三峡水库消落区土壤理化特征及磷赋存形态研究

应用淡水沉积物中磷形态的标准测试程序(SMT)对三峡水库腹心地带(巫山-重庆主城区段)淹没消落区土壤磷的赋存形态进行了分级测定,并分析了各形态磷之间,以及各形态磷与样品理化特征(如全氮(TN)、有机质(SOM)、酸碱性(pH)、氧化还原电位(ORP))之间的相关性.结果表明,研究区域内,淹没消落区土壤全磷含量在0.28～1.32g·kg-1之间,平均值为0.63g·kg-1;无机磷和有机磷平均含量分别为0.46g·kg-1和0.13g·kg-1,占全磷百分比分别为72.3%和21.7%,淹没消落区土壤中的磷以无机磷为主,有机磷为辅,从各形态磷含量及相对含量的变化范围来看,表现为钙结合态磷>有机磷>铁铝结合态磷,土壤全磷含量增加主要来自钙结合态磷部分,其次是有机磷.淹没消落区土壤活性磷组分(铁铝结合态磷和有机磷之和)含量分布范围在0.04～0.39g·kg-1之间,平均值为0.20g·kg-1,占全磷比例达到33.0%,消落区土壤活性磷组分在适宜的环境条件下会成为水体的二次污染源,淹没消落区土壤磷对水体富营养化的潜在影响不容忽视;淹没消落区土壤全磷与无机磷和钙结合态磷,有机磷与铁铝结合态磷、全氮及有机质有显著相关性,表明钙结合态磷为无机磷和全磷的主要赋存形态,有机磷、铁铝结合态磷、全氮和有机质同源;有机磷同土壤酸碱性呈显著正相关,同氧化还原电位呈显著负相关,表明土壤酸碱性和氧化还原电位的变化可影响有机磷的含量与分布.     

Spatial and temporal variability of agricultural pollutants in an agricultural headwater stream within a multipond system, southeastern China

The spatial and temporal variability of nutrients and suspended solids were investigated for two years in a 1.8 km agricultural headwater stream, located by Chaohu Lake, southeastern China. The stream form was greatly modified by human activities into channelized, pond and estuary shapes. The stream could be divided into 4 channelized reaches(1.3 km), a pond reach(0.15 km) and 3 estuary reaches(0.36 km). It was found that nutrients and TSS concentrations in the stream showed temporal variability, and higher concentrations occurred in months with high precipitation and intensive agricultural activities. And, retention of total nitrogen ( TN ), nitrate ( NO3-N ),ammonium( NH4^ -N) and total suspended solids (TSS) predominantly occurred in the pond reach and estuary reaches with larger width and low current velocity. Pollutants retained in these reaches accounted for more than 50% of those retained in whole stream. The retention mostly happened in the rain-runoff events and it was 7 to 27 times than that in base flow. The results showed that the channelized reach was the most important source for pollutants release under either runoff or base flow, and its release accounted for more than 90% of whole stream release.There was a high spatial variability of nutrients retention in different channelized reaches. The channelized reach directly discharging into the pond did always retain nutrients and TSS under base flow and runoff conditions, whereas the other channelized reaches performed differently in different hydrological conditions. The high spatial and temporal variability of nutrients and TSS in the stream indicated that anthropogenic disturbance of the agricultural headwater stream, such as channelization and excavation, would be expected to decrease the capacity of nutrients retention in the stream.     

沉积物扰动持续时间对悬浮物中磷形态数量分布的影响

为了探讨沉积物扰动时间(分别扰动10 min和9 h)对悬浮物中形态磷转化的影响,以太湖月亮湾沉积物和上覆水为对象,开展室内模拟试验,分析悬浮物中不同形态磷间的转化过程.结果表明,扰动时间越长,上覆水溶解性总磷(DTP)含量越高.对照试验中,上覆水中DTP含量远高于扰动试验.磷形态分析表明,随着试验时间的延长,扰动作用下(10 min,9 h),铁铝结合态磷(Fe/Al-P)占总磷(Tot-P)的质量分数逐渐降低,第10 d分别降至42.5%(10 min)和38.1%(9 h).试验结束,则有所升高.相反,钙结合态磷(HCl-P)占Tot-P的质量分数则在第10 d分别达到最大(48.9%,10 min)和(53.7%,9 h).这说明沉积物扰动促进了悬浮物中易释放态磷向难释放态磷的转化.     

诺氟沙星对海月水母螅状体Hsp70基因、GTP结合蛋白基因和氧化应激蛋白基因表达的影响

诺氟沙星(norfloxacin,NFLX)广泛应用于水产养殖中的鱼类细菌性疾病治疗。为探讨诺氟沙星对海洋生物的毒性作用,选择海月水母螅状体为受试生物,考察了不同浓度诺氟沙星和不同暴露时间对GTP结合蛋白(GTP binding protein)、氧化应激蛋白(oxidative stress protein)和热休克70 k Da蛋白(heat shock 70 k Da protein,Hsp70)表达量的影响。结果表明,NFLX对海月水母螅状体的48 h的半致死浓度(48 h-LC_(50))是415.1 mg·L~(-1),NFLX对海月水母螅状体的毒性属于低毒。随着NFLX浓度的升高和培养时间的延长,Hsp70基因在第7天浓度300 mg·L~(-1)时表达量受到显著性诱导(P0.05),较对照组升高9.1倍;GTP结合蛋白基因和氧化应激蛋白基因的表达量都呈现先急剧升高后降低的趋势。2个基因均在第1天受到显著性诱导(P0.05),分别在NFLX浓度100 mg·L~(-1)和300 mg·L~(-1)时表达量达到最大值,较对照组升高10.15倍和50.5倍。Hsp70基因、GTP结合蛋白基因和氧化应激蛋白基因在实验期间都对NFLX表现出较好的响应。     

石墨烯与抑癌基因p53 DNA片段相互作用的分子模拟与光谱学验证

石墨烯(graphene,G)及其衍生物由于具有独特的理化性质,被广泛应用于能源、生物医学等领域,但尚缺乏其对生物体和环境潜在危害的研究。采用分子动力学模拟并结合光谱学方法(紫外可见吸收光谱、紫外变温实验及荧光光谱),分析了石墨烯与抑癌基因p53启动子区DNA片段(p53-DNA)间的相互作用,并探讨了相关作用机制。石墨烯的部分芳香环与p53-DNA碱基的芳香环之间存在π-π堆积作用,两者可以通过嵌插作用进行结合,同时还通过沟槽作用进一步结合。光谱实验进一步证实,在石墨烯作用下,p53-DNA的熔点(Tm)值升高,EB-DNA体系发生静态荧光淬灭,说明石墨烯能与p53-DNA结合;同时,p53-DNA与石墨烯结合后在260 nm处的吸光度升高,说明石墨烯对p53-DNA的双螺旋结构具有一定的破坏作用。上述研究结果从分子水平上分析了石墨烯与p53-DNA间的相互作用机制,有助于进一步阐明石墨烯的毒性作用机理。     

不同污染程度湖泊沉积物中不同粒级可转化态氮分布

研究了污染程度不同的五里湖、月湖、东太湖和贡湖不同粒级沉积物中总可转化态氮以及各形态可转化态氮的含量与分布.结果表明:4个湖泊的沉积物各粒级中各形态可转化态氮的含量及其地球化学特征均不相同.强氧化剂可提取态氮(SOEF-N)是释放能力最弱的形态,为可转化态氮的主体,占总可转化态氮的66.97%～87.97%.离子交换态氮(IEF-N)结合能力最弱,是最容易被释放的形态,为可转化态无机氮的主体,占总可转化态氮的7.37%～22.25%.同一粒级中,各形态可转化态氮对氮循环的贡献为SOEF-N最大,IEF-N其次,强碱可浸取态氮(SAEF-N)与弱酸可浸取态氮(WAEF-N)最低.随着沉积物粒级的由粗到细,总可转化态氮以及各形态可转化态氮含量均呈逐渐增加趋势.沉积物细颗粒部分对氮循环的可能贡献占绝对的主体,是粗颗粒部分的几倍到几十倍.相比而言,污染程度轻的贡湖和东太湖沉积物无论总可转化态氮还是各形态可转化态氮,细颗粒部分的相对含量均低于污染程度重的五里湖和月湖沉积物.      

模拟酸雨对酸性土壤铝溶出及其形态转化的影响

研究了我国南方酸沉降区主要土壤类型在模拟酸雨影响下,土壤中铝离子释放及铝形态转化的特点。结果表明,酸雨淋洗造成土壤中铝离子释放,酸雨pH值越低,铝离子释放量越大;酸雨淋洗还造成土壤中铝形态发生变化,酸雨pH越低,土壤中羟基态铝和腐殖质铝含量愈低,交换态铝含量越高,土壤中铝对植物和生态系统的危害性也越大。     

New insights into the characterization of the binding of tetracycline analogues with lysozyme: a biophysical study

Tetracycline (TC), chlortetracycline (CTC) and oxytetracycline (OTC) are the most common members of the widely used veterinary drug tetracyclines, the residue of which in the environment can enter human body, being potentially harmful. Lysozyme is a monomeric protein widely distributed in the nature including human beings, having many physiological and pharmaceutical functions. The aim of this study was to examine the interaction of lysozyme with the three tetracyclines (TC, CTC and OTC) through spectroscopic and molecular modeling methods. The experimental results revealed that all the three tetracyclines (TCs) can interact with lysozyme with one binding site to form TCs-lysozyme complex, mainly through electrostatic forces with the affinity order: CTC > TC > OTC. The binding of TCs can cause conformational and some microenvironmental changes of lysozyme. Furthermore, molecular docking was applied to define the specific binding sites, the results of which show that all the three TCs can bind into lysozyme cleft and interact with the key active-site residues Glu 35 or Asp 52, resulting in competitive inhibition of lysozyme activity. The accurate and full basic data in the work is beneficial to clarifying the binding mechanism of TCs with lysozyme in vivo.     

Investigating differential binding of polychlorinated dibenzo-p-dioxins/dibenzofurans in soil and soil components using selective supercritical fluid extraction

Supercritical fluid extraction (SFE) with pure carbon dioxide was performed at increasingly strong conditions to investigate differential binding of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in two impacted soils, in their sieved size fractions, and in small (a few mg) samples of industry-related waste products separated from impacted soil. The binding strengths of PCDD/Fs were shown to be different in the two soils, and in their different soil particle size fractions. As might be expected based on surface area considerations, one soil showed the strongest binding in the smallest (<5 μm) sieved fraction. However, the other soil showed the strongest binding in the larger sized fractions, possibly indicating that process-related particles could be controlling PCDD/F binding. Selective SFE of various types of particles including black carbon and charcoal (separated from soil), and from a suspected process anode residue did show different PCDD/F binding behavior ranging from quite weak binding (charcoal) to very strong binding (anode particles). Shifts to the stronger SFE fractions in the soils after activated carbon treatment agreed well with the decreases previously found in the uptake of PCDD/Fs by earthworms, as well as decreases in their freely-dissolved aqueous concentrations in soil/water slurries. These results show that, as previously demonstrated for PAHs and PCBs, selective SFE can be a useful tool to investigate differences in PCDD/F binding behaviors in impacted soils and sediments and their component parts, as well as a rapid tool for estimating the effectiveness of activated carbon treatments on decreasing the bioavailability of PCDD/Fs in soils and sediments.     

Investigation of metal ions binding of humic substances using fluorescence emission and synchronous‐scan spectroscopy

Abstract

The binding site interactions of IHSS humic substances, Suwannee River Humic Acid, Suwannee River Fulvic Acid, Nordic Fulvic Acid, and Aldrich Humic Acid with various metals ions and a herbicide, methyl viologen were investigated using fluorescence emission and synchronous‐scan spectroscopy. The metal ions used were, Fe(III), Cr(III), Cr(VI), Pb(II), Cu(II) and Ni(II). Stern‐Volmer constants, K_SV for these quenchers were determined at pH 4 and 8 using an ionic strength of 0.1M. For all four humic substances, and at both pH studied, Fe(III) was found to be the most efficient quencher. Quenching efficiency was found to be 3–10 times higher at pH 8. The bimolecular quenching rate constants were found to exceed the maximum considered for diffusion controlled interactions, and indicate that the fluorophore and quencher are in close physical association. Synchronous‐scan spectra were found to change with pH and provided useful information on binding site interactions between humic substances and these quenchers.