Determination of 1‐octanol/water partition coefficients of isocyanate compounds by an HPLC method

The octanol/water partition coefficients (P _ow) of six monoisocyanate and five diisocyanate compounds were determined by high performance liquid chromatograph (HPLC) methods. Two HPLC peaks, a broad tailed peak followed by a sharp one, were observed with all compounds. The later peak was identified as the isocyanate compound. The P _ow value for each isocyanate compound was determined by fitting the capacity factor of the peak to the regression equation drawn from those of reference compounds. The hydrophobic substituent constants for the isocyanate group were calculated with each of the compounds. The value of this constant was strongly dependent on the type of carbon bound to the isocyanate group and the average values for the aromatic and aliphatic isocyanate groups were 0.35 and — 0.52, respectively. Because of the reactivity of those compounds in the aquatic environment, the P _ow has little relevance to calculation of their environmental fate and ecotoxicity.     

基于梅尔倒谱系数的矿山复杂微震信号自动识别分类方法

为了实现矿山复杂微震信号的自动高效识别与分类，保证后续微震分析的时效性和准确性，运用梅尔倒谱系数法，将原始的4种微震信号(岩体破裂、爆破振动、电磁干扰和钻机凿岩)转化为梅尔标度上的非线性频谱，再转换到倒谱域上，结合其在时域上的差分得到1组24维的特征参数向量，利用这些特征参数向量训练构建各类事件对应的混合高斯隐马尔可夫识别模型，进而实现对微震信号的自动识别分类。研究结果表明:运用基于梅尔倒谱系数的微震信号识别分类方法对矿山实际微震数据进行测试，微震事件的识别分类准确率达到92.46%，具有较高的准确性，为实现微震监测系统的实时性分析提供了技术支持。     

Acid-catalyzed heterogeneous reaction of 3-methyl-2-buten-1-ol with hydrogen peroxide

Acid-catalyzed heterogeneous oxidation with hydrogen peroxide(H2O2) has been suggested to be a potential pathway for secondary organic aerosol(SOA) formation from isoprene and its oxidation products. However, knowledge of the chemical mechanism and kinetics for this process is still incomplete. 3-Methyl-2-buten-1-ol(MBO321), an aliphatic alcohol structurally similar to isoprene, is emitted by pine forests and widely used in the manufacturing industries. Herein the uptake of MBO321 into H2SO4–H2O2mixed solution was investigated using a flow-tube reactor coupled to a mass spectrometer. The reactive uptake coefficients(γ) were acquired for the first time and were found to increase rapidly with increasing acid concentration. Corresponding aqueous-phase reactions were performed to further study the mechanism of this acid-catalyzed reaction. MBO321 could convert to 2-methyl-3-buten-2-ol(MBO232) and yield isoprene in acidic media. Organic hydroperoxides(ROOHs) were found to be generated through the acid-catalyzed route,which could undergo a rearrangement reaction and result in the formation of acetone and acetaldehyde. Organosulfates, which have been proposed to be SOA tracer compounds in the atmosphere, were also produced during the oxidation process. These results suggest that the heterogeneous acid-catalyzed reaction of MBO321 with H2O2 may contribute to SOA mass under certain atmospheric conditions.     

Occurrence, polarity and bioavailability of dissolved organic matter in the Huangpu River, China

Dissolved organic matter （DOM） plays an important role in biogeochemical cycles in aquatic ecosystem. To investigate the characteristics of DOM in Huangpu River {the last tributary of the Yangtze River）, surface water samples were collected along the river from December 2011 to June, 2013. The concentrations of dissolved organic carbon （DOC）, the absorbance and fluorescence spectrum of DOM in water samples were measured. Fluorescent DOM in the Huangpu River was decomposed into four components by the parallel factor analysis （PARAFAC）, including one humic-like substance and three protein-like substances. It showed that high spatial variability of DOC concentration was observed in the upstream water compared to the downstream water, and so did the absorbance coefficients of chromophoric dissolved organic matter and the total fluorescence intensities of different PARAFAC components of DOM. Furthermore, there was a large difference between the polarity and bioavailability of DOM in the Huangpu River. Polar compounds dominated tyrosine-like component of fluorescent DOM in all seasons. Tryptophan-like and humic-like substances had more polar fraction in summer and autumn than those in winter, while aromatic protein-like materials had the highest polar fraction in winter. Almost all of fluorescent DOM components were refractory in spring, while less than 20% of fluorescent DOM in average were biodegradable within 4 weeks in other seasons. We concluded that the spatial variation in the abundance of DOM in the Huangpu River is mainly affected by the water discharges from the Hangjiahu Plain and the seasonal difference in polarity and bioavailability of DOM is largely determined by its origins.     

中小城市空气环境指标的多角度分析研究——以楚雄市为例

文章根据楚雄市空气污染数据,采用统计的方法从不同的角度探求中小城市空气污染指标的变化规律,并求出三种污染物的同时置信区间及它们之间的关联性。结果表明:楚雄市的空气污染主要由SO2造成,室外空气质量能达到一类地区的水平,三种污染物之间两两相关性较弱,但整体相关性较强,同时根据结论提出了相应的建议。     

决策偏好对水环境污染物总量分配的影响

总量分配是制订污染物总量控制方案的基础,在总量分配方法中合理性指数法是由各因素组成的多目标分配方法,是一种新方法、新思路.由于各因素之间对应的权重系数通常采用专家打分方法确定,因此,分析主观性对总量分配结果的影响具有十分重要的意义.论文共选取30名不同领域的人员,并进行分组,分别对权重因子进行打分,分析不同类型的人员权重分布的特点及其对污染物总量分配结果的影响.研究结果表明:不同人员的权重因子对污染物总量分配具有一定的影响,对最后的决策结果产生一定的不确定性.从分配总量结果来看,TN、TP平均值分别为1.64万t·a-1、0.12万t·a-1,标准差分别为0.16万t·a-1、0.014万t·a-1,变差系数分别为0.09、0.12;从分组结果来看,管理人员一致性较好,研究人员一致性较差.总体而言,综合考虑不同领域专家的意见是保持总量分配方案的合理性和一致性的有效途径.     

邻苯二甲酸酯类化合物正辛醇-水分配系数的QSPR研究

采用PM3算法计算邻苯二甲酸酯类化合物(PAEs)的量子化学参数,应用偏最小二乘(PLS)算法建立了PAEs的正辛醇-水分配系数(K_OW)的定量结构-性质相关(QSPR)模型.模型的结果表明,用量子化学参数建立的QSPR模型相关性显著,具有较好的稳健性和预测能力,因此,利用该模型可对其他PAEs分子的lgK_OW值进行初步预测.模型的结果表明,影响lgK_OW的主要量子化学参数是分子总能量TE、相对分子质量M_r、平均分子极化率α和分子生成热ΔH_f.lgK_OW随着M_r和α的增大而增大,随着TE和ΔH_f的增大而减小.     

Inter-species differences for polychlorinated biphenyls and polybrominated diphenyl ethers in marine top predators from the Southern North Sea: Part 2. Biomagnification in harbour seals and harbour porpoises

Harbour porpoises (Phocoena phocoena) and harbour seals (Phoca vitulina) were found to differ in the ability to metabolize polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Biomagnification factors (BMFs), calculated between both predators and their prey (sole - Solea solea and whiting - Merlangius merlangus), had a large range of variation (between 0.5 and 91 for PCBs and between 0.6 and 53 for PBDEs). For the higher chlorinated PCBs and the highest brominated PBDEs, the BMF values in adult males were significantly higher than in the juvenile individuals of both species. BMF values of hexa- to octa-PCBs were the highest, suggesting reduced ability to degrade these congeners. Harbour porpoises had higher BMFs for lower chlorinated PCBs and for all PBDEs compared to harbour seals. Other factors, which may influence biomagnification, such as the octanol-water partition coefficients and the trophic level position measured through stable isotope (δ¹⁵N) analysis, were found to be of lesser importance to predict biomagnification in the studied food chain.     

Influence of residual surfactants on DNAPL characterization using partitioning tracers

The partitioning tracer technique is among the DNAPL source-zone characterization methods being evaluated, while surfactant in-situ flushing is receiving attention as an innovative technology for enhanced source-zone cleanup. Here, we examine in batch and column experiments the magnitude of artifacts introduced in estimating DNAPL content when residual surfactants are present. The batch equilibrium tests, using residual surfactants ranging from 0.05 to 0.5 wt.%, showed that as the surfactant concentrations increased, the tracer partition coefficients decreased linearly for sodium hexadecyl diphenyl oxide disulfonate (DowFax 8390), increased linearly for polyoxyethylene (10) oleyl ether (Brij 97), and decreased slightly or exhibited no observable trend for sodium dihexyl sulfosuccinate (AMA 80). Results from column tests using clean sand with residual DowFax 8390 and Tetrachloroethylene (PCE) were consistent with those of batch tests. In the presence of DowFax 8390 (less than 0.5 wt.%), the PCE saturations were underestimated by up to 20%. Adsorbed surfactants on a loamy sand with positively charged oxides showed false indications of PCE saturation based on partitioning tracers in the absence of PCE. Using no surfactant (background soil) gave a false PCE saturation of 0.0004, while soil contacted by AMA 80, Brij 97, and DowFax 8390 gave false PCE saturations of 0.0024, 0.043, and 0.23, respectively.     

黄土高原植被演替不同阶段植物系数的变化与适应性评价

用4年长期定位试验资料,利用植物系数、蒸散量、土壤含水量和土壤水分对植物的有效性等指标,研究了黄土高原植被群落不同演替阶段(草本群落→灌木群落→早期森林群落→顶级群落)的耗水特性与生态适应性。结果表明:不同演替阶段,群落实际蒸散量主要受降水控制,群落间差异不显著(P＞0.05);土壤含水量是早期森林群落明显高于其它群落,草本群落明显高于灌木群落(P＜0.05);植物系数是灌木群落＞草本群落＞乔木群落,而顶级群落大于早期森林群落;土壤水分对植物的有效性是早期森林和顶级群落明显高于草本和灌木群落(P＜0.05)。因此,进行植被建设不但要考虑植物系数还要考虑土壤水分对不同植物的有效性。