土壤及土壤矿物对类胡敏酸的吸附解吸及其影响因素研究

应用平衡吸附法,研究了不同pH值、离子强度、类胡敏酸浓度和接触时间条件下,黑土、白浆土及蒙脱石对类胡敏酸(HLA)的吸附作用.结果表明:随着HLA浓度的增加,土壤及蒙脱石对HLA的吸附量增加.黑土、白浆土及蒙脱石对HLA的吸附等温线均为L型,其吸附不可逆性表现为白浆土＞蒙脱石＞黑土.通过Langmiur方程计算,蒙脱石、白浆土对HLA达到吸附平衡时的最大吸附量分别为764.7、790.3 mg·g-1,而黑土为35.27 mg·g-1.Freundlich方程可以很好地描述白浆土、蒙脱石对HLA的吸附和解吸等温线,而Temkin方程可以很好地描述黑土对HLA的吸附和解吸等温线.同时,3种材料的吸附自由能△G°＜0,吸附热Qm ＞0,表明其对HLA的吸附是自发的、放热的过程.随着pH的升高,黑土、白浆土及蒙脱石对HLA的吸附量减少;随离子强度的增加,黑土、白浆土及蒙脱石对HLA的吸附量增大.黑土、白浆土及蒙脱石对HLA的吸附动力学过程划分为快反应和慢反应阶段,其中,蒙脱石、白浆土对HLA的吸附动力学过程用一级动力学方程拟合的效果最好,而对黑土而言,用Elovich方程描述更合适.     

电子供体对地下水中高氯酸盐生物去除的影响研究

通过静态实验,考察了电子供体类型及用量对厌氧条件下微生物去除地下水中高氯酸盐的影响.结果表明,电子供体醋酸盐和H₂的加入,可以明显提高ClO₄^-的去除率,驯化后的微生物去除ClO₄^-的速率比未加入电子供体时提高约1.4~3倍.Monod动态模型能很好地拟合两种电子供体环境下ClO₄^-的微生物去除过程,分别以醋酸盐和H₂作为电子供体时,基质半饱和常数K_s为12.6 mg·L^-1和2.2 mg·L^-1,最大比基质消耗速率V_m为0.45 d^-1和0.08 d^-1.动力学参数表明,本实验条件下,异养型混合菌去除ClO₄^-的效果明显优于自养型混合菌;在少数受高浓度ClO₄^-污染的地下水环境中,为了提高ClO₄^-的去除速率只有通过增加菌体浓度或提高微生物酶的活性来实现.随着电子供体醋酸盐用量增加,ClO₄^-的(比)消耗速率逐渐增大.当初始CH₃COO^-与ClO₄^-的比例为3.80 mg(COD)/mg(ClO₄^-)时,比消耗速率v最大(0.27 d^-1).     

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: Kinetics, isotherms and thermodynamics

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qm /SSA) and SSA-normalized adsorption coefficient (Kd /SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (△ G0 ) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (△ H0 ), G0 and free energy of adsorption (Ea ), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and K d /SSA or q m /SSA.     

Factors influencing the contents of metals and As in soils around the watershed of Guanting Reservoir, China

Topsoil samples from 61 sites around the Guanting Reservoir,China,were measured for Cu,Zn,Cr,Ni,Cd,Pb and As concentrations.The mean concentrations of Cu,Zn,Cr,Ni,Cd,Pb and As were 16.8,59.4,37.8,18.3,0.32,20.1 and 8.67 mg/kg dry weight,respectively.Factors that influence the dynamics of these metals in soils around the watersheds of Beijing reservoirs were examined.The influence of atmospheric deposition,land use,soil texture,soil type and soil chemical parameters on metal contents in soils was investigated.Atmospheric deposition,land use and soil texture were the important factors affecting heavy metal residues.Soil type and soil chemical parameters were also involved in heavy metal retention in soils.The data provided in this study are considered crucial for reservoir remediation,especially since the Guanting Reservoir will serve as one of the main drinking water sources for Beijing in the foreseeable future.     

Sulfur-containing amino acid methionine as the precursor of volatile organic sulfur compounds in algea-induced black bloom

After the application of methionine, a progressive and significant increase occurred in five volatile organic sulfur compounds (VOSCs): methanethiol (MeSH), dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS) and dimethyl tetrasulfide (DMTeS). Even in the untreated control without a methionine addition, methionine and its catabolites (VOSCs, mainly DMDS) were found in considerable amounts that were high enough to account for the water’s offensive odor. However, blackening only occurred in two methionine-amended treatments. The VOSCs production was observed to precede black color development, and the reaching of a peak value for total VOSCs was often followed by water blackening. The presence of glucose stimulated the degradation of methionine while postponing the occurrence of the black color and inhibiting the production of VOSCs. In addition, DMDS was found to be the most abundant species produced after the addition of methionine alone, and DMTeS appeared to be the most important compound produced after the addition of methionine+glucose. These results suggest that methionine acted as an important precursor of the VOSCs in lakes suffering from algea-induced black bloom. The existence of glucose may change the transformation pathway of methionine into VOSCs to form larger molecular weight compounds, such as DMTS and DMTeS.     

Allelopathic effects of gallic acid from Aegiceras corniculatum on Cyclotella caspia

High abundance of algae and eutrophication were observed in mangrove wetlands and these were estimated to be associated with root exudates of some specific mangrove plants to a certain extent.Root exudates form allelopathic effects from mangroves.The main secondary metabolites of Aegiceras corniculatum had been detected to be organic phenolic acids.Gallic acid had been isolated and identified from A.corniculatum.The half-maximal inhibitory concentration of gallic acid on alge Cyclotella caspia was tested as 15.46mg/L.The effects on algal cell morphology were mainly shown as elongated cells,with no apparent cell inclusions,such as oil droplets,chloroplast.At a dose of 2mg/L,gallic acid had a stimulative effect on the specific growth rate of algae on day 3.The contents of malondialdehyde,superoxide dismutase,soluble carbohydrates and chlorophyll a in algal cells showed an overall "low promotion and high suppression".Our results could provide preliminary and valuable reference on the complex influences of mangroves on microecology and microbial communities in the rhizosphere system.     

Competitive sorption between 17α-ethinyl estradiol and bisphenol A/4-n-nonylphenol by soils

The sorption of 17α-ethinyl estradiol(EE2),bisphenol A(BPA),and 4-n-nonylphenol(NP) in single systems and the sorption of EE2 with different initial aqueous concentrations of BPA or NP were examined using three soils.Results showed that all sorption isotherms were nonlinear and fit the Freundlich model.The degree of nonlinearity was in the order BPA(0.537-0.686) > EE2(0.705-0.858) > NP(0.875-0.0.951) in single systems.The isotherm linearity index of EE2 sorption calculated by the Freundlich model for Loam,Silt Loam and Silt increased from 0.758,0.705 and 0.858,to 0.889,0.910 and 0.969,respectively,when BPA concentration increased from 0 to 1000 μg/L,but the effect of NP was comparably minimal.Additionally,EE2 significantly suppressed the sorption of BPA,but insignificantly suppressed that of NP.These findings can be attributed to the difference of sorption affinity of EE2,NP and BPA on the hard carbon(e.g.,black carbon) of soil organic matter that dominated the sorption in the low equilibrium aqueous concentration range of endocrine-disrupting chemicals(EDCs).Competitive sorption among EDCs presents new challenges for predicting the transport and fate of EDCs under the influence of co-solutes.     

Multi-factors influencing the spatial distribution of polycyclic aromatic hydrocarbons in soils surrounding drinking water protection zone

We selected the Guanting Reservoir in Beijing, China as a case where an industrial area locates on the upwind corner to study the influence of human activities and natural processes on the distribution of polycyclic aromatic hydrocarbons (PAHs) in soils. Soil PAH concentrations in the study area follow a log-normal probability distribution function, suggesting that distribution of PAH in soils was affected by human activities. Distribution of PAHs in soils was significantly affected by the point source that high PAH concentrations were observed in near industrial area with an obvious declining trend from the northwest to the southeast which was the prevailing wind direction in this area. Away from the influence of point source, distribution of PAHs in soils was found to significantly correlate with total organic carbon content, while the influences of agricultural land uses and type of soil texture on the total soil PAHs contents and ring compositions were quite limited. The results can provide some evidences and data on the pollutant accumulation in drink water protection area influenced by natural processes and human activities.     

Electrochemical and spectroscopic characteristics of dissolved organic matter in a forest soil profile

Dissolved organic matter （DOM） represents one of the most mobile and reactive organic compounds in ecosystem and plays an important role in the fate and transport of soil organic pollutants, nutrient cycling and more importantly global climate change. Electrochemical methods were first employed to evaluate DOM redox properties, and spectroscopic approaches were utilized to obtain information concerning its composition and structure. DOM was extracted from a forest soil profile with five horizons. Differential pulse voltammetry indicated that there were more redox-active moieties in the DOM from upper horizons than in that from lower horizons. Cyclic voltammetry further showed that these moieties were reversible in electron transfer. Chronoamperometry was employed to quantify the electron transfer capacity of DOM, including electron acceptor capacity and electron donor capacity, both of which decreased sharply with increasing depth. FT-IR, UV-Vis and fluorescence spectra results suggested that DOM from the upper horizons was enriched with aromatic and humic structures while that from the lower horizons was rich in aliphatic carbon, which supported the findings obtained by electrochemical approaches. Electrochemical approaches combined with spectroscopic methods were applied to evaluate the characteristics of DOM extracted along a forest soil profile. The electrochemical properties of DOM, which can be rapidly and simply obtained, provide insight into the migration and transformation of DOM along a soil profile and will aid in better understanding of the biogeochemical role of DOM in natural environments.     

An online monitoring system for atmospheric nitrous acid (HONO) based on stripping coil and ion chromatography

A new instrument for measuring atmospheric nitrous acid(HONO) was developed,consisting of a double-wall glass stripping coil sampler coupled with ion chromatography(SC-IC).SC-IC is featured by small size(50 × 35 × 25 cm) and modular construction,including three independent parts:the sampling unit,the transfer and supporting unit,and the detection unit.High collection efficiency(> 99%) was achieved with 25 μmol/L Na2CO3 as absorption solution even in the presence of highly acidic compounds.This instrument has a detection limit of 8 pptv at 15 min time resolution,with a measurement uncertainty of 7%.Potential interferences from NOx,NO2+SO2,NO2+VOCs,HONO+O3,HNO3,peroxyacetyl nitrite(PAN) and particle nitrite were quantified in laboratory studies and were found to be insignificant under typical atmospheric conditions.Within the framework of the 3C-STAR project,inter-comparison between the SC-IC and LOPAP(long path liquid absorption photometer) was conducted at a rural site in the Pearl River Delta.Good agreement was achieved between the two instruments over three weeks.Both instruments determined a clear diurnal profile of ambient HONO concentrations from 0.1 to 2.5 ppbv.However,deviations were found for low ambient HONO concentrations(i.e.< 0.3 ppbv),which cannot be explained by previous investigated interference species.To accurately determine the HONO budget under illuminated conditions,more intercomparison of HONO measurement techniques is still needed in future studies,especially at low HONO concentrations.