Organic Pollutants In Groundwater Research Articles

Electron transfer-mediated peroxymonosulfate activation through monoatomic Fe–pyridinic N4 moiety in biochar-based catalyst for electron-rich pollutants degradation in groundwater

Pollution of groundwater by electron-rich refractory organic pollutants (e-ROPs) is detrimental to ecological integrity and human health. Biochar (BC)-based single-atom Fe catalysts (Fe–SACs) triggering nonradical peroxymonosulfate (PMS) process has shown great potential in addressing this problem. Nevertheless, the successful formation and precise regulation of active sites on BC remain formidable challenges. Herein, co-pyrolysis of BC derived from shrimp shells and N-containing supramolecular organic frameworks with a hexagonal cavity structure of Fe3+–N3 (Fe–SOFs) was, for the first time, used to prepare an efficient and inexpensive BC-based Fe–SAC (Fe–MCA@SS). The Fe–N bond was successfully grafted from Fe–SOFs onto BC and subsequently transformed into monoatomic Fe–pyridinic N4. Moreover, Fe–MCA@SS successfully triggered an efficient nonradical PMS process, degrading 94.5 % of aniline (AN) within 5 min. Mediated electron transfer (MET) mechanism was primarily responsible for AN removal. MET was attributed to the following factors: the synergistic effect of the stronger chemical adsorption of PMS with an Fe atom in Fe–pyridinic N4 active sites, the higher redox potential of [Fe–MCA@SS/PMS]*, and the value of the lowest unoccupied molecular orbital of AN being larger than the value of highest occupied molecular orbital of [Fe–MCA@SS/PMS]*. This study sheds new light on the preparation of BC-based SACs catalyst with efficient nonradical oxidation ability and an excellent feasibility to remove electron-rich organic pollutants in groundwater.

Effect and mechanisms of pollutant removal in tetrachloroethylene contaminated water by persulfate-dithionite remediation system

Tetrachloroethylene (PCE) is a common organic pollutant in industrial process, and the scope and extent of PCE pollution to groundwater are increasing in recent years. In this study, an emerging and effective method was used to purify PCE contaminated water by activating persulfate (PS) with dithionite (DTN). The addition ratio of PS and DTN were optimized in the removal of PCE by PS-DTN system and the optimal molar ratio of PS to DTN was 1 to 1 at the maximum PCE removal rate, and it was applicable in the pH range of 3-12. In PCE simulated wastewater, PCE removal rate in PS-DTN system exceeded 90% within 48 hours, which was 66% higher than that in PS-NaOH system, and the degradation process followed pseudo-first-order kinetics with the reaction rate constant being 0.068 h-1. The dominant active species in PS-DTN system was proved to be sulfate radical on PCE degradation based on the radical quenching experiments and ESR analysis. HCO3- and low concentration of natural organic matter (NOM) could promote the removal of PCE, while Cl- and high NOM concentration had no adverse effect on PCE degradation. Few chlorinated intermediates (<2.77%) were produced and the dechlorination rate of PCE reached 95%, indicating a low secondary pollution risk. In simulated groundwater containing aquifer media, PS-DTN system could still degrade PCE to a certain extent, but the non-target reaction triggered by iron minerals on the medium mainly inhibited PCE degradation. The study showed that PS-DTN system was promising in degrading organic pollutants in groundwater.

Insights into the potential applications of permanganate/peroxymonosulfate systems: enhancement via amorphous MnO2, effects of water matrices, and optimization using response surface methodology.

In this study, we developed a novel self-catalytic oxidation system involving peroxymonosulfate (PMS) and permanganate (KMnO4), named as CUPP, to efficiently mineralize sulfamethoxazole (SMX) in groundwater. It was found that amorphous MnO2 derived from the in situ reduction of KMnO4 can directly adsorb HSO5-, a complex hydroxyl group, mediate the internal disproportionation reaction of HSO5- with the manganese complex, and effectively activate PMS, thereby promoting the oxidation of SMX and its degradation intermediates through sulfonate radiation. Furthermore, by using electron spin resonance (EPR), HPLC/MS full scan, and response surface methodology, the coexistence of HO˙, SO4-˙, O2-˙, 1O2, and active chlorine (Cl2, HOCl) in the CUPP system was confirmed. A total of 24 intermediate products were detected, and four possible degradation pathways were identified for SMX. In addition, it was found that the CUPP system has a strong impact resistance to pH variations, groundwater anions, and natural organic matter stress. Undoubtedly, the CUPP system presents an innovative approach for the degradation of various emerging organic pollutants in groundwater.

Selective Removal of Organic Pollutants in Groundwater and Surface Water by Persulfate-Assisted Advanced Oxidation: The Role of Electron-Donating Capacity.

The efficiency of persulfate-assisted advanced oxidation processes (PS-AOPs) in degrading organic pollutants is affected by the electron-donating capability of organic substances present in the water source. In this study, we systematically investigate the electron-donating capacity (EDC) difference between groundwater and surface water and demonstrate the dependence of removal efficiency on the EDC of target water by PS-AOPs with carbon nanotubes (CNTs) as a catalyst. Laboratory analyses and field experiments reveal that the CNT/PS system exhibits higher performance in organic pollutant removal in groundwater with a high concentration of phenols, compared to surface water, which is rich in quinones. We attribute this disparity to the selective electron transfer pathway induced by potential difference between PS-CNT and organic substance-CNT intermediates, which preferentially degrade organic substances with stronger electron-donating capability. This study provides valuable insights into the inherent selective removal mechanism and application scenarios of electron transfer process-dominated PS-AOPs for water treatment based on the electron-donating capacity of organic pollutants.

Distribution, source identification, and health risk of emerging organic contaminants in groundwater of Xiong'an New Area, Northern China

Groundwater contamination in China has been greatly concerned due to dramatically increasing fresh water demand accompanied by economic development. However, little is known about aquifer vulnerability to hazardous matters especially in previously contaminated site of rapidly urbanizing cities. Here, we collected 90 groundwater samples from Xiong'an New Area during wet and dry seasons of 2019 and characterized the composition and distribution of emerging organic contaminants (EOCs) in this strategically developing city. A total of 89 EOCs, assigned to organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and volatile organic compounds (VOCs), were detected with the frequencies ranging from 1.11 %–85.6 %. Methyl tert-butyl ether (16.3 μg/L), Epoxid A (6.15 μg/L), and α-Lindane (5.15 μg/L) could be identified as major contributors to groundwater organic pollution. Significant aggregation of groundwater EOCs along Tang River were found due to historical residue and accumulation from wastewater storage there before 2017. Significant seasonal variations (p < 0.05) in the types and concentrations of EOCs could be attributed to discrepant pollution sources between varying seasons. Human health effects from exposure to groundwater EOCs were further evaluated with negligible risk (<10−4) in most samples (97.8 %) and notable risk (10−6–10−4) in several monitored wells (2.20 %) located along Tanghe Sewage Reservoir. This study provides new evidences for aquifer vulnerability to hazardous matters in historically contaminated sites and is of significant to groundwater pollution controlling and drinking water safety for rapidly urbanizing cities.

Synergistic action of ferrate and biochar in the removal of trichloroethylene from water: Little biochar addition, large ferrate activity improvement

Ferrate (Fe(VI)) is strongly considered an efficient green oxidant for degrading organic pollutants in groundwater. However, overdosage is often used to achieve the desired efficiency, resulting in adverse effects on the groundwater quality and the ecological environment and high costs. This study aimed to enhance the removal of trichloroethylene (TCE) using Fe(VI) by investigating the synergistic action of a ferrate-biochar system. 1 h into the reaction, the TCE degradation rate had increased from 18.7% to 96.0% and the K2FeO4 concentration had increased from 1 mM to 25 mM. The pH strongly influenced the TCE degradation by K2FeO4 by affecting the stability, species, and consequent oxidation capacity of K2FeO4. Co-existing metal cations in the solution could enhance the K2FeO4 self-decay by facilitating the electron transfer process. Biochar addition significantly enhanced TCE removal by K2FeO4 (up to 4.4 times) compared with the combined removal via individual oxidation and adsorption systems. Significant enhancement comparable to that of a high 16 mM Fe(VI) dosage was obtained with 666 mg/L biochar and 5 mM Fe(VI). The enhancement mechanisms by which biochar addition enhanced the TCE removal by K2FeO4 included the oxidation process by prior to TCE adsorption onto biochar, an enhanced electron transfer of Fe(VI) reduction by the biochar functional group, and an enhanced adsorption capacity of biochar owing to its peroxidation by Fe(VI). Thus, compared to individual and excessive chemical oxidation, the ferrate-biochar composite system provides a promising strategy for improving the TCE removal efficiency with lower oxidant consumption and less negative ecological impacts.

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.

Developing novel persulfate pellets to remediate BTEXs-contaminated groundwater

Organic-contaminated groundwater poses a growing threat to environmental sustainability and human health. As a passive plume control technology, permeable reactive barriers (PRBs)have become a popular method for groundwater pollutants degradation due to their cost-effective and sustainable merits. However, active materials adopted in conventional PRBs have the shortcomings of easy deactivation and speedy consumption. As an alternative, slow-release materials can be used as PRBs fillers to treat contaminated groundwater because of their long chemical release time. In this study, novel slow-release persulfate pellets were prepared and tested for their release capabilities and effectiveness in the remediation of groundwater organic pollution. Results show that each pellet's release efficiency and average release rate within 14 days were 87.36 % and 46.80 mg-persulfate/d, respectively, when the mass ratio of sodium persulfate to paraffin was 3/1. Dissolution and diffusion via pores are the main mechanisms of the persulfate delivery from slow-release pellets in water. Moreover, solution pH, ionic species and addition of quartz sand into release pellets play dissimilar effects on the release kinetics. Results from column experiments indicate that the pellets could expand the PS influence range in the barrier and continuously remediate BTEXs-contaminated groundwater (initial concentration of each compound = 50 mg/L) and reach 64.2–85.1 % removal efficiency. The results of electron spin resonance (ESR) spectroscopy show that both SO4− and OH contribute to the removal of BTEXs. This study demonstrates the potential feasibility of slow-release persulfate materials for groundwater pollution treatments by PRBs, which inspires for future field applications.

Identification and Risk Assessment of Priority Control Organic Pollutants in Groundwater in the Junggar Basin in Xinjiang, P.R. China.

The Junggar Basin in Xinjiang is located in the hinterland of Eurasia, where the groundwater is a significant resource and has important ecological functions. The introduction of harmful organic pollutants into groundwater from increasing human activities and rapid socioeconomic development may lead to groundwater pollution at various levels. Therefore, to develop an effective regulatory framework, establishing a list of priority control organic pollutants (PCOPs) is in urgent need. In this study, a method of ranking the priority of pollutants based on their prevalence (Pv), occurrence (O) and persistent bioaccumulative toxicity (PBT) has been developed. PvOPBT in the environment was applied in the screening of PCOPs among 34 organic pollutants and the risk assessment of screened PCOPs in groundwater in the Junggar Basin. The results show that the PCOPs in groundwater were benzo[a]pyrene, 1,2-dichloroethane, trichloromethane and DDT. Among the pollutants, benzo[a]pyrene, 1,2-dichloroethane and DDT showed high potential ecological risk, whilst trichloromethane represented low potential ecological risk. With the exception of benzo[a]pyrene, which had high potential health risks, the other screened PCOPs had low potential health risks. Unlike the scatter distribution of groundwater benzo[a]pyrene, the 1,2-dichloroethane and trichloromethane in groundwater were mainly concentrated in the central part of the southern margin and the northern margin of the Junggar Basin, while the DDT in groundwater was only distributed in Jinghe County (in the southwest) and Beitun City (in the north). Industrial and agricultural activities were the main controlling factors that affected the distribution of PCOPs.

Recyclable Fe/S co-doped nanocarbon derived from metal-organic framework as a peroxymonosulfate activator for efficient removal of 2,4-dichlorophenol.

In this study, a recyclable Fe/S co-doped nanocarbon (Fe/S-NC) was successfully prepared by the pyrolysis of ZIF-8 confined with Fe(II) and added S. Characterization showed that a highly graphitized carbon-based material co-doped with sulfur and iron was successfully prepared. This Fe/S-NC can efficiently activate PMS to remove organic pollutants in water. The effect of different synthesis conditions on the degradation efficiency of 2,4-DCP was studied by orthogonal experiments. The optimized Fe/S-NC/PMS system exhibited excellent catalytic performance and could degrade more than 99.7% of 2,4-DCP within 30min. Even after 5 cycles, the degradation efficiency could still be maintained above 96.3%, which proved that the catalytic system had good cycle performance. In addition, the effect of pH on catalytic performance showed that the degradation rate of 2,4-DCP exceeds 96.7% in the pH range of groundwater (pH = 5-9). We had confirmed that the free radicals that caused 2,4-DCP degradation were SO4·-, ·OH, O2·-, and 1O2, which played important roles in degrading organic pollutants. These research results show that the Fe/S-NC/PMS system can be used as an efficient, stable, and environmentally friendly system to treat organic pollutants in groundwater.

Assessment of the effects of COVID-19 lockdown period on groundwater quality of a significant rice land in an urban area of Türkiye.

In the current research, the impact of the COVID-19 lockdown period on groundwater quality of Lower Meriç Plain (Thrace Region of Türkiye) was evaluated. Some significant nutrient characteristics (NO3−, NO2−, and PO43−), salinity characteristics (EC, TDS, and salinity), and physical characteristics (temperature, DO, pH, and turbidity) were investigated in groundwater samples collected from 45 sampling points in pre-lockdown and lockdown periods. Water quality index (WQI) and nutrient pollution index (NPI), Pearson correlation index (PCI), cluster analysis (CA), one-way ANOVA test (OWAT), and factor analysis (FA) were applied to assess ecological risk. Excluding recorded statistical differences in temperature and DO due to climatic conditions (p < 0.05), levels of all the investigated water quality parameters show no statistically significant differences and no significant reduction in pollutants measured in the lockdown period. On the contrary, the WQI and NPI scores have increased between the rates of 4.76–27.10% during the lockdown period. In the lockdown period, although the reduction of industry or limited production of many industrial facilities reduced the inorganic contaminant releases to the environment, ongoing agricultural activities and domestic wastes caused to prevent the reduction of organic pollutants in groundwater of the region during the lockdown period.Graphical abstract Supplementary InformationThe online version contains supplementary material available at 10.1007/s11356-022-20959-8.

Facet-dependent Fe(II) redox chemistry on iron oxide for organic pollutant transformation and mechanisms

Fe(II) redox chemistry is a pivotal process of biogeochemical Fe cycle and the transformation of organic pollutants in subsurface aquifers, while its interfacial reactivity on iron oxides with varying surface chemistries remains largely unexplored. In this study, the redox processes of Fe(II) on two hematite with highly exposed {001} and {110} facets and their impacts on the transformation of nitrobenzene were investigated. Results suggest that Fe(II) adsorption is the rate-limiting step of the redox chain reactions, controlling the reduction potential (EH). Nitrobenzene activates the facet electron transfer on hematite, leading to nitrobenzene reduction and Fe(II) oxidation. Moreover, {001} facet exhibits a higher reactivity and electron transport efficiency than {110} facet, which is attributed to a lower site density (0.809 #Fe/nm2) and a lower EH of hematite {001} facet than that of {110} facet. It is worth noting that the facet-dependent reduction activity is more intense at low pH or high Fe(II) activity. A slight dissolution of {110} facet was observed, indicating hematite {001} facet exhibits higher thermodynamic stability than {110} facet. This study confirms the facet-dependent reducing activity of surface bound Fe(II) on hematite, providing a new perspective for in-depth understanding of the interfacial reactions on hematite. The findings of this work broaden the biogeochemical process of Fe cycle in subsurface environments and its impact on the fate of organic pollutants in groundwater.

Passive Sampling with Active Carbon Fibres in the Determination of Organic Pollutants in Groundwater

Legislation addressing the quality of groundwater and increasing concerns over public health calls for the development of analytical methods that can produce accurate and precise results at the ppt level. Passive sampling has been recognised as a helpful tool in identifying various organic pollutants in groundwater, even when their presence had not yet been identified through conventional groundwater quality monitoring. The article presents an analytical method involving a simple and cost-effective passive sampling device using Zorflex® activated carbon fibres (ACFs) for the qualitative monitoring of a broad range of organic pollutants in water in a single run. The applicability of the method developed was tested in three hydrogeological studies. In the first case, we present a non-targeted qualitative screening and a list of 892 different contaminants detected in the groundwater in Slovenia. In the second case, we discuss the presence and origin of organic compounds in the groundwater from a pilot area of the urban aquifer, Ljubljansko polje. The third case presents a comparison of results between passive and grab sampling. Passive sampling with ACFs confirmed the presence of a pollutant, even when it had not been previously detected through a quantitative method.

Monodispersed CuO nanoparticles supported on mineral substrates for groundwater remediation via a nonradical pathway

Nonradical oxidation based on singlet oxygen (1O2) has attracted great interest in groundwater remediation due to the selective oxidation property and good resistance to background constituents. Herein, recoverable CuO nanoparticles (NPs) supported on mineral substrates (SiO2) were prepared by calcination of surface-coated metal-plant phenolic networks and explored for peroxymonosulfate (PMS) activation to generate 1O2 for degrading organic pollutants in groundwater. CuO NPs with a close particle size (40 nm) were spatially monodispersed on SiO2 substrates, allowing highly exposure of active sites and consequently leading to outstanding catalytic performance. Efficient removal of various organic pollutants was obtained by the supported CuO NPs/PMS system under wide operation conditions, e.g., working pH, background anions and natural organic matters. Chemical scavenging experiments, electron paramagnetic resonance tests, furfuryl alcohol decay and solvent dependency experiments confirmed the formation of 1O2 and its dominant role in pollutants removal. In situ characterization with ATR-FTIR and Raman spectroscopy and computational calculation revealed that a redox cycle of surface Cu(II)-Cu(III)-Cu(II) was responsible for the generation of 1O2. The feasibility of the supported CuO NPs/PMS for actual groundwater remediation was evaluated via a flow-through test in a fixed-bed column, which manifested long-term durability, high mineralization ratio and low metal ion leaching.

Exploration of Hydrogeochemical Characterization and Assessment of Organic Pollution Characteristics of Shallow Groundwater near a Chemical Plant That Discharged Sewage Illegally

Groundwater plays a significant role in domestic use and agricultural irrigation in rural areas of northern China. The untreated wastewater from the chemical plant was directly discharged into a seepage well, resulting in the pollution of groundwater. Assessing characteristics of groundwater organic pollution and identifying evolutionary mechanisms of hydrogeochemistry are beneficial for groundwater protection and sustainable management. Statistical methods (correlation analysis (CA) and principal component analysis (PCA)) combined with hydrogeochemical methods including Piper, Gibbs, Gaillardet, and ions binary diagrams and the chloride alkalinity index were employed to explore hydrogeochemical characteristics and evolutionary mechanisms. The results showed that cations were predominantly located at the Ca2+ end and anions were mostly close to the SO42− and Cl− end. The ion concentrations of groundwater were mainly affected by water–rock interactions. The weathering or dissolution of silicate (i.e., aluminosilicate minerals), evaporite (i.e., halite and gypsum), carbonate minerals (i.e., calcite and dolomite), cation exchange, and anthropogenic activities contribute to the chemical compositions of groundwater. Based on CA and PCA, the dissolution of halide minerals and the use of pesticides and fertilizers were the main factors controlling water chemistry. Additionally, the dissolution of sulfur-bearing minerals and gypsum was the key factor controlling the concentrations of Ca2+ and Mg2+. Application of mathematical statistical methods characterized that the exceedance rate of seven organic compounds with high detection rates were as follows: carbon tetrachloride (39.83%) &gt; 1,1,2-trichloroethane (28.81%) &gt; chloroform (10.17%) &gt; trichloroethene (6.78%) &gt; 1,1,2,2-tetrachloroethane (5.93%) &gt; perchloroethylene (5.08%) &gt; trichlorofluoromethane (0.85%). Simultaneously, pollution under the influence of volatilization and diffusion was significantly less than that in the direction of groundwater runoff.

Application of sludge biochar combined with peroxydisulfate to degrade fluoroquinolones: Efficiency, mechanisms and implication for ISCO

Peroxydisulfate (PDS) is increasingly used for in situ chemical oxidation (ISCO) of organic pollutants in groundwater, but the efficient and applicable activator is still scarce. In this study, sludge-derived biochar (SDBC) was prepared by pyrolysis to activate PDS, which could effectively degrade the fluoroquinolone antibiotics (FQs, levofloxacin, enrofloxacin, norfloxacin and ciprofloxacin). Compared with pig manure and corn straw derived biochar, SDBC showed higher efficiency in PDS activation. Singlet oxygen (1O2) was identified as the major reactive species, and the surface-bonded radicals also contributed to the FQs degradation. The selective oxidation of FQs by 1O2 was first reported, which followed the trend of enrofloxacin ~ levofloxacin > norfloxacin ~ ciprofloxacin. The CO and Fe2+ on SDBC were the dominant reactive sites for PDS activating. Products analysis revealed that FQs degradation proceeds via the cleavage of the piperazine ring, breaking of the quinolone ring, decarboxylation, and defluorination. Moreover, the tertiary amine of N (4) on enrofloxacin was more reactive towards singlet oxygen than the secondary amine of N (4) on ciprofloxacin, inducing the faster degradation and de-toxicity of enrofloxacin in the reaction system. SDBC showed high reusability in PDS activation and negligible metals leachates were detected. The column study proved the efficiency of PDS/SDBC in groundwater remediation.

Effective electrocatalytic hydrodechlorination of 2,4,6-trichlorophenol by a novel Pd/MnO2/Ni foam cathode

Pd modified electrodes possess problems such as easy agglomeration and low electrolytic ability, and the use of manganese dioxide (MnO2) to facilitate Pd reduction of organic pollutants is just started. However, there is still a limited understanding of how to match the Pd load and MnO2 to realize optimal dechlorination efficiency at minimum cost. Here, a Pd/MnO2/Ni foam cathode was successfully fabricated and applied for the efficient electrochemical dechlorination of 2,4,6-trichlorophenol (2,4,6-TCP). The optimal electrocatalytic hydrodechlorination (ECH) performance with 2,4,6-TCP dechlorination efficiency (92.58% in 180 min) was obtained when the concentration of PdCl2 precipitation was 1 mmol/L, the deposition time of MnO2 was 300 s and cathode potential was −0.8 V. Performance influenced by the exogenous factors (e.g., initial pH and coexisted ions) were further investigated. It was found that the neutral pH was the most favorable for ECH and a reduction in dechlorination efficiency (6%∼47.6%) was observed in presence of 5 mmol/L of NO2−, NO3−, S2− or SO32−. Cyclic voltammetry (CV) and quenching experiments verified the existence of three hydrogen species on Pd surface, including adsorbed atomic hydrogen (H*ads), absorbed atomic hydrogen (H*abs), and molecular hydrogen (H2). And the introduction of MnO2 promoted the generation of atomic H*. Only adsorbed atomic hydrogen (H*ads) was confirmed that it truly facilitated the ECH process. Besides H*ads induced reduction, the direct reduction by cathode electrons also participated in the 2,4,6-TCP dechlorination process. Pd/MnO2/Ni foam cathode shows excellent dechlorination performance, fine stability and recyclable potential, which provides strategies for the effective degradation of persistent halogenated organic pollutants in groundwater.

Probabilistic human health-risk assessment and influencing factors of aromatic hydrocarbon in groundwater near urban industrial complexes in Northeast China

Organic pollutants are common in the environment, very difficult to remove, and pose a serious threat to human health. Probabilistic risk assessment advances conservative single-point estimation and brings a new perspective to risk assessment. From 2009 to 2019, we monitored the distribution of major pollutants in an industrial park in Northeastern China. The result showed the maximum concentration of benzene reached 73,680 μg/L in 2009, benzo[a]pyrene reached 36.80 ng/L in 2016. These concentrations are significantly above the levels set by Chinese regulatory agencies. The single-factor index increases year by year, and pollutants gradually spread from the pollution leakage source to surrounding areas. A new method was used to quantify the human health risk from groundwater organic pollution accurately, based on the triangular fuzzy numbers coupled with the Monte Carlo simulation. The Monte Carlo simulation was used to simulate the triangular fuzzy numbers. This simplified the operation between the triangular fuzzy numbers and their function successfully and obtained the risk as a set of values. The results indicated that non-carcinogenic risk was negligible in all age groups (children, adolescents, and adults). Conversely, when it comes to carcinogenic risks, adults were about 50–270 times the tolerable level of risk due to long exposure years and wide skin contact areas. Oral ingestion played an essential role in total exposure (>90%) compared to dermal contact. Control of exposure duration and intake should be prioritized when making decisions to reduce risk uncertainty. Monte Carlo simulation–triangular fuzzy numbers can effectively reduce the risk of uncertainty and reflect the complex conditions of the groundwater environment for small amounts of data or inaccurate data.

In-situ generation of reactive oxygen species using combination of electrochemical oxidation and metal sulfide

In-situ chemical oxidation (ISCO) is commonly practiced to degrade organic pollutants in various fields. However, ISCO is deteriorated the oxidation efficiency due to the non-selective and self-decomposition of reagents. Therefore, in-situ generation of oxidants is being proposed to compensate for the demerits of conventional ISCO. In this study, the aim is to suggest a novel in-situ generation system using the combination of electrochemical oxidation (EO) and pyrite oxidation. It is hypothesized that EO system can generate the oxygen species, which can activate the pyrite surface to produce more oxidants. We evaluated three systems (1) EO system (2) pyrite oxidation system (3) combined system using sulfanilamide as a common antibiotic. The EO system degraded completely sulfanilamide and generated 150 μM of H2O2 and 8 mg/L of DO even at 10 mA. In other words, EO system can directly oxidize the sulfanilamide and produce oxygen species. The pyrite system produced 204 and 24 μM of hydroxyl radicals at pH 3 under oxic and anoxic conditions, respectively, and 118 and 20 μM at pH 7. Pyrite oxidation can generate more reactive species in the presence of oxygen. The combined system enhanced the oxidation-rate constant to 1.5 times (from 0.2561 to 0.3502 h−1). The additional supply of oxygen showed a higher oxidation rate to 1.5 and 1.3 times higher than single EO or pyrite oxidation, respectively. As a result, the co-presence of pyrite and oxygen shows a synergistic effect on the oxidation of the organic pollutant. Our results suggest that electrochemical generation of the oxygen species in the presence of pyrite is a promising technique to oxidize organic pollutants in groundwater.

Persulfate-based controlled release beads for in situ chemical oxidation of common organic pollutants

Groundwater contamination by organic pollutants is a growing threat to the environment and human health. As a cost-effective method, in situ chemical oxidation (ISCO) treatment has become a popular technical method to degrade groundwater pollutants. However, conventional ISCO treatment can suffer from a number of operational issues, such as tailing and concentration rebound, and thus the long-term treatment effectiveness is less desirable. As an alternative approach to the conventional ISCO method, controlled release materials are designated to gradually release oxidant chemicals to treat polluted groundwater with an extended chemical release duration and a reduced peak release rate. In this study, novel persulfate-paraffin based controlled release bead (CRB) materials were prepared and tested in a laboratory setting for their applicability in groundwater organic pollution remediation. It shows that bead size and temperature can substantially affect the release kinetics of persulfate from the CRBs, while the impact of solution pH and the presence of matrix anions are insignificant. Moreover, degradation experiments of benzene, toluene, ethylbenzene, and xylene pollutants show that the performance of CRBs, particularly within a short period after being delivered in situ, is on par with the conventional ISCO method using aqueous persulfate. This study expands our understanding and capacity in adopting controlled release materials for groundwater remediation. This study promotes the potential field application of such novel controlled release materials for environmental remediation of groundwater.