Standard monitoring programs give limited insight into groundwater status, especially transformation products (TPs) formed by natural processes or advanced oxidation processes (AOP), are normally underrepresented. In this study, using suspect and non-target screening, we performed a comprehensive analysis of groundwater before and after AOP by UV/H₂O₂ and consecutively installed biological activated carbon filters (BAC). By non-target screening, up to 413 compounds were detected in the groundwater, with an average 70% removal by AOP. However, a similar number of compounds were formed during the process, shown in groundwater from three waterworks. The most polar compounds were typically the most stable during the AOP. A subsequent BAC filter showed removal of 95% of the TPs, but only 46% removal of the AOP remaining precursors. The BAC removal for polar compounds was highly dependent on the acidic and basic functional groups of the molecules. 49 compounds of a wide polarity range could be identified by supercritical fluid chromatography (SFC) and liquid chromatography (LC) with high resolution mass spectrometry (HRMS); of these, 29 compounds were already present in the groundwater. To the best of our knowledge, five compounds have never been reported before in groundwater (4-chlorobenzenesulfonic acid, dibutylamine, N-phenlybenzenesulfonamide, 2-(methylthio)benzothiazole and benzothiazole-2-sulfonate). A further five rarely reported compounds are reported for the first time in Danish groundwater (2,4,6-trichlorophenol, 2,5-dichlorobenzenesulfonic acid, trifluormethansulfonic acid, pyrimidinol and benzymethylamine). Twenty of the identified compounds were formed by AOP, of which 10 have never been reported before in groundwater. All detected compounds could be related to agricultural and industrial products as well as artificial sweeteners. Whereas dechlorination was a common AOP degradation pathway for chlorophenols, the (ultra-) short chain PFAs showed no removal in our study. We prioritized 11 compounds as of concern, however, the toxicity for many compounds remains unknown, especially for the TPs.

This study demonstrated that nitrogen-doped carbon materials (NCMs) could effectively catalyze the chlorine elimination process in hexachloroethane (HCA) declorination in sulfide-containing environments for the first time. The kₒbₛ values of HCA dechlorination by sulfide in the presence of 10 mg/L NCMs were higher than that of no mediator at pH 7.3 by one or two orders of magnitude. The catalytic capabilities of NCMs on HCA dechlorination were evident in common ranges of natural pH (5.3–8.9) and it could be accelerated by the increase of pH but be suppressed by the presence of dissolved humic acid. Moreover, NCMs exhibited much better catalytic capability on HCA dechlorination compared to the carbon materials, mainly owing to the combined contributions of pyridine N, including enhanced nucleophilic attack to HCA molecule by generating newborn C–S–S and activation of HCA molecule by elongating C–Cl bonds. The functions of pyridine N in micron-sized NCMs with mesopores were better than in nano-sized NCMs on HCA dechlorination. These findings displayed the potential of NCMs, when released into sulfide-containing environments, may significantly increase the dechlorination of chlorinated aliphatic hydrocarbons.

The feasibility and effectiveness of iron turning waste as low cost and sustainable permeable reactive barrier (PRB) media for remediating dieldrin, endrin, dichlorodiphenyltrichloroethane (DDT), and lindane individually (batch system) and combined (continuous flow column) in water were investigated. After 10 min of reaction in a batch system, removal of endrin, dieldrin, and DDT was higher (86–91 %) than lindane (41 %) using 1 g of iron turning waste in 200 mL of pesticide solution (20 μg/L for each pesticide). Among the studied pesticides, only lindane removal decreased substantially in the presence of nitrate (37 %) and magnesium (18 %). Acidic water environment (pH = 4) favored the pesticide removal than neutral and basic environments. For the column experiments, sand alone as PRB media was ineffective for remediating the pesticides in water. When only iron turning was used, the removal efficiencies of lindane, endrin, and dieldrin were 83–88 % and remained stable during 60 min of the experiments. DDT removal was less than other pesticides (58 %). Sandwiching the iron turning waste media between two sand layers improved DDT removal (79 %) as well as limited the iron content below a permissible level in product water. In a long-term PRB column performance evaluation, iron turning waste (150 g) removed all pesticides in water (initial concentration of each pesticide = 2 μg/L) effectively (≥94 %) at a hydraulic retention time of 1.6 h. Iron turning waste, which was mainly in the form of zerovalent iron (Fe⁰), was oxidized to ferrous (Fe²⁺) and ferric (Fe³⁺) iron during its reaction with pesticides, and electrons donated by Fe⁰ and Fe²⁺ were responsible for complete dechlorination of all the pesticides. Therefore, it can be used as inexpensive and sustainable PRB media for groundwater remediation especially in developing countries where groundwater contamination with pesticides is more prevalent.

Xanthan gels were assessed to control the reductive dechlorination of hexachlorocyclohexanes (HCHs) and trichlorobenzenes (TCBs) in a strong permeability contrast and high velocity sedimentary aquifer. An alkaline degradation was selected because of the low cost of NaOH and Ca(OH)₂. The rheology of alkaline xanthan gels and their ability to deliver alkalinity homogeneously, while maintaining the latter, were studied. Whereas the xanthan gels behaved like non-Newtonian shear-thinning fluids, alkalinity and Ca(OH)₂ microparticles had detrimental effects, yet, the latter decreased with the shear-rate. Breakthrough curves for the NaOH and Ca(OH)₂ in xanthan solutions, carried out in the lowest permeability soil (9.9 μm²), demonstrated the excellent transmission of alkalinity, while moderate pressure gradients were applied. Injection velocities ranging from 1.8 to 3.8 m h⁻¹ are anticipated in the field, given the permeability range from 9.9 to 848.7 μm². Despite a permeability contrast of 8.7 in an anisotropic aquifer model, the NaOH and the Ca(OH)₂ both in xanthan gels spread only 5- and 7-times faster in the higher permeability zone, demonstrating that the delivery was enhanced. Moreover, the alkaline gels which were injected into a high permeability layer under lateral water flow, showed a persistent blocking effect and longevity (timescale of weeks), in contrast to the alkaline solution in absence of xanthan. Kinetics of alkaline dechlorination carried out on the historically contaminated soil, using the Ca(OH)₂ suspension in xanthan solution, showed that HCHs were converted in TCBs by dehydrodechlorination, whereas the latter were then degraded by reductive hydrogenolysis. Degradation kinetics were achieved within 30 h for the major and most reactive fraction of HCHs.

Anaerobic reductive treatment technologies offer cost-effective and large-scale treatment of chlorinated compounds, including polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). The information about the degradation rates of these compounds in natural settings is critical but difficult to obtain because of slow degradation processes. Establishing a relationship between biotransformation rate and abundance of biomarkers is one of the most critical challenges faced by the bioremediation industry. When solved for a given contaminant, it may result in significant cost savings because of serving as a basis for action. In the current review, we have summarized the studies highlighting the use of biomarkers, particularly DNA and RNA, as a proxy for reductive dechlorination of chlorinated ethenes. As the use of biomarkers for predicting biotransformation rates has not yet been executed for PCDD/Fs, we propose the extension of the same knowledge for dioxins, where slow degradation rates further necessitate the need for developing the biomarker-rate relationship. For this, we have first retrieved and calculated the bioremediation rates of different PCDD/Fs and then highlighted the key sequences that can be used as potential biomarkers. We have also discussed the implications and hurdles in developing such a relationship. Improvements in current techniques and collaboration with some other fields, such as biokinetic modeling, can improve the predictive capability of the biomarkers so that they can be used for effectively predicting biotransformation rates of dioxins and related compounds. In the future, a valid and established relationship between biomarkers and biotransformation rates of dioxin may result in significant cost savings, whilst also serving as a basis for action.

In this study, the YH consortium, an ethene-producing culture, was used to evaluate the effect of vitamin B₁₂ (VB₁₂) on trichloroethene (TCE) dechlorination by transferring the original TCE-reducing culture with or without adding exogenous VB₁₂. Ultra-high performance liquid chromatography - tandem mass spectrometry (UPLC-MS/MS) was applied to detect the concentrations of VB₁₂ and its lower ligand 5,6-dimethylbenzimidazole (DMB) in the cultures. After three successive VB₁₂ starvation cycles, the dechlorination of TCE stopped mostly at cis-dichloroethene (cDCE), and no ethene was found; methane production increased significantly, and no VB₁₂ was detected. Results suggest that the co-cultured microbes may not be able to provide enough VB₁₂ as a cofactor for the growth of Dehalococcoides in the YH culture, possibly due to the competition for corrinoids between Dehalococcoides and methanogens. The relative abundances of 16 S rRNA gene of Dehalococcoides and reductive dehalogenase genes tceA or vcrA were lower in the cultures without VB₁₂ compared with the cultures with VB₁₂. VB₁₂ limitation changed the microbial community structures of the consortia. In the absence of VB₁₂, the microbial community shifted from dominance of Chloroflexi to Proteobacteria after three consecutive VB₁₂ starvation cycles, and the dechlorinating genus Dehalococcoides declined from 42.9% to 13.5%. In addition, Geobacter, Clostridium, and Desulfovibrio were also present in the cultures without VB₁₂. Furthermore, the abundance of archaea increased under VB₁₂ limited conditions. Methanobacterium and Methanosarcina were the predominant archaea in the culture without VB₁₂.

The study was conducted to demonstrate the influence of extracellular secretions from Microbacterium on the reductive dechlorination of tetrachloroethene (PCE). A series of mixed cultures were established from a paddy soil sample. In the mixed cultures amended with extracellular secretions from Microbacterium, PCE was rapidly and completely converted into cis-1,2-dichloroethene (cis-DCE) and trans-1,2-dichloroethene (trans-DCE) within 40 days. The unamended mixed cultures showed weak signs of dechlorination after a pronounced lag phase, and trichloroethene (TCE) was accumulated as a major end product. This result means that amendment with extracellular secretions from Microbacterium shortened the lag phase, increased the dechlorination velocity and promoted the production of less-chlorinated chloroethene. The results were corroborated by defined subculture experiments, which proved that microorganisms from unamended mixed cultures could also be stimulated by extracellular secretions from Microbacterium. Desulfitobacterium was identified as the main dechlorinating population in all mixed cultures by direct PCR. Additionally, the 16S rRNA gene copies of Desulfitobacterium increased by one or two orders of magnitude with PCE dechlorination, which provided corroborative evidence for the identification result. The volatile fatty acids were monitored, and most interestingly, a close association between propionate oxidation and dechlorination was found, which has rarely been mentioned before. It was assumed that the oxidation of propionate provided hydrogen for dechlorination, while dechlorination facilitated the shift of the reaction toward propionate oxidation by reducing the partial pressure of hydrogen.

Biodegradation of 1,4-dioxane was examined in packed quartz and soil column flow-through systems. The inhibitory effects of co-contaminants, specifically trichloroethene (TCE), 1,1-dichloroethene (1,1-DCE), and copper (Cu²⁺) ions, were investigated in the columns either with or without bioaugmentation with a 1,4-dioxane degrading bacterium Pseudonocardia dioxanivorans CB1190. Results indicate that CB1190 cells readily grew and colonized in the columns, leading to significant degradation of 1,4-dioxane under oxic conditions. Degradation of 1,4-dioxane was also observed in the native soil (without bioaugmentation), which had been previously subjected to enhanced reductive dechlorination treatment for co-contaminants TCE and 1,1-DCE. Bioaugmentation of the soil with CB1190 resulted in nearly complete degradation at influent concentrations of 3–10 mg L⁻¹ 1,4-dioxane and a residence reaction time of 40–80 h, but the presence of co-contaminants, 1,1-DCE and Cu²⁺ ions (up to 10 mg L⁻¹), partially inhibited 1,4-dioxane degradation in the untreated and bioaugmented soil columns. However, the inhibitory effects were much less severe in the column flow-through systems than those previously observed in planktonic cultures, which showed near complete inhibition at the same co-contaminant concentrations. These observations demonstrate a low susceptibility of soil microbes to the toxicity of 1,1-DCE and Cu²⁺ in packed soil flow-through systems, and thus have important implications for predicting biodegradation potential and developing sustainable, cost-effective technologies for in situ remediation of 1,4-dioxane contaminated soils and groundwater.

Applying an electric field to stimulate the microbial reductive dechlorination of polychlorinated biphenyls (PCBs) represents a promising approach for bioremediation of PCB-contaminated sites. This study aimed to demonstrate the biocathodic film-facilitated reduction of PCB 61 in a sediment-based bioelectrochemical reactor (BER) and, more importantly, the characterizations of electrode-microbe interaction from microbial and electrochemical perspectives particularly in a time-dependent manner. The application of a cathodic potential (−0.45 V vs. SHE) significantly improved the rate and extent of PCB 61 dechlorination compared to the open-circuit scenario (without electrical stimulation), and the addition of an external surfactant further increased the dechlorination, with Tween 80 exerting more pronounced effects than rhamnolipid. The bacterial composition of the biofilms and the bioelectrochemical kinetics of the BERs were found to be time-dependent and to vary considerably with the incubation time and slightly with the coexistence of an external surfactant. Excellent correlations were observed between the dechlorination rate and the relative abundance of Dehalogenimonas, Dechloromonas, and Geobacter, the dechlorination rate and the cathodic current density recorded from the chronoamperometry tests, and the dechlorination rate and the charge transfer resistance derived from the electrochemical impedance tests, with respect to the 120 day-operation. After day 120, PCB 61 was resistant to further appreciable reduction, but substantial hydrogen production was detected, and the bacterial community and electrochemical parameters observed on day 180 were not distinctly different from those on day 120.

Short chain chlorinated paraffins (SCCPs) are ubiquitously present as persistent organic pollutants in the environment. However, little information on the interaction of SCCPs with plants is currently available. In this work, young pumpkin plants (Cucurbita maxima × C. Moschata) were hydroponically exposed to the congener of chlorinated decane, 1,2,5,5,6,9,10-heptachlorodecane (1,2,5,5,6,9,10-HepCD), to investigate the uptake, translocation and transformation of chlorinated decanes in the intact plants. It was found that parent HepCD was taken up by the pumpkin roots, translocated from root to shoots, and phytovolatilized from pumpkin plants to air via the plant transpiration flux. Our data suggested that dechlorination of 1,2,5,5,6,9,10-HepCD to lower chlorinated decanes and rearrangement of chlorine atoms in the molecule were all mediated by the whole pumpkin seedlings. Chlorinated decanes were found in the shoots and roots of blank controls, indicating that chlorinated decanes in the air could be absorbed by leaves and translocated from shoots to roots. Lower chlorinated congeners (C10H17Cl5) tended to detain in air compared to higher chlorinated congeners (C10H16Cl6 and other C10H15Cl7). Potential transformation pathway and behavior of 1,2,5,5,6,9,10-HepCD in pumpkin were proposed based on these experiments.