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At least 55 records · Page 3

Antarctic ozone - Meteoric control of HNO3

Atmospheric circulation leads to an accumulation of debris from meteors in the Antarctic stratosphere at the beginning of austral spring. The major component of meteoric material is alkaline, comprised predominantly of the oxides of magnesium and iron. These metals may neutralize the natural acidity of stratospheric aerosols, remove nitric acid from the gas phase, and bond it as metal nitrates in the aerosol phase. Removal of nitric acid vapor has been previously shown to be a critical link in the photochemical depletion of ozone in the Antarctic spring, by allowing for increased catalytic loss from chlorine and bromine.

Prather, Michael J.↗

Interactions between HCl, NO(x), and H2O ice in the Antarctic stratosphere - Implications for ozone

The role of PSC particles in determining the distributions of HCl and chlorine radicals is studied. The thermodynamics of HCl in ice is discussed, showing that significant quantities of HCl may be dissolved in ice when PSCs form. It is argued that HCl and HNO3 will be removed from the gas phase early in the condensation process, when only small quantities of H2O have been condensed, reflecting the thermodynamic properties of the solid phases of HCl, HNO3, and H2O. Rapid heterogeneous chemical reactions then volatilize reactive chlorine gases and convert NO(x) to solid-phase nitrates, which can be removed by gravitational settling. Analysis of the suite of heterogeneous chemical processes in the polar stratosphere implies a threshold for HCl concentrations, above which chemical loss rates for ozone increase dramatically.

Wofsy, S. C.↗

Part I: Predicting performance of Purolite A532E resins for remediation of comingled contaminants in groundwater

Ion exchange (IX) resins are used in pump-and-treat (P&T) facilities to remove soluble groundwater contaminants. However, natural anions present at concentrations orders of magnitude higher than contaminants can compete for IX sites and impact resin lifecycles. Here, the Hanford Site’s 200 West Area P&T facility (Washington State, USA) was selected as a case study because it currently uses two IX resins: Purolite® A532E (A532E) to remove pertechnetate (TcO 4 - ) and DOWEX 21K (DOWEX) to remove uranium from groundwater. Nitrate (NO 3 - ), sulfate (SO 4 2- ), chloride (Cl - ), and carbonate (CO 3 2- ) anions have been identified to potentially compete for A532E and DOWEX IX sites. Hanford-relevant anion groundwater concentrations were used to design a series of laboratory-scale batch experiments to evaluate the impact of competing anions on resin performance and potential kinetic effects. These data are then modeled to obtain Cl--normalized equilibrium exchange coefficients (K) needed to predict IX resin performance. The work is presented in two parts, with IX performance evaluated for A532E in Part I and DOWEX in Part II. Part I results demonstrate that TcO 4 - uptake is not impacted by NO 3 - , SO 4 2- , Cl - , CO 3 2- (as HCO 3 - ) and U(VI) carbonate anions, with K TcO4-/Cl- > 4,000, likely due to the high selectivity of A532E trihexylammonium sites for the large, weakly hydrated TcO 4 - anion. Other anion K values were K NO3-/Cl- = 20, K SO4--/Cl- = 0.2, K HCO3-/Cl- = 0.09, K U/Cl- = 370–1000. These K values provide conservative parameters for predicting A532E performance, and demonstrate that, under these test conditions, A532E will remove TcO 4 - from current and future influent streams to meet groundwater treatment objectives.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Membrane consisting of polyquaternary amine ion exchange polymer network interpenetrating the chains of thermoplastic matrix polymer

An ion exchange membrane was formed from a solution containing dissolved matrix polymer and a set of monomers which are capable of reacting to form a polyquaternary ion exchange material; for example vinyl pyride and a dihalo hydrocarbon. After casting solution and evaporation of the volatile component's, a relatively strong ion exchange membrane was obtained which is capable of removing anions, such as nitrate or chromate from water. The ion exchange polymer forms an interpenetrating network with the chains of the matrix polymer.

Rembaum, A.↗

Humidity-induced room-temperature decomposition of Au contacted indium phosphide

It has been found that Au-contacted InP is chemically unstable at room temperature in a humid ambient due to the leaching action of indium nitrate islands that continually remove In from the contact metallization and thus, in effect, from the Inp substrate. While similar appearing islands form on Au-contacted GaAs, that system appears to be stable since leaching of the group III element does not take place.

Fatemi, Navid S.↗

A Novel Ion Exchange System to Purify Mixed ISS Waste Water Brines for Chemical Production and Enhanced Water Recovery

Current International Space Station water recovery regimes produce a sizable portion of waste water brine. This brine is highly toxic and water recovery is poor: a highly wasteful proposition. With new biological techniques that do not require waste water chemical pretreatment, the resulting brine would be chromium-free and nitrate rich which can allow possible fertilizer recovery for future plant systems. Using a system of ion exchange resins we can remove hardness, sulfate, phosphate and nitrate from these brines to leave only sodium and potassium chloride. At this point modern chlor-alkali cells can be utilized to produce a low salt stream as well as an acid and base stream. The first stream can be used to gain higher water recovery through recycle to the water separation stage while the last two streams can be used to regenerate the ion exchange beds used here, as well as other ion exchange beds in the ISS. Conveniently these waste products from ion exchange regeneration would be suitable as plant fertilizer. In this report we go over the performance of state of the art resins designed for high selectivity of target ions under brine conditions. Using ersatz ISS waste water we can evaluate the performance of specific resins and calculate mass balances to determine resin effectiveness and process viability. If this system is feasible then we will be one step closer to closed loop environmental control and life support systems (ECLSS) for current or future applications.

brine↗

A Novel Ion Exchange System to Purify Mixed ISS Waste Water Brines for Chemical Production and Enhanced Water Recovery

Current International Space Station water recovery regimes produce a sizable portion of waste water brine. This brine is highly toxic and water recovery is poor: a highly wasteful proposition. With new biological techniques that do not require waste water chemical pretreatment, the resulting brine would be chromium-free and nitrate rich which can allow possible fertilizer recovery for future plant systems. Using a system of ion exchange resins we can remove hardness, sulfate, phosphate and nitrate from these brines to leave only sodium and potassium chloride. At this point modern chlor-alkali cells can be utilized to produce a low salt stream as well as an acid and base stream. The first stream can be used to gain higher water recovery through recycle to the water separation stage while the last two streams can be used to regenerate the ion exchange beds used here, as well as other ion exchange beds in the ISS. Conveniently these waste products from ion exchange regeneration would be suitable as plant fertilizer. In this report we go over the performance of state of the art resins designed for high selectivity of target ions under brine conditions. Using ersatz ISS waste water we can evaluate the performance of specific resins and calculate mass balances to determine resin effectiveness and process viability. If this system is feasible then we will be one step closer to closed loop environmental control and life support systems (ECLSS) for current or future applications.

Water Brines↗

In-Situ Measurements of HCN and CH3CN in the Pacific Troposphere: Sources, Sinks, and Comparisons with Spectroscopic Observations

We report the first in-situ measurements of hydrogen cyanide (HCN) and acetonitrile (CH3CN) from the Pacific troposphere (0-12 km) obtained during the NASA/Trace-P mission (Feb.-April, 2001). Mean HCN and CH3CN mixing ratios of 243 (+/-118) ppt and 149 (+/-56) ppt respectively, were measured. The in-situ observations correspond to a total HCN column of 4.4-4.9 x 10(exp 15) molec. cm(exp -2) and a CH3CN column of 2.8-3.0 x 10(exp 15) molec. cm(exp -2). This HCN column is in good agreement with available spectroscopic observations. The atmospheric concentrations of HCN and CH3CN were greatly influenced by outflow of pollution from Asia. There is a linear relationship between the mixing ratios of HCN and CH3CN, and in turn these are well correlated with tracers of biomass combustion (e.g. CH3Cl, CO). Relative enhancements with respect to known tracers of biomass combustion within selected plumes in the free troposphere, and pollution episodes in the boundary layer allow an estimation of a global biomass burning source of 0.8+/-0.4 Tg (N)/y for HCN and 0.4+/-0.1 Tg (N)/y for CH3CN. In comparison, emissions from automobiles and industry are quite small (<0.05 Tg (N)/y). The vertical structure of HCN and CH3CN indicated reduced mixing ratios in the MBL (Marine Boundary Layer). Using, a simple box model, the observed gradients across the top of the MBL are used to derive an oceanic flux of 6.7 x 10(exp -15) g (N) cm(exp -2)/s for HCN and 4.8 x 10(exp -15) g (N) cm(exp -2)/s for CH3CN. An air-sea exchange model is used to conclude that this flux can be maintained if the oceans are under-saturated in HCN and CH3CN by 23% and 17%, respectively. It is inferred that oceanic loss is a dominant sink for these nitrites, and they deposit some 1.3 Tg (N) of nitrogen annually to the oceans. Assuming reaction with OH radicals and loss to the oceans as the major removal processes, a mean atmospheric residence time of 4.7 months for HCN and 5.1 months for CH3CN is calculated. A global budget analysis shows that the sources and sinks of HCN and CH3CN are roughly in balance. There are indications that biogenic sources may also be present. Mechanisms involved in nitrate formation during combustion and removal in the oceans are poorly understood.

Singh, Hanwant B.↗

Analysis of Microbial Communities as Indicators of Microbially Induced Corrosion Potential in Stainless Steel Piping

The 200 West Area Pump-and-Treat (200W P&T) facility is part of the final remedy decision for the 200 ZP-1 Operable Unit (OU) and is the interim remedial action for 200-UP-1 OU at the Hanford Site. The facility also treats water from other sources across the site, including 200-DV-1 OU perched water, groundwater from the 200-BP-5 OU, and leachate from the Environmental Restoration Disposal Facility. The facility originally operated a biological treatment process for nitrate that resulted in systemic biofouling and loss of injection well capacity, requiring frequent and costly well rehabilitation. Biofouling has also contributed to corrosion of welds and pitting of stainless-steel piping at the facility. The biological treatment for nitrate was suspended at the end of 2019 calendar year to eliminate negative impacts from biological treatments which improve facility operations and treatment of carbon tetrachloride. Evaluation of the 200W P&T facility’s response to operational improvements, specifically the suspension of the biological treatment, provides information on the potential for continued microbially induced corrosion (MIC). To this end, historical data sets (2015-2017) were compared with molecular biological analyses of 200W P&T water samples from 2018-2020 to quantify trends in total microbial biomass and specific microbial indicator species (iron, sulfate, nitrate, and manganese reducing bacteria) known to cause and enhance metal corrosion. Results showed unequivocal reductions (in excess of 90%) in all microbiological indicators measured following the suspension of the biological treatment. Although abundance measurements for all corrosive MIC populations initially declined after removal of the treatment system, nitrate-reducing bacteria (nirK) and sulfate-reducing bacteria remain highly abundant in the system, an order of magnitude higher than the number of cells present prior to the removal of the biological treatment system [5.14e (1.4) cells/L, vs. 1.14e (0.07) cells/L, reported as average (±SD) for n=3]. In addition, there was an unexpected inflection point in 2019 where all microbial indicators increased unexpectedly in abundance in 2020 by as much as two orders of magnitude compared to 2019 samples. Given the limited number of water samples available for this analysis, the cause of the increase in microbial indicators post-biological treatment has not yet been determined. Systematic sampling of the facility for continued monitoring is recommended so that the responses of MIC populations can be evaluated to ensure that further corrosion is avoided, allowing the 200W P&T facility to operate safely and efficiently at design capacity.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Plutonium Retention by Crystalline Silicotitanate under Hyperalkaline Conditions Relevant to Tank-Side Cesium-Removal at the Hanford Site

Crystalline silicotitanate (CST) is used in Hanford’s Tank-Side Cesium-Removal (TSCR) process to selectively remove Cs-137 from highly caustic, nitrate-rich tank supernatants. Recent testing with actual waste samples suggests that CST can also retain measurable plutonium (Pu), which could affect radiological classification and disposal pathways for spent CST. To quantify this behavior, Pu partitioning to CST was studied under Hanford-relevant conditions using batch-contact experiments in a representative simulant (2 M NaNO3, 0.7 M NaOH). Isotherm data were measured and distribution ratios calculated, with Cs+ uptake used as benchmark. Under low-carbonate conditions, Pu was retained strongly by CST in systems initially contacted with either PuO2 nanoparticles (Pu(IV)) or aqueous Pu(VI), with distribution ratios of ~2,200–3,700 mL/g, generally exceeding those for Cs+ (~400–1,000 mL/g). Increasing carbonate concentration strongly reduced PuO2 nanoparticle retention; at [Na2CO3] = 1 M, distribution ratios decreased by up to one order of magnitude to roughly 100–300 mL/g. Electron microscopy suggests that Pu retention involves a combination of mechanisms such as PuO2 NP aggregation induced by CST leachate components, and association with CST bead surfaces.

Neumann, J.↗

Harnessing Photoelectrochemistry for Wastewater Nitrate Treatment Coupled with Resource Recovery

Wastewater is a misplaced resource well suited to recover nutrients, value-added chemicals, energy, and clean water. A photoelectrochemical device is proposed to transform wastewater nitrates to ammonia and nitrous oxide, coupled with water oxidation. Numerical models were developed to quantify the dependence of process efficiencies and nitrogen-removal rates on light absorber band gaps, electrocatalytic kinetic parameters, competing oxygen reduction and hydrogen evolution reactions, and the reacting nitrate species concentrations that affect the mass-transfer limited current densities. With a single light-absorber and state-of-the-art catalysts, optimal solar-to-chemical efficiencies of 7% and 10% and nitrogen-removal rates of 260 and 395 gN m -2 day -1 are predicted for nitrate reduction to ammonia and nitrous oxide, respectively. The influence of competing reactions on the performance depends on the nitrate concentration and band gap of the light absorber modeled. Oxygen reduction is more dominant than hydrogen evolution to compete with the nitrate reduction reaction, but it is mass-transfer limited. Even with kinetic parameters that enhanced the driving forces for the competing reactions, the performance is only minimally affected by these reactions for optimally selected band gaps and nitrate concentrations larger than 100 mM. Here, theoretically predicted peak nitrogen removal rates and specific energy intensities are competitive with reported estimates for electrochemical and Sharon-Anammox processes for ammonia recovery and nitrogen removal, respectively. This result, together with the added benefit of harnessing sunlight to produce value-added products, indicates promise in the photoelectrochemical approach as a tertiary pathway to recover nutrients and energy from wastewater nitrates.

25 ENERGY STORAGE↗

Nitrate and Nitrite at Hanford – From Tanks to Natural Attenuation

Washington River Protection Solutions, LLC (WRPS) contracted Pacific Northwest National Laboratory (PNNL) in support of their maturation testing and analysis to develop and deploy an ambient temperature solidification/stabilization process for low-activity waste (LAW) (referred to as “grout” in this report). The intent of this effort is to support a sample-and-send regulatory and processing strategy in the Hanford 200 West Area, specifically considering grout waste forms disposal at Hanford in the Integrated Disposal Facility (IDF). Currently the disposal of grouted LAW is not an option because the IDF is not permitted to receive this waste form. The material presented in this report is intended to help inform the U.S. Department of Energy (DOE), the site operating contractors, regulatory agencies, and stakeholders of the future implications of IDF disposal of a grouted LAW waste form, specifically for the behavior of nitrate (NO 3 - ) and nitrite (NO 2 - ) at the Hanford. The only calculation of nitrate release from a hypothetical grouted LAW inventory in the IDF showed that the overall release was slightly above the compliance limit of 45 mg/L nitrate and 3.32 mg/L nitrate after 1000 years (Asmussen et al. 2019). As such, uncertainty around the impact of nitrate and nitrite release from the IDF was identified in the recent National Academies of Sciences study of Hanford supplemental LAW by both the national laboratory team and Hanford stakeholders (Bates et al. 2023). However, these calculations (and others for the IDF involving secondary waste grout) may be conservative as no nitrate and nitrite retention in the grout waste form was assumed, nor any attenuation in the subsurface. There is evidence from the literature of processes that can attenuate nitrate migration both in the waste form and in the Hanford subsurface. If found to be technically defensible and likely to occur in the IDF and associated subsurface, then these processes should be included in modeling of the IDF to represent the behavior of nitrate and nitrite more accurately. Doing so would remove unnecessary conservatism in the modeling projections and reduce the uncertainty in assessments of facility compliance of a grouted LAW waste form in the IDF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mercury Removal from Contaminated Water by Wood-Based Biochar Depends on Natural Organic Matter and Ionic Composition

Biochars can remove potentially toxic elements, such as inorganic mercury [Hg(II)] from contaminated waters. However, their performance in complex water matrices is rarely investigated, and the combined roles of natural organic matter (NOM) and ionic composition in the removal of Hg(II) by biochar remain unclear. Here, we investigate the influence of NOM and major ions such as chloride (Cl – ), nitrate (NO 3 – ), calcium (Ca 2+ ), and sodium (Na + ) on Hg(II) removal by a wood-based biochar (SWP700). Multiple sorption sites containing sulfur (S) were located within the porous SWP700. In the absence of NOM, Hg(II) removal was driven by these sites. Ca 2+ bridging was important in enhancing removal of negatively charged Hg(II)-chloro complexes. In the presence of NOM, formation of soluble Hg-NOM complexes (as seen from speciation calculations), which have limited access to biochar pores, suppressed Hg(II) removal, but Cl – and Ca 2+ could still facilitate it. The ability of Ca 2+ to aggregate NOM, including Hg-NOM complexes, promoted Hg(II) removal from the dissolved fraction (<0.45 μm). Hg(II) removal in the presence of Cl – followed a stepwise mechanism. Weakly bound oxygen functional groups in NOM were outcompeted by Cl – , forming smaller-sized Hg(II)-chloro complexes, which could access additional intraparticle sorption sites. Therein, Cl – was outcompeted by S, which finally immobilized Hg(II) in SWP700 as confirmed by extended X-ray absorption fine structure spectroscopy. We conclude that in NOM containing oxic waters, with relatively high molar ratios of Cl – : NOM and Ca 2+ : NOM, Hg(II) removal can still be effective with SWP700.

54 ENVIRONMENTAL SCIENCES↗

Enhanced alkaline hydrolysis and biodegradability studies of nitrocellulose-bearing missile propellant

Large amounts of energetic materials which have been accumulated over the years in various manufacturing and military installations must be disposed of in an environmentally sound manner. Historically, the method of choice for destruction of obsolete or aging energetic materials has been open burning or open detonation (OB/OD). This destruction approach has become undesirable due to air pollution problems. Therefore, there is a need for new technologies which will effectively and economically deal with the disposal of energetic materials. Along those lines, we have investigated a chemical/biological process for the safe destruction and disposal of a double base solid rocket propellant (AHH), which was used in several 8 inch projectile systems. The solid propellant is made of nitrocellulose and nitroglycerin as energetic components, two lead salts which act as ballistic modifiers, triacetin as a plasticizer and 2-Nitrodiphenylamine (2-NDPA) as a stabilizer. A process train is being developed to convert the organic components of the propellant to biodegradable products and remove the lead from the process stream. The solid propellant is first hydrolyzed through an enhanced alkaline hydrolysis process step. Following lead removal and neutralization, the digested liquor rich in nitrates and nitrites is found to be easily biodegradable. The digestion rate of the intact ground propellant as well as the release of nitrite and nitrate groups were substantially increased when ultrasound were supplied to the alkaline reaction medium compared to the conventional alkaline hydrolysis. The effects of reaction time, temperature, sodium hydroxide concentration and other relevant parameters on the digestion efficiency and biodegradability have been studied. The present work indicates that the AHH propellant can be disposed of safely with a combination of physiochemical and biological processes.

Sidhoum, Mohammed↗

Ammonium-coordinated exchanger (ACE) functionalized silica sorbents for recovering/removing aqueous anionic contaminants

There are limited studies of functionalized silica anion exchange sorbents used for critical/heavy metal recovery/removal relative to polymeric and other inorganic materials. This work features ammonium-coordinated exchanger (ACE) anion exchange particle sorbents prepared by either acid-washing epoxy-crosslinked polyethylenimine (PEI) hydrogen bonded within/to a silica particle sorbent (two-step method) or reacting a di-chlorinated crosslinker, α,α-dichloro-p-xylene (DPX), with PEI within silica (single-step method). Energy dispersive X-ray spectroscopy (EDS) and infrared spectroscopy confirmed the presence of -NH 2 + ···Cl - and -NH 3 + ···Cl - groups, which removed oxyanionic species –arsenate, selenate, chromate, sulfate, phosphate, and nitrate– plus bromide from ideal solutions, authentic acid mine drainage (AMD), and authentic flue gas desulfurization (FGD) wastewater. Affinity of the anions for ACE varied across single- and mixed-element solutions. However, affinity for CrO 4 2- was among the highest in both cases. Total anion uptake by the optimized ACE, PEI-E3-HCl_1.1, reached 1.2 mmol anion/g-sorb. (0.56 mmol CrO 4 2- /g), or ∼2.3 mmol negative charge/g-sorb. This was close to the 0.52 mmol CrO 4 2- /g of a commercial anion exchange resin. Near-consistent removal of 20–80 % of each anion from FGD during an eight-cycle adsorption-desorption (1 M NaCl) test predicted good ACE viability for testing under practical conditions at larger scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Contrasting Capability of Single Atom Palladium for Thermocatalytic versus Electrocatalytic Nitrate Reduction Reaction

The occurrence of high concentrations of nitrate in various water resources is a significant environmental and human health threat, demanding effective removal technologies. Single atom alloys (SAAs) have emerged as a promising bimetallic material architecture in various thermocatalytic and electrocatalytic schemes including nitrate reduction reaction (NRR). This study suggests that there exists a stark contrast between thermocatalytic (T-NRR) and electrocatalytic (E-NRR) pathways that resulted in dramatic differences in SAA performances. Among Pd/Cu nanoalloys with varying Pd–Cu ratios from 1:100 to 100:1, Pd/Cu (1:100) SAA exhibited the greatest activity (TOF Pd = 2 min –1 ) and highest N 2 selectivity (94%) for E-NRR, while the same SAA performed poorly for T-NRR as compared to other nanoalloy counterparts. DFT calculations demonstrate that the improved performance and N 2 selectivity of Pd/Cu (1:100) in E-NRR compared to T-NRR originate from the higher stability of NO 3 * in electrocatalysis and a lower N 2 formation barrier than NH due to localized pH effects and the ability to extract protons from water. Here, this study establishes the performance and mechanistic differences of SAA and nanoalloys for T-NRR versus E-NRR.

36 MATERIALS SCIENCE↗

Dominant nitrogen metabolisms of a warm, seasonally anoxic freshwater ecosystem revealed using genome resolved metatranscriptomics

In aquatic ecosystems where primary productivity is limited by nitrogen (N), whether continuously, seasonally, or in concert with additional nutrient limitations, increased inorganic N availability can reshape ecosystem structure and function, potentially resulting in eutrophication and even harmful algal blooms. Whereas microbial metabolic processes such as mineralization and dissimilatory nitrate reduction to ammonium increase inorganic N availability, denitrification removes bioavailable N from the ecosystem. Therefore, understanding these key microbial mechanisms is critical to the sustainable management and environmental stewardship of inland freshwater resources. This study identifies and characterizes these crucial metabolisms in a warm, seasonally anoxic ecosystem. Results are contextualized by an ecological understanding of the study system derived from a multi-year continuous monitoring effort. This unique data set is the first of its kind in this largely understudied ecosystem (tropical lakes) and also provides insight into microbiome function and associated taxa in warm, anoxic freshwaters.

59 BASIC BIOLOGICAL SCIENCES↗

Synergistic interactions between anammox and dissimilatory nitrate reducing bacteria sustains reactor performance across variable nitrogen loading ratios

Anaerobic ammonium oxidizing (anammox) bacteria are utilized for high efficiency nitrogen removal from nitrogen-laden sidestreams in wastewater treatment plants. The anammox bacteria form a variety of competitive and mutualistic interactions with heterotrophic bacteria that often employ denitrification or dissimilatory nitrate reduction to ammonium (DNRA) for energy generation. These interactions can be heavily influenced by the influent ratio of ammonium to nitrite, NH 4 + :NO 2 - , where deviations from the widely acknowledged stoichiometric ratio (1:1.32) have been demonstrated to have deleterious effects on anammox efficiency. Thus, it is important to understand how variable NH 4 + :NO 2 - ratios impact the microbial ecology of anammox reactors. We observed the response of the microbial community in a lab scale anammox membrane bioreactor (MBR) to changes in the influent NH 4 + :NO 2 - ratio using both 16S rRNA gene and shotgun metagenomic sequencing. Ammonium removal efficiency decreased from 99.77 ± 0.04% when the ratio was 1:1.32 (prior to day 89) to 90.85 ± 0.29% when the ratio was decreased to 1:1.1 (day 89–202) and 90.14 ± 0.09% when the ratio was changed to 1:1.13 (day 169–200). Over this same timespan, the overall nitrogen removal efficiency (NRE) remained relatively unchanged (85.26 ± 0.01% from day 0–89, compared to 85.49 ± 0.01% from day 89–169, and 83.04 ± 0.01% from day 169–200). When the ratio was slightly increased to 1:1.17–1:1.2 (day 202–253), the ammonium removal efficiency increased to 97.28 ± 0.45% and the NRE increased to 88.21 ± 0.01%. Analysis of 16S rRNA gene sequences demonstrated increased relative abundance of taxa belonging to Bacteroidetes, Chloroflexi, and Ignavibacteriae over the course of the experiment. The relative abundance of Planctomycetes, the phylum to which anammox bacteria belong, decreased from 77.19% at the beginning of the experiment to 12.24% by the end of the experiment. Analysis of metagenome assembled genomes (MAGs) indicated increased abundance of bacteria with nrfAH genes used for DNRA after the introduction of lower influent NH 4 + :NO 2 - ratios. The high relative abundance of DNRA bacteria coinciding with sustained bioreactor performance indicates a mutualistic relationship between the anammox and DNRA bacteria. Understanding these interactions could support more robust bioreactor operation at variable nitrogen loading ratios.

59 BASIC BIOLOGICAL SCIENCES↗