Nanobubbles improve peroxymonosulfate-based advanced oxidation: High efficiency, low toxicity/cost, and novel collaborative mechanism.

Cl- activated peroxymonosulfate (PMS) oxidation technology can effectively degrade pollutants, but the generation of chlorinated disinfection byproducts (DBPs) limits the application of this technology in water treatment. In this study, a method of nanobubbles (NBs) synergistic Cl-/PMS system was designed to try to improve this technology. The results showed the synergistic effects of NBs/Cl-/PMS were significant and universal while its upgrade rate was from 12.89% to 34.97%. Moreover, the synergistic effects can be further improved by increasing the concentration and Zeta potential of NBs. The main synergistic effects of NBs/Cl-/PMS system were due to the electrostatic attraction of negatively charged NBs to Na+ from NaCl, K+ from PMS, and H+ from phenol, which acted as a "bridge" between Cl- and HSO5- as well as phenol and Cl-/HSO5-, increasing active substance concentration. In addition, the addition of NBs completely changed the oxidation system of Cl-/PMS from one that increases environmental toxicity to one that reduces it. The reason was that the electrostatic attraction of NBs changed the active sites and degradation pathway of phenol, greatly reducing the production of highly toxic DBPs. This study developed a novel environmentally friendly oxidation technology, which provides an effective strategy to reduce the generation of DBPs in the Cl-/PMS system.

Unlocking the power of activated carbon-mediated peracetic acid activation for efficient antibiotics abatement in groundwater: Coupling the processes of electron transfer, radical production, and adsorption.

The activation of peracetic acid (PAA) by activated carbon (AC) is a promising approach for reducing micropollutants in groundwater. However, to harness the PAA/AC system's potential and achieve sustainable and low-impact groundwater remediation, it is crucial to quantify the individual contributions of active species. In this study, we developed a combined degradation kinetic and adsorption mass transfer model to elucidate the roles of free radicals, electron transfer processes (ETP), and adsorption on the degradation of antibiotics by PAA in groundwater. Our findings reveal that ETP predominantly facilitated the activation of PAA by modified activated carbon (AC600), contributing to ∼61% of the overall degradation of sulfamethoxazole (SMX). The carbonyl group (CO) on the surface of AC600 was identified as a probable site for the ETP. Free radicals contributed to ∼39% of the degradation, while adsorption was negligible. Thermodynamic and activation energy analyses indicate that the degradation of SMX within the PAA/AC600 system requires a relatively low energy input (27.66 kJ/mol), which is within the lower range of various heterogeneous Fenton-like reactions, thus making it easily achievable. These novel insights enhance our understanding of the AC600-mediated PAA activation mechanism and lay the groundwork for developing efficient and sustainable technologies for mitigating groundwater pollution. ENVIRONMENTAL IMPLICATION: The antibiotics in groundwater raises alarming environmental concerns. As groundwater serves as a primary source of drinking water for nearly half the global population, the development of eco-friendly technologies for antibiotic-contaminated groundwater remediation becomes imperative. The innovative PAA/AC600 system demonstrates significant efficacy in degrading micropollutants, particularly sulfonamide antibiotics. By integrating degradation kinetics and adsorption mass transfer models, this study sheds light on the intricate mechanisms involved, emphasizing the potential of carbon materials as sustainable tools in the ongoing battle for clean and safe groundwater.

A novel mycelial pellet applied to remove polycyclic aromatic hydrocarbons: High adsorption performance & its mechanisms.

Mycelial pellets formed by Penicillium thomii ZJJ were applied as efficient biosorbents for the removal of polycyclic aromatic hydrocarbons (PAHs), which are a type of ubiquitous harmful hydrophobic pollutants. The live mycelial pellets were able to remove 93.48 % of pyrene at a concentration of 100 mg/L within 48 h, demonstrating a maximum adsorption capacity of 285.63 mg/g. Meanwhile, the heat-killed one also achieved a removal rate of 65.01 %. Among the six typical PAHs (pyrene, phenanthrene, fluorene, anthracene, fluoranthene, benzo[a]pyrene), the mycelial pellets preferentially adsorbed the high molecular weight PAHs, which also have higher toxicity, resulting in higher removal efficiency. The experimental results showed that the biosorption of mycelial pellets was mainly a spontaneous physical adsorption process that occurred as a monolayer on a homogeneous surface, with mass transfer being the key rate-limiting step. The main adsorption sites on the surface of mycelia were carboxyl and N-containing groups. Extracellular polymeric substances (EPS) produced by mycelial pellets could enhance adsorption, and its coupling with dead mycelia could achieve basically the same removal effect to that of living one. It can be concluded that biosorption by mycelial pellets occurred due to the influence of electrostatic and hydrophobic interactions, consisting of five steps. Furthermore, the potential applicability of mycelial pellets has been investigated considering diverse factors. The mycelia showed high environmental tolerance, which could effectively remove pyrene across a wide range of pH and salt concentration. And pellets diameters and humic acid concentration had a significant effect on microbial adsorption effect. Based on a cost-effectiveness analysis, mycelium pellets were found to be a low-cost adsorbent. The research outcomes facilitate a thorough comprehension of the adsorption process of pyrene by mycelial pellets and their relevant applications, proposing a cost-effective method without potential environmental issues (heat-killed mycelial pellets plus EPS) to removal PAHs.

Comprehensive evaluation of antibiotics pollution the Yangtze River basin, China: Emission, multimedia fate and risk assessment.

Antibiotics have attracted global attention because of their potential ecological and health risks. The emission, multimedia fate and risk of 18 selected antibiotics in the entire Yangtze River basin were evaluated by using a level Ⅳ fugacity model. High antibiotic emissions were found in the middle and lower reaches of the Yangtze River basin. The total antibiotic emissions in the Yangtze River basin exceeded 1600 tons per year between 2013 and 2021. The spatial distribution of antibiotics concentration was the upper Yangtze River > middle Yangtze River > lower Yangtze River, which is positively correlated with animal husbandry size in the basin. Temperature and precipitation increases may decrease the antibiotic concentrations in the environment. Transfer fluxes showed that source emission inputs, advection processes, and degradation fluxes contributed more to the total input and output. High ecological risks in the water environment were found in 2018, 2019, 2020, and 2021. The comprehensive health risk assessment through drinking water and fish consumption routes showed that a small part of the Yangtze River basin is at medium risk, and children have a relatively high degree of health risk. This study provides a scientific basis for the pollution control of antibiotics at the basin scale.

Targeted degradation of naphthalene by peroxymonosulfate activation using molecularly imprinted biochar.

Polycyclic aromatic hydrocarbons (PAHs) in aquatic environments are threatening ecosystems and human health. In this work, an effective and environmentally friendly catalyst based on biochar and molecular imprinting technology (MIT) was developed for the targeted degradation of PAHs by activating peroxymonosulfate. The results show that the adsorption amount of naphthalene (NAP) by molecularly imprinted biochar (MIP@BC) can reach 82% of the equilibrium adsorption capacity within 5 min, and it had well targeted adsorption for NAP in the solution mixture of NAP, QL and SMX. According to the comparison between the removal rates of NAP and QL by MIP@BC/PMS or BC/PMS system in respective pure solutions or mixed solutions, the MIP@BC/PMS system can better resist the interference of competing pollutants (i.e., QL) compared to the BC/PMS system; that is, MIP@BC had a good ability to selectively degrade NAP. Besides, the removal rate of NAP by MIP@BC/PMS gradually decreased as pH increased. The addition of Cl- greatly promoted the targeted removal of NAP in the MIP@BC/PMS system, while HCO3- and CO32- both had an inhibitory effect. Furthermore, SO4•-, O2•- and 1O2 produced by BC activating PMS dominated the NAP degradation, and it was inferred that the vacated imprinted cavities after NAP degradation can continue to selectively adsorb NAP and this could facilitate the reusability of the material. This study can promote the research on the targeted degradation of PAHs through the synergism of biochar/PMS advanced oxidation processes and MIT.

Resource utilization of rice straw to prepare biochar as peroxymonosulfate activator for naphthalene removal: Performances, mechanisms, environmental impact and applicability in groundwater.

Herein, biochar was prepared using rice straw, and it served as the peroxymonosulfate (PMS) activator to degrade naphthalene (NAP). The results showed that pyrolysis temperature has played an important role in regulating biochar structure and properties. The biochar prepared at 900°C (BC900) had the best activation capacity and could remove NAP in a wide range of initial pH (5-11). In the system of BC900/PMS, multi-reactive species were produced, in which 1O2 and electron transfer mainly contributed to NAP degradation. In addition, the interference of complex groundwater components on the NAP removal rate must get attention. Cl- had a significant promotional effect but risked the formation of chlorinated disinfection by-products. HCO3-, CO32-, and humic acid (HA) had an inhibitory effect; surfactants had compatibility problems with the BC900/PMS system, which could lead to unproductive consumption of PMS. Significantly, the BC900/PMS system showed satisfactory remediation performance in spiked natural groundwater and soil, and it could solve the problem of persistent groundwater contamination caused by NAP desorption from the soil. Besides, the degradation pathway of NAP was proposed, and the BC900/PMS system could degrade NAP into low or nontoxic products. These suggest that the BC900/PMS system has promising applications in in-situ groundwater remediation.

Effects of functional group loss on biochar activated persulfate in-situ remediation of phenol pollution in groundwater and its countermeasures.

Biochar is considered a good activator for use in advanced oxidation technology. However, dissolved solids (DS) released from biochar cause unstable activation efficiency. Biochar prepared from saccharification residue of barley straw (BC-SR) had less DS than that prepared directly from barley straw (BC-O). Moreover, BC-SR had a higher C content, degree of aromatization, and electrical conductivity than BC-O. Although the effects of BC-O and BC-SR on activation of Persulfate (PS) to remove phenol were similar, the activation effect of DS from BC-O was 73% higher than that of DS from BC-SR. Moreover, the activation effect of DS was shown to originate from its functional groups. Importantly, BC-SR had higher activation stability than BC-O owing to the stable graphitized carbon structure of BC-SR. Identification of reactive oxygen species showed that SO4•-, •OH, and 1O2 were all effective in degradation by BC-SR/PS and BC-O/PS systems, but their relative contributions differed. Furthermore, BC-SR as an activator showed high anti-interference ability in the complex groundwater matrix, indicating it has practical application value. Overall, this study provides novel insight that can facilitate the design and optimization of a green, economical, stable, and efficient biochar-activated PS for groundwater organic pollution remediation.

Kinetics of Hydroxyl Radical Production from Oxygenation of Reduced Iron Minerals and Their Reactivity with Trichloroethene: Effects of Iron Amounts, Iron Species, and Sulfate Reducing Bacteria.

Reactive oxygen species generated during the oxygenation of different ferrous species have been documented at groundwater field sites, but their effect on pollutant destruction remains an open question. To address this knowledge gap, a kinetic model was developed to probe mechanisms of •OH production and reactivity with trichloroethene (TCE) and competing species in the presence of reduced iron minerals (RIM) and oxygen in batch experiments. RIM slurries were formed by combining different amounts of Fe(II) and sulfide (with Fe(II):S ratios from 1:1 to 50:1) or Fe(II) and sulfate with sulfate reducing bacteria (SRB) added. Extents of TCE oxidation and •OH production were both greater with RIM prepared under more reducing conditions (more added Fe(II)) and then amended with O2. Kinetic rate constants from modeling indicate that •OH production from free Fe(II) dominates •OH production from solid Fe(II) and that TCE competes for •OH with Fe(II) and organic matter (OM). Competition with OM only occurs in experiments with SRB, which include cells and their exudates. Experimental results indicate that cells and/or exudates also provide electron equivalents to reform Fe(II) from oxidized RIM. Our work provides new insights into mechanisms and environmental significance of TCE oxidation by •OH produced from oxygenation of RIM. However, further work is necessary to confirm the relative importance of reaction pathways identified here and to probe potentially unaccounted for mechanisms that affect abiotic TCE oxidation in natural systems.

Modeling EDTA-facilitated cadmium migration in high- and low-permeability systems using MODFLOW and RT3D.

Cadmium (Cd) has impacted groundwater resources and can pose a serious threat to human health and the environment. Its fate in groundwater is complex and challenging to predict, as it is affected by adsorption to sediments, complexation with aqueous phase ligands, and variations in hydraulic conductivity. In this study, a 2D reactive transport model based on MODFLOW and RT3D is used to simulate published experimental results of cadmium migration without and with EDTA present in a flow cell containing high- and low-permeability zones (i.e., HPZs and LPZs). The model is then extended to conceptual flow cells with more complex LPZ configurations. Simulation results generally match the experimental data well, and analysis of experimental and simulated Cd effluent concentration profiles shows that EDTA enhances Cd removal from LPZs relative to water alone. Simulation results indicate that faster Cd removal is due to EDTA complexation with adsorbed Cd in LPZs, which enhances its solubilization and subsequent back diffusion. Lastly, simulation results show that with increasing LPZ heterogeneity more Cd is retained in flow cells, and EDTA is more effective in enhancing Cd removal relative to water alone; these results are attributed to more LPZ-HPZ interfaces that enhance Cd mass transfer into LPZs during contamination, and enhance EDTA mass transfer into LPZs to promote cleanup. Overall, the results highlight the promise of using EDTA to remove Cd from heterogeneous sites, but caution is advised due to model simplicity and lack of consideration of changes in solution pH, redox potential, or competing cations.

Synthesis and Surface Properties of Photoresponsive Gemini Surfactants: Implication for Remediating PAHs-Contaminated Groundwater.

The efficient utility of surfactants remains a daunting task for groundwater remediation. In this study, we have synthesized a conventional photoresponsive surfactant 4-[4-[(4-butylphenyl)azo]phenoxy]butyldimethylethylammonium bromide (AzoPB) and a gemini photoresponsive surfactant N1,N2-bis[4-[4-[(4-butylphenyl)azo]phenoxy]butyl]-N1,N2-tetramethylethane-1,2-diammonium bromide (AzoPBT) for solubilizing PAHs in groundwater. The two surfactants' photosensitivity, surface properties, and solubilization/release ability for phenanthrene (Phe) and acenaphthylene (Ace) were studied in detail. Under UV-light irradiation for 15-20 s, the two surfactants can be converted from trans to cis, while cis-to-trans isomerization can be achieved under visible-light irradiation for 1 min. Compared to AzoPB, AzoPBT exhibited strong surface properties such as lower critical micelle concentration (0.52 mM), surface tension (γ, 28.94 mN·m-1), minimum area (Amin, 1.72 × 10-8 nm2), and higher maximum adsorption (Γmax, 96.55 mol·m-2). The solubility of Phe and Ace in the AzoPBT aqueous solution (12.84 and 14.27 mg/L) was much higher than that in the AzoPB aqueous solution (7.51 and 8.77 mg/L) and gradually increased as the surfactant concentration increased in both aqueous solutions. Compared to AzoPB, gemini surfactant AzoPBT exhibited stronger solubilization ability. After four cycles of cis-trans isomerization conversion, AzoPBT could still reduce the hydrophobicity of Phe in natural groundwater, although the solubility of Phe decreased slightly. Additionally, the release capacity of AzoPBT was significantly higher than that of AzoPB during the cyclic solubilization-release process. The results indicated that gemini photoresponsive surfactants should be preferable to conventional photoresponsive surfactants for groundwater remediation due to their higher solubilization and release efficiency for Phe in the cyclic solubilization and release process, which can improve repair efficiency, minimize secondary pollution, and reduce remediation costs.

Oxidation of sulfamethazine by peracetic acid activated with biochar: Reactive oxygen species contribution and toxicity change.

Peracetic acid (PAA) as an emerging oxidative has been concerned increasingly due to its high oxidation capacity and low byproducts formation potential. This study was to investigate the oxidation of sulfamethazine (SMZ) by PAA activated with activated biochar (ABC) after thermal modification. The results demonstrated that PAA could be effectively activated by ABC to degrade SMZ in a wide pH range (3-9), which followed the pseudo-second-order kinetics (R2 > 0.99). Both non-radicals (singlet oxygen) and free radicals (alkoxy radicals, hydroxyl radicals) existed in the ABC/PAA system, and the degradation of SMZ was dominated by singlet oxygen. Humic acid (HA), SO42- and HCO3- slightly inhibited the degradation of SMZ in the ABC/PAA process, while Cl- and Br- promoted the degradation of SMZ. The cleavage of S-N, S-C bond, and SO2 extraction reaction rearrangement was the main oxidation process of SMZ. Meanwhile, the results of the ECOSAR program showed that the acute toxicity of most by-products was significantly reduced compared to SMZ, which revealed the potential applicability of the ABC/PAA process in the treatment of antibiotics pollution and their detoxification.

Simulation and risk assessment of typical antibiotics in the multi-media environment of the Yangtze River Estuary under tidal effect.

Frequent human activities in estuary areas lead to the release of a large number of antibiotics, which poses a great threat to human health. However, there are very limited studies about the influence of the special natural phenomena on the occurrence and migration of antibiotics in the environment. In this study, we simulated the migration and transformation of six typical antibiotics, including oxytetracycline (OTC), tetracycline (TC), norfloxacin (NOR), ofloxacin (OFX), erythromycin (ETM), and amoxicillin (AMOX), in the environmental media from 2011 to 2019 in the Yangtze River Estuary, by using the level III multi-media fugacity model combined with the factor of tides. The simulation results showed that the most antibiotics mainly existed in soil and sediment while erythromycin were found mainly in water. The concentrations of antibiotics in air, freshwater, seawater, groundwater, sediment, and soil were 10-23-10-25, 0.1-12 ng/L, 0.02-7 ng/L, 0.02-16 ng/L, 0.1-13 ng/g, and 0.1-15 ng/g respectively. Sensitivity analysis showed that the degradation rate (Km) and the soil-to-water runoff coefficient (Kl) were important model parameters, indicating that hydrodynamic conditions had a significant impact on the migration of antibiotics in various environmental phases in estuarine areas. Tide can enhance the exchange between water bodies and cause the transformation of the antibiotics from freshwater to seawater and groundwater, which improved the accuracy of the model, especially the seawater and soil phase. Risk assessments showed that amoxicillin, erythromycin, ofloxacin, and norfloxacin posed a threat to the estuarine environment, but the current source of drinking water did not affect human health. Our findings suggested that, when one would like to exam the occurrence and migration of antibiotics in environment, more consideration should be given to the natural phenomena, in addition to human activities and the nature of antibiotics.

Mechanisms and product toxicity of activated carbon/peracetic acid for degradation of sulfamethoxazole: implications for groundwater remediation.

Carbon-based materials activated peracetic acid (PAA) to repair groundwater is an environmentally friendly and low-cost technology to overcome secondary pollution problems. In this study, thermally modified activated carbon (AC600) was applied to activate PAA to degrade sulfamethoxazole (SMX). And the effect of groundwater pH, chloride ion (Cl-), bicarbonate (HCO3-), sulfate ion (SO42-), and natural organic matter (NOM) on SMX removal by AC600/PAA process was studied in detail. PAA could be effectively activated by AC600. Increasing AC600 dose (10-100mg/L) or PAA dosages (0.065-0.39 mM) generally enhanced the SMX removal, the excellent performance in SMX removal was achieved at 50 mg/L AC600 and 0.26 mM PAA. The removal of SMX was well-described by second-order kinetic, with the rate constant (kobs) of 10.79 M-1s-1, both much greater than the removal constants of PAA alone (0.034 M-1s-1) and AC600 alone (1.774 M-1s-1). R-O·(CH3C(O)OO·, CH3C(O)O·) and electron-transfer process were proved to be responsible for the removal of SMX while HO· and 1O2 made little to no contribution to the novel PAA/AC600 system, which differs from typical advanced oxidation processes. The SMX can be removed effectively over a wide pH range (3-9), exhibiting a remarkable pH-tolerant performance. Sulfate ion (SO42-), dissolved oxygen (DO), NOM displayed negligible influence on the SMX removal. Bicarbonate (HCO3-) exerted an inhibitory effect on SMX abatement, while chloride ion (Cl-) promoted the removal of SMX. This showed excellent anti-interference capacity and satisfactory decontamination performance under actual groundwater conditions. Furthermore, the degradation pathways of SMX were proposed, there was no obvious difference in the acute toxicity of the mixed products during the degradation process. It will facilitate further research of metal-free catalyst/PAA system as a new strategy for groundwater in-situ remediation technology.

Heavy metal transport driven by seawater-freshwater interface dynamics: The role of colloid mobilization and aquifer pore structure change.

Co-transport of colloidal substances and pollutants is a pivotal link that significantly affects the environment of coastal groundwater. The effect of colloid mobilization and aquifer pore structure change on heavy metal transport driven by seawater-freshwater interface dynamics is not fully understood. In this study, packed column experiments were conducted to model the seawater intrusion (SWI) and freshwater replenishment (FWR) processes using a sampled medium from a coastal sandy aquifer. Hydrodynamic, hydrochemical variables, and heavy metal (Pb, Cu, Cd) transport during the propagation of the seawater-freshwater interface were tested and analyzed. During the SWI stage, cation exchange induced heavy metal liberations, and it developed peak concentrations synchronized with the seawater-freshwater interface at the pore volume of 1.00. The colloid-facilitated transport for heavy metals was the predominant mechanism in the FWR stage, characterized by a peak release lagging the interface propagation by approximately 0.5 pore volumes. Because the colloidal fraction was mobilized during aquifer desalination, it lagged behind the decline of the salinity gradient. Furthermore, Derjaguin-Landau-Verwey-Overbeek (DLVO) calculations explained that the replenishment decreased the depth of the secondary energy minimum of the colloids; meanwhile, the thickness of the electrical double layer increased from 0.63 nm to 10.14 nm, resulting in a repulsive energy barrier up to 3,213 kT. The transport of colloids led to a reduction in porosity from 18.16% to 2.28% of the total immobile domain. At these times, the dimension of the transported colloids evolved, showing a size-selective transport and therefore regulating the total emission fluxes of the heavy metals. These mechanisms were proposed to be incorporated in colloid filtration theory for targeting the coastal scenario.

Transport of TiO2 and CeO2 nanoparticles in saturated porous media in the presence of surfactants with environmentally relevant concentrations.

Nanomaterials are threatening the environment and human health, but there has been little discussion about the stability and mobility of nanoparticles (NPs) in saturated porous media at environmentally relevant concentrations of surfactants, which is a knowledge gap in exploring the fate of engineered NPs in groundwater. Therefore, the influences of the anionic surfactant (sodium dodecylbenzene sulfonate, SDBS), the cationic surfactant (cetyltrimethylammonium bromide, CTAB), and the nonionic surfactant (Tween-80) with environmentally relevant concentrations of 0, 5, 10, and 20 mg/L on nano-TiO2 (nTiO2, negatively charged) and nano-CeO2 (nCeO2, positively charged) transport through saturated porous media were examined by column experiments. On the whole, with increasing SDBS concentration from 0 to 20 mg/L, the concentration peak of nTiO2 and nCeO2 in effluents increased by approximately 0.2 and 0.3 (dimensionless concentration, C/C0), respectively, because of enhanced stability and reduced aggregate size resulting from enhanced electrostatic and steric repulsions. By contrast, the transportability of NPs significantly decreased with increasing CTAB concentration due to the attachment of positive charges, which was opposite to the charge on the medium surface and facilitated the NP deposition. On the other hand, the addition of Tween-80 had no significant influence on the stability and mobility of nTiO2 and nCeO2. The results were also demonstrated by the colloid filtration theory (CFT) modeling and the Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction calculations; it might promote the assessment and remediation of NP pollution in subsurface environments.

Multimedia fate model and risk assessment of typical antibiotics in the integrated demonstration zone of the Yangtze River Delta, China.

Due to the widespread consumption of antibiotics by humans and animals, antibiotic residues from human and animal excrements are released into the environment through domestic sewage and breeding wastewater, which ultimately affect the ecological environment and human health. In this study, the concentrations of 10 antibiotics in the air, water, soil, and sediment from 2013 to 2019 in Qingpu District of the integrated demonstration zone of the Yangtze River Delta were predicated by developing a dynamic Level IV fugacity model. The influence of seasonal environmental factors (e.g., temperature, rainfall) on the distribution and migration of antibiotics in multi-media was also explored. The simulation results show that the 10 antibiotics mainly existed in water and sediment. The concentrations of antibiotics in air, water, soil, and sediment were 0-7.629 × 10-14 ng/L, 1.187 × 10-10-16.793 ng/L, 1.042 × 10-14-3.500 × 10-11 ng/g and 8.015 × 10-12-14.188 ng/g, respectively. It was also found that the increase in temperature and rainfall can reduce the migration rate of some antibiotics into the water and sediment phases. The flux analysis of the cross-media migration and transformation of antibiotics in Qingpu District shows that advection was the prime input and output paths of antibiotics in the water. Moreover, the prime input and output paths of antibiotics in sediment were sedimentation from water to sediment and degradation. Sensitivity analysis shows that the characteristics of antibiotic emission, degradation rate, and Koc were the most influential parameters for target chemicals. The results of risk assessment based on Monte Carlo method reveal that the overall risk level of antibiotics in sediment was relatively risk-free, and the risk of antibiotics in water decreased in the order of tetracyclines > ß-lactams > fluoroquinolones > macrolides > sulfonamides.

Review on the contamination and remediation of polycyclic aromatic hydrocarbons (PAHs) in coastal soil and sediments.

The rapid economic and population growth in coastal areas is causing increasingly serious polycyclic aromatic hydrocarbons (PAHs) pollution in these regions. This review compared the PAHs pollution characteristics of different coastal areas, including industrial zones, commercial ports, touristic cities, aquacultural & agricultural areas, oil & gas exploitation areas and megacities. Currently there are various treatment methods to remediate soils and sediments contaminated with PAHs. However, it is necessary to provide a comprehensive overview of all the available remediation technologies up to date, so appropriate technologies can be selected to remediate PAHs pollution. In view of that, we analyzed the characteristics of the remediation mechanism, summarized the remediation methods for soil or sediments in coastal areas, which were physical repair, chemical oxidation, bioremediation and integrated approaches. Besides, this review also reported the development of new multi-functional green and sustainable systems, namely, micro-nano bubble (MNB), biochar, reversible surfactants and peracetic acid. While physical repair, expensive but efficient, was regarded as a suitable method for the PAHs remediation in coastal areas because of land shortage, integrated approaches would produce better results. The ultimate aim of the review was to ensure the successful restructuring of PAHs contaminated soil and sediments in coastal areas. Due to the environment heterogeneity, PAHs pollution in coastal areas remains as a daunting challenge. Therefore, new and suitable technologies are still needed to address the environmental issue.

Human health risk assessment of selected pharmaceuticals in the five major river basins, China.

Pharmaceuticals in aquatic environment have raised wide attention in recent years due to their potential adverse effects and bioaccumulation in biota. China has been a major producer and consumer of pharmaceuticals, however, the potential human health risk of these chemicals is yet to be determined in China. In this study, we evaluated available exposure data for twenty pharmaceuticals in surface waters from Chinese five major river basins (the Yangtze, Haihe, Pearl, Songliao, and Yellow River Basins), and human health risk assessment was performed. Based on the concentration data and risk data, we conducted research on the source, cause, and control measures of the pharmaceuticals. The twenty pharmaceuticals were found to be ubiquitous in China with median concentrations between 0.09 and 304 ng/L. The estimated daily intake of pharmaceuticals from drinking water and eating fish was calculated. The intake via drinking water was significantly lower than that via eating fish. The risk quotients via water intake and fish consumption ranged from 0 to 17.2, with estrogen and sulfapyridine highest among the twenty pharmaceuticals. High risks of exposure were mainly in North China, including the Haihe and Songliao River Basins. This is the first analysis in Chinese major river basins that has filled the gaps in the research on the human health risks of pharmaceuticals. The results of the study provide basic information of pharmaceutical intake from drinking water and eating fish in China and provide insights into the risk management guidance of pharmaceuticals, and will facilitate the optimization of health advisories and policy making.

Contaminant occurrence and migration between high- and low-permeability zones in groundwater systems: A review.

In recent decades, water quality problems that impact human health, especially groundwater pollution, have been intensely studied, and this has contributed to new ideas and policies around the world such as Low Impact Development (LID) and Superfund legislation. The fundamental to many of these problems is pollutant occurrence and migration in saturated porous media, especially in groundwater. Such environments often contain contrasting zones of high and low permeability with significant differences in hydraulic conductivity (~10-4 and 10-8 m/s, respectively). High-permeability zones (HPZs) represent the primary pathways for pollutant transport in groundwater, while low-permeability zones (LPZs) are often diffusion dominated and serve as both sinks and sources (i.e., via back-diffusion) of pollutants over many decades. In this review, concepts and mechanisms of solute source depletion, contaminant accumulation, and back-diffusion in high- and low-permeability systems are presented, and new insights gained from both experimental and numerical studies are analyzed and summarized. We find that effluent monitoring and novel image analysis techniques have been adroitly used to investigate temporal and spatial evolutions of contaminant concentration; simultaneously, mathematical models are constantly upscaled to verify, optimize and extend the experimental data. However, the spatial concentration data during back-diffusion lacks diversity due to the limitations of pollutant species in studies, the microscopic mechanisms controlling pollutant transformation are poorly understood, and the impacts of these reactions on contaminant back-diffusion are rarely considered. Hence, most simulation models have not been adequately validated and are not capable of accurately predicting pollutant fate and cleanup in realistic heterogeneous aquifers. Based on these, some hypotheses and perspectives are mentioned to promote the investigation of contaminant migration in high- and low-permeability systems in groundwater.

Effects of EDTA on adsorption of Cd(II) and Pb(II) by soil minerals in low-permeability layers: batch experiments and microscopic characterization.

Ethylenediaminetetraacetic acid (EDTA) can serve as a washing agent in the remediation of low-permeability layers contaminated by heavy metals (HMs). Therefore, batch adsorption experiments, where pure quartz (SM1) and mineral mixtures (SM2) were used as typical soil minerals (SMs) in low-permeability layers, were implemented to explore the effects of different EDTA concentrations, pH, and exogenous chemicals on the HM-SM-EDTA adsorption system. As the EDTA concentration increased, it gradually cut down the maximum Cd adsorption capacities of SM1 and SM2 from approximately 135 to 55 mg/kg and 2660 to 1453 mg/kg; and the maximum Pb adsorption capacities of SM1 and SM2 were reduced from 660 to 306 mg/kg and 19,677 to 19,262 mg/kg, respectively. When the initial mole ratio (MR = moles of HM ions/sum of moles of HM ions and EDTA) was closer to 0.5, the effect of EDTA was more effective. Additionally, EDTA worked well at pH below 7.0 and 4.0 for Cd and Pb, respectively. Low-molecular-weight organic acids (LMWOAs) affected the system mainly by bridging, complexation, adsorption site competition, and reductive dissolution. Cu2+, Fe2+ ions could significantly increase the Cd and Pb adsorption onto SM2. Notably, there were characteristic changes in mineral particles, including attachment of EDTA and microparticles, agglomeration, connection, and smoother surfaces, making the specific surface area (SSA) decrease from 16.73 to 12.59 m2/g. All findings indicated that EDTA could effectively and economically reduce the HM adsorption capacity of SMs at the reasonable MR value, contact time, and pH; EDTA reduced the HM adsorption capacity of SMs not only by complexation with HM ions but also by decreasing SSA and blocking active sites. Hence, the acquired insight from the presented study can help to promote the remediation of contaminated low-permeability layers in groundwater.