations of nitrogenous and sulfurous compounds in natural environments. Results obtained differed largely for the conversion mole ratios (ammonium/sulfate), and even the intermediate and final products of sulfate reduction. Thus, the hypothesis of biological conversion pathways of ammonium and sulfate in anammox consortia is implausible. In this study, continuous reactor experiments (with working volume of 3.8L) and batch tests were conducted under normal anaerobic (0.2≤DO<0.5 mg/L) / strict anaerobic (DO<0.2 mg/L) conditions with different biomass proportions to verify the SRAO phenomena and identify possible pathways behind substrate conversion. Key findings were that SRAO occurred only in cases of high amounts of inoculant biomass under normal anaerobic condition, while absent under strict anaerobic conditions for same anammox consortia. Mass balance and stoichiometry were checked based on experimental results and the thermodynamics proposed by previous studies were critically discussed. Thus anammox bacteria do not possess the ability to oxidize ammonium with sulfate as electron acceptor and the assumed SRAO could, in fact, be a combination of aerobic ammonium oxidation, anammox and heterotrophic sulfate reduction processes.
A method was proposed to identify the main influence factors of soil heavy metals. The influence degree of different environmental factors was ranked. Parent material, soil type, land use and industrial activity were main factors. Interactions between some factors obviously affected soil heavy metal distribution.
Identifying the factors that influence the heavy metal contents of soil could reveal the sources of soil heavy metal pollution. In this study, a categorical regression was used to identify the factors that influence soil heavy metals. First, environmental factors were associated with soil heavy metal data, and then, the degree of influence of different factors on the soil heavy metal contents in Beijing was analyzed using a categorical regression. The results showed that the soil parent material, soil type, land use type, and industrial activity were the main influencing factors, which suggested that these four factors were important sources of soil heavy metals in Beijing. In addition, population density had a certain influence on the soil Pb and Zn contents. The distribution of soil As, Cd, Pb, and Zn was markedly influenced by interactions, such as traffic activity and land use type, industrial activity and population density. The spatial distribution of soil heavy metal hotspots corresponded well with the influencing factors, such as industrial activity, population density, and soil parent material. In this study, the main factors affecting soil heavy metals were identified, and the degree of their influence was ranked. A categorical regression represents a suitable method for identifying the factors that influence soil heavy metal contents and could be used to study the genetic process of regional soil heavy metal pollution.
