气溶胶OCEC切割点确定方法改进及应用

用MOUDI采样器分级(0.18～18μm,8级)采集北京(BD)及美国亚特兰大(GT)2011年7、8月大气气溶胶样品,测定有机碳(OC)及元素碳(EC).结果表明,由于石英膜结构在灼烧过程中变化,空白膜激光值在OCEC分析过程会随温度改变而变化,且整体呈下降趋势,扣除空白膜激光值变化后手动确定切割点,即激光校正切割可以提高切割点准确性.采用激光校正切割法得到的OC、EC浓度及粒径分布与有氧无氧切割法不同.一些样品切割点出现在通氧前,原因可能是气溶胶中金属等可在无氧环境中催化氧化EC或受热后分解、变色的吸光物质含量较高等.GT气溶胶碳质组分浓度低于BD,且除GT采样点EC外,均呈双峰分布.BD及GT两个采样点OC浓度在0.56～1.0μm、3.2～5.6μm两个粒径段出现峰值,采样期间BD峰值浓度分别为(2.82±1.59)μg.m-3、(1.95±0.76)μg.m-3,GT峰值浓度分别为(1.28±0.41)μg.m-3、(0.64±0.19)μg.m-3.BD采样点EC浓度峰值出现在1.0～1.8μm、3.2～5.6μm,分别为(0.32±0.24)μg.m-3、(0.26±0.19)μg.m-3.GT采样点EC呈三峰分布,集中于粒径更小的气溶胶中,粒径为0.18～0.56μm气溶胶中EC含量占总采样粒径段44.6%.GT采样点OC、EC浓度均较BD更集中于积聚模态,原因可能为夏季GT主要污染源是机动车尾气排放,而BD存在较多工业活动等排放.     

碳纳米管/BiOBr复合材料的制备及其光催化性能

采用一步溶剂热的方法成功制备了微量多壁碳纳米管（MWCNT）修饰的溴氧化铋（BiOBr）复合材料,实现了对盐酸四环素（TC）的高效稳定降解.在MWCNT添加量为0.01mg（0.001wt%）时,制得的MWCNT/BiOBr催化剂具有较低的光致发光强度、较大的光电流和较小的EIS弧,显著提高了光催化效率.性能的显著提高是由于MWCNT的高捕获电子能力,它不仅能增强光吸收,而且还加速了电荷载流子的分离.通过自由基捕获实验和电子自旋共振（ESR）确定其主要活性组分为·O₂^-,并提出了提高复合材料光催化活性的可能机理.     

Serum concentrations of persistent organic pollutants (POPs) in the inhabitants of a Sicilian city

Background

Polychlorinated biphenyls (PCBs) and organochlorine pesticides are common environmental contaminants that have been associated with human health problems.

Objectives

To assess serum concentrations of several organochlorine contaminants in general population living in a city with an ancient agricultural tradition and to identify possible exposure sources in Sicily.

Methods

A cross-sectional study was conducted on 101 individuals. Each participant answered a face-to-face questionnaire submitted by well-trained personnel and provided a serum sample which was analyzed for the concentrations of PCBs, HCB, HCHs and DDTs by using gas-chromatography coupled with mass spectrometry.

Results

HCB, p,p′-DDE, PCB 138, PCB 153 and PCB 180 were detected in more than 80% of the study participants. The ng g⁻¹ lipid median concentrations were: 18.6 for HCB; 175.1 for p,p′-DDE; 22. for PCB 138; 32.5 for PCB 153 and 23.0 for PCB 180. PCB 153 and PCB 138, PCB 138 and PCB 180, PCB 153 and PCB 180, and p,p′-DDE and HCB showed a high correlation each other (p < 0.05). HCB and p,p′-DDE concentrations were significantly higher in subjects >49 years old (adj-p = 0.03 in 50-69 years old and adj-p < 0.001 in >69 years old, respectively) whereas PCB 138, PCB 153 and PCB 180 concentrations were higher in males (adj-p = 0.03), in subjects >69 years old (adj-p = 0.04) and in current smokers (adj-p = 0.04).

Conclusions

The present study shows that serum concentrations of organochlorine compounds detected in subjects living in a small Sicilian city with ancient agricultural tradition are similar to those found in subjects living in urban areas of other countries. However, further investigations are needed to compare data from rural/urban areas in the same country, assessing correlations between serum concentrations of several chemical compounds and potential health effects in general population.     

三维荧光光谱法研究四环素与活性污泥EPS的相互作用

用三维荧光光谱仪研究了活性污泥EPS(Extracellular polymeric substances)和四环素的相互作用。活性污泥EPS中发现2种类蛋白荧光峰A(Ex/Em=225/340)和B(Ex/Em=280/338),其荧光强度随着盐酸四环素的加入而显著降低,峰A和盐酸四环素结合生成了不发荧光的物质,而峰B和盐酸四环素结合生成的物质在Ex/Em=295/416 nm处发荧光。峰A和峰B与盐酸四环素的相互作用适合用修正后的Stern-Volmer和Hill模型拟合,盐酸四环素和峰A的结合点位数、结合常数分别为1.33、7.02,大于和峰B的结合点位数和结合常数,说明盐酸四环素和荧光峰A的结合比较稳定。猝灭速率常数kq远远大于最大扩散碰撞猝灭速率常数(2.0×1010L(/mol.s)),表明峰A和峰B和盐酸四环素相互作用的荧光猝灭主要是静态猝灭过程。因此土壤和水环境中大量存在EPS会影响盐酸四环素在环境中的迁移转化。     

TC18钛合金在海洋大气环境中的腐蚀行为研究

目的为TC18钛合金应用范围扩展和产品结构的设计与选材提供有益的借鉴和参考。方法采用宏微观腐蚀形貌、静态力学性能、断裂韧度、疲劳裂纹扩展速率研究TC18钛合金在海洋大气环境下暴露6年的腐蚀行为。结果 TC18钛合金在微观形貌上未见点蚀坑等明显腐蚀,抗拉强度和断裂韧度随海洋环境试验时间的延长呈下降趋势,试验4年,TC18断裂韧度下降了6.7%,其断口形貌表现为准解理断口。在da/d N-ΔK双对数坐标中,2,4,6年三个试验周期中两者均呈现很好的线性关系,Paris公式da/d N=C(ΔK)~n中,参数分别为C_1=5.846×10~(-11),n_1=2.320,C_2=6.01×10~(-14),n_2=3.48,C_3=1.81×10~(-13),n_3=3.30。结论 TC18钛合金在海洋大气环境下表现出较低的腐蚀敏感性。     

四环素类抗生素污染畜禽粪便的厌氧消化特征

应用间歇试验研究了外源添加四环素(TC)和金霉素(CTC)的猪粪中温(35℃)厌氧消化特征及抗生素的降解过程.结果表明,猪粪厌氧水解酸化过程中产生的挥发性脂肪酸以丙酸为主,乙酸次之;相比于CTC添加组,TC+CTC混合添加组对易降解有机物的水解酸化有明显的抑制作用;添加TC、CTC和TC+CTC组在45 d的消化期内累积产甲烷量分别为386.4、406.0和412.1 mL,与不添加TC和CTC的对照组(464.6 mL)相比,分别减少了16.8%、12.6%、11.3%.四环素和金霉素的降解过程符合一级反应动力学方程;四环素降解的半衰期为14～18 d,金霉素为10 d.经过45 d厌氧消化处理后,四环素的降解率达88.6%～91.6%,金霉素达97.7%～98.2%.因此,畜禽粪便厌氧消化处理不仅能回收生物质能源,还能降解残留的四环素类抗生素,有效地降低抗生素污染产生的生态风险.     

中国部分城市自来水的总有机碳测定

自来水是城镇居民的主要生活用水来源,用总有机碳(TOC)方法可快速监测其有机污染情况,保障人民生活质量。测定了国内13个城市的自来水TOC值,一定程度上反映了当前国内自来水的有机污染现状。     

Size distribution of black (BC) and total carbon (TC) in Vienna and Ljubljana

During two campaigns in winter 2004, size segregated impactor samples (0.1-10 microm) and filter samples were taken in two Central European cities (Vienna, Austria and Ljubljana, Slovenia). The impactor samples were analyzed for major inorganic ions and short-chain organic acids, total carbon (TC) and black carbon (BC). Maximum concentrations of total mass were 71.6 microg m(-3) in Vienna and 73.1 microg m(-3) in Ljubljana. Minimum concentrations in Vienna were only half those in Ljubljana. The BC content of the aerosol was similar (ca. 8%), but the BC/TC ratio was higher in Vienna than in Ljubljana (0.39 vs. 0.29), reflecting the different contribution of diesel traffic emissions. The mass median diameters of the submicron size distributions of all major fractions (total mass, TC, BC and SO(4)(2-)) were smaller in Vienna (0.43 microm, 0.41 microm, 0.38 microm and 0.48 microm, respectively) than in Ljubljana (0.55 microm, 0.44 microm, 0.42 microm and 0.60 microm, respectively). Impactor/filter ratios for total mass were 0.79 in Vienna and 0.82 in Ljubljana, while the ratios for BC were 0.56 in Vienna and 0.49 in Ljubljana. An estimation of the mixing state of accumulation mode BC indicated that 33% and 37% of BC, respectively, are mixed externally to the aerosol in the accumulation size range in Vienna and Ljubljana.     

可见光激发下模拟海水中四环素光降解的机制和路径

为了探明海水体系中多相光催化降解污染物的机制和路径,研究了在可见光激发下不同介孔TiO₂光催化降解纯水和模拟海水中四环素(TC)的过程,明确了不同盐离子对光催化降解过程的影响.结合自由基捕获实验,电子自旋共振(ESR)光谱和中间产物分析研究了光降解污染物的主要活性物种和模拟海水中TC降解途径.结果表明,模拟海水中TC光催化过程会受到显著抑制,手性介孔TiO₂催化剂对TC光降解反应速率相比其在纯水体系降低了70%左右,而非手性TiO₂光催化剂在海水体系中几乎不能降解TC.模拟海水中阴离子对光降解过程影响较小,但Mg²⁺和Ca²⁺存在会显著抑制光催化过程.无论在纯水还是模拟海水中,可见光激发后催化剂产生的活性物种都是空穴为主,因此模拟海水中降解路径与纯水体系中相同.盐离子不会抑制活性物种的产生,但Mg²⁺和Ca²⁺会富集在TC分子中电负性强的原子周边,阻碍空穴等对TC分子中电负性强原子的攻击,从而抑制了光催化降解效率.     

玉龙雪山PM2.5稳定碳同位素特征及来源分析

于2020年4~8月在青藏高原东南部玉龙雪山进行PM_2.5采样,共采集44个样本,测定其水溶性离子成分、水溶性有机碳(WSOC)浓度、总碳(TC)浓度及其稳定碳同位素组成(δ¹³C_TC).结果表明,玉龙雪山春夏季TC浓度分别为(7.1±3.8)μg/m³和(2.9±0.7)μg/m³,WSOC浓度分别为(3.3±2.1)μg/m³和(1.5±0.4)μg/m³,均呈现春高夏低的变化趋势.春夏季δ¹³C_TC值分别为(-24.7±1.0)‰和(-26.0±0.6)‰,春季较夏季偏正,表明可能受到不同来源影响.通过对非海盐钾离子(nss-K⁺)相关性、NASA火点图及后向轨迹分析可知,东南亚地区春季生物质燃烧可能是主导原因.利用贝叶斯模型计算玉龙雪山PM_2.5中TC来源贡献,结果表明春季主要来源于生物质燃烧和煤燃烧,贡献比分别为60.6%和23.5%;夏季主要来源于生物质燃烧、植物蒸发和机动车排放,同时二次有机气溶胶形成对TC的贡献也不可忽视.