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.

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.

Electrochemical detection of NOx gas based on disposable paper-based analytical device using a copper nanoparticles-modified screen-printed graphene electrode.

A disposable gas-sensing paper-based device (gPAD) was fabricated in origami design which integrates the gas adsorbent and the electrochemical detection zone in a single device. The gPAD for the determination of NOx gas uses a screen-printed graphene electrode modified with copper nanoparticles (CuNP/SPGE) to achieve high sensitivity and selectivity. The gPAD detects both, NO and NO2 (as NOx) with same current responses. The measurement could be performed directly through differential pulse voltammetry (DPV) with a detection limit as low as 0.23 vppm and 0.03 vppm with exposure times of 25 min and 1 h, respectively. The reproducibility in terms of relative standard deviation was less than 5.1% (n = 7 devices) at 25, 75 and 125 vppm NO2 and the life-time of this device was more than 30 days. The gPAD was applied to detect NOx in air and exhaust gases from cars. In comparison with spectrophotometry, there are no significant differences between both methods using a paired t-test of the results on a 95% confidence level. The designed gPAD can provide a new template model for other gas sensors with features of disposability and portability for fieldwork analysis at low cost.

Exposición ambiental a dióxido de nitrógeno y salud respiratoria a los 2 años en la Cohorte INMA-Valencia / Exposure to nitrogen dioxide and respiratory health at 2 years in the INMA-Valencia cohort

Objetivo: Analizar la relación entre la exposición a dióxido de nitrógeno (NO2) en las etapas prenatal y posnatal y la incidencia de problemas respiratorios en niños/as hasta los 2 años de edad. Método: La población consistió en 624 niños/as de la cohorte INMA-Valencia. Se estimó la exposición individual al NO2 en el exterior de la vivienda durante el periodo prenatal y hasta los 2 años de edad, a partir de la combinación de datos empíricos y el desarrollo de métodos geoestadísticos. Se aplicó un cuestionario para obtener la información sobre los síntomas respiratorios a los 2 años. La asociación entre la exposición al NO2 y los eventos respiratorios se realizó mediante regresión logística multivariante. Resultados: La incidencia acumulada fue del 16,3% para tos persistente, del 34,9% para episodios de sibilancias y del 27,6% para las infecciones respiratorias de vías bajas. No se encontró asociación entre los síntomas respiratorios y la exposición al NO2 en el conjunto de los/las niños/as. Sin embargo, sí se encontró una asociación entre la exposición al NO2 y la tos persistente en el segundo año de vida en los/las niños/as con antecedentes familiares de alergias. Conclusión: La exposición al NO2 ambiental contribuiría a la presencia de tos persistente en los/las niños/as con antecedentes familiares de alergias

Objective: To analyze the association between exposure to nitrogen dioxide (NO2) during pregnancy and the postnatal period up to the age of 2 years old and the incidence of respiratory problems in children from the INMA-Valencia cohort. Methods: The study population included 624 children from the INMA-Valencia cohort. Individual exposure to NO2 was estimated in different environments outside the home during pregnancy and up to the age of 2 using empirical measurement and data from geo-statistical methods. Respiratory symptoms were obtained from a questionnaire applied at the age of two. The association between NO2 exposure and respiratory symptoms was performed using multivariate logistic regression. Results: The cumulative incidence was 16.3% for persistent cough, 34.9% for wheezing and 27.6% for lower respiratory tract infections. No association was found between respiratory symptoms and exposure to NO2 in any of the children. However an association between NO2 exposure and persistent cough was found at two years of life in the children with a parental history of allergy. Conclusion: NO2 exposure would lead to persistent cough in children with a parental history of allergies

Oxidative Nitration of Styrenes for the Recycling of Low-Concentrated Nitrogen Dioxide in Air.

The oxidative nitration of styrenes in ethyl acetate represents a metal-free, environmentally friendly, and sustainable technique to recover even low concentrations of NO2 in air. Favorable features are that the product mixture comprising nitroalcohols, nitroketones, and nitro nitrates simplifies at lower concentrations of NO2 . Experiments in a miniplant-type 10 L wet scrubber demonstrated that the recycling technique is well applicable on larger scales at which initial NO2 concentrations of >10 000 ppm were reliably reduced to less than 40 ppm.

Development of an activated carbon filter to remove NO2 and HONO in indoor air.

To obtain the optimum removal efficiency of NO2 and HONO by coated activated carbon (ACs), the influencing factors, including the loading rate, metal and non-metal precursors, and mixture ratios, were investigated. The NOx removal efficiency (RE) for K, with the same loading (1.0 wt.%), was generally higher than for those loaded with Cu or Mn. The RE of NO2 was also higher when KOH was used as the K precursor, compared to other K precursors (KI, KNO3, and KMnO4). In addition, the REs by the ACs loaded with K were approximately 38-55% higher than those by uncoated ACs. Overall, the REs (above 95%) of HONO and NOx with 3% KOH were the highest of the coated AC filters that were tested. Additionally, the REs of NOx and HONO using a mixing ratio of 6 (2.5% PABA (p-aminobenzoic acid)+6% H3PO4):4 (3% KOH) were the highest of all the coatings tested (both metal and non-metal). The results of this study show that AC loaded with various coatings has the potential to effectively reduce NO2 and HONO levels in indoor air.

Experimental study of NO2 reduction in N2/Ar and O2/Ar mixtures by pulsed corona discharge.

Non-thermal plasma technology has been regarded as a promising alternative technology for NOx removal. The understanding of NO2 reduction characteristics is extremely important since NO2 reduction could lower the total NO oxidation rate in the plasma atmosphere. In this study, NO2 reduction was experimentally investigated using a non-thermal plasma reactor driven by a pulsed power supply for different simulated gas compositions and operating parameters. The NO2 reduction was promoted by increasing the specific energy density (SED), and the highest conversion rates were 33.7%, 42.1% and 25.7% for Ar, N2/Ar and O2/Ar, respectively. For a given SED, the NO2 conversion rate had the order N2/Ar>Ar>O2/Ar. The highest energy yield of 3.31g/kWh was obtained in N2/Ar plasma and decreased with increasing SED; the same trends were also found in the other two gas compositions. The conversion rate decreased with increasing initial NO2 concentration. Furthermore, the presence of N2 or O2 led to different reaction pathways for NO2 conversion due to the formation of different dominating reactive radicals.

The etymological role of the main atmosphere pollutants in development of human diseases.

The aim of research was monitoring of the main atmospheric air pollutants concentration on Adjara Autonomous Republic territory in order to determine their role in causing different diseases. The following atmospheric air pollutants have been determined in Batumi: dust, carbon monoxide, sulfur and nitrogen dioxide. The number of diseases registered in Adjara Autonomous Republic, which may be linked to the air pollution, has been studied. These are the following: chronic and nonspecific bronchitis, asthma and asthma status diseases, allergic rhinitis, trachea-, bronchi- and lung malignant tumor. In order to reduce the number of risk-factors significant attention should be paid to the proper functionality of the vehicles and systematic observations should continue on the chemical pollution of the air to make proper decisions to reduce the number of diseases.

Variación espacial de la exposición a contaminación atmosférica en la ciudad de Valencia y su relación con un índice de privación / The spatial distribution of population exposure to outdoor air pollution in Valencia (Spain) and its association with a privation index

Objetivo: Evaluar la variación espacial de la exposición a dióxido de nitrógeno (NO2) en la ciudad de Valencia y su relación con la privación socioeconómica y la edad. Métodos: La población por sección censal (SC) procede del Instituto Nacional de Estadística. Los niveles de NO2 se midieron en 100 puntos del área de estudio, mediante captadores pasivos, en tres campañas entre 2002 y 2004. Se utilizó regresión por usos del suelo (LUR) para obtener el mapa de los niveles de NO2. Las predicciones del LUR se compararon con las proporcionadas por: a) el captador más cercano de la red de vigilancia, b) el captador pasivo más cercano, c) el conjunto de captadores en un entorno y d) kriging. Se asignaron niveles de contaminación para cada SC. Se analizó la relación entre los niveles de NO2, un índice de privación con cinco categorías y la edad (>65 años). Resultados: El modelo LUR resultó el método más preciso. Más del 99% de la población superó los niveles de seguridad propuestos por la Organización Mundial de la Salud. Se encontró una relación inversa entre los niveles de NO2 y el índice de privación (β = -2,01μg/m3 en el quintil de mayor privación respecto al de menor, IC95%: -3,07 a -0,95), y una relación directa con la edad (β = 0,12μg/m3 por incremento en unidad porcentual de población >65 años, IC95%: 0,08 a 0,16). Conclusiones: El método permitió obtener mapas de contaminación y describir la relación entre niveles de NO2 y características sociodemográficas (AU)

Objective: To evaluate spatial variation in exposure to nitrogen dioxide (NO2) air pollution in the city of Valencia, Spain, and its association with socioeconomic deprivation and age. Methods: Census tract population data were obtained from the National Statistics Institute of Spain. Outdoor NO2 was monitored in 100 sites in the study area, through the use of passive samplers, in three campaigns between 2002 and April 2004. Land use regression (LUR) was used to obtain a map of NO2 levels. The LUR predictions were compared with the NO2 level obtained by: a) the nearest sampler of the monitoring network, b) the nearest passive sampler, c) the mean distance-weighted levels of the samplers in the neighborhood, and d) the NO2 level obtained by using Kriging. For each census tract, the NO2 levels were obtained. The association of NO2 air pollution exposure with population age (>65 years) and the 5-category deprivation index was analyzed. Results: The LUR models showed less error than the other prediction methods. The safety levels proposed by the World Health Organization were exceeded in more than 99% of the population. An inverse relationship was found between NO2 levels and the deprivation index (β = -2.01μg/m3 in the most deprived quintile compared with lower deprivation, 95%CI: -3.07; -0.95) and a direct relationship was found with age (β = 0.12μg/m3 per unit increase in percentage of the population > 65 years, 95%CI: 0.08; 0.16). Conclusions: The method allowed pollution maps to be obtained and the association between NO2 levels and sociodemographic characteristics to be described (AU)

Measurements of tropospheric NO2 in Romania using a zenith-sky mobile DOAS system and comparisons with satellite observations.

In this paper we present a new method for retrieving tropospheric NO2 Vertical Column Density (VCD) from zenith-sky Differential Optical Absorption Spectroscopy (DOAS) measurements using mobile observations. This method was used during three days in the summer of 2011 in Romania, being to our knowledge the first mobile DOAS measurements peformed in this country. The measurements were carried out over large and different areas using a mobile DOAS system installed in a car. We present here a step-by-step retrieval of tropospheric VCD using complementary observations from ground and space which take into account the stratospheric contribution, which is a step forward compared to other similar studies. The detailed error budget indicates that the typical uncertainty on the retrieved NO2tropospheric VCD is less than 25%. The resulting ground-based data set is compared to satellite measurements from the Ozone Monitoring Instrument (OMI) and the Global Ozone Monitoring Experiment-2 (GOME-2). For instance, on 18 July 2011, in an industrial area located at 47.03°N, 22.45°E, GOME-2 observes a tropospheric VCD value of (3.4 ± 1.9) × 1015 molec./cm2, while average mobile measurements in the same area give a value of (3.4 ± 0.7) × 10(15) molec./cm2. On 22 August 2011, around Ploiesti city (44.99°N, 26.1°E), the tropospheric VCD observed by satellites is (3.3 ± 1.9) × 10(15) molec./cm2 (GOME-2) and (3.2 ± 3.2) × 10(15) molec./cm2 (OMI), while average mobile measurements give (3.8 ± 0.8) × 10(15) molec./cm2. Average ground measurements over "clean areas", on 18 July 2011, give (2.5 ± 0.6) × 10(15) molec./cm2 while the satellite observes a value of (1.8 ± 1.3) × 10(15) molec./cm2.

Effects of pyrolysis temperature, time and leaf litter and powder coal ash addition on sludge-derived adsorbents for nitrogen oxide.

The objective of this research was to seek a cost effective solution to prepare adsorbents for nitrogen oxide from surplus sludge. Leaf litter and powder coal ash were used as cheap and easily available additives. An adsorbent for nitrogen oxide was prepared by pyrolysis of dried sludge mixed with zinc chloride. Under optimum pyrolysis conditions of 375°C for 90 min and a zinc chloride content of 30%, the surface area of the adsorbent with leaf litter was 514.41 m(2)/g, the surface area of the adsorbent with powder coal ash was 432.34 m(2)/g, respectively, corresponding to an increase of 90.70% and 60.27% when compared to the adsorbent without the additives. The saturated adsorption quantity of the adsorbent with leaf litter reached 271 mg/g at 20°C. The results indicated that the sludge-derived adsorbent was quite promising for nitrogen oxide removal.

[Characteristic research of shortcut denitrification in synthetic ammonia industrial wastewater treatment process].

Active sludge was from a pilot-scale synthetic ammonia industrial wastewater treatment plant with a strengthen anoxic-oxic (A/O) technology. The zero order kinetic model was suit for describing shortcut and complete denitrification process. Experimental results showed that shortcut denitrification could reduce 14.1% carbon source consumption and 55.7% denitrification time, respectively, comparing with complete denitrification. The maximum specific denitrification rate was 0.509 g x (g x d)(-1) with an initial NO2(-) -N concentration of 36.82 mg x L(-1) and pH 7.5. In the industrial practice, it must be avoided pH higher than 9.0 in anoxic zone for industrial treatment. Replication-selective denitrifying bacteria showed a strong adaptability to methanol and ethanol, but showed maladaptation to other small molecular and easily biodegradable organics, such as glucose and acetic acid.

The measurement of the sink properties of triethanolamine (TEA) as a coating for collecting NO2 by using annular diffusion denuders.

This study evaluates the use oftriethanolamine (TEA) as an alternative to routinely used active carbon employed as a coating for collecting NO2 on a diffusion denuder. The study is based on laboratory experiments made by using annular diffusion denuders coated with TEA. The pre-exponential and exponential factors for the first term of the Gormley-Kennedy equation applied to annular geometry were estimated and compared with the corresponding values for other coatings used in previous studies published in the literature. It was found that TEA does not behave as a perfect sink in comparison with other coatings such as treated active carbon and alkaline guaiacol.

Validation of a spatiotemporal land use regression model incorporating fixed site monitors.

Land use regression (LUR) has been widely adopted as a method of describing spatial variation in air pollutants; however, traditional LUR methods are not suitable for characterizing short-term or time-variable exposures. Our aim was to develop and validate a spatiotemporal LUR model for use in epidemiological studies examining health effects attributable to time-variable air pollution exposures. A network of 42 NO(2) passive samplers was deployed for 12 two week periods over three years. A mixed effects model was tested using a combination of spatial predictors, and readings from fixed site continuous monitors, in order to predict NO(2) values for any two week period over three years in the defined study area. The final model, including terms based on traffic density at 50 and 150 m, population density within 500 m, commercial land use area within 750 m, and NO(2) concentrations at a central fixed site monitor, explained over 80% of the overall variation in NO(2) concentrations. We suggest that such a model can be used to study the association between variable air pollutant exposures and health effects in epidemiological studies.

[Identification and phylogenetic analysis of an isolated denitrifier from rotating drum biofilter].

A heterotrophic denitrifying strain named ND1 has been isolated from rotating drum biofilter (RDB) which was mainly used for the treatment of exhaust gas such as NOx. It was proved to be Gram-negative. In addition, it was able to form dry and wrinkled colonies on the medium, adhere on the agar surface, produce yellow pigments and be motile with a single polar flagellum. It was indentified as the Pseudomonas stutzeri according to morphological and physiological biochemical characteristics and 16S rDNA sequence analysis. Under the conditions of pH 7.2 and temperature 30 degrees C, the NO3- -N removal efficiency by ND1 was up to 100% in 5 days,while the NO2- -N degradation ratio was only 85% by the strain DN1 when subjected to the same condition as the above.

Novel process of simultaneous removal of SO2 and NO2 by sodium humate solution.

A novel simultaneous flue gas desulfurization and denitrification (FGDD) process using sodium humate (HA-Na) solution was proposed. This study relates to the SO2/NO2 absorption efficiency and products of simultaneous removing SO2 and NO2 in a bubbling reactor, especially the effect of recycled water on the SO2/NO2 absorption. Under alkaline conditions, the sulfate content in S-containing compound decreases with the increase of NO2 concentration, whereas there is a contrary result under acidic conditions. Whether the absorption liquid is alkaline or acidic, the presence of NO2 improves the SO2 absorption into HA-Na solution, because NO2 may promote the oxidation of sulfite to sulfate. It seems that the presence of SO2 is unfavorable for the NO2 absorption, but the NO2 absorption efficiency can be improved with the cycle number rising due to the increasing amount of sulfite. Although all the ion concentrations of Na+,SO4(2-),SO3(2-), and NO3- have a gradual increase as the cycle number rises, the ion concentrations of SO4(2-) and Na+ are far more than that of the other ions, which results in a slight decrease of the SO2 absorption efficiency. However, the initial pH of HA-Na solution prepared by recycled water decreases from 10 to 8.1 with the cycle number increasing from 1 to 10, whereas the final pH (the pH after absorption reaction is finished) remains almost constant (3.3). The SO2 absorption efficiency is above 98% and the NO2 absorption efficiency may reach above 95% in the optimal condition in this process. The chief byproduct is a compound fertilizer consisting of humic acid (HA), sulfate, and nitrate.

Field validation of the Ogawa diffusive sampler for NO2 and NOx in a cold climate.

A small-scale field trial in Umeå, Sweden with Ogawa samplers and a chemiluminescence instrument indicated that the NO(2) concentration was underestimated with respect to the reference monitor, if calculated according to the manufacturer's Ogawa sampling protocol. By co-locating Ogawa samplers and reference monitors at six sites in two Swedish cities, uptake rates were determined for NO(2) and NO(x) better applicable to the Swedish conditions and climate. The concentrations of NO(2) and NO(x) calculated according to the instruction manual of the sampler and using the field-determined uptake rates were compared with values derived from chemiluminescence monitors for each week over which samples were taken. When calculated according to the manufacturer's suggested protocol, the Ogawa sampler underestimated the NO(2) concentrations by 9.1% on average for all samples (N = 53), with respect to the reference monitor. In contrast, NO(x) concentrations were overestimated by a mean value of 15% for all samples (N = 45). By using the field determined uptake rates for the calculation of NO(2) and NO(x) a better estimation of the concentrations was obtained. The ratio between concentrations determined with the Ogawa samplers and chemiluminescence monitors was then 1.02 for all measurements of NO(2) and 1.00 for NO(x). Precision, expressed as the mean coefficient of variation, was 6.4% for six, 6-replicate measurements of NO(2) and 3.7% for five, 6-replicate measurements of NO(x).

Active carbons prepared by chemical activation of plum stones and their application in removal of NO2.

A technology of obtaining active carbon from plum stones by chemical activation with KOH is described. The effect of carbonisation temperature as well as activation procedure on the textural parameters, acid-base character of the surface and sorption properties of active carbons has been checked. The sorption properties of the activated carbons obtained were characterised by determination of nitrogen dioxide adsorption in dry and wet conditions. The final products were microporous activated carbons of well-developed surface area varying from 2174 to 3228 m(2)/g and pore volume from 1.09 to 1.61 cm(3)/g, showing different acid-base character of the surface. The results obtained in our study have proved that a suitable choice of the carbonisation and activation procedure for plum stones can produce activated carbons with high capacity of nitrogen dioxide, reaching to 67 and 42 mg NO(2)/g in dry and wet conditions, respectively. The results of our study have also shown that the adsorption ability of carbonaceous sorbents depends both on the method of preparation as well as on the textural parameters and acid-base properties of their surface.

Further development of a new flow-through directional passive air sampler for monitoring ambient nitrogen dioxide.

We have previously introduced a new type of rotatable flow-through directional passive air sampler (DPAS) for monitoring trace air pollutants in ambient air. In wind tunnel tests, the sampler turns into the prevailing wind direction and retains NO(2) (used as a test pollutant) on an internal sampling medium ring of triethanolamine (TEA)-coated meshes to indicate the source of pollution. However, these meshes can become saturated, after exposure times of tens of hours or a few days, due to the relatively small masses of TEA which can be coated onto them. This paper outlines the saturation problem and presents a possible redesign of the DPAS sampling approach, to allow longer-term (weeks-months) deployments, where air passes over larger volumes of TEA retained in a compartmentalised carousel. Investigations varying the volume, depth and mixing of TEA in sampling compartments suggested that the limiting step of NO(2) uptake was its rate of supply from the atmosphere. In wind tunnel trials, NO(2) uptake into TEA continued linearly in response to a stable air concentration over periods of tens of days, showing no signs of saturation. Uptake was wind velocity dependent across the range of 0.50, 2.00, 5.00 and 8.00 m s(-1). Results indicate that the total sampling time and storage capacity of the TEA for NO(2) can be varied to meet deployment time requirements, indicating that long-term, cheap, directional passive air sampling is achievable.

Photochemical removal of NO(2) by using 172-nm Xe(2) excimer lamp in N(2) or air at atmospheric pressure.

Photochemical removal of NO(2) in N(2) or air (5-20% O(2)) mixtures was studied by using 172-nm Xe(2) excimer lamps to develop a new simple photochemical aftertreatment technique of NO(2) in air at atmospheric pressure without using any catalysts. When a high power lamp (300 mW/cm(2)) was used, the conversion of NO(2) (200-1000 ppm) to N(2) and O(2) in N(2) was >93% after 1 min irradiation, whereas that to N(2)O(5), HNO(3), N(2), and O(2) in air (10% O(2)) was 100% after 5s irradiation in a batch system. In a flow system, about 92% of NO(2) (200 ppm) in N(2) was converted to N(2) and O(2), whereas NO(2) (200-400 ppm) in air (20% O(2)) could be completely converted to N(2)O(5), HNO(3), N(2), and O(2) at a flow rate of 1l/min. It was found that NO could also be decomposed to N(2) and O(2) under 172-nm irradiation, though the removal rate is slower than that of NO(2) by a factor of 3.8. A simple model analysis assuming a consecutive reaction NO(2)-->NO-->N+O indicated that 86% of NO(2) is decomposed directly into N+O(2) and the rest is dissociated into NO+O under 172-nm irradiation. These results led us to conclude that the present technique is a new promising catalyst-free photochemical aftertreatment method of NO(2) in N(2) and air in a flow system.