Research on the degradation mechanism of pyridine in drinking water by dielectric barrier discharge

Pyridine, an important chemical raw material, is widely used in industry, for example in textiles,leather, printing, dyeing, etc. In this research, a dielectric barrier discharge(DBD) system was developed to remove pyridine, as a representative type of nitrogen heterocyclic compound in drinking water. First, the influence of the active species inhibitors tertiary butanol alcohol(TBA),HCO_3~-, and CO_3~(2-)on the degradation rate of pyridine was investigated to verify the existence of active species produced by the strong ionization discharge in the system. The intermediate and final products generated in the degradation process of pyridine were confirmed and analyzed through a series of analytical techniques, including liquid chromatography–mass spectrometry(LC–MS), high performance liquid chromatography(HPLC), ion chromatography(IC), total organic carbon(TOC) analysis, ultraviolet(UV) spectroscopy, etc. The results showed that the degradation of pyridine was mainly due to the strong oxidizing power of ozone and hydroxyl radical produced by the DBD system. Several intermediate products including 3-hydroxyl pyridine, fumaric acid, 2, 3-dihydroxypyridine, and oxalic acid were detected. Nitrogen was removed from the pyridine molecule to form nitrate. Through analysis of the degradation mechanism of pyridine, the oxidation pathway was deduced. The study provided a theoretical and experimental basis for the application of DBD strong ionization discharge in treatment of nitrogen heterocyclic compounds in drinking water.     

Assessment of the maximum allowed acid deposition load at current stage in China

Soil acidification caused by acid deposition has been significant in some forests in southern China. We present an approach for assessing the current stage maximum allowed load (SML) of acid deposition for terrestrial system in the country. The main idea was that soil base cation exchange as a finite buffer to acidity was included in the soil acidity mass balance calculation at current acidification stage. We calculated the SML for five forests in southern China. The usual critical loads for the same forests were also calculated by the steady state mass balance model for comparison. The results showed that the SML is a more tolerant limit than the critical load for the forests with soils not acidified seriously at current stage. However, the SML become a more stringent limit to acid deposition when the forest soils have acidified seriously to very low base cation saturation. In this case the SML assessment is beneficial for the soils recovering from a serious acidified state. Based on a national scale database, the SML mapping for non-agricultural soil system in China was carried out.     

三峡库区主要水域典型抗生素分布及生态风险评估

为评价三峡库区主要水域典型抗生素的污染状况和生态风险,利用固相萃取-高效液相色谱-串联三重四极杆质谱联用法（SPE-HPLC-MS/MS）,分析三峡库区长江干流和6条支流表层水体中6类28种抗生素的质量浓度,根据欧盟环境风险评价方法计算RQ_S（风险商值）及RQ_sum（联合风险商值）,并按照Hernando等提出评级方法评价研究区域的生态风险等级.结果表明:三峡库区7条河流共检出4类10种抗生素,质量浓度范围为0.6~218.0 ng/L,其中除OFX（氧氟沙星）和CAP（氯霉素）外,其余8种[SDI（磺胺嘧啶）、SMX（磺胺甲唑）、SMZ（磺胺二甲嘧啶）、ERM（红霉素）、ROM（罗红霉素）、TYL（泰乐菌素）、FF（氟苯尼考）、LIN（林可霉素）]均为畜禽药品,并且FF、LIN在我国畜禽药品中使用量排名居前五位.7条河流抗生素RQ_sum由高到低依次为濑溪河>琼江>綦江>碧溪河>嘉陵江>长江>乌江,其中,濑溪河RQ_sum高达5.532,SMX、ERM和OFX均为高风险,说明其对濑溪河水体中相应的水生生物表现出较高的毒性风险;琼江、綦江、碧溪河和嘉陵江的RQ_sum均处于1~2之间,表现出较高生态风险,但4条河流检出抗生素的单个RQ_S均小于1,处于低风险;长江的RQ_sum为0.605,检出抗生素中TYL、ERM和ROM处于中风险,其余为低风险;乌江的RQ_sum为0.013,检出抗生素均处于低风险,说明水体受人类活动干扰最小.研究显示,三峡库区主要水域中抗生素含量略低于其他水域,但应进一步强化对畜禽养殖行业抗生素使用的监管,开展畜禽粪污还田技术规范中抗生素含量限制的相关研究.      

重庆市夏秋季VOCs对臭氧和二次有机气溶胶生成潜势的估算

为估算重庆市夏秋季VOCs（挥发性有机物）对O₃和SOA（二次有机气溶胶）的生成潜势,利用在线GC-MS/FID在2015年8月22日-9月23日对重庆市区点和郊区点VOCs开展了为期一个月的实时观测,获得市区点和郊区点$ \varphi $（TVOCs）（总挥发性有机物）分别为41.35×10-9和22.72×10-9,其中市区点以烷烃（35.2%）和烯炔烃（25.2%）为主,郊区点以含氧挥发性有机物（oxygenated volatile organic compounds,OVOCs）（30.6%）和烷烃（26.0%）为主.结合最大增量反应活性量化市区点和郊区点VOCs的OFPs（臭氧生成潜势）分别为149.11×10-9和71.09×10-9,市区点OFPs最大的是乙烯、丙烯、甲苯、C8和C9的芳香烃等,郊区点OFPs最大的VOCs是丙烯醛、异戊二烯和甲基乙烯基酮.结合气溶胶生成系数量化郊区点和市区点VOCs对SOA的生成贡献分别为0.36和1.26 μg/m3,相比国内其余城市VOCs的SOAP（二次有机气溶胶生成潜势）较小,主要以甲基环己烷、正壬烷、正葵烷和十一烷等高碳烷烃,以及甲苯、苯、二甲苯和乙苯等芳香烃的SOAP为主.研究显示,控制烯炔烃和芳香烃的浓度有助于控制重庆市O₃的生成,控制高碳烷烃和芳香烃则有助于控制重庆市SOA的生成.      

Capability of cation exchange technology to remove proven N-nitrosodimethylamine precursors

N-nitrosodimethylamine(NDMA) precursors consist of a positively charged dimethylamine group and a non-polar moiety, which inspired us to develop a targeted cation exchange technology to remove NDMA precursors. In this study, we tested the removal of two representative NDMA precursors, dimethylamine(DMA) and ranitidine(RNTD), by strong acidic cation exchange resin. The results showed that pH greatly affected the exchange efficiency, with high removal(DMA 78% and RNTD 94%) observed at pH pk_a-1 when the molar ratio of exchange capacity to precursor was 4. The exchange order was obtained as follows: Ca~(2+) Mg~(2+) RNTD~+ K~+ DMA~+ NH_4~+ Na~+. The partition coefficient of DMA~+to Na~+was 1.41 ± 0.26, while that of RNTD~+to Na~+was 12.1 ± 1.9. The pseudo second-order equation fitted the cation exchange kinetics well. Bivalent inorganic cations such as Ca~(2+)were found to have a notable effect on NA precursor removal in softening column test. Besides DMA and RNTD, cation exchange process also worked well for removing other 7 model NDMA precursors. Overall, NDMA precursor removal can be an added benefit of making use of cation exchange water softening processes.     

覆盖金属氧化物对湖泊沉积物溶解性有机质特征的影响

为揭示不同金属氧化物对湖泊沉积物DOM（溶解性有机质）影响机制,通过室内模拟试验,在沉积物表层分别覆盖Fe、Al、Mn氧化物及湖沙后培养1 a,并利用三维荧光和紫外光谱方法进行表征.结果表明:① 覆盖Al、Fe、Mn氧化物和湖沙主要降低了0~3 cm沉积物的w（DOC）,降幅分别为8.61%、6.27%、22.38%和0.44%. ② 沉积物中DOM的类络氨酸峰（peak B₁）和类色氨酸峰（peak T₂）均产生较大变化.其中三种氧化物均显著降低了上层沉积物中DOM的peak T₂,使底层DOM的peakT₂显著增加. Mn氧化物使DOM的peak B₁降低,Fe和Al氧化物使DOM的peak B₁增加,湖沙则使两类峰均降低. ③ 覆盖金属氧化物改变了沉积物DOM结构特征,其中覆盖Fe氧化物增强了其芳香性,而覆盖Mn氧化物和Al氧化却降低其芳香性,但三者均使DOM腐质化程度及官能团数量增加,并使FI（Fluorescence Index,荧光指数）增大,表明DOM向生物源转化.研究显示,沉积物表层覆盖金属氧化物影响了沉积物中DOM迁移和转化,并促进了其降解,导致其分子量和腐殖化程度增加.      

原子吸收法测定海水中铁含量的不确定度评定

为了保证海水中铁元素含量的检测质量,更好地深入了解铁在整个海水体系的生物地球化学中扮演的角色,需科学地评定检测结果的分散性。文章依据《测量不确定度的评定与表示》(JJF1059-1999)的理论,以浙江近海海水为例,评定原子吸收法测定海水中铁含量的不确定度。测得浙江近海样品中铁的浓度为5.2μg/L,扩展不确定度U=0.8μg/L(k=2)。通过对各不确定度分量进行评定发现,利用该方法测定海水中铁含量时,对其合成标准不确定度的主要贡献来自于样品制备过程,尤其是萃取过程。     

2001-2010年三江源区草地净生态系统生产力估算

三江源区位于青藏高原腹地,是我国长江、黄河、澜沧江三大河流的发源地.为了准确估算该地区草地生态系统的净生态系统生产力,收集整理了2001—2010年青藏高原10个通量观测站点的观测数据,构建了三江源区草地生态系统NEP（net ecosystem production,净生态系统生产力）估算模型,并在站点尺度进行了模型参数化和精度验证;结合区域尺度气象和遥感数据,估算了三江源区草地生态系统NEP.结果表明:① 2001—2010年三江源区草地生态系统多年平均NEP空间分布具有明显的空间异质性,大部分地区表现为碳汇,NEP（以C计）平均值为41.8 g/（m2·a）.② 三江源区草地生态系统NEP呈波动增加趋势,从2001年的20.0 g/（m2·a）增至2010年的82.5 g/（m2·a）;除2002年表现为弱碳源外,其余年份均表现为碳汇,并以2010年碳汇能力为最强.③ 2001—2010年三江源区草地生态系统NEP平均年增长率为5.4 g/m2;NEP年际变化率空间分布显示,大部分地区NEP呈增加趋势,仅有东南部和中部部分区域NEP呈下降趋势.研究显示,2001—2010年三江源区草地生态系统表现为碳汇,并且由于气候的暖湿化趋势,碳汇强度总体表现为增强.      

苯酚的褐煤吸附过程及影响因素分析

以污染物苯酚为研究对象,褐煤作为吸附剂,通过批量实验研究了褐煤对废水中苯酚的吸附特性,考察了褐煤粒径、褐煤投加量、反应温度、反应p H、反应时间对吸附作用的影响,并对吸附过程进行了分析。采用Lagergren动力学方程和拟二级吸附动力学方程分析苯酚吸附过程,结果表明,褐煤对苯酚的吸附动力学曲线更符合拟二级吸附动力学方程,反应初始速率随着苯酚初始浓度的升高而增大,但随着煤粉粒径的增大而减小。颗粒内扩散模型对苯酚的吸附动力学曲线分析结果表明:苯酚在褐煤上的吸附首先经历了速率较快的膜扩散控制阶段,进而经历了吸附较缓慢的颗粒内扩散控制阶段,最后到达吸附平衡,褐煤对苯酚的吸附过程主要受到颗粒内扩散控制。     

美国市政污水处理排放标准制定对中国的启示

在概述美国市政污水处理排放标准制度体系的基础上,介绍了其制定基于技术的排放限值和基于水质的排放限值的方法,阐述了其制定的科学性,并指出了中国市政污水处理排放标准中存在的相应问题。最后,根据美国制定排放标准限值的经验,对我国污水处理排放标准进行了思考,并提出了科学制定排放标准的方法和建议。