Six polyoxotungstate-based transition metal compounds for electrochemical capacitor application and a comparative analysis of factors affecting capacitances.

Six different polyoxotungstate-based transition metal complexes were synthesized, namely [Cu5(2,2'-bpy)5(µ2-Cl)2(PO4)2(H2O)2][HPW12O40]·2H2O (1), [Cu1.5(2,2'-bpy)1.5(inic)2(H2O)1.5]3[H1.5PW12O40]2·16.25H2O (2), [Cu(2,2'-bpy)2]2[SiW12O40]·10H2O (3), [Zn(phen)3]2[PWVWVI11O40]·5H2O (4), [Zn(phen)2(H2O)]2[SiW12O40]·2H2O (5), and [Zn(2,2'-bpy)2]2[SiW12O40] (6) (2,2'-bpy = 2,2'-bipyridine, inic = isonicotinic acid, phen = 1,10-phenanthroline). Compound 1 is based on [HPW12O40]2- anions, which are accommodated within the open channels of a supramolecular network formed by novel Cu-P-Cl coordination clusters. Compound 2 is constructed from [H1.5PW12O40]1.5- and novel [Cu1.5(2,2'-bpy)1.5(inic)2(H2O)1.5]+ coordination fragments, and polyoxoanions are encapsulated within the pores created by the copper coordination fragments, resulting in a unique three-dimensional supramolecular architecture. Compound 3 is a two-dimensional structure formed through the covalent linkage between [SiW12O40]4- and [Cu(2,2'-bpy)2]2+. Compound 4 is a supramolecular architecture formed by [PWVWVI11O40]4- and [Zn(phen)3]2+ coordination fragments, while compound 5 is a supramolecular structure based on POM bi-supported Zn coordination complexes. Compound 6 is a two-dimensional framework structure constituted by [SiW12O40]4- and [Zn(2,2'-bpy)2]2+via covalent interactions. In addition, electrochemical measurement results show that the copper-based tungstate compounds 1-3 and zinc-based tungstate compounds 4-6 exhibit different performances and durabilities as electrochemical capacitors (compound 1 shows the highest specific capacitance of 94.0 F g-1 at 1.5 A g-1, whereas compound 6 maintains the best cycling stability with the capacity retention of 80.7% after 1000 cycles at 4 A g-1.). This study contributes to the development of POM-based transition metal complexes with high capacitance by providing insights into the design and synthesis process.

Mapping the Contribution of Biomass Burning to Persistent Organic Pollutants in the Air of the Indo-China Peninsula Based on a Passive Air Monitoring Network.

Biomass burning (BB) is an important source of atmospheric persistent organic pollutants (POPs) across the world. However, there are few field-based regional studies regarding the POPs released from BB. Due to the current limitations of emission factors and satellites, the contribution of BB to airborne POPs is still not well understood. In this study, with the simultaneous monitoring of BB biomarkers and POPs based on polyurethane foam-based passive air sampling technique, we mapped the contribution of BB to polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the Indo-China Peninsula. Spearman correlations between levoglucosan and 16 PCBs (rs = 0.264-0.767, p < 0.05) and 2 OCPs (rs = 0.250-0.328, p < 0.05) confirmed that BB may facilitate POP emissions. Source apportionment indicated that BB contributed 9.3% to the total PCB and OCP mass. The high contribution of positive matrix factorization-resolved BB to PCBs and OCPs was almost consistent with their concentration distributions in the open BB season but not completely consistent with those in the pre-monsoon and/or monsoon seasons. Their contribution distributions may reflect the use history and geographic distribution in secondary sources of POPs. The field-based contribution dataset of BB to POPs is significant in improving regional BB emission inventories and model prediction.

DDT, Chlordane, and Hexachlorobenzene in the Air of the Pearl River Delta Revisited: A Tale of Source, History, and Monsoon.

Although organochlorine pesticides (OCPs) have been banned for more than three decades, their concentrations have only decreased gradually. This may be largely attributable to their environmental persistence, illegal application, and exemption usage. This study assessed the historic and current regional context for dichlorodiphenyltrichloroethane (DDT), chlordane, and hexachlorobenzene (HCB), which were added to the Stockholm Convention in 2001. An air sampling campaign was carried out in 2018 in nine cities of the Pearl River Delta (PRD), where the historical OCP application was the most intensive in China. Different seasonalities were observed: DDT exhibited higher concentrations in summer than in winter; chlordane showed less seasonal variation, whereas HCB was higher in winter. The unique coupling of summer monsoon with DDT-infused paint usage, winter monsoon with HCB-combustion emission, and local chlordane emission jointly presents a dynamic picture of these OCPs in the PRD air. We used the BETR Global model to back-calculate annual local emissions, which accounted for insignificant contributions to the nationally documented production (<1‰). Local emissions were the main sources of p,p'-DDT and chlordane, while ocean sources were limited (<4%). This study shows that geographic-anthropogenic factors, including source, history, and air circulation pattern, combine to affect the regional fate of OCP compounds.

Spatiotemporal variations of chlorinated paraffins in PM2.5 from Chinese cities: Implication of the shifting and upgrading of its industries.

To highlight the levels and distributions and to assess the risk of human exposure of chlorinated paraffins (CPs) in PM2.5 in China, the concentrations and homologue patterns of short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) in PM2.5 from 10 cities in China were studied in 2013 and 2014. The mean concentrations of ΣSCCPs and ΣMCCPs were 19.9 ± 41.1 ng m-3 and 15.6 ± 18.6 ng m-3, respectively. Unexpectedly, the highest pollution levels occurred in two central cities (Xinxiang and Taiyuan) rather than in well-known eastern megacities such as Beijing, Nanjing, Shanghai, and Guangzhou. By comparing with earlier research, it has indicated the trend of CPs industry shifting from large eastern cities to small and medium-sized cities in central China to some extent. In addition, the composition pattern of SCCPs demonstrated an obviously differences from previous studies, with C11 and Cl7 predominating and accounting for 45.1% and 24.9%, respectively. Meanwhile, the ratio of MCCPs/SCCPs in most cities was less than 1.00 except for Guangzhou (1.92), Shanghai (1.29), and Taiyuan (1.11). Combined with the results of correlation analysis and principal component analysis, the observed pollution characteristics of CPs in PM2.5 had similar sources, which were more influenced by the ratio of MCCPs/SCCPs than by organic carbon, elemental carbon, temperature, population, and gross domestic product. Overall, the composition of CPs reflected the characteristics of local industrial production and consumption, and also implied efforts of Chinese enterprises to reduce the content of short carbon groups of CPs production. The CPs mainly deposited in head airways during the process of entering the human respiratory system. However, at the present levels, there was no significant carcinogenic effect for human health.

Evidence for Major Contributions of Unintentionally Produced PCBs in the Air of China: Implications for the National Source Inventory.

Polychlorinated biphenyls (PCBs) were not widely manufactured or used in China before they became the subject of international bans on production. Recent work has shown that they have reached China associated with imported wastes and that there are considerable unintentional sources of PCBs that have only recently been identified. As such, it was hypothesized that the source inventory and profile of PCBs may be different or unique in China, compared to countries where they were widely used and which have been widely studied. For the first time in this study, we undertook a complete analysis of 209 PCB congeners and assessed the contribution of unintentionally produced PCBs (UP-PCBs) in the atmosphere of China, using polyurethane foam passive air samplers (PUF-PAS) deployed across a wide range of Chinese locations. ∑209 PCBs ranged from 9 to 6856 pg/m3 (median: 95 pg/m3) during three deployments in 2016-2017. PCB 11 was one of the most detected congeners, contributing 33 ± 19% to ∑209 PCBs. The main sources to airborne PCBs in China were estimated and ranked as pigment/painting (34%), metallurgical industry/combustion (31%), e-waste (23%), and petrochemical/plastic industry (6%). For typical Aroclor-PCBs, e-waste sources were dominated (>50%). Results from our study indicate that UP-PCBs have become the controlling source in the atmosphere of China, and an effective control strategy is urgently needed to mitigate emissions from multiple industrial sources.

Effect of SiO2 nanoparticle on the physical and chemical properties of eco-friendly agar/sodium alginate nanocomposite film.

Agar/sodium alginate (AG/SA) nanocomposite films were prepared using solution casting method in presence of various concentrations of nano-SiO2 (2.5, 5, 7.5, and 10 wt%). The effect of nano-SiO2 concentration on the nanocomposite film was investigated. The result of Fourier transform infrared (FTIR) illustrated the formation of hydrogen bonding between nano-SiO2 and polysaccharide. As nano-SiO2 concentration rose from 0 to 10 wt%, the tensile strength and elongation at break all increased up to maximum, respectively. The tensile strength and elongation at break of film containing 10 wt% nano-SiO2 increased by 65.29% and 60.38% respectively when compared to those of film prepared without nano-SiO2. The reason for enhancing in tensile strength might be related to the formation of molecular interaction. The film containing 2.5 wt% nano-SiO2 had maximum water contact angle and minimum water vapor permeability among those of all films prepared in this work. However, the film containing 10 wt% nano-SiO2 had minimum swelling degree and water solubility, further demonstrating the formation of strong interaction. The addition of nano-SiO2 improved the properties of film against UV light and thermal stability. Overall, the addition of nano-SiO2 enhanced the mechanical properties, water resistance and thermal stability of polysaccharide film.

Concentration, source identification, and exposure risk assessment of PM2.5-bound parent PAHs and nitro-PAHs in atmosphere from typical Chinese cities.

Sixteen parent PAHs and twelve nitro-PAHs were measured in PM2.5 samples collected over one year (2013-2014) at nine urban sites in China. During the sampling period, concentrations of individual nitro-PAHs were one or two orders of magnitude lower than their parent PAHs. Typical seasonal variations in parent PAH concentrations, which increased 10- to 80- fold in winter compared to summer, were observed in this study. Conversely, the mean atmospheric concentrations of nitro-PAHs were similar in all four seasons, with the exception of 9-nitroanthracene (9n-Ant). Compared to other nitro-PAHs which were secondary formation products, 9n-Ant had a higher concentration and made up a larger proportion of total nitro-PAHs. Positive matrix factorization results indicated that 9n-Ant sources included biomass burning (20%), vehicle exhaust emissions (43%), and secondary formation (30%). Overall, the elevated concentrations of parent PAHs observed in winter correlated with the contribution from coal combustion at all sites, especially in north China (>80%). The contribution of secondary formation products to total nitro-PAHs was measured during the summer, and was especially high in the larger cities such as Shanghai (84%), Beijing (76%), Guangzhou (60%), and Chengdu (64%), largely due to the summer concentrations of parent PAHs were markedly lower than in winter.

New halogenated flame retardants in the atmosphere of nine urban areas in China: Pollution characteristics, source analysis and variation trends.

Since the ban of polybrominated diphenyl ethers (PBDEs) excluding deca-BDE in China, new halogenated flame retardants (NHFRs), such as new brominated flame retardants and Dechlorane Plus, have become widely used. In this study, we assessed the atmospheric gaseous and particulate levels of eight NHFRs in nine urban areas in China. We detected high mean atmospheric (vapour plus particle phases) concentrations of tetrabromophthalate (TBPH) (74.8 pg m-3) and decabromodiphenyl ethane (DBDPE) (68.8 pg m-3), two major NHFRs. Most of the gaseous and particulate NHFR concentrations presented seasonal variations (from summer to autumn), possibly driven by temperature. Spatially, concentrations and patterns of the NHFRs differed among the nine cities. Significantly higher concentrations were detected in cities with higher gross domestic products. The composition, especially the DBDPE/TBPH ratio (S), were clearly different among the cities, which pattern in each city are likely driven by variations in the type of industries operating in each city. Based on the temporal analysis of other researches and our data, PBDE levels have decreased markedly, while NHFRs levels have increased. Since high NHFR levels had detrimental effects on public health, NHFRs research warrants more attention.

Experimental Study on the Role of Sedimentation and Degradation Processes on Atmospheric Deposition of Persistent Organic Pollutants in a Subtropical Water Column.

The goal of this study is to experimentally assess the role of vertical sinking and degradation processes of persistent organic pollutants (POPs) in a subtropical water column. This was done by measuring the concentrations of selected typical organochlorine pesticides, including hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), dichlorodiphenyltrichloroethanes (DDTs), trans-chlordane (TC), and cis-chlordane (CC), in atmosphere (gas phase), water (dissolved and particulate phases), and sedimentation samples simultaneously from October 2011 to April 2013 in a subtropical lake. The fugacity ratios suggested net deposition for α-HCH, γ-HCH, p,p'-DDT, p,p'-DDD, p,p'-DDE, o,p'-DDT, TC, and CC, indicating that the subtropical lake was acting as a "sink" for these chemicals. The enantiomer fractions of α-HCH, o,p'-DDT, TC, and CC in the dissolved phase samples were much more deviated from the racemic values than were those in the air samples, suggesting that these chemicals have suffered microbial degradation in the subtropical lake. In fact, 99% to 100% of atmospheric input of α-HCH and γ-HCH to the subtropical lake was estimated to be depleted via microbial degradation, while the role of hydrolysis and vertical sinking was very small. For more hydrophobic p,p'-DDT, o,p'-DDT, TC, and CC, the role of vertical sinking was 2 to 3 orders of magnitude larger than that for α-HCH and γ-HCH. Microbial degradation was also very important for removing p,p'-DDT, o,p'-DDT, TC, and CC from the water column.

Impacts of human activities on the spatial distribution and sources of polychlorinated naphthalenes in the middle and lower reaches of the Yellow River.

The concentrations and compositions of polychlorinated naphthalenes (PCNs) in sediments and suspended particulate matters (SPM) in the middle and lower reaches of the Yellow River were investigated. The mean concentrations of PCNs were 7.15 ± 19.3 ng/g dw in the sediment and 38.1 ± 58.4 ng/g dw in SPM. Tri- and tetra-CNs were the dominant homologue groups in most samples. CN-23 was the predominant congener at all sites, and its presence may be attributed to coal combustion. Combustion indicators showed that local combustion source was the main contributor to the PCN concentrations. These sources were related to the energy structure of this region, where coal is the most important energy resource. Human activities, including industrial thermal processes and reservoir construction, were major factors affecting PCN levels and hydrological conditions, which strongly influenced the environmental fate of PCNs in the Yellow River.

A large dipole moment to promote gelation for 4-nitrophenylacrylonitrile derivatives with gelation-induced emission enhancement properties.

A series of 4-nitrophenylacrylonitrile and phenylacrylonitrile derivatives consisting of a carbazole moiety was synthesized. Some of these derivatives with longer alkyl chains and a nitro group could gelatinize some organic solvents, such as ethanol, n-butanol, ethyl acetate, and DMSO. By contrast, phenylacrylonitrile derivatives did not form gels in measured solvents. This result proved that the electron-withdrawing nitro moiety was important for gel formation because it conferred the molecules with large dipole moments, which enhanced the intermolecular interaction. Analyses by UV-vis absorption, X-ray diffraction, and scanning electron microscopy showed that the gelator molecules could self-assemble into one-dimensional nanofibers with layer packing, which further twisted into thicker fibers and formed three-dimensional networks in the gel phase. The single crystal structure of C4CNPA implied that the gelators might adopt an anti-parallel molecular stacking because of their larger ground-state dipole moment. Interestingly, the organogels had enhanced fluorescence relative to solutions at the same concentrations.

D-π-A-π-D type benzothiadiazole-triphenylamine based small molecules containing cyano on the π-bridge for solution-processed organic solar cells with high open-circuit voltage.

Two novel D-π-A-π-D structured small molecules composed of benzothiadiazole and triphenylamine were designed and synthesized. with cyano on the π-bridge exhibited a deep HOMO energy level, resulting in an impressive V(OC) of up to 1.04 V with a PCE of 3.85%, while non-cyano substituted yielded a V(OC) of 0.94 V and a PCE of 1.99%.

Hybrid self-assembly of a pi gelator and fullerene derivative with photoinduced electron transfer for photocurrent generation.

A pi-conjugated organogelator (1) was synthesized, and its gelation ability was checked. It was found that it is an excellent gelator for some organic solvents, such as dichloromethane, benzene, o-dichlorobenzene, and DMSO/water. It can self-assemble into 1-D nanofibers induced by hydrogen bonding and pi-pi interactions. Moreover, 1 could form a hybrid gel with C(60)COOH by hydrogen bonds in which 1 and C(60)COOH can act as an electron donor and acceptor, respectively. It was found that the active film from the hybrid 1-D self-assemblies of 1 and C(60)COOH showed remarkably higher photocurrent generation compared with that containing 1 and C(60) because of the construction of interdigitated and ordered assemblies of donors and acceptors.

Temporal trends of hydrocarbons in sediment cores from the Pearl River Estuary and the northern South China Sea.

Concentrations and fluxes of unresolved complex mixture of hydrocarbons (UCM) and polycyclic aromatic hydrocarbons (PAHs) were analyzed for two (210)Pb dated sediment cores from the Pearl River Estuary (PRE) and the adjacent northern South China Sea (NSCS). Compound-specific stable carbon isotopic compositions of individual n-alkanes were also measured for identification of the hydrocarbon sources. The historical records of PAHs in the NSCS reflected the economic development in the Pearl River Delta during the 20th century. PAHs in the NSCS predominantly derive from combustion of coal and biomass, whereas PAHs in the PRE are a mixture of petrogenic and pyrogenic in origins. The isotopic profiles reveal that the petrogenic hydrocarbons in the PRE originate predominantly from local spillage/leakage of lube oil and crude oils. The accumulation rates of pyrogenic PAHs have significantly increased, whereas UCM accumulation has slightly declined in the NSCS in the recent three decades.

Time trends of polybrominated diphenyl ethers in sediment cores from the Pearl River Estuary, South China.

The present study provides information on the time trend of PBDEs in three sediment cores from the Pearl River Estuary (PRE), South China, using 210Pb dating technique. The sigmaPBDEs (except for BDE 209) concentrations in all sediment cores increased gradually from the bottom (mid-1970s) to the middle layer (later 1980s and early 1990s) followed by different temporal trends in different locations to the surface sediments, reflecting the variations in the consumption of commercial penta-BDEs mixture in different regions of the Pearl River Delta. The BDE 209 concentrations remained constant until 1990 and thereafter increased exponentially to the present, with doubling times of 2.6 +/- 0.5-6.4 +/- 1.6 years, suggesting the increasing market demands for deca-BDE mixture after 1990 in China. The inventories of sigmaPBDEs and BDE 209 in sediments of the PRE were 56.0 and 368.2 ng cm(-2), respectively, and the total burden of PBDEs in the PRE were estimated at 8.6 metric tons. The current sigmaPBDEs and BDE 209 fluxes to the PRE were 2.1 and 29.7 ng cm(-2) yr(-1), respectively. The concurrent increase of BDE 209 fluxes and the annual gross industrial output values of electronics manufacturing revealed that the rapid growth of electronics manufacturing in this region since the early 1990s was responsible for the sharp rise of BDE 209 fluxes in the past decade. The PBDE congener compositions of the cores indicated the various input pathways for PBDEs transport to different locations of the estuary.

Temporal trends of nonylphenol and bisphenol A contamination in the Pearl River Estuary and the adjacent South China Sea recorded by dated sedimentary cores.

Three dated sedimentary cores were collected for the investigation of temporal trends and the environmental loadings of nonylphenol (NP) and bisphenol A (BPA) in recent decades in the Pearl River Estuary (PRE), South China and the adjacent South China Sea (SCS). The peak fluxes of NP and BPA occurred in the mid-1980s in the PRE, coincident with the rapid economic growth in China. The decline of NP and BPA fluxes is attributable to the implementation of sewage treatment in the late 1980s in the Pearl River Delta (PRD). Multi-model distributions were observed for the fluxes of NP and BPA in the SCS with the peak fluxes occurring in the late 1950s and the mid-1970s respectively. The fluxes of NP and BPA have increased since the 1990s due to the lack of adequate wastewater treatment facilities and the constant economic growth. Nonylphenol was quantifiably detected in sediments predating its widespread application (1940s), suggesting the downward penetration of NP in the sediment columns. The characterization results revealed that NP and BPA were preserved well and the isomer-selective degradation of NP did not occur significantly in the sediment cores. The environmental loadings of NP and BPA in the PRE sediments were roughly estimated to be 124 t and 1.7 t respectively over the past 30 years.

Tracing anthropogenic contamination in the Pearl River estuarine and marine environment of South China Sea using sterols and other organic molecular markers.

5beta-Coprostanol together with eight other sterols and unresolved complex mixtures (UCMs) were quantitatively investigated for surficial sediments and surface waters to assess the impacts of anthropogenic activities on the Pearl River estuarine and marine environment of South China Sea. The studied area extends from the Pearl River Estuary southward to the open sea. 5beta-Coprostanol concentrations ranged from trace amounts to 53 microgg(-1) TOC in surficial sediments. The highest levels and highest percentages of coprostanol were found in the Pearl River estuary, especially in the inner estuary and those sites close to the submarine outfalls of Hong Kong. For waters, only in estuarine samples was coprostanol quantitatively detected, ranging from 11 to 299 ngL(-1). Bimodal UCM "humps" were observed for most sediment samples, with concentrations ranging from 215 to 10,491 microg g(-1) TOC in sediments and from 2 to 26 mcirogL(-1) in waters, respectively. Progressive seaward declines in concentrations were found for both 5beta-coprostanol and UCM in surficial sediments. Trace or no 5beta-coprostanol was found in open-sea samples. Concentrations of coprostanol and UCM in surficial sediments are correlated. These results imply that there are obvious anthropogenic contaminations in the Pearl River estuary. The submarine outfalls in Hong Kong represent important sources of the sewage pollution to the Pearl River estuarine sediments evidenced by a combination of coprostanol concentration, diagnostic indices, sterol profiles and UCM. No obvious dispersion or transport of the sewage contamination occurred from the Pearl River estuary to the open South China Sea indicated by fecal sterol biomarkers.

[Over one hundred year sedimentary record of polycyclic aromatic hydrocarbons in the Pearl River Estuary, South China].

The western shoal of the Lingding Bay is known to be an important deposition zone of terrestrial substance in the Pearl River Estuary (PRE). In this study, the vertical variations of concentration and fluxes of polycyclic aromatic hydrocarbon (PAH) are investigated in a core from the west shoal of Lingding Bay. In combining with 210Pb-dating, the PAHs sedimentary record in the last 100 years is reconstructed. The sigmaPAH concentration ranged from 59 ng x g(-1) to 330 ng x g(-1) throughout the core with two distinct peaks. An initial increase in sigmaPAH concentration was found around the 1860s, followed with the first maximum in the 1950s. There was a decrease in total PAHs concentration and flux in 1960s and 1970s. A sharp increase in PAHs levels was observed from 1980s and a maximum was found in the 1990s. PAHs diagnostic ratios indicate that PAH in the sediment core are mainly of pyrolytic origin. PAHs concentrations are found to correlate positively with the Gross Domestic Production, vehicle numbers and power generation in the surrounding regions, indicating that the PAHs in the sediment core are mainly anthropogenic. Atmospheric deposition and land runoff may serve as the important pathway of PAHs input to the sediment.