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Photocatalytic Reductive Debromination of Polybrominated Diphenyl Ethers

Yukun Zhao, Yuanyuan Wang, Hongwei Ji, Wanhong Ma, Chuncheng Chen*, Jincai Zhao*

Progress in Chemistry. 2017, 29(9): 911-918. https://doi.org/10.7536/PC170510

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Yukun Zhao, Yuanyuan Wang, Hongwei Ji, Wanhong Ma, Chuncheng Chen*, Jincai Zhao*. Photocatalytic Reductive Debromination of Polybrominated Diphenyl Ethers[J]. Progress in Chemistry, 2017, 29(9): 911-918.

Global extensive concerns have been caused by polybrominated diphenyl ethers (PBDEs),because of their universal existence and potential toxicity in ecological environment. The use of solar energy, high selectivity and the mild reaction conditions make photocatalysis become a promising technique for the removal of these pollutants. Recently, great progress has been made in photocatalytic degradation of polyhalogenated organic pollutions. This review mainly focuses on TiO₂-based photocatalytic reduction of PBDEs, which are typical polyhalogenated aromatic hydrocarbons. The ways to improve photocatalytic reductive efficiency and the reaction mechanism have been described. In addition, the promising future of PBDEs photocatalytic reductive debromination is prospected.
Contents
1 Introduction
2 An overview of PBDEs
3 Photocatalytic reductive debromination of PBDEs
3.1 Photocatalytic reductive debromination based on TiO₂
3.2 Photoreductive debromination based on halogen bonding under visible light
4 Proton-coupled electron transfer based on photocatalytic reductive process of PBDEs
5 Conclusion
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Analytical Methods, Environmental Pollutions and Toxicity of Short Chain Chlorinated Paraffins

Yawei Wang, Ying Wang, Guibin Jiang

Progress in Chemistry. 2017, 29(9): 919-929. https://doi.org/10.7536/PC170504

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Yawei Wang, Ying Wang, Guibin Jiang. Analytical Methods, Environmental Pollutions and Toxicity of Short Chain Chlorinated Paraffins[J]. Progress in Chemistry, 2017, 29(9): 919-929.

Short chain chlorinated paraffins (SCCPs),as a class of emerging organic pollutants, have been listed in the candidates of potential persistent organic pollutants (POPs) under the Stockholm Convention(SC)in 2006, and the POPs review committees considered SCCPs to fulfill the criteria of Annex A of the SC in 2017. Due to their broad industrial production and application in China, SCCPs have been found in high levels in different environmental matrixes. In this paper, the sources, releases, analytical methods, the current pollution situation in various environmental matrixes and the toxicity of SCCPs are reviewed. Meanwhile, the problems in present studies and the future research demands are also summarized in this paper.
Contents
1 Introduction
2 The sources and releases of chlorinated paraffins
3 The analytical methods of short chain chlorinated paraffins
3.1 The pretreatment method
3.2 The instrument analysis
4 The current pollutions situation of short chain chlorinated paraffins in multi-environmental medium
4.1 Air and dust
4.2 Water
4.3 Sludge, sediment and soil
4.4 Organisms
4.5 Food
5 The toxicity of short chain chlorinated paraffins
6 Conclusion
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Chemiluminescence Generation from Haloaromatic Pollutants:Structure-Activity Relationship, Molecular Mechanism and Potential Applications

Benzhan Zhu, Linna Xie, Chen Shen, Huiying Gao, Liya Zhu, Li Mao

Progress in Chemistry. 2017, 29(9): 930-942. https://doi.org/10.7536/PC170503

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Benzhan Zhu, Linna Xie, Chen Shen, Huiying Gao, Liya Zhu, Li Mao. Chemiluminescence Generation from Haloaromatic Pollutants:Structure-Activity Relationship, Molecular Mechanism and Potential Applications[J]. Progress in Chemistry, 2017, 29(9): 930-942.

The ubiquitous distribution of halogenated aromatic pollutants (XAr)coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced oxidation processes (AOPs) have been employed as an "environmental-green" technology for treatment and degradation of such recalcitrant and highly toxic XAr. During our study on the molecular mechanism of metal-independent hydroxyl radicals (·OH) production by halogenated quinones and H₂O₂, we unexpectedly find that an unprecedented·OH-dependent two-step intrinsic chemiluminescene (CL) can be produced by H₂O₂ and tetrachloro-p-benzoquinone, which is the major carcinogenic metabolite of the widely-used wood preservative pentachlorophenol. We further find that·OH-producing AOPs-mediated degradation of pentachlorophenol and all other XAr could produce intrinsic CL that is directly dependent on the formation of the extremely reactive·OH.A systematic structure-activity relationship study for all 19 chlorinated phenols demonstrates that the CL increases with an increasing number of chlorine-substitution in general. More interestingly, a relatively good correlation is noticed that not only between CL intensity and chlorinated quinoid intermediates, but also between CL emission and semiquinone radicals. Taken together, we propose that·OH-dependent formation of quinoid intermediates, quinone-1,2-dioxetane and electronically excited carbonyl species is responsible for this unusual intrinsic CL production.A rapid, sensitive, simple, and effective CL method has been developed to not only detect and measure trace amount of XAr in real environment, but also to provide useful information for predicting the toxicity or monitoring the degradation kinetics of XAr. These findings may have broad chemical, environmental and biological implications for future studies on remediation of other halogenated persistent organic pollutants by AOPs.
Contents
1 Introduction
2 An·OH-dependent CL could be generated by carcinogenic polyhalogenated quinones and H₂O₂
2.1 The CL system of tetrachloro-1,4-benzoquinone (TCBQ) and H₂O₂
2.2 Possible light-emitting intermediates
2.3 Molecular mechanism for·OH-dependent CL generation
2.4 Other halogenated quinones could generate similar·OH-dependent CL
3 Intrinsic·OH-dependent CL could also be produced from degradation of pentachlorophenol (PCP) during advanced oxidation processes
3.1 An intrinsic CL emission from advanced oxidation of PCP by the classic Fenton system
3.2 The primary intermediates and ring-opening product
3.3 Possible molecular mechanism for CL emission during·OH-dependent PCP degradation
4 The structure-activity relationship study on the CL emission from the degradation of chlorinated phenols
4.1 Chlorinated phenols could generate CL during the·OH-generating AOPs
4.2 A good correlation between CL emission and the formation of chlorinated quinoid intermediates
4.3 Possible molecular basis for the correlation between CL emission and chlorinated phenols
4.4 A good correlation between CL emission and the formation of the chlorinated semiquinone radicals
4.5 Relatively good correlations between CL and the toxicity/degradation rate of chlorinated phenols
5 Other halogenated aromatic compounds could generate intrinsic CL during their advanced degradation by·OH-generating systems
6 Conclusion
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Organic Contaminants in the Pearl River Delta, South China:Environmental Behavior and Human Exposure

Lianjun Bao, Ying Guo, Liangying Liu, Eddy Y. Zeng*

Progress in Chemistry. 2017, 29(9): 943-961. https://doi.org/10.7536/PC170516

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Lianjun Bao, Ying Guo, Liangying Liu, Eddy Y. Zeng*. Organic Contaminants in the Pearl River Delta, South China:Environmental Behavior and Human Exposure[J]. Progress in Chemistry, 2017, 29(9): 943-961.

The Pearl River Delta is one of the most developed but also one of the most polluted regions in China.The severe environmental pollution is undoubtedly going to hinder the sustainable development of regional economy and cause human health risks.A variety of legacy and emerging organic contaminants have been ubiquitously found in various environmental compartments, biota, and human tissues.These include polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), organophosphate esters flame retardants (OPEs) and many others.Comprehensive understanding of the environmental behaviors of organic contaminants and their human exposures is essential for policy makers to carry out effective measures to reduce the contaminants.Inter-compartmental transfer, e.g., sediment-water, air-water and soil-water, of organic contaminants are important geochemical processes governing their environmental behavior.This review aims to summarize the current status of sampling techniques for measuring the inter-compartmental exchange flux of hydrophobic organic chemicals, to summarize the current knowledge on the environmental behavior e.g., atmospheric dry and wet deposition, soil inventory, riverine fluxes, of organic contaminants, and human exposure to typical organic contaminants in the Pearl River Delta region.The limitations of current researches and prospects of future studies on environmental behaviors of organic contaminants and their human exposures are also outlined.
Contents
1 Introduction
2 Techniques for measuring the inter-compartmental exchange flux of hydrophobic organic chemicals
2.1 Active sampling techniques
2.2 Passive sampling techniques
3 Environmental behavior of organic contaminants
3.1 Atmospheric dry and wet deposition
3.2 Soil inventory
3.3 Riverine fluxes
3.4 Organic contaminants in coastal and estuarine sediments
4 Human exposure to typical organic contaminants and health risk assessment in the PRD
4.1 Methods to investigate human exposure to contaminants
4.2 Biomonitoring in human exposure assessment to contaminants
4.3 Human exposure to typical organic contaminants in the PRD
4.4 Recent viewpoints in study of human exposure to organic contaminants
5 Conclusion
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Research Progress on Particulate Organonitrates

Fangting Gu, Min Hu*, Jing Zheng, Song Guo

Progress in Chemistry. 2017, 29(9): 962-969. https://doi.org/10.7536/PC170324

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Fangting Gu, Min Hu*, Jing Zheng, Song Guo. Research Progress on Particulate Organonitrates[J]. Progress in Chemistry, 2017, 29(9): 962-969.

Particulate organonitrates are formed from volatile organic compounds (VOCs) oxidation by radicals. A portion of semi-volatile gas-phase organonitrates can be incorporate into aerosol by oxidation reactions or portioning, and has been an important component of secondary organic aerosol (SOA). Particulate organonitrates study has become one of the important aspects of atmospheric chemistry. Given the large number and variability of chemical constituents, and possible chemical transformations of organonitrates, such characterization presents a key problem for research. Based on recent research progress on particulate organonitrates, this paper summarizes the formation mechanism and quantification method of particulate organonitrates. Profiting from the application of high time resolution techniques, field measurements has become the major approach of particulate organonitrates study. Thermal dissociation-laser induced fluorescence (TD-LIF) and aerosol mass spectrometers (AMS) have been used to quantify and provide the evolution processes of particulate organonirates. Meanwhile, chemical ionization mass spectrometer(CIMS)allows for the determination of molecular ion composition of organonitrates, promising to become the important direction of study of particulate organonirates in future field measurements. To have a deep insight on precursor and atmospheric chemistry processes of particulate organonirates, future research should focus on the combination of field measurement, modeling simulation and laboratory simulation, and these will also lead to a more comprehensive understanding of formation mechanism of particulate organonirates.
Contents
1 Introduction
2 Research progress on particulate organonitrates
2.1 Formation mechanism of particle-phase organonitrates
2.2 Measurements and quantification methods of particulate organonitrates
2.3 Formation and environmental effects of particulate organonitrates
3 Conclusion and outlook
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Global Review of Mercury Biogeochemical Processes in Forest Ecosystems

Xun Wang, Wei Yuan, Xinbin Feng

Progress in Chemistry. 2017, 29(9): 970-980. https://doi.org/10.7536/PC170343

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Xun Wang, Wei Yuan, Xinbin Feng. Global Review of Mercury Biogeochemical Processes in Forest Ecosystems[J]. Progress in Chemistry, 2017, 29(9): 970-980.

Global forest ecosystems account for 31% of global land areas, and the cycling of materials in the forest has been considered the most complicated among all terrestrial ecosystems also from the perspective of mercury (Hg). Elucidation of the Hg biogeochemical processes in the forest ecosystem yields insights on how atmospheric mercury is evaded and sequestered in terrestrial landscapes and the fundamental understanding of Hg biogeochemical processes in such an environmentally complex system also bridges the knowledge gap in quantifying global mercury budgets driven by global biogeochemical processes. However, there is a large knowledge gap in the role of forest ecosystem whether as a sink or source in global atmospheric Hg cycling. The review represents the current new understanding of the interacting processes of multiple Hg exchange, transformation and Hg isotope fractionation in this environmentally important compartment on the basis of studies during last two decades about Hg mass balance in global forest ecosystems, the processes of Hg accumulation in forest soil and the Hg isotope fractionation during Hg biogeochemical processes in such ecosystems. Finally, forthcoming research emphasis and directions of the field are proposed at the end of the review given the existing knowledge gap in this area.
Contents
1 Introduction
2 Mercury biogeochemical processes in the forest ecosystems
3 Traditional mass balance studies of mercury in forest ecosystems
3.1 Elucidation of high litterfall mercury deposition in China:implication on global forest mercury cycling
3.2 Elucidation of low mercury runoff in forest ecosystems of China
4 Mercury accumulation in forest soil
4.1 Mercury loss during initial decomposition
4.2 Mercury accumulation during decomposition
5 Mercury isotopes chemistry in forest ecosystems
5.1 Isotope fractionation during air-foliage mercury flux
5.2 Isotope fractionation during air-soil mercury flux
5.3 Application of mercury isotopes in forest ecosystems
6 Conclusion and outlook
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Heterogeneous Fenton Catalytic Water Treatment Technology and Mechanism

Lai Lyu, Chun Hu

Progress in Chemistry. 2017, 29(9): 981-999. https://doi.org/10.7536/PC170552

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Lai Lyu, Chun Hu. Heterogeneous Fenton Catalytic Water Treatment Technology and Mechanism[J]. Progress in Chemistry, 2017, 29(9): 981-999.

Heterogeneous Fenton catalytic water treatment technology is an effective method for degradation of organic pollutants in water. Compared to the homogeneous Fenton reaction, it has the advantages of recyclability, wide pH response range, easy solid-liquid separation and non-production of iron sludge. This article mainly reviews the classical Fenton reaction mechanism, the heterogeneous Fenton reaction mechanism, and the developed heterogeneous Fenton/Fenton-like catalysts based on the basic mechanism. The bottleneck problems of the present heterogeneous Fenton system, including low activity under neutral condition, poor stability of the catalyst and low utilization efficiency of H₂O₂, are summarized. Particularly, the emphasis is to introduce the developed new type heterogeneous Fenton systems, including the one-center Cu-based Fenton-like system and the dual-center Fenton-like system, for solving the bottleneck problems. We think the dual-center Fenton-like system has actually broke the concept of the classical Fenton reaction, creating the electron-rich centers and electron-deficiency centers based on the polarization theory of electron distribution, which realizes the efficiently selective reduction of hydrogen peroxide and oxidative degradation of pollutants, solving the technical bottleneck problems of the classical Fenton reaction in water treatment.
Contents
1 Introduction
2 Classical Fenton reaction mechanism
3 Heterogeneous Fenton catalytic reaction mechanism
3.1 Heterogeneous Fenton reaction mechanism without considering organic pollutants
3.2 Heterogeneous Fenton reaction mechanism in consideration of organic pollutants
4 Development and utilization of heterogeneous Fenton catalysts
4.1 Zero-valent metal catalyst
4.2 Transition metal oxide catalyst
4.3 Metal species-supported catalysts
4.4 Metal ions-doped catalysts
5 Existing problems of heterogeneous Fenton catalytic system
6 Development of novel heterogeneous Fenton system and its catalytic mechanism for degradation of organic pollutants in water
6.1 One-center heterogeneous Fenton system
6.2 Dual-center heterogeneous Fenton-like system induced by lattice oxygen
6.3 Dual-center heterogeneous Fenton-like system induced by surface organic ligand
7 Conclusion and outlook
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Application of in vivo Solid-Phase Microextraction on Pollutants Analysis in Living Animals and Plants

Li Yin, Jianqiao Xu*, Zhoubing Huang, Guosheng Chen, Siming Huang, Gangfeng Ouyang*

Progress in Chemistry. 2017, 29(9): 1000-1007. https://doi.org/10.7536/PC170618

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Li Yin, Jianqiao Xu*, Zhoubing Huang, Guosheng Chen, Siming Huang, Gangfeng Ouyang*. Application of in vivo Solid-Phase Microextraction on Pollutants Analysis in Living Animals and Plants[J]. Progress in Chemistry, 2017, 29(9): 1000-1007.

As a sampling and sample preparation technique which is convenient, rapid as well as environmentally-friendly, solid-phase microextraction has attracted widespread attention. Within the scope of its application on in vivo analysis, solid-phase microextraction has been gradually used for highly-efficient detection of various analytes of interest in living animals and plants with the new illustrations on extraction kinetics of solid-phase microextraction, together with development on novel in vivo sampling fibers. In this article we give an overview of the proposal of various calibration methods for quantification, recent investigations on the extraction kinetics of in vivo sampling, and preparations of novel samplers for in vivo solid-phase microextraction, apart from rapid detection of multiple pollutants in living animals or plants, as well as continuous long-term monitoring of uptake and elimination of pollutants therein. Potential application and future trends of development of in vivo solid-phase microextraction are also discussed.
Contents
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Generation Mechanism and Fate Behaviors of Environmental Persistent Free Radicals

Lin Han, Baoliang Chen*

Progress in Chemistry. 2017, 29(9): 1008-1020. https://doi.org/10.7536/PC170566

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Lin Han, Baoliang Chen*. Generation Mechanism and Fate Behaviors of Environmental Persistent Free Radicals[J]. Progress in Chemistry, 2017, 29(9): 1008-1020.

Environmental persistent free radicals (EPFRs) can persist in environment for hours to days, and have potential environmental and public health impacts, which has attracted more and more attention in recent years. Environmental persistent free radicals are found to exist in a variety of environmental media, such as combustion particles and organic contaminated soil, and they are considered to be an emerging pollutant recently. Compared with transient free radicals, environmental persistent free radicals have received relatively less attention, and the generating mechanisms and environmental impacts remain unclear. Meanwhile, environmental persistent free radicals are widely distributed in the environment, which makes them more complex in their research. This review highlights EPFRs from the following aspects:detection methods, generating mechanisms, speciation types, environmental characteristics (persistence, stability, and reactivity), the harm to the environment and the elimination method. By studying the fate behaviors of environmental persistent free radicals, this article proposes a possible migration pathway in environment. The purpose of this review is to have a more comprehensive understanding of the EPFRs, especially to help reduce the harm to the human and environment, and provide scientific basis for researchers to have a deeper study on it.
Contents
1 Introduction
2 Environmental persistent free radicals (EPFRs)
3 Generation mechanism of EPFRs
3.1 The media of the EPFRs formation
3.2 The precursors of the EPFRs
3.3 The influential conditions of EPFRs formation
3.4 The formation mechanism of the EPFRs
4 Species of EPFRs
5 Persistence and stability of EPFRs
6 Reactivity of EPFRs and its application on the environmental pollution control
7 Potential hazards of EPFRs and its elimination methods
7.1 Potential hazards of EPFRs
7.2 Elimination methods of EPFRs
8 Environmental chemistry behaviors of EPFRs
9 Conclusion
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Environmental Transformation of Engineered Carbon Nanomaterials and Its Implications

Xuguang Li, Tingting Du, Jin Liu, Xinlei Liu, Pengkun Ma, Yu Qi, Wei Chen*

Progress in Chemistry. 2017, 29(9): 1021-1029. https://doi.org/10.7536/PC170522

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Xuguang Li, Tingting Du, Jin Liu, Xinlei Liu, Pengkun Ma, Yu Qi, Wei Chen*. Environmental Transformation of Engineered Carbon Nanomaterials and Its Implications[J]. Progress in Chemistry, 2017, 29(9): 1021-1029.

Engineered carbon nanomaterials have shown great promise in many applications. With the rapid increase in the production and use of these materials, their environmental behaviors and implications have received much attention. Carbon nanomaterials can undergo significant physical, chemical and biological transformation in the environment, resulting in remarkable changes in their surface charge, hydrophobicity and surface functionality. Environmental transformation of carbon nanomaterials can significantly affect their colloidal stability, transport and toxicity, as well as their capabilities to accumulate/mobilize environmental contaminants and to catalyze environmentally relevant reactions. Thus, environmental transformation largely dictates the environmental behaviors and implications of carbon nanomaterials. This paper summarizes the recent key research findings in the area, with an emphasis on the underlying mechanisms and structure-effect correlations.
Contents
1 Introduction
2 Transformation of engineered carbon nanomaterials
2.1 Physical transformation of carbon nanomaterials
2.2 Chemical transformation of carbon nanomaterials
2.3 Biological transformation of carbon nanomaterials
3 Effects of environmental transformation on environmental processes and implications of carbon nanomaterials
3.1 Environmental transformation affects transport of carbon nanomaterials
3.2 Environmental transformation affects capability of carbon nanoparticles to accumulate and mobilize contaminants
3.3 Environmental transformation affects catalytic efficiency of carbon nanomaterials
4 Conclusion
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The Mechanism, Materials and Reactors of Photocatalytic Disinfection in Water and Wastewater Treatment

Hongtao Yu, Shuo Chen, Xie Quan*, Zhenhua Zhang

Progress in Chemistry. 2017, 29(9): 1030-1041. https://doi.org/10.7536/PC170734

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Hongtao Yu, Shuo Chen, Xie Quan*, Zhenhua Zhang. The Mechanism, Materials and Reactors of Photocatalytic Disinfection in Water and Wastewater Treatment[J]. Progress in Chemistry, 2017, 29(9): 1030-1041.

Traditional disinfection technologies not only consume corrosive agents (such as Cl₂ and O₃) but also generate toxic disinfection by-products. Without these drawbacks, ultraviolet disinfection technology has been used widely in water and wastewater treatment. However, some pathogenic bacteria can repair their ultraviolet damage and reactivate, which brings health risk. Photocatalytic disinfection is a safe alternative, since photogenerated reactive oxygen species are confirmed to destroy not only DNA but also plasma membrane and effluent protein, then killing pathogenic bacteria utterly. Furthermore, both UV and photogenerated reactive oxygen species participate in the sterilization process and increase the rate of disinfection. Therefore, compared to ultraviolet disinfection, photocatalysis displays a superior ability to kill microorganisms fastly and thoroughly. This paper presents the advantages of photocatalysis over other disinfection technologies including chlorine-containing disinfectant, ozone and ultraviolet. Special attention is paid to the disinfection mechanisms of various photogenerated oxidative radicals. Typical photocatalytic composites including semiconductor-carbon with membrane stress, semiconductor-metal with oxidative stress and semiconductor-DNA aptamer with ability to capture microbial cell are summarized. Furthermore, three kinds of possible application modes of photocatalytic disinfection, including annular reactors, fixed bed reactors and membrane separation reactors, are reviewed. Finally, research prospects are proposed for the future development of photocatalysis in disinfection.
Contents
1 Introduction
2 Disinfection mechanism on photogenerated reactive oxygen species
2.1 Hydroxyl radical
2.2 Singlet oxygen
2.3 Hydrogen peroxide
2.4 Halogenic radical
3 Pathogenic microorganisms
3.1 Common bacteria
3.2 Viruses
3.3 Protozoa
3.4 Antibiotic resistant bacteria and antibiotic resistance genes
4 Photocatalytic materials for disinfection
4.1 TiO₂
4.2 Non-TiO₂-based photocatalysts
4.3 Composite of photocatalyst and nano carbon material with membrane stress
4.4 Composite of photocatalyst and nano metal materials with oxidative stress
4.5 Composite of photocatalyst and DNA aptamer
5 Reactors for photocatalytic disinfection
5.1 Annular reactors
5.2 Fixed bed reactors
5.3 Membrane separation reactors
6 Conclusion
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Environmental Processes of Dissolved Black Carbon

Chenhui Wei, Heyun Fu, Xiaolei Qu, Dongqiang Zhu

Progress in Chemistry. 2017, 29(9): 1042-1052. https://doi.org/10.7536/PC170444

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Chenhui Wei, Heyun Fu, Xiaolei Qu, Dongqiang Zhu. Environmental Processes of Dissolved Black Carbon[J]. Progress in Chemistry, 2017, 29(9): 1042-1052.

Dissolved black carbon (DBC) is the water-soluble fraction of the black carbon continuum, being the key flux that connects two major black carbon pools:the soils and the ocean sediments. DBC is also an important component of the dissolved organic matter pool. It has rich aromatic clusters and oxygen-containing functional groups including carboxyl, hydroxyl, and carbonyl groups. DBC plays an important role in the sorption and environmental transformation of pollutants. Thus, research on the biogeochemical behavior of DBC is key to the understanding of the global carbon cycle as well as the environmental fate and impact of pollutants. The present paper reviews the previous studies on the environmental processes of DBC. The discussion covers the qualitative and quantitative analytical methods of DBC, its spatiotemporal distribution, its structural characteristics and environmental transformation, as well as its impacts on the sorption, redox transformation and photo transformation of pollutants in the environments. Then the new research directions addressing current knowledge gaps are proposed.
Contents
1 Introduction
2 Analytical methods and the spatiotemporal distribution of DBC
2.1 Qualitative and quantitative analytical methods for DBC
2.2 Spatiotemporal distribution of DBC
3 Structural characteristics and environmental transformation of DBC
3.1 Structural characteristics of DBC
3.2 Environmental transformation of DBC
4 Impacts of DBC on the environmental behavior of pollutants
4.1 Impacts of DBC on the sorption behavior of pollutants
4.2 Impacts of DBC on the redox reactions of pollutants
4.3 Impacts of DBC on the photoconversion reactions of pollutants
5 Conclusion
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The Application of Micro-Mechanism of Crystal Changes under the Surface/Interface Control in Treating Chromium-Containing Residues

Weizhen Liu, Jiayi Zheng, Zhicheng Wu, Zhangbin Liu, Zhang Lin

Progress in Chemistry. 2017, 29(9): 1053-1061. https://doi.org/10.7536/PC170513

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Weizhen Liu, Jiayi Zheng, Zhicheng Wu, Zhangbin Liu, Zhang Lin. The Application of Micro-Mechanism of Crystal Changes under the Surface/Interface Control in Treating Chromium-Containing Residues[J]. Progress in Chemistry, 2017, 29(9): 1053-1061.

As one of the primary strategic metal, chromium plays an important role in the national economy in China. However, the chromium resource is seriously insufficient meanwhile the chromium pollution is severe in China. This article elaborates the advantages and disadvantages of the current detoxification methods and chromium extraction methods for the chromium-containing residues as well as the bottlenecks they are faced with. It points out that, for developing an effective extraction method for chromium from chromium-containing residues, the micro-structural analysis for the mineral phases of the chromium-containing residues and the thorough investigation on the chemical states, combined forms and distribution of chromium in each mineral phase are crucial. Moreover, this article summarizes the current international research of the micro-structural analysis of chromium-containing residues. This article also introduces the work of our research group that applies the understanding of micro-mechanism of crystal growth and transformation under the surface/interface control on chromium extraction from chromium-containing residue. This new idea and technology are instructional for achieving the combination of detoxification and reclamation for chromium-containing residues. Finally, the potentiality and developing tendency of this idea as well as the technologies of chromium extraction from chromium-containing residue via crystal growth and mineral phase transformation are prospected.
Contents
1 Introduction
2 The current researches on disposal of chromium-containing residue
2.1 Detoxification methods
2.2 Chromium extraction methods
3 Micro-structural analysis of chromium-containing residue
4 Chromium extractions under the guidance of micro-structural analysis
5 Conclusion
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Adsorption of Radionuclide Uranium onto Carbon-Based Nanomaterials from Aqueous Systems

Yu Liang, Pengcheng Gu, Wen Yao, Shujun Yu, Jian Wang, Xiangke Wang*

Progress in Chemistry. 2017, 29(9): 1062-1071. https://doi.org/10.7536/PC170427

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Yu Liang, Pengcheng Gu, Wen Yao, Shujun Yu, Jian Wang, Xiangke Wang*. Adsorption of Radionuclide Uranium onto Carbon-Based Nanomaterials from Aqueous Systems[J]. Progress in Chemistry, 2017, 29(9): 1062-1071.

With the development of nuclear technology, the radioactive nuclide pollution such as uranium pollution is threating the human health. Uranium is the major constituent of nuclear fuel and the key nuclide in spent fuel reprocessing. Carbon-based nanomaterials are promising for uranium removal due to their large specific surface area, excellent acid stability, higher radiation and thermal resistance. In this review, carbon-based nanomaterials such as carbon nanotubes, graphene and other carbon materials used as adsorbents for uranium removal have been summarized. The relevant synthetic methods, removal performance and adsorption mechanism are also discussed. And the adsorption performance of carbon-based materials can be improved by surface oxidization and physical or chemical modifications such as coating, grafting functional groups or molecules. However, the practical application of carbon-based nanomaterials has been limited because of their high cost and complicated synthesis process. Therefore, how to develop a low-cost, mature process technology and application system will be an important research direction in the future.
Contents
1 Introduction
2 The species of carbon-based nanomaterials
2.1 Carbon nanotubes
2.2 Graphene
2.3 Other carbon-based nanomaterials
3 Adsorption mechanism and influencing factors
4 Conclusion and outlook
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The Interaction Between Nano Zero-Valent Iron and Soil Components and Its Environmental Implication

Yanlong Wang, Daohui Lin*

Progress in Chemistry. 2017, 29(9): 1072-1081. https://doi.org/10.7536/PC170526

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Yanlong Wang, Daohui Lin*. The Interaction Between Nano Zero-Valent Iron and Soil Components and Its Environmental Implication[J]. Progress in Chemistry, 2017, 29(9): 1072-1081.

Nano zero-valent iron (nZVI), possessing excellent reductive activity and adsorption performance, has been and will be widely applied in the remediation of contaminated soil and groundwater. However, superior reactive nZVI can also interact with soil components, which may not only affect soil properties and its ecological functions but also impact on the existing form and remediation function of nZVI.Interactions between nZVI and soil air, pore water, clay minerals, organic matter, and microorganism are addressed, and the influences on the soil composition and property and on the transformation and function of nZVI are discussed. Under the influence of soil components, nZVI may be transformed to various iron-based chemicals, such as Fe₃O₄, γ-Fe₂O₃, α-Fe₂O₃, α-FeOOH, and γ-FeOOH. Meanwhile, nZVI and its derivates would affect the soil environment by altering soil air composition, pore water pH, and/or physicochemical properties of soil clay minerals and organic matter. Furthermore, nZVI can also affect the soil microbial community, facilitating or inhibiting microbial growth and reproduction. The microbe initiating transformation can regulate the remediation function and fate of nZVI in the soil environment. At the end of the text, future research directions are put forward. This review is believed to boost scientific research and technology advance in environmental applications of nZVI.
Contents
1 Introduction
2 Interaction between nZVI and soil air and its environmental implication
2.1 Interaction between soil air and nZVI and its effect on the transformation and function of nZVI
2.2 Effects of nZVI on soil air and its environmental implication
3 Interaction between nZVI and soil pore water and its environmental implication
3.1 Interaction between soil pore water and nZVI and its effect on the transformation and function of nZVI
3.2 Environmental behavior of nZVI in soil pore water
3.3 Effects of nZVI on soil pore water and its environmental implication
4 Interaction between nZVI and clay minerals and its environmental implication
4.1 Interaction between clay minerals and nZVI and its effect on the transformation and function of nZVI
4.2 Effects of nZVI on clay minerals and its environmental implication
5 Interaction between nZVI and soil organic matter and its environmental implication
5.1 Interaction between soil organic matter and nZVI and its effect on the transformation and function of nZVI
5.2 Effects of nZVI on soil organic matter and its environmental implication
6 Interaction between nZVI and soil microorganisms and its environmental implication
6.1 Toxicity mechanisms of nZVI to soil microorganisms
6.2 Effects of nZVI on soil microbial community structure
6.3 Interaction between soil microorganisms and nZVI and its potential impact
7 Conclusion
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Research Progress and Challenge of Synthetic Musks:from Personal Care, Environment Pollution to Human Health

Yanpeng Gao, Guiying Li, Shengtao Ma, Taicheng An*

Progress in Chemistry. 2017, 29(9): 1082-1092. https://doi.org/10.7536/PC170448

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Yanpeng Gao, Guiying Li, Shengtao Ma, Taicheng An*. Research Progress and Challenge of Synthetic Musks:from Personal Care, Environment Pollution to Human Health[J]. Progress in Chemistry, 2017, 29(9): 1082-1092.

Synthetic Musks (SMs) are widely used as fragrance ingredients in various personal care products and consumer goods, due to their fragrance smell similar to natural musk. Given the extensive use and large amount of consumption as well as incomplete disposal in conventional wastewater treatment plants (WWTP), SMs are discharged into aquatic environment and frequently detected in aquatic organisms, air and even human milk, blood, and adipose tissues, resulting in the potential adverse effects on ecological environment and human health. Therefore, SMs became an important kind of emerging organic contaminants (EOCs). In this study, the current research progress on the environmental pollution, transformation mechanisms, environmental fate and health effect of SMs are reviewed in detail. Although the conclusion that the aquatic toxicity and human estrogenic effects are found to be increased during the transformation, the transformation mechanisms of SMs in different environmental matrix as well as organisms are still unclear, even that the toxicity of transformation/metabolism products is rarely attempted.The relationship between exposure mode of SMs and damage mechanism of human health is still unclear. In addition, the relative research of the effect on ecological environments and human health of emerging SMs such as macrocyclic musk and alicyclic musk is also deserved to be considered.
Contents
1 Introduction
1.1 Introduction of synthetic musk
1.2 Usage and human exposure
2 Environmental pollution
2.1 Synthetic musk in atmosphere and indoor dust
2.2 Synthetic musk in aquatic environment
2.3 Synthetic musk in organism
3 The transformation process and mechanism
3.1 Biodegradation
3.2 Photochemical degradation
3.3 Advanced oxidation degradation
4 Adverse effects on organisms
5 Adverse effects on human health
6 Conclusion and outlook
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Natural Origins, Concentration Levels, and Formation Mechanisms of Organohalogens in the Environment

Lijuan Jin, Baoliang Chen*

Progress in Chemistry. 2017, 29(9): 1093-1114. https://doi.org/10.7536/PC170563

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Lijuan Jin, Baoliang Chen*. Natural Origins, Concentration Levels, and Formation Mechanisms of Organohalogens in the Environment[J]. Progress in Chemistry, 2017, 29(9): 1093-1114.

Organohalogens are one of the most important pollutants in the environment, of which the environmental chemical behavior, control methods and health effects have aroused great concern around the world, but they are always considered as anthropogenic compounds, such as polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), chlorophenols (CPs) and bromophenols (BPs). Currently, however more and more organohalogens are known to be produced naturally in the environment, and they are widely distributed in the environment, including marine, terrestrial, desert and polar region. Because of their high toxicity, persistence, bioaccumulation potential, and carcinogenicity, and sometimes even acting as environmental hormone substances, the majority of which have a bad effect on human causing mental and psychological harm, most of these pollutants are regulated in many countries. Moreover, natural organohalogens' origin, concentration level, formation mechanism and fate in environment are critical to correctly assess its environmental risk, as well as to set proper environmental standards and safe concentration threshold. As research of natural organohalogens is emerging rapidly all over the world, this review summarizes the marine, terrestrial and other sources of natural organohalogens, their physical and chemical properties, and concentration levels of some typical compounds. The formation mechanisms of biotic and abiotic pathways are highlighted. The transport and fate of natural organohalogens in the environment are discussed. Some general analytical methods are also mentioned in this review.The currently research trends and existing questions are prospected, and the formation molecular mechanisms and environmental transport behaviors of natural organohalogens are worthwhile studying.
Contents
1 Introduction
2 Natural origin of organohalogens
2.1 Marine source
2.2 Terrestrial source
2.3 Other source
3 Formation mechanism of natural organohalogens
3.1 Biotic mechanism
3.2 Abiotic mechanism
3.3 Influential factors
4 Concentration level of some typical natural organohalogens
5 Fate of transport and transformation in environment
6 General analytical methods
7 Conclusion
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Environment Pollutants Removal with Bi-Based Photocatalysts

Xing Ding, Xianglong Yang, Zhongliang Xiong, Hao Chen, Lizhi Zhang

Progress in Chemistry. 2017, 29(9): 1115-1126. https://doi.org/10.7536/PC170443

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Xing Ding, Xianglong Yang, Zhongliang Xiong, Hao Chen, Lizhi Zhang. Environment Pollutants Removal with Bi-Based Photocatalysts[J]. Progress in Chemistry, 2017, 29(9): 1115-1126.

In recent years, Bi-based semiconductor materials have gained considerable attention. Their unique layered structure and suitable band gap endow them with superior visible light photocatalytic activities, which is promising in environment pollutants removal. This article mainly reviews the recent advances in environment contaminants removal with Bi-based photocatalysts. We first introduce several well-known Bi-based semiconductor materials and their preparation methods, and then summarize their applications for air purification, organic wastewater treatment, heavy metal ions removal, disinfection, and finally discuss the major problems in the field of bismuth-based photocatalysts, and prospect their further development in the future.
Contents
1 Introduction
2Bi-based photocatalysts and their preparation methods
2.1 Unary Bi-based photocatalysts
2.2 Binary Bi-based photocatalysts
2.3 Bismuth oxyhalides
3 Environment pollutants removal with Bi-based photocatalysts
3.1 Air purification
3.2 Refractory organic wastewater treatment
3.3 Inorganic wastewater treatment
3.4 Disinfection
4 Conclusion
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Solid-Phase Microextraction Fibers Based on Novel Materials:Preparation and Application

Li Yin, Jianqiao Xu*, Zhoubing Huang, Guosheng Chen, Juan Zheng, Gangfeng Ouyang*

Progress in Chemistry. 2017, 29(9): 1127-1141. https://doi.org/10.7536/PC170610

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Li Yin, Jianqiao Xu*, Zhoubing Huang, Guosheng Chen, Juan Zheng, Gangfeng Ouyang*. Solid-Phase Microextraction Fibers Based on Novel Materials:Preparation and Application[J]. Progress in Chemistry, 2017, 29(9): 1127-1141.

Convenient, rapid as well as environmentally-friendly, solid-phase microextraction is(SPME) a sample preparation technique, which draws widespread attention among the scientific community. The extraction phases in the SPME fibers determine their selectivity and extraction efficiency, hence, a series of new fiber coatings with excellent physical and chemical properties are developed for detection of various small organic molecules in complex sample matrices. Herein, we give a brief review of some materials widely used for the preparation of new SPME fibers, including polymers, carbonaceous materials, metal-organic framework, and some other materials, with the emphasis on the fiber preparation methodologies, the microstructures and extraction properties of the novel fiber coatings, together with applications of the synthesized fibers on environmental analysis, food analysis and inspection on textile and leather samples. Furthermore, future developing trends and application prospects of the new fiber coatings are discussed.
Contents
1 Introduction
2 Polymers
2.1 Commonly used polymers
2.2 Porous polymers
2.3 Molecularly-imprinted polymers
2.4 Polyelectrolytes
2.5 Electrospining
3 Carbonaceous materials
3.1 Graphene
3.2 Carbon nanotubes
3.3 Porous carbons
4 Metal-organic framework
4.1 MIL
4.2 MAF
4.3 Bio-MOFs
4.4 MOF@IL
4.5 MOF-polymer composite
5 Other materials
5.1 Titanium dioxide nanomaterials
5.2 C18
5.3 Mesoporous organosilica
6 Conclusion
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The Properties, Generation and Environmental Significance of Mn (Ⅲ)

Dandan Rao, Bo Sun, Junlian Qiao, Xiaohong Guan

Progress in Chemistry. 2017, 29(9): 1142-1153. https://doi.org/10.7536/PC170437

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Dandan Rao, Bo Sun, Junlian Qiao, Xiaohong Guan. The Properties, Generation and Environmental Significance of Mn (Ⅲ)[J]. Progress in Chemistry, 2017, 29(9): 1142-1153.

Manganese,as a transition metal with various valences (0~+7),is abundant and widely spread.Manganese (Ⅲ)[Mn (Ⅲ)] can act as both electron acceptor and electron donor.Soluble Mn (Ⅲ) has long been overlooked due to the easy disproportionation and difficulty in detection.However,recent studies show that Mn (Ⅲ) can spread widely in pore water and sediment oxic/anoxic interfaces,playing important roles in biogeochemical redox processes.Further,Mn (Ⅲ) with/without ligands show promises in oxidation of contaminants.Therefore,this review summarizes:(1) the presence of Mn (Ⅲ) in aquatic environment and its generation routes,illustrates the involvement of ligands and biological activities;(2) the methods of preparing Mn (Ⅲ) with/without ligands in lab and quantifying the concentration of Mn (Ⅲ);(3) the hydrolysis constants,disproportionation properties,and redox potentials of Mn (Ⅲ);(4) the environmental significance and possible application of Mn (Ⅲ).Finally,the research needs are proposed.
Contents
1 Introduction
2 Generation of Mn(Ⅲ)
2.1 Mn(Ⅲ) generation in nature
2.2 Mn(Ⅲ) preparation and detection in laboratory
3 Some aspects of chemistry of soluble Mn(Ⅲ)
3.1 Common Mn(Ⅲ) complexes
3.2 Stability constants of Mn(Ⅲ) complexes
3.3 Hydrolysis constants of Mn(Ⅲ)
3.4 Absorption spectra of Mn(Ⅲ)
3.5 Redox potentials of Mn(Ⅲ)
4 Environmental significance of Mn(Ⅲ)
5 Application of Mn(Ⅲ) in water treatment
6 Conclusion
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Intimate Coupling of Photocatalysis and Biodegradation to Synchronously Degrade Pollutants

Rui Ding, Feng Zhao

Progress in Chemistry. 2017, 29(9): 1154-1158. https://doi.org/10.7536/PC170414

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Rui Ding, Feng Zhao. Intimate Coupling of Photocatalysis and Biodegradation to Synchronously Degrade Pollutants[J]. Progress in Chemistry, 2017, 29(9): 1154-1158.

Due to the growing emerging contaminants in water, how to overcome the defect of traditional sewage treatment method with the new technology has become a current research hot spot. Intimate coupling of photocatalysis and biodegradation (ICPB) as a new method of pollutant removal, which contains the advantages of biological treatment and the efficient and rapid characteristics of photocatalytic reactions, has attracted a lot of attention and become an important research field. The system is mainly composed of porous carriers, photocatalytic materials and biofilms. The key principle of ICPB is that bio-recalcitrant pollutants are transformed to biodegradable products by photocatalysis that occurs on the surface of porous carriers. The biodegradable products are simultaneously mineralized by the biofilm that cultivated in the carriers. The bacteria can keep activity even under the harsh light because of the protection of carriers. The combination of photocatalysis and biodegradation has been used to degrade a variety of contaminants with efficiency and rapidity. This technology breaks the traditional concept, which holds the point that photocatalytic reaction and biodegradation must be separated in different reactors, improves the sewage purification ability and saves the cost. This review introduces the different types of carriers, photocatalysts and biofilm, and presents the main applications in purification of sewage and possible development direction and trend in the future.
Contents
1 Introduction
2 The carriers
2.1 Macroporous cellulosic cubes
2.2 Porous ceramic particles
2.3 Polyurethane sponge
3 Photocatalyst materials
3.1 Ultraviolet-light photocatalysts
3.2 Visible-light photocatalysts
4 Biofilm
5 Applications
5.1 Denitrification
5.2 Dechlorination
5.3 Degradation of reactive dyes
5.4 Degradation of antibiotics
6 Conclusion and Outlook

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