硝基苯在渭河沉积物中双模式吸附阻滞因子

采用批量平衡法对硝基苯在渭河沉积物中的吸附特性进行了研究, 结果表明,沉积物的有机质含量和性状对硝基苯的吸附过程具有较大的影响,有机质含量和孔隙力场对硝基苯会发生竞争吸附,以Linear和Langmuir等温吸附式耦合的双模式吸附模型可以较好地描述硝基苯在河流沉积物中的吸附特性,以此获得表征其在沉积物中吸附的特性参数,通过求解对流-弥散方程的反问题,获得了双模式吸附阻滞因子数学表达式,计算出硝基苯在该沉积物中吸附的阻滞因子,并得出阻滞因子越小,硝基苯污染的环境风险越大,不仅为硝基苯在河流-地下水系统中的迁移转化规律提供了可靠参数,而且可有效预警硝基苯污染的风险程度,为管理部门提供污染防治的决策依据。     

Distribution and variability of redox zones controlling spatial variability of arsenic in the Mississippi River Valley alluvial aquifer, southeastern Arkansas

Twenty one of 118 irrigation water wells in the shallow (25-30 m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (<0.5 to 77 microg/L) exceeding 10 microg/L. Sediment and groundwater samples were collected and analyzed from the sites of the highest, median, and lowest concentrations of As in groundwater in the alluvial aquifers located at Jefferson County, Arkansas. A traditional five-step sequential extraction was performed to differentiate the exchangeable, carbonate, amorphous Fe and Mn oxide, organic, and hot HNO(3)-leachable fraction of As and other compounds in sediments. The Chao reagent (0.25 M hydroxylamine hydrochloride in 0.25 M HCl) removes amorphous Fe and Mn oxides and oxyhydroxides (present as coatings on grains and amorphous minerals) by reductive dissolution and is a measure of reducible Fe and Mn in sediments. The hot HNO(3) extraction removes mostly crystalline metal oxides and all other labile forms of As. Significant total As (20%) is complexed with amorphous Fe and Mn oxides in sediments. Arsenic abundance is not significant in carbonates or organic matter. Significant (40-70 microg/kg) exchangeable As is only present at shallow depth (0-1 m below ground surface). Arsenic is positively correlated to Fe extracted by Chao reagent (r=0.83) and hot HNO(3) (r=0.85). Arsenic extracted by Chao reagent decreases significantly with depth as compared to As extracted by hot HNO(3). Fe (II)/Fe (the ratio of Fe concentration in the extracts of Chao reagent and hot HNO(3)) is positively correlated (r=0.76) to As extracted from Chao reagent. Although Fe (II)/Fe increases with depth, the relative abundance of reducible Fe decreases noticeably with depth. The amount of reducible Fe, as well as As complexed to amorphous Fe and Mn oxides and oxyhydroxides decreases with depth. Possible explanations for the decrease in reducible Fe and its complexed As with depth include historic flushing of As and Fe from hydrous ferric oxides (HFO) by microbially-mediated reductive dissolution and aging of HFO to crystalline phases. Hydrogeochemical data suggests that the groundwater in the area falls in the mildly reducing (suboxic) to relatively highly reducing (anoxic) zone, and points to reductive dissolution of HFO as the dominant As release mechanism. Spatial variability of gypsum solubility and simultaneous SO(4)(2-) reduction with co-precipitation of As and sulfide is an important limiting process controlling the concentration of As in groundwater in the area.     

自制填料与常用湿地填料除磷能力的比较

用石英砂、石灰、水泥和铝粉等材料制作人工湿地填料,并对自制填料、粉煤灰块和钢渣等6种填料的等温吸附特性进行研究,发现自制填料在较低与较高浓度P溶液中吸附率都最高,在P浓度为(10～50 mg/L)时,平均吸附率达96.8%,其次是粉煤灰和钢渣,分别为87.6%和85.4%;填料对P的理论饱和吸附量分别为:自制填料(2 413.6 mg/kg)>粉煤灰块(1 605.8 mg/kg)>钢渣(1 277.5 mg/kg)>碎砖(451.6 mg/kg)>碎石(182.5 mg/kg)>砾石(18.4 mg/kg);填料中金属矿物成分含量高、比表面积大,是除P效果好的原因。     

Mercury in sediment and fish from North Mississippi Lakes

Sediments and/or fish were collected from Sardis, Enid and Grenada Lakes, which are located in three different watersheds in North Mississippi, in order to assess mercury contamination. The mean total mercury concentration in sediments from Enid Lake in 1997 was 0.154 mg Hg/kg, while 1998 sediment concentrations in Sardis, Enid and Grenada Lakes were 0.112, 0.088 and 0.133 mg Hg/kg, respectively. Sediment mercury concentrations in 1999 were similar in all three lakes but, generally lower than 1998. Mean total mercury concentrations in edible fillets of fish collected from Enid Lake in 1998 were above the human health FDA action level (>1.0 mg Hg/kg) for bass (1.40), crappie (1.69) and gar (1.89); however, tissue concentrations were less than 1.0 mg Hg/kg in carp (0.63) and catfish (0.82). Human hazard indexes for each species was 1 for both adults and children, indicating that there is a potential for toxic effects to occur. In addition, calculated consumption limits indicate that adults may consume 4–12 oz. of fish per month, depending on the species consumed. For children, 2 oz. per month may be consumed. Further studies are needed to determine the exact environmental consequences and human health impacts associated with mercury contamination in North Mississippi and the Southeastern United States.     

Comparison of batch, stirred flow chamber, and column experiments to study adsorption, desorption and transport of carbofuran within two acidic soils

Different methods (batch, column and stirred flow chamber experiments) used for adsorption and desorption of carbofuran studies were compared. All tested methods showed that the carbofuran adsorption was higher in the soil with the higher organic matter content, whereas the opposite behaviour was observed for the percentage of carbofuran desorbed. However, different methods have revealed some discrepancies in carbofuran adsorption/desorption kinetics. Although batch method showed interesting data on equilibrium experiments, such as a low heterogeneity for the carbofuran adsorption sites independent of soil organic matter content, it had some disadvantages for carbofuran adsorption/desorption kinetic studies. The disadvantages were related with the excessive limitations of this method on kinetics, i.e., no difference could be detected between different soils. However, with column and stirred flow chamber methods the carbofuran adsorption/desorption kinetics of different soils could be compared. Moreover, the absolute values of carbofuran adsorption/desorption and its rate were higher in the stirred flow chamber than in the batch and column experiments. Using stirred flow chamber experiments the carbofuran desorption was significantly faster than its adsorption, whereas carbofuran using column experiments they were similar. These discrepancies should be considered when the results obtained only with one method is discussed.     

Comparison of competitive and synergetic adsorption of three phenolic compounds on river sediment

Knowledge of toxic chemical sorption by soil/sediment is critical for environmental risk assessment of toxic chemicals, especially for the multi-sorbate system in river ecosystem. Sorption characteristics of 2, 4-Dichlorophenol, 2, 4-Dinitrophenol and 2, 4-Dimethyphenol on sediment were investigated. Adsorption isotherms in single- and multi-sorbate systems fitted well the Freundlich model. The adsorption effects were different among three selected phenolic compounds in single- and multi-sorbate systems. The synergetic affect that 2, 4-Dinitrophenol and 2, 4-Dimethyphenol bring to 2, 4-Dichlorophenol can be explained by the compression of double electronic layer and the charge neutrality. Adsorption kinetic results showed that pseudo-second-order model can be used to describe the experimental data and the adsorption affinity of phenolic compounds influenced greatly by the adsorption velocity. The present study suggests that the fate and transport of emerging pollutants such as phenolic compounds could be affected in the presence of different hydrophobic pollutants in aquatic systems.     

Mitigation of two pyrethroid insecticides in a Mississippi Delta constructed wetland

Constructed wetlands are a suggested best management practice to help mitigate agricultural runoff before entering receiving aquatic ecosystems. A constructed wetland system (180 m × 30 m), comprising a sediment retention basin and two treatment cells, was used to determine the fate and transport of simulated runoff containing the pyrethroid insecticides lambda-cyhalothrin and cyfluthrin, as well as suspended sediment. Wetland water, sediment, and plant samples were collected spatially and temporally over 55 d. Results showed 49 and 76% of the study's measured lambda-cyhalothrin and cyfluthrin masses were associated with vegetation, respectively. Based on conservative effects concentrations for invertebrates and regression analyses of maximum observed wetland aqueous concentrations, a wetland length of 215 m × 30 m width would be required to adequately mitigate 1% pesticide runoff from a 14 ha contributing area. Results of this experiment can be used to model future design specifications for constructed wetland mitigation of pyrethroid insecticides.     

Physical versus chemical effects on bacterial and bromide transport as determined from on site sediment column pulse experiments

Twenty-eight bacterial and Br transport experiments were performed in the field to determine the effects of physical and chemical heterogeneity of the aquifer sediment. The experiments were performed using groundwater from two field locations to examine the effects of groundwater chemistry on transport. Groundwater was extracted from multilevel samplers and pumped through 7-cm-long columns of intact sediment or repacked sieved and coated or uncoated sediment from the underlying aquifer. Two bacterial strains, Comamonas sp. DA001 and Paenibacillus polymyxa FER-02, were injected along with Br into the influent end of columns to examine the effect of cell morphology and cell surface properties on bacterial transport. The effects of column sediment grain size and mineral coatings coupled with groundwater geochemistry were also investigated. Significant irreversible attachment of DA001 was observed in the Fe oxyhydroxide-coated columns, but only in the suboxic groundwater where the concentrations of dissolved organic carbon (DOC) were ca. 1 ppm. In the oxic groundwater where DOC was ca. 8 ppm, little attachment of DA001 to the Fe oxyhydroxide-coated columns was observed. This indicates that DOC can significantly reduce bacterial attachment due electrostatic interactions. The larger and more negatively charged FER-02 displayed increasing attachment with decreasing grain size regardless of DOC concentration, and modeling of FER-02 attachment revealed that the presence of Fe and Al coatings on the sediment also promoted attachment. Finally, the presence of Al coatings and Al containing minerals appeared to significantly retard the Br tracer regardless of the concentration of DOC. These findings suggest that DOC in shallow oxic groundwater aquifers can significantly enhance the transport of bacteria by reducing attachment to Fe, Mn and Al oxyhydroxides. This effect appears to be profound for weakly and strongly charged hydrophilic bacteria and may contribute to differences in observations between laboratory experiments versus field-scale investigations particularly if the groundwater pH remains subneutral and Fe oxyhydroxide phases exist. These observation validate the novel approach taken in the experiments outlined here of performing laboratory-scale experiments on site to facilitate the use of fresh groundwater and thus be more representative of in situ groundwater conditions.     

Significance of metal exchange in EDDS-flushing column experiments

Chelating agents have been widely studied for extracting heavy metals from contaminated soils, and the effectiveness of EDDS ([S,S]-ethylene-diamine-disuccinic acid) has aroused extensive attention because of its biodegradability in the natural environment. However, in the course of EDDS-flushing, metal exchange of newly extracted metal-EDDS complexes with other sorbed metals and mineral cations may result in metal re-adsorption on the soil surfaces. Therefore, this study investigated the relative significance of metal exchange under different travel distances of chelant complexes, characteristics of soil contamination, and solution pH in the column experiments. As a result of metal exchange, the elution of Zn and Pb was retarded and the cumulative extraction was lower than those of Ni and Cu, especially over a longer travel distance. Compared with the field-contaminated soils, the effects of metal exchange were even more substantial in the artificially contaminated soil because of a greater amount of extractable metals and a larger proportion of weakly bound fractions. By contrast, metal exchange was insignificant at pH 8, probably due to less adsorption of metal-EDDS complexes. These findings highlight the conditions under which metal exchange of metal-EDDS complexes and the resulting impacts are more significant during EDDS-flushing.     

4种人工湿地填料对磷的吸附特性分析

采用等温吸附、吸附动力学、填料饱和吸附后磷素释放实验,研究了紫色土、河沙、页岩、石灰岩对磷的吸附特征,结果表明Langmuir和Freundlich等温吸附方程均能很好地拟合各填料对磷的吸附特征,各填料对磷的最大吸附量大小顺序依次为石灰岩(666.67 mg/kg)河沙(500.00 mg/kg)页岩(434.78 mg/kg)紫色土(416.67 mg/kg);从反应速率来看,吸附过程都可分为快、中、慢3个阶段;相对一级动力学方程、双常数方程而言,Elovich方程对4种填料的吸附动力学特征拟合最好,决定系数R~2在0.831～0.966之间;从磷的解吸率来看,各填料释磷大小顺序依次为河沙(4.257%)页岩(3.803%)石灰岩(3.638%)紫色土(2.134%)。综合考察得出,石灰岩更适合作为人工湿地污水除磷的填料。     

Trace organic and heavy metal pollutants in the Mississippi River

A study was conducted to characterize and measure organic and heavy metal pollutants in the Mississippi River. Water samples were collected along the entire length of the river, and were screened for semivolatile organics by capillary GC and for heavy metals by atomic absorption spectrophotometry. Four water samples were further examined for semivolatile organics by capillary GC/MS. Eight heavy metals and more than sixty distinct organic chemicals were identified including alkylbenzenes, various halogenated organics, five herbicides or derivatives, plasticizers, polynuclear aromatic hydrocarbons (PAHs), saturated hydrocarbons, and three miscellaneous organics. All organic compounds were detected at the parts-per-trillion (pptr) level. In spite of the limited nature of the sampling effort, the large number of data derived from this study suggests the need for a more rigorous monitoring of the river for a wide spectrum of chemical pollutants.     

人工湿地基质对NH4＋-N吸附性能

为研究建筑废物红砖和工业废物煤渣用作人工湿地脱氮基质的可行性,分别通过静态吸附实验和动态NHf—N去除效果实验进行考察。结果表明,红砖和煤渣对NH4＋-N最大静态吸附量分别为0．2533mg／g和0．0533mg／g,其吸附等温曲线均符合Freundlich型吸附方程,吸附常数分别为0．0419和0．0091;红砖煤渣组合对污水中NH4＋-N平均动态脱除率达到41．18％,高于红砖的37．63％和煤渣的30．92％。     

Using polymer mats to biodegrade atrazine in groundwater: laboratory column experiments

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats to deliver oxygen into groundwater to induce biodegradation of the pesticides atrazine, terbutryn and fenamiphos contaminating groundwater in Perth, Western Australia. The polymer mats, composed of woven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2-m-long flow-through soil columns. The polymer mats proved efficient in delivering dissolved oxygen to anaerobic groundwater. Dissolved oxygen concentrations increased from <0.2 mg l(-1) to approximately 4 mg l(-1). Degradation rates of atrazine in oxygenated groundwater were relatively high with a zero-order rate of 240-380 microg l(-1) or a first-order half-life of 0.35 days. Amendment with an additional carbon source showed no significant improvement in biodegradation rates, suggesting that organic carbon was not limiting biodegradation. Atrazine degradation rates estimated in the column experiments were similar to rates determined in laboratory culture experiments, using pure cultures of atrazine-mineralising bacteria. No significant degradation of terbutryn or fenamiphos was observed under the experimental conditions within the time frames of the study. Results from these experiments indicate that remediation of atrazine in a contaminated aquifer may be achievable by delivery of oxygen using an in situ polymer mat system.     

蛭石人工湿地中吸附-生物转化系统脱氮能力及其机理研究

以蛭石为吸附介质构建了3个人工湿地处理单元：跌流曝气系统(I)、挂膜蛭石床系统(Ⅱ)和无挂膜对照系统（Ⅲ）。在氨氮浓度为20 mg/L水平上,研究比较了蛭石与挂膜蛭石系统的纯基质吸附与基质吸附加生物转化脱氮能力的差异。结果表明：蛭石能有效去除废水中的氨氮。与系统Ⅲ相比,系统Ⅰ和Ⅱ的氨氮平均去除率提高了20%,且具有处理效果稳定的特点。通过跌流曝气供氧进一步提高氨氮去除率,在试验末期,系统I氨氮去除率高于系统Ⅱ24%左右。无植物处理系统中氨氮的降解主要由基质吸附和生物转化共同完成,生物转化在脱氮中的贡献率最大可达87.4%。生物转化除了硝化反硝化作用外,可能还存在厌氧氨氧化过程。相关性分析结果表明,影响人工湿地硝化反硝化强度的主要因素有溶解氧、硝化反硝化菌数量及生物膜生物量。     

3种人工湿地基质对磷的吸附特性

选用页岩、陶粒和砾石3种基质进行等温吸附和吸附动力学试验,研究其对磷的吸附特性。结果表明,Freun-dlich和Langmuir方程均能较好地拟合各基质对磷的吸附特征,并且用Freundlich方程的拟合效果要好于Langmuir方程;基质对磷的理论饱和吸附量大小依次为页岩(527.992 mg/kg)>陶粒(328.165 mg/kg)>砾石(129.729 mg/kg);页岩最大磷吸附量随粒径增加而减小;各基质对磷的吸附过程分为快、中、慢3个阶段,3种基质对磷的吸附速率依次为页岩>陶粒>砾石;准二级动力学方程、双常数方程和Elovich方程均能较好地描述人工湿地基质对磷的吸附动力学特征,但从相关系数来看,准二级动力学方程的描述更为准确。     

Radionuclide transport and retardation in rock fracture and crushed rock column experiments

Transport and retardation of non-sorbing tritiated water and chloride and slightly sorbing sodium was studied in Syyry area SY-KR7 mica gneiss, in altered porous tonalite and in fresh tonalite. Experiments were performed using dynamic fracture and crushed rock column methods. Static batch method for sodium was introduced to compare retardation values from static and dynamic experiments. The ¹⁴C-PMMA method was used to study the pore structure of matrices. The pore aperture distribution was evaluated from Hg-porosimetry determinations and the surface areas were determined using the B.E.T. method. The flow characteristics and transport behavior of tracers were interpreted using a numerical compartment model for dispersion. The effect of matrix diffusion was calculated using an analytical solution to the advection-matrix diffusion problem in which surface retardation was taken into account. Radionuclide transport behavior in rock fractures was explained on the basis of rock structure.     

海河干流、大沽排污河沉积物中有机氯农药的残留状况

调查了海河干流和大沽排污河沉积物中持久性有机氯杀虫剂(OCPs)的残留状况.在所选取的16个断面沉积物样品中均有大量HCHs、DDTs检出,表明海河和大沽排污河的DDT和HCH污染相当严重.海河沉积物中HCHs和DDTs总质量浓度分别为3.30～75.96、1.57～221.57 ng/g.大沽排污河沉积物中HCHs和DDTs的残留量分别为2.30～124.61、11.28～237.30ng/g.与国内外部分河流表层沉积物中HCHs、DDTs的含量相比,海河和大沽排污河沉积物中有机氯农药含量较高.最后根据两条河流沉积物中的OCPs的残留量,分析了其可能的污染源.     

Reactive transport of 85Sr in a chernobyl sand column: static and dynamic experiments and modeling

The effects of nonlinear sorption and competition with major cations present in the soil solution on radioactive strontium transport in an eolian sand were examined. Three laboratory techniques were used to identify and quantify the chemical and hydrodynamic processes involved in strontium transport: batch experiments, stirred flow-through reactor experiments and saturated laboratory columns. The major goal was to compare the results obtained under static and dynamic conditions and to describe in a deterministic manner the predominant processes involved in radioactive strontium transport in such systems. Experiments under dynamic conditions, namely flow-through reactor and column experiments, were in very good agreement even though the solid/liquid ratio was very different. The experimental data obtained from the flow-through reactor study pointed to a nonlinear, instantaneous and reversible sorption process. Miscible displacement experiments were conducted to demonstrate the competition between stable and radioactive strontium and to quantify its effect on the 85Sr retardation factor. The results were modeled using the PHREEQC computer code. A suitable cation-exchange model was used to describe the solute/soil reaction. The model successfully described the results of the entire set of miscible displacement experiments using the same set of parameter values for the reaction calculations. The column study revealed that the stable Sr aqueous concentration was the most sensitive variable of the model, and that the initial state of the sand/solution system had also to be controlled to explain and describe the measured retardation factor of radioactive strontium. From these observations, propositions can be made to explain the discrepancies observed between some data obtained from static (batches) and dynamic (reactor and column) experiments. Desorbed antecedent species (stable Sr) are removed from the column or reactor in the flow system but continue to compete for sorption sites in the batch system. Batch experiments are simple and fast, and provide a very useful means of multiplying data. However, interpretation becomes difficult when different species compete for sorption sites in the soil/solution system. A combination of batches, flow-through reactor and column experiments, coupled with hydrogeochemical modeling, would seem to offer a very powerful tool for identifying and quantifying the predominant processes on a cubic decimeter scale (dm3) and for providing a range of radioactive strontium retardation factor as a function of the geochemistry of the soil/solution system.     

Fate of seven pesticides in an aerobic aquifer studied in column experiments

The fate of selected pesticides (bentazone, isoproturon, DNOC, MCPP, dichlorprop and 2,4-D) and a metabolite (2,6-dichlorobenzamide (BAM)) was investigated under aerobic conditions in column experiments using aquifer material and low concentrations of pesticides (approximately 25 microg/l). A solute transport model accounting for kinetic sorption and degradation was used to estimate sorption and degradation parameters. Isoproturon and DNOC were significantly retarded by sorption, whereas the retardation of the phenoxy acids (MCPP, 2,4-D and dichlorprop), BAM and bentazone was very low. After lag periods of 16-33 days for the phenoxy acids and 80 days for DNOC, these pesticides were degraded quickly with 0.-order rate constants of 1.3-2.6 microg/l/day. None of the most probable degradation products were detected.     

TCE recovery mechanisms using micellar and alcohol solutions: phase diagrams and sand column experiments

Forty-one phase diagrams and fifteen sand column experiments were conducted to evaluate the efficiency of three types of washing solutions to recover trichloroethylene (TCE) at residual saturation and to identify the recovery mechanisms involved. This study demonstrates that: (1) an alcohol and a surfactant combination is more efficient than an alcohol used alone in water; (2) the prediction of the dominant recovery mechanism from the tie line slopes in phase diagram is accurate and can be reproduced in sand column experiments; and (3) TCE recovery efficiency in sand column experiments is generally well represented by the position of the miscibility curve in phase diagrams in the low concentration range. However, the miscibility curve alone is not sufficient to exactly predict the TCE recovery mechanisms involved. Tie line slopes and the critical tie line have to be taken into consideration to select the active matter as well as its concentration and to predict the dominant recovery mechanism in sand column experiments. The sand column experiments quantified the recovery efficiency of each solution and identified the proportion of the recovery mechanisms (mobilisation vs. solubilisation). Washing solutions with an active matter concentration above the critical tie line caused dominating mobilisation. Mobilisation was also dominant when the active matter of the washing solution partitioned into the organic phase and the active matter concentration was below the critical tie line. Solubilisation and emulsification were dominant for washing solutions containing active matter, which principally partitioned into the aqueous phase and an active matter concentration below the critical tie line.