Enhanced removal of toluene in heterogeneous aquifers through injecting encapsulated ozone micro-nano bubble water.

Organic contaminants have a tendency to accumulate in low-permeability aquifers, making their removal challenging and creating a bottleneck in groundwater remediation efforts. The use of ozone micro-nano bubbles, due to their smaller size compared to traditional macrobubbles, shows potential for efficient penetration into the low-permeability aquifer and effective oxidization of contaminants. This study conducted batch experiments, column studies, and 2D tank experiments to systematically investigate the remediation efficiency of toluene in a heterogeneous aquifer using ozonated water (OW), ozone micro-bubble water (OMBW), and encapsulated ozone micro-nano bubble water (EOMBW) with rhamnolipid. Experimental results showed that rhamnolipid effectively increased the densities and reduced the sizes of micro-nano bubbles, leading to improved ozone preservation and enhanced toluene degradation. Nanobubbles exhibited higher mobility compared to microbubbles in porous media, while rhamnolipid increased the density of penetrated nanobubbles by 9.6 times. EOMBW demonstrated superior efficiency in oxidizing toluene in low-permeability aquifers, and a numerical model was developed to successfully simulate the ozone and toluene concentration. The model revealed that the increased oxidation rate by EOMBW was attributed to the preservation of ozone in micro-nano bubbles and the enhanced toluene oxidation rate. These findings contribute significantly to the application of EOMBW in heterogeneous aquifer remediation.

Microplastic release and sulfate reduction response in the early stage of a simulated landfill.

Landfills are essential facilities for treating and disposing municipal solid waste. They emit sulfur-containing odors and serve as an important sink for a new type of pollutant called microplastics (MPs). This study focused on the initial stage of anaerobic degradation to establish the relationship between the release of MPs and odor generation. Our findings show the rapid release of MPs into the leachate in the early stage of landfill and their predominant accumulation in the leachate sediment. The circulating leachate contained 1.45 times higher concentrations of MPs than the noncirculating leachate, with a peak concentration of 39 items·L-1. In addition, fragmentation of MPs occurred. The percentage of MPs with particle sizes of 2.5-5 mm decreased from 66.70 % to 22.32 %, while those measuring 0.1-0.5 mm increased by 33.12 %. A positive correlation was observed between MP release and sulfate reduction. Although leachate circulation increased the release of MPs, it also reduced the overall release time and total amount of MPs exported from the landfill. Compared with the initial landfill waste, the leachate operation mode, regardless of circulation, resulted in a 6.15-8.93-fold increase in MP release. These findings provide a valuable foundation for the simultaneous regulation of traditional pollutant odor and new pollutants (MPs) in landfills.

Effect of dissolved organic matter on selective oxidation of toluene by ozone micro-nano bubble water.

The oxidation capacity of ozone micro-nano bubble water (OMBW) was always higher than ozonated water due to enhanced contact by bubble interface, while the effect of coexisted dissolved organic matter (DOM) on the oxidation efficiency was still unclear. In this paper, batch experiments were carried out to investigate the selective oxidation of toluene by both OMBW and ozonated water (OW) with coexisted DOM in water. Five types of background solutions were applied in this study, including humic acid solution, fulvic acid solution and three types of diluted landfill leachates at the same content of total organic carbon. Results showed that coexisted DOM had a greater inhibition effect on toluene oxidation rate by OMBW, and the oxidation rate of toluene by OMBW and OW became close. It was mainly caused by the decreased reaction rate between toluene and hydroxyl radical (kT-OH·) in OMBW after the introduction of DOM, which competed for the adsorption sites on micro-nano bubble interface. The fraction of ozone to oxidize toluene as well as kT-OH· was in positive correlations with SUVA254 and the content of humic acid-like substances, but negatively correlated with E2/E3, content of tryptophan-like proteins and content of fulvic acid-like substances. In addition, increasing the ozone dose was not effective in increasing the utilization rate of ozone in OMBW due to limited adsorption sites on micro-nano bubble interface. The paper was conductive to the application of ozone micro-nano bubble water in groundwater remediation with complex water matrices.

Soil heterogeneity influence on the distribution of heavy metals in soil during acid rain infiltration: Experimental and numerical modeling.

Acid rain is a global environmental problem that mobilizes heavy metals in soils, while the distribution and geochemical fraction of heavy metals during acid rain infiltration in heterogeneous soils are still unclear. In this study, we performed column experiments to investigate the distribution and geochemical fraction of Cu, Pb, Ni and Cd in heterogeneously layered soils during continuous acid rain infiltration. Chloride ion used as a conservative tracer was found to be uniformly distributed during acid rain infiltration, showing insignificant preferential flow effects in the column. In contrast, however, the distribution of heavy metals was highly non-uniform, especially in the silty soil at the lower part of the column, indicating a heterogeneous distribution of adsorption capacity. In addition, in the control experiments with neutral rain infiltration, uniform distribution of heavy metals was observed, indicating that the heterogeneous distribution of adsorption coefficient during acid rain infiltration was mainly caused by different pH buffering capacities. A numerical model considering water flow and solute transport was developed, where the average water-solid distribution coefficient (Kd) in Layer 2 was only 1.5-12.5% of that in Layer 1 during acid rain infiltration. The model could predict the variation of heavy metal concentrations in soil with the majority of error less than 35%, confirming that different Kd induced the heterogeneous distribution of heavy metals. In addition, the geochemical fraction of heavy metals in the upper coarse sand layer remained stable, while the acid-extractable fractions in the lower loam and silt loam layer gradually increased. Our findings suggest that soil heterogeneity, especially chemical heterogeneity affected by rainfall acidity, has an important influence on the infiltration, migration and geochemical fraction of heavy metals in soils. This study could help guide the risk assessment of heavy metal-contaminated sites that were polluted by acid rain or landfill leachate.

Attachment and detachment of large microplastics in saturated porous media and its influencing factors.

Groundwater contamination by microplastics (MPs) has been gradually regarded as a potential human health risk, which calls for detailed investigation of MPs transport behavior in saturated zone. In this study, a series of sand column experiments were carried out to investigate the transport characteristics of large MPs with its diameter of 10-20 µm in porous media, in which the effects of different hydrological conditions and MPs characteristics were examined. Experimental results showed that the increase of water flow rate from 2.2 to 7.5 mL/min significantly increased the maximal outlet MPs concentration by two orders of magnitude, while a larger ratio of MPs diameter to soil particle diameter decreased its mobility. The increase of water salinity from 0 to 25 mmol/L (NaCl) decreased the maximal outlet MPs concentration by 50.5-68.4% for different sized MPs. Since chemical aging would lead to the formation of oxygen-containing functional groups and make MPs more negatively charged, it greatly increased the maximal outlet MPs concentration by 0.53-5.67 times. Compared with the traditional attachment model (AM), the attachment-detachment model (ADM) could better simulate the gradual desorption of large MPs from soil in the process of clean water flushing, indicating the nonnegligible detachment of large MPs from soil. In ADM, the desorption coefficient gradually decreased in the process of clean water flushing, which was only 31.6% of the initial value after flushing kept for 10 PV. Moreover, the equations to calculate the adsorption and desorption coefficients of MPs in the saturated zone were developed, which considered both MPs and aquifer characteristics. Results from this study described the desorption of large MPs in porous media under various conditions, which expands our knowledge about the fate and risk of MPs in underground environment.

Effect of site hydrological conditions and soil aggregate sizes on the stabilization of heavy metals (Cu, Ni, Pb, Zn) by biochar.

Biochar is a popular material that would effectively immobilize heavy metals in soil, which can greatly decrease the health risk of heavy metals. Although many previous studies have studied the immobilization of heavy metals by biochar, the influence of hydrological conditions on the immobilization effect is still not clear. This paper carried out column experiments to study the effect of fluctuating groundwater table on Cu, Ni, Pb, Zn distribution and speciation with the addition of biochar from pyrolysis of swine manure. Experimental results showed that biochar could significantly decrease the leaching toxicity of Cu and Ni by 24.4% and 44.7% respectively, while the immobilization effect of Pb and Zn was relatively insignificant. The average reduction percentage of bioavailable Cu was 14.5%, 39.5% and 33.3% in the unsaturated zone, fluctuating zone and saturated zone respectively, showing the better immobilization effect in the fluctuating zone and saturated zone. The residual fraction of heavy metals increased significantly after the addition of biochar, and the increase of residual fraction was larger in small soil aggregates. This study helped illustrate the influence of hydrological conditions and soil aggregate sizes on the stabilization effect of heavy metals by biochar, which could be used to guide the remediation process of sites contaminated by heavy metals.

Kinetics and mechanism of haloacetaldehyde formation from the reaction of acetaldehyde and chlorine.

Haloacetaldehydes (HALs) are the third prevalent group of disinfection by-products (DBPs) by weight in drinking water, and their cytotoxicity and genotoxicity are higher than regulated DBPs. In order to understand their formation mechanism during chlorination and ozonation-chlorination, this study examined the reaction kinetics of chloral hydrate (CH), dichloroacetaldehyde (DCA), chloroacetaldehyde (CA) and acetaldehyde by chlorine at different pH values and chlorine doses. The results showed that the reaction rate constants increased with pH and chlorine dose, except that the degradation of CH would not be affected by the presence of free chlorine. At the same pH and chlorine dose, the half-lives of CH, DCA, CA and acetaldehyde were in the order of CH > acetaldehyde â‰« DCA > CA. A kinetic model used to predict the formation of HALs and chloroform during chlorination of acetaldehyde was developed, and the predicted data fitted well with the measured data. As pre-ozonation could oxidize natural organic matter to acetaldehydes, the concentration of acetaldehyde formed after pre-ozonation was used to calculate the HAL yields during ozonation-chlorination by the kinetic model, which fitted the experimental results well. The kinetic model elucidated that the formation mechanism of HALs was a stepwise substitution process on the α-hydrogen of acetaldehyde during chlorination.

Optimization of ozone dosage in an ozone contact tank using a numerical model.

Ozone has been widely applied in drinking water and wastewater treatment plants, and it is essential to determine the ozone dosage and its ratio in ozone contact tank to increase the ozone absorption and utilization rates. Batch experiments were performed to determine the first-order reaction rate coefficient of ozone (k1) in different raw water qualities. Results showed that k1 had an exponential decaying relationship with the ozone consumption amount (ΔO3). Based on the ozone mass transfer and decomposition kinetics, a numerical model was developed to optimize the total ozone dosage and its ratio in three aeration parts by calculating the ozone absorption and utilization rates in an ozone contact tank. The ozone absorption rate was little affected by the water quality, and an even distribution of ozone could greatly increase the ozone absorption rate. However, the ozone utilization rate was tightly related with the water quality. For waters that consumed ozone quickly, ozone should be dosed equally in three aeration parts to increase the ozone utilization rate up to 94.3%. Otherwise, more ozone should be dosed in the first aeration part. An increase in ozone utilization rate would induce an increase in the degree of water purification. This model could give theoretical support for the determination of ozone dosage and its ratio in water treatment plants rather than experience.

A numerical model to optimize LNAPL remediation by multi-phase extraction.

Light non-aqueous phase liquid (LNAPL) contaminated sites pose a risk to human health and the natural environment. Multi-phase extraction (MPE) is one of the most widely used technologies to remediate these sites. Thus, it is important to optimize MPE systems to improve their effectiveness and cost-efficiency. In this study, we developed a numerical model to optimize LNAPL mass removal by MPE, in which the aquifer domain was simplified as a cylinder with a single MPE extraction well located at the center. A dual-pump extraction system was applied to the model, which involved vacuum enhanced recovery to remove volatilized gaseous phase contaminants and a submerged pump to remove NAPL and contaminants in groundwater. After the model was validated with field data, the results showed that the contaminant extraction rate varied with the LNAPL thickness and submerged pump position. For benzene selected as the contaminant of concern, greater LNAPL extraction rates were achieved when the initial LNAPL thickness was large (>1.5 m) or in aquifers of high permeability (>2.45 × 10-10 m2). Importantly, it was discovered that in highly permeable coarse sand and gravel, the submerged pump ought to be placed within the LNAPL layer, whereas the pump should be placed below the water-NAPL interface in fine to medium sand aquifers. It was also found that an optimal liquid pumping rates exist, beyond which contaminant mass removal rates do not increase. Furthermore, it was found that in aquifers contaminated with thin LNAPL layers, mass transfer modelling that assumes equilibrium between the phases may greatly overestimate the accumulated mass of contaminants removed and, therefore, non-equilibrium modelling should be adopted. Finally, a cost analysis was carried out to compare the costs of remediating a contaminated site with MPE and by an alternative chemical oxidation approach. The MPE technology was found to be more cost effective when the initial thickness of LNAPL was relatively thin. In summary, the numerical model developed in this study is a useful tool for optimizing MPE system design.

Mechanism of ozonation enhanced formation of haloacetaldehydes during subsequent chlorination.

Haloacetaldehydes (HAs) are the third prevalent group of disinfection by-products of great health concern. A bench-scale study was performed to investigate the formation and speciation of HAs in raw and treated waters after chlorination and ozonation-chlorination. Pre-ozonation resulted in enhanced HA formation during subsequent chlorination, and the HA yields from ozonation-chlorination were 1.66 and 1.63 times higher than that from chlorination of raw and treated waters. The mechanism about the increase of HA formation during ozonation-chlorination was systematically investigated in this study. The results showed that acetaldehyde formed after ozonation was the dominant precursor for the enhanced HA formation during subsequent chlorination. Increase in pH and chlorine dose increased HA formation during acetaldehyde chlorination. Based on the kinetic studies on the HA formation during acetaldehyde chlorination and the HA stabilities with and without free chlorine, it was found that chlorine was incorporated into the α-hydrogen in acetaldehyde to form a sequence of mono-, di- and tri-chloroacetaldehyde. During this process, these three chlorinated acetaldehydes would also undergo base-catalyzed hydrolysis through decarburization and dehalogenation pathways. This study elucidated that acetaldehyde formed after ozonation resulted in the increase of HA formation during subsequent chlorination. This study also revealed the formation pathway of HA during chlorination of acetaldehyde, which would help to minimize HA formation at drinking water plants.

High stress low-flow (HSLF) sampling: A newly proposed groundwater purge and sampling approach.

Representative groundwater sampling is critical for establishing contaminant distributions, evaluating the effectiveness of remediation operations, monitoring the protection of human health and the environment, and sustainably managing groundwater resources. However, traditional low flow (low stress) or three-well-volume purge well sampling techniques can render high labor costs or high wastewater volumes. Newly developed passive samplers can only deal with limited analytical needs. A new High Stress Low Flow (HSLF) method is proposed involving dual pumping rates, which may significantly reduce purge time and wastewater production, while maintaining analytical needs, thus offering a new tool to promote green and sustainable remediation. A three-dimension numerical model was used to evaluate the potential benefits of the proposed HSLF approach. Compared to low flow sampling and three-well-volume purge methods, it was calculated that HSLF can reduce sampling time by up to 81.0% and 81.3%, respectively, and reduce wastewater production by up to 12.5% and 91.2%, respectively. The improvement achieved was affected by formation characteristics (e.g. hydraulic conductivity) and operation parameters (e.g. pumping rates and drawdown control). Further optimization and field testing is required to recognize the full potential of this newly proposed method.

Pathway fraction of bromate formation during O3 and O3/H2O2 processes in drinking water treatment.

Ozone process has been widely used for drinking water treatment recently. In the oxidation process, bromate is formed by three pathways, i.e., the direct pathway, the direct-indirect pathway and the indirect-direct pathway. This study developed a method to calculate the percentage of these three pathways for bromate formation during O3 process and O3/H2O2 process. Two kinds of water, distilled water containing bromide (DW) and surface water from the Yellow River (SW) were selected as raw rater. The result showed that in natural water systems, the direct-indirect pathway was dominant for bromate formation during the oxidation process. When 3 mg L(-1) O3 was used as the only oxidant, nearly 26% of bromide ion was transferred into bromate in two kinds of water after 80 min. The dominant pathway in DW was the direct pathway (48.5%) and the direct-indirect pathway (46.5%), while that was the direct-indirect pathway (68.9%) in SW. When O3/H2O2 were used as oxidants, as the H2O2 dosage increased, the fractions of bromate formation by direct pathway and direct-indirect pathway decreased, while that by indirect-direct pathway increased. The conversion ratio from bromide to bromate first kept stable or increased, then decreased and reached its minimum when [H2O2]/[O3] ratio was 1.0 in DW and 1.5 in SW. Under this condition the indirect-direct pathway took the largest fraction of 70.7% in DW and 64.0% in SW, respectively.