Oxidative decomposition of formaldehyde by metal oxides at room temperature

Formaldehyde (HCHO) is still a major indoor air pollutant in Japanese air-tight houses and is the subject of numerous complaints regarding health disorders. Authors have developed a passive-type air-cleaning material and an air cleaner using manganese oxide (77% MnO₂) as an active component and successfully reduced indoor HCHO concentrations in newly built multi-family houses. In this study, the reactivity between manganese oxide and HCHO was discussed. We tested the removal efficiencies of several metal oxides for HCHO in a static reaction vessel and found manganese oxide could react with HCHO and release carbon dioxide even at room temperature. The reactivity and mechanisms were discussed for the proposed chemical reactions. A mass balance study proved that a major product through the heterogeneous reaction between manganese oxide and HCHO was carbon dioxide. Harmful by-products (HCOOH and CO) were not found.     

Formaldehyde Dose-Response in Healthy Nonsmokers

Industrial, commercial, and domestic levels of formaldehyde exposure range from <0.1 to >5.0 ppm. Irritation of the eyes and upper respiratory tract predominate, and bronchoconstriction is described in case reports. However, pulmonary function and irritant symptoms together have not been assessed over a range of HCHO concentrations in a controlled environment. We investigated dose response in both symptoms and pulmonary function associated with 3-h exposures to 0.0-3.0 ppm HCHO in a controlled environmental chamber. Ten subjects were randomly exposed to 0.0, 0.5, 1.0, and 2.0 ppm HCHO at rest plus 2.0 ppm HCHO with exercise and nine additional subjects were randomly exposed to 0.0,1.0,2.0, and 3.0 ppm HCHO at rest plus 2.0 ppm HCHO with exercise. Significant dose-response relationships in odor and eye irritation were observed (p < 0.05). Nasal flow resistance was increased at 3.0 ppm (p < 0.01), but not at 2.0 ppm HCHO. There were no significant decrements in pulmonary function (FVC, FEV₁, FEF_25-75%, SGaw) or increases in bronchial reactivity to methacholine (log PD_35SGaw) with exposure to 0.5-3.0 ppm HCHO at rest or to 2.0 ppm HCHO with exercise.     

Ambient formaldehyde and its contributing factor to ozone and OH radical in a rural area

Formaldehyde (HCHO), as well as correlative pollutants was measured from 1 to 31 July in 2007 at Mazhuang, a rural site located in the east of China. Gaseous HCHO was scrubbed from the air with an acidic 2,4-dinitrophenylhydrazine (DNPH) solution, which leaded to the reaction of HCHO with DNPH and produced a stable product, 2,4-dinitrophenylhydrazone, followed by online analysis by high-performance liquid chromatography (HPLC) coupled with Ultraviolet detector. During the observation period, mixing ratios of HCHO ranged from 0.2 ppbv to 6.2 ppbv, with an average of 1.5 ± 0.67 ppbv. HCHO shows an evident diurnal variation, the maximum appeared during 12:00–14:00. The average concentration diurnal variations of measured HCHO, ozone (O₃), Methylhydroperoxides (MHP, CH₃OOH), hydrogen peroxide (H₂O₂), nitrogen oxides (NO_x) and meteorological parameters were compared. The similar variations of HCHO, O₃ and radiation imply that photo-oxidation of hydrocarbons might be the major source for HCHO. Based on the maximum incremental reactivity (MIR) coefficient of HCHO, the calculation shows that HCHO contributes about 20% to total observed O₃ during the study period. In order to compare the contributions of O₃, HCHO and HONO to OH radical, photolysis rate parameters (J-values) of the three compounds were calculated by the Tropospheric Ultraviolet and Visible (TUV) Radiation Model (4.4 version). Based on the comparison, this study reaches the conclusion that O₃ is the dominant source of OH radical at Mazhuang. This study also uses P(HCHO)/P(O₃) which represents the ratio of contrbutions of HCHO and O₃ to OH radical, to discuss the action of HCHO in OH radical soucers. The result shows that P(HCHO)/P(O₃) is 12.5% on average, with the maximum of 21.0% at 13:00_P.M. and minimum of 7.5% before 9:00_A.M. and after 17:00_P.M..Therefore HCHO is also an important source of OH radical and cannot be ignored.     

Effects of formaldehyde-enriched mists on Pseudotsuga menziesii (Mirbel) Franco and Lobaria pulmonaria (L.) Hoffm

The atmosphere in some areas is polluted with formaldehyde (HCHO); however, little is known about effects of HCHO on plants at concentrations resembling those in polluted areas. The effects of simulated fogwater enriched with HCHO on seedlings of Pseudotsuga menziesii (Mirbel) Franco (Douglas fir) and pendants of Lobaria pulmonaria (L.) Hoffm. were assessed. Plants were treated with HCHO-enriched fog (target concentrations of 100, 500, and 1000 microm) during five 4-night mist sessions. Growth and nitrogenase activity (acetylene reduction rate) for lichens and growth and timing of bud-break for Douglas fir were monitored. Nitrogenase activity was lowest in lichens treated at the highest HCHO concentration after all but the first mist session, and it declined significantly with increasing HCHO concentration after the final mist session (R(2) = 0.60, p = 0.02). However, differences in nitrogenase activity among treatments were generally not statistically significant (most p values from ANOVAs were >/= 0.20). Formaldehyde did not affect growth of the lichens. Budbreak of Douglas firs was slightly delayed and height growth was slightly depressed with increasing HCHO concentration, although effects were not statistically significant.     

臭氧/紫外联合降解甲醛的试验研究

在臭氧单独作用、紫外光单独作用和UV/O₃ 3种条件下分别对甲醛进行降解试验，研究表明,臭氧和紫外在降解甲醛的试验中存在明显的协同促进作用。单独臭氧对甲醛降解效果并不显著。紫外单独作用时，对甲醛几乎没有降解作用。在UV/O₃条件下，甲醛的降解率大大提高，特别是在高浓度臭氧条件下，降解率高达63％。臭氧浓度增大，降解率增大；紫外光强度增大，降解效果提高；气体流量增大，降解率下降；湿度增大，降解率提高。对甲醛降解试验进行动力学研究，结果表明，光照强度和臭氧浓度增大，一级反应速率增大，提高臭氧浓度要比加强紫外强度更能促进甲醛的降解。     

低温等离子体法处理甲醛气体

报道用低温等离子体的方法去除甲醛气体,主要考察了电场强度、进口浓度及填料对于甲醛气体去除效率的影响。实验研究结果表明,随着电场强度的增加,进口浓度的降低和在反应器中加有填料都会提高甲醛气体的去除效率。低温等离子体方法去除甲醛气体的机理可分为2部分:电子与污染物分子的直接碰撞和电场产生的活性粒子与污染物分子之间发生的一系列化学反应。     

Effect of formaldehyde on Cu(II) removal from synthetic complexed solutions by ion exchange

The effect of formaldehyde (HCHO) on the ion exchange of Cu(II) from an equimolar EDTA (ethylenediaminetetraacetic acid, H(4)L) solution with a strong-base Amberlite IRA-400 resin was studied. Experiments were conducted as a function of the initial concentration of Cu(II) (0.5-10 mM), solution pH (1.0-6.0), HCHO concentration (0-6 vol%), and temperature (15-35 degrees C). It was shown that the amount of exchange of Cu(II), which exists in the form of complexed anions CuL(2-), increased with increasing solution pH and reached a plateau at an equilibrium pH (pH(e)) of 3.5. However, the amount of exchange decreased with increasing HCHO concentration up to 3 vol% but then slightly decreased with a further increase in HCHO concentration. Such effect of added HCHO was determined by the following two factors: the competitive exchange of HCOO(-) anions and the enhanced exchange of Cu(I) in the form of complexed anions CuL(3-). The exchange isotherm obtained at a fixed pH(e) could be well described by the Langmuir equation. The isosteric enthalpy change for the present ion exchange process was also evaluated and discussed.     

膜吸收法净化低浓度甲醛和氨气

基于膜吸收技术自制双层平板式膜吸收器，搭建净化低浓度甲醛和氨气污染模拟系统，考察不同膜结构参数、进气流量、吸收剂流量等因素对其净化效果的影响。结果表明，聚偏氟乙烯PVDF对低浓度甲醛和氨气的净化效率高于聚四氟乙烯PTFE。对同一材质膜，随着膜孔隙率的增大，甲醛和氨气的净化率呈上升趋势。随着进气流量的增加。甲醛和氨气的净化效率降低；而吸收剂流量对其净化效率影响不大。对于所有实验条件，平均膜孔径为0．22μm的PVDF4#在进气流量ug=120L／h时，甲醛和氨气的净化效率最高，分别达94．7％和96．3％。     

Scavenging of atmospheric formaldehyde by wet precipitation

Despite the great importance that formaldehyde has in atmospheric photochemistry, few studies have been reported on rain water. In this paper, concentrations of HCHO in rain fractions within rain events are presented. Two sampling sites were chosen: one at Mexico City, a great polluted urban area, and the second at Rancho Viejo, a forested area under the meteorological influence of the city. The results show a general decrease during the early portion of the rain event. This seems to indicate that below-cloud scavenging is the most important mechanism while, from the small variations observed in the latter portion of the rainfall, it is possible to assume within-cloud scavenging as the predominant mechanism. Using the HCHO concentrations in rain water, the mixing ratios were estimated for the two sampling sites. The values were 0.68 ppb and 0.44 ppb at Mexico City and Rancho Viejo, respectively. Measurements at ground level in Mexico City gave a mean HCHO concentration in air of 24 ppb, much higher than the estimated mixing ratio. The high levels of HCHO found in ambient air and in rain water reflect anthropogenic emissions as the potential atmospheric sources.     

Seasonal variability of formaldehyde production from photolysis of rainwater dissolved organic carbon

Photochemical production of formaldehyde (HCHO) was measured in rainwater from 13 precipitation events in Wilmington, North Carolina, USA under conditions of simulated sunlight. HCHO concentrations increased in all samples irradiated with no changes observed in dark controls. HCHO photoproduction rates were strongly correlated with dissolved organic carbon (DOC) suggesting HCHO was derived from direct or indirect photolysis of rainwater DOC. The higher photoproduction rates (0.03–2.9 μM h^?1) relative to those reported for surface waters suggests that rainwater DOC is more photolabile in terms of HCHO production than surface waters. HCHO photoproduction rates were higher in growing season (1.0 ± 1.0 μM h^?1) compared to non-growing season (0.08 ± 0.05 μM h^?1) even when rates were normalized for DOC (6.8 ± 3.6 μM h^?1 mM C^?1 versus 1.8 ± 1.0 μM h^?1 mM C^?1). The higher growing season rate may be related to seasonal differences in the composition of DOC as evidenced by differences in fluorescence per unit carbon of rainwater samples. Irradiation of C18 extracts of rainwater also produced HCHO, but at lower rates compared to corresponding whole rain samples, suggesting that hydrophyllic components of rainwater play a role in HCHO photoproduction. Our results indicate that photolysis of rainwater DOC produces significant amounts of HCHO, and possibly other low molecular weight organic compounds, likely increasing its reactivity and bioavailability.     

Formaldehyde and carbon dioxide air concentrations and their relationship with indoor environmental factors in daycare centers

The aim of this study was to measure the air concentrations of carbon dioxide (CO₂) and formaldehyde (HCHO) in daycare centers to determine relevant influencing factors, including temperature, relative humidity (RH), type of facility, number of children, type of ventilation system, ventilation time, and air cleaning system. The authors measured HCHO, CO₂, temperature, and RH in the center of classrooms in 289 daycare centers. Spearman’s correlation and Mann–Whitney analyses were used to examine the relationships and differences in HCHO and CO₂ for varying temperatures, RH values, and categorical indoor environmental factors. There were no significant differences in the HCHO and CO₂ air concentrations with varying numbers of children, ventilation times, or ventilation and air cleaning system types. However, both the HCHO and CO₂ air concentrations were significantly different for varying RH values, which were divided into five categories (p < 0.001). Only the HCHO air concentrations were significantly different for varying temperatures, which were divided into five categories (p < 0.001). Significant correlations were found between HCHO air concentrations and the temperature (r = 0.35, p < 0.0001), RH (r = 0.51, p < 0.0001), and CO₂ (r = 0.36, p < 0.0001). The study results support maintaining an appropriate temperature and RH range for reducing airborne HCHO in daycare centers. Further research is needed to elucidate the precise mechanisms responsible for the relationships observed in this study.

Implications: Data from 289 daycare centers in Seoul, South Korea, indicate that HCHO concentrations show a positive correlation with indoor temperature and relative humidity. This indicates that keeping temperatures low will help keep HCHO concentrations low, by both a direct and an indirect effect, since low temperatures also cause low relative humidity.     

Variations and sources of ambient formaldehyde for the 2008 Beijing Olympic games

As the host city of the 2008 Olympic games, Beijing implemented a series of air pollution control measures before and during the Olympic games. Ambient formaldehyde (HCHO) concentrations were measured using a fluorometric instrument based on a diffusion scrubber and the Hantzsch reaction; hydrocarbons were simultaneously measured using gas chromatography–mass spectrometry (GC–MS). Meteorological parameters, CO, O₃, and NO₂ concentrations were measured by standard commercial instrumentation. In four separate periods: (a) before the vehicle plate number control (3–19 July); (b) during the Olympic Games (8–24 August); (c) during the Paralympic Games (6–17 September) and (d) after the vehicle control was ceased (21–28 September), the average HCHO mixing ratios were 7.31 ± 2.67 ppbv, 5.54 ± 2.41 ppbv, 8.72 ± 2.48 ppbv, and 6.42 ± 2.79 ppbv, while the total non-methane hydrocarbons (NMHCs) measured were 30.41 ± 18.08 ppbv, 18.12 ± 9.38 ppbv, 30.50 ± 13.37 ppbv, and 33.33 ± 15.85 ppbv, respectively. Both HCHO and NMHC levels were the lowest during the Olympic games, and increased again during the Paralympic games even with the same vehicle control measures operative. Similar diurnal HCHO and O₃ patterns indicated that photo-oxidation of NMHCs may be the major source of HCHO. The diurnal profile of total NMHCs was very similar to that of NO₂ and CO: morning and evening peaks appeared in rush hours, indicating even after strict vehicle control, automobile emission may still be the dominant source of the HCHO precursors. The contributions of HCHO, alkanes, alkenes, and aromatics to OH loss rates were also calculated. HCHO contributed 22 ± 3% to the total VOCs and 24 ± 1% to the total OH loss rate. HCHO was not only important in term of abundance, but also important in chemical reactivity in the air.     

Radical precursors and related species from traffic as observed and modeled at an urban highway junction

Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals and are believed to favor ozone formation significantly. Traffic emission data for both compounds are scarce and mostly outdated. A better knowledge of today's HCHO and HONO emissions related to traffic is needed to refine air quality models. Here the authors report results from continuous ambient air measurements taken at a highway junction in Houston, Texas, from July 15 to October 15, 2009. The observational data were compared with emission estimates from currently available mobile emission models (MOBILE6; MOVES [MOtor Vehicle Emission Simulator]). Observations indicated a molar carbon monoxide (CO) versus nitrogen oxides (NO_x) ratio of 6.01 ± 0.15 (r ² = 0.91), which is in agreement with other field studies. Both MOBILE6 and MOVES overestimate this emission ratio by 92% and 24%, respectively. For HCHO/CO, an overall slope of 3.14 ± 0.14 g HCHO/kg CO was observed. Whereas MOBILE6 largely underestimates this ratio by 77%, MOVES calculates somewhat higher HCHO/CO ratios (1.87) than MOBILE6, but is still significantly lower than the observed ratio. MOVES shows high HCHO/CO ratios during the early morning hours due to heavy-duty diesel off-network emissions. The differences of the modeled CO/NO_x and HCHO/CO ratios are largely due to higher NO_x and HCHO emissions in MOVES (30% and 57%, respectively, increased from MOBILE6 for 2009), as CO emissions were about the same in both models. The observed HONO/NO_x emission ratio is around 0.017 ± 0.0009 kg HONO/kg NO_x which is twice as high as in MOVES. The observed NO₂/NO_x emission ratio is around 0.16 ± 0.01 kg NO₂/kg NO_x, which is a bit more than 50% higher than in MOVES. MOVES overestimates the CO/CO₂ emission ratio by a factor of 3 compared with the observations, which is 0.0033 ± 0.0002 kg CO/kg CO₂. This as well as CO/NO_x overestimation is coming from light-duty gasoline vehicles.

Implications: Nitrous acid (HONO) and formaldehyde (HCHO) are important precursors for radicals that ultimately contribute to ozone formation. There still exist uncertainties in emission sources of HONO and HCHO and thus regional air quality modeling still tend to underestimate concentrations of free radicals in the atmosphere. This paper demonstrates that the latest U.S. Environmental Protection Agency (EPA) traffic emission model MOVES still shows significant deviations from observed emission ratios, in particular underestimation of HCHO/CO and HONO/NO_x ratios. Improving the performance of MOVES may improve regional air quality modeling.     

Kinetics of the tropospheric formaldehyde loss onto mineral dust and urban surfaces

The kinetics of the heterogeneous reaction between gaseous HCHO and TiO₂/SiO₂ mineral coatings were investigated using a coated-wall flow tube to mimic HCHO loss on mineral aerosol and TiO₂ coated depolluting urban surfaces. The measured uptake kinetics were strongly enhanced when the flow tube was irradiated with 340–420 nm UV light with an irradiance of 1.45 mW cm^?2. The associated BET uptake coefficients ranged from (3.00 ± 0.45) × 10^?9 to (2.26 ± 0.34) × 10^?6 and were strongly dependent on HCHO initial concentration, relative humidity, temperature, and TiO₂ content in the mineral coating, which ranged from 3.5 to 32.5 ppbv, 6–70%, 278–303 K, and 1–100 %wt, respectively. The measured kinetics were well described using a Langmuir–Hinshelwood type formalism. The estimated uptake coefficients were used to discuss the importance of heterogeneous HCHO surface loss, in terms of deposition lifetimes, as compared to major homogeneous gas-phase losses such as OH reaction and photolysis. It is found that deposition may compete with gas-phase removal of HCHO in a dense urban environment if more than 10% of the urban surface is covered with TiO₂ treated material.     

Removal of formaldehyde from indoor air by passive type air-cleaning materials

We have developed a board-like air-cleaning material consisting of activated carbon particles and manganese oxides, by which HCHO gas is decomposed into carbon dioxide even at room temperature. In this study, we investigated removal efficiencies of the air-cleaning board in a passive mode using a kinetic approach. First-order removal rate constant, k, corresponding to air change rate was characterized for the board as a function of the ratio of applied board area to space volume, S/V, and was found directly proportional to S/V with a slope of 25 at 25°C. The performance of the board was evaluated in a full-size laboratory with a constant gas generation. The board suppressed the increase of indoor HCHO concentration and the time course fitted to a theoretical curve. Then, field tests of the air-cleaning board were conducted in newly constructed multi-family houses in Japan from May 1998 to January 1999. The board not only reduced indoor HCHO concentration from 0.21 to 0.04 ppm for more than 7 months, but also enhanced the loss of HCHO gas from building materials in apartments.     

Partitioning of formaldehyde between air and ice at −35°C to −5°C

The equilibrium partitioning of formaldehyde (HCHO) between air and snow was studied in a series of laboratory experiments conducted at −5°C, −15°C, and −35°C, in order to understand how partitioning of HCHO between air and polar snow varies with temperature, and thus seasonally on the ice sheet. Measured partitioning coefficients were 56, 93, and 245 mol l⁻¹ atm⁻¹ for −5°C, −15°C and −35°C, respectively, showing a similar trend as the values previously estimated from field observations. Estimates of the pseudo-first-order rate coefficient for air–snow exchange for the same three temperatures were 4.1×10⁻⁴, 1.1×10⁻⁴, and 1.1×10⁻⁵ s⁻¹, respectively. This implies a time scale for air–snow equilibration of the order of hours to days for HCHO accumulated at or near the ice–air interface on snow grains. Comparing the current laboratory partitioning coefficients with those estimated from measurements of air and freshly fallen snow in Greenland during summer demonstrates that the snow is supersaturated and should degas HCHO to the surrounding air. During this degassing, polar snow should be a significant source of HCHO to the lower troposphere.     

Impacts of a strong cold front on concentrations of HONO,HCHO, O3, and NO2 in the heavy traffic urban area of Beijing

Much rain and strong winds caused by a cold front occurred in Beijing during the period of Sep. 27 to Oct. 4, 2004 and led to sharp drops in maximum and mean concentrations of HONO, HCHO, O₃, and NO₂, i.e., the maximum concentrations were reduced by 5.9, 21.3, 45.6, and 44.4 ppb, respectively, and the mean concentrations were decreased by 4.0, 5.5, 30.3, and 32.3 ppb, respectively. For daily HO_x production rates HONO photolysis was the largest contributor and over 90% contributions were from photolysis of HONO and HCHO. Large number and area percentages of soot aggregate from PM10, and high correlations between concentrations of PM10 and chemical formation of HONO suggested that heterogeneous reactions of NO₂ on surfaces of soot aggregate could be a key source of HONO in the heavy traffic areas of Beijing during the night and should be considered in air quality simulations for such areas.     

Vehicle emissions of radical precursors and related species observed in the 2009 SHARP campaign

The 2009 Study of Houston Atmospheric Radical Precursors (SHARP) field campaign had several components that yielded information on the primary vehicular emissions of formaldehyde (HCHO) and nitrous acid (HONO), in addition to many other species. Analysis of HONO measurements at the Moody Tower site in Houston, TX, yielded emission ratios of HONO to the vehicle exhaust tracer species NO_x and CO of 14 pptv/ppbv and 2.3 pptv/ppbv, somewhat smaller than recently published results from the Galleria site, although evidence is presented that the Moody Tower values should be upper limits to the true ratios of directly emitted HONO, and are consistent with ratios used in current standard emissions models. Several other Moody Tower emission ratios are presented, in particular a value for HCHO/CO of 2.4 pptv/ppbv. Considering only estimates of random errors, this would be significantly lower than a previous value, though the small sample size and possible systematic differences should be taken into account. Emission factors for CO, NO_x, and HCHO, as well as various volatile organic compounds (VOCs), were derived from mobile laboratory measurements both in the Washburn Tunnel and in on-road exhaust plume observations. These two sets of results and others reported in the literature all agree well, and are substantially larger than the CO, NO_x, and HCHO emission factors derived from the emission ratios reported from the Galleria site.

Implications: Emission factors for the species measured in the various components of the 2009 SHARP campaign in Houston, TX, including HCHO, HONO, CO, CO₂, nitrogen oxides, and VOCs, are needed to support regional air quality monitoring. Components of the SHARP campaign measured these species in several different ways, each with their own potential for systematic errors and differences in vehicle fleets sampled. Comparisons between data sets suggest that differences in sampling place and time may result in quite different emission factors, while also showing that different vehicle mixes can yield surprisingly similar emission factors.     

Investigation and modeling of diurnal variation in suburban ambient formaldehyde concentration

Environmental Science and Pollution Research - Formaldehyde (HCHO) is a naturally occurring compound found in ambient air which can induce cancer and sick-building syndrome. It plays an important...     

Rainwater formaldehyde: concentration,deposition and photochemical formation

Formaldehyde (HCHO) concentrations were measured in 116 rain samples in Wilmington, NC from June 1996 to February 1998. Concentrations ranged from below the detection limit of 10 nM, to 13 μM, in the range of HCHO levels reported at other locations worldwide. The volume-weighted annual average rainwater formaldehyde concentration was 3.3±0.3 μM and comprised approximately 3% of the measured dissolved organic carbon. Using the volume weighted average HCHO concentration and annual precipitation of 1.4 m, an annual formaldehyde deposition of 4.6 mmol m⁻² yr⁻¹ was determined. Rainwater is a significant source of formaldehyde to surface waters and may contribute as much as 30 times the resident amount found in natural waters of southeastern North Carolina during the summer. Formaldehyde concentrations did not correlate with precipitation volume suggesting continuous supply during rain events. Evidence is presented which indicates part of this supply may be from direct photochemical production in the aqueous phase. Formaldehyde levels exhibited a distinct seasonal oscillation, with higher concentrations during the summer. This pattern is similar to that observed with other rainwater parameters at this site including pH, nitrate, and ammonium, and is most likely the result of increased photochemical production, as well as biogenic and anthropogenic emissions during summer months. The concentration of formaldehyde in both winter El Nino rains and summer tropical rains was less than half its concentration in non-El Nino or non-tropical events, suggesting significant terrestrial input. Formaldehyde was correlated with hydrogen peroxide and non-sea-salt sulfate deposition suggesting a relationship between HCHO, H₂O₂, S(VI) within the troposphere.