基于遗传-支持向量机和遗传-径向基神经网络的有机物正辛醇-水分配系数QSPR研究

基于遗传算法(GA)的因子筛选和支持向量机(SVM)的非线性回归,提出了1种改进的有机物定量结构-性质相关(QSPR)建模方法--遗传-支持向量机(GA-SVM),并将其用于38种食品工业常用有机物正辛醇-水分配系数(Kow)的QSPR建模.结果显示,QSPR模型选取了分子量、Hansen极性、沸点、含氧率和含氢率5种参数;模型的预测值与实测值间的误差平方和(SSE)、均方差(RMSE)和决定系数(R2)分别为0.048、0,036和0.999,表明模型具有较强的预测能力;同时,交叉验证的结果(SSE=0.295,RMSE=0.089,R2=0.995)也表明,模型具有良好的稳健性,因此,GA-SVM算法适用于对有机物正辛醇-水分配系数的QSPR建模.此外,将基于GA-SVM的QSPR模型分别与基于遗传-径向基神经网络(GA-RBFNN)和基于线性算法的模型进行了比较,结果表明,应用GA-SVM建立的QSPR模型无论从稳健性还是预测能力上都优于应用其它2种算法建立的模型,因此,GA-SVM算法比GA-RBFNN和线性算法更适合于对有机物正辛醇-水分配系数进行QSPR建模.     

酚类化合物气相色谱保留指数的定量结构相关性研究

应用偏最小二乘回归技术建立了102种酚类化合物气相色谱保留指数与分子全息结构间的相关模型,在最佳建模条件下得到非交叉验证相关系数(r2)为0.965,交叉验证相关系数(q_LOO2)为0.963. 从102种酚类化合物中随机选出68种作为训练集,其余作为测试集,来验证分子全息QSRR模型的预测能力和稳健性. 在最佳建模条件对训练集进行偏最小二乘回归分析,r2为0.967,q_LOO2为0.927. 用训练集数据所建立的QSRR模型预测测试集中酚类化合物的色谱保留指数,结果表明,基于训练集所建立的QSRR模型具有很高的预测能力和稳健性,可以对测试集酚类化合物的气相色谱保留指数进行很好的预测. 此外,利用最佳全息定量结构保留关系(HQSRR)模型的色码图,探讨酚类化合物中的不同侧链基团对其色谱保留性质的影响,及其在固定相上的色谱保留机理.      

用电性拓扑态预测苯砜基乙酸酯对发光菌的毒性效应

应用电性拓扑态(Electrotopological State, E-state)指数模拟分析了a-取代苯砜基乙酸酯类化合物对发光菌的毒性(15min-EC50, mmol/L),构建了一个4变量QSAR模型.模型的相关系数(R²a_dj)和标准偏差(SD)分别为0.944和0.062,模型具有较高的预测能力和可靠性.模型分析表明,砜基和酯基是该类化合物的活性中心;化合物的疏水能力以及化合物与受体分子间的偶极/极化作用和氢键效应对化合物毒性起着重要影响.     

北方农田镉污染土壤玉米生产阈值及产区划分初探

为探究我国北方镉(Cd)污染农田中玉米安全生产的土壤阈值以及产区划分,于部分北方玉米主要产区(含不同程度Cd污染)收集了 129套点对点的土壤-玉米样品,分析了土壤理化性质与土壤、玉米籽粒Cd含量之间的相关性,利用多元线性回归法和物种敏感度分布曲线法(SSD)推导不同土壤情景下土壤Cd的生态阈值,并进行了玉米"宜产、限产、禁产"产区划分.结果表明,研究区土壤与玉米籽粒中Cd含量超标分别为99.62％和49.61％;玉米籽粒中Cd富集系数(BCF)与土壤pH、土壤有机质(SOM)、阳离子交换量(CEC)和土壤有效态Cd含量(DTPA浸提)均呈极显著相关性(P＜0.01).多元线性回归法的预测可解释因变量71.9％的变异量;基于研究区土壤特性以及参考资料,划分3种不同土壤情景分别为,情景1:6.5＜pH≤7.5,土壤 ω(SOM)=15 g·kg-1,土壤 CEC=15 cmol·kg-1;情景2:7.5＜pH＜8.5,土壤 ω(SOM)=20 g·kg-1,土壤 CEC=20 cmol·kg-1;情景3:pH≥8.5,土壤 ω(SOM)=17 g·kg-1,土壤 CEC=17 cmol.kg-1,利用 SSD 法中 Logistic 函数模型推导以上3种情景的粮食宜产区土壤Cd阈值分别为3.00、3.80和3.11 mg·kg-1;禁产区阈值为8.95、9.10和7.21 mg～kg-1,当土壤Cd含量介于宜产区阈值与禁产区阈值之间时该区域划分为粮食限产区;玉米用于饲料使用时3种情景下的饲料宜产区阈值分别为14.94、18.90和15.55 mg·kg-1,禁产区阈值分别为44.93、45.40和36.05 mg·kg-1,两者之间的区域为饲料限产区.以上方法和结果可为我国北方农田土壤的安全生产提供参考,并为土壤生态阈值的标准制定提供科学依据.     

过去百年吕梁山南端油松生长特征及其与气候变化的关系

理解树木生长对气候变化和人类活动干扰的响应有助于未来森林管理和双碳政策的落实。本文基于采自吕梁山南端的油松（Pinus tabuliformis Carr.）树轮样本建立了标准树轮宽度年表。通过Pearson相关分析发现树轮年表对研究区3—7月土壤湿度（r=0.60,P<0.01,n=37）、5—6月平均最低温度（r=-0.37,P<0.01,n=63）和5月降水量（r=0.31,P<0.05,n=64）响应敏感,说明水分条件（降水和土壤湿度）是影响研究区油松径向生长的主要限制因子,温度则是通过调控土壤湿度进而影响树木径向生长过程。近百年来（1926—2011年）,研究区油松发生了三次生长释放事件（1932年,1977—1980年,2001—2011年）和一次生长抑制事件（1991—1994年）。生长释放事件在次数、持续时间和发生强度上都高于生长抑制事件。适宜（不适宜）的水热组合能够促进生长释放（抑制）,人类活动干扰也能够诱发生长事件。空间相关分析揭示树轮年表与研究区及周边较大范围的气候环境变化密切相关。本研究对深入了解该地区油松树种生长特征及其对气候与人类活动干扰的...     

苯甲酸类化合物对发光菌的毒性及定量构效

测定了9种苯甲酸类化合物在pH=7时对发光菌的急性毒性(15min-EC50)。应用两种理化参数TSA和ELUMO对毒性数据进行了定量构效关系(QSARs)研究,并在此基础上初步探讨了苯甲酸类化合物的毒性机制。结果表明,苯甲酸类化合物对发光菌的毒性随取代基团的种类及取代位置不同而不同;苯甲酸类化合物对发光菌的致毒机制中可能有亲电作用发生,毒性可用TSA和ELUMO来联合描述。     

Property-performance relationship of core-shell structured black TiO2 photocatalyst for environmental remediation

● Properties and performance relationship of CSBT photocatalyst were investigated. ● Properties of CSBT were controlled by simply manipulating glycerol content. ● Performance was linked to semiconducting and physicochemical properties. ● CSBT (W:G ratio 9:1) had better performance with lower energy consumption. ● Phenols were reduced by 48.30% at a cost of $2.4127 per unit volume of effluent. Understanding the relationship between the properties and performance of black titanium dioxide with core-shell structure (CSBT) for environmental remediation is crucial for improving its prospects in practical applications. In this study, CSBT was synthesized using a glycerol-assisted sol-gel approach. The effect of different water-to-glycerol ratios (W:G = 1:0, 9:1, 2:1, and 1:1) on the semiconducting and physicochemical properties of CSBT was investigated. The effectiveness of CSBT in removing phenolic compounds (PHCs) from real agro-industrial wastewater was studied. The CSBT synthesized with a W:G ratio of 9:1 has optimized properties for enhanced removal of PHCs. It has a distinct core-shell structure and an appropriate amount of Ti³⁺ cations (11.18%), which play a crucial role in enhancing the performance of CSBT. When exposed to visible light, the CSBT performed better: 48.30% of PHCs were removed after 180 min, compared to only 21.95% for TiO₂ without core-shell structure. The CSBT consumed only 45.5235 kWh/m³ of electrical energy per order of magnitude and cost $2.4127 per unit volume of treated agro-industrial wastewater. Under the conditions tested, the CSBT demonstrated exceptional stability and reusability. The CSBT showed promising results in the treatment of phenols-containing agro-industrial wastewater.     

The relationships between mercury and selenium in plankton and fish from a tropical food web

Background, aim, and scope  Selenium (Se) has been shown to reduce mercury (Hg) bioavailability and trophic transfer in aquatic ecosystems. The study of methylmercury (MeHg) and Se bioaccumulation by plankton is therefore of great significance in order to obtain a better understanding of the estuarine processes concerning Hg and Se accumulation and biomagnification throughout the food web. In the western South Atlantic, few studies have documented trace element and MeHg in fish tissues. No previous study about trace elements and MeHg in plankton has been conducted concerning tropical marine food webs. Se, Hg, and MeHg were determined in two size classes of plankton, microplankton (70–290 μm) and mesoplankton (≥290 μm), and also in muscle tissues and livers of four fish species of different trophic levels (Mugil liza, a planktivorous fish; Bagre spp., an omnivorous fish; Micropogonias furnieri, a benthic carnivorous fish; and Centropomus undecimalis, a pelagic carnivorous fish) from a polluted estuary in the Brazilian Southeast coast, Guanabara Bay. Biological and ecological factors such as body length, feeding habits, and trophic transfer were considered in order to outline the relationships between these two elements. The differences in trace element levels among the different trophic levels were investigated. Materials and methods  Fish were collected from July 2004 to August 2005 at Guanabara Bay. Plankton was collected from six locations within the bay in August 2005. Total mercury (THg) was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. MeHg analysis was conducted by digesting samples with an alcoholic potassium hydroxide solution followed by dithizone-toluene extraction. MeHg was then identified and quantified in the toluene layer by gas chromatography with an electron capture detector (GC-ECD). Se was determined by AAS using graphite tube with Pin platform and Zeeman background correction. Results and discussion  Total mercury, MeHg, and Se increased with plankton size class. THg and Se values were below 2.0 and 4.8 μg g⁻¹ dry wt in microplankton and mesoplankton, respectively. A large excess of molar concentrations of Se in relation to THg was observed in both plankton size class and both fish tissues. Plankton presented the lowest concentrations of this element. In fish, the liver showed the highest THg and Se concentrations. THg and Se in muscle were higher in Centropomus undecimalis (3.4 and 25.5 nmol g⁻¹) than in Micropogonias furnieri (2.9 and 15.3 nmol g⁻¹), Bagre spp (1.3 and 3.4 nmol g⁻¹) and Mugil liza (0.3 and 5.1 nmol g⁻¹), respectively. The trophic transfer of THg and Se was observed between trophic levels from prey (considering microplankton and mesoplankton) to top predator (fish). The top predators in this ecosystem, Centropomus undecimalis and Micropogonias furnieri, presented similar MeHg concentrations in muscles and liver. Microplankton presented lower ratios of methylmercury to total mercury concentration (MeHg/THg) (34%) than those found in mesoplankton (69%) and in the muscle of planktivorous fish, Mugil liza (56%). The other fish species presented similar MeHg/THg in muscle tissue (of around 100%). M. liza showed lower MeHg/THg in the liver than C. undecimalis (35%), M. furnieri (31%) and Bagre spp. (22%). Significant positive linear relationships were observed between the molar concentrations of THg and Se in the muscle tissue of M. furnieri and M. liza. These fish species also showed significant inverse linear relationships between hepatic MeHg and Se, suggesting a strong antagonistic effect of Se on MeHg assimilation and accumulation. Conclusions  Differences found among the concentrations THg, MeHg, and Se in microplankton, mesozooplankton, and fishes were probably related to the preferred prey and bioavailability of these elements in the marine environment. The increasing concentration of MeHg and Se at successively higher trophic levels of the food web of Guanabara Bay corresponds to a transfer between trophic levels from the lower trophic level to the top-level predator, suggesting that MeHg and Se were biomagnified throughout the food web. Hg and Se were positively correlated with the fish standard length, suggesting that larger and older fish bioaccumulated more of these trace elements. THg, MeHg, and Se were a function of the plankton size. Recommendations and perspectives  There is a need to assess the role of selenium in mercury accumulation in tropical ecosystems. Without further studies of the speciation of selenium in livers of fishes from this region, the precise role of this element, if any, cannot be verified in positively affecting mercury accumulation. Further studies of this element in the study of marine species should include liver samples containing relatively high concentrations of mercury. A basin-wide survey of selenium in fishes is also recommended.     

海岸带综合管理的区域性特征及其发展机制

在综述国内外海岸带综合管理（ＩＣＺＭ）进展的基础上，以人地关系地域系统为理论基础，论述了ＩＣＺＭ的区域性特征。从地理学看，海岩带是一个开放的复杂的巨系统，有着明确的边界范围，具有可度量性。从管理学看，其模式的多样性反映了区域自然条件和社会条件的差异性，是人地关系双向运动平衡协调的结果，从社会学看，其战略实施先在地方级别上应用，在获得足够的经验或成熟之后，再推广到地区级、省级和国家级的计划中去的空间     

长江流域污染物输出对河口水质的影响

基于EFDC模型建立长江口及邻近海域三维水质模型,模拟2004—2007年不同水期的ρ(COD_Mn)、ρ(DIN)、ρ(PO₄3--P)状况,分析水质分布的变化特征,研究流域污染物输出对河口水质分布的影响. 根据GB 3097—1997《海水水质标准》,长江口门以上ρ(COD_Mn)为Ⅱ类水质,ρ(DIN)、ρ(PO₄3--P)为劣Ⅳ类,并且有明显的分层现象. 枯水期各指标等值线均向东北方向延伸,丰水期和平水期向东南延伸,丰水期流域污染物输出对河口水质的影响最大,不同类别水体的分布形态和水体面积年际变化不明显. 按不同时期ρ(COD_Mn)、ρ(DIN)、ρ(PO₄3--P)分布面积进行统计,长江口ρ(COD_Mn)、ρ(DIN)、ρ(PO₄3--P)分布与流域污染物输出之间有显著关系,河口水质分布面积与流域污染物输出之间存在定量的压力-响应关系.ρ(COD_Mn)、ρ(DIN)、ρ(PO₄3--P)达Ⅳ类以上水体面积(y)与流域污染物输出通量(x)的关系分别为:y_CODMn=2 061.4 ln x_CODMn-15 357.0,y_DIN=1 386.8 ln x_DIN-6 546.1,y_PO43--P=2 219.3 ln x_PO43--P-6 166.1.