粤港澳大湾区NO2污染的时空特征及影响因素分析

利用Aura卫星搭载的臭氧观测仪（OMI）反演的对流层NO₂柱密度数据,分析了自2005年以来粤港澳大湾区（GBA）对流层NO₂柱密度的空间分布特征、时间变化趋势及其影响因素.研究结果表明GBA对流层NO₂柱密度从2005~2018年呈减少的趋势,每年递减约为2.8%.小波系数显示时间演化过程中存在9个月的主振荡周期,冬季浓度较高,夏季较低.人为排放和各种自然因素,导致了GBA对流层NO₂柱浓度月变化在时间和空间上存在明显差异,最小值和最大值分别出现在6和12月,多年平均值分别为3.9665×10¹⁵和12.3423×10¹⁵molec/cm².NO₂在空间分布上呈现明显的空间分异特征,冬季12月最明显.NO₂污染严重的高值区主要出现在中部地区,如广州市、佛山市和中山市,最大的对流层NO₂柱密度可达18.8306×10¹⁵molec/cm²,大约是周边地区的3 倍,且高污染区域向四周逐渐扩散,连成一片.低值区主要在北部的肇庆市和东部的惠州市,多年平均的对流层NO₂柱密度约为7.1400×10¹⁵molec/cm².对流层NO₂柱密度的增长率在不同区域的变化趋势呈现明显的差异,变化范围为-15×10¹⁵~6×10¹⁵molec/cm²,增长率百分比范围为-65%~65%.出现增长的地区主要是肇庆市北部和惠州市东部的低值区;对流层NO₂出现明显减少的区域集中在中部的高值区,减少量最大的地区为广州市、佛山市和中山市交界处.     

核壳结构KNbO3@Co(OH)2的制备及其活化过一硫酸盐降解帕珠沙星的研究

制备了以KNbO₃为载体材料的Co（OH）₂复合材料并对其进行了详细的表征,分析了材料的组成成分、组成形态进而确定了其为核壳结构形貌的KNbO₃@Co（OH）₂.利用合成的样品作为催化剂活化过一硫酸盐（peroxymonosulfate,PMS）来降解帕珠沙星（pazufloxacin,PZF）,结果表明制备的催化剂对PZF的去除效率显著增加.讨论了不同初始PMS剂量对降解效率的影响,发现随着PMS增加可活化生成更多的硫酸根自由基（sulfate radicals,SO₄^·-）和羟基自由基（hydroxyl radicals,HO^·）来降解PZF,但继续增大PMS用量降解效率未见明显提升.酸性和中性pH值条件下利于反应活化PMS降解PZF,而碱性体系减缓反应,甚至强碱体系更易形成Co（OH）₂沉淀不利于反应体系中活性组分CoOH⁺的形成,大大抑制了催化性能.此外,在体系中加入淬灭剂叔丁醇（tert-Butanol,TBA）或者乙醇（ethanol,ETOH）进行自由基的淬灭实验,结果表明SO₄^·-自由基为体系降解PZF过程中主要贡献的自由基,而HO^·自由基的贡献较少.催化剂具有较好的稳定性5次循环之后仍能在10 min之内完全去除PZF.本研究提出了新的思路为制备其他载体的Co（OH）₂核壳结构提供参考依据,同时将该催化剂结合高级氧化技术应用到水体新兴有机污染物净化领域具有很好的应用前景.     

Plasmonic silver/silver oxide nanoparticles anchored bismuth vanadate as a novel visible-light ternary photocatalyst for degrading pharmaceutical micropollutants

The degradation of pharmaceutical micropollutants is an intensifying environmental problem and synthesis of efficient photocatalysts for this purpose is one of the foremost challenges worldwide. Therefore, this study was conducted to develop novel plasmonic Ag/Ag₂O/BiVO₄ nanocomposite photocatalysts by simple precipitation and thermal decomposition methods, which could exhibit higher photocatalytic activity for mineralized pharmaceutical micropollutants. Among the different treatments, the best performance was observed for the Ag/Ag₂O/BiVO₄ nanocomposites (5 wt.%; 10 min's visible light irradiation) which exhibited 6.57 times higher photodegradation rate than the pure BiVO₄. Further, the effects of different influencing factors on the photodegradation system of tetracycline hydrochloride (TC-HCl) were investigated and the feasibility for its practical application was explored through the specific light sources, water source and cycle experiments. The mechanistic study demonstrated that the photogenerated holes (h⁺), superoxide radicals (?O₂^?) and hydroxyl radicals (?OH) participated in TC-HCl removal process, which is different from the pure BiVO₄ reaction system. Hence, the present work can provide a new approach for the formation of novel plasmonic photocatalysts with high photoactivity and can act as effective practical application for environmental remediation.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

Will polycentric cities cause more CO2 emissions? A case study of 232 Chinese cities

From 2000 to 2010 China experienced rapid economic development and urbanization. Many cities in economically developed areas have developed from a single-center status to polycentricity. In this study, we used exploratory spatial data analysis (ESDA) to identify the population centers, which identified 232 cities in China as having urban centers. COMP was used to represent urban agglomeration, and POLYD (representing how far is the city's sub-centers to the main center), POLYC (representing the number of a city's centers), and POLYP (representing the population distributed between the main center and the sub-centers) were used to indicate urban polycentricity. Night light data were used to determine the CO₂ emissions from various cities in China. A mixed model was used to study the impact of urban aggregation and polycentric data on the CO₂ emission efficiency in 2000 and 2010. The study found that cities with higher compactness were distributed in coastal areas, and the cities with higher multicentricity were distributed in the Yangtze River Delta and Shandong Province. The more compact the city was, the less conducive it was to improving CO₂ emission efficiency. Polycentric development of the city was conducive to improving the CO₂ emission efficiency, but the number of urban centers had no significant relationship with the CO₂ emission efficiency. Our research showed that the compactness and multicentricity of the city had an impact on the CO₂ emission efficiency and provided some planning suggestions for the low carbon development of the city.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

深圳市龙岗区大气颗粒物中多溴联苯醚的污染特征研究

为了解深圳市龙岗区大气颗粒物中多溴联苯醚的污染状况,于2017年1月、4月、8月和11月分别采集龙岗区大气颗粒物样品.利用气相色谱-质谱联用仪（GC/MS）对深圳市龙岗区4个功能区（工业区、商业区、居民区和生态区）的80个大气颗粒物样品进行检测,得到PBDEs（多溴联苯醚）8种单体（BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183、BDE-209）的质量浓度,同时研究了大气颗粒物中PBDEs质量浓度的时空分布特征.结果表明:①深圳市龙岗区大气颗粒物中ρ（∑₈PBDEs）（∑₈PBDEs为PBDEs 8种单体的加和）范围为0.07~77.80 pg/m3,ρ（∑₈PBDEs）年均值为（6.86±14.17）pg/m3.ρ（BDE-209）范围为0.01~76.23 pg/m3,年均值为（5.10±13.58）pg/m3,BDE-209为主要污染单体.② 4个功能区的ρ（∑₈PBDEs）平均值大小顺序依次为工业区（13.65 pg/m3）>商业区（7.75 pg/m3）>生态区（3.95 pg/m3）>居民区（2.19 pg/m3）,工业区是环境空气颗粒物中PBDEs的主要污染区.③ ρ（∑₈PBDEs）平均值的季节性变化规律为春季（13.32 pg/m3）>冬季（9.18 pg/m3）>秋季（2.17 pg/m3）>夏季（1.51 pg/m3）,符合深圳市亚热带海洋季风气温和气候对环境空气中颗粒物质量浓度的影响规律.研究显示,深圳市龙岗区大气颗粒物中PBDEs质量浓度处于较高水平,污染严重,建议减少含PBDEs产品的生产、使用和运输等活动,或找到更利于环境安全和人体健康的替代品,降低PBDEs对该地区的污染.      

污泥腐殖酸对Cd2+的吸附特性

为了促进污水处理厂剩余污泥的资源化利用,探索S-HA（sludge-based humic acid, 污泥腐殖酸）对溶液中重金属Cd2+的吸附特性.采用国际腐殖酸协会（IHSS）推荐的方法提取S-HA,通过元素分析、FT-IR（傅里叶红外光谱分析）和SEM-EDS（外观形态分析）等方法,考察溶液pH和共存阳离子对吸附过程的影响,并对吸附过程分别进行了吸附动力学模型、等温吸附模型和吸附热力学模型拟合,同时通过对比S-HA吸附前后的红外光谱和扫描电镜-能谱图片,探索S-HA对Cd2+的吸附机制.结果表明:①S-HA表面呈松散的簇团状,含有大量的羧基、醇羟基和酚羟基等含氧官能团,芳香度较高,含有较多的脂肪链结构;S-HA在吸附水中Cd2+的过程中,Cd2+与S-HA表面上的酚羟基、羧基等官能团发生了络合作用.②S-HA对Cd2+的吸附量随溶液pH升高而增加,溶液中Na+、NH₄+和Ca2+等共存阳离子的存在不利于S-HA对Cd2+的吸附,其中Ca2+的存在对S-HA吸附Cd2+影响最大.③S-HA对Cd2+的吸附由快吸附、慢吸附和吸附平衡3个阶段组成,吸附平衡时间为12 h;吸附过程符合准二级动力学模型,其整体吸附速度由液膜扩散和颗粒内扩散共同控制;吸附等温线符合Freundlich等温吸附模型,25℃下的最大吸附量为19.29 mg/g,Cd2+在S-HA上的吸附是自发吸热反应.研究显示:污水处理厂剩余污泥提取的S-HA对Cd2+具有较好的吸附效果;S-HA对Cd2+的吸附过程同时存在着物理吸附和化学吸附;高pH对S-HA吸附Cd2+有促进作用,而高离子强度对S-HA吸附Cd2+有抑制作用.      

闽江河口养虾塘养殖期和非养殖期CO2通量变化特征

为揭示河口区陆基养虾塘从养殖期到非养殖期一年间的CO₂通量变化,以福建省闽江河口鳝鱼滩陆基养虾塘为研究对象,于2016年5月-2017年3月采用悬浮箱/静态箱-气相色谱法对养虾塘养殖期水-大气界面和非养殖期沉积物-大气界面白天CO₂垂直通量进行原位观测.结果表明:①养虾塘在整个研究期间CO₂通量变化范围为-62.87~162.81 mg/（m2·h）,平均值为（42.66±18.12）mg/（m2·h）,总体上表现为大气CO₂的释放源,且呈非养殖期CO₂通量平均值[（78.51±16.61）mg/（m2·h）]显著高于养殖期[（17.98±18.26）mg/（m2·h）]的特征.②养殖期间,养虾塘CO₂通量呈"排放-吸收"交替变化的特征,而非养殖期养虾塘一直是大气CO₂的净排放源.③养虾塘养殖期CO₂通量时间变化特征主要受到ρ（DOC）（DOC为总溶解有机碳）、ρ（SO₄2-）、ρ（Cl-）、盐度、pH、ρ（Chla）（Chla为叶绿素a）的影响,其中,pH和ρ（SO₄2-）是其主要影响因子,而ρ（TDN）（TDN为总溶解氮）、ρ（TDP）（TDP为总溶解磷）、ρ（SO₄2-）对非养殖期CO₂通量时间变化影响较大.研究显示,滨海陆基养殖塘是大气CO₂的重要来源,其排放通量多低于河流、水库等水生生态系统,但高于湖泊生态系统;养殖塘CO₂通量受人为影响明显,其较高的变异性与养殖生物、饲料投放以及浮游藻类有关.      

福建省2005-2017年大气边界层SO2的时空变化特征

为研究近年来福建省SO₂污染的时空动态特征,利用臭氧观测仪（ozone monitoring instrument,OMI）卫星遥感反演的PBL（planetary boundary layer,大气边界层）SO₂柱含量数据,分析了2005-2017年福建省PBL SO₂柱含量的时空间分布特征.结果表明:①在长时间尺度上,PBL SO₂柱含量的变化趋势可分为2个时段,其中,2005-2011年PBL SO₂柱含量呈逐渐上升趋势,6 a增加了约0.027 DU,增长率约为6.12%;2011-2017年PBL SO₂柱含量呈下降趋势,7 a减少了约0.018 DU,下降率约为3.89%.②PBL SO₂柱含量呈明显的周期性变化特征,最小值和最大值分别出现在6月和12月,多年平均值分别约为0.383和0.555 DU.③PBL SO₂柱含量的3个高值区分别出现在沿海的福州市,厦门市、漳州市东部和泉州市西部,三明市和南平市部分地区,这3个高值区多年平均PBL SO₂柱含量分别约为0.505、0.495和0.485 DU.从城市尺度上来看,PBL SO₂柱含量最大值出现在厦门市,其多年平均值为（0.486±0.015）DU;其次为福州市,PBL SO₂柱含量多年平均值为（0.465±0.026）DU;最低值出现在漳州市,PBL SO₂柱含量多年平均值为（0.429±0.020）DU.④福建省PBL SO₂柱含量变化趋势在空间分布上存在明显的差异,不同时期、不同区域变化趋势不一致.2005-2011年PBL SO₂柱含量的变化范围为-0.13~0.18 DU,变化率范围为-25%~50%,PBL SO₂柱含量出现增长的区域主要是在高值区,如龙岩市西部、厦门市北部以及三明市东部等区域;2011-2017年PBL SO₂柱含量的变化范围为-0.13~0.15 DU,变化率范围为-29%~34%.2011-2017年福州市和厦门市PBL SO₂柱含量下降最为明显,减少了约0.10 DU,下降率约为25%.研究显示,卫星遥感估算的PBL SO₂柱含量具有一定的可靠性,可以用于区域SO₂污染的研究.