珠江广州段水体微表层与次表层中多环芳烃的分布与组成

2009年3月对珠江广州段微表层与次表层水中多环芳烃(PAHs)的分布与组成进行了研究.结果表明,珠江广州段微表层和次表层水中16种溶解态PAHs浓度为622.0～2132.2ng·L-1,与DOC存在正相关关系;颗粒态为316.7～639.5ng·L-1,与颗粒物浓度存在明显的线性相关;PAHs的组成以2～3环为主,溶解态中2～3环PAHs占总量的86.0%～95.7%,明显高于颗粒态中2～3环PAHs占总量的(68.8%～84.0%)百分比,PAHs的辛醇-水分配系数及其物理化学性质是造成这一差异的主要原因;微表层对PAHs有一定的富集作用,富集因数EF在1.1～1.5之间(溶解态1.2～1.5,颗粒态1.1～1.3).     

多环芳烃（PAHs）在不同腐殖酸组分中的赋存特征和氧化降解效果研究

选取腐殖酸重要组分胡敏酸、富里酸、胡敏素为研究对象,研究了不同老化时间下多环芳烃(PAHs)在腐殖酸各组分中的赋存特征.同时,探究了过硫酸钠、高锰酸钾、芬顿试剂、过氧化氢4种氧化剂氧化PAHs过程中污染物在腐殖酸和上清液中的分布情况,确定胡敏酸、富里酸、胡敏素中PAHs的降解效率.实验结果表明,PAHs在胡敏素中存在吸附滞后现象,老化前期胡敏素对PAHs的吸附速率慢、吸附量少,但老化后期出现吸附量的反超,因此,胡敏素、胡敏酸和富里酸中PAHs的最终吸附量并没有明显差异.高环PAHs在3种腐殖酸组分中的吸附速率和最终吸附量远小于低、中环PAHs.过硫酸钠和高锰酸钾能够较好地去除胡敏酸、富里酸、胡敏素中的大部分PAHs,去除率均在95%左右,芬顿试剂对胡敏酸、富里酸和胡敏素中总PAHs的去除效果差别不大,去除率均在79.36%~88.05%之间;过氧化氢对胡敏酸和胡敏素中PAHs的去除率分别为82.82%和61.77%,而对富里酸中PAHs的去除效果最差,去除率仅为43.96%.过硫酸钠和高锰酸钾是氧化PAHs类有机污染土壤的最佳氧化剂,能够有效提高不同组分腐殖酸中PAHs的去除率.     

PAC对再生水中典型有机物吸附动力学和热力学研究

通过粉末活性炭(PAC)吸附再生水中3类典型有机物(腐殖酸、多糖和蛋白质)进行等温线吸附、动力学吸附及吸附前后其粒径变化试验,研究PAC吸附不同有机物的热力学和动力学特性。结果表明,吸附等温线中Freundlich方程拟合结果最好,吸附过程为单分子层吸附,PAC对腐殖酸的吸附效果最好,对多糖的吸附效果最差;热力学研究发现,PAC对3类有机物的吸附过程为自发放热过程。吸附动力学研究发现,PAC吸附3种有机物的最佳接触时间均为12 h;准二级动力学方程更适合描述PAC的吸附过程,其对有机物的吸附由液膜扩散和颗粒内扩散联合作用;PAC吸附腐殖酸的扩散速率最快,吸附量也最大。PAC吸附有机物后的粒径均不同程度地增大,吸附多糖时增加最多,吸附腐殖酸时增加最小。     

天然水体中重金属的化学稳定性

通过对湘江中的重金属污染物进行了综合研究,直接测定化学形态,化学平衡模式计算及沉积物释放模拟试验等三种途径来评价其化学稳定性。研究结果表明,其中生物直接可给级分含量很少,有机络合、颗粒吸附和沉淀等形态构成溶解化合态的缓冲级分,极大部分重金属含在固体颗粒残渣级分中。由此推断,水体中的重金属污染物具有较高的化学稳定性。本文提出了根据存在形态和化学稳定性来评价水体中重金属污染物环境容量及排放负荷的概念,并对湘江水体的排解负荷及 pH 值的化学稳定临界区域提出具体建议。     

滴水湖及其鲫鱼体内PAHs分布特征与影响因素分析

通过测定滴水湖水体、颗粒物和沉积物体系PAHs含量,探讨其分布与组成特征、影响因素及污染来源.结果表明,滴水湖水体中溶解态、颗粒态和沉积物中PAHs平均浓度分别为16.78ng/L、33.02ng/g和40.98ng/g.统计分析表明,水体酸碱度以及电导率与溶解态低环PAHs之间存在显著相关性,总有机碳(TOC)与沉积物中高环PAHs浓度之间存在显著相关性.溶解态的PAHs来源主要表现为草、木和煤的高温燃烧,部分样点表现为石油源;颗粒态PAHs则主要表现为高温燃烧以及石油泄漏源;而沉积物PAHs的来源则较复杂,除了草、木及煤的高温燃烧源和石油泄漏源,还有部分样点表现为石油的高温燃烧源.鲫鱼肌肉、卵部以及鳃部PAHs含量的测定结果表明,鲫鱼不同部位对PAHs的富集能力具有较大差异.鳃部总PAHs含量最高,其次为鲫肉部分,鲫卵所含PAHs浓度最少.与国内外其他研究相比较,滴水湖鲫鱼体内PAHs含量处于较低水平,但鲫鱼部分样品的BaP等当量浓度略高于EPA规定的可食性生物器官中PAHs含量的上限值.     

城市交通干道降雨径流中PAHs的污染特征

以上海、温州市典型交通干道地表径流为研究对象,分析了样品中16种溶解态和颗粒态PAHs浓度,了解了城市交通干道降雨径流中PAHs污染特征及其动态变化过程.结果表明,径流中∑PAHs(包括溶解相、颗粒相)浓度范围为919.8～16711.6ng·L-1,溶解相中PAHs浓度要远低于颗粒相(分别为4.9～1558.0ng·L-1,635.4～16624.0ng·L-1).通过对3场降雨事件中PAHs浓度随降雨过程变化的研究,可以发现并不是所有道路径流都有初期冲刷效应,初期冲刷的产生受雨前干期、降雨强度以及径流量等因素共同作用,因此简单拦截初期径流并不能十分有效地降低PAHs污染负荷.径流中PAHs在颗粒相-水相间的分配系数Kp值为2.3×104～2.5×106L·kg-1,随着悬浮颗粒物含量增加而减少,这可能跟径流过程中颗粒物粒径组成有关.     

北京城区屋面径流中PAHs的初期冲刷效应

为研究北京城区典型屋面径流中PAHs的污染特征,采集并分析了3种材料屋面的径流中颗粒相和溶解相PAHs的浓度.在分析屋面径流中PAHs初期冲刷效应的基础上,提出了描述初期冲刷的定量参数FFn-Max,据此探讨了降雨特征对屋面径流中PAHs初期冲刷效应的影响.结果表明,屋面径流中总PAHs和颗粒相PAHs均存在明显的初期...     

腐殖酸对NH+4-N在饱和含水层中迁移的影响

通过等温吸附实验,研究了有和无腐殖酸2种情况下,NH 4＋-N在石英砂上的等温吸附过程,并运用Langmuir方程和Freundlich方程进行了拟合,计算了不同条件下NH 4＋-N在石英砂上的最大吸附量;通过室内土柱模拟实验,测定了不同时间内土柱出水中的NH 4＋-N、NO 3--N和NO 2--N的含量,分析了腐殖酸在饱和含水层中对水中NH 4＋-N迁移转化的影响,并运用伪二级动力学方程和二阶段吸附速率方程对动力学过程进行了拟合.结果表明,Langmuir方程和Freundlich方程均能很好地描述NH 4＋-N的等温吸附过程;腐殖酸的存在增加了石英砂对NH 4＋-N的吸附量,无腐殖酸时NH 4＋-N最大吸附量为0.205mg.g-1,有腐殖酸时NH 4＋-N最大吸附量为0.354 mg.g-1.室内土柱实验结果表明,在实验前期,腐殖酸通过增加吸附空间而增大了NH 4＋-N吸附量;当吸附饱和后,腐殖酸可能为硝化细菌等微生物提供碳源和能量,参与NH 4＋-N转化为NO 3--N和NO 2--N的化学反应,使有腐殖酸条件下的NH 4＋-N出水浓度始终低于无腐殖酸条件.伪二级动力学方程和二阶段吸附速率方程均能很好地描述NH 4＋-N的吸附过程（无腐殖酸条件下R2=0.992 3,R2=0.994 4;有腐殖酸条件下R2=0.997 7,R2=0.998 1）,推测石英砂对NH 4＋-N的吸附属于化学吸附过程;通过比较二阶段吸附速率常数k3（有、无腐殖酸时分别为0.247和0.143）和k4（有、无腐殖酸时分别为0.006 27和0.001 7）,发现NH 4＋-N的吸附主要表现为第一阶段吸附,不定向地吸附在石英砂表面的活性点位上,且腐殖酸的存在使NH 4＋-N的平衡吸附量qe增大.     

辽河流域多环芳烃(PAHs)的分布特征及来源解析

采用气相色谱-质谱(GC/MS)的分析方法,对辽河水系主要河流的表层水和悬浮物中的16种PAHs进行了定量分析,并对其分布特征、污染水平以及来源进行了探讨。结果显示:颗粒态PAHs的浓度范围为0.41～76.45μg.g-1,溶解态PAHs的浓度范围为32.57～108.47ng.L-1,西辽河PAHs的浓度比东辽河以及辽河干流中PAHs的浓度要高。在多环芳烃组成上,溶解态和颗粒态样品的PAHs均以低环数(二、三环)为主,且溶解态中低环数PAHs所占比例较颗粒态中所占的比例高。其中,溶解态中二环的PAHs比例最高(平均为68.19%),颗粒态中三环的PAHs比例最高(平均为66.28%)。相对于国内外其他河流,辽河流域的PAHs污染处于较低水平,部分河流受到一定程度的污染。辽河水系中PAHs的来源主要是以石油类和化石类燃料燃烧为主的混合源,这与辽宁复杂的能源结构密切相关。     

微生物对沉积物主要化学组分吸附重金属能力的影响

通过松花江水中微生物与铁、锰氧化物和腐殖酸形成的复合物质的比表面积及吸附Pb、Cd能力的分析,探讨微生物对沉积物中主要化学组分理化性质的影响及机理.结果表明:锰氧化物的比表面积大于铁氧化物和腐殖酸,与微生物结合后比表面积均不同程度增加. 固体物质的比表面积与吸附Pb和Cd的能力并不完全一致,与它们对重金属的吸附机制不同有关.复合物质的的吸附能力并不符合加和模型,微生物的存在掩盖了铁、锰氧化物和腐殖酸表面部分官能团,造成了复合物质的吸附量小于各组分的吸附量之和.     

Kinetics study of aqueous sorption of phenanthrene to humic acids and sediments

IntroductionThesorptionofhydrophobicorganiccontaminants(HOCs)onnaturalgeosorbentsplaysasignificantroleintheirtransport,degradationandultimatefateintheaquaticenvironment (Alexander,1995 ;Luthy ,1997;Weber,2 0 0 1) .Sincethelate 1970s,theorganicmatter(OM)ha…     

腐殖酸极性与有机农药吸附行为的关系

用不同的方法对腐殖酸(HA)进行了结构改性处理,并用元素分析仪、红外光谱仪和电位滴定仪对改性前后的HA进行了表征;通过振荡平衡法,研究了HA改性前后对有机农药甲基对硫磷、西维因、克百威的吸附行为.结果表明,水解处理使得HA的碳水化合物结构减少,肟化处理使得HA的C=N结构增加,氧化处理使HA的芳香环发生开环反应、-COOH基团增加,肟化和氧化处理均使得HA极性增强;有机农药甲基对硫磷、西维因、克百威通过分配作用吸附于HA,分配系数Kd与HA有的机碳含量成正比,HA的极性越强,吸附量越小.     

Humic acid transport in saturated porous media: Influence of flow velocity and influent concentration

Understanding the transport of humic acids（HAs） in porous media can provide important and practical evidence needed for accurate prediction of organic/inorganic contaminant transport in different environmental media and interfaces. A series of column transport experiments was conducted to evaluate the transport of HA in different porous media at different flow velocities and influent HA concentrations. Low flow velocity and influent concentration were found to favor the adsorption and deposition of HA onto sand grains packed into columns and to give higher equilibrium distribution coefficients and deposition rate coefficients, which resulted in an increased fraction of HA being retained in columns.Consequently, retardation factors were increased and the transport of HA through the columns was delayed. These results suggest that the transport of HA in porous media is primarily controlled by the attachment of HA to the solid matrix. Accordingly, this attachment should be considered in studies of HA behavior in porous media.     

土壤腐殖酸对毒死蜱的吸附

采用平衡振荡法进行农药毒死蜱在5种土壤腐殖酸上的吸附试验.结果表明,毒死蜱在不同土壤腐殖酸上的吸附行为表现出一定的差异,并均可Linear方程和Freundlich方程来描述;5种土壤腐殖酸对毒死蜱吸附能力都很强,吸附率均较高(平均值在72.57%～88.21%之间),大小顺序为:紫色潮土HA＞黄壤HA＞中性紫色土HA＞酸性紫色土HA＞腐殖土HA,此顺序与腐殖酸腐殖化程度一致;pH=2时,腐殖酸对毒死蜱的吸附能力显著增大;离子强度对毒死蜱的吸附影响不明显;腐殖酸添加量越大,单位质量的腐殖酸吸附量越小.     

土壤胡敏酸对菲的吸附特征研究

通过模拟实验研究了不同来源的7种土壤样品及从中提取的胡敏酸(HA)对菲的吸附特征,应用元素分析仪和固相核磁共振光谱(CP／MAS^13C-NMR)对7种土壤样品中的胡敏酸进行了表征并计算其芳香度和脂化度．实验结果表明,不同来源土壤对菲吸附的Freundllich吸附系数(Kt)不同,其有机碳标化的分配系数(K IM)也存在一定的差异．另外,由于不同来源土壤中HA的结构和组成差异明显,土壤HA对疏水性有机污染物的吸附规律也表现出不同的特征．土壤中HA对菲吸附过程的有机碳标化的分配系数(K oc)与土壤HA的芳香度具有正相关性．     

Comparative sorption and desorption behaviors of PFHxS and PFOS on sequentially extracted humic substances

The sorption and desorption behaviors of two perfluoroalkane sulfonates（PFSAs）, including perfluorohexane sulfonate（PFHx S） and perfluorooctane sulfonate（PFOS） on two humic acids（HAs） and humin（HM）, which were extracted from a peat soil, were investigated. The sorption kinetics and isotherms showed that the sorption of PFOS on the humic substances（HSs） was much higher than PFHx S. For the same PFSA compound, the sorption on HSs followed the order of HM 〉 HA2 〉 HA1. These suggest that hydrophobic interaction plays a key role in the sorption of PFSAs on HSs. The sorption capacities of PFSAs on HSs were significantly related to their aliphaticity, but negatively correlated to aromatic carbons,indicating the importance of aliphatic groups in the sorption of PFSAs. Compared to PFOS,PFHx S displayed distinct desorption hysteresis, probably due to irreversible pore deformation after sorption of PFHx S. The sorption of the two PFSAs on HSs decreased with an increase in p H in the solution. This is ascribed to the electrostatic interaction and hydrogen bonding at lower p H. Hydrophobic interaction might also be stronger at lower p H due to the aggregation of HSs.     

Characterization of humic acids extracted from the sediments of the various rivers and lakes in China

The humic acids (HAs) isolated from the sediments of the various rivers,lakes,and reservoirs in China were studied using elemental analyzer,fourier transform infrared (FT-IR),and CP/MAS 13C nuclear magnetic resonance (NMR) spectroscopy.The results showed that the HAs were characterized by some common chemical and physicochemical properties,but they also pose some differences in the C-containing functional groups.The C/N,C/H,O/C,and O/H ratios differ widely for the various HAs,showing that the elemental comp...     

Influence of organic amendments on the sorption of pentachlorophenol on soils

The influence of pH on the sorption of pentachlorophenol (PCP) onto three organic amendments, char, humic acid (HA) and peat, and the effect of organic amendments on PCP sorption to three kinds of soils were evaluated. The sorption of PCP on these sorbents fitted the Freundlich model well, suggesting that PCP sorption isotherms were nonlinear with exponential coefficient (N) value lower than 1. The PCP sorption capacity on three organic amendments and the N values increased with decreasing pH. The sorption capacities were in the order: char > HA > peat. Organic amendments resulted in an enhancement of sorption capacities of soils. The N values of PCP sorption on soils were decreased by char amendment and increased by HA and peat amendments. This study demonstrated that application of traditional organic amendments led to the enhancement of PCP sorption by soils. This information may aid both in predicting environmental fates of hydrophobic ionizable organic compounds and in developing remediation strategies for them.     

去矿物前后碱萃取腐殖酸的化学组成与结构特征

本文采用改进的化学分离方法对Pahokee泥炭和稻田土壤中的腐殖酸进行了分离,得到了两类腐殖酸:去矿物前腐殖酸(HA-I)和去矿物后腐殖酸(HA-II),其中HA-II为前人未所顾及。然后采用元素分析、固体13C核磁共振、热解-色谱-质谱等技术对HA-I和HA-II的化学组成和结构进行了分析。结果显示HA-II在总腐殖酸中占有的比例分别是11.8%(泥炭)和37.1%(土壤)。HA-I和HA-II在化学组成和性质结构上有明显的差异,O/C原子比都表现为HA-IIH/CSSHA-I,表明从HA-I到HA-II,Pahokee泥炭和稻田土壤腐殖酸中的含氧基团都减少,Pahokee泥炭腐殖酸则脂族基团减少,而稻田土壤腐殖酸的脂族基团增加。这种HA-I和HA-II在结构性质上的变化在13C NMR和热解分析时也都得到了验证。另外热解分析还表明HA-I含有更多的易分解的结构组分,而HA-II则含有更多的难分解的结构组分。这些研究都说明HA-II与HA-I相比,在组成和结构特征上存在一些差异,含有更多的难分解的结构单元。本项研究结果对于理解土壤沉积物体系中腐殖酸的化学特征和地球化学过程与行为具有重要意义。     

Comparative characterization of two natural humic acids in the Pearl River Basin, China and their environmental implications

Two humic acids (HAs) were isolated from contaminated river sediments present under comparative conditions in the Pearl River Basin, China. YFHA (the HA extracted at an open pyrite mining area in Yunfu) exhibited a lower absorption intensity for certain bands in the Fourier transform infrared spectra, a lower E4/E6 value (the UV absorbances at 465 nm (E4) and 665 nm (E6)), a lower apparent molecular weight, a lower polarity and a lower oxygen functionality in comparison with GZHA (the HA isolated at an urban living area in Guangzhou). All these differences indicated a higher degree of humification of YFHA than GZHA. Overall, the enrichment patterns of permanent heavy metals in the studied HAs were similar to those in corresponding sediments. In particular, YFHA exhibited high enrichment of trace element Tl, a characteristic concomitant from the mining of the pyrite minerals. The adsorption isotherms of two HAs for goethite and pyrolusite, two representative geological materials, conformed to the Langmuir equation. Based on the qualitative relationships between the Langmuir constants of the adsorption isotherms and the chemical characteristics of HAs, the main mechanism of HA adsorption on these materials was suggested to be hydrophobic interaction. This study highlighted the promising use of HA as a peculiar bio-indicator of uncommon trace metal contaminations. The HA adsorption mechanism on representative geological materials further provided a theoretical basis for the study on the unusual metal behavior in complex environmental settings.