Construction of C-S and C-Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis.

A mild photoredox catalyzed construction of sulfides, disulfides, selenides, sulfoxides and sulfones from unstrained ketone precursors is introduced. Combination of this deacylative process with SN 2 or coupling reactions provides novel and convenient modular strategies toward unsymmetrical or symmetric disulfides. Reactivity studies favor a bromine radical that initiates a HAT (Hydrogen Atom Transfer) from the aminal intermediate resulting in expulsion of a C-centered radical that is intercepted to make C-S and C-Se bonds. Gram scale reactions, broad substrate scope and tolerance towards various functional groups render this method appealing for future applications in the synthesis of organosulfur and selenium complexes.

Base-promoted tandem synthesis of 2-azaaryl indoline.

A novel tandem method to synthesize 2-azaaryl indoline promoted by LiN(SiMe3)2 from 2-azaaryl methyl amine and 2-fluoro benzyl bromides was developed. Mechanistic investigation indicated that this tandem cyclization was initiated by selective benzyl C-SN2 substitution followed by an intramolecular SNAr reaction. Diverse 2-azaaryl indoles could also be obtained via simple functional transformations.

Source Tracking and Risk Assessment of Pharmaceutical and Personal Care Products in Surface Waters of Qingdao, China, with Emphasis on Influence of Animal Farming in Rural Areas.

The occurrence and potential sources of pharmaceuticals and personal care products (PPCPs) in surface waters from a large coastal city Qingdao, North China, were investigated. Forty-five compounds were analyzed by high-performance liquid chromatography-tandem mass spectrometry. The results showed that 28 compounds of PPCPs were detected. The most frequently detected compounds were atrazine, clarithromycin, nonylphenol, and bisphenol A with the detection rates > 90%. Paracetamol showed the highest concentration up to 4400 ng/L (mean 152.5 ng/L), followed by ampicillin (max. 2980 ng/L) with the highest mean concentration (229.3 ng/L), iopromide (max. 1744 ng/L, mean 74.5 ng/L), atrazine (max. 1612 ng/L, mean 96.1 ng/L), and bisphenol A (max. 1384 ng/L, mean 78.3 ng/L). The contamination levels and composition profiles of PPCPs along the rivers flowing through rural and urban areas and in seawater showed large spatial variability. Typical source markers and principle component analysis were used to track and differentiate the potential PPCP sources. The emphases of the study were the influence of animal farming in rural areas on PPCP composition profiles and the ecological risk. The results indicated that PPCPs in Qingdao surface water mainly came from three potential sources, i.e., treated wastewater (effluents from WWTPs), untreated wastewater, and nonpoint sources in agricultural areas.

Balanced N and C input recommendations for rain-fed maize production in northern China based on N balances and grain yields.

BACKGROUND: This study aimed to assess longer-term (1993-2009) effects of combined applications of fertiliser, maize stover, and cattle manure on maize yields, partial nitrogen (N) and carbon (C) balances, and water and N-use efficiencies, to guide N and C input recommendations for rain-fed maize production in northern China. RESULTS: The field trial, with three factors at five levels and 12 treatments, was conducted at Shouyang Dryland-Farming Experimental Station, Shanxi, China. Data analysis revealed higher N balances but lower C balances significantly occurred in a dry year than in a wet year. Positive N balances related to higher N inputs resulted in higher soil available N, even downward to deep layers with increasing N inputs, while positive C balances due to higher C inputs could be benefit to increase soil organic C. Based on partial N balances and grain yields, N and C inputs at ranges of 100 kg N ha-1 and 1.9-2.9 Mg C ha-1 could be recommended for target yields of 6.7-7.2 Mg ha-1 in rain-fed maize production. CONCLUSION: The study suggests that N balances close to neutral be given priority to improving N-use efficiency, and more positive C balances also be important for sustaining target yields and soil fertility levels. © 2017 Society of Chemical Industry.

Dynamic characteristics and evolution laws of underground brine in Mahai salt lake of Qaidam Basin during mining process.

In the late stage of underground brine mining in salt lakes, the method of injecting fresh water is often used to extract the salt from the brine storage medium. This method of freshwater displacement breaks the original water-rock equilibrium and changes the evolution process of the original underground brine. To explore the mechanism of salt release in saline water-bearing media under conditions of relatively fresh lake water dissolution, this paper analyzes the changes in the chemical parameters of brine from 168 sampling points in the Mahai salt lake in the Qaidam Basin at three stages (before exploitation, during exploitation, and late exploitation) by correlation analysis, ion ratio analysis, and other methods and investigate the variations in porosity and the evolution laws of brine. The results show that the changes in the main ion content and brine mineralization during the exploitation process are small. The changes in Ca2+ content are significant due to the low solubility of calcium minerals, the precipitation of gypsum during the mixing process, and the adsorption of cations by alternating with Ca2+. Primary intergranular pore skeletons are easily corroded to form secondary pores, which increase the geological porosity. Na+ and Cl- are the dominant ions in the brine in the study area, but the concentration of Ca2 + decreased significantly under the influence of mining, by 41.7% in the middle period and 24.5% in the late period. The correlation between Ca2+ and salinity changes significantly in different mining stages, and the reason for the decrease of Ca2+ may be due to the influence of mineral dissolution, mixing, and anion-cation exchange. The porosity of the layer in the study area showed the opposite trend of Ca2+, and the porosity increased first and then decreased. The innovation of this paper lies in analyzing the reasons and mechanisms of the disturbance of artificial dissolution mining on stratum structure by comparing the hydrochemical characteristics and porosity of underground brine storage media in three different mining stages. The research in this paper provides a theoretical basis for the calculation of brine resource reserves and the sustainable development of underground brine in salt lake areas.

Preparation of a Green Sustained-Release Microcapsule-Type Anti-Icing Agent for Asphalt Pavement and Its Application Demonstration Project.

Salt-storage additives (SSAs) were added to the asphalt mixtures during the construction stage, and the formed anti-icing asphalt pavement (AIAP) played an active and smart role in continuous snow melting, which could avoid traffic accidents and provide positive support for winter road maintenance in cold areas. In this study, a novel and economical green sustained-release microcapsule salt-storage anti-icing agent was prepared by using solid waste porous sustained-release skeleton loading organic acetate salt as the core material and styrene-acrylic-acrylate copolymer P(AA-MA-BA-St) as the wall material, which have less corrosiveness and extended the release time. By comparing the physical properties of different solid waste porous carriers and corrosion inhibitors, the blast furnace slag and NaHCO3 were selected as the sustained-release skeleton and corrosion inhibitors. The optimal conditions of the synthesis of vesicle wall materials were investigated: 3.8 wt % acrylic acid polymerized at 110 °C with 3 wt % AIBN and for 3.5 h, and the relative ice-snow melting capacity of the prepared sustained-release microcapsule-type anti-icing agent (SMAA) product was 90.8%. The best proportion of the SMAA used to replace a part of the equal mass of mineral powder in the SMA-13 asphalt mixtures was 5.5 wt %, and it could satisfy the requirements of road performance. Moreover, we applied the SMAA product to the 5 cm thick surface layer of SMA-13 of the section K64 + 992 ∼ K65 + 193.641 over the main line ramp at the Sizhuang Toll Station of Beijing-Xiong'an highways to construct AIAP. Compared with adjacent sections of the road without SMAA in winter snowfall, the pilot test section has a very good melting effect. This study contributes to the development of long-acting environment-friendly materials for SSAs to reduce the cost of winter road maintenance, and the obtained product has very promising prospects for practical applications.

A preliminary study on the eco-environmental geological issue of in-situ oil shale mining by a physical model.

As traditional methods of oil shale production emitting high levels of pollutants, in-situ exploitation has aroused great concerns. In order to study the effect of in-situ pyrolysis products on the underground environment, an in-situ oil shale exploitation of underground environment impact laboratory simulation system was designed. Based on the hydrogeological condition of oil shale area in Nong'an City, a physical simulation test was conducted. It was found the temperature of surrounding layers continued to be perturbed after heating of the formation had stopped. The time during which the temperature was perturbed was about 4-5 times the heating period. During the simulation test, stray gas migration through fractures and faults was considered a mechanism for groundwater contamination. In the test, the maximum TOC content in aquifer was the value of 97.0 mg/L. The maximum total petroleum hydrocarbon (TPH) content of the simulated formation was 129 mg/kg after oil pyrolysis.

Removal of copper ions from aqueous solution by calcium alginate immobilized kaolin.

Kaolin has been widely used as an adsorbent to remove heavy metal ions from aqueous solutions. However, the lower heavy metal adsorption capacity of kaolin limits its practical application. A novel environmental friendly material, calcium alginate immobilized kaolin (kaolin/CA), was prepared using a sol-gel method. The effects of contact time, pH, adsorbent dose, and temperature on Cu2+ adsorption by kaolin/CA were investigated. The Langmuir isotherm was used to describe the experimental adsorption, the maximum Cu2+ adsorption capacity of the kaolin/CA reached up to 53.63 mg/g. The thermodynamic studies showed that the adsorption reaction was a spontaneous and endothermic process.

A lutidine-promoted photoredox catalytic atom-transfer radical cyclization reaction for the synthesis of 4-bromo-3,3-dialkyl-octahydro-indol-2-ones.

Reported herein is a visible-light-catalyzed photoredox atom-transfer radical cyclization (ATRC) halo-alkylation of 1,6-dienes with α-halo-ketones as the ATRC reagent. This process exhibits high atom economy, high step economy, and high redox economy, which can directly construct a 4-bromo-3,3-dialkyl-octahydro-indol-2-one core under mild conditions in one pot, and lutidine is found to be the key promoter for this ATRC process.

Aroylchlorination of 1,6-Dienes via a Photoredox Catalytic Atom-Transfer Radical Cyclization Process.

A method using aroyl chlorides as atom-transfer radical cyclization agents in a novel visible-light photocatalytic aroylchlorination reaction is developed. The overall transformation involves the formation of two new C-C bonds and one new C-Cl bond in a one-pot process. The advantages of this reaction include high atom/step/redox economy, mild conditions, operational simplicity, and broad substrate scopes.

Distribution and ecotoxicological effects of polyhalogenated carbazoles in sediments from Jiaozhou Bay wetland.

A suite of eight polyhalogenated carbazole (PHCZ) congeners were detected in sediments of the Jiaozhou Bay wetland. 3,6-dichlorocarbazole (36-CCZ), and 3,6-dibromocarbazole (36-BCZ) were detected in all samples. The concentrations of ΣPHCZs ranged from 6.9 to 33.4 ng/g dry weight (dw). The recovery of surrogate standard ranged from 85 to 109%. Significant relationships were found between the concentrations of 36-CCZ and those of the other three detected compounds (36-BCZ, 36-ICZ, and 1368-BCZ). However, with regard to the other chemicals, only 1368-BCZ was related to 36-ICZ. The toxic equivalent (TEQ) was used to assess the relative toxicity of PHCZs, which ranged within 0.1-3.9 pg TEQ/g dw in sediment. The inventory of ΣPHCZs was 58.9 kg. These results indicate that PHCZs are widely distributed in the Jiaozhou wetland and the dyeing and finishing industries may be important contamination sources of PHCZs.

Sorption of polyhalogenated carbazoles (PHCs) to microplastics.

The sorption of 5 Polyhalogenated carbazoles (PHCs) [3,6-dibromocarbazole (3,6-BCZ), 3,6-dichlorocarbazole (3,6-CCZ), 3,6-diiodocarbazole (3,6-ICZ), 2,7-dibromocarbazole (2,7-BCZ) and 3-bromocarbazole (3-BCZ)] on to three microplastics [polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PVC)] in a simulated seawater system are studied. Sorption isotherms demonstrated that PVC had the maximum sorption capacity, which can be attributed to polar-polar interaction. The sorption kinetics model showed that the sorption process was controlled by both intraparticle and film diffusion. The sorption of PHCs to microplastics was significantly influenced by temperature, the sorption capacity first increased gradually and then decreased with the increasing temperature. Increasing the salinity decreased the sorption of PHCs onto PP, PE, PVC microplastics. Our results indicated that all three kinds of microplastics can serve as carriers for PHCs in the aquatic environment, which put marine ecosystems at higher risks.

DUT-58 (Co) Derived Synthesis of Co Clusters as Efficient Oxygen Reduction Electrocatalyst for Zinc-Air Battery.

To meet the requirement of fuel cells and metal-air batteries, non-noble metal catalysts have to be developed to replace precious platinum-based catalysts. Herein, Co nanoclusters (≈2 nm) are anchored on nitrogen-doped reduced graphene oxide (Co/N-r-GO) by using DUT-58 (Co) metal-organic framework and GO as precursors. Compared with single-atom catalysts usually with ultralow concentration (<0.5 wt%), Co nanoclusters are more beneficial to break the O-O bond to ensure four electronic way for oxygen reduction reaction (ORR), since they can provide more adsorption centers for reactants. Therefore, as expected, the sample with 6.67 wt% Co content (Co/N-r-GO-5%-850) exhibits better ORR activity with a higher half-wave potential of 0.831 V, a more positive onset potential of 0.921 V than Pt/C, and a comparable limiting current density in alkaline medium. The Co nanoclusters enhance the catalytic performance for ORR in three aspects: quantum size effects, metal-support interactions, and low-coordination environment of metal centers. Furthermore, the sample is assembled into a zinc-air battery as the outstanding durable ORR catalyst. It displays a higher specific capacity (795 mAh g-1 at the current density 50 mA cm-2) and power density (175 mW cm-2) than Pt/C (731 mAh g-1 and 164 mW cm-2, respectively).

Determination of heterocyclic brominated flame retardants tris-(2, 3-dibromopropyl) isocyanurate and hexabromocyclododecane in sediment from Jiaozhou Bay wetland.

The concentration and distribution of tris-(2,3-dibromopropyl) isocyanurate (TBC) and the three isomers of hexabromocyclododecane (HBCDs) were analyzed in the sediment of Jiaozhou Bay wetland in China. The concentrations of TBC and the three isomers of HBCDs (α-HBCD, ß-HBCD, γ-HBCD) were in the ranges of 1.20 to 8.76, 1.03 to 5.69, 1.13 to 5.46, and 1.18 to 15.04ng·g-1 dw (dry weight), respectively. γ-HBCD was the predominant congener with an average proportion of 52.42% of ΣHBCDs, average inventory of HBCDs was about 93.53ng∙cm-2. Depending on the function of wetland, the concentration of HBCDs tended to decrease as the distance to the Xiaojianxi refuse landfill increased. Compared with previous research studies, the concentration of TBC and HBCDs in the Jiaozhou Bay wetland was at a relatively high level. Therefore, more attention should be paid to TBC and HBCDs on account of their persistent impact on human health and the environment.

[Emissions of methyl halides from coastal salt marshes: A review].

Methyl halides are the major carrier of halogens in the atmosphere, and they play an important role in tropospheric and stratospheric ozone depletion. Meanwhile, methyl halides can act as greenhouse gases in the atmosphere, and they are also environmentally significant because of their toxicity. Coastal salt marshes, the important intertidal ecosystems at the land-ocean interface, have been considered to be a large potential natural source of methyl halides. In this paper, the research status of the natural source or sink of methyl halides, the mechanisms of their emission from coastal salt marshes and affecting factors were summarized. In view of this, the following research fields need to be strengthened in the future: 1) Long time-scale and large region-range researches about the emission of methyl halides and the evaluation of their source and sink function, 2) Accurate quantification of contribution rates of different plant species and various biological types to fluxes of methyl halides, 3) Further researches on effects of the tidal fluctuation process and flooding duration on methyl halides emission, 4) Effects of the global change and human activities on methyl halides emission.

New non-PBDE brominated flame retardants in sediment and plant samples from Jiaozhou Bay wetland.

Seven non-polybrominated diphenyl ethers (non-PBDE) (TBB, TBX, PBT, PBEB, HBB, DBHCTD and BB153) were analyzed in sediment and plant samples which were collected from Xiaojianxi landfill to Dagu river estuary in Jiaozhou Bay wetland. The species of non-PBDE were different in sediment and plant samples with the concentration of 0.41-9.66ngg(-1) and 0.15-1.2ngg(-1), respectively. DBHCTD was the main non-PBDE compared with other target compounds and its concentration was 1.21-9.66ngg(-1)dw. Generally, the concentration of non-PBDE in sediment showed a decreasing tendency while discrete decline in plant has been revealed. Furthermore, DBHCTD, HBB, as well as other BFRs, might have a common BFRs degradation or similar accumulation potential in sediment, as their Pearson relationship p<0.05. Generally, the content of non-PBDE in Jiaozhou Bay wetland was higher than other published research. Therefore, more attention should be paid to non-PBDE on account of their persisting impact on human health and environment.

[Spatial-temporal distributions of dissolved inorganic carbon and its affecting factors in the Yellow River estuary].

Estuary is an important area contributing to the global carbon cycle. In order to analyze the spatial-temporal distribution characteristics of the dissolved inorganic carbon (DIC) in the surface water of Yellow River estuary. Samples were collected in spring, summer, fall, winter of 2013, and discussed the correlation between the content of DIC and environmental factors. The results show that, the DIC concentration of the surface water in Yellow River estuary is in a range of 26.34-39.43 mg x L(-1), and the DIC concentration in freshwater side is higher than that in the sea side. In some areas where the salinity is less than 15 per thousand, the DIC concentration appears significant losses-the maximum loss is 20.46%. Seasonal distribution of performance in descending order is spring, fall, winter, summer. Through principal component analysis, it shows that water temperature, suspended solids, salinity and chlorophyll a are the main factors affecting the variation of the DIC concentration in surface water, their contribution rate is as high as 83% , and alkalinity, pH, dissolved organic carbon, dissolved oxygen and other factors can not be ignored. The loss of DIC in the low area is due to the calcium carbonate sedimentation. DIC presents a gradually increasing trend, which is mainly due to the effects of water retention time, temperature, outside input and environmental conditions.

[Hydrochemical characteristics and formation mechanism of shallow groundwater in the Yellow River Delta].

Understanding the chemical characteristics of groundwater in the Yellow River Delta is very important. It can provide a useful reference for the development and construction of the Yellow River Delta High-efficiency Ecological Economic Zone and ecological regulation in the lower Yellow River. Based on partitioning the sediment environment and the recharge-runoff-discharge system, we studied the hydrochemical features and causes of shallow groundwater in the Yellow River Delta by mathematical statistics and geostatistics, Piper diagram, ion ratios and so on. Following results are obtained: 1) Major cations and anions such as Na+, Mg2+, Ca2+, Cl(-), SO4(2-), HCO3(-) and TDS concentrations range from 0.1-25.0 g x L(-1), 3.6-3 815.0 mg x L(-1), 5.6-3 377.0 mg x L(-1), 0.1-45.1 g x L(-1), 24.2-4 947.0 mg x L(-1), 62.6-850.0 mg x L(-1) and 0.4-80.7 g x L(-1). Average ion concentrations further indicate that Cl(-), Na+ and TDS concentrations are high while HCO3(-), CO3(2-) and K+ concentrations are very low in the study area. 2) The Cl(-) and TDS concentrations of shallow groundwater possess conspicuous directional spatial variability and gradually increase along the groundwater flow direction, showing that Cl(-) is the most critical ion of shallow groundwater. 3) From the recharge area to the discharge area, shallow groundwater changes from the Na+ -Mg2+ -Ca2+ -Cl(-) -SO4(2-) facies to the Na -Mg2 + -Ca2+ -Cl(-), Mg2+ -Na+ -Ca2+ -Cl(-) and Na+ -Mg2+ -Cl(-) facies, finally evolves into Na+ -Cl(-) facies in the coast. 4) Ion ratios indicate that the following main hydrochemical processes are inferred to control the shallow groundwater chemical composition: mixing, evaporation concentrating, mineral dissolution, cation exchange and adsorption and human activities. These findings strongly suggest that changes of the Yellow River water course and seawater intrusion are key drivers to form the chemical characteristics of shallow groundwater in the region.

[Evapotranspiration of winter wheat field in North China Plain].

By using eddy covariance and remote sensing techniques, the relationships between winter wheat soil moisture content and farmland evapotranspiration or canopy temperature were analyzed at field scale under various environmental conditions in the North China Plain. The results showed that when the soil moisture content was below 65% of field capacity, the evaporative fraction under full canopy was low and stable during the middle part of clear days. Under clear sky condition, there was a good non-linear correlation between latent heat flux and crop canopy temperature with diurnal and seasonal patterns. The temperature difference between crop canopy and air as well as the relative evapotranspiration had a close link to the relative moisture content of 0 - 100 cm soil layer. Based on the in situ measurements of daily evapotranspiration amount (ET(d)), daily net radiation flux (Rn(d), mm), average canopy temperature (T(e), degrees C) from 13 : 30 to 14: 00, and daily maximum air temperature (T(a max), degrees C) during the field experiment, the parameters of simplified estimation model for daily evapotranspiration were established.