Hexanitrohexaazaisowurtzitane (CL-20) is an emerging explosive that may replace the currently used explosives such as RDX and HMX, but little is known about its fate in soil. The present study was conducted to determine degradation products of CL-20 in two sandy soils under abiotic and biotic anaerobic conditions. Biotic degradation was prevalent in the slightly acidic VT soil, which contained a greater organic C content, while the slightly alkaline SAC soil favored hydrolysis. CL-20 degradation was accompanied by the formation of formate, glyoxal, nitrite, ammonium, and nitrous oxide. Biotic degradation of CL-20 occurred through the formation of its denitrohydrogenated derivative (m/z 393 Da) while hydrolysis occurred through the formation of a ring cleavage product (m/z 156 Da) that was tentatively identified as CH2N-C(N-NO2)-CHN-CHO or its isomer N(NO2)CH-CHN-CO-CHNH. Due to their chemical specificity, these two intermediates may be considered as markers of in situ attenuation of CL-20 in soil. Two key intermediates of CL-20 degradation are potential markers of its natural attenuation in soil.

Nitrogen loss via overland flow from agricultural land use is a global threat to waterways. On-farm denitrifying woodchip bioreactors can mitigate NO₃⁻ exports by increasing denitrification capacity. However, denitrification in sub-optimal conditions releases the greenhouse gas nitrous oxide (N₂O), swapping the pollution from aquatic to atmospheric reservoirs. Here, we assess NO₃⁻-N removal and N₂O emissions from a new edge-of-field surface-flow bioreactor during ten rain events on intensive farming land. Nitrate removal rates (NRR) varied between 5.4 and 76.2 g NO₃⁻-N m⁻³ wetted woodchip d⁻¹ with a mean of 30.3 ± 7.3 g NO₃⁻-N m⁻³. The nitrate removal efficiency (NRE) was ∼73% in ideal hydrological conditions and ∼18% in non-ideal conditions. The fraction of NO₃⁻-N converted to N₂O (rN₂O) in the bioreactor was ∼3.3 fold lower than the expected 0.75% IPCC emission factor. We update the global bioreactor estimated Q₁₀ (NRR increase every 10 °C) from a recent meta-analysis with previously unavailable data to >20 °C, yielding a new global Q₁₀ factor of 3.1. Mean N₂O CO₂-eq emissions (431.9 ± 125.4 g CO₂-eq emissions day⁻¹) indicate that the bioreactor was not significantly swapping aquatic NO₃⁻ for N₂O pollution. Our estimated NO₃⁻-N removal from the bioreactor (9.9 kg NO₃⁻-N ha⁻¹ yr⁻¹) costs US$13.14 per kg NO₃⁻-N removed and represents ∼30% NO₃⁻-N removal when incorporating all flow and overflow events. Overall, edge-of-field surface-flow bioreactors seem to be a cost-effective solution to reduce NO₃⁻-N runoff with minor pollution swapping to N₂O.

As(V) reduction mediated by microorganisms might be an essential process in resisting As toxicity since As(V) is the major species in the landfill. LSZ has been considered as a trigger of all types of microbial activity inside a landfill site. This research investigated the microbial As(V)-reducing behavior in LSZ. The results revealed that higher As(V)-reduction efficiency in higher As(V) content-stress LSZ scenario. The corresponding microbial diversity also varied with the As(V) content. The microbial community structure was related to arrA and arsC distribution, which encode respiratory As(V) reductase and cytoplasmic As(V) reductase, respectively. The landfill As bio-reduction pathways were modeled, as well as the As functional gene distribution among different As(V) contents at different landfill stages. The C, N, and S metabolic processes generally affected the As(V)-resistance genes distribution. Thiosulfate oxidation, denitrification, and dissimilatory nitrate reduction positively affected arsC, while dissimilatory sulfate reduction and methanogenesis trended to play a negative role. This research provides new insight into As(V) bio-reduction inside a landfill site in terms of functional genes distribution and correlation with nutrient elements metabolic processes.

Denitrifying anaerobic methane oxidation (DAMO) plays an important role in the element cycle of wetlands. In recent years, the content of antibiotics in wetlands has gradually increased due to human activities. However, the impact of antibiotics on the ecological function of DAMO remains unclear. Here we studied the influence of three high-content quinolone antibiotics (QNs) on DAMO in the sediments of the Baiyangdian Wetland. The results show that QNs can significantly promote the potential DAMO rates. Moreover, the enhancement of potential DAMO rates is positively correlated with the dosage of QNs. This promotion effect of QNs on nitrate-DAMO can be attributed to the hormesis phenomenon or their inhibition of substrate competitors. As antibacterial agents, QNs inhibit nitrite-DAMO conducted by bacteria, but greatly promote nitrate-DAMO conducted by archaea. These results suggest that the short-term effect of QNs on DAMO in wetlands is promotion rather than inhibition.

The extensive use of nano-TiO₂ has caused concerns regarding their potential environmental risks. However, the stress responses and self-recovery potential of nitrogen removal and greenhouse gas N₂O emissions after long-term nano-TiO₂ exposure have seldom been addressed yet. This study explored the long-term effects of nano-TiO₂ on biological nitrogen transformations in a sequencing batch reactor at four levels (1, 10, 25, and 50 mg/L), and the reactor's self-recovery potential was assessed. The results showed that nano-TiO₂ exhibited a dose-dependent inhibitory effect on the removal efficiencies of ammonia nitrogen and total nitrogen, whereas N₂O emissions unexpectedly increased. The promoted N₂O emissions were probably due to the inhibition of denitrification processes, including the reduction of the denitrifying-related N₂O reductase activity and the abundance of the denitrifying bacteria Flavobacterium. The inhibition of carbon source metabolism, the inefficient electron transfer efficiency, and the electronic competition between the denitrifying enzymes would be in charge of the deterioration of denitrification performance. After the withdrawal of nano-TiO₂ from the influent, the nitrogen transformation efficiencies and the N₂O emissions of activated sludge recovered entirely within 30 days, possibly attributed to the insensitive bacteria survival and the microbial community diversity. Overall, this study will promote the current understanding of the stress responses and the self-recovery potential of BNR systems to nanoparticle exposure.

Estuaries are considered as important sources of the global emission of greenhouse gases (GHGs). Urbanized estuaries often experience eutrophication under strong anthropogenic activities. Eutrophication can enhance phytoplankton abundance, leading to carbon dioxide (CO₂) consumption in the water column. Only a few studies have evaluated the relationship between GHGs and eutrophication in estuaries. In this study, we assessed the concentrations and fluxes of CO₂, methane (CH₄) and nitrous oxide (N₂O) in combination with a suite of biogeochemical variables in four sampling campaigns over two years in a highly urbanized tropical estuary in Southeast Asia (the Saigon River Estuary, Vietnam). The impact of eutrophication on GHGs was evaluated through several statistical methods and interpreted by biological processes. The average concentrations of CO₂, CH₄ and N₂O at the Saigon River in 2019–2020 were 3174 ± 1725 μgC-CO₂ L⁻¹, 5.9 ± 16.8 μgC-CH₄ L⁻¹ and 3.0 ± 4.8 μgN-N₂O L⁻¹, respectively. Their concentrations were 13–18 times, 52–332 times, and 9–37 times higher than the global mean concentrations of GHGs, respectively. While CO₂ concentration had no clear seasonal pattern, N₂O and CH₄ concentrations significantly differed between the dry and the rainy seasons. The increase in eutrophication status along the dense urban area was linearly correlated with the increase in GHGs concentrations. The presence of both nitrification and denitrification resulted in elevated N₂O concentrations in this urban area of the estuary. The high concentration of CO₂ was contributed by the high concentration of organic carbon and mineralization process. GHGs fluxes at the Saigon River Estuary were comparable to other urbanized estuaries regardless of climatic condition. Control of eutrophication in urbanized estuaries through the implantation of efficient wastewater treatment facilities will be an effective solution in mitigating the global warming potential caused by estuarine emissions.

The widespread use of decabromodiphenyl ether (BDE-209) resulted in its deposition in environmental media and biological matrices. However, to date, few studies focused on the effect of BDE-209 on microorganisms, and those available were investigated via an enclosed system completely cutting off the communication between testing system and its native environment. Herein, 4.0 mg/g BDE-209 acute exposure induced a 20% decline of NOX-N (the sum of NO₃⁻–N and NO₂⁻–N) removal efficiency and a significant accumulation of NO₂⁻–N and N₂O. These inhibitory effects presented in a BDE-209 concentration-dependent manner. Using a semi-continuous microcosm, the inhibitory effects of BDE-209 on denitrification were observed to be significantly enhanced with the extending of exposure duration. Denitrifying genes assay illustrated that BDE-209 has an insignificant effect on the global abundance of denitrifying bacteria because of microbial exchange with its overlying water. But the utilization of electron donor (carbon substrate), the activity of electron transport system and denitrifying enzymes were significantly inhibited by BDE-209 exposure in a exposure-duration-dependent manner. Finally, insufficient electron donor and lower efficiency of electron transport and utilization on denitrifying enzymes deteriorated the denitrification performance. These results provided a new insight into BDE-209 influence on denitrification in the natural environment.

Microplastic (MP) contamination is ubiquitous in agricultural soils. As a cost-effective soil amendment, biochar (BC) often coincides with MP exposure. However, little research has been conducted regarding the independent and combined effects of MPs and BC on the soil microbiome and N₂O/CH₄ emissions. Therefore, in this study, polyethylene terephthalate (PET) and wheat straw-derived BC were used, respectively, as representative MP and BC during an entire rice growth period. The high-throughput sequencing results showed that PET alone lowered bacterial diversity by 26.7%, while PET and BC co-existence did not induce apparent change. The relative abundances of some microbes (e.g., Cyanobacteria, Verrucomicrobia, and Bacteroidetes) that are associated with C and N cycling were changed at the phylum and class levels by all the treatments. In comparison with the control, the treatment of BC, PET, and their co-existence reduced the cumulative CH₄ emissions by 50%, 53%, and 61%, respectively. The higher mitigation by BC + PET may be the result of higher soil Eh and a consequently lower methanogenesis functional gene mcrA abundance in the treated soils. In addition, BC and PET alone, as well as their combined treatment, increased the abundance of nitrification genes, enhancing the soil nitrification process. However, the relative contribution of the nitrification process to N₂O emission was possibly lower than that of denitrification, in which the N₂O reductase gene nosZ was found to be the primary gene regulating N₂O emissions. BC alone increased nosZ abundance by 42.3%, thereby showing the potential in suppressing N₂O emission. In contrast, when BC was co-added with PET, the nosZ abundance lowered possibly because of increased soil aeration, and thus its cumulative N₂O emission was 38% higher than the BC treatment. Overall, these results demonstrated that BC and PET function differently in soil ecosystems when they coexisted.

The occurrence of excessive ammonium in groundwater threatens human and aquatic ecosystem health across many places worldwide. As the fate of ammonium in groundwater systems is often affected by a complex mixture of transport and biogeochemical transformation processes, identifying the sources of groundwater ammonium is an important prerequisite for planning effective mitigation strategies. Elevated ammonium was found in both a shallow and an underlying deep groundwater system in an alluvial aquifer system beneath an agricultural area in the central Yangtze River Basin, China. In this study we develop and apply a novel, indirect approach, which couples the random forest classification (RFC) of machine learning method and fluorescence excitation-emission matrices with parallel factor analysis (EEM-PARAFAC), to distinguish multiple sources of ammonium in a multi-layer aquifer. EEM-PARAFAC was applied to provide insights into potential ammonium sources as well as the carbon and nitrogen cycling processes affecting ammonium fate. Specifically, RFC was used to unravel the different key factors controlling the high levels of ammonium prevailing in the shallow and deep aquifer sections, respectively. Our results reveal that high concentrations of ammonium in the shallow groundwater system primarily originate from anthropogenic sources, before being modulated by intensive microbially mediated nitrogen transformation processes such as nitrification, denitrification and dissimilatory nitrate reduction to ammonium (DNRA). By contrast, the linkage between high concentrations of ammonium and decomposition of soil organic matter, which ubiquitously contained nitrogen, suggested that mineralization of soil organic nitrogen compounds is the primary mechanism for the enrichment of ammonium in deeper groundwaters.

Denitrification, as both origins and sinks of N₂O, occurs extensively, and is of critical importance for regulating N₂O emissions in acidified soils. However, whether soil acidification stimulates N₂O emissions, and if so for what reason contributes to stimulate the emissions is uncertain and how the N₂O fractions from fungal (ffD) and bacterial (fbD) denitrification change with soil pH is unclear. Thus, a pH gradient (6.2, 7.1, 8.7) was set via manipulating cropland soils (initial pH 8.7) in North China to illustrate the effect of soil acidification on fungal and bacterial denitrification after the addition of KNO₃ and glucose. For source partitioning, we used and compared SP/δ¹⁸O mapping approach (SP/δ¹⁸O MAP) and acetylene inhibition technique combined isotope two endmember mixing model (AIT-IEM). The results showed significantly higher N₂O emissions in the acidified soils (pH 6.2 and pH 7.1) compared with the initial soil (pH 8.7). The cumulative N₂O emissions during the whole incubation period (15 days) ranged from 7.1 mg N kg⁻¹ for pH 8.7–18.9 mg N kg⁻¹ for pH 6.2. With the addition of glucose, relative to treatments without glucose, this emission also increased with the decrement of pH values, and were significantly stimulated. Similarly, the highest N₂O emissions and N₂O/(N₂O + N₂) ratios (rN₂O) were observed in the pH 6.2 treatment. But the difference was the highest cumulative N₂O + N₂ emissions, which were recorded in the pH 7.1 treatment based on SP/δ¹⁸O MAP. Based on both approaches, ffD values slightly increased with the acidification of soil, and bacterial denitrification was the dominant pathway in all treatments. The SP/δ¹⁸O MAP data indicated that both the rN₂O and ffD were lower compared to AIT-IEM. It has been known for long that low pH may lead to high rN₂O of denitrification and ffD, but our documentation of a pervasive pH-control of rN₂O and ffD by utilizing combined SP/δ¹⁸O MAP and AIT-IEM is new. The results of the evaluated N₂O emissions by acidified soils are finely explained by high rN₂O and enhanced ffD. We argue that soil pH management should be high on the agenda for mitigating N₂O emissions in the future, particularly for regions where long-term excessive nitrogen fertilizer is likely to acidify the soils.