Potential interferences in photolytic nitrogen dioxide converters for ambient air monitoring: Evaluation of a prototype

ABSTRACT

Mixing ratios of the criteria air contaminant nitrogen dioxide (NO₂) are commonly quantified by reduction to nitric oxide (NO) using a photolytic converter followed by NO-O₃ chemiluminescence (CL). In this work, the performance of a photolytic NO₂ converter prototype originally designed for continuous emission monitoring and emitting light at 395 nm was evaluated. Mixing ratios of NO₂ and NO_x (= NO + NO₂) entering and exiting the converter were monitored by blue diode laser cavity ring-down spectroscopy (CRDS). The NO₂ photolysis frequency was determined by measuring the rate of conversion to NO as a function of converter residence time and found to be 4.2 s^?1. A maximum 96% conversion of NO₂ to NO over a large dynamic range was achieved at a residence time of (1.5 ± 0.3) s, independent of relative humidity. Interferences from odd nitrogen (NO_y) species such as peroxyacyl nitrates (PAN; RC(O)O₂NO₂), alkyl nitrates (AN; RONO₂), nitrous acid (HONO), and nitric acid (HNO₃) were evaluated by operating the prototype converter outside its optimum operating range (i.e., at higher pressure and longer residence time) for easier quantification of interferences. Four mechanisms that generate artifacts and interferences were identified as follows: direct photolysis, foremost of HONO at a rate constant of 6% that of NO₂; thermal decomposition, primarily of PAN; surface promoted photochemistry; and secondary chemistry in the connecting tubing. These interferences are likely present to a certain degree in all photolytic converters currently in use but are rarely evaluated or reported. Recommendations for improved performance of photolytic converters include operating at lower cell pressure and higher flow rates, thermal management that ideally results in a match of photolysis cell temperature with ambient conditions, and minimization of connecting tubing length. When properly implemented, these interferences can be made negligibly small when measuring NO₂ in ambient air.

Implications: A new near-UV photolytic converter for measurement of the criteria pollutant nitrogen dioxide (NO₂) in ambient air by CL was characterized. Four mechanisms that generate interferences were identified and investigated experimentally: direct photolysis of HONO which occurred at a rate constant 6% that of NO₂, thermal decomposition of PAN and N₂O₅, surface promoted chemistry involving HNO₃, and secondary chemistry involving NO in the tubing connecting the converter and CL analyzer. These interferences are predicted to occur in all NO₂ P-CL systems but can be avoided by appropriate thermal management and operating at high flow rates.     

Continuous monitoring of odours from a composting plant using electronic noses

The odour impact of a composting plant situated in an urbanized area was evaluated by continuously monitoring the ambient air close to the plant during a period of about 4 days using two electronic noses. One electronic nose was installed in a nearby house, and the other one inside the perimeter of the composting plant in order to compare the response of both instruments. The results of the monitoring are represented by tables that report the olfactory class and the odour concentration value attributed to the analyzed air for each of the 370 measurements carried out during the monitoring period. The electronic nose installed at the house detected the presence of odours coming from the composting plant for about 7.8% of the monitoring total duration. Of the odour detections, 86% (25 of 29 measurements) were classified as belonging to the olfactory class corresponding to the open air storage of the waste screening overflows heaps, which was therefore identified to be the major odour source of the monitored composting plant. In correspondence of the measurements during which the electronic nose inside the house detected the presence of odours from the composting plant, the olfactory classes recognized by both instruments coincide. Moreover, the electronic nose at the house detected the presence of odours from the composting plant at issue in correspondence of each odour perception of the house occupants. The results of the study show the possibility of using an electronic nose for environmental odours monitoring, which enables the classification of the quality of the air and to quantify the olfactory nuisance from an industrial source in terms of duration and odour concentration.     

Toxic effects of waterborne polychlorinated biphenyls and sex differences in an endangered goodeid fish (Girardinichthys viviparus)

Polychlorinated biphenyls (PCBs) elicit toxic effects in different species. PCBs undergo biotransformation by enzymes associated with the mixed functional oxidase system, such as cytochrome P450 (cyt P450), this biotransformation being sex-dependent. No other metabolic pathways are known, however, in connection with this process. Thus, the present study aims to evaluate the effects of waterborne PCBs at sublethal nominal concentrations (0.92 mg PCBs/L) on the black-fin goodeid Girardinichthys viviparus, an endangered fish native to the Valley of Mexico, as well as any sex differences related to PCB biotransformation. Eight-month-old adult fish born in the laboratory were exposed for 1, 2, 4, 8 and 16 days to half the LC(0) (calculated concentration at which no deaths occurred after 96 h) determined by an acute toxicity test. Specimens were sacrificed following exposure and the liver was used to evaluate different biomarkers: cyt P450 concentration and alcohol dehydrogenase (ADH) and ethoxyresorufin O-deethylase (EROD) activities. Results show sexual differentiation with regard to all biomarkers in both the control group and PCB-treated fish, with higher values found in males. The induction rate of cyt P450 remained constant throughout the study in males. In females, induction peaked on day 4, coinciding with maximum EROD activity, and fell significantly thereafter. EROD was lower in PCB-treated males than in the control group, but was greater in magnitude. ADH was significantly induced in both sexes from day 2 to day 16 of exposure. The highest response as compared to the control group occurred on day 8 in females. A correlation was found between ADH activity and exposure to PCBs. Three possible action mechanisms, operating either individually or concurrently, are proposed.     

Azo dye biodegradation by microbial cultures immobilized in alginate beads

Microbial degradation of azo dyes usually starts in anaerobic conditions with a reductive cleavage of the azo bond, followed by an aerobic step necessary for the degradation of the aromatic amines formed. Because some reductive processes take place also in presence of molecular oxygen, a one-step azo dye degrading process has been investigated. A microbial consortium able to degrade ethyl orange in aerobic conditions has been selected and immobilized in alginate beads coated with polyacrylamide resin. Different concentrations of ethyl orange have been completely degraded in the presence of 1% glucose or starch as cosubstrates, and different beads preparation procedures have been studied to determine the best condition for microbial degradation. The catalytic activity of the immobilized consortium improved during five serial processes carried out for 30 days at room temperature. Three pure cultures were then isolated from the consortium. The one with the greatest degrading activity, a filamentous fungus, had a degradative capacity similar to that of the whole consortium.     

Brain cortical assessment by MRI in fetuses with left congenital diaphragmatic hernia

Objective

To evaluate fetal brain development using MRI (magnetic resonance imaging) in CDH (congenital diaphragmatic hernia).

Methods

52 isolated left CDH and 104 control fetuses were imaged using MRI. Brain morphometry (Biparietal diameter—BPD, brain fronto-occipital diameter—BFOD, third ventricle, posterior ventricles, transcerebellar diameter—TCD, anteroposterior and craniocaudal cerebellar vermis diameter—AP and CC) and cortical structures (bilateral cingulate fissure—CF, insular fissure—IF, insular depth - ID) were compared with controls using Mann–Whitney test.

Results

Median gestational age at MRI (p = 0.95)and the median biparietal diameter (p = 0.737) were comparable. Among morphometric parameters, only the brain fronto-occipital diameter was significantly smaller in CDH (p = 0.001) and the third ventricle was significantly greater in CDH (<0.0001). Among cortical structures, the cingulate and insular fissures were significantly deeper in CDH fetuses (p < 0.0001) as the insular depth ID was smaller in CDH (p < 0.03).

Conclusions

CDH fetuses have a smaller fronto-occipital diameter, reduced insular depth, deeper cingulate and insular fissure, and greater third ventricle width as compared to controls. These findings suggest that left CDH may have an impact on fetal brain development with an overall reduction in brain volume.