Enhanced phosphate removal using zirconium hydroxide encapsulated in quaternized cellulose

Zirconium-based materials are efficient adsorbent for aqueous phosphate removal. However, current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity. Here, we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose (QC–Zr) for the selective phosphate removal. Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional (3D) cross-linked cellulose chains. The maximum P adsorption capacity of QC–Zr was 83.6 mg P/g. Furthermore, the QC–Zr shows high P adsorption performance in a wide pH range, generally due to the electrostatic effects of quaternized cellulose. The enhanced adsorption of P was also achieved in the presence of competing anions (including Cl^?, NO₃^?, ${\text{SO}}_4^{2?}$, ${\text{SO}}_4^{\mathrm{4}?}$) and humic acid (HA) even at a molar ratio up to 20 levels. The column adsorption capacity of QC–Zr reached 4000 bed volumes (BV) at EBCT = 0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L. Mechanism study revealed that both –N⁺(CH₃)₃ groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between –N⁺(CH₃)₃ and phosphate, and the formation of zirconium hydrogen phosphate (Zr(HPO₄)x). The ³¹P nuclear magnetic resonance (NMR) study implied that P surface–precipitated and inner–sphere complexed with zirconium hydroxide at a ratio of 3:1.     

Origins of black carbon from anthropogenic emissions and open biomass burning transported to Xishuangbanna, Southwest China

Black carbon (BC) has importance regarding aerosol composition, radiative balance, and human exposure. This study adopted a backward-trajectory approach to quantify the origins of BC from anthropogenic emissions ($\mathrm{B}{\mathrm{C}}_{\text{An}}$) and open biomass burning ($\mathrm{B}{\mathrm{C}}_{\text{BB}}$) transported to Xishuangbanna in 2017. Haze months, between haze and clean months, and clean months in Xishuangbanna were defined according to daily PM_2.5 concentrations of >75, 35–75, and <35 µg/m³, respectively. Results showed that the transport efficiency density (TED) of BC transported to Xishuangbanna was controlled by the prevailing winds in different seasons. The yearly contributions to the effective emission intensity of $\mathrm{B}{\mathrm{C}}_{\text{An}}$ and $\mathrm{B}{\mathrm{C}}_{\text{BB}}$ transported to Xishuangbanna were 52% and 48%, respectively. However, when haze occurred in Xishuangbanna, the average $\mathrm{B}{\mathrm{C}}_{\text{An}}$ and $\mathrm{B}{\mathrm{C}}_{\text{BB}}$ contributions were 23% and 77%, respectively. This suggests that open biomass burning (BB) becomes the dominant source in haze months. Myanmar, India, and Laos were the dominant source regions of BC transported to Xishuangbanna during haze months, accounting for 59%, 18%, and 13% of the total, respectively. Furthermore, India was identified as the most important source regions of $\mathrm{B}{\mathrm{C}}_{\text{An}}$ transported to Xishuangbanna in haze months, accounting for 14%. The two countries making the greatest contributions to $\mathrm{B}{\mathrm{C}}_{\text{BB}}$ transported to Xishuangbanna were Myanmar and Laos in haze months, accounting for 55% and 13%, respectively. BC emissions from Xishuangbanna had minimal effects on the results of the present study. It is suggested that open BB in Myanmar and Laos, and anthropogenic emissions in India were responsible for poor air quality in Xishuangbanna.     

Retrieval of refractive index of ultrafine single particle using hygroscopic growth factor obtained by high sensitive surface plasmon resonance microscopy

When exposed to different relative humidities (RHs), the optical properties of atmospheric aerosols will change because of changes in the aerosol particle size and complex refractive index (RI), which will affect haze formation and global climate change. The potential contributions of ultrafine particles to the atmospheric optical characteristics and to haze spreading cannot be ignored because of their high particle number concentrations and strong diffusibility; measurement of the optical properties of wet ultrafine particles is thus highly important for environmental assessment. Therefore, a surface plasmon resonance microscopy with azimuthal rotation illumination (SPRM-ARI) system is designed to determine the RIs of single particle aerosols with diameters of less than 100 nm in the hygroscopic growth process. Measurements are taken using mixed single particles with different mass ratios. The RIs of mixed single aerosols at different RHs are retrieved by measuring the scattering light intensity using the SPRM-ARI system and almost all the RIs of the bicomponent particles with different mass ratios decrease with increasing water content under high RH conditions. Finally, for each of the bicomponent particles, the maximum standard deviations for the retrieved RI values are only $2.06\times {10}^{-3}$, $3.08\times {10}^{-3}$ and $3.83\times {10}^{-3}$, corresponding to the NaCl and NaNO₃ bicomponent particles with a 3:1 mass ratio at 76.0% RH, the NaCl and glucose particles with a 1:3 mass ratio at 89.0% RH, and the NaCl and OA particles with a 1:1 mass ratio at 78.0% RH, respectively; these results indicate that the high-sensitivity SPRM-ARI system can measure the RI effectively and accurately.     

Competitive role of nitrogen functionalities of N doped GO and sensitizing effect of Bi2O3 QDs on TiO2 for water remediation

The promising solar irradiated photocatalyst by pairing of bismuth oxide quantum dots (BQDs) doped TiO₂ with nitrogen doped graphene oxide (NGO) nanocomposite (NGO/BQDs-TiO₂) was fabricated. It was used for degradation of organic pollutants like 2,4-dichlorophenol (2,4-DCP) and stable dyes, i.e. Rhodamine B and Congo Red. X-ray diffraction (XRD) profile of NGO showed reduction in oxygenic functional groups and restoring of graphitic crystal structure. The characteristic diffraction peaks of TiO₂ and its composites showed crystalline anatase TiO₂. Morphological images represent spherical shaped TiO₂ evenly covered with BQDs spread on NGO sheet. The surface linkages of $\text{NO}?\mathrm{O}?\text{Ti}$, $\mathrm{C}?\mathrm{O}?\text{Ti}$, $\mathrm{B}\mathrm{i}?\mathrm{O}?\text{Ti}$ and vibrational modes are observed by Fourier transform infrared spectroscopy (FTIR) and Raman studies. BQDs and NGO modified TiO₂ results into red shifting in visible region as studied in diffused reflectance spectroscopy (DRS). NGO and BQDs in TiO₂ are linked with defect centers which reduced the recombination of free charge carriers by quenching of photoluminescence (PL) intensities. X-ray photoelectron spectroscopy (XPS) shows that no peak related to $\mathrm{C}?\mathrm{O}$ in NGO/BQDs-TiO₂ is observed. This indicated that doping of nitrogen into GO has reduced some oxygen functional groups. Nitrogen functionalities in NGO and photosensitizing effect of BQDs in ternary composite have improved photocatalytic activity against organic pollutants. Intermediate byproducts during photo degradation process of 2,4-DCP were studied through high performance liquid chromatography (HPLC). Study of radical scavengers indicated that ${\mathrm{O}}_2^{·?}$ has significant role for degradation of 2,4-DCP. Our investigations propose that fabricated nanohybrid architecture has potential for degradation of environmental pollutions.     

Modeling of spatial and temporal variations of ozone-NOx-VOC sensitivity based on photochemical indicators in China

Comprehensive air quality model with extensions (CAMx)-decoupled direct method (DDM) was used to simulate ozone-NO_x-VOCs sensitivity of for May–November in 2016–2018 in China. Based on the relationship between the simulated ozone (O₃) sensitivity values and the ratio of formaldehyde (HCHO) to NO₂ (FNR) and the ratio of production rate of hydrogen peroxide (H₂O₂) to production rate of nitric acid (HNO₃) ($P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$), the localized range of FNR and $P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$ thresholds in different regions in China were obtained. The overall simulated FNR values are about 1.640–2.520, and $P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$ values are about 0.540–0.830 for the transition regime. Model simulated O₃ sensitivities or region specific FNR or $P_{{\mathrm{H}}_2{\mathrm{O}}_2}/P_{\text{HN}{\mathrm{O}}_3}$ thresholds should be applied to ensure the accurate local O₃ sensitivity regimes. Using the tropospheric column FNR values from ozone monitoring instrument (OMI) satellite data as an indicator with the simulated threshold values, the spatial distributions of O₃ formation regimes in China are determined. The O₃ sensitivity regimes from eastern to central China are gradually from VOC-limited, transition to NO_x-limited spatially, and moving toward to transition or NO_x-limited regime from 2005 to 2019 temporally.     

Effectiveness evaluation of water-sprinkling in controlling urban fugitive road dust based on TRAKER method: A case study in Baoding, China

Fugitive road dust (FRD) contributes a great deal to urban rainwater and air pollution and is commonly controlled by water-sprinkling in most Chinese cities. However, there is a lack of information on its effectiveness. We used the Testing Re-entrained Aerosol Kinetic Emissions from Roads (TRAKER) method to monitor different types of roads in Baoding city before and within 1 hr after water-sprinkling and obtained the road dirtiness index (a) and PM concentration in the road environment ($T_{\mathrm{T}}^{*}$), to evaluate the removal efficiency for PM deposited on the road surface (${\eta }_a$) and the reduction efficiency for the PM concentration in the road environment (${\eta }_{\text{PM}}$). The results give that the ${\eta }_a$ for three types of roads is ranked: branch road (87%-–100%) > major arterial road (80%-83%) > minor arterial road (68%-77%), and the ${\eta }_{\text{PM}}$ ranked: minor arterial road (70%) > branch road (46%-58%) > major arterial road (37%-53%). The ${\eta }_a$ and ${\eta }_{\text{PM}}$ varied non-linearly with time and presented a quadratic curve. The average effective control time (${\eta }_{\mathit{a}}$> 0) was 62 min on the major and minor arterial roads, and much longer than 1 hr on branch roads. The ${\eta }_{\text{PM}}$ values diminished completely by 72 min on average from the end of sprinkling for the three types of roads. Water-sprinkling can remove PM₁₀ particles from the road surface and reduce their concentration in the road environment more thoroughly than PM_2.5. Our findings could be helpful for controlling urban FRD emissions more efficiently and precisely.     

Chemical and olfactive impacts of organic matters on odor emission patterns from the simulated construction and demolition waste landfills

The explosive increase of construction and demolition waste (CDW) caused the insufficient source separation and emergency disposal at domestic waste landfills in many developing countries. Some organic fractions were introduced to the CDW landfill process and resulted in serious odor pollution. To comprehensively explore the impacts of organic matters on odor emission patterns, five CDW landfills (OIL), with organic matters/ inert CDW components (O/I) from 5% to 30%, and the control group only with inert components (IL) or organics (OL) were simulated at the laboratory. The chemical and olfactive characters of odors were evaluated using the emission rate of 94 odorants content (ER_total), theory odor concentration (TOC_total), and e-nose concentration (ER_ENC), and their correlations with waste properties were also analyzed. It was found that the main contributors to ER_total (IL: 93.0% NH₃; OIL: 41.6% sulfides, 31.0% NH₃, 25.9% oxygenated compounds) and TOC total (IL: 64.1% CH₃SH, 28.2% NH₃; OIL: 71.7% CH₃SH, 24.8% H₂S) changed significantly. With the rise of O/I, ER_total, TOC_total, and ER_ENC increased by 10.9, 20.6, and 2.1 times, respectively. And the organics content in CDW should be less than 10% (i.e., DOC<101.3 mg/L). The good regressions between waste properties (DOC, DN, pH) and ${\mathrm{ER}}_{\stackrel{?}{\mathrm{ENC}}}$ (r=0.86, 0.86, -0.88, p<0.05), ${\mathrm{TOC}}_{\stackrel{?}{\mathrm{total}}}$ (r=0.82, 0.79, -0.82, p<0.05) implied that the carbon sources and acidic substances relating to organics degradation might result in that increase. Besides, the correlation analysis results (${\mathrm{ER}}_{\stackrel{?}{\mathrm{ENC}}}$ vs. ${\mathrm{TOC}}_{\stackrel{?}{\mathrm{total}}}$, r=0.96, p<0.01; vs. ${\mathrm{ER}}_{\stackrel{?}{\mathrm{total}}}$, r=0.86, p<0.05) indicated that e-nose perhaps was a reliable odor continuous monitoring tool for CDW landfills.     

Effects of sludge age on anaerobic acidification of waste activated sludge: Volatile fatty acids production and phosphorus release

Effects of sludge age on volatile fatty acids (VFAs) production and Phosphorus (P) release during anaerobic acidification of waste activated sludge (WAS) were investigated. Sequencing batch reactors (SBR) fed with simulating domestic sewage were applied to produce WAS of different sludge ages, and batch tests were used for anaerobic acidification. The maximum dissolved total organic carbon, release of  ${\text{PO}}_4^{3+}?\mathrm{P}$, and accumulation of acetate (C2), propionate (C3), butyrate (C4), and valerate (C5) decreased by 56.2%, 55.8%, 52.6%, 43.7%, 82.4% and 84.8%, respectively, as the sludge age of WAS increased from 5 to 40 days. Limited degradation of protein played a dominating role in decreasing DTOC and VFAs production. Moreover, the increase in molecular weight of organics and organic nitrogen content in the supernatant after acidification suggested that the refractory protein in WAS increased as sludge age extended. Although the production of C2, C3, C4, and C5 from WAS decreased as the sludge age increased, the proportions of C2 and C3 in VFAs increased, which might be due to the declined production of C5 from protein and the faded genus Dechlorobacter. Keeping sludge age of WAS at a relatively low level (<10 days) is more appropriate for anaerobic acidification of WAS as internal carbon sources and P resource.     

Adsorptive removal of phosphate by the bimetallic hydroxide nanocomposites embedded in pomegranate peel

This study aimed to fabricate new and effective material for the efficiency of phosphate adsorption. Two types of adsorbent materials, the zirconium hydroxides embedded in pomegranate peel (Zr/Peel) and zirconium-lanthanum hydroxides embedded in pomegranate peel (Zr–La/Peel) were developed. Scanning electronic microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and x-ray diffraction (XRD) were evaluated to give insight into the physicochemical properties of these adsorbents. Zr–La/Peel exceeded the adsorption efficiency of Zr/Peel adsorbents in batch adsorption experiments at the same pH level. The peel as a host can strive to have a strong “shielding effect” to increase the steadiness of the entrenched Zr and La elements. La and Zr are hydroxide metals that emit many hydrogen ions during the hydrolysis reaction, which contribute to protonation and electrostatic attraction. The highest adsorption capacity of La–Zr/Peel for phosphate was calculated to be 40.21 mg/g, and pseudo second-order equation is very well fitted for kinetic adsorption. Phosphate adsorption efficiency was reduced by an increase of pH. With the background of coexisting Cl^?, little effect on adsorption efficiency was observed, while adsorption capacities were reduced by almost 20–30% with the coexistence of ${{\text{SO}}_4}^{2?}$, ${{\text{NO}}_3}^{?}$ and humic acid (HA).     

Experimental and theoretical studies on NO selective catalytic oxidation over α-MnO2

Based on the experimental and theoretical methods, the NO selective catalytic oxidation process was proposed. The experimental results indicated that lattice oxygen was the active site for NO oxide over the $\mathrm{\alpha }$-MnO₂(110) surface. In the theoretical study, DFT (density functional theory) and periodic slab modeling were performed on an $\mathrm{\alpha }$-MnO₂(110) surface, and two possible NO oxidation mechanisms over the surface were proposed. The non-defect $\mathrm{\alpha }$-MnO₂(110) surface showed the highest stability, and the surface O_s (the second layer oxygen atoms) position was the most active and stable site. O₂ molecule enhanced the joint adsorption process of two NO molecules. The reaction process, including O₂ dissociation and O=N-O-O-N=O formation, was calculated to carry out the NO catalytic oxidation mechanism over $\mathrm{\alpha }$-MnO₂(110). The results showed that NO oxidation over the $\mathrm{\alpha }$-MnO₂(110) surface exhibited the greatest possibility following the route of O=N-O-O-N=O formation. Meanwhile, the formation of O=N-O-O-N=O was the rate-determining step.     

国际化学危险品分类体系简介

介绍了当前国际化学危险品的各种分类体系,对比了GHS与TDG、EU_CLP、DOT、WHMIS等对化学危险品的具体分类。有助于GHS的理解与掌握,全面推进GHS在我国的实施。     

土壤整体质量的生态毒性评价

土壤样品采自沈阳西部污灌区 .进行了污染物 (重金属和矿物油 )含量分析和生态毒性试验 .重金属采用原子吸收分光光度仪测定 ,矿物油采用紫外分光光度计测定 .生态毒性试验分别参照国际标准组织 (ISO)和OECD指南 ,进行了植物毒性试验、蚯蚓毒性试验和蚕豆根尖微核试验 .植物试验以小麦种子发芽根伸长抑制率为试验终点 ,试验周期50h ,蚯蚓毒性试验以蚯蚓死亡率、体重增长抑制率为试验终点 ,试验周期28d .土壤中矿物油含量在145mg/kg～1121mg/kg ,重金属Cd为0.34mg/kg～1.81mg/kg .土壤对植物和蚯蚓显示不同程度的毒性效应 ,土壤的蚕豆根尖微核率明显高于对照 .种子发芽根伸长抑制率为2.0%至-35.1% ,蚯蚓死亡率为0%～40%.体重增长抑制率由14d的-2.3%～-19.4%在28d增加到-2.1%～10.7% ,蚕豆根尖微核率最高达6.62/100.研究表明 ,土壤中的污染物积累较低 ,但具有明显的生态毒性 .     

多目标规划在预测区域总产值-排污-水质协调解中的应用研究

以某区域水环境－经济系统为研究实例，寻求值－排污－水质综合协调解方法，寻求净收益最大时的总体规划方案。建立目标参数规划模型，寻求不同生产规模条件下的产值－排污－水质协调解，又探讨了水环境标准约束下的某化工区废水治理费用的计算方法，提出了以供决策者选择的方案。     

滇池富营养化特性评价

介绍了滇池水质状况,对滇池富营养化特性进行了分析和评价,并提出了对策.     

生态保护地协同管控成效评估

分区分类管理是我国生态保护的重要管控制度,生态保护地是事关国家生态安全的关键区域,开展生态保护地保护成效评估及不同类型生态保护地之间的协同管控成效评估具有重要意义。以吉林省自然保护地和重点生态功能区等生态保护地（即禁止开发区和限制开发区）为研究对象,以重要生态空间、植被生态、水源涵养功能为主要内容,基于“禁止开发区—限制开发区—省域”的管控梯度差异,评估分析了生态保护地的协同管控成效。结果表明：（1）从重要生态空间协同管控成效来看,自然保护地的重要生态空间面积比例最高、人类活动干扰指数最低,这与生态保护管控严格程度呈现很好地正相关。但是1980—2015年间重要生态空间面积比例均有所减少,减少幅度与管控严格程度没有表现出正相关。（2）从植被生态协同管控成效来看,植被覆盖总体呈现出自东向西逐步降低的特点,与东部分布有重点生态功能区和森林类自然保护区、西部分布较多的湿地类自然保护地的空间特征一致。但是,由于湿地及水域类型自然保护地面积占比较高,且分布在吉林西部草原和平原区的面积比例较高,自然保护地的年际变化较大、且植被覆盖稳定度低于重点生态功能区。（3）从水源涵养功能协同管控成效来看,水源涵养能力呈现出东部和西部高、中部低的特点,与这两个区域主要分布有森林、草地和湿地等重要生态空间密切相关,也与分布着大面积的重点生态功能区和各类自然保护地密切相关。自然保护区的水源涵养能力最高,且年际变化最小、稳定性最高。     

乌海市城区环境噪声现状分析

对乌海市《城市区域环境噪声标准》适用区域进行了划分,以乌海市2011年城区环境噪声监测统计数据为基础,分析了乌海市暴露在不同等效声级下的城区面积分布状况和达标情况。     

后勤装备防腐涂层加速试验环境谱研究

结合后勤装备服役特点,综合考虑亚热带沿海地区湿热、紫外光照、盐雾等主要腐蚀因素的影响,建立了适用于后勤装备表面涂层的加速试验环境谱,给出了各环境块的具体确定方法,并且提出了建立加速谱与装备实际使用环境的当量加速关系的方法。为后勤装备外露关键部位涂层使用寿命评定、涂层有效性检验和腐蚀修理方案制定提供了重要的依据。     

烟气脱硫副产物的综合利用

通过分析烟气脱硫石膏的性能 ,介绍了脱硫石膏的利用情况和研究进展 ,利用脱硫石膏生产建筑材料 ,如 β石膏和α石膏的工艺日臻成熟 ,利用脱硫石膏生产水泥辅料已进入工业化 ,而利用脱硫石膏生产充填尾砂胶结剂已经完成试验阶段 ,脱硫石膏在农业上也有很广泛的用途。     

天津市机动车二次有机气溶胶生成潜势的估算

通过隧道实验得到天津市机动车排放的挥发性有机物(VOCs)的物种信息及各物种的浓度数据,检测得到88种VOCs,其中23种VOCs具有二次有机气溶胶(SOA)生成潜势.基于天津市机动车尾气挥发性有机污染物的监测数据,利用气溶胶生成系数(FAC)对天津市机动车排放VOCs的二次有机气溶胶生成潜势进行了估算.结果表明,邻-二甲苯、甲苯、苯、间-二甲苯、对-二甲苯、对-二乙苯是对SOA生成贡献最大的6个物种,各自SOA生成量分别为973.97,721.05,687.31,592.09,571.31,538.59t/a,分别占SOA生成潜势的13.87%、10.27%、9.79%、8.43%、8.13%、7.67%;芳香烃是对SOA生成贡献最大的前体物,其SOA生成量占SOA生成潜势的88.95%.因此,减少机动车芳香烃类物质的排放,可有效地减少SOA的生成量.     

氯苯类化合物的生物降解

经过2个月的驯化,从某染料厂和某毛纺厂活性污泥中分离出能够生长于1,4-二氯苯、1,2,4-三氯苯和六氯苯的4种微生物.通过测定该混合菌降解氯苯类化合物过程中的累积好氧量、微生物生长曲线及降解产物Cl^-的释放,证明在好氧条件下该混合菌能够以1,4二氯苯和1,2,4-三氯苯为唯一碳源和能源,降解产物Cl^-浓度的变化与微生物生长周期有关.通过好氧振荡瓶培养法测得3种氯苯的生物降解顺序为:1,4-二氯苯[356.7μg/(L·d)]>1,2,4-三氯苯[110.4μg/(L·d)]>六氯苯[～6μg/(L·d)],说明氯取代数越多,氯苯类化合物越难被好氧降解.