Uptake of Dissolved and Oil Phase Organic Chemicals by Bacteria

Hydrophobic organic chemicals (HOCs) discharged into soil and ground water will partition into gaseous, aqueous, oil, and sorbed phases. Knowledge of how bacteria assimilate HOCs is important to individuals involved in evaluating intrinsic, or engineered, bioremediation. The majority of bacteria isolated from the subsurface are gram-negative. The outer membrane of gram-negative organisms acts as a selective barrier to many solutes, including hydrophobic chemicals. Thus, diffusional transport of a hydrophobic solute through the outer membrane may be the rate-limiting step in biodegradation. Bacteria may also produce biosurfactants that can facilitate cell-oil contact or assist solubilization of oil and sorbed phases.     

Use of slow-release fertilizer and biopolymers for stimulating hydrocarbon biodegradation in oil-contaminated beach sediments

Nutrient concentration and hydrocarbon bioavailability are key factors affecting biodegradation rates of oil in contaminated beach sediments. The effect of a slow-release fertilizer, Osmocote, as well as two biopolymers, chitin and chitosan, on the bioremediation of oil-spiked beach sediments was investigated using an open irrigation system over a 56-day period under laboratory conditions. Osmocote was effective in sustaining a high level of nutrients in leached sediments, as well as elevated levels of microbial activity and rates of hydrocarbon biodegradation. Chitin was more biodegradable than chitosan and gradually released nitrogen into the sediment. The addition of chitin or chitosan to the Osmocote amended sediments enhanced biodegradation rates of the alkanes relative to the presence of Osmocote alone, where chitosan was more effective than chitin due to its greater oil sorption capacity. Furthermore, chitosan significantly enhanced the biodegradation rates of all target polycyclic aromatic hydrocarbons.     

The influence of biogeochemical conditions and level of model complexity when simulating cometabolic biodegradation in sorbent-water systems

Eighteen models with different levels of complexity for representing sorption, mass transfer, and biodegradation are used to simulate the biodegradation of toluene (primary substrate) and TCE (cometabolic substrate). The simulations are conducted for hypothetical completely mixed systems of various scenarios with regard to sorbent, microbial composition, and solute concentrations. The purpose of the suite of simulations is to investigate the sensitivity of different modeling approaches in simulating the bio-attenuation of co-existing solutes in sorbent-water systems. The sensitivity of results to the modeling approach depends on the biogeochemical conditions of the system. For example, the results are insensitive to the type of sorption model in systems with low sorption strength and slow biodegradation rates, and insensitive to the biodegradation rate model if mass transfer controlled. Differences among model results are generally greater when evaluated in terms of total mass removal rather than aqueous phase concentration reduction. The fate of the cometabolite is more sensitive to the proper consideration of co-solute effects than is the fate of the primary substrate. For a given system, graphical comparison of a characteristic mass transfer rate coefficient (α_mt) versus a characteristic biodegradation rate coefficient (α_bio) provides an indication of how sensitivity to the different processes may be expected to change with time and can guide the selection of an appropriate level of model complexity.     

土壤水环境中有机污染物生物处理过程模型研究

生物处理是一种经济有效处理土壤水环境中有机污染物的手段,本文在研究土地生物处理过程的基础上,建立了综合描述有机污染物在土壤－水－微生物系统中扩散、吸附／解吸、屏蔽和生物降解过程的数学模型。为确定模型中各参数在模型计算中的作用和相对重要性,进行了参数灵敏度分析,预计数学模型可以定量预测有机污染物进行土地生物处理所需的要时间和程度,为构建土地生物处理工程提供参考。     

The Role of Bioattenuation in the Management of Aromatic Hydrocarbon Plumes in Aquifers

Ground water scientists have made significant advances in understanding the soil interactions, hydrogeology, fate and transport, and subsurface microbiology of aromatic hydrocarbons (BTEX) in aquifer systems. It is now generally recognized that a major factor responsible for the attenuation and mass reduction of BTEX in plumes is the widespread occurrence of hydrocarbon biodegradation by indigenous soil microorganisms in aquifer material. Most well-studied BTEX plumes that develop from the accidental release of gasoline fuels contain low levels of soluble hydrocarbons (< 1 to 5000 ppb) and have been shown to be spatially confined because of natural biotransformation mechanisms. These in situ processes are controlled by source and aquifer characteristics, permeability, sorption, and geochemical properties of the aquifer. Many laboratory subsoil-ground water microcosms and field studies (10 to 20 C) have demonstrated the rapid biodecay (1 to SO percent/day for microcosms and 0.5 to 1.5 percent/day for plumes) of these aromatic compounds under primarily aerobic conditions (i.e., those with sufficient dissolved oxygen). The ability to implement ground water bioremediation will depend upon our understanding of source control and aquifer recharge effects on the spatial distribution of plumes. In addition, estimating the biodegradation of sorbed BTEX, determining limits and potential for in situ biostimulation of soluble plumes, and establishing data requirements for predictive modeling of natural attenuation will be useful for this remediation technology. The use of these tools to manage ground water quality appears to represent the most practical alternative, particularly for low-risk ground water supplies.     

Bacterial Production Stimulated Across the Zone of Influence of a Ground Water Circulation Well in a BTEX-Contaminated Aquifer

Benzene, toluene, ethylbenzene, and xylene (BTEX) hydrocarbons are typically the most abundant carbon source for bacteria in gasoline-contaminated ground water. In situ bioremediation strategies often involve stimulating bacterial heterotrophic production in an attempt to increase carbon demand of the assemblage. This may, in turn, stimulate biodegradation of contaminant hydrocarbons. In this study, ground water circulation wells (GCWs) were used as an in situ treatment for a fuel-contaminated aquifer to stimulate bacterial production, purportedly by increasing oxygen transfer to the subsurface, circulating limiting nutrients, enhancing bioavailability of hydrocarbons, or by removing metabolically inhibitory volatile organics. Bacterial production, as measured by rates of bacterial protein synthesis, was stimulated across the zone of influence (ZOI) of a series of GCWs. Productivity increased from ∼10² to >10⁵ ng C/L hour across the ZOI, suggesting that treatment stimulated overall biodegradation of carbon sources present in the ground water. However, even if BTEX carbon met all bacterial carbon demand, biodegradation would account for <4.3% of the total estimated BTEX removed from the ground water. Although bacterial productivity measurements alone cannot prove the effectiveness of in situ bioremediation, they can estimate the maximum amount of contaminant that may be biodegraded by a treatment system.     

Modelling the fate of oxidisable organic contaminants in groundwater

Subsurface contamination by organic chemicals is a pervasive environmental problem, susceptible to remediation by natural or enhanced attenuation approaches or more highly engineered methods such as pump-and-treat, amongst others. Such remediation approaches, along with risk assessment or the pressing need to address complex scientific questions, have driven the development of integrated modelling tools that incorporate physical, biological and geochemical processes.We provide a comprehensive modelling framework, including geochemical reactions and interphase mass transfer processes such as sorption/desorption, non-aqueous phase liquid dissolution and mineral precipitatation/dissolution, all of which can be in equilibrium or kinetically controlled. This framework is used to simulate microbially mediated transformation/degradation processes and the attendant microbial population growth and decay. Solution algorithms, particularly the split-operator (SO) approach, are described, along with a brief résumé of numerical solution methods. Some of the available numerical models are described, mainly those constructed using available flow, transport and geochemical reaction packages. The general modelling framework is illustrated by pertinent examples, showing the degradation of dissolved organics by microbial activity limited by the availability of nutrients or electron acceptors (i.e., changing redox states), as well as concomitant secondary reactions. Two field-scale modelling examples are discussed, the Vejen landfill (Denmark) and an example where metal contamination is remediated by redox changes wrought by injection of a dissolved organic compound. A summary is provided of current and likely future challenges to modelling of oxidisable organics in the subsurface.     

Biological reduction of chlorinated solvents: Batch-scale geochemical modeling

Simulation of biodegradation of chlorinated solvents in dense non-aqueous phase liquid (DNAPL) source zones requires a model that accounts for the complexity of processes involved and that is consistent with available laboratory studies. This paper describes such a comprehensive modeling framework that includes microbially mediated degradation processes, microbial population growth and decay, geochemical reactions, as well as interphase mass transfer processes such as DNAPL dissolution, gas formation and mineral precipitation/dissolution. All these processes can be in equilibrium or kinetically controlled. A batch modeling example was presented where the degradation of trichloroethene (TCE) and its byproducts and concomitant reactions (e.g., electron donor fermentation, sulfate reduction, pH buffering by calcite dissolution) were simulated. Local and global sensitivity analysis techniques were applied to delineate the dominant model parameters and processes. Sensitivity analysis indicated that accurate values for parameters related to dichloroethene (DCE) and vinyl chloride (VC) degradation (i.e., DCE and VC maximum utilization rates, yield due to DCE utilization, decay rate for DCE/VC dechlorinators) are important for prediction of the overall dechlorination time. These parameters influence the maximum growth rate of the DCE and VC dechlorinating microorganisms and, thus, the time required for a small initial population to reach a sufficient concentration to significantly affect the overall rate of dechlorination. Self-inhibition of chlorinated ethenes at high concentrations and natural buffering provided by the sediment were also shown to significantly influence the dechlorination time. Furthermore, the analysis indicated that the rates of the competing, nonchlorinated electron-accepting processes relative to the dechlorination kinetics also affect the overall dechlorination time. Results demonstrated that the model developed is a flexible research tool that is able to provide valuable insight into the fundamental processes and their complex interactions during bioremediation of chlorinated ethenes in DNAPL source zones.     

Analytical approximation to characterize the performance of in situ aquifer bioremediation

The performance of in situ bioremediation to remove organic contaminants from contaminated aquifers depends on the physical and biochemical parameters. We characterize the performance by the contaminant removal rate and the region where biodegradation occurs, the biologically active zone (BAZ). The numerical fronts obtained by one-dimensional in situ bioremediation modeling reveal a traveling wave behavior: fronts of microbial mass, organic contaminant and electron acceptor move with a constant velocity and constant front shape through the domain. Hence, only one front shape and a linear relation between the front position and time is found for each of the three compounds. We derive analytical approximations for the traveling wave front shape and front position that agree perfectly with the traveling wave behavior resulting from the bioremediation model. Using these analytical approximations, we determine the contaminant removal rate and the BAZ. Furthermore, we assess the influence of the physical and biochemical parameters on the performance of the in situ bioremediation technique.     

Engineering and hydrogeological problems associated with in situ treatment

Abstract

Most organic materials that contaminate soil and the subsurface environment are readily degraded by natural biological processes. To this degree, in situ bioremediation can be thought of as a highly successful purification process. However, some organic molecules are naturally refractory to biodegradation, or other environmental factors induce molecular recalcitrance such as the absence of a proper microbial population or the presence of unsuitable environmental conditions. Examples of recalcitrant groundwater contaminants are soluble components of petroleum hydrocarbons (BTEX) and chlorinated aliphatic hydrocarbons (CAHs). Organic recalcitrance may be changed through introduction of degrading populations of microorganisms or by changing the environmental conditions through introduction of nutrients or other chemicals. The most significant engineering deficiency in in situ bioremediation is the absence of proven methods to introduce such materials into the subsurface environment for efficient mixing with microorganisms and the contaminants of concern.     

Research progress on aging of organic pollutants in geosorbents:a review

Geosorbents are the main host of anthropogenic organic pollutants and play a vital role in their fate and transport in the natural environment.Soil and sediment are the most common and abundant geosorbents in the natural environment;their interactions with organic pollutants,especially sorption and desorption processes,have been extensively studied from the perspectives of thermodynamics and kinetics.Recently,the aging of organic pollutants in geosorbents has drawn increased attention,leading to an improved understanding of interactions between organic pollutants and geosorbents and informing remediation criteria.Aging has been deemed important in accurately assessing ecologic and health risks of organic pollutants,and both positive and negative impacts have been reported in studies of natural and artificial sorbents.This paper summarizes recent research progress on organic pollutant aging in geosorbents,including related mechanism research,influence factors,bioavailability assessments,and biological and physicochemical remediation of aged organic pollutants.We also discuss issues in the current research and bring forward suggestions for future study.     

Effect of pH on binding of pyrene to hydrophobic fractions of dissolved organic matter(DOM) isolated from lake water

In order to better understand the compositional and structural complexity of dissolved organic matter(DOM) macromolecules and provide mechanistic information on the binding of hydrophobic organic contaminants(HOCs) to DOM, we fractionated large amounts of lake water into three hydrophobic DOM-fractions. The variation of the partitioning coef?cients(K_(DOC)) of pyrene at different p H levels was examined by ?orescence quenching titration. Results show that, relative to the more polar acidic DOM-fractions, the hydrophobic neutral fraction exhibits a higher sorption ability to pyrene. Generally, the sorption of pyrene to the three hydrophobic fractions is strongly pH-dependent. The K_(DOC) values of pyrene generally increase with decreasing p H levels, which is especially obvious in the sorption of pyrene to the fulvic acid fractions, suggesting that the binding is controlled by hydrophobic interactions. The mechanisms underlying the binding of pyrene to the hydrophobic fractions were also discussed. Our data are bene?cial to further understanding the binding of HOCs to DOM and how it has been affected,which may result in more accurate predictions of K_(DOC).     

Experimental Study and Mathematical Modeling of Hg and Cu Transformations in the Water–Bottom Sediment System

The results of laboratory modeling of transformations of the ionic forms of Hg and Cu are discussed. The processes considered include the formation of organic and inorganic complexes, sorption on mineral suspension and bottom sediment. A peak in the concentration of organic complex of metals is found to exist. Published data are used to study the physicochemical mechanism of metal transformations in the water–bottom sediment system and to develop a mathematical model of these processes. An explanation is given to the metal concentration peak, which forms in water as a result of the competition between complex formation and sorption processes. Comparison of the experimental and model curves allowed the evaluation of the kinetic coefficients of the complex formation and sorption stages.     

Kinetic partitioning of Co,Mn, Cs,Fe, Ag,Zn and Cd in fresh waters (Loire) mixed with brackish waters (Loire estuary): experimental and modelling approaches

To simulate the behavior of radionuclides along a salinity gradient, in vitro sorption and desorption kinetics of Co, Mn, Cs, Fe, Ag, Zn and Cd were studied in Loire river water and the macrotidal Loire estuarine water over two different seasons. Partitioning between the dissolved phase and suspended solids were followed up over 100 h after adding radioactive tracers to freshly collected freshwater (sorption stage); this stage was followed by desorption in fresh and estuarine waters. A kinetic model describing the interactions between trace metals and particles under a salinity gradient was developed and calibrated. Among parameters and/or processes that control the fate and behavior of contaminated particles during their transfer in estuarine systems, this study shows that the speciation of trace metals is controlled by: (i) the chemical water composition: for all the elements except for Fe, desorption increased with salinity; however, the amplitude of such an effect strongly depended on the element and/or on the composition of the particulate phase (and consequently on the season); (ii) the possibility for a given element to form (or not) stable surface particle moieties such as oxides or inner-sphere complexes; (iii) the distribution of a given element among different types of sites characterised by different binding forces that can lead (or not) to re-adsorption processes after mixing of contaminated particles with uncontaminated water.Our model enabled the quantification of the contribution and the characteristic time of reactions that took place over short and long periods on the global partitioning between particulate and dissolved phases during sorption and desorption and to determine the extent to which these reactions were modified by the salinity.     

More realistic soil cleanup standards with dual-equilibrium desorption

The desorption of contaminants from soils/sediments is one of the most important processes controlling contaminant transport and environmental risks. None of the currently adopted desorption models can accurately quantify desorption at relatively low concentrations; these models often overestimate the desorption and thus the risks of hydrophobic organic chemicals, such as benzene and chlorinated solvents. In reality, desorption is generally found to be biphasic, with two soil-phase compartments. A new dual-equilibrium desorption (DED) model has been developed to account for the biphasic desorption. This model has been tested using a wide range of laboratory and field data and has been used to explain key observations related to underground storage tank plumes. The DED model relates the amount of a chemical sorbed to the aqueous concentration, with simple parameters including octanol-water partition coefficient, solubility, and fractional organic carbon; thus, it is the only biphasic model, to date, that is based on readily available parameters. The DED model can be easily incorporated into standard risk and transport models. According to this model, many regulatory standards of soils and sediments could be increased without increasing the risks.     

Bioremediation of oil-contaminated sediments on an inter-tidal shoreline using a slow-release fertilizer and chitosan

A 95-day field trial on the bioremediation of oil in beach sediment using Osmocote and chitosan was conducted on an inter-tidal foreshore in Singapore. Osmocote was the key factor in enhancing nutrient levels in sediments, the metabolic activity of the indigenous microbial biomass, and the biodegradation of aliphatics and polycyclic aromatic hydrocarbons (PAHs) with ring number of 2 and 3. In contrast, chitosan did not enhance these parameters in the presence of Osmocote. However, the addition of chitosan to Osmocote amended sediments significantly enhanced biodegradation of recalcitrant 4–6-ring PAHs. This is most likely due to the high oil adsorbancy capacity of chitosan, which enhances the bioavailability of high ring number PAHs to the microbial biomass.     

Demonstration of a Microbiologically Enhanced Vertical Ground Water Circulation Well Technology at a Superfund Site

A full-scale ground water circulation well (GCW) system was installed and operated to demonstrate in situ remediation of soil and ground water impacted with a mixture of chlorinated and nonchlorinated organic compounds at a Superfund site in upstate New York. System performance and applicability under site-specific conditions were evaluated based on the system's ability to meet the New York State Department of Environmental Conservation (NYSDEC) cleanup goals for target compounds in ground water and soil. Contaminants from the unsaturated zone were mobilized (volatilized) by one-way vacuum extraction, and treated via enhanced biodegradation (bioventing). In the saturated zone, contaminants were mobilized by soil flushing (solubilized) and treated by a combination of air stripping and biodegradation. An in situ aqueous phase bioreactor, and an ex situ gas phase bioreactor, were integrated into the system to enhance treatment via bioremediation. After 15 months of operation, the mass of target contaminants in soil and ground water combined had been reduced by 75%. Removal by biological mechanisms ranged from 35% to 56% of the total observed mass reduction. The in situ and the ex situ bioreactors mineralized 79% and 76%, respectively, of their target biodegradable contaminant loads. Results indicate that some mass reduction in target contaminants may have been from aerobic and aerobic processes within the circulation cell. Nonchlorinated compounds were relatively easy to mobilize (volatilize, solubilize, and/or transport) and treat when compared to chlorinated compounds. The data collected during the 15-month study indicate that remediation could be accomplished at the Sweden-3 Chapman site using the technology tested.     

Sorption and desorption behavior of residual antidepressants and caffeine in freshwater sediment and sewage sludge

The use of antidepressants is widespread in modern times. Thus, they present a potential risk for ecosystems due to occurrence in domestic sewage containing unaltered metabolites and structures, even after the treatment plants have processed the sewage. The current research investigated the sorption and desorption of antidepressants(citalopram, venlafaxine, fluoxetine, sertraline, and amitriptyline) and caffeine from freshwater sediment and sewage sludge. The samples of freshwater sediment were ...     

The Bioavailability of Dissolved,Particulate, and Adsorbed Organic Carbon in Groundwater Systems

Dissolved organic carbon (DOC) is the smallest amount of organic carbon present in aquifer systems and is typically dwarfed by amounts of particulate organic carbon (POC) and adsorbed organic carbon (AOC). Research conducted over the last half century, however, has shown that these dissolved, particulate, and adsorbed compartments interact dynamically with each other. That suggests the hypothesis that the bioavailability of DOC in groundwater may indicate the bioavailability of the associated POC and AOC compartments as well. If that proves to be the case, it would greatly simplify the process of evaluating the bioavailability of total organic carbon present in groundwater systems. That hypothesis was examined by (1) comparing DOC bioavailability between two aquifers receiving modern atmospheric recharge, but with the recharge passing through POC/AOC sources of substantially different geologic ages, and (2) measuring POC/AOC bioavailability in sediments in from two aquifers before and after injection with bioavailable DOC consisting of dissolved sugars and emulsified vegetable oil. The results of both comparisons are consistent with the hypothesis that DOC bioavailability in groundwater reflects the bioavailability of the associated POC and AOC compartments and vice versa. Thus, DOC bioavailability may be a useful indicator of an aquifer's potential to drive reduction/oxidation processes that affect the chemical quality of groundwater.