Degradation of Dissolved RDX, NQ, and DNAN by Cathodic Processes in an Electrochemical Flow-Through Reactor.

Both legacy munitions compounds (e.g., RDX) and new insensitive high explosives (e.g. DNAN, NQ) are being manufactured and utilized concurrently, and there exists a need for wastewater treatment systems that are able to degrade both classes of explosives. Electrochemical systems offer treatment possibilities using inexpensive materials and no chemical additions. Electrochemically induced removal of RDX, NQ, and DNAN were separately studied within an electrochemical plug flow reactor hosting a stainless steel (SS) cathode and downstream Ti/MMO anode. Varying wire mesh cathodes and operating conditions were evaluated in an effort to identify the optimal cathode material, to determine the relative contributions of cathodically-induced removal processes, to shorten time to steady-state removal conditions, and to find practical ranges of operating conditions. Applied current allowed the cathode to support munitions removal mainly by direct reduction at the cathode surface, and the secondary reactions of cathodically-induced alkaline hydrolysis and catalytic hydrogenation by adsorbed H on Ni-containing cathode surfaces might contribute to some munitions degradation. The optimal cathode material was identified as SS grade 316, possibly due to its superior Ni content and lack of corrosion protection coating. Higher current, longer cathode length, and smaller mesh pore sizes resulted in slightly greater removal extents and shorter acclimation times to steady state removal conditions, but there are practical upper limits to these properties. Higher Ni content within SS improved RDX and NQ removal but does not affect DNAN removal. Prolonged use of SS grade 316 showed no debilitating changes in electrical performance or chemical content.

Heterogeneous Fenton-Like Catalysis of Electrogenerated H2O2 for Dissolved RDX Removal.

New insensitive high explosives pose great challenges to conventional explosives manufacturing wastewater treatment processes and require advanced methods to effectively and efficiently mineralize these recalcitrant pollutants. Oxidation processes that utilize the fundamental techniques of Fenton chemistry optimized to overcome conventional limitations are vital to provide efficient degradation of these pollutants while maintaining cost-effectiveness and scalability. In this manner, utilizing heterogeneous catalysts and in-situ generated H2O2 to degrade IHEs is proposed. For heterogeneous catalyst optimization, varying the surface chemistry of activated carbon for use as a catalyst removes precipitation complications associated with iron species in Fenton chemistry while including removal by adsorption. Activated carbon impregnated with 5% MnO2 in the presence of H2O2 realized a high concentration of hydroxyl radical formation - 140 µM with 10 mM H2O2 - while maintaining low cost and relative ease of synthesis. This AC-Mn5 catalyst performed effectively over a wide pH range and in the presence of varying H2O2 concentrations with a sufficient effective lifetime. In-situ generation of H2O2 removes the logistical and economic constraints associated with external H2O2, with hydrophobic carbon electrodes utilizing generated gaseous O2 for 2-electron oxygen reduction reactions. In a novel flow-through reactor, gaseous O2 is generated on a titanium/mixed metal oxide anode with subsequent H2O2 electrogeneration on a hydrophobic microporous-layered carbon cloth cathode. This reactor is able to electrogenerate 2 mM H2O2 at an optimized current intensity of 150 mA and over a wide range of flow rates, influent pH values, and through multiple iterations. Coupling these two optimization methods realizes the production of highly oxidative hydroxyl radicals by Fenton-like catalysis of electrogenerated H2O2 on the surface of an MnO2-impregnated activated carbon catalyst. This method incorporates electrochemically induced oxidation of munitions in addition to removal by adsorption while maintaining cost-effectiveness and scalability. It is anticipated this platform holds great promise to eliminate analogous contaminants.

Quantitative Method for Comparative Assessment of Particle Removal Efficiency of Fabric Masks as Alternatives to Standard Surgical Masks for PPE.

In response to the COVID-19 pandemic, cloth masks are being used to control the spread of virus, but the efficacy of these loose-fitting masks is not well known. Here, tools and methods typically used to assess tight-fitting respirators were modified to quantify the efficacy of community-produced and commercially produced fabric masks as personal protective equipment. Two particle counters concurrently sample ambient air and air inside the masks; mask performance is evaluated by mean particle removal efficiency and statistical variability when worn as designed and with a nylon overlayer, to independently assess fit and material. Worn as designed, both commercial surgical masks and cloth masks had widely varying effectiveness (53%-75% and 28%-91% particle removal efficiency, respectively). Most surgical-style masks improved with the nylon overlayer, indicating poor fit. This rapid testing method uses widely available hardware, requires only a few calculations from collected data, and provides both a holistic and aspect-wise evaluation of mask performance.

In Situ Investigation of Performance Reference Compound-Based Estimates of PCB Equilibrated Passive Sampler Concentrations and Cfree in the Marine Water Column.

Low-density polyethylene sheets are used as passive samplers for aquatic environmental monitoring to measure the freely dissolved concentration (Cfree ) of hydrophobic organic contaminants (HOCs). Freely dissolved HOCs in water will partition into the polyethylene until a thermodynamic equilibrium is achieved; that is, the HOC's activity in the passive sampler is the same as its activity in the surrounding environment. One way to evaluate the equilibrium status or estimate the uptake kinetics is by using performance reference compounds (PRCs). A fractional equilibrium (feq ) can be determined for target HOCs, under the assumption that PRC desorption from the passive sampler occurs at the same rate as for the unlabeled target HOCs. However, few investigations have evaluated how effectively and accurately PRCs estimate target contaminant Cfree under in situ conditions. In the present study, polyethylene passive samplers were preloaded with 6 13 C-labeled polychlorinated biphenyls (PCBs) as PRCs; deployed in New Bedford Harbor, Massachusetts, USA; and collected after 30-, 56-, 99-, and 129-d deployments. Using this unique temporal sampling design, PRC results from each deployment were fit to a diffusion model to estimate the Cfree of 27 PCB congeners and compare the results between the different deployment times. Smaller PCBs had variable concentrations over the 4 deployments, whereas mid-molecular weight PCBs had consistent Cfree measurements for all deployments (relative standard deviation <20%). High-molecular weight PCBs had the largest Cfree estimates after 30 d; these estimates and their standard deviations decreased with longer deployment times. These findings suggest that when targeting PCBs with more than 6 chlorines or contaminants with a log octanol-water partition coefficient ≥6.5, a deployment time longer than 30 d may be prudent. Environ Toxicol Chem 2020;39:1165-1173. © 2020 SETAC.

Side-stream enhanced biological phosphorus removal (S2EBPR) process improves system performance - A full-scale comparative study.

To address the common challenges in enhanced biological phosphorus removal (EBPR) related to stability and unfavorable influent carbon to phosphorus ratio, a side-stream EBPR (S2EBPR) process that involves a side-stream anaerobic biological sludge hydrolysis and fermentation reactor was proposed as an emerging alternative. In this study, a full-scale pilot testing was performed with side-by-side operation of a conventional anaerobic-anoxic-aerobic (A2O) process versus a S2EBPR process. A comparison of the performance, activity and microbial community between the two configurations was performed. The results demonstrated that, with the same influent wastewater characteristics, S2EBPR configuration showed improved P removal performance and stability than the conventional A2O configuration, especially when the mixers in the side-stream anaerobic reactor were operated intermittently. Mass balance analysis illustrated that both denitrification and EBPR were enhanced in S2EBPR configuration, where return activated sludge was diverted into the anaerobic zone to promote fermentation and enrichment of polyphosphate accumulating organisms (PAOs), and the influent was bypassed to the anoxic zone for enhancing denitrification. A relatively higher PAO activity and total PAO abundance were observed in S2EBPR than in A2O configuration, accompanied by a higher degree of dependence on glycolysis pathway than tricarboxylic acid cycle. No significant difference in the relative abundances of putative PAOs, including Ca. Accumulibacter and Tetrasphaera, were observed between the two configurations. However, higher microbial community diversity indices were observed in S2EBPR configuration than in conventional one. In addition, consistently lower relative abundance of known glycogen accumulating organisms (GAOs) was observed in S2EBPR system. Extended anaerobic retention time and conditions that generate continuous and more complex volatile fatty acids in the side-stream anaerobic reactor of S2EBPR process likely give more competitive advantage for PAOs over GAOs. PAOs exhibited sustained EBPR activity and delayed decay under extended anaerobic condition, likely due to their versatile metabolic pathways depending on the availability and utilization of multiple intracellular polymers. This study provided new insights into the effects of implementing side-stream EBPR configuration on microbial populations, EBPR activity profiles and resulted system performance.

Bioaccumulation in Functionally Different Species: Ongoing Input of PCBs with Sediment Deposition to Activated Carbon Remediated Bed Sediments.

Activated carbon-amended bed sediments reduced total polychlorinated biphenyl (PCB) accumulation in 3 functionally different marine species, sandworms (Alitta virens), hard clams (Mercenaria mercenaria), and sheepshead minnows (Cyprinodon variegatus), during both clean and contaminated ongoing sediment inputs. Mesocosm experiments were conducted for 90 d to evaluate native, field-aged bed sediment PCBs, and ongoing input PCBs added 3 times a week. Simulated in situ remediation applied an activated carbon dose equal to the native organic carbon content that was premixed into the bed sediment for 1 mo. The highest bioaccumulation of native PCBs was in worms that remained in and directly ingested the sediment, whereas the highest bioaccumulation of the input PCBs was in fish that were exposed to the water column. When periodic PCB-contaminated sediment inputs were introduced to the water column, the activated carbon remedy had minimal effect on the input PCBs, whereas the native bed PCBs still dominated bioaccumulation in the control (no activated carbon). Therefore, remediation of only the local bedded sediment in environmental systems with ongoing contaminant inputs may have lower efficacy for fish and other pelagic and epibenthic organisms. While ongoing inputs continue to obscure remedial outcomes at contaminated sediment sites, the present study showed clear effectiveness of activated carbon amendment remediation on native PCBs despite these inputs but no remediation effectiveness for the input-associated PCBs (at least within the present study duration). Environ Toxicol Chem 2019;38:2326-2336. Published 2019 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Advancing the Use of Passive Sampling in Risk Assessment and Management of Sediments Contaminated with Hydrophobic Organic Chemicals: Results of an International Ex Situ Passive Sampling Interlaboratory Comparison.

This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of ∼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (

Cross Validation of Two Partitioning-Based Sampling Approaches in Mesocosms Containing PCB Contaminated Field Sediment, Biota, and Activated Carbon Amendment.

The Gold Standard for determining freely dissolved concentrations (Cfree) of hydrophobic organic compounds in sediment interstitial water would be in situ deployment combined with equilibrium sampling, which is generally difficult to achieve. In the present study, ex situ equilibrium sampling with multiple thicknesses of silicone and in situ pre-equilibrium sampling with low density polyethylene (LDPE) loaded with performance reference compounds were applied independently to measure polychlorinated biphenyls (PCBs) in mesocosms with (1) New Bedford Harbor sediment (MA, U.S.A.), (2) sediment and biota, and (3) activated carbon amended sediment and biota. The aim was to cross validate the two different sampling approaches. Around 100 PCB congeners were quantified in the two sampling polymers, and the results confirmed the good precision of both methods and were in overall good agreement with recently published LDPE to silicone partition ratios. Further, the methods yielded Cfree in good agreement for all three experiments. The average ratio between Cfree determined by the two methods was factor 1.4 ± 0.3 (range: 0.6-2.0), and the results thus cross-validated the two sampling approaches. For future investigations, specific aims and requirements in terms of application, data treatment, and data quality requirements should dictate the selection of the most appropriate partitioning-based sampling approach.

Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities.

Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency's maximum contaminant levels, and low levels of both gasoline range (0-8 ppb) and diesel range organic compounds (DRO; 0-157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation.

Predicting bioaccumulation of polycyclic aromatic hydrocarbons in soft-shelled clams (Mya arenaria) using field deployments of polyethylene passive samplers.

Biota-sediment accumulation factors (BSAF), frequently used to predict tissue concentrations of organisms living within and above sediments contaminated with hydrophobic organic chemicals, often produce inaccurate estimates. Hence, freely dissolved porewater concentrations, CW , have also been investigated as predictors of organism tissue concentrations, but they are more difficult to measure than bulk sediment concentrations (used with BSAF). In situ passive sampling methods, however, make it possible to deduce CW with less effort than required to measure the value directly and make it possible to relate CW with tissue concentrations of undisturbed, native organisms. In the present study, polyethylene passive samplers containing performance reference compounds (d10-phenanthrene, d10-pyrene, and d12-chrysene) were deployed in diverse sediment beds near Boston, Massachusetts, USA, for a 1-wk period. Clams (Mya arenaria) and sediments were then collected from the deployed sediment beds. Concentrations of 3 polycyclic aromatic hydrocarbons (PAHs; phenanthrene, pyrene, and chrysene) were measured in the porewaters, in clam tissues, and in the bulk sediment. Biota-sediment accumulation factors and polyethylene-deduced CW were used to predict organism tissue concentrations. Ratios of predicted-to-measured values showed that the BSAF method over-predicted tissue concentrations in M. arenaria by up to 2 orders of magnitude. The polyethylene-deduced CW method resulted in average ratios closer to 1 (0.43 ± 0.26, 3.7 ± 2.5, and 1.1 ± 1.2 for phenanthrene, pyrene, and chrysene, respectively, N = 26, uncertainty = ± 1σ).

Evaluating cost when selecting performance reference compounds for the environmental deployment of polyethylene passive samplers.

A challenge in environmental passive sampling is determining when equilibrium is achieved between the sampler, target contaminants, and environmental phases. A common approach is the use of performance reference compounds (PRCs) to estimate target contaminant sampling rates and indicate degree of sampler equilibrium. One logistical issue associated with using PRCs is their sometimes exorbitant cost. To address PRC expense, this investigation 1) compared the performance of inexpensive PRCs (deuterated PAHs) and expensive PRCs ((13) C-labeled PCBs) to estimate dissolved PCB concentrations in freshwater and marine deployments, and 2) evaluated the use of smaller quantities of PRC relative to regular amounts used for estimating dissolved PAH and PCB concentrations. Saltwater and freshwater site average differences between total dissolved PCB concentrations calculated using the 2 classes of PRCs was 34 pg/L (20%) and 340 pg/L (51%), respectively, and in some deployments, statistical differences in PCB concentrations generated by the 2 types of PRCs were detected. However, no statistical differences were detected between total dissolved PAH and PCB for the 3 quantities of PRCs. In both investigations, individual dissolved PCB congeners and PAH compounds demonstrated comparable behavior as those expressed as total PCB or PAH dissolved concentrations. This research provides evidence that in some applications passive sampling using inexpensive and smaller quantities of PRCs can yield cost savings of approximately 75%. This approach appears most promising in the marine water column and when focusing on dissolved concentrations of low and medium molecular weight congeners or total PCBs.

Calculating the diffusive flux of persistent organic pollutants between sediments and the water column on the Palos Verdes shelf superfund site using polymeric passive samplers.

Passive samplers were deployed to the seafloor at a marine Superfund site on the Palos Verdes Shelf, California, USA, and used to determine water concentrations of persistent organic pollutants (POPs) in the surface sediments and near-bottom water. A model of Fickian diffusion across a thin water boundary layer at the sediment-water interface was used to calculate flux of contaminants due to molecular diffusion. Concentrations at four stations were used to calculate the flux of DDE, DDD, DDMU, and selected PCB congeners from sediments to the water column. Three passive sampling materials were compared: PE strips, POM strips, and SPME fibers. Performance reference compounds (PRCs) were used with PE and POM to correct for incomplete equilibration, and the resulting POP concentrations, determined by each material, agreed within 1 order of magnitude. SPME fibers, without PRC corrections, produced values that were generally much lower (1 to 2 orders of magnitude) than those measured using PE and POM, indicating that SPME may not have been fully equilibrated with waters being sampled. In addition, diffusive fluxes measured using PE strips at stations outside of a pilot remedial sand cap area were similar to those measured at a station inside the capped area: 240 to 260 ng cm(-2) y(-1) for p,p'-DDE. The largest diffusive fluxes of POPs were calculated at station 8C, the site where the highest sediment concentrations have been measured in the past, 1100 ng cm(-2) y(-1) for p,p'-DDE.

Passive sampling to measure baseline dissolved persistent organic pollutant concentrations in the water column of the Palos Verdes Shelf Superfund site.

Passive sampling was used to deduce water concentrations of persistent organic pollutants (POPs) in the vicinity of a marine Superfund site on the Palos Verdes Shelf, California, USA. Precalibrated solid phase microextraction (SPME) fibers and polyethylene (PE) strips that were preloaded with performance reference compounds (PRCs) were codeployed for 32 d along an 11-station gradient at bottom, surface, and midwater depths. Retrieved samplers were analyzed for DDT congeners and their breakdown products (DDE, DDD, DDMU, and DDNU) and 43 PCB congeners using GC-EI- and NCI-MS. PRCs were used to calculate compound-specific fractional equilibration achieved in situ for the PE samplers, using both an exponential approach to equilibrium (EAE) and numerical integration of Fickian diffusion (NI) models. The highest observed concentrations were for p,p'-DDE, with 2200 and 990 pg/L deduced from PE and SPME, respectively. The difference in these estimates could be largely attributed to uncertainty in equilibrium partition coefficients, unaccounted for disequilibrium between samplers and water, or different time scales over which the samplers average. The concordance between PE and SPME estimated concentrations for DDE was high (R(2) = 0.95). PCBs were only detected in PE samplers, due to their much larger size. Near-bottom waters adjacent to and down current from sediments with the highest bulk concentrations exhibited aqueous concentrations of DDTs and PCBs that exceeded Ambient Water Quality Criteria (AWQC) for human and aquatic health, indicating the need for future monitoring to determine the effectiveness of remedial activities taken to reduce adverse effects of contaminated surface sediments.

Using performance reference compounds in polyethylene passive samplers to deduce sediment porewater concentrations for numerous target chemicals.

Polymeric passive samplers are useful for assessing hydrophobic organic chemical contamination in sediment beds. Here, an improved method is described for measuring concentrations of contaminants in porewater by using performance reference compounds (deuterated phenanthrene, pyrene, and chrysene) to calibrate sampler/site-specific mass transfer behavior. The method employs a one-dimensional diffusion model of chemical exchange between a polymer sheet of finite thickness and an unmixed sediment bed. The model is parametrized by diffusivities and partition coefficients for both the sampler and sediment. This method was applied to estimate porewater concentrations for seventeen PAHs from polymeric samplers deployed for 3-10 days in homogenized sediment from a coal-tar contaminated site. The accuracy of the method was verified by comparing the passive sampler results to concentrations measured through liquid-liquid extraction of physically separated porewaters, with corrections for sorption to colloidal organic carbon. The measurements made using the two methods matched within about a factor of 2.0 (+/-0.9) for the 17 target PAHs.

Measurement of freely dissolved PAH concentrations in sediment beds using passive sampling with low-density polyethylene strips.

To assess hydrophobic organic chemical (HOC) contamination in sediments, a method was developed using polyethylene (PE) passive samplers inserted directly in the intact sediment beds to measure freely dissolved HOC concentrations. Performance reference compounds (PRCs: d10-phenanthrene, d10-pyrene, and d12-chrysene), impregnated into the PE before use, allowed porewater concentrations to be deduced after exposure times much shorter than would be required for sampler equilibration (days instead of months). Three diverse sediments were used in the laboratory, and PE-deduced porewater concentrations of six native PAHs (phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene, and chrysene) matched results from air-bridge testing and from direct porewater extractions after correcting for colloid effects. PE strips, deployed from a boat in Boston Harbor, yielded concentrations that were like those measured in porewaters from a sediment core collected nearby. Notably, equilibrium partitioning (EqP) estimates were always much higher (up to 100x) than those measured using the other methods, suggesting the large inaccuracy of that approach. Hence, PE passive sampling appears to greatly improve the accuracy of assessing the hazards posed by compounds like PAHs in sediment beds.

Polyethylene devices: passive samplers for measuring dissolved hydrophobic organic compounds in aquatic environments.

We demonstrate the use of polyethylene devices (PEDs) for assessing hydrophobic organic compounds (HOCs) in aquatic environments. Like semipermeable membrane devices (SPMDs) and solid-phase microextraction (SPME), PEDs passively accumulate HOCs in proportion to their freely dissolved concentrations. Polyethylene-water partition constants (K(PEW)S) were measured in the laboratory for eight polycyclic aromatic hydrocarbons (PAHs), five polychlorinated biphenyls (PCBs), and one polychlorinated dibenzop-dioxin (PCDD), and these were found to correlate with octanol-water partition constants (K(OW)s; log K(PEW) = 1.13 log K(OW) - 0.86, R2 = 0.89). Temperature and salinity dependencies of K(PEW) values for the HOCs tested were well predicted with excess enthalpies of solution in water and Setschenow constants, respectively. We also showed that standards, impregnated in the PED before deployment, can be used to correct for incomplete equilibrations. Using PEDs, we measured phenanthrene and pyrene at ng/L concentrations and 2,2',5,5'-tetrachlorobiphenyl at pg/L concentrations in Boston Harbor seawater, consistent with our findings using traditional procedures. PEDs are cheap and robust samplers, competent to accomplish in situ, time-averaged passive sampling with fast equilibration times (approximately days) and simplified laboratory analyses.