Metal-Organic Frameworks against Toxic Chemicals.

Materials capable of the safe and efficient capture or degradation of toxic chemicals, including chemical warfare agents (CWAs) and toxic industrial chemicals (TICs), are critically important in the modern age due to continuous threats of these chemicals to human life, both directly and indirectly. Metal-organic frameworks (MOFs), atomically precise hybrid materials that are synthesized via the self-assembly of metal cations or clusters and organic linkers, offer a unique solid adsorbent design platform due to their great synthetic versatility. This review will focus on recent advancements in MOF-based adsorbent design for protection against chemical warfare agents (organophosphorus nerve agents, blistering agents, and their simulants) and toxic industrial chemicals such as H2S, NH3, SO2, CO, NO2, and NO.

Extracorporeal Ammonia Clearance for Hyperammonemia in Critically Ill Patients: A Scoping Review.

INTRODUCTION: Hyperammonemia is a life-threatening condition. However, clearance of ammonia via extracorporeal treatment has not been systematically evaluated. METHODS: We searched EMBASE and MEDLINE databases. We included all publications reporting ammonia clearance by extracorporeal treatment in adult and pediatric patients with clearance estimated by direct dialysate ammonia measurement or calculated by formula. Two reviewers screened and extracted data independently. RESULTS: We found 1,770 articles with 312 appropriate for assessment and 28 studies meeting eligibility criteria. Most of the studies were case reports. Hyperammonemia was typically secondary to inborn errors of metabolisms in children and to liver failure in adult patients. Ammonia clearance was most commonly reported during continuous renal replacement therapy (CRRT) and appeared to vary markedly from <5 mL/min/m2 to >250 mL/min/m2. When measured during intermittent hemodialysis (IHD), clearance was highest and correlated with blood flow rate (R2 = 0.853; p < 0.001). When measured during CRRT, ammonia clearance could be substantial and correlated with effluent flow rate (EFR; R2 = 0.584; p < 0.001). Neither correlated with ammonia reduction. Peritoneal dialysis (PD) achieved minimal clearance, and other extracorporeal techniques were rarely studied. CONCLUSIONS: Extracorporeal ammonia clearance varies widely with sometimes implausible values. Treatment modality, blood flow, and EFR, however, appear to affect such clearance with IHD achieving the highest values, PD achieving minimal values, and CRRT achieving substantial values especially at high EFRs. The role of other techniques remains unclear. These findings can help inform practice and future studies.

Immobilization of Rhodopseudomonas palustris P1 on glass pumice to improve the removal of NH4 + -N and NO2 - -N from aquaculture pond water.

We conducted this research in order to investigate the potential of a new material called glass pumice for use as a microorganism immobilization carrier to improve aquaculture pond water quality. The pH adjustment capacity and the Rhodopseudomonas palustris P1 cell adsorption capacity of glass pumice were measured. The immobilized Rps. palustris P1 and the free sample were compared to determine which had an enhanced NH4 + -N and NO2 - -N removal efficiency. The results showed that glass pumice significantly affected the pH of the acid solution (P < 0.05); the pH increased from 3.0 ± 0.08 to 7.21 ± 0.13 in 12 H. Rps. palustris P1 adsorption to glass pumice was rapid and reached equilibrium within 60 Min. The Langmuir adsorption parameter data showed that glass pumice had a higher affinity for Rps. palustris P1 than SiO2 powder, with an adsorption capacity of 4.02 × 108  cells g-1 . The maximum NH4 + -N and NO2 - -N removal rates by immobilized Rps. palustris P1 were 134.82 ± 0.67% and 93.68 ± 0.14% higher than those of nonimmobilized P1, respectively. Based on the above results, we propose that glass pumice is potential as a microorganism carrier material in aquaculture water treatment.

Pilot Scale Study: First Demonstration of Hydrophobic Membranes for the Removal of Ammonia Molecules from Rendering Condensate Wastewater.

Hydrophobic membrane contactors represent a promising solution to the problem of recycling ammoniacal nitrogen (N-NH4) molecules from waste, water or wastewater resources. The process has been shown to work best with wastewater streams that present high N-NH4 concentrations, low buffering capacities and low total suspended solids. The removal of N-NH4 from rendering condensate, produced during heat treatment of waste animal tissue, was assessed in this research using a hydrophobic membrane contactor. This study investigates how the molecular composition of rendering condensate wastewater undergo changes in its chemistry in order to achieve suitability to be treated using hydrophobic membranes and form a suitable product. The main objective was to test the ammonia stripping technology using two types of hydrophobic membrane materials, polypropylene (PP) and polytetrafluoroethylene (PTFE) at pilot scale and carry out: (i) Process modification for NH3 molecule removal and (ii) product characterization from the process. The results demonstrate that PP membranes are not compatible with the condensate waste as it caused wetting. The PTFE membranes showed potential and had a longer lifetime than the PP membranes and removed up to 64% of NH3 molecules from the condensate waste. The product formed contained a 30% concentrated ammonium sulphate salt which has a potential application as a fertilizer. This is the first demonstration of hydrophobic membrane contactors for treatment of condensate wastewater.

Comparative assessment of modeling and experimental data of ammonia removal from pre-digested chicken manure.

The aim of this study was to interpret the development of Anammox activity by a mathematical model in an UASB reactor -originally inoculated with methanogenic granules- at which Anammox progress has been also experimentally observed while treating chicken manure digestate. Since ammonium is derived from anaerobic degradation of nitrogenous compounds in chicken manure similar to any other nitrogen-rich organic wastes; the reactor was operated intentionally at favorable conditions [i.e.; with external nitrite source for NH4 +:NO2 -≅1.0] in order to make Anammox process to prevail as operation continued. Results indicated significant ammonia removals (60% on average) although influent concentration was gradually increased up to 200 mg L-1. A modeling exercise has been undertaken to investigate the performance of the laboratory scale UASB reactor. In this scope, the experimental results were modeled by using Mantis2 model within GPS-X 6.5 simulation software that included several built in libraries. Accordingly, effluent chemical oxygen demand (COD) and total ammonia nitrogen (TAN) concentrations could be predicted with reasonably good accuracy demonstrating successful calibration. The regression coefficient (R2 ) and mean relative absolute error (MRAE) parameters were found as 0.66 and 16% and 0.70 and 19%, respectively.

Waste Brick as Constructed Wetland Fillers to Treat the Tail Water of Sewage Treatment Plant.

Adopting the concept of "using waste to treat waste", the waste bricks will be used for constructed wetland filling. Integrated vertical-flow constructed wetland (IVCW) studied on the purification effect in influent water under three hydraulic loads (0.15, 0.25, 0.35 m/day). The results show that the waste bricks can be used as the carrier for the growth of the system biofilm, and have positive effects on the removal of pollutants in the influent water. Under three different hydraulic load conditions, the vertical flow of CWs can significantly reduce the load of water intake. In the low hydraulic load condition of 0.15 m/day, the average removal rates of chemical oxygen demand (COD), ammonia nitrogen (NH3-N), total nitrogen (TN), and total phosphorus (TP) can reach 66.52%, 72.10%, 56.53% and 91.55% in this system, respectively. The influent pool on removal efficiency of pollutants was obviously higher than that of the upper pool, especially in the inlet surface 0-30 cm ranges. This research has achieved the effect of using "waste" to treat wastewater, which has strong practical significance and popularization value.

An Investigation of PS-b-PEO Polymersomes for the Oral Treatment and Diagnosis of Hyperammonemia.

Ammonia-scavenging transmembrane pH-gradient poly(styrene)-b-poly(ethylene oxide) polymersomes are investigated for the oral treatment and diagnosis of hyperammonemia, a condition associated with serious neurologic complications in patients with liver disease as well as in infants with urea cycle disorders. While these polymersomes are highly stable in simulated intestinal fluids at extreme bile salt and osmolality conditions, they unexpectedly do not reduce plasmatic ammonia levels in cirrhotic rats after oral dosing. Incubation in dietary fiber hydrogels mimicking the colonic environment suggests that the vesicles are probably destabilized during the dehydration of the intestinal chyme. The findings question the relevance of commonly used simulated intestinal fluids for studying vesicular stability. With the encapsulation of a pH-sensitive dye in the polymersome core, the local pH increase upon ammonia influx could be exploited to assess the ammonia concentration in the plasma of healthy and cirrhotic rats as well as in other fluids. Due to its high sensitivity and selectivity, this polymersome-based assay could prove useful in the monitoring of hyperammonemic patients and in other applications such as drug screening tests.

Hyperammonemia, the Last Indication of High-Volume Hemodiafiltration in Adult and Children: A Structured Review.

Ammonia is a neurotoxic molecule that causes cerebral edema and encephalopathy. Ammonia is either produced in excess or poorly purified during severe hepatic insufficiency, poisoning, infection, and inborn errors of metabolism. During continuous renal replacement therapy, ammonia clearance is determined by the dialysate flow rate and the dialyzer surface area. Extra-renal blood purification for ammonia clearance has been studied in neonates with urea cycle disorders. Prognostic factors affecting patient outcome are thought to be the duration of coma, the patient's clinical status prior to dialysis, and the ammonia removal rate. In this review, we discuss the various dialytic modalities used for ammonia clearance as well as the thresholds for initiating dialysis and the better strategy ensures rapid patient protection from cerebral edema and herniation induced by hyperammonemia.

Application of Near-Infrared Optical Feedback Cavity Enhanced Absorption Spectroscopy (OF-CEAS) to the Detection of Ammonia in Exhaled Human Breath.

The qualitative and quantitative analysis to trace gas in exhaled human breath has become a promising technique in biomedical applications such as disease diagnosis and health status monitoring. This paper describes an application of a high spectral resolution optical feedback cavity enhanced absorption spectroscopy (OF-CEAS) for ammonia detection in exhaled human breath, and the main interference of gases such as CO2 and H2O are approximately eliminated at the same time. With appropriate optical feedback, a fibered distributed feedback (DFB) diode laser emitting at 1531.6 nm is locked to the resonance of a V-shaped cavity with a free spectral range (FSR) of 300 MHz and a finesse of 14,610. A minimum detectable absorption coefficient of αmin = 2.3 × 10-9 cm-1 is achieved in a single scan within 5 s, yielding a detection limit of 17 ppb for NH3 in breath gas at low pressure, and this stable system allows the detection limit down to 4.5 ppb when the spectra to be averaged over 16 laser scans. Different from typical CEAS with a static cavity, which is limited by the FSR in frequency space, the attainable spectral resolution of our experimental setup can be up to 0.002 cm-1 owing to the simultaneous laser frequency tuning and cavity dither. Hence, the absorption line profile is more accurate, which is most suitable for low-pressure trace gas detection. This work has great potential for accurate selectivity and high sensitivity applications in human breath analysis and atmosphere sciences.

Evaluation of a Cost-Effective Ammonia Monitoring System for Continuous Real-Time Concentration Measurements in a Fattening Pig Barn.

Ammonia (NH3) emission is one of the major environmental issues in livestock farming. Gas measurements are required to study the emission process, to establish emission factors, and to assess the efficiency of emission reduction techniques. However, the current methods for acquiring reference measurements of NH3 are either high in cost or labor intensive. In this study, a cost-effective ammonia monitoring system (AMS) was constructed from a commercially-available gas analyzing module based on tunable diode laser absorption (TDLA) spectroscopy. To cope with the negative measurement biases caused by differing inlet pressures, a set of correction equations was formulated. Field validation of the AMS on NH3 measurement was conducted in a fattening pig barn, where the system was compared to a Fourier-transform infrared (FTIR) spectroscopy analyzer. Under two test conditions in a fattening pig barn, the absolute error of the AMS measurements with respect to the average obtained values between the AMS and the FTIR was respectively 0.66 and 0.08 ppmv, corresponding to 5.9% and 0.5% relative error. Potential sources of the measurement uncertainties in both the AMS and FTIR were discussed. The test results demonstrated that the AMS was capable of performing high-quality measurement with sub-ppm accuracy, making it a promising cost-effective tool for establishing NH3 emission factors and studying NH3 emission processes in pig houses.

Highly Sensitive, Printable Nanostructured Conductive Polymer Wireless Sensor for Food Spoilage Detection.

Near-field communication (NFC) labeling technology has been recently used to endow smartphones with nonline-of-sight sensing functions to improve the environment, human health, and quality of life. For applications in detecting food spoilage, the development of a sensor with high enough sensitivity to act as a switch for an NFC tag remains a challenge. In this Letter, we developed a nanostructured conductive polymer-based gas sensor with high sensitivity of Δ R/ R0 = 225% toward 5 ppm ammonia NH3 and unprecedented sensitivities of 46% and 17% toward 5 ppm putrescine and cadaverine, respectively. The gas sensor plays a critical role as a sensitive switch in the circuit of the NFC tag and enables a smartphone to readout meat spoilage when the concentration of biogenic amines is over a preset threshold. We envision the broad potential use of such intelligent sensing for food status monitoring applications in daily life, storage and supply chains.

Simultaneous removal of hydrogen sulfide and ammonia using a combined system with absorption and electrochemical oxidation.

Hydrogen sulfide (H2S) and ammonia (NH3), common impurities in biogas, need to be removed before utilizing it. In this study, a combined system, which consisted of an absorption column and an electrochemical oxidation reactor, was tested to simultaneously remove these impurities. The effects of the current density and the chemical loading rate on the system performance were investigated. Firstly, the mass transfer coefficients for the absorption column were determined at various gas flow rates. More mass of NH3 was transferred, compared with that of H2S, because of its higher solubility. In the electro-oxidation reactor, reactive chlorine species (RCSs) were generated and oxidized both H2S and NH3; however, NH3 started to degrade only after H2S was completely eliminated. At a current density of 400 A/m2, the current efficiencies of H2S and NH3 were 23.1% and 5.9%, respectively. In the combined system, the removal efficiency of H2S was closely related to the mass ratio of the H2S transferred and the RCSs generated. The removal efficiency of H2S was greater than 99% when the ratio was less than 1. The mass transfer potential and the oxidation kinetics should be balanced to improve the system performance for the simultaneous removal of H2S and NH3.

Low-cost physicochemical treatment for removal of ammonia, phosphate and nitrate contaminants from landfill leachate.

Four low-cost materials, oyster shells, pumice stone, sand and zeolite were employed as adsorbents in an adsorption batch assays investigating the removal of ammonia, phosphate and nitrate from an aqueous solution. These compounds were chosen as they represent typical compounds found in landfill leachate (LFL). Assay performance was evaluated by the Langmuir and Freundlich adsorption isotherms. The top two materials, oyster shells and pumice stone, were employed as adsorbents in a fixed-bed column trial examining the effect of bed height and flow rate on the treatment of a synthetic LFL. The trial concluded that the highest rates of adsorption were achieved using bed heights of 20 cm with a flow rate of 5 mL min-1. After optimization, the system was employed for the treatment of LFL from Powerstown landfill, Carlow, Ireland. Ammonia and nitrate were effectively removed by both adsorption materials resulting in a reduction of influent ammonia and nitrate concentrations to below the national discharge limits set for these compounds of ≤4 mg L-1 and ≤50 mg L-1, respectively. In contrast, although similar high removal efficiencies were observed for phosphate, these rates were not maintained during the test period with overall results indicating reduced phosphate adsorption in comparison to the other compounds tested.

Use of potassium adsorption filter for the removal of ammonia and potassium from red blood cell solution for neonates.

BACKGROUND: Ammonia in the plasma usually does not pass through the blood-brain barrier (BBB). However, it can affect the brain as a neurotoxin in neonates with anemia of prematurity. Excess intake of ammonia should therefore be restricted in conditions involving BBB breakdown, such as in premature neonates. A potassium adsorption filter (PAF) can remove not only potassium, but also ammonia from red blood cell (RBC) solution. PAF for neonates (PAF-n) has been recently introduced using small satellite packs. We evaluated the effects of PAF-n on the removal of ammonia and potassium from RBC solution in small satellite packs. STUDY DESIGN AND METHODS: RBC solutions were obtained from the Japanese Red Cross Society. Two units of RBC solution (280 mL) were divided into four satellite packs (70 mL/pack). The RBC solution was passed through PAF-n (Kawasumi Laboratories Inc.) that was primed with saline (100 mL) before use. The concentrations of ammonia and potassium were measured in the solution before and after filtration (four samples of 10 mL each of filtered RBC solution) by Biomedical Laboratories. RESULTS: Approximately 47 to 82 and 84% to 93% of ammonia and potassium were removed from the RBC solution, respectively, without dilution with saline. CONCLUSION: PAF-n can remove ammonia and potassium from RBC solution in small satellite packs. PAF-n could therefore improve the clinical prognosis of neonates with poorly developed BBB by limiting the delivery of excess ammonia found in the RBC solution.

(Bio)electrochemical ammonia recovery: progress and perspectives.

In recent years, (bio)electrochemical systems (B)ES have emerged as an energy efficient alternative for the recovery of TAN (total ammonia nitrogen, including ammonia and ammonium) from wastewater. In these systems, TAN is removed or concentrated from the wastewater under the influence of an electrical current and transported to the cathode. Subsequently, it can be removed or recovered through stripping, chemisorption, or forward osmosis. A crucial parameter that determines the energy required to recover TAN is the load ratio: the ratio between TAN loading and applied current. For electrochemical TAN recovery, an energy input is required, while in bioelectrochemical recovery, electric energy can be recovered together with TAN. Bioelectrochemical recovery relies on the microbial oxidation of COD for the production of electrons, which drives TAN transport. Here, the state-of-the-art of (bio)electrochemical TAN recovery is described, the performance of (B)ES for TAN recovery is analyzed, the potential of different wastewaters for BES-based TAN recovery is evaluated, the microorganisms found on bioanodes that treat wastewater high in TAN are reported, and the toxic effect of the typical conditions in such systems (e.g., high pH, TAN, and salt concentrations) are described. For future application, toxicity effects for electrochemically active bacteria need better understanding, and the technologies need to be demonstrated on larger scale.

Two-stage partial nitritation-anammox process for high-rate mainstream deammonification.

Increasing information supported that achieving high-rate mainstream deammonification through two-stage partial nitritation (PN)-anammox process should be a better option than through single-stage process. However, direct experimental evidence was limited so far. Herein, a two-stage PN-anammox process was successfully operated for nitrogen removal from low-strength wastewater in winter. Influent shift from synthetic wastewater to actual anaerobically pretreated sewage had little impact on the process performance. Promising nitrogen removal rates (NRRs) of 0.28-0.07 kg N m-3 d-1 with an average effluent concentration of 5.2 mg TN L-1 were achieved for the anaerobically pretreated sewage treatment at 15-7 °C. Moreover, nearly all the degradable COD in the pretreated sewage was steadily removed in the first-stage PN reactor, despite the varied influent COD concentrations of 22-78 mg L-1 and the operating temperature decrease, suggesting the positive role of the first-stage PN in protecting anammox bacteria. The low temperature seemingly was the only deterministic factor inhibiting the anammox activity, and hence made the anammox reaction to be the rate-limiting step for nitrogen removal in the two-stage PN-anammox process. Unexpectedly, nearly all the anammox bacteria remained active at low temperatures with the process actual anammox activity reached about 76-85% of their maximum potential, implying that higher NRRs would be easily realized through bioaugmentation or enrichment of anammox bacteria. Overall, the present investigation provides direct and valuable information for implementing the two-stage PN-anammox process to treat mainstream municipal wastewater. A control strategy was also proposed to optimize the operation of the two-stage mainstream deammonification process.

Indium Nitrite (InN)-Based Ultrasensitive and Selective Ammonia Sensor Using an External Silicone Oil Filter for Medical Application.

Ammonia is an essential biomarker for noninvasive diagnosis of liver malfunction. Therefore, selective detection of ammonia is essential for medical application. Here, we demonstrate a portable device to selectively detect sub-ppm ammonia gas. The presented gas sensor is composed of a Pt coating on top of an ultrathin Indium nitrite (InN) epilayer with a lower detection limit of 0.2 ppm, at operating temperature of 200 °C, and detection time of 1 min. The sensor connected with the external filter of nonpolar 500 CS silicone oil to diagnose liver malfunction. The absorption of 0.7 ppm acetone and 0.4 ppm ammonia gas in 10 cc silicone oil is 80% (0.56 ppm) and 21.11% (0.084 ppm), respectively, with a flow rate of 10 cc/min at 25 °C. The absorption of acetone gas is 6.66-fold higher as compared to ammonia gas. The percentage variation in response for 0.7 ppm ammonia and 0.7 ppm acetone with and without silicone oil on InN sensor is 17.5% and 4%, and 22.5%, and 14% respectively. Furthermore, the percentage variation in response for 0.7 ppm ammonia gas with silicone oil on InN sensor is 4.3-fold higher than that of 0.7 ppm acetone. The results show that the InN sensor is suitable for diagnosis of liver malfunction.

Airlift bioreactor system for simultaneous removal of hydrogen sulfide and ammonia from synthetic and actual waste gases.

The effectiveness of an airlift reactor system in simultaneously removing hydrogen sulfide (H2S) and ammonia (NH3) from synthetic and actual waste gases was investigated. The effects of various parameters, including the ratio of inoculum dilution, the gas concentration, the gas retention time, catalyst addition, the bubble size, and light intensity, on H2S and NH3 removal were investigated. The results revealed that optimal gas removal could be achieved by employing an activated inoculum, using a small bubble stone, applying reinforced fluorescent light, adding Fe2O3 catalysts, and applying a gas retention time of 20 s. The shock loading did not substantially affect the removal efficiency of the airlift bioreactor. Moreover, more than 98.5% of H2S and 99.6% of NH3 were removed in treating actual waste gases. Fifteen bands or species were observed in a profile from denaturing gradient gel electrophoresis during waste gas treatment. Phylogenetic analysis revealed the phylum Proteobacteria to be predominant. Six bacterial strains were consistently present during the entire operating period; however, only Rhodobacter capsulatus, Rhodopseudomonas palustris, and Arthrobacter oxydans were relatively abundant in the system. The photosynthetic bacteria R. capsulatus and R. palustris were responsible for H2S oxidation, especially when the reinforced fluorescent light was used. The heterotrophic nitrifier A. oxydans was responsible for NH3 oxidation. To our knowledge, this is the first report on simultaneous H2S and NH3 removal using an airlift bioreactor system. It clearly demonstrates the effectiveness of the system in treating actual waste gases containing H2S and NH3.

Effect of competing ions and causticization on the ammonia adsorption by a novel poly ligand exchanger (PLE) ammonia adsorption reagent.

In this paper, a poly ligand exchanger, Cu(II)-loaded chelating resin named ammonia adsorption reagent (AMAR), bearing the functional group of weak iminodiacetate acid, was prepared to efficiently remove ammonia from solutions. Batch adsorption equilibrium experiments were conducted under a range of conditions. The effects of pH on the removal of ammonia by AMAR were investigated at 25 °C. The copper loaded on the resin forms a complex with NH3 in solution under alkaline condition. The effect of alkaline dosage (AD) on the ammonia adsorption was investigated. The maximum breakthrough bed volumes were obtained when the AD was set as 0.75 mmol OH-/mL. The higher AD did not guarantee the better ammonia removal efficiency due to the forming of Cu(OH)2 precipitate between OH- in solutions and Cu(II) on the resin. The effect of competing ions on the adsorption breakthrough curve of virgin AMAR and causticized AMAR was also investigated. The results demonstrated that the existence of competing ions had a negative impact on the adsorption capacity for both virgin AMAR and causticized AMAR. After causticization, the AMAR was more resistant to the competing ions comparing with virgin AMAR. The bivalent Ca2+ affects the ammonia adsorption more than does the monovalent Na+.

Electrochemically-assisted ammonia recovery from wastewater using a floating electrode.

This work presents and explores a novel methodology for the removal and recovery of ammonia from wastewater based upon two mechanisms: electrochemical oxidation and a previously unreported electrochemically-assisted surface transfer mechanism. Recovery of ammonia is enabled by placing a porous cathodic electrode at the wastewater-air interface. In this configuration, the cathode creates local alkalinity and an electric field that draws ammonium ions towards the wastewater-air interface, resulting in near-linear reductions of dissolved ammonium irrespective of concentration. This approach leads to significant ammonia recovery without the need for ion-exchange membranes. In addition, anodic reactions that simultaneously occur at depth in the wastewater induce ammonia oxidation in accordance with proven mechanisms. The floating electrode approach offers improved ammonia removal efficiency in comparison to electrooxidation. Trials conducted on synthetic wastewater (900 mg NH4+-N l-1) and filtered anaerobic centrate (560 mg NH4+-N l-1) demonstrated ammonia concentration decreases up to 216 mg l-1 hr-1 and 110 mg l-1 hr-1, respectively, under the application of 5 mA cm-2 current density. The technology would be best used to treat municipal and industrial wastewaters possessing high ammonia concentration, including anaerobic digester centrate and urine, and offers potential to assist in removing ammonia from environmental waters.