共存镉/铜对沉积物(生物膜)中主要组分吸附阿特拉津的影响

采用选择性萃取分离技术对沉积物(生物膜)中非残渣态组分(铁、锰氧化物和有机质)进行分离,研究阿特拉津(atrazine,AT)-Cd-Cu系中共存重金属对选择性萃取前后沉积物(生物膜)吸附AT的影响.研究结果表明:共存体系中,沉积物(生物膜)中铁氧化物对AT的吸附贡献最大,其次是有机质,而锰氧化物则抑制AT的吸附;共存镉促进了AT在沉积物(生物膜)原样及各非残渣态组分上的吸附,镉质量浓度为0.2 mg/L时,促进作用最显著,各组分对阿特拉津的吸附贡献增加了3.20%～32.31%(沉积物)和1.61%～17.10%(生物膜),但随镉质量浓度的增加,其促进作用减弱;共存铜抑制沉积物(生物膜)原样及铁氧化物、有机质对AT的吸附,铜质量浓度为75.0 mg/L时,其抑制作用最强,铁氧化物和有机质对阿特拉津的吸附贡献分别降低了29.21%、22.36%(沉积物)和9.46%、77.27%(生物膜),但同时减弱了锰氧化物对AT吸附的抑制作用,其吸附贡献分别提高了28.98%(沉积物)和17.46%(生物膜).     

水体悬浮颗粒物主要组分的萃取分离及重金属的分布特征

为了考察悬浮颗粒物中主要组分对重金属的富集作用,采用选择性萃取法分离长春市伊通河和南湖悬浮颗粒物中的铁、锰氧化物,优化了萃取条件,测定了悬浮颗粒物中的铁、锰氧化物和有机质等组分中富集Cu,Pb和Zn的含量,分析了上述3种重金属在悬浮颗粒物主要组分中的分布特征。结果表明,0.006 mol/L NH2OH.HCl 0.01 mol/L HNO3萃取30 min可以单独萃取悬浮颗粒物中大部分的锰氧化物,0.8 mol/L Na2S2O4(pH=6.0)萃取40 min可以同时萃取铁、锰氧化物,而对非目的组分的影响较小;悬浮颗粒物对Cu、Pb、Zn重金属有明显的富集作用,其中Cu主要结合在悬浮颗粒物的有机质组分中,Pb主要富集在铁、锰氧化物中,锰氧化物和有机质对Zn的分布起主要的富集作用。     

沉水植物黑藻对沉积物磷吸附动力学的影响

在室内模拟条件下,通过吸附动力学实验,研究了沉水植物黑藻对沉积物吸附磷动力学模型拟合和吸附速度的影响,并从有机质和铁铝氧化物含量的角度,讨论了沉水植物黑藻对沉积物吸附磷动力学的影响机理。初步得出如下结论:(1)一级反应动力学模型虽然从模型拟合的角度达到了极显著水平,但不能真实地反映沉水植物对沉积物吸附磷动力学过程的影响。其余三个模型均能很好地反映,其中抛物线扩散模型的拟合效果最好,修正的Elovich模型和双常数速率模型的拟合效果较好。种植沉水植物与否并不影响这一趋势;(2)沉水植物黑藻提高了沉积物吸附磷的强度和速度,特别是提高了0～0.5h内的吸附速度,沉水植物影响有机质和铁铝氧化物含量是增强沉积物吸附磷强度和速度的重要机理。     

自然水体采集的生物膜上铁、锰氧化物的萃取分离

采用选择性萃取分离技术对自然水体采集的生物膜上铁、锰氧化物进行萃取分离研究,考察该技术的适用性。参考人工培养生物膜的萃取方法,分别用NH₂OH·HCl和Na₂S₂O₄为萃取剂选择性萃取生物膜上的锰氧化物和铁、锰氧化物。实验中分别依次只改变萃取剂浓度、萃取液酸度或萃取时间,保持其它两个因素不变,分别考察这三个因素对萃取效果的影响,从中选出对铁、锰氧化物萃取率高而对有机质影响小的条件为最佳条件。用选定的最佳条件对不同时间和地点采集的生物膜进行萃取,发现对目的组分的萃取率可达70.8%~94.6%,而对非目的组分的影响很小（3.3%~11.0%）,满足萃取分离的要求。这说明选择性萃取技术可以广泛应用于自然水体采集的生物膜上铁、锰氧化物的萃取分离。     

几种亚热带土壤铁锰胶膜和基质的表面化学特征

以我国亚热带的黄褐土、黄棕壤和红壤为材料,研究了土壤铁锰胶膜和其基质的表面化学性质及其对重金属元素的吸附和氧化特点。结果表明,与基质土壤相比,铁锰胶膜的比表面积大,电荷零点(PZC)低,这与其富含粘粒、有机质和铁锰氧化物等有关;铁锰胶膜经脱锰处理后,比表面积明显降低。由盐滴定-电位滴定(STPT)法测得黄褐土、黄棕壤、红壤基质的PZC分别为3.13、3.65和3.90;黄棕壤和红壤铁锰胶膜的PZC分别为3.26和3.42。铁锰胶膜对Pb2 、Cu2 、Cd2 和Zn2 的吸附和对Cr3 的氧化能力比基质的强。铁锰胶膜经脱锰处理后,对Pb2 、Cu2 、Cd2 和Zn2 的最大吸附量比未处理时降低了53%～100%;其氧化Cr3 生成Cr6 的量比铁锰胶膜的降低了87%～100%。说明黄褐土、黄棕壤和红壤的铁锰胶膜中,氧化锰是吸附重金属离子和氧化Cr3 的主体。     

高砷含水层沉积物含铁矿物特性及其对砷的水文地球化学作用

含水层沉积物中含铁矿物的特征与活性会影响砷的迁移转化行为。通过内蒙古含水层沉积物含铁矿物的溶解、还原动力学实验,研究了沉积物含铁矿物特征和活性及其与砷运移的关系。结果表明,沉积物中具还原活性的铁氧化物总量(m0)与岩性有关,细砂为52 μmol/g,黏土为45 μmol/g。初始还原速率k′均在10-5 s-1的数量级。表征活性均匀度的参数γ值介于合成铁氧化物矿物和表层沉积物之间。沉积物中Fe(Ⅲ)氧化物的还原活性主要介于人造纤铁矿与针铁矿的活性水平范围内。沉积物中可能存在两类活性水平不同的Fe(Ⅲ)氧化物。As更倾向于吸附在活性较强的Fe(Ⅲ)氧化物上。还原环境中,活性较强的Fe(Ⅲ)氧化物的还原性溶解,促进了沉积物中砷的释放。     

河套平原沉积物中铀的赋存形态及其与地下水铀浓度的关系

采用Tessier的五步提取法,对位于河套平原杭锦后旗沙海乡四个钻孔沉积物进行铀的五个赋存形态(包括可交换态、碳酸盐吸附态、铁锰氧化物吸附态、有机物或硫化物吸附态和基质态)分布特征研究。结果发现,铁锰氧化物结合态铀含量为0.140~0.328 mg/kg,占总铀量的34.7%;基质态中铀的含量为0.256~0.405 mg/kg,占44.0%。对于铁锰氧化物结合态,铀含量与铁、锰含量呈正相关性,其中铀与铁线性相关系数0.311~0.482,铀与锰线性相关系数0.506~0.642。表明,沉积物中锰氧化物对铀含量的影响大于铁氧化物对铀含量的影响。进一步研究发现,沉积物岩性对铀含量的影响较大,总铀在细砂中平均含量为0.088 mg/kg,在黏土中平均量为0.260 mg/kg。不同深度地下水中铀浓度和沉积物铀含量的研究表明,随深度增加,地下水中铀浓度与含水层沉积物中铀含量均呈降低的趋势。地下水中铀浓度受含水层中可交换态铀含量的直接影响。     

大同盆地砷中毒病区沉积物中砷的吸附行为和影响因素分析

沉积物对砷的吸附-解吸作用是控制砷在地下水中的迁移和转化的决定性因素。对砷中毒重病区大同盆地山胡县沉积物中砷的吸附行为和影响因素研究结果表明,沉积物对砷的吸附符合Freundlich吸附等温模式,吸附量主要与沉积物颗粒大小、黏土矿物质量分数和类型、铁铝氧化物质量分数以及沉积物中As的质量分数有关,有机质质量分数对砷的吸附量影响需进一步深入研究。铝硅酸盐、铁铝氧化物质量分数较高且颗粒较细的黏土和亚黏土类沉积物对砷的吸附性较强;而铝硅酸盐、铁铝氧化物质量分数较低且颗粒较粗的细砂和粉砂类沉积物对砷的吸附性较差,其所处的含水层也是形成高砷地下水的主要含水层。pH值为5．5～8．0时,砷的吸附量最大。大同盆地高砷地下水pH条件非常不利于沉积物中砷的吸附,易形成高砷地下水。该区地下水10℃左右的温度条件非常有利于沉积物对砷的吸附,但由于影响因素较多,且地下水的温度在不同季节会发生一定的变化,其产生的影响还有待进一步研究。     

潮滩沉积物-水界面磷、铁的高分辨率分布特征及生物地球化学行为

为了解潮间带微环境中磷、铁元素的分布和耦合规律及对磷释放的影响,借助薄膜扩散梯度技术（ZrO-Chelex DGT）原位高分辨率获取九龙江口红树林潮滩孔隙水剖面的溶解活性磷（DRP）、Fe2+浓度,并测定沉积物相应的理化参数.研究结果表明:（1）在表层孔隙水中,DRP、Fe2+浓度呈现显著的正相关性,证实了磷、铁元素的耦合关系以及沉积物铁氧化物对磷吸附/解吸附的控制作用;（2）在深部还原带,DRP浓度相对Fe2+浓度具有较大的波动,主要受到沉积物异质性以及红树植物吸收等的影响;（3）根据表层孔隙水中DRP的浓度梯度计算获得磷的分子扩散通量为0.000 64~0.006 00 μg·cm-2·d-1,结果远低于一般湖泊沉积物内源磷的扩散通量,原因是富铁且具较深氧化带的潮滩沉积物中的磷-铁耦合关系有效地抑制了磷的释放.      

江汉平原高砷含水层沉积物地球化学特征

选取江汉平原典型地下水砷中毒区仙桃市沙湖原种场为研究区,对3个长50m的钻孔沉积物砷含量与赋存形态及其他化学组成进行了分析。结果表明区内沉积物砷质量分数为1.35~107.5mg/kg(平均值为12.8mg/kg)。黏土或亚黏土层中砷含量较高,这与细粒沉积物中铁锰氧化物、黏土矿物对砷的吸附有关。地下20m左右深度内含水层沉积物中砷含量最高,相应地下水中砷质量浓度高达到1 000μg/L。草酸-草酸铵选择性提取结果指示沉积物中10%~77%(平均38%)的As与无定形铁氢氧化物结合,表明无定形铁氢氧化物还原性溶解可能是控制砷释放与还原的主要地球化学过程,并且有机质生物氧化机制极大地促进了该过程。然而,沉积物中仅1.2%~23%的铁被草酸-草酸铵提取,含水层中砷浓度主要受铁的氢氧化物还原性溶解影响,但其他形式的铁、有机物的吸附作用亦控制着砷的含量。     

不同粒径泥沙共存吸附动力学模式研究

天然水体中泥沙组成具有非恒定性和非均匀性,而不同粒径泥沙的吸附能力差异很大.因此.讨论天然水体中泥沙对重金属污染物的自净能力,必须研究不同粒径泥沙共存(即非均匀沙)的吸附模式.通过系统室内静态试验,研究了不同粒径泥沙共存吸附的吸附动力学模式.它表明,不同粒径泥沙共存吸附体系各粒径之间不存在竞争和干扰,共存体系单位重量泥沙的吸附量等于各粒径泥沙单独存在,在相同条件下单位重量泥沙的吸附量乘以其在共存体系中所占份额的和.这在一定程度上解决了天然河流水体泥沙吸附量的计算问题.     

苏州城市河道底泥对磷酸盐的吸附与释放特征

为了探讨苏州古城区河道底泥对磷酸盐的吸附-释放特征,文中分别从改变上覆水的pH值、底泥吸附-释放动力学和等温吸附实验三个方面进行了研究。结果表明:(1)随着上覆水pH值的增大,苏州河道底泥对磷的吸附量逐渐减小;(2)底泥对磷的吸附过程是一个复合动力学过程,通常包括快吸附和慢吸附两个过程。底泥对磷的快速吸附在2h内快速进行,之后为慢吸附过程,到6h左右,基本达到一种动态吸附平衡;底泥对磷释放的动力学过程也包括快释放和慢释放过程。底泥释放磷在1·5h内快速进行,之后进入慢释放过程,磷酸盐含量基本稳定,达到释放平衡;(3)底泥具有较大的吸附磷的能力。随着上覆水的磷酸盐浓度增高,底泥吸附磷酸盐的量也增加。上覆水与底泥的比值越大,底泥对磷的吸附率越小。     

Actualizing the role of morphometry in riverine hazards in an Eastern Himalayan river

Phosphorus (P) plays an important role in the eutrophication of river and marine environments. The adsorption-desorption processes of P by estuarine sediment were studied to better understand the P behaviour in the Loughor Estuary in Carmarthen Bay, UK. Three types of models were used to estimate the P adsorption isotherm for five sediment samples from the Loughor Estuary. The Langmuir adsorption isotherm showed a good fit with the linear (data) isotherm. The P desorption from bed sediment was measured as the easy exchangeable P (MgCl₂ extractable). A negative correlation was found between adsorbed P in bed sediment and median particle size. A positive correlation was also found between P adsorbed and metals such as iron (Fe), aluminium (Al) and calcium (Ca) as well as the total organic carbon (TOC).

     

Marine scavenging: Trace metal adsorption by interfacial sediment from MANOP Site H

The adsorption of thirteen trace metals from seawater was studied on interfacial sediment from MANOP site H. The adsorption data indicate a long (~20 day) equilibration time for most metals, an increase in adsorption with an increase in pH and particle concentration, a dependence of adsorption on total metal concentration at high adsorption densities, and a lack of correlation between metal binding ability and metal hydrolysis in solution.Apparent equilibrium binding constants normalized to the total number of available sites on the solid were determined for metal binding with the interfacial sediment. The binding constants indicate that the affinity sequence for metal interactions with the interfacial sediment is: Pb > Fe > Sn ? Co≈ Mn > Cu > Be > Sc ? Zn > Ni > Cd ? Ba > Cs at pH 7.82 in seawater.A comparison of the binding constants for suspended particles, interfacial sediment, and surface sediment indicate that the composition of particles influences the binding ability of the particles. Biogenic particles tend to bind most metals more strongly than lithogenic or authigenic particles.Based on limited data, there is a strong positive correlation between the measured binding constants and the observed partitioning of metals between sediment and seawater.     

重金属迁移转化模型研究

大量重金属污染物迁移转化的现象和研究成果都表明重金属以泥沙颗粒为载体迁移转化,描述重金属在天然水体中的迁移转化必须紧紧抓住泥沙颗粒运动及重金属与泥沙之间的转化关系进行.为此在对现有的重金属迁移转化数学模型进行概括分类的基础上,根据水沙运动与污染物相互作用关系,分析了泥沙颗粒运动及重金属吸附解吸不平衡过程,并结合水沙数学模型,建立了重金属迁移转化的耦合模型.同时在模型合理性分析的基础上,对模型进行了计算分析,分析表明模型能够合理地反映重金属污染物在水体中的迁移转化过程.     

Adsorption and surface complexation modeling of palladium,rhodium and platinum in surficial semi-arid soils and sediment

Sorption isotherms, time-dependent adsorption and surface complexation modeling studies were used to investigate the post-depositional mobility of three of the platinum group-elements (Pd, Rh, and Pt) in semi-arid soil and sediment samples with varying surface properties. The acidity constants (Log K_a1 and Log K_a2), optimized from batch titration data, ranged from 4.69 to 5.34 for Log K_a1 and from −6.51 to −7.61 for Log K_a2, suggesting the occurrence of both protonation and deprotonation reactions on the solid surfaces. Partition coefficients and removal rates of the metals had a general trend of Pd > Pt > Rh. The sediment sample, with the highest clay content and exchangeable cation concentrations, also had the highest affinity for the metals. The times required for sediment to adsorb 63% of the metals were 2.63 h, 4.08 h and 10.64 h for Pd, Pt and Rh, respectively. The FITEQL program successfully optimized the conditional binding constants of the metals on the solids from batch adsorption data. The constants decreased in the order of Pd > Rh > Pt, which was consistent with the observed high affinity of the solids for Pd. The modeling results also showed that aqueous Pd was the least sensitive to pH followed by Rh and Pt. However, metal adsorption below the points of zero net proton charges (ca. pH 6.7) is attributable to the involvement of permanent negatively charged binding sites in the adsorption process. Notably, partition coefficients, removal rates and conditional binding constants all showed a high affinity of Pd for the solids. A similarity between the model outputs and the batch adsorption data indicates the suitability of the model for describing the mobility and retention of the three metals in semi-arid soils and sediments.     

Pore water geochemistry near the sediment-water interface of a zoned, freshwater wetland in the southeastern United States

 Sediment and its associated pore water were collected from a zoned, freshwater, riparian wetland, located in the Talladega National Forest, northeastern Hale County, Alabama, to study the porewater chemistry and its spatial changes within and between the wetland ecological zones. Obvious changes in pH, Eh and element concentrations were observed between the different wetland ecological zones. Major cations (Ca, Mg, and Na) and trace elements (B, Ba, Sr, and Mn) have very good spatial correlation with Fe and Mn distributions, both in the pore water and the sediment, suggesting that adsorption on, and desorption from, iron and manganese oxyhydroxides are important processes controlling the distributions of these elements in the wetland sediment. However, an equilibrium adsorption model is not able to explain the distribution of trace elements between the pore water and sediment. A redox kinetic model gives similar vertical profiles for iron and the correlated elements as those measured in the field and thus suggests that the relative rates of ferrous iron oxidation and the reductive dissolution of ferric iron in the sediment are important variables determining the distributions of these elements in the wetland pore waters. Received: 31 October 1996 · Accepted: 27 May 1997     

Effect of heavy metals and surfactants on the adsorption of phenolic compounds on sediment

The effects of different heavy metals (copper and mercury), cationic surfactants cetylpyridinium chloride, anionic surfactant sodium dodecylbenzenesulfonate and the chemistry of the solution (pH value) on the adsorption of three selected phenolic compounds (2, 4-Dichlorophenol, 2, 4-Dinitro-phenol and 2, 4-Dimethyphenol) on sediment were studied. Results indicated that in the sediment-water system with phenolic compounds: (1) all of the data could be simulated by Freundlich equation; (2) the experiments studying pH effects showed that the adsorption capacity of 2, 4-Dichlorophenol and 2, 4-Dimethyphenol were quite potentia Hydrogenii dependent and increased with decrease in potentia Hydrogenii, while 2, 4-Dinitrophenol followed the different trend; (3) As the concentration increased from 0 to 0.2?mM for Cu²⁺, the Freundlich capacity coefficient constant varied from 62.84 to 325.1 for 2, 4-Dichlorophenol, from 13.1 to 82.179 for 2, 4-Dinitrophenol and from 29.433 to 7.976 for 2, 4-Dimethyphenol, respectively. The Freundlich capacity coefficient constant of 2, 4-Dichlorophenol, 2, 4-Dinitrophenol and 2, 4-Dimethyphenol varied from 62.84 and 421.43, 13.1 and 138.1, 29.433 and 1.381, respectively, with concentration of Hg²⁺ increased from 0 to 0.04?mM, respectively; (4) the adsorption of 2, 4-Dichlorophenol and 2, 4-Dimethyphenol were accentuated by cetylpyridinium chloride but suppressed by sodium dodecylbenzenesulfonate, whereas the adsorption of 2, 4-Dinitrophenol on sediment was enhanced by both cationic and anionic surfactants, effects that are consistent with electrostatic and hydrophobic interactions among ionic surfactants, phenolic compounds and sediment. The results are believed to provide a useful insight into describing the transport and fate of phenolic compounds in natural environments.     

考虑泥沙影响的污染物输运年龄数值模拟

自然水体中污染物的迁移、转化规律与经泥沙吸附后的沉降、再悬浮等泥沙过程密切相关,其机制尚不明确。采用污染物输运年龄对泥沙影响进行了量化分析,并应用于南黄海辐射沙脊群西洋海域。基于水体中泥沙-污染物模型,推导了考虑泥沙影响的污染物输运年龄的计算方程,通过数值模拟分析了污染物分配系数KD对污染物输运年龄空间分布的影响。研究成果表明:计入泥沙影响后,污染物浓度显著减小,污染物输运年龄随之增大,表明泥沙对污染物扩散起阻碍作用;污染物分配系数KD表征泥沙吸附能力,污染物输运年龄与其呈一定的正相关性,当该系数达到一定值(KD=10^3L/g)时,泥沙吸附能力趋于饱和,污染物输运年龄不再发生显著改变。     

泥沙吸附重金属污染物室内静态试验研究

从吸附反应动力学方程和质量守恒方程出发,导得室内静态试验中泥沙吸附量和水相重金属浓度随时间变化的计算公式,并得出泥沙平衡吸附量和水相平衡浓度随泥沙吸附特性、水相重金属离子初始浓度和泥沙浓度变化的计算公式。结合室内试验,认为泥沙浓度不影响吸附特性参数,如饱和吸附量b、吸附-解吸速率常数k及吸附速率系数k1.