Field study of TCE diffusion profiles below DNAPL to assess aquitard integrity

An area where a free-product accumulation of trichloroethylene (TCE) dense non-aqueous phase liquid (DNAPL) occurs at the bottom of a 10-m-thick surficial sand aquifer was studied to determine the integrity of the underlying, 20-m-thick, clayey silt aquitard formed of glaciolacustrine sediment. TCE concentration-versus-depth profiles determined from aquitard cores collected at five locations indicated penetration of detectable TCE 2.5 to 3.0 m into the aquitard. Two of the profiles show persistent DNAPL at the aquitard interface, while two others indicate that DNAPL, present initially, was completely dissolved away producing concentration declines at the aquitard interface. The fifth profile suggests shallow DNAPL penetration (<0.5 m) into the aquitard, however, this penetration, which was likely caused by cross-contamination during core collection or cone penetrometry (CPT) of the aquitard interface, did not increase the maximum depth of TCE penetration. Combining the field profiles with one-dimensional model simulations, downward migration of the aqueous TCE front, defined as the EPA MCL of 5 microg/l, which was below the analytical detection limit, was projected to a distance between 4 and 5 m below the top of the aquitard. Using a single set of estimated aquitard parameter values, simulations of aqueous TCE migration into the aquitard provided a good fit to four of the field profiles with a migration time of 35 to 45 years, consistent with the history of TCE use at the site. These simulations indicate aqueous TCE migration is diffusion-dominated with only small advective influence by the downward groundwater velocity of 2 to 3 cm/year or less in the aquitard due to pumping of the underlying aquifer to supply water to the facility in the past 50 years. The applicability of the parameter values was confirmed by in situ diffusion experiments of 1-year duration, in which stainless steel cylinders containing DNAPL were inserted into the aquitard. The diffusion-dominated nature of the profiles indicates that the aquitard provides long-term protection of the underlying aquifer from contamination from this DNAPL zone. Simulations of long-term migration of the TCE solute front indicate breakthrough to the lower aquifer at 1200 years for the no advection scenario and at 500 years if the strong downward hydraulic gradient persists. However, even after breakthrough, the mass flux through the aquitard to the underlying aquifer remains relatively low, and when considered in terms of potential impacts to pumping wells, concentrations are not expected to increase significantly above present-day MCLs. The use of contaminant profiles of different time and distance scales, in addition to hydraulic data, dramatically improves the ability to assess aquitard integrity, and provides improved transport parameter values for estimating contaminant arrival times and fluxes. The apparent lack of deep preferential pathways for TCE migration, such as open fractures, is probably due to the softness of the silty aquitard deposit and minimal physical or chemical weathering of the aquitard provides long-term protection of the underlying aquifer from contamination from this DNAPL zone. Simulations of long-term migration of the TCE solute front indicate breakthrough to the lower aquifer at 1200 years for the no advection scenario and at 500 years if the strong downward hydraulic gradient persists. However, even after the breakthrough, the mass flux through the aquitard to the underlying aquifer remains relatively low, and when considered in terms of potential impacts to pumping wells , concentrations are not expected to increase significantly above present-day MCLs. The use of contaminant profiles of different time and distance scales, in addition to hydraulic data, dramatically improves the ability to assess aquitard integrity, and provides improved transport parameter values for estimating contaminant arrival times and fluxes. The apparent lack of deep preferential pathways for TCE migration, such as open fractures, is probably due to the softness of the silty aquitard deposit and minimal physical or chemical weathering of the aquitard.     

The use of ionic liquids based on choline chloride for metal deposition: A green alternative?

Ionic liquids are studied intensively for different applications. They tend to be denoted as “green solvents”, largely because of their low vapour pressure. In recent years toxicity and biotoxicity of ionic liquids have also been investigated, which proved that not all of these are “green”. In this paper the use of ionic liquids based on choline chloride and ethylene glycol in electrochemistry is discussed in the context of their use as green solvents. Due to their low toxicity and ready biodegradability, these deep eutectic solvents are promising for the electrodeposition of metals. The influence of the use of these liquids as metal deposition baths on the waste water is investigated. Drag-out was found to be the most influencing parameter on the environmental impact of the process, as it is three times higher compared to classical solutions due to the higher viscosity of the ionic liquid. There are no major changes needed in the rinsing configuration of classic electroplating plants, and ion exchange to remove the metal out of the waste water was not hindered by the presence of the ionic liquid. The formation of by-products during the deposition of metals has to be further investigated and evaluated in consideration of the environmental impact.     

Fire accident investigation of an explosion caused by static electricity in a propylene plant

This study investigated a 2010 fire and explosion that occurred at a polypropylene (PP) and copper-clad laminate high-tech plant in Taiwan. Liquid acetone leakage caused the fire and explosion. One person was killed and five were injured; property damage was estimated at US$20 million. In contrast to conventional plants, high-tech plants have sophisticated instrumentation, highly complex pipelines, and confined spaces. In addition, the floor area in a high-tech plant is large and frequently contains a channel through the ground floor to the second or third floor. This channel design enables the fire compartment to be destroyed. Therefore, the system cannot confine the fire to a specific area, thus hindering fire-relief operations. In this study, the original fire outbreak occurred in the PP processing area on the ground floor. The acetone storage tank was located on the third floor. The investigation conducted at the fire site of the situations of the burning (bursting) loss determined that the acetone liquid leaked and dripped from floor cracks and tunnel oven to the PP processing area. Because the PP manufacturing process rapidly generates static electricity, the flammable liquids made contact with the source of ignition, which caused the explosion and fire. Various procedures, such as those involving the operating environment of production, packaging, and processing in a high-tech plant, are likely to produce static electricity in a workplace. Improved electrostatic management can prevent the loss of property and lives, liquid acetone leakage, and loss of equipment caused by static electricity fire.     

In-situ surfactant/surfactant-nutrient mix-enhanced bioremediation of NAPL (fuel)-contaminated sandy soil aquifers

SCOPE AND BACKGROUND: Contamination of soils, aquifers and groundwater by nonaqueous phase liquid (NAPL) pollutants constitutes a major environmental issue of concern, worldwide. The residual (biodegradation-resistant) hydrophobic fuel hydrocarbons entrapped in the soil porous matrix, possess a particular bioremediation challenge due to their becoming virtually immobile, nor desorbable, or water dispersible. Consequently, they are not available as substrates to the micro-organism-based biodegradation. MATERIALS AND METHODS: Our research involves the development of economically feasible, surfactant/surfactant-nutrient mix (SSNM)-enhanced bioremediation methodologies for sustainable, in situ bioremediation of fuel-contaminated aquifers. This requires, methodologically, (a) the optimization, via in vitro 'flow' (columns) lab experiments and screening processes, of an effective mixture for the intended SSNM-enhanced bioremediation; and (b) the study of the combined effect of the optimized SSNM on the solubilization/mobilization and biodegradation of NAPL (fuel) in in vitro site/aquifer-simulated bioremediation. RESULTS AND DISCUSSION: The essence of our findings: (1) kerosene's maximum enhanced mobilization - f = 3.6, compared with that of deionized water, was achieved with an SSNM having the composition of linear alkylbenzene sulfonate (LABS): coco-amphodiacetate (containing N): surfactant-nutrient X (containing both N and P) = 0.15: 0.15: 0.05 g/L, respectively; (2) 62-64% of the initial amount of kerosene in the initially saturated soil matrix, 'packed' in a column, has been eluted from it during approximately 30 days, compared with 68% of kerosene biodegradation in 'vessel' settings, in 21 days. CONCLUSIONS: (1) The indigenous microorganisms present in th vadose zones of fuel-contaminated sandy soil aquifers are potentially capable of unassisted removal of approximately 80% of the initially contained fuel (kerosene), during a period of about 42 days; (2) the major effects of the SSNM addition are (a) enhanced mobilization of the bulky NAPL; and (b) enhanced desorbtion/ solubilization/dispersion of the entrapped NAPL which, in turn, facilitate their enhanced biodegradation. RECOMMENDATIONS AND PERSPECTIVE: Our findings suggest that pre-optimized, biodegradable SSNM is essential for surfactants-based bioremediation of NAPL-contaminated aquifers, in order to make this in-situ methodology both technologically and economically feasible.     

Surfactant dissolution and mobilization of LNAPL contaminants in aquifers

Improper disposal, accidental spills and leaks of non-aqueousphase liquids (NAPL) such as gasoline, fuel oil and creosote result in long-term persistent sources of groundwater pollution.Column and 2-D tanks experiments were conducted to evaluate the use of surfactant-enhanced recovery of light non-aqueous phase liquids (LNAPL) in groundwater aquifers. These experiments focused on the use of surfactants to promote dissolution and mobilization in addition to evaluating the increase of aqueous phase permeability as residual NAPL is recovered. Further experiments are presented that show the innovative use of surfactants during primary pumping to recover free product canpotentially increase the amount of free product recovered, canpotentially reduce the amount of residual NAPL remaining afterprimary pumping and performs better than the use of surfactantsto mobilize trapped residual NAPL.     

Evaluation of thermal properties and process hazard of three ionic liquids through thermodynamic calculations and equilibrium methods

Industrial and new energy applications of ionic liquids (ILs) may have to be used at high temperatures conditions, such as in batteries and fuel applications, which may cause thermal hazards. However, there are few studies on the thermal hazards of ILs. To ensure the thermal safety of ILs processes, three commonly used ILs were selected for analysis: 1-butyl-3-methylimidazolium nitrate ([Bmim]NO₃), 1-butyl-2,3-dimethylimidazolium nitrate ([Bmmim]NO₃), and 1,3-dimethylimidazolium nitrate ([Mmim]NO₃). The process hazards under adiabatic conditions demonstrated that [Bmmim]NO₃ and [Mmim]NO₃ have extensive explosion hazards. The self-reaction characteristics determined by the isothermal test indicated that the ILs are nth reactions, and the thermal decomposition features were also determined by thermogravimetric analysis. The data were obtained with a nonlinear thermodynamic model and used to establish the basic thermal hazards of the three ILs. In addition, based on the thermal equilibrium theory, the critical safety parameters can be inferred. The effects of heat transfer in 25.0 g and 50.0 g containers were discussed. The results show that [Mmim]NO₃ will produce a thermal runaway reaction at a lower temperature (<100 °C) and has the shortest reaction time (<1 day), which means [Mmim]NO₃ is considered to be the most hazardous material among the three ILs studied.     

Droplets behaviors of flashing jet in accidental release of superheated liquid

Structural failure of an industrial superheated liquid tank or pipe usually results in the flashing jet consisting of a mixture of massive droplets and vapor due to the violent phase transition. In this work, experiments on small-scale releases were carried out with a 20 L storage tank to investigate the droplets behaviors of flashing jets after accidental releases of superheated liquid. Distribution of droplets axial, radial and vertical velocities, as well as droplets diameter along the centreline of flashing jet, were acquired employing a Phase Doppler Anemometry (PDA). The influence of storage pressure, superheat, and nozzle diameter was also studied. Results show that the distribution of actual droplets with different velocities and diameters follows the normal distribution. Droplets mean three-dimensional velocities on the central axis of flashing jet decrease exponentially with the increase of axial distance. The droplets mean diameter first decreases exponentially and finally keeps sable at about 10 μm. Among three-dimensional velocities, the axial velocity is the highest and the vertical velocity is the lowest. Droplets mean three-dimensional velocities increase with the increase of storage pressure, superheat, and nozzle diameter. The droplets mean diameter decreases with the increase of superheat and nozzle diameter but increases with the increase of storage pressure.     

Expression alterations of cytochromes P4501A1, 2E1, and 3A,and their receptors AhR and PXR caused by 1-octyl-3-methylimidazolium chloride in mouse mammary carcinoma cells

Cytochrome P450s (CYPs) play a key role in the metabolism of a wide range of environmental xenobiotics and endogenous compounds. The expression and activity levels of CYPs can be elevated by a process of induction involving the activation of nuclear receptors. The effects of the ionic liquid 1-octyl-3-methylimidazolium chloride ([C₈mim][Cl]) on the expression of cytochrome P450 members, including CYP1A1, CYP2E1, and CYP3A, as well as on aryl hydrocarbon receptor (AhR) and pregnane X receptor (PXR) in mouse mammary carcinoma cells (EMT6) were investigated by using quantitative real-time PCR in the present study. The results reveal that [C₈mim][Cl]-exposure up-regulates the expressions of CYP1A1, CYP2E1, and CYP3A at mRNA level, suggesting that imidazolium-based ionic liquids can activate CYPs. Our results also suggest that [C₈mim][Cl]-mediated CYP3A induction be PXR-dependent. This result may be beneficial to evaluating the environmental toxicity of imidazolium-based ionic liquids and investigating the metabolism of imidazolium-derivative drugs.     

负载咪唑型离子液体硅胶吸附材料制备及应用研究

制备了3种取代咪唑键合的硅胶负载型离子液体(甲基咪唑-SIL、氨丙基咪唑-SIL及十二烷基咪唑-SIL),比较了其对水中双酚A(BPA)的吸附能力。在该研究的实验条件下,BPA在十二烷基咪唑-SIL与水溶液之间的分配系数K_d值高达(2.58±0.02)×10³ L/kg,氨丙基咪唑-SIL、甲基咪唑-SIL的K_d值也分别达到(2.26±0.28)×10、(2.71±0.16)×10 L/kg。采用甲醇为洗脱液,可以对十二烷基咪唑-SIL相中的BPA进行有效回收,2次洗脱的合并回收率为106.7%±4.8%。以十二烷基咪唑-SIL作为被动采样装置的接收相,对污水处理厂出水中BPA进行了被动采样监测应用的微宇宙实验研究。结果表明,在实验周期内,十二烷基咪唑-SIL被动采样器对水体中BPA的被动采集呈线性,其采集速率为0.33 L/d,与以HLB为接收相的商品化被动采样器接近,并且同HLB固相萃取填料相比,离子液体接收相对BPA的采集更具选择性,基质效应较小,可作为被动采样监测装置的理想接收相材料。     

Dense Nonaqueous Phase Liquid Tracer Tests: Experimental Results

Two dense nonaqueous phase liquid (DNAPL) tracer tests werecarried out in a shallow aquifer north of Fort Worth, TX. i-Propanolwas used as the nonpartitioning tracer; n-hexanol and n-octanol werethe partitioning tracers. Field data, mathematical modeling, theresults of column tests, and field tracer tests with NaCl were usedin designing the DNAPL tracer tests. The results indicated the presenceof DNAPL at both sites tested; semi-quantitative estimates of theamounts of DNAPL present were obtained by mathematical modeling.Interpretation was complicated by heterogeneity of the aquifer andmass transport effects.