不同类型堆肥中腐殖酸与富里酸的光谱特性和分子量分布

以中药渣(HR)、小麦秸秆(WS)和稻壳(RH)为辅料工业化生产的鸡粪堆肥中的腐殖酸(HA)和富里酸(FA)为研究对象,系统对比分析了不同类型堆肥腐殖质(HSs)的光谱特性和分子量分布。结果表明,3类堆肥中HA的芳香性均高于FA,HR和RH堆肥中HA和FA的芳香化程度均高于WS堆肥。三维荧光区域体积积分结果显示,HA的类腐殖质含量(Ⅲ+Ⅴ,86%～91%)高于FA(56%～64%),而FA的类蛋白物质(Ⅰ+Ⅱ,28%～37%)远高于HA(5%～9%),表明HA具有更高的腐殖化程度和分子量特征;其次,RH和WS堆肥中FA分别含有更多的类富里酸和类腐殖酸,而HR堆肥中FA的类络氨酸组分更多。傅里叶红外光谱分析发现,FA比HA含有更多的酰胺和羧酸,其中HR、WS和RH堆肥中FA分别富含芳香族羧酸、酰胺和多糖结构。元素分析结果显示,与FA相比,堆肥HA具有较高的C/N比和较低的O/C比,表明HA具有更多的不饱和结构,而FA具有更多的含氧官能团。添加不同辅料的堆肥中,WS堆肥HSs的脂肪化程度最高。高效体积排阻色谱结果显示,HA比FA具有更宽的高分子量分布(>2×10⁴     

松花江腐殖酸的提取、表征及与重金属的络合作用

本文提得了第二松花江水及底泥中的黄腐酸(FA)和棕腐酸(HA),测定了总酸性基、羧基、醌基等官能团并进行了元素分析,研究了红外、紫外及荧光光谱,与一般水体腐殖酸的特征相同。 选用凝胶过滤法研究了腐殖酸与汞、镉、锌的络合作用,测定了水及底泥的FA和HA对Zn、Cd、Hg的络合容量,其趋势为Hg>Cd>Zn,计算了条件稳定常数,logA值显示出汞与腐殖酸的稳定性高于汞与水体中除S~(2-)及SH-外的其它配位络合物,合成了腐殖酸汞固体络合物,用红外光谱确定其络合作用,测定了腐殖酸汞在水中的溶解度。     

城市污染河道沉积物有机质的氧化稳定性

为了研究城市河道沉积物有机质的氧化稳定性,以氧化稳定系数(Kos)和腐殖化程度(HA/FA)作为评价指标,在用H2O2处理沉积物的基础上,探讨城市污染河道有机质含量、有机质组成等对氧化稳定性的影响.结果显示,污染河道沉积物有机质含量明显高于自然水生态系统沉积物有机质含量;富里酸(FA)、胡敏酸(HA)、胡敏素(HM)是污染河道沉积物有机质主要赋存形式,其中胡敏素是主体,占全部有机质的65%以上;易氧化有机质(OMr)和难氧化有机质(OMd)与总有机质含量均显著正相关(P0.05);OMd的含量可以更直观地反映河道污染程度;重污染河道沉积物有机质去除量较高;随着有机质的去除,沉积物Kos在总体上有上升的趋势;不同形态有机组分其Kos差异性明显(P0.05),以HM为主的紧结态腐殖质的Kos值最高;用HA/FA和OMr可从大体上表征沉积物的氧化稳定性;HA、FA是影响城市河道沉积物氧化稳定性的主要因素.     

腐殖酸对铜的吸附与解吸特征

采用铜离子选择电极研究了铜在腐殖酸两组分(富里酸FA、胡敏酸HA)中的吸附-解吸特征,以及介质pH对这种吸附-解吸的影响。结果表明,腐殖酸对铜的吸附量为FA>HA,吸附强度为HA>FA,解吸量FA-Cu>HA-Cu。腐殖酸两组分对铜的吸附,当介质pH为4.00～7.00时,很好地符合Langmuir等温吸附方程;当pH<4.0时,符合Freundlich方程。FA、HA与铜作用的条件稳定常数与介质pH有关,pH提高则条件稳定常数增大;但在低pH段和高pH段,其增长规律不一致,当4.00相似文献   

Cu2+、Cd2+、Zn2+对两种单胞藻的毒害作用

分别用不同浓度 (c =0 .0 1～ 2 .34mmol/L)的Cu2 + 、Cd2 + 、Zn2 + 处理亚心型大扁藻 (Plztymonassp.)和小球藻(Chlorelavulagris) ,观察了重金属离子对其生长、呼吸及其被富集的情况 .结果表明 :① 3种离子的毒性强度的顺序为Cu2 + >Cd2 + >Zn2 + ;亚心型大扁藻的耐受力大于小球藻 ;②Cu2 + 对生长的抑制最强 ,两种藻的c(EC50 ,72h)分别为 0 .2 11mmol/L和 0 .2 89mmol/L ;Cd2 + 对生长的抑制稍弱 ,两种藻的c(EC50 ,72h)分别为 0 .4 38mmol/L和 0 .2 4 1mmol/L ;Zn2 + 对生长的抑制最弱 ,其c(EC50 ,72h)分别为 0 .75 4mmol/L和 0 .30 8mmol/L ;③在c(EC50 )毒害浓度下 ,两种单胞藻均提前进入生长静止期 ,缩短了种群生长周期 ;呼吸作用先增强后降低 ;④在c(EC50 )毒害浓度下 ,两种藻对Cu2 + 、Zn2 + 的富集量为 4 5 82～ 4 12 83.7mgkg-1,对Cd2 + 的富集量 5 0 0～ 2 72 3.6mgkg-1.图 2表 3参 8     

不同分子量的腐殖酸存在下2种无机砷的生物毒性效应研究

水环境中天然有机质会与砷形成络合物,进而影响砷的迁移、转化和生物毒性。研究利用超滤方法将腐殖酸(humic acid, HA)分为5个不同分子量的组分,以大型溞为受试生物,探究了不同分子量HA存在下砷对大型溞的毒性效应。结果表明,不同分子量的HA均缓解了As(Ⅲ)和As(Ⅴ)对大型溞的氧化应激损伤和细胞膜损伤,并降低了砷对MT的诱导量。其中1～30 k Da的HA对砷的缓解效果最好,1 k Da的HA毒性缓解效果最差,可能的原因是HA与砷的络合增加溶液中络合态砷的含量,而络合态砷难以进入细胞并被生物利用。不同分子量的HA对砷毒性的缓解差异与其跟砷的络合比例不同有关。     

氧化石墨烯对沉积物中重金属Cu的稳定固化研究

以一种新型碳基材料——氧化石墨烯(GO)为吸附剂,以乌梁素海表层沉积物中重金属Cu为研究对象,考察了GO投加量、沉积物pH值、有机质种类及其质量分数在35 d老化时间内对Cu稳定固化效果的影响。实验中利用电位法测定沉积物的pH值和氧化还原电位值(ORP),通过BCR连续提取法分析Cu各形态含量的分布。研究结果表明,随着GO投加量(2%、4%、6%、8%和10%)的增加,GO可以有效地将Cu从不稳定状态转化为稳定状态。在质量分数为10%时,Cu的酸可提取态较原始状态减少3.76%,残渣态增加28.16%。另外在不同pH(6、7、8和9)下,GO对Cu的稳定效果不同,表现出pH=9pH=8pH=7pH=6的递减关系;并且当pH=9时,沉积物的ORP值在整个老化时间内最低。选用腐殖酸(HA)和富里酸(FA)两种有机质研究其对GO稳定沉积物中Cu的影响。结果发现,加入HA和FA后,GO对沉积物中Cu的稳定效果明显提高,且随着HA和FA质量分数(1%、5%、10%和15%)的增加而增加,当质量分数为15%时固定效果最好。GO+15%HA使重金属Cu的残渣态增加了34.95%,GO+15%FA使重金属Cu残渣态增加了32.96%。以上实验数据表明,GO可以有效地将沉积物中Cu从不稳定态转化为稳定合态,降低沉积物中Cu向上覆水释放的风险。该研究围绕乌梁素海上覆水环境开展实验,以期望对高寒地区重金属污染沉积物的修复提供一种新的思路。     

有机质对Cu2+在棕壤及其各粒级微团聚体中吸附解吸特性的影响

采用平衡液吸附法和NH4AC、EDTA溶液解吸法,研究了有机质对Cu2+在棕壤及其各粒级微团聚体中(<10 μm,10～50μm,50～250 μm)的吸附解吸过程中的影响,为寻求有效控制土壤中Cu2+环境行为的对策措施提供理论支撑.研究结果表明,各粒级微团聚体中有机质对Cu2+的吸附能力随粒级的减小而增强,原土仅次于<10 μm微团聚体.就吸附机制而言,去除有机质后的原土及其各粒级微团聚体在不同吸附机制控制下的吸附能力也有所变化,表现为:去除有机质后,棕壤及各粒级微团聚体对Cu2+的静电吸附能力增强,络合吸附能力和专性吸附的能力均有所降低.分析表明,原土及其不同粒级微团聚体对Cu2+的吸附能力及稳定性的差异,与其重要组成成分有机质有关.     

Cu2+、Zn2+和Cd2+对蟾蜍蝌蚪的联合毒性

以蟾蜍蝌蚪为试验材料,采用联合指数相加法,研究了重金属铜(Cu)、锌(Zn)和镉(Cd)离子对蟾蜍蝌蚪的急性毒性和联合毒性效应.结果表明,Cu2 、Zn2 和Cd2 对蟾蜍蝌蚪的毒性顺序为Cu2 >Cd2 >Zn2 ,48 h的半致死浓度LC50分别为0.514、9.224、33.56 mg L-1;96 h的半致死浓度LC50分别为0.288、8.142、30.76 mg L-1.联合毒性试验结果表明,Cu2 与Zn2 及Zn2 与Cd2 共存时的联合毒性为拮抗作用;Cu2 与Cd2 共存时的联合毒性为毒性剧增的协同作用;Cu2 、Zn2 与Cd2 三者联合时的毒性为协同作用.表6参18     

Cu2+、Cd2+和Cr6+对斑马鱼联合毒性作用和生物预警的研究

为了研究重金属对水生生物的联合毒性作用,以斑马鱼为受试生物,采用半静态法,在研究Cu2、Cd2和Cr6+对斑马鱼单一毒性的基础上,以获得的Cu2+、Cd2+和Cr6+的96 h-LC50数据,利用等效应曲线法研究了Cu-Cd、Cu-Cr和Cd-Cr的联合毒性作用,并综合分析环境毒理学指标的测定结果,考察利用斑马鱼作为水...     

Photosensitivity sources of dissolved organic matter from wastewater treatment plants and their mediation effect on 17α-ethinylestradiol photodegradation

● EE2 photodegradation behavior in the presence of four WWTPs’ DOM was explored. ● The ³DOM* played a major role in the EE2 photodegradation mediated by WWTPs’ DOM. ● The A²/O process DOM contained more aromatic and oxygen-containing substances. ● Possible photosensitivity sources of DOM in the A²/O process were proposed. Dissolved organic matter (DOM) from each treatment process of wastewater treatment plants (WWTPs) contains abundant photosensitive substances, which could significantly affect the photodegradation of 17α-ethinylestradiol (EE2). Nevertheless, information about EE2 photodegradation behavior mediated by DOM from diverse WWTPs and the photosensitivity sources of such DOM are inadequate. This study explored the photodegradation behavior of EE2 mediated by four typical WWTPs’ DOM solutions and investigated the photosensitivity sources of DOM in the anaerobic-anoxic-oxic (A²/O) process. The parallel factor analysis identified three varying fluorescing components of these DOM, tryptophan-like substances or protein-like substances, microbial humus-like substances, and humic-like components. The photodegradation rate constants of EE2 were positively associated with the humification degree of DOM (P < 0.05). The triplet state substances were responsible for the degradation of EE2. DOM extracted from the A²/O process, especially in the secondary treatment process had the fastest EE2 photodegradation rate compared to that of the other three processes. Four types of components (water-soluble organic matter (WSOM), extracellular polymeric substance, humic acid, and fulvic acid) were separated from the A²/O process DOM. WSOM had the highest promotion effect on EE2 photodegradation. Fulvic acid-like components and humic acid-like organic compounds in WSOM were speculated to be important photosensitivity substances that can generate triplet state substances. This research explored the physicochemical properties and photosensitive sources of DOM in WWTPs, and explained the fate of estrogens photodegradation in natural waters.     

Ⅱ.尾矿砂对重金属的吸附作用

本文研究了尾矿砂颗粒对Cu,pb,Cd三种重金属离子的吸附作用,以及各种环境条件因素对颗粒表面吸附作用的影响。实验结果表明,细微尾矿砂颗粒对溶液中的重金属离子具有较强烈的吸附作用,并且强烈地依赖于溶液的pH。根据表面络合反应,对尾矿砂颗粒表面基团可能参与的表面络合反应和吸附的重金属形态进行了讨论,并应用简化络合反应模式,求取了尾矿砂颗粒与Cu,Pb,Cd的表面络合形成的条件稳定常数pK_(ad)。     

森林新近凋落叶溶出DOM的性质及其对菲增溶作用的影响

凋落叶作为森林凋落物的主要组成部分,其溶出的大量有机质也是森林土壤可溶性有机质（DOM）的主要来源之一。研究森林凋落叶溶出DOM对PAHs增溶作用的影响有利于合理预测及评价森林土壤中PAHs的环境行为和生态风险。本研究采集了南亚热带常绿阔叶人工林的4种常见树种--尾叶桉（Eucalyptus urophylla）、木荷（Schima superba）、大叶相思（Acacia auriculiformis）和湿地松（Pinus elliottii）的新近凋落叶为试验材料,研究其DOM含量、组成与性质,对比分析了不同凋落叶DOM对菲的増溶作用及其与DOM性质的相关关系。结果表明,4种凋落叶的可溶性有机碳（DOC）质量分数在C 11.61~36.25 mg·g-1之间,其中尾叶桉的含量最大,湿地松最小。尾叶桉和木荷DOM的主要组分是可溶性糖（SS）和可溶性酚（SP）,两者总C量占DOC的比例超过47%,而大叶相思和湿地松中SS和SP两者总量所占比例均低于30%。另外,4种凋落叶DOM的质量分数（以C计）与其电导率的线性关系图中有明显转折点,说明它们均具有表面活性剂的性质。凋落叶DOM在临界胶束浓度（CMC）之上对菲具有不同程度的増溶作用,其与菲的结合系数（logKDOC）的大小顺序为尾叶桉（3.05 L·kg-1）＞木荷（3.02 L·kg-1）＞大叶相思（2.79 L·kg-1）＞湿地松（2.54 L·kg-1）,这表明尾叶桉和木荷DOM的增溶作用明显高于大叶相思和湿地松DOM。经分析表明,logKDOC与各DOM在254、280 nm处的特征紫外吸光度值（SUV-A254、SUV-A280）及其SS、SP的相对含量均呈显著正相关（p＜0.01）,与A240/A420、A254/A400比值呈显著负相关（p＜0.01）,说明DOM的芳香化程度越高,分子量越大, SS与SP所占比例越高,其对菲的増溶效果越明显。     

小球藻对水中有机酸类稀土配合物的富集

通过ＭＩＮＴＥＱＡ２程序研究了稀土有机酸类配合物在小球藻中的生物富集作用，结果表明：富集作用可用表面配合模型（ＳｕｒｆａｃｅＣｏｏｒｄｉｎａｔｉｏｎＭｏｄｅｌ）来解释，对同一稀土而言，其富集能力的大小与其有机酸１：１配合物的稳定常数呈负相关，稀土一ＥＤＴＡ，ＮＴＡ〉Ｃｉｔｒａｔｅ，Ｔａｒｔｒａｔｅ的配合物在小球藻中的富集能力小于相应的稀土离子，而稀土而与Ａｃｅｔａｔｅ的配合物要大于相应的稀土离子。     

Phenanthrene adsorption by soils treated with humic substances under different pH and temperature conditions

The mobility of phenanthrene (PHE) in soils depends on its sorption and is influenced by either the existing soil humus or exogenous humic substances. Exogenous humic acids (HAs) were added to soil to enhance the amount of soil organic carbon (SOC) by 2.5, 5.0, and 10.0 g kg⁻¹. PHE desorption of the treated soils was determined at two pH levels (3.0 and 6.0) and temperatures (15 and 25 °C). Soil PHE adsorption was related to pH and the type and quantity of added HAs. Humic acid (HA) and fulvic acid (FA) derived from peat had different effects on adsorption of PHE. Adsorption increased at first and then decreased with increasing quantity of exogenous FA. When the soil solution pH (in 0.005 M CaCl₂) was 4.5 or 3.0, the turning points were 2.5 g FA kg⁻¹ at pH 3.0 and 5 g FA kg⁻¹ at pH 4.5. When soil solution pH was 6, the amount of adsorbed PHE was enhanced with increasing exogenous HAs (HA or FA) and amount of adsorption by soil treated with FA was higher than with HA. Adsorption of PHE in the FA treatment at 10.0 g kg⁻¹ was lower than the controls (untreated soil or treatment with HAs at 0 g kg⁻¹) when the soil solution pH was 3.0. This suggests that FA adsorbed by soil was desorbed at low pH and would then increase PHE solubility, and PHE then combined with FA. PHE adsorption was usually higher under lower pH and/or lower temperature conditions. PHE sorption fitted the Freundlich isotherm, indicating that exogenous humic substances influenced adsorption of phenanthrene, which in turn was affected by environmental conditions such as pH and temperature. Thus, exogenous humic substances can be used to control the mobility of soil PAHs under appropriate conditions to decrease PAH contamination.     

堆肥处理对污泥腐殖物质组成和光谱学特征的影响

采用凝胶(Sephadex G-75)色谱、荧光光谱和红外光谱法研究了污泥堆肥的HA和FA在堆制前后的组成与结构特征变化．凝胶色谱分析表明,污泥经过63d堆腐后,HA中大分子组分含量明显提高;而FA则由不同分子量物质组成,其中小分子量物质占主要部分,在堆腐以后,FA中大分子物质含量下降30％,小分子量物质含量则相对增加．同时,荧光光谱、红外光谱的结果表明：随着污泥堆肥的进行,HA中有机物不饱和结构的多聚化或联合程度增大,芳香结构物质含量增加;但经过堆制的FA具有更多的结构简单的低分子量物质和更低的芳构化水平．     

Characterization of interaction between different adsorbents and copper by simulation experiments using sediment-extracted organic matter from Taihu Lake,China

The complex capacity of different types of organic matters （OMs） for Cu was quantitatively studied by simulation experiments using different adsorbents prepared from the sediment in Taihu Lake. The free Cu was measured with ion selective electrode （ISE） and complex capacity was calculated using a conditional formation constant model. The result indicated that the complex capacity was 0.048 mmol·g-1, 0.009 and 0.005 mmol.g-1for raw sediment, sediment without DOM, sediment without insoluble organic matters but with DOM and sediment without OM. Insoluble organic matter played a major role in the sorption of Cu in sediment and it can adsorb most Cu from water column. In the solution, Cu mainly existed as a complex with DOM and the DOM-Cu complexation capacity was 327.87 mg. g-1. The change of TOC and pH indicated ion-exchange in the interaction between free Cu and DOM. When the Cu concentration in the experiment reached the complex capacity of DOM, precipitation was the major mechanism to remove Cu from water phase, which was observed from UV absorbance change of DOM, that is, its aromaticity increased while molecular weight decreased. The desorption result indi- cated that DOM was more capable of desorbing Cu from adsorbents without OM than adsorbent with OM. The desorbed quantity with DOM was 1.65, 1.78 and 2.25 times higher than that with water for adsorbents without OM, raw adsorbents （sediment） and adsorbents without DOM.     

Molecular dynamics of stability and structures in phytochelatin complexes with Zn,Cu, Fe,Mg, and Ca: Implications for metal detoxification

Phytochelatins, or (γ-glutamyl-cysteine) _n -glycine, are specialized peptides produced by plants and algae to mitigate toxic metal exposure, for instance in response to high levels of metals such as Cu, Cd, and Zn. Stability constants and structural characterization of metal–phytochelatin complexes are lacking. This information is required to gain mechanistic insights on the metal selectivity of phytochelatins. Here, we studied structural coordination and thermodynamic stability by performing molecular dynamics simulations of a fully hydrated phytochelatin molecule complexed with Ca²⁺, Mg²⁺, Fe²⁺, Zn²⁺, and Cu²⁺. Our results predict the following decreasing order for the thermodynamic stability of the phytochelatin complexes: Zn²⁺ ≥ Cu²⁺ ≥ Fe²⁺ > Mg²⁺ > Ca²⁺. The favorable binding energies with Zn²⁺ and Cu²⁺ over the other metal cations can be explained by shorter binding distances and greater coordination from carboxylate and keto O atoms. Conformational rearrangement of phytochelatin following metal chelation was captured by monitoring changes in the solvent-accessible volume. Accessibility of solvent molecules to the phytochelatin structure was inversely proportional to the distance between the coordinated ligands and the chelated metal. These new findings demonstrate the influence of the metal–phytochelatin structure on the metal-binding thermodynamics and the phytochelatin conformation, both of which are important to evaluate the intracellular role of phytochelatin in mediating algal response to toxic heavy metal exposure.     

Abiotic association of phthalic acid esters with humic acid of a sludge landfill

The abiotic association between phthalic acid esters (PAEs) and humic substances (HS) in sludge landfill plays an important role in the fate and stability of PAEs. An equilibrium dialysis combined with ¹⁴C-labeling was used to study the abiotic association of two abundant PAEs (diethyl phthalate and di-n-butyl phthalate) with humic acid (HA) isolated from a sludge landfill with different stabilization times and different molecular weights. Elemental analysis and Fourier Transform Infrared Spectrophotometer (FTIR) suggested that high K _A value of HA was related to the high aromatic content and large molecular weight of HA. The results indicated that the association strength of PAEs with HA depended on both the properties of the PAEs and the characteristics of HA. The K _A values of the association were strongly dependent on solution pH, and decreased dramatically as the pH was increased from 3.0 to 9.0. The results suggested that nonspecific hydrophobic interaction between PAEs and HA was the main contributor to the association of the PAEs with HA. The interactive hydrogen-bonds between the HA and the PAEs molecules may also be involved in the association.     

交替冻融对东北典型土壤腐殖质的影响

以受季节性冻融过程影响显著的东北地区的黑土、暗棕壤和水稻土为例,采用实验室模拟的方法,研究交替冻融循环过程（分别在-20℃和20℃下处理）对土壤腐殖质的影响。研究表明：交替冻融后,黑土和暗棕壤松结态腐殖质质量分数分别增加了39%和28%,HA/FA分别上升了45%和35%;水稻土松结态腐殖质质量分数和HA/FA分别下降了18%和31%。三维荧光结果进一步验证,黑土、暗棕壤在交替冻融中土壤芳香化程度增高,HA/FA上升,而水稻土则相反。黑土和暗棕壤松结态腐殖质和HA/FA升高,主要是微生物分解作用和土壤大团聚体破坏等原因造成,水稻土松结态腐殖质和HA/FA降低,主要是水稻土的缺氧环境造成。