Investigation of carbonyl compound sources at a rural site in the Yangtze River Delta region of China

Carbonyl compounds are important intermediates in atmospheric photochemistry, but their primary sources are still not understood well. In this work, carbonyls, hydrocarbons, and alkyl nitrates were continuously measured during November 2011 at a rural site in the Yangtze River Delta region of China. Mixing ratios of carbonyls and hydrocarbons showed large fluctuations during the entire measurement. The average level for total measured volatile organic compounds during the pollution episode from 25th to 27th November, 2011 was 91.6 ppb, about 7 times the value for the clean period of 7th-8th, November, 2011. To preliminarily identify toluene sources at this site, the emission ratio of toluene to benzene (T/B) during the pollution episode was determined based on photochemical ages derived from the relationship of alkyl nitrates to their parent alkanes. The calculated T/B was 5.8 ppb/ppb, significantly higher than the values of 0.2-1.7 ppb/ppb for vehicular exhaust and other combustion sources, indicating the dominant influence of industrial emissions on ambient toluene. The contributions of industrial sources to ambient carbonyls were then calculated using a multiple linear regression fit model that used toluene and alkyl nitrates as respective tracers for industrial emission and secondary production. During the pollution episode, 18.5%, 69.0%, and 52.9% of measured formaldehyde, acetaldehyde, and acetone were considered to be attributable to industrial emissions. The emission ratios relative to toluene for formaldehyde, acetaldehyde, and acetone were determined to be 0.10, 0.20 and 0.40 ppb/ppb, respectively. More research on industrial carbonyl emission characteristics is needed to understand carbonyl sources better.     

Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid(OA) on the immobilization of Pb(Ⅱ) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(Ⅱ) by KH2PO4, phosphate rock(PR), activated phosphate rock(APR) and synthetic hydroxyapatite(HAP) at different phosphate:Pb(P:Pb) molar ratios(0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or Ca Cl2, Community Bureau of Reference(BCR) sequential extraction and toxicity characteristic leaching procedure(TCLP)methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was 5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was 5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

Fabrication of ion doped WO3 photocatalysts through bulk and surface doping

Na⁺ doped WO₃ nanowire photocatalysts were prepared by using post-treatment (surface doping) and in situ (bulk doping) doping methods. Photocatalytic degradation of Methyl Blue was tested under visible light irradiation, the results showed that 1 wt.% Na⁺ bulk-doped WO₃ performed better, with higher photoactivity than surface-doped WO₃. Photoelectrochemical characterization revealed the differences in the photocatalytic process for surface doping and bulk doping. Uniform bulk doping could generate more electron–hole pairs, while minimizing the chance of electron–hole recombination. Some bulk properties such as the bandgap, Fermi level and band position could also be adjusted by bulk doping, but not by surface doping.     

Excretion of manure-borne estrogens and androgens and their potential risk estimation in the Yangtze River Basin

The Yangtze River is the longest river in China, and the river basin spans one fifth of the area of the whole country. Based on statistical data, the excretion of manure-borne steroid hormones, including steroid estrogens(SEs) and steroid androgens(SAs), in 10 provinces of China within the region has been estimated. The potential environmental and ecological risk of manure-borne steroid estrogens to the surface water in this region was also assessed. The manure-borne SE and SA excretions in the 10 provinces and municipalities vary in the order: Sichuan Hunan Hubei Yunnan Jiangsu Anhui Jiangxi Chongqing Qinghai Shanghai. The highest increase of manure-borne SEs(1434.3 kg)and SAs(408.5 kg) was found in Hunan and Hubei provinces, respectively, and the total excretion in 2013 was 65% more than 15 years earlier in these two provinces. However, the emissions in Anhui and Shanghai decreased in this 15 year period of time. Swine urine,chicken feces, cattle urine, and laying hen feces were considered the dominant sources of manure-borne E1, βE2, αE2, and SAs, respectively. Although Jiangsu province did not have the largest excretion of manure-borne SEs, it had the highest level of predicted17β-estradiol equivalency(EEQs) value of 16.65 ng/L in surface water because of the limited surface water resources. According to the lowest observable effect level of 10 ng/L for17β-estradiol, the manure-borne SEs in Jiangsu province might potentially pose ecological risk to its wild aquatic organisms.     

植物叶蜡正构烷烃分子分布特征与植被类型的关系

<正>构烷烃是自然界中广泛分布的生物标志化合物,其链长及主峰碳常被用来指示古气候和古植被变化。我们测定了贡嘎山、太白山和黄土高原地区65个植物样品叶蜡正构烷烃的分子分布特征,并对1232个木本和草本植物(包括本实验的65个样品)的正构烷烃比值进行统计。研究表明:木本和草本植物正构烷烃中C_(29)和C_(31)含量基本均较高,其相对丰度变化很大,其中木本植物主峰碳为C_(27)或C_(29)的占61.9%,草本植物主峰碳为C_(31)的占65.2%。三元相图分析也表明,木本和草本植物C_(27)、C_(29)和C_(31)的相对丰度重叠部分较大,而以C_(27)、C_(29)和C_(31)为标准对木本和草本植物进行判别分析的准确度为69.5%。研究结果表明C_(27)、C_(29)和C_(31)主峰碳丰度不能作为区分木本和草本植物的有效指标。同样,利用C_(31)/C_(29)或C_(31)/C_(27)也不能够区分木本和草本植物。我们发现以C_(33)/(C_(33)十C_(29))=0.30为标准对木本和草本植物进行判别分析的准确度为81.5%,而以C_(33)/(C_(33)+C_(27))=0.20为标准对灌木和草本植物进行判别分析的准确度为85.7%,表明某些正构烷烃比值可能具有区分木本和草本植物的潜力,但结合1232个木本和草本植物数据统计发现,正构烷烃比值不能有效区分木本和草本植物。因此,应谨慎利用正构烷烃主峰碳及比值进行植被恢复,这可能为古气候和古植被重建提供必要的参考。     

贵州镇远提钒尾渣固体废弃物二次资源利用研究

为了开发无尾矿、少尾矿提钒工艺,对贵州镇远江古钒矿实验室扩大试验流程产生的尾矿进行资源化利用研究,尾渣物质组成研究表明:提钒尾渣的主要化学成分为二氧化硅,主要矿物为石英,尾渣放射性检测结果高于建筑物主体墙材中放射性指标的要求,不能直接应用于建筑主体材料.经用尾渣烧成水泥试验结果表明:尾渣烧成的水泥熟料基本化学成分、物理性能测试结果符合GB/T 21372-2008硅酸盐水泥熟料要求.     

小煤柱巷道围岩变形的力学机理及演化过程研究

为研究小煤柱巷道围岩变形力学机理与演化过程,以石槽村矿某回风巷为研究对象,采用理论分析、FLAC3D数值模拟以及现场实测等方法,分析小煤柱条件下巷道围岩变形的主要影响因素以及表征特点。研究结果表明:侧压系数为巷道围岩变形的主控因素;侧压系数与巷道顶底板位移量呈正比关系,与两帮位移量呈反比关系;回风巷每次受采动影响时,变形可分为巷道稳定阶段、位移分化阶段以及位移加速变化阶段;围岩变形主要发生在一次采动影响时,此时巷道变形呈现明显的不对称,左右两帮的位移量差异明显,巷道的中心位置明显偏移。研究结果可为小煤柱巷道围岩支护提供技术参考。     

To roll or not to roll: nyctinastic behavior in young leaves of sacred lotus,Nelumbo nucifera

The Science of Nature -     

富油煤热解产物在粉砂介质中的吸附行为研究

富油煤原位热解产生的油、气等有机物会通过岩层的压裂缝进入含水层,产生一系列环境行为效应.为探究富油煤热解产物对地下水的影响,以陕北榆神府矿区富油煤与含水介质粉砂为研究对象,采用批量平衡试验,开展了粉砂对煤焦油不同组分的吸附动力学与吸附热力学研究.结果表明：粉砂对煤焦油中酚油、萘油、洗油、蒽油、沥青的动力学吸附均符合准二级动力学方程,等温吸附模型符合Freundlich方程,说明粉砂对5种组分的吸附为单分子层化学吸附;受富油煤热解焦油组分含量差异影响,粉砂对5种组分的吸附量表现为酚油<萘油<洗油<蒽油<沥青,其最大吸附量分别为0.4520、0.7926、1.9015、3.6336、11.8001 mg·g^-1,吸附量总和占煤焦油含量的68%~85%;随着温度的升高,粉砂对5种组分的吸附能力均有所减弱,表明升高温度不利于吸附行为的进行,且反应的ΔG⁰<0表明粉砂对5种组分的吸附过程主要以化学吸附为主且属于放热反应.     

鄱阳湖河湖交错区软体动物重金属富集与迁移特征分析

河湖交错区是鄱阳湖流域重金属污染物进入湖泊的主要通道,也是重金属富集的场所.本文通过在鄱阳湖河湖交错区采集软体动物样品,分析样品的肌肉和内脏中铁（Fe）、锰（Mn）、铜（Cu）、锌（Zn）、铬（Cr）、镍（Ni）、砷（As）、镉（Cd）、铅（Pb）和锑（Sb）的含量,利用生物-沉积物累积因子和碳氮稳定同位素对鄱阳湖软体动物重金属的富集特征及营养结构和食源关系进行研究,并利用综合目标危险系数进行健康风险评估.结果表明：①鄱阳湖软体动物重金属含量存在显著的种间和组织间的差异,且受体长体重的稀释作用,与所在栖息地的关系不大,但与区域背景环境存在明显的对应关系,均低于水产限量标准值.软体动物对重金属Cu、Zn和Cd具有明显的富集能力,蚌（圆顶珠蚌、三角帆蚌、背瘤丽蚌和褶纹冠蚌）易从环境中富集更多的Mn和Cd,而螺（铜锈环棱螺和大沼螺）则易富集Cu和Zn;②软体动物δ¹³C值为-29.84‰~-21.13‰,δ¹⁵N值为4.09‰~11.51‰,螺和蚌存在明显不同的食物来源.软体动物中的重金属并不随δ¹⁵N值的变化表现出显著的改变,但与δ¹³C值存在显著的线性关系;其中Cu和Zn与δ¹³C值表现为显著的正相关关系,而Mn、Cr、As、Cd、Pb和Sb表现为显著的负相关关系;③健康风险评估结果表明,不论是成人还是儿童,综合目标危险系数（TTHQ） 均大于1,表明鄱阳湖河湖交错区软体动物重金属的富集会对人群食用产生较为显著的健康风险,其中Mn和As是主要的贡献者,且食用蚌的风险略高于螺.研究结果可为鄱阳湖水生态安全、水生生物多样性保护及食品安全评估提供科学依据和理论支撑.