Exploring the Utility of Compound-Specific Isotope Analysis for Assessing Ferrous Iron-Mediated Reduction of RDX in the Subsurface.

Subsurface contamination with the explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) at ordnance production and testing sites is a problem because of the persistence, mobility, and toxicity of RDX and the formation of toxic products under anoxic conditions. While the utility of compound-specific isotope analysis for inferring natural attenuation pathways from stable isotope ratios has been demonstrated, the stable isotope fractionation for RDX reduction by iron-bearing minerals remains unknown. Here, we evaluated N and C isotope fractionation of RDX during reduction by Fe(II) associated with Fe minerals and natural sediments and applied N isotope ratios to the assessment of mineral-catalyzed RDX reduction in a contaminant plume and in sediment columns treated by in situ chemical reduction. Laboratory studies revealed that RDX was reduced to nitroso compounds without denitration and the concomitant ring cleavage. Fe(II)/iron oxide mineral-catalyzed reactions exhibited N isotope enrichment factors, εN, between -6.3±0.3‰ and -8.2±0.2‰, corresponding to an apparent 15N kinetic isotope effect of 1.04-1.05. The observed variations of the δ15N of ∼15‰ in RDX from groundwater samples suggested an extent of reductive transformation of 85% at an ammunition plant. Conversely, we observed masking of N isotope fractionation after RDX reduction in laboratory flow-through systems, which was presumably due to limited accessibility to reactive Fe(II).

Estimating natural gas emissions from underground pipelines using surface concentration measurements☆.

Rapid response to underground natural gas leaks could mitigate methane emissions and reduce risks to the environment, human health and safety. Identification of large, potentially hazardous leaks could have environmental and safety benefits, including improved prioritization of response efforts and enhanced understanding of relative climate impacts of emission point sources. However, quantitative estimation of underground leakage rates remains challenging, considering the complex nature of methane transport processes. We demonstrate a novel method for estimating underground leak rates based on controlled underground natural gas release experiments at the field scale. The proposed method is based on incorporation of easily measurable field parameters into a dimensionless concentration number, ε, which considers soil and fluid characteristics. A series of field experiments was conducted to evaluate the relationship between the underground leakage rate and surface methane concentration data over varying soil and pipeline conditions. Peak surface methane concentrations increased with leakage rate, while surface concentrations consistently decreased exponentially with distance from the source. Deviations between the estimated and actual leakage rates ranged from 9% to 33%. A numerical modeling study was carried out by the TOUGH3 simulator to further evaluate how leak rate and subsurface methane transport processes affect the resulting methane surface profile. These findings show that the proposed leak rate estimation method may be useful for prioritizing leak repair, and warrant broader field-scale method validation studies. A method was developed to estimate fugitive emission rates from underground natural gas pipeline leaks. The method could be applied across a range of soil and surface covering conditions.

Mineral identity, natural organic matter, and repeated contaminant exposures do not affect the carbon and nitrogen isotope fractionation of 2,4-dinitroanisole during abiotic reduction.

The recent development of insensitive munitions, such as 2,4-dinitroanisole (DNAN), as components of military explosives has generated concern for potential subsurface contamination and created a need to fully characterize their transformation processes. Compound specific isotope analysis (CSIA) has proven to be a useful means of assessing transformation pathways according to characteristic stable isotope fractionation patterns. The C and N isotope fractionation of DNAN associated with abiotic and enzymatic hydrolysis was recently assessed. The extent to which DNAN isotope fractionation will be affected by other potentially competing transformation pathways known for nitroaromatic compounds (e.g., reduction) and if previous knowledge can be extrapolated to other environmental matrices remains to be understood. Here, we investigated the C and N isotope fractionation and reaction rate constants of DNAN during abiotic reduction mediated by mineral-associated Fe(ii) species as a function of mineral type, natural organic matter presence, and repeated exposures to DNAN. Though rate constants varied, N and C apparent kinetic isotope effects (AKIEs) remained consistent across all experiments (averaged values of 15N-AKIE = 1.0317 ± 0.0064 and 13C-AKIE = 1.0008 ± 0.0005) and revealed significant 15N- and minimal 13C-enrichment in agreement with previous work on nitroaromatic compounds. Moreover, the observed fractionation was clearly distinct from trends for abiotic and enzymatic hydrolysis. This study provides a strengthened basis for the use of CSIA as a robust tool for monitoring DNAN degradation in complex environmental matrices as a component of future remediation efforts.

Sorption of Poly- and Perfluoroalkyl Substances (PFASs) Relevant to Aqueous Film-Forming Foam (AFFF)-Impacted Groundwater by Biochars and Activated Carbon.

Despite growing concerns about human exposure to perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS), other poly- and perfluoroalkyl substances (PFASs) derived from aqueous film-forming foams (AFFFs) have garnered little attention. While these other PFASs may also be present in AFFF-impacted drinking water, their removal by conventional drinking-water treatment is poorly understood. This study compared the removal of 30 PFASs, including 13 recently discovered PFASs, from an AFFF-impacted drinking water using carbonaceous sorbents (i.e., granular activated carbon, GAC). The approach combined laboratory batch experiments and modeling: batch sorption data were used to determine partition coefficients (Kd) and calibrate a transport model based on intraparticle diffusion-limited sorption kinetics, which was used to make forward predictions of PFAS breakthrough during GAC adsorption. While strong retention was predicted for PFOS and PFOA, nearly all of the recently discovered polyfluorinated chemicals and PFOS-like PFASs detected in the AFFF-impacted drinking water were predicted to break through GAC systems before both PFOS and PFOA. These model breakthrough results were used to evaluate a simplified approach to predicting PFAS removal by GAC using compound-specific retention times on a C18 column (RTC18). Overall, this study reveals that GAC systems for the treatment of AFFF-impacted sources of water for PFOA and PFOS likely achieve poor removal, when operated only for the treatment of PFOS and PFOA, of many unmonitored PFASs of unknown toxicity.

Organic Carbon Amendments for Enhanced Biological Attenuation of Trace Organic Contaminants in Biochar-Amended Stormwater Biofilters.

This study sought to evaluate how dissolved organic carbon (DOC) affects attenuation of trace organic contaminants (TOrCs) in biochar-amended stormwater biofilters. It was hypothesized that (1) DOC-augmented runoff would demonstrate enhanced TOrC biodegradation and (2) biochar-amended sand bearing DOC-cultivated biofilms would achieve enhanced TOrC attenuation due to sorptive retention and biodegradation. Microcosm and column experiments were conducted utilizing actual runoff, DOC from straw and compost, and a suite of TOrCs. Biodegradation of TOrCs in runoff was more enhanced by compost DOC than straw DOC (particularly for atrazine, prometon, benzotriazole, and fipronil). 16S rRNA gene quantification and sequencing revealed that growth-induced microbial community changes were, among replicates, most consistent for compost-augmented microcosms and least consistent for raw runoff microcosms. Compost DOC most robustly enhanced utilization of TOrCs as carbon substrates, possibly due to higher residual nutrient levels upon TOrC exposure. Sand columns containing just 0.5 wt % biochar maintained sorptive TOrC retention in the presence of compost-DOC-cultivated biofilms, and TOrC removal was further enhanced by biological activity. Overall, these results suggest that coamendment with biochar and compost may robustly enhance TOrC attenuation in stormwater biofilters, a finding of significance for efforts to mitigate the impacts of runoff on water quality.

Biochar and activated carbon for enhanced trace organic contaminant retention in stormwater infiltration systems.

To assess the effectiveness of biochar and activated carbon (AC) for enhanced trace organic contaminant (TOrC) retention in stormwater infiltration systems, an approach combining forward-prediction modeling and laboratory verification experiments was employed. Batch and column tests were conducted using representative TOrCs and synthetic stormwater. Based on batch screening tests, two commercially available biochars (BN-biochar and MCG-biochar) and an AC were investigated. The AC exhibited the strongest sorption, followed by MCG-biochar and BN-biochar. Langmuir isotherms provided better fits to equilibrium data than Freundlich isotherms. Due to superior sorption kinetics, 0.2 wt % MCG-biochar in saturated sand columns retained TOrCs more effectively than 1.0 wt % BN-biochar. A forward-prediction intraparticle diffusion model based on the Langmuir isotherm adequately predicted column results when calibrated using only batch parameters, as indicated by a Monte Carlo uncertainty analysis. Case study simulations estimated that an infiltration basin amended with F300-AC or MCG-biochar could obtain sorption-retarded breakthrough times for atrazine of 54 or 5.8 years, respectively, at a 1 in./h infiltration rate. These results indicate that biochars or ACs with superior sorption capacity and kinetics can enhance TOrC retention in infiltration systems, and performance under various conditions can be predicted using results from batch tests.

Synthesis and reactivity of an isolable cobalt(I) complex containing a ß-diketiminate-based acyclic tetradentate ligand.

A model for cobalamin was synthesized using a new monoanionic tetradentate nitrogen donor ligand; 2-(4-tolyl)-1,3-bis(2-isopropylpyridyl)propenediimine (Tol-BDI((2-pp)2)H) (1), which utilizes isopropylpyridines as pendant arms on a ß-diketiminate (BDI) backbone. During the synthesis of 1, the rearrangement product, Tol-BDI((2-pp)(4-pp))H (2) was observed. Metalation of 1 with zinc iodide and cobalt chloride yielded the corresponding Tol-BDI((2-pp)2)ZnI (3) and Tol-BDI((2-pp)2)CoCl (4) complexes. The redox properties of 4 in comparison to cobalamin were examined through electrochemical studies. Electrochemical and bulk reduction of complex 4 gave a diamagnetic cobalt(I) complex, Tol-BDI((2-pp)2)Co (5). Reactivity of 5 toward C-X bonds was investigated using methyl iodide and 1-iodo-2-(trimethylsilyl)acetylene, yielding Tol-BDI((2-pp)2)Co(CH(3))I and Tol-BDI((2-pp)2)Co(C(2)Si(CH(3))(3))I respectively. Synthesis and characterization details for these complexes, including the crystal structure of 3, are reported.