Transport and Adhesion of Escherichia coli JM109 in Soil Aquifer Treatment (SAT): One-Dimensional Column Study

Bacteria transport and adhesion experiments under water-saturated and partially saturated conditions were examined over a wide range of ionic strength, from 1 to 100 mM KCl, CaCl₂, and MgCl₂, and at water contents of 0.15 and 0.22 in sand columns packed with three different sands, baked, sterilized, and raw sands in order to investigate the effects of ionic strength, water content, and porous media type on the microbial adhesion in soil aquifer treatment (SAT). Well-characterized Escherichia coli JM109 were used as model bacterial cells in this study. Column study results showed that bacterial deposition rates increased with increasing ionic strength and decreasing water content, and were higher in raw sand columns than those in other sand columns. The Derjaguin–Landau–Verwey–Overbeek (DLVO) theory was applied to experimental results in order to consider the interaction energies between the bacterial cells and collector grains; results revealed that a considerable amount of bacterial cells was weakly deposited onto the solid surfaces in secondary minimum.     

Numerical Modeling on the Effect of Dissolved Oxygen on Nitrogen Transformation and Transport in Unsaturated Porous System

Nitrogen pollution in groundwater resulting from wastewater application to land is a common problem, and it causes a major threat to groundwater-based drinking water supplies. In this study, a numerical model is developed to study the nitrogen species transport and transformation in unsaturated porous media. Further, a new mass transfer module for dissolved oxygen (DO) is incorporated in the one-dimensional numerical model for nitrogen species transport to describe the fate and transport of nitrogen species, dissolved oxygen, dissolved organic carbon (DOC), and biomass. The spatial and temporal variation of dissolved oxygen is incorporated in the model through the mass transfer from gaseous phase to water phase in an unsaturated porous system. The numerical results of the water flow model and single species and multispecies transport model in an unsaturated zone developed for this purpose have been validated with the available analytical/numerical solution. The developed model is applied in clay loam, silt, and sand soils to analyze the transport behavior of nitrogen species under unsaturated condition. The numerical results suggest that the high rate of oxygen mass transfer from the air phase to the water phase positively increases the dissolved oxygen in the applied wastewater and enhances the nitrification process. Because of this high oxygen mass transfer, the nitrate nitrogen concentration significantly increases in the unsaturated zone and the same is transported to a larger depth at higher simulation period. On the other hand, the low rate of oxygen mass transfer implicitly enhances the denitrification process and finally reduces the nitrate nitrogen concentration in the unsaturated zone. The numerical results also show that the nitrate nitrogen transport is rapid in sandy soil when compared with clay loam and silty soils under high oxygen mass transfer rate. In essence, the high oxygen mass transfer rate significantly increases the nitrate nitrogen in the unsaturated zone, especially at a greater depth at larger time levels and eventually affects the groundwater quality.     

有机改性对凹凸棒黏土吸附四环素类抗生素的影响

采用OECD guideline 106批量平衡吸附法研究四环素类抗生素在十六烷基三甲基溴化铵改性凹凸棒黏土(CTAB-ATP)上的吸附作用,并考察了溶液pH、吸附剂的投加量、离子强度对吸附过程的影响。结果表明,CTAB-ATP对四环素、土霉素、金霉素3种四环素类抗生素的吸附容量随着溶液pH的增加而增加;随着吸附剂投加量的增大而减小;随着离子强度的增加呈现缓慢减小的趋势。CTAB-ATP对四环素、土霉素、金霉素的吸附过程均符合准二级动力学模型(r0.998),吸附等温线较好地符合Langmuir等温式。有机改性凹凸棒黏土的疏水性增强,提高了对有机污染物的吸附能力,其沉降性能良好,这使其作为一种吸附剂用于实际抗生素废水的处理成为可能。     

Natural Jordanian zeolite: removal of heavy metal ions from water samples using column and batch methods

The adsorption behavior of natural Jordanian zeolites with respect to Cd(2 + ), Cu(2 + ), Pb(2 + ), and Zn(2 + ) was studied in order to consider its application to purity metal finishing drinking and waste water samples under different conditions such as zeolite particle size, ionic strength and initial metal ion concentration. In the present work, a new method was developed to remove the heavy metal by using a glass column as the one that used in column chromatography and to make a comparative between the batch experiment and column experiment by using natural Jordanian zeolite as adsorbent and some heavy metals as adsorbate. The column method was used using different metal ions concentrations ranged from 5 to 20 mg/L with average particle size of zeolite ranged between 90 and 350 mum, and ionic strength ranged from 0.01 to 0.05. Atomic absorption spectrometry was used for analysis of these heavy metal ions, the results obtained in this study indicated that zeolitic tuff is an efficient ion exchanger for removing heavy metals, in particular the fine particle sizes of zeolite at pH 6, whereas, no clear effect of low ionic strength values is noticed on the removal process. Equilibrium modeling of the removal showed that the adsorption of Cd(2 + ), Cu(2 + ), Pb(2 + ), and Zn(2 + ) were fitted to Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich (DKR). The sorption energy E determined in the DKR equation (9.129, 10.000, 10.541, and 11.180 kJ/mol for Zn(2 + ), Cu(2 + ), Cd(2 + ) and Pb(2 + ) respectively) which revealed the nature of the ion-exchange mechanism.     

Simulating the Sorptive Removal of Dissolved Copper by Biocarrier Beads

Biocarrier beads containing the dead biomass of Bacillus drentensis immobilized in polymer polysulfone were synthesized in order to remove heavy metals from wastewater. A series of batch experiments were carried out to identify the sorption mechanisms and the theoretical nature of the underlying processes. A mathematical model was developed to simulate the fate and transport of copper ions in a saturated fixed bed packed with biocarrier beads. Mass balance equations were established to represent the migration and distribution of metal ions in the biocarrier beads and the surrounding bulk liquid. Numerical experiments were performed using the proposed model for quantitative analysis of the temporal changes in the distribution of copper ions in and around the biocarrier beads in a fixed bed. The simulation results show that the biosorption of heavy metals by the biocarrier beads depends largely on surface adsorption. A sensitivity analysis was carried out on the major design parameters in a fixed bed. The effects of bed height, flow velocity, and influent concentration were examined by assessing a simulated breakthrough curve. The breakthrough time occurs earlier for a decreasing bed height and increasing flow velocity and influent Cu(II) concentration, whereas the slope at 50 % breakthrough becomes steeper as the flow velocity increases and the influent concentration decreases. The simulation results show that the proposed mathematical model can provide a quantitative analysis of the distribution of metal adsorbate in and around porous particulate adsorbents in a fixed bed and that it can be used as an effective predictive tool.     

Effects of pH on the water solubility and 1-octanol-water partition coefficient of 2,4,6-tribromophenol

2,4,6-Tribromophenol (TBP) is expected to exist in both ionic and non-ionic forms in the environment due to ionisation of the phenolic group at near neutral pH. In this study, the water solubility (Sw) and 1-octanol-water partition coefficient (Kow) of aqueous solutions of TBP at various pH values were measured using the shake flask method. The ionisation resulted in increasing Sw and decreasing Kow by two to three orders of magnitude. From the experimental results, the environmental partitioning characteristics of TBP and the effect of pH on partitioning were discussed through a comparison with the properties of tetrabromobisphenol A (TBBP-A), which has two phenolic groups. Furthermore, the pH dependence of Sw and Kow was represented using a Henderson-Hasselbalch type model and the validity of the model was evaluated. The model was found to be highly useful for predicting the pH dependence within the range of pH 3 to 9.     

Adsorption of antimony(V) by floodplain soils, amorphous iron(III) hydroxide and humic acid

Antimony (Sb) emissions to the environment are increasing, and there is a dearth of knowledge regarding Sb fate and behaviour in natural systems. In particular, there is a lack of understanding of sorption of the oxidised Sb(V) species onto soils and soil phases. In this study sorption of Sb(V) by two organic rich soils with high levels of oxalate extractable Fe was examined over the pH range of 2.5-7. Furthermore, the sorption behaviour of Sb(V) was examined in two phases mimicking those dominant in the experimental soils, namely a solid humic acid and an amorphous Fe(OH)3, across the same pH range. Sorption of Sb by the soils and the humic acid fitted a Freundlich type isotherm, with the equation parameters reflecting changes in bonding affinity corresponding to pH changes. The soils sorbed >75% of the added Sb in all trials, and 80-100% at pH values less than approximately 6.5. The Fe(OH)3 retained >95% of the added Sb in all experiments. The humic acid sorbed up to 60% of the added Sb at acidic pH values, but sorption decreased to zero at higher pH values. Further adsorption studies are recommended, such as examining the effects of ion competition and changes in ionic strength.     

Impact of growth conditions on transport behavior of E. coli

The aim of this investigation is to determine the effect that growth solution has on the cell surface properties and transport behavior of eleven Escherichia coli isolates through saturated porous media. The two growth solutions used were a standard laboratory growth medium (LB) and a dairy manure extract solution. In general, cells grown in manure extract were more hydrophobic, had a more negative zeta potential, had lower amounts of surface macromolecules, and had lower attachment efficiencies than isolates grown in LB. An inverse relationship between the natural log of zeta potential and the attachment efficiency of the isolates for the cells grown in LB media was the only statistically significant correlation observed between transport behavior and cell characteristics of the isolates. This study shows the need to consider growth conditions when studying bacteria to better mimic the environmental stresses that bacteria undergo in the natural environment. This approach could lead to a better understanding of the behavior of manure-derived bacteria in aquatic and terrestrial environments.     

Kinetic and isotherms studies of phosphorus adsorption onto natural riparian wetland sediments: linear and non-linear methods

Riparian wetlands provide critical functions for the improvement of surface water quality and storage of nutrients. Correspondingly, investigation of the adsorption characteristic and capacity of nutrients onto its sediments is benefit for utilizing and protecting the ecosystem services provided by riparian areas. The Langmuir and Freundlich isotherms and pseudo-second-order kinetic model were applied by using both linear least-squares and trial-and-error non-linear regression methods based on the batch experiments data. The results indicated that the transformations of non-linear isotherms to linear forms would affect the determination process significantly, but the non-linear regression method could prevent such errors. Non-linear Langmuir and Freundlich isotherms both fitted well with the phosphorus adsorption process (r ²?>?0.94). Moreover, the influences of temperature and ionic strength on the adsorption of phosphorus onto natural riparian wetland sediments were also studied. Higher temperatures were suitable for phosphorus uptake from aqueous solution using the present riparian wetland sediments. The adsorption capacity increased with the enhancement of ionic strength in agreement with the formation of inner-sphere complexes. The quick adsorption of phosphorus by the sediments mainly occurred within 10 min. The adsorption kinetic was well-fitted by pseudo-second-order kinetic model (r ²?>?0.99). The scanning electron microscopy (SEM) and Fourier transformation infrared (FT-IR) spectra analyses before and after phosphorus adsorption revealed the main adsorption mechanisms in the present system.     

Estimating overall persistence and long-range transport potential of persistent organic pollutants: a comparison of seven multimedia mass balance models and atmospheric transport models

Two different approaches to modeling the environmental fate of organic chemicals have been developed in recent years. The first approach is applied in multimedia box models, calculating average concentrations in homogeneous boxes which represent the different environmental media, based on intermedia partitioning, transport, and degradation processes. In the second approach, used in atmospheric transport models, the spatially and temporally variable atmospheric dynamics form the basis for calculating the environmental distribution of chemicals, from which also exchange processes to other environmental media are modeled. The main goal of the present study was to investigate if the multimedia mass balance models CliMoChem, SimpleBox, EVn-BETR, G-CIEMS, OECD Tool and the atmospheric transport models MSCE-POP and ADEPT predict the same rankings of the overall persistence (P(ov)) and long-range transport potential (LRTP) of POPs, and to explain differences and similarities between the rankings by the mass distributions and inter-compartment mass flows. The study was performed for a group of 14 reference chemicals. For P(ov), the models yield consistent results, owing to the large influence of phase partitioning parameters and degradation rate constants, which are used similarly by all models. Concerning LRTP, there are larger differences between the models than for P(ov), due to different LRTP calculation methods and spatial model resolutions. Between atmospheric transport models and multimedia fate models, no large differences in mass distributions and inter-compartment flows can be recognized. Deviations in mass flows are mainly caused by the geometrical design of the models.     

Centrifugal study of zone of influence during air-sparging

Air sparging (AS) is one of the groundwater remediation techniques for remediating volatile organic compounds (VOCs) in saturated soil. However, in spite of the success of air sparging as a remediation technique for the cleanup of contaminated soils, to date, the fundamental mechanisms or the physics of air flow through porous media is not well understood. In this study, centrifugal modeling tests were performed to investigate air flow rates and the evolution of the zone of influence during the air sparging under various g-levels. The test results show that with the increase in sparging pressure the mass flow rate of the air sparging volume increases. The air mass flow rate increases linearly with the effective sparging pressure ratio, which is the difference between sparging pressure and hydrostatic pressure normalized with respect to the effective overburden pressure at the sparging point. Also the slope of mass flow rate with effective sparging pressure ratio increases with higher g-levels. This variation of the slope of mass flow rate of air sparging volume versus effective sparging pressure ratio, M, is linear with g-level confirming that the air flow through soil for a given effective sparging pressure ratio only depends on the g-level. The test results also show that with increasing sparging pressure, the zone of influence (ZOI), which consists of the width at the tip of the cone or lateral intrusion and the cone angle, will lead to an increase in both lateral intrusion and the cone angle. With a further increase in air injection pressure, the cone angle reaches a constant value while the lateral intrusion becomes the main contributor to the enlargement of the ZOI. However, beyond a certain value of effective sparging pressure ratio, there is no further enlargement of the ZOI.     

Study of the effect of pH, salinity and DOC on fluorescence of synthetic mixtures of freshwater and marine salts

In order to provide support for the discussion of the fate of organic matter in estuaries, a laboratory simulation was performed by changing freshwater ionic strength, pH and organic matter content. The change in spectroscopic characteristics caused by variations in salinity, pH and organic matter concentration in the filtered samples was observed by UV-Vis and fluorescence spectroscopy. The increase in emission fluorescence intensity of dissolved organic matter (DOM) due to increasing salinity (in the range 0 to 5 g l-1) is affected by the pH of the samples. The emission fluorescence intensity at the three maxima observed in the fluorescence spectra, is linearly correlated with dissolved organic carbon (DOC) concentration at several salinity values in the same sample. The increase in organic matter concentration caused a shift in the emission peak wavelength at 410 nm for several salinity values. We concluded that it is necessary to take into account the influence of salinity and pH on emission fluorescence of dissolved organic matter if it is to be used as a tracer in estuarine or near shore areas.     

Colloid-Associated Groundwater Contaminant Transport in Homogeneous Saturated Porous Media: Mathematical and Numerical Modeling

During the past two decades, significant efforts have been made to study contaminant transport in the presence of colloids. Several researchers reported that colloidal particles could enhance the migration of contaminants in groundwater by reducing retardation factor. When the colloidal particles are present in the aquifer, the subsurface system can be considered as a three-phase system with two solid phases and an aqueous phase. The interaction between contaminants, colloids, and solid matrix should be considered in assessing the fate and transport of the contaminant in the groundwater flow system. In this study, a one-dimensional numerical model is developed by employing a fully implicit finite difference method. This model is based on mass balance equations and mass partition mechanisms between the carriers and solid matrix, as well as between the carriers and contaminants in a saturated homogeneous porous medium. This phenomenon is presented by two approaches: equilibrium approach and fully kinetic first-order approach. The formulation of the model can be simplified by employing equilibrium partitioning of particles. However, contaminant transport can be predicted more accurately in realistic situations by kinetic modeling. To test the sensitivity of the model, the effect of the various chemical and physical coefficients on the migration of contaminant was investigated. The results of numerical modeling matched favorably with experimental data reported in the literature.     

The role of hydrodynamics, matrix and sampling duration in passive sampling of polar compounds with Empore SDB-RPS disks

There is an increasing need to monitor concentrations of polar organic contaminants in the aquatic environment. Integrative passive samplers can be used to assess time weighted average aqueous concentrations, provided calibration data are available and sampling rates are known. The sampling rate depends on environmental factors, such as temperature and water flow rate. Here we introduce an apparatus to investigate the sampling properties of passive samplers using river-like flow conditions and ambient environmental matrices: river water and treated sewage effluent. As a model sampler we selected Empore SDB-RPS disks in a Chemcatcher housing. The disks were exposed for 1 to 8 days at flow rates between 0.03 and 0.4 m s(-1). Samples were analysed using a bioassay for estrogenic activity and by LC-MS-MS target analysis of the pharmaceuticals sulfamethoxazole, carbamazepine and clarithromycin. In order to assess sampling rates of SDB disks, we also measured aqueous concentrations of the pharmaceuticals. Sampling rates increased with increasing flow rate and this relationship was not affected by the environmental matrix. However, SDB disks were only sampling in the integrative mode at low flow rates <0.1 m s(-1) and/or for short sampling times. The duration of linear uptake was particularly short for sulfamethoxazole (1 day) and longer for clarithromycin (5 days). At 0.03 m s(-1) and 12-14 degrees C, the sampling rate of SDB disks was 0.09 L day(-1) for clarithromycin, 0.14 L day(-1) for sulfamethoxazole and 0.25 L day(-1) for carbamazepine. The results show that under controlled conditions, SDB disks can be effectively used as passive sampling devices.     

An automatic monitor of formaldehyde in air by a monitoring tape method

An automatic monitor has been developed for measuring formaldehyde in air using a sensitive tape for formaldehyde. It is based on the color change of the tape on reaction with formaldehyde. The porous cellulose tape, containing silica gel as an absorbent and impregnated with the processing solution containing hydroxylamine sulfate, Methyl Yellow (pH indicator; pH 2.9-4.0, red-yellow), glycerin and methanol, was found to be a highly sensitive means of detecting formaldehyde and maintains a stable sensitivity. When the tape was exposed to a sample of air containing formaldehyde, the color of the tape changed from yellow to red. The degree of color change was proportional to the concentration of formaldehyde at a constant sampling time and flow rate, and it could be recorded by measuring the intensity of reflected light (555 nm). The tape could be used to detect down to 0.08 ppm (World Health Organization standard) of formaldehyde with a sampling time of 30 min and a flow rate of 100 mL min-1. Reproducibility tests showed that the relative standard deviation of response (n = 10) was 3.8% for 0.1 ppm formaldehyde. The monitor is simple, specific, capable of unattended operation and is recommended for both laboratory and field operation.     

Migration of pollutants in groundwater. VI. Flushing of DNAPL droplets/ganglia

Models for describing the flushing of DNAPL from contaminated aquifers are developed, and the dependence of the calculated cleanup times on the model parameters is explored. Diffusion transport from isolated DNAPL droplets, from low-permeability porous spherical domains containing distributed DNAPL droplets, and from low-permeability porous planar lamellae containing distributed DNAPL is analyzed, and the resulting expressions then coupled with the equations for advective transport of dissolved VOC by means of natural uniform flow and a system of injection and recovery wells generating a two-dimensional flow field. The models are readily run on currently available microcomputers. The results of computations with the models are consistent with the severe tailing and slow rates of remediation which are generally observed when DNAPLs are removed by flushing.     

Effects of adsorption onto silica sand particles on the hydrolysis of tetracycline antibiotics

Due to high usage of tetracycline antibiotics, concerns have been raised about their environmental fate. In this study, potential changes in the pseudo-first-order hydrolysis rate constants for three tetracyclines, tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC), were evaluated by measuring the rate constants in batch and column leaching experiments. The first-order hydrolysis rate constants were measured at pH 5, 7, and 9 using batch tests. The values were highest at pH 7 for all three tetracyclines (0.0030 ± 0.0004, 0.0042 ± 0.0001, and 0.0323 ± 0.0003 h(-1) for TC, OTC, and CTC, respectively), indicating relatively short environmental half-lives of tetracyclines. Interestingly, it was found that the rates of degradation of the parent tetracyclines were much faster when silica sand was present in a batch solution or when the solution was passed through a silica column. For example, the ratios of the first-order degradation rate constants obtained in the column experiments to those in batch experiments were 13.2, 2.1, and 2.0 for TC, OTC, and CTC at a volumetric flow rate of 0.08 mL h(-1), with an observed tendency for this ratio to increase with an increased flow rate. This indicates that the silica surface may serve as a catalyst for hydrolysis and that the actual environmental half-lives of tetracycline antibiotics could be shorter than those estimated from laboratory hydrolysis rate constants using the standard batch protocol. Furthermore, the toxicity of the column effluent containing hydrolysis metabolites was assessed using bioluminescence inhibition in Vibrio fischeri. It was estimated that the toxicity of the metabolites of CTC was lower than that of their parent compound, whereas the toxicity of metabolites of TC and OTC was as high as or higher than that of their parent compounds.     

Assessment of cyclodextrin-enhanced extraction of crude oil from contaminated porous media

The purpose of this study was to evaluate the effects of cyclodextrin (CD) on the extraction of Macondo well oil from contaminated porous media over a range of hydroxypropyl-β-CD (HPβCD) concentrations. To our knowledge, this is the first dataset on this type of CD yet assembled for an actual crude oil. The results showed that HPβCD can significantly increase oil extraction efficiency, demonstrated by increasing concentrations of all tested normal alkanes (nC(15)-nC(35)) and polyaromatic hydrocarbons (PAHs) in the aqueous phase with increasing CD concentration. A linear relationship between the extraction enhancement effect and CD concentration were verified experimentally and high correlation coefficients for total PAHs (R(2) = 0.82) and alkanes (R(2) = 0.99) were determined. For a 20% CD solution, 3.13 wt% of alkanes and 32.12 wt% of total PAHs were extracted to the aqueous phase, which was significantly more than what was extracted with water only (0.04% and 0.21% for alkanes and PAHs, respectively). This result shows that the remediation of oil contaminated media can be significantly enhanced through the use of HPβCD solutions in flushing or pump and treat operations to remove sorbed oil. The CD extraction enhancement effect decreases with increasing n-alkane chain length for the carbon number range tested. CD significantly enhanced PAH extraction from sand and the enhancement effect increased in the order of parent compounds < C-1 substituted < C-2 substituted < C-3 substituted for most PAHs tested. This study provides important information to assess the feasibility of using CD as a near-shore agent to enhance the cleanup of oil contaminated porous media.     

两性磁化炭添加比例对河流沿岸土吸附Cu2+的影响

将两性(十二烷基二甲基甜菜碱)修饰磁化炭分别以质量分数0、1%和2%加入嘉陵江流域(川渝段)内苍溪(CX)、南部(NB)、嘉陵(JL)和合川(HC)沿岸土中,考察各混合土样对Cu^2+的等温吸附和热力学特征。结果表明:混合土样对Cu^2+的最大吸附量为58.36 mmol/kg~366.85 mmol/kg,添加等量两性磁化炭时各混合土样对Cu^2+吸附量表现为JL>NB>CX>HC的趋势,且添加比越高吸附能力越强。各混合土样对Cu^2+的吸附为自发、吸热和熵增的反应过程,对Cu^2+的吸附量与温度和pH值均呈正相关关系。当离子强度为0.1 mol/L时,各混合土样(除HC外)对Cu^2+的吸附量最大。     

Retention capacities of several bryophytes for Hg(II) with special reference to the elevation and morphology of moss growth

Hg(II) Retention capacities of nine bryophyte species, collected from Jinfo Mountains (JFM) in Chongqing, China, had been investigated with special reference to the effect of morphology and elevation of moss growth. Results indicated that adsorption capacities of bryophytes for Hg(II) became stronger with the increase of multi-branches and leafy-shoots, as well as the elevation of moss growth, which was observed both in adsorption isotherm and adsorption kinetics experiments. Contrarily, the desorption kinetics showed a decrease tendency with the increase of multi-branches and leafy-shoots and the elevation of moss growth. The results demonstrated that bryophytes with higher multi-branches and leafy-shoots and higher growth elevation had a stronger adsorption capacity and a weaker desorption tendency, and therefore had a stronger retention capacity to Hg(II). The results disclosed the different relative sensitivity and retention capacity of mosses to pollution resulting from heavy metals, due to the differences in growth elevation and morphology. These should be considered when bryophytes were chosen as a tool for biomonitoring materials to environmental pollution, especially caused by Hg(II).