Chlorinated volatile organic compounds (CVOCs) and 1,4-dioxane kinetics and equilibrium adsorption studies on selective macrocyclic adsorbents.

Chlorinated volatile organic compounds (CVOCs) are often found in combination with 1,4-dioxane which has been used as a solvent stabilizer. It would be desirable to separate these compounds since biodegradation of 1,4-dioxane follows an aerobic pathway while anaerobic conditions are needed for biodegrading CVOCs. Conventional adsorbents such as activated carbon (AC) and carbonaceous resins have high adsorption capacities for 1,4-dioxane and CVOCs but lack selectivity, limiting their use for separation (Liu et al., 2019). In the current work, two macrocyclic adsorbents, ß-CD-TFN and Res-TFN, were examined for selective adsorption of chlorinated ethenes in the presence of 1,4-dioxane. Both adsorbents exhibited rapid adsorption of the CVOCs and minimal adsorption of 1,4-dioxane. Res-TFN had a higher adsorption capacity for CVOCs than ß-CD-TFN (measured linear partition coefficient, Kd 2140 -9750 L⋅kg-1 versus 192-918 L⋅kg-1 for 1,1, DCE, cis-1,2-DCE and TCE, respectively) and was highly selective for CVOCs(TCE Kd ~117 Kd for 1,4-dioxane). By comparison, TCE and 1,4-dioxane adsorption on AC was approximately equal at 100 µg⋅L-1 and approximately 1/3 of the adsorption of TCE on the Res-TFN. The greater adsorption and selectivity of Res-TFN suggest that it can be used as a selective adsorbent to separate CVOCs from 1,4-dioxane to allow separate biodegradation.

Catalytic Hydrolysis-Oxidation of Halogenated Methanes over Phase- and Defect-Engineered CePO4: Halogenated Byproduct-Free and Stable Elimination.

Catalytic elimination of halogenated volatile organic compound (HVOC) emissions was still a huge challenge through conventional catalytic combustion technology, such as the formation of halogenated byproducts and the destruction of the catalyst structure; hence, more efficient catalysts or a new route was eagerly desired. In this work, crystal phase- and defect-engineered CePO4 was rationally designed and presented abundant acid sites, moderate redox ability, and superior thermal/chemical stability; the halogenated byproduct-free and stable elimination of HVOCs was achieved especially in the presence of H2O. Hexagonal and defective CePO4 with more structural H2O and Brønsted/Lewis acid sites was more reactive and durable compared with monoclinic CePO4. Based on the phase and defect engineering of CePO4, in situ diffuse reflectance infrared Fourier transform spectra (DRIFTS), and kinetic isotope effect experiments, a hydrolysis-oxidation pathway characterized by the direct involvement of H2O was proposed. Initiatively, an external electric field (5 mA) significantly accelerated the elimination of HVOCs and even 90% conversion of dichloromethane could be obtained at 170 °C over hexagonal CePO4. The structure-performance-dependent relationships of the engineered CePO4 contributed to the rational design of efficient catalysts for HVOC elimination, and this pioneering work on external electric field-assisted catalytic hydrolysis-oxidation established an innovative HVOC elimination route.

Evaluating groundwater ecosystem dynamics in response to post in-situ remediation of mixed chlorinated volatile organic compounds (CVOCs): An insight into microbial community resilience, adaptability, and metabolic functionality for sustainable remediation and ecosystem restoration.

The in-situ remediation of groundwater contaminated with mixed chlorinated volatile organic compounds (CVOCs) has become a significant global research interest. However, limited attention has been given in understanding the effects of these remediation efforts on the groundwater microbial communities, which are vital for maintaining ecosystem health through their involvement in biogeochemical cycles. Hence, this study aimed to provide valuable insights into the impacts of in-situ remediation methods on groundwater microbial communities and ecosystem functionality, employing high-throughput sequencing coupled with functional and physiological assays. The results showed that both bioremediation and chemical remediation methods adversely affected microbial diversity and abundance compared to non-polluted sites. Certain taxa such as Pseudomonas, Acinetobacter, and Vogesella were sensitive to these remediation methods, while Aquabacterium exhibited greater adaptability. Functional annotation unveiled the beneficial impact of bioremediation on the sulfur cycle and specific taxa such as Cellvibrio, Massilia, Algoriphagus, and Flavobacterium which showed a significant positive relationship with dark oxidation of sulfur compounds. In contrast, chemical remediation showed adverse impacts on the nitrogen cycle with a reduced abundance of nitrogen and nitrate respiration along with a reduced utilization of amines (nitrogen rich substrate). The findings of this study offer valuable insights into the potential impacts of in-situ remediation methods on groundwater microbial communities and ecosystem functionality, emphasizing the need for meticulous consideration to ensure the implementation of effective and sustainable remediation strategies that safeguard ecosystem health and function.

Underpinning the ecological response of mixed chlorinated volatile organic compounds (CVOCs) associated with contaminated and bioremediated groundwaters: A potential nexus of microbial community structure and function for strategizing efficient bioremediation.

Understanding the structure, dynamics, and functionality of microbial communities is essential for developing sustainable and effective bioremediation strategies, particularly for sites contaminated with mixed chlorinated volatile organic compounds (CVOCs), which can make the biodegradation process more complex and challenging. In this study, 16S rRNA amplicon sequencing revealed a significant change in microbial distribution in response to CVOCs contamination. The loss of sensitive taxa such as Proteobacteria and Acidobacteriota was observed, while CVOCs-resistant taxa such as Campilobacterota were found significantly enriched in contaminated sites. Additionally, varying abundances of crucial enzymes involved in the sequential biodegradation of CVOCs were expressed depending on the contamination level. Association analysis revealed that specific genera such as Sulfurospirillum, Azospira, Trichlorobacter, Acidiphilium, and Magnetospririllum could relatively survive under higher levels of CVOC contamination, whereas pH, ORP and temperature had a negative influence in their abundance and distribution. However, Dechloromonas, Thiobacillus, Pseudarcicella, Hydrogenophaga, and Sulfuritalea showed a negative relationship with CVOC contamination, highlighting their sensitivity towards CVOC contamination. These findings provide valuable insights into the relationship among ecological responses, the groundwater bacterial community, and their functionality in response to mixed CVOC contamination, offering a fundamental basis for developing effective and sustainable bioremediation strategies for CVOC-contaminated groundwater systems.

Insights into the Electronic Structure Effect of SnMnOx Nanorod Catalysts for Low-Temperature Catalytic Combustion of o-Dichlorobenzene.

For the catalytic combustion reaction of chlorinated volatile organic compounds (CVOCs), the redox properties and acid sites of the catalyst surface are key factors in determining the activity, selectivity, and chlorine-resistance stability. Herein, a series of SnMnOx catalysts for the catalytic combustion of CVOCs were prepared by the changing of Sn-doping way to regulate the electron valance state of Mn element, including reflux (R-SnMnOx ), co-precipitation (C-SnMnOx ) and impregnation (I-SnMnOx ). It was discovered that the R-SnMnOx catalyst had better activity and chlorine resistance than the R-MnOx , C-SnMnOx and I-SnMnOx catalyst, and we discovered that the doping ways of Sn in MnOx catalyst could regulate greatly the surface acidity, active oxygen species, the chemical state of Mnn+ species, and redox ability. Especially, the R-SnMnOx catalysts exhibit excellent water resistance, and the reasons were related to the strong interaction of Snn+ and Mnn+ , which could promote obviously the dispersion of active Mn species, form a large number of acid sites, provide the abundant lattice oxygen species, and own the excellent redox ability, which accelerate the rate of charge transfer between Snn+ and Mnn+ (Sn4+ +Mn2+ →Sn2+ +Mn4+ ) to produce the abundant active species and accelerate the rapid conversion of benzene and intermediates conversion.

Promoted wet peroxide oxidation of chlorinated volatile organic compounds catalyzed by FeOCl supported on macro-microporous biomass-derived activated carbon.

Chlorinated volatile organic compounds (CVOCs) are a recalcitrant class of air pollutants, and the strongly oxidizing reactive oxygen species (ROS) generated in advanced oxidation processes (AOPs) are promising to degrade them. In this study, a FeOCl-loaded biomass-derived activated carbon (BAC) has been used as an adsorbent for accumulating CVOCs and catalyst for activating H2O2 to construct a wet scrubber for the removal of airborne CVOCs. In addition to well-developed micropores, the BAC has macropores mimicking those of biostructures, which allows CVOCs to diffuse easily to its adsorption sites and catalytic sites. Probe experiments have revealed HO• to be the dominant ROS in the FeOCl/BAC + H2O2 system. The wet scrubber performs well at pH 3 and H2O2 concentrations as low as a few mM. It is capable of removing over 90% of dichloroethane, trichloroethylene, dichloromethane and chlorobenzene from air. By applying pulsed dosing or continuous dosing to replenish H2O2 to maintain its appropriate concentration, the system achieves good long-term efficiency. A dichloroethane degradation pathway is proposed based on the analysis of intermediates. This work may provide inspiration for the design of catalyst exploiting the inherent structure of biomass for catalytic wet oxidation of CVOCs or other contaminants.

Crystal Engineering of TiO2 for Enhanced Catalytic Oxidation of 1,2-Dichloroethane on a Pt/TiO2 Catalyst.

Crystal engineering of metal oxide supports represents an emerging strategy to improve the catalytic performance of noble metal catalysts in catalytic oxidation of chlorinated volatile organic compounds (CVOCs). Herein, Pt catalysts on a TiO2 support with different crystal phases (rutile, anatase, and mixed phase (P25)) were prepared for catalytic oxidation of 1,2-dichloroethane (DCE). The Pt catalyst on P25-TiO2 (Pt/TiO2-P) showed optimal activity, selectivity, and stability, even under high-space velocity and humidity conditions. Due to the strong interaction between Pt and P25-TiO2 originating from the more lattice defects of TiO2, the Pt/TiO2-P catalyst possessed stable Pt0 and Pt2+ species during DCE oxidation and superior redox property, resulting in high activity and stability. Furthermore, the Pt/TiO2-P catalyst possessed abundant hydroxyl groups, which prompted the removal of chlorine species in the form of HCl and significantly decreased the selectivity of vinyl chloride (VC) as the main byproduct. On the other hand, the Pt/TiO2-P catalyst exhibited a different reaction path, in which the hydroxyl groups on its surface activated DCE to form VC and enolic species, besides the lattice oxygen of TiO2 for the Pt catalysts on rutile and anatase TiO2. This work provides guidance for the rational design of catalysts for CVOCs.

Optimization of Co3O4 surface sites for photo-ozone catalytic mineralization of dichloromethane.

Obtaining high removal rate of chlorinated volatile organic compounds (CVOCs) and CO2 selectivity with a low ratio of O3/CVOC and energy consumption is challenging. Dodecylamine was used in this study to create active sites on Co3O4 for photo-ozone catalytic mineralization of dichloromethane (DCM). Amine-Co3O4-450 is a dodecylamine-modified sample with high density of Co3+, Co2+, and hydroxyl due to its nanosheet structure and exposed (112) facets. The optimized surface significantly enhanced the cleavage of the C-Cl bond at low temperatures. Photocatalysis primarily participated in the oxidation of intermediates following DCM dichlorination and significantly improved CO2 selectivity. The respective DCM removal rate and mineralization efficiency of Amine-Co3O4-450 with an O3/DCM molar ratio of 1.27 and one-sun irradiation were 14.9 and 15.0 times higher than the sum of those in the presence of light irradiation or O3 alone. This finding indicated that a strong synergistic effect exists between O3 and light.

Contaminant Back Diffusion from Low-Conductivity Matrices: Case Studies of Remedial Strategies.

Recalcitrant groundwater contamination is a common problem at hazardous waste sites worldwide. Groundwater contamination persists despite decades of remediation efforts at many sites because contaminants sorbed or dissolved within low-conductivity zones can back diffuse into high-conductivity zones, and therefore act as a continuing source of contamination to flowing groundwater. A review of the available literature on remediation of plume persistence due to back diffusion was conducted, and four sites were selected as case studies. Remediation at the sites included pump and treat, enhanced bioremediation, and thermal treatment. Our review highlights that a relatively small number of sites have been studied in sufficient detail to fully evaluate remediation of back diffusion; however, three general conclusions can be made based on the review. First, it is difficult to assess the significance of back diffusion without sufficient data to distinguish between multiple factors contributing to contaminant rebound and plume persistence. Second, high-resolution vertical samples are decidedly valuable for back diffusion assessment but are generally lacking in post-treatment assessments. Third, complete contaminant mass removal from back diffusion sources may not always be possible. Partial contaminant mass removal may nonetheless have potential benefits, similar to partial mass removal from primary DNAPL source zones.

Insights into synergistic oxidation mechanism of Hg0 and chlorobenzene over MnCo2O4 microsphere with oxygen vacancy and acidic site.

The simultaneous control of Hg0 and chlorinated organics has become the frontier of environmental engineering but still lacks the understanding of synergistic oxidation mechanism. Herein, we designed a Mn-Co catalyst with abundant oxygen vacancies and acidities, which delivered more than 90 % oxidation performance of Hg0 within 100-325 °C and achieved 90 % conversion of chlorobenzene at 220 °C. A synergistic effect was observed in the oxidation of Hg0 and chlorobenzene. Experimental and computational results revealed that Lewis acid over Mn site weakened C-Cl bands of chlorobenzene by electronic traction. The strong interaction between adsorbed mercury and Cl further promoted dechlorination process to generate HgCl2 gas, while accelerating the nucleophilic substitution of Brønsted acid attacking the benzene ring over Co site, consequently triggering synergistic oxidation of Hg0 and chlorobenzene. Oxygen vacancies enhanced the initial adsorption of Hg0 and chlorobenzene. Meanwhile, the interfacial charge-transfer from Hg-d to Cl-p orbitals alleviated deactivation of Lewis acid and slowed down the consumption of Brønsted acid, which accelerated the conversion of intermediates to CO2/H2O and promoted deep oxidation of chlorobenzene. This work provides a unique insight into the promotion of the synergistic oxidation of Hg0 and chlorobenzene and is expected to guide the industrial applications.

Simultaneously Constructing Active Sites and Regulating Mn-O Strength of Ru-Substituted Perovskite for Efficient Oxidation and Hydrolysis Oxidation of Chlorobenzene.

Chlorinated volatile organic compounds (CVOCs) are a class of hazardous pollutants that severely threaten environmental safety and human health. Although the catalytic oxidation technique for CVOCs elimination is effective, enhancing the catalytic efficiency and simultaneously inhibiting the production of organic byproducts is still of great challenge. Herein, Ru-substituted LaMn(Ru)O3+ δ perovskite with Ru-O-Mn structure and weakened Mn-O bond strength has been developed for catalytic oxidation of chlorobenzene (CB). The formed Ru-O-Mn structure serves as favorable sites for CB adsorption and activation, while the weakening of Mn-O bond strength facilitates the formation of active oxygen species and improves oxygen mobility and catalyst reducibility. Therefore, LaMn(Ru)O3+ δ exhibits superior low-temperature activity with the temperature of 90% CB conversion decreasing by over 90 °C compared with pristine perovskite, and the deep oxidation of chlorinated byproducts produced in low temperature is also accelerated. Furthermore, the introduction of water vapor into reaction system triggers the process of hydrolysis oxidation that promotes CB destruction and inhibits the generation of chlorinated byproducts, due to the higher-activity *OOH species generated from the dissociated H2 O reacting with adsorbed oxygen. This work can provide a unique, high-efficiency, and facile strategy for CVOCs degradation and environmental improvement.

Core-shell CoCuOx@MOx (MNb, Ti and Ce) catalysts with outstanding durability and resistance to H2O for the catalytic combustion of o-dichlorobenzene.

Configuring Co-based catalysts with excellent activity, durability, anti-H2O capability and superior chlorine resistance is an effective strategy for catalytic combustion of CVOCs. In this work, we elaborated a CoCuOx catalysts with the same core but different shell. The CoCuOx dodecahedron surface was successfully coated with shells of Nb2O5, TiO2, and CeO2 using a range of conventional synthesis methods. The prepared core-shell catalysts (CoCuOx@TiO2 and CoCuOx@Nb2O5) were found to generate plentiful acid sites and abundant lattice oxygen species, indicating a strong interaction between the core and shell layers that resulted in a significant enhancement of catalytic activity. Additionally, by-products generation was successfully controlled by acid sites and lattice oxygen species. More importantly, the core-shell structure design significantly improved the thermal stability and anti-H2O capability of the catalysts. Furthermore, the possible formation pathways and reaction mechanisms were proposed based on in-situ FTIR and selectivity analysis.

Abatement of binary gaseous chlorinated VOC by biotrickling filter: Performance, interactions, and microbial community.

The treatment of waste-gas containing chlorinated volatile organic compounds (CVOCs) has become a difficult issue in current air pollution control. Biotrickling filters (BTFs) have been recognized to be applicable for the treatment of CVOCs, but research on the biodegradation of binary gaseous CVOCs is rare. Herein, a BTF inoculated with Methylobacterium (M.) rhodesianum H13, Starkeya sp. T-2 and activated sludge was established to investigate the biodegradation of the gaseous dichloromethane (DCM) and 1,2-dichloroethane (1,2-DCE) and their interactions implicated. The bioaugmented BTF showed a faster startup (13 days), better removal efficiencies of DCM (80%) and 1,2-DCE (72%), and superior mineralization (65.9%) than that inoculated with activated sludge alone. The ECs of DCM and 1,2-DCE were positively related with the inlet load when the total inlet load was <50 g m-3 h-1. However, inlet loads higher than 50 g m-3 h-1 led to dramatic drop of the RE of DCM and 1,2-DCE due to the limitation of the degradation capacity of microorganisms and the toxic effect of high-concentration substrates. Besides, BTF could stand a lower shock load of 400 mg m-3, while higher shock loads would deteriorate the RE of DCM and 1,2-DCE. And BTF showed better impact resistance toward DCM than 1,2-DCE, probably because the 1,2-DCE biodegrading bacteria was more sensitive to the concentration change. For the same reason, the removal recovery of DCM after starvation was quicker than 1,2-DCE. Kinetic interactions were quantified by the EC-SKIP model, results of which revealed that DCM cast negative effect on 1,2-DCE biodegradation, while 1,2-DCE could promote DCM biodegradation. Moreover, both the results of real-time PCR and high-throughput sequencing showed M. rhodesianum H13 had stronger competitiveness and adaptability than Starkeya sp. T-2. The survived M. rhodesianum H13 and Starkeya sp. T-2 after starvation robustly demonstrated the success of bioaugmentation as well as its great potential of engineering application.

Progress of catalytic oxidation of typical chlorined volatile organic compounds (CVOCs): A review.

Chlorinated volatile organic compounds (CVOCs) are still a part of the current atmospheric environmental problems that cannot be ignored, but unlike conventional VOCs, the presence of Cl causes various catalyst deactivations in the catalytic process. In this paper, we focus on six common CVOCs and discuss various behavioral mechanisms of the whole catalytic process from six aspects: catalyst selection, factors affecting the catalytic effect, changes in catalytic behavior in the presence of different gases, catalyst poisoning deactivation behavior, degradation products and degradation mechanisms to provide guidance for further development of low-temperature and efficient CVOCs catalysts.

Adsorption-enforced Fenton-like process using activated carbon-supported iron oxychloride catalyst for wet scrubbing of airborne dichloroethane.

Wet scrubbing is a low-cost process for disposing of air pollutants. Nevertheless, this method is rarely used for the treatment of volatile organic compounds (VOCs) because of their poor water solubility. In this study, we used a unique wet scrubbing system containing H2O2 and activated carbon (AC)-supported iron oxychloride (FeOCl) nanoparticles to remove airborne dichloroethane (DCE). The operating conditions of the wet scrubber were optimized, and the mechanism was explored. The results showed that the adsorption of dissolved DCE onto AC promoted its transfer from air to water, while the accumulation of DCE on AC facilitated its oxidation by •OH generated on FeOCl catalyst. The wet scrubber performed well at pH 3 and low H2O2 concentrations. By pulsed or continuous dosing H2O2, the cooperative adsorption-catalytic oxidation allowed long-term DCE removal from air. Benefiting from satisfactory cost-effectiveness, avoidance of toxic byproduct formation, and less corrosion and catalyst poisoning, wet scrubbers coupled with cooperative adsorption and heterogeneous advanced oxidation processes could have broad application potentials in VOC control.

Recent Advances of Chlorinated Volatile Organic Compounds' Oxidation Catalyzed by Multiple Catalysts: Reasonable Adjustment of Acidity and Redox Properties.

The severe hazard of chlorinated volatile organic compounds (CVOCs) to human health and the natural environment makes their abatement technology a key topic of global environmental research. Due to the existence of Cl, the byproducts of CVOCs in the catalytic combustion process are complex and toxic, and the possible generation of dioxin becomes a potential risk to the environment. Well-qualified CVOC catalysts should process favorable low-temperature catalytic oxidation ability, excellent selectivity, and good resistance to poisoning, which are governed by the reasonable adjustment of acidity and redox properties. This review overviews the application of different types of multicomponent catalysts, that is, supported noble metal catalysts, transition metal oxide/zeolite catalysts, composite transition metal oxide catalysts, and acid-modified catalysts, for CVOC degradation from the perspective of balance between acidity and redox properties. This review also highlights the synergistic degradation of CVOCs and NOx from the perspective of acidity and redox properties. We expect this work to inspire and guide researchers from both the academic and industrial communities and help pave the way for breakthroughs in fundamental research and industrial applications in this field.

Pt and Mo Co-Decorated MnO2 Nanorods with Superior Resistance to H2O, Sintering, and HCl for Catalytic Oxidation of Chlorobenzene.

MnO2 nanorods with exposed (110), (100), or (310) facets were prepared and investigated for catalytic oxidation of chlorobenzene, then the (110)-exposed MnO2 nanorod was screened as the candidate parent and further modified by Pt and/or Mo with different contents. The loading of Pt enhanced activity and versatility of the pristine MnO2, but the polychlorinated byproducts and Cl2 were promoted, conversely, as the decoration of Mo inhibited the polychlorinated byproducts and improved durability. Determination of structure and properties suggested that Pt facilitated the formation of more oxygen vacancies/Mn3+ and surface adsorbed oxygen weakened the bonds of surface lattice oxygen, while Mo stabilized surface lattice oxygen and increased acid sites, especially Brønsted acid sites. Expectedly, Pt and Mo bifunctionally modified MnO2 presented a preferable activity, selectivity, and durability along with the super resistance to H2O, high-temperature, and HCl, and no prominent deactivation was observed within 30 h at 300 °C under dry and humid conditions, even at high-temperature aging at 600 °C and HCl-pretreatment (7 h). In this work, the optimized Mo and Pt codecorated MnO2 was considered a promising catalyst toward practical applications for catalytic oxidation of actual Cl-VOCs emissions.

Sequential anaerobic and aerobic bioaugmentation for commingled groundwater contamination of trichloroethene and 1,4-dioxane.

Chlorinated solvents, notably trichloroethene (TCE), and the cyclic ether stabilizer, 1,4-dioxane (dioxane), have been frequently detected commingling in contaminated aquifers. Here we developed a sequential anaerobic and aerobic treatment strategy effective to mitigate the co-contamination of TCE and dioxane, particularly when dioxane is present at ppb levels relevant to many impacted sites. After the primary anaerobic treatment by a halorespiring consortium SDC-9, TCE was effectively removed, though lingering less-chlorinated metabolites, vinyl chloride (VC) and cis-dichloroethene (cDCE). Subsequent aerobic bioaugmentation with Azoarcus sp. DD4, a cometabolic dioxane degrader, demonstrated the ability of DD4 to degrade dioxane at an initial concentration of 20 µg/L to below 0.4 µg/L and its dominance (~7%) in microcosms fed with propane. Even better, DD4 can also transform VC and cDCE in tandem, though cDCE and VC at relatively high concentrations (e.g., 1 mg/L) posed inhibition to propane assimilation and cell growth of DD4. Mutagenesis of DD4 revealed group-2 toluene monooxygenase and group-5 propane monooxygenase are responsible for cDCE and VC co-oxidation, respectively. Overall, we demonstrated the feasibility of a treatment train combining reductive dehalogenation and aerobic co-oxidation processes in tandem to not only effectively clean up prevalent co-contamination of TCE and dioxane at trace levels but also mitigate persistent products (e.g., cDCE and VC) when complete reductive dehalogenation of less-chlorinated ethenes occurs slowly in the field.

Biotechnology and nanotechnology for remediation of chlorinated volatile organic compounds: current perspectives.

Chlorinated volatile organic compounds (CVOCs) are persistent organic pollutants which are harmful to public health and the environment. Many CVOCs occur in substantial quantities in groundwater and soil, even though their use has been more carefully managed and restricted in recent years. This review summarizes recent data on several innovative treatment solutions for CVOC-affected media including bioremediation, phytoremediation, nanoscale zero-valent iron (nZVI)-based reductive dehalogenation, and photooxidation. There is no optimally developed single technology; therefore, the possibility of using combined technologies for CVOC remediation, for example bioremediation integrated with reduction by nZVI, is presented. Some methods are still in the development stage. Advantages and disadvantages of each treatment strategy are provided. It is hoped that this paper can provide a basic framework for selection of successful CVOC remediation strategies.

Effect of hydrogeological and anthropogenic factors on the spatial and temporal distribution of CVOCs in the karst system of northern Puerto Rico.

This study evaluates factors affecting the spatial and temporal distribution of chlorinated volatile organic contaminants (CVOCs) in the highly productive aquifers of the karst region in northern Puerto Rico (KR-NPR). Historical records from 1982 to 2016 are analyzed using spatial and statistical methods to evaluate hydrogeological and anthropogenic factors affecting the presence and concentrations of multiple CVOCs in the KR-NPR. Results show extensive spatial and temporal distributions of CVOCs, as single entities and as mixtures. It is found that at least one type of CVOC is present above detection limits in 64% of the samples and 77% of the sampling sites during the study period. CVOC distribution in the KR-NPR is contaminant-dependent, with some species being strongly influenced by the source of contamination and hydrogeological characteristics of the system. Persistent presence of CVOCs in the KR-NPR system, even after contaminated sites have been subjected to active remediation, reflect the high capacity of the system to store and slowly release contaminants over long periods of time. This study shows that karst aquifers are highly vulnerable to contamination and can serve as a long-term route of contaminants to potential points of exposure.