Determination of formaldehyde and acetaldehyde levels in poly(ethylene terephthalate) (PET) bottled mineral water using a simple and rapid analytical method.

A simple and rapid analytical method was developed for the determination of formaldehyde (FA) and acetaldehyde (AA) contents in water. FA and AA were derivatized by 2,4-dinitrophenylhydrazine in an LC vial for 20 min at room temperature, about 25 °C, and analyzed using LC-MS/MS. The calibration curve exhibited excellent linearity for FA and AA concentrations of 2-150 ng/mL. Recovery tests using ultra-pure water and commercially available PET-bottled mineral water samples showed good trueness and precision. We determined the FA and AA contents in 105 PET-bottled mineral water samples on the Japanese market using this method. FA was detected in 61% of the samples at levels from 2.6 to 31.4 ng/mL, while AA was detected in 68% at levels from 5.3 to 143.5 ng/mL. These results demonstrate that the concentrations of FA and AA in PET-bottled mineral water on the Japanese market have not changed significantly over the last decade.

Removing Formaldehyde-Induced Peptidyl Crosslinks Enables Mass Spectrometry Imaging of Peptide Hormone Distributions from Formalin-Fixed Paraffin-Embedded Tissues.

Linking molecular and chemical changes to human disease states depends on the availability of appropriate clinical samples, mostly preserved as formalin-fixed paraffin-embedded (FFPE) specimens stored in tissue banks. Mass spectrometry imaging (MSI) enables the visualization of the spatiotemporal distribution of molecules in biological samples. However, MSI is not effective for imaging FFPE tissues because of the chemical modifications of analytes, including complex crosslinking between nucleophilic moieties. Here we used an MS-compatible inorganic nucleophile, hydroxylamine hydrochloride, to chemically reverse inter- and intra-crosslinks from endogenous molecules. The analyte restoration appears specific for formaldehyde-reactive amino acids. This approach enabled the MSI-assisted localization of pancreatic peptides expressed in the alpha, beta, and gamma cells. Pancreatic islet-like distributions of islet hormones were observed in human FFPE tissues preserved for more than five years, demonstrating that samples from biobanks can effectively be investigated with MSI.

Biotechnology progress for removal of indoor gaseous formaldehyde.

Formaldehyde is a ubiquitous carcinogenic indoor pollutant. The treatment of formaldehyde has attracted increasing social attention. Over the past few decades, an increasing number of publications have reported approaches for removing indoor formaldehyde. These potential strategies include physical adsorption, chemical catalysis, and biodegradation. Although physical adsorption is widely used, it does not really remove pollution. Chemical catalysis is very efficient but adds the risk of introducing secondary pollutants. Biological removal strategies have attracted more research attention than the first two methods, because it is more efficient, clean, and economical. Plants and bacteria are the common organisms used in formaldehyde removal. However, both have limitations and shortcomings when used alone. This review discusses the mechanisms, applications, and improvements of existing biological methods for the removal of indoor gaseous formaldehyde. A combination strategy relying on plants, bacteria, and physical adsorbents exhibits best ability to remove formaldehyde efficiently, economically, and safely. When this combination system is integrated with a heating, ventilation, air conditioning, and cooling (HVAC) system, a practical combined system can be established in formaldehyde removal. Multivariate interactions of biological and non-biological factors are needed for the future development of indoor formaldehyde removal. KEY POINTS: • Indoor gaseous formaldehyde removal is necessary especially for new residence. • Biological removal strategies have attracted increasing research attentions. • Combined system of plants, bacteria, and physical adsorbents exhibits best efficiency. • Integrated device of biological and non-biological factors will be potential practical.

The Study of an Ultraviolet Radiation Technique for Removal of the Indoor Air Volatile Organic Compounds and Bioaerosol.

This study examined the use of high dosages of ultraviolet germicidal irradiation (UVGI) (253.7 nm) to deal with various concentrations of air pollutants, such as formaldehyde (HCHO), total volatile organic compounds (TVOC), under various conditions of humidity. A number of irradiation methods were applied for various durations in field studies to examine the efficiency of removing HCHO, TVOC, bacteria, and fungi. The removal efficiency of air pollutants (HCHO and bacteria) through long-term exposure to UVGI appears to increase with time. The effects on TVOC and fungi concentration were insignificant in the first week; however, improvements were observed in the second week. No differences were observed regarding the removal of HCHO and TVOC among the various irradiation methods in this study; however significant differences were observed in the removal of bacteria and fungi.

Gaseous formaldehyde removal: A laminated plate fabricated with activated carbon, polyimide, and copper foil with adjustable surface temperature and capable of in situ thermal regeneration.

Formaldehyde is one of the most common indoor air pollutants in Chinese residences. This study introduces a novel laminated plate with adjustable surface temperature to remove gaseous formaldehyde. The plate is fabricated with activated carbon, polyimide, and copper foil via thermal compression. The plate can be regenerated in situ by applying a direct current to the copper foil. Adsorption-regeneration cycle tests were conducted to evaluate the plate's formaldehyde removal performance. The overall removal efficiency of the fabricated laminated plate with glue mass fraction of 25% and thickness of 1.5 mm was about 30% at the face velocity of 0.8-1.2 m/s. The pressure drop was about 5 Pa. Its removal ability can be regenerated in situ in 8 minutes by increasing the surface temperature to 80°C. The fabricated laminated plate showed good durability after 52 cycles of adsorption-regeneration tests. The results indicate that the proposed laminated plate can enhance the purifying efficiency and enlarge the life span of ordinary, cheap sorbents. It makes cheap materials with low performance suitable for air purification.

Characterization and adsorption capacity of potassium permanganate used to modify activated carbon filter media for indoor formaldehyde removal.

This study examined the effect of potassium permanganate (KMnO4)-modified activated carbon for formaldehyde removal under different face velocities and different initial formaldehyde concentrations in building environment. We chose the coconut shell activated carbon due to their high density and purity. Moreover, they have a clear environmental advantage over coal-based carbons, particularly in terms of acidification potential. The chemical properties were characterized by FTIR to show the functional groups, EDS to calculate each component of their energy bands to know how the ratio is. Also, the morphology of the surface was examined with scanning electron microscopy (SEM). The BET determines specific surface area, pore size, and pore volume. It was found that where the initial formaldehyde concentration and the face velocity are low, adsorption capacity is high. The adsorption isotherms of formaldehyde on modified activated carbon are well fitted by both Langmuir and Freundlich equations. The rate parameter for the pseudo-first-order model, pseudo-second-order model, and intraparticle diffusion model was compared. The correlation coefficient of pseudo-second-order kinetic model (0.999 > R2 > 0.9548) is higher than the coefficient of pseudo-first-order kinetic model (0.5785 < R2 < 0.8755) and intraparticle diffusion model (0.9752 < R2 < 0.9898). Thus, pseudo-second-order kinetic model is more apposite to discuss the adsorption kinetic in this test, and the overall rate of the modified activated carbon adsorption process appears to be influenced by more than one step that is both the intraparticle diffusion model and membrane diffusion.

Indoor levels of volatile organic compounds and formaldehyde from emission sources at elderly care centers in Korea.

The objective of this study is to characterize indoor and outdoor levels of volatile organic compounds (VOCs) and formaldehyde (HCHO) and identify indoor emission sources in thirty elderly care centers (ECCs) located in the Seoul metropolitan city and Gyeonggi province in Korea. Air monitoring samples from indoor and outdoor environments were collected from January to December in 2007. Statistical analyses of indoor and outdoor VOCs and HCHO levels in three rooms (a bedroom, living, and dining rooms) of each ECC were performed, and these were compared to identify environmental factors associated with an increase of indoor pollution levels. Total volatile organic compounds (TVOC) levels were significantly (p<0.05) different between indoor (230.7±1.7 µg/m3) and outdoor (137.8±1.9 µg/m3) environments, with an I/O ratio of 1.67. The indoor HCHO level (20.1±1.6 µg/m3) was significantly (p<0.05) higher than the outdoor level (8.1±1.9 µg/m3), with an I/O ratio of 2.48. Indoor VOCs and HCHO levels in the bedrooms were significantly (p<0.05) higher than those in the living and dining rooms. Furthermore, indoor levels of VOCs and HCHO at ECCs were significantly (p<0.05) different depending on environmental factors such as the use of carpet, paint, and wooden furniture. In multiple regression analysis, indoor VOCs and HCHO levels at ECCs were significantly (p<0.05) correlated with two micro-environmental factors: the use of carpet and paint. This study confirmed that indoor VOCs and HCHO levels were significantly higher than those in outdoor environments. These air pollutants were mainly emitted from indoor sources, such as carpet, paint, and construction materials at the ECCs in Korea.

E-cigarettes can emit formaldehyde at high levels under conditions that have been reported to be non-averse to users.

E-cigarette aerosol emission studies typically focus on benchmarking toxicant levels versus those of cigarettes. However, such studies do not fully account for the distinct chemical makeup of e-liquids and their unique properties. These approaches often conclude that there are fewer and lower levels of toxins produced by e-cigarettes than by cigarettes. In 2015, we reported the discovery of new hemiacetals derived from the reaction of formaldehyde and the e-liquid solvents. The main finding was that they constituted a significant proportion of potentially undetected formaldehyde. Moreover, unlike gaseous formaldehyde, the hemiacetals reside in the aerosol particulate phase, and thus are capable of delivering formaldehyde more deeply into the lungs. However, the findings were criticized by those claiming that some of the results were obtained under conditions that are averse to vapers. A "reinvestigation" of our study was recently published addressing this latter issue. However, this reinvestigation ignored major details, including no mention of the formaldehyde hemiacetals. Herein, we isolated both gaseous formaldehyde and formaldehyde hemiacetals at an intermediate power level claimed, in the "reinvestigation", to be relevant to "non-averse," "normal" usage. The results were that both gaseous formaldehyde and formaldehyde from hemiacetals were produced at levels above OSHA workplace limits.

Removal of organic phosphorus and formaldehyde in glyphosate wastewater by CWO and the lime-catalyzed formose reaction.

Glyphosate (PMG) wastewater with 40-600 mg/L organic phosphorus (OP) and 1-4% CH2O was treated by catalytic wet oxidation (CWO) and the lime-catalyzed formose reaction to remove total phosphorus (TP) and improve biodegradability. Activated carbons (ACs) modified by H2O2 oxidation and thermal treatment with melamine were used as CWO catalysts and characterized by N2 adsorption/desorption and XPS. The CWO experiments were performed in an autoclave reactor at 110-130 °C and 1.0 MPa. The modified AC showed higher catalytic activity than the parent AC due to the introduction of nitrogen-containing functional groups, exhibited over 90% OP removal for various real PMG wastewaters, and had good stability for 20 consecutive CWO runs. The CWO effluents were further treated by lime at 80 °C to remove TP and CH2O. The treated effluents, containing 0.5-12 mg/L TP and 20-60 mg/L CH2O, showed good biodegradability with a BOD5/COD ratio of 0.31-0.41. The combination of CWO and lime is an effective treatment method prior to biological treatment for solving the problems of OP and CH2O encountered by the glyphosate industry.

A novel microbial fuel cell sensor with biocathode sensing element.

The traditional microbial fuel cell (MFC) sensor with bioanode as sensing element delivers limited sensitivity to toxicity monitoring, restricted application to only anaerobic and organic rich water body, and increased potential fault warning to the combined shock of organic matter/toxicity. In this study, the biocathode for oxygen reduction reaction was employed for the first time as the sensing element in MFC sensor for toxicity monitoring. The results shown that the sensitivity of MFC sensor with biocathode sensing element (7.4±2.0 to 67.5±4.0mA%-1cm-2) was much greater than that showed by bioanode sensing element (3.4±1.5 to 5.5±0.7mA%-1cm-2). The biocathode sensing element achieved the lowest detection limit reported to date using MFC sensor for formaldehyde detection (0.0005%), while the bioanode was more applicable for higher concentration (>0.0025%). There was a quicker response of biocathode sensing element with the increase of conductivity and dissolved oxygen (DO). The biocathode sensing element made the MFC sensor directly applied to clean water body monitoring, e.g., drinking water and reclaimed water, without the amending of background organic matter, and it also decreased the warning failure when challenged by a combined shock of organic matter/toxicity.

The use of charcoal in modified cigarette filters for mainstream smoke carbonyl reduction.

Carbonyls are harmful and potentially harmful constituents (HPHCs) in mainstream cigarette smoke (MSS). Carbonyls, including formaldehyde and acrolein, are carcinogenic or mutagenic in a dose-dependent manner. Past studies demonstrate significant reduction of HPHCs by charcoal filtration. However, limits of charcoal filtration and cigarette design have not yet been investigated in a systematic manner. Objective data is needed concerning the feasibility of HPHC reduction in combustible filtered cigarettes. This systematic study evaluates the effect of charcoal filtration on carbonyl reduction in MSS. We modified filters of ten popular cigarette products with predetermined quantities (100-400 mg) of charcoal in a plug-space-plug configuration. MSS carbonyls, as well as total particulate matter, tar, nicotine, carbon monoxide (TNCO), and draw resistance were quantified. Significant carbonyl reductions were observed across all cigarette products as charcoal loading increased. At the highest charcoal loadings, carbonyls were reduced by nearly 99%. Tar and nicotine decreased modestly (<20%) compared to reductions in carbonyls. Increased draw resistance was significant at only the highest charcoal loadings. This work addresses information gaps in the science base that can inform the evaluation of charcoal filtration as an available technological adaptation to cigarette design which reduces levels of carbonyls in MSS.

A Novel Optimization Technique to Improve Gas Recognition by Electronic Noses Based on the Enhanced Krill Herd Algorithm.

An electronic nose (E-nose) is an intelligent system that we will use in this paper to distinguish three indoor pollutant gases (benzene (C6H6), toluene (C7H8), formaldehyde (CH2O)) and carbon monoxide (CO). The algorithm is a key part of an E-nose system mainly composed of data processing and pattern recognition. In this paper, we employ support vector machine (SVM) to distinguish indoor pollutant gases and two of its parameters need to be optimized, so in order to improve the performance of SVM, in other words, to get a higher gas recognition rate, an effective enhanced krill herd algorithm (EKH) based on a novel decision weighting factor computing method is proposed to optimize the two SVM parameters. Krill herd (KH) is an effective method in practice, however, on occasion, it cannot avoid the influence of some local best solutions so it cannot always find the global optimization value. In addition its search ability relies fully on randomness, so it cannot always converge rapidly. To address these issues we propose an enhanced KH (EKH) to improve the global searching and convergence speed performance of KH. To obtain a more accurate model of the krill behavior, an updated crossover operator is added to the approach. We can guarantee the krill group are diversiform at the early stage of iterations, and have a good performance in local searching ability at the later stage of iterations. The recognition results of EKH are compared with those of other optimization algorithms (including KH, chaotic KH (CKH), quantum-behaved particle swarm optimization (QPSO), particle swarm optimization (PSO) and genetic algorithm (GA)), and we can find that EKH is better than the other considered methods. The research results verify that EKH not only significantly improves the performance of our E-nose system, but also provides a good beginning and theoretical basis for further study about other improved krill algorithms' applications in all E-nose application areas.

Effect of endophytic Bacillus cereus ERBP inoculation into non-native host: Potentials and challenges for airborne formaldehyde removal.

Phytoremediation could be a cost-effective, environmentally friendly approach for the treatment of indoor air. However, some drawbacks still dispute the expediency of phytotechnology. Our objectives were to investigate the competency of plant growth-promoting (PGP) endophytic Bacillus cereus ERBP (endophyte root blue pea), isolated from the root of Clitoria ternatea, to colonize and stabilize within Zamioculcas zamiifolia and Euphorbia milii as non-native hosts without causing any disease or stress symptoms. Moreover, the impact of B. cereus ERBP on the natural shoot endophytic community and for the airborne formaldehyde removal capability of non-native hosts was assessed. Non-native Z. zamiifolia was effectively inoculated with B. cereus ERBP through soil as the most efficient method of endophyte inoculation. Denaturing gradient gel electrophoresis profiling of the shoot endophytic community verified the colonization and stability of B. cereus ERBP within its non-native host during a 20-d fumigation period without interfering with the natural shoot endophytic diversity of Z. zamiifolia. B. cereus ERBP conferred full protection to its non-native host against formaldehyde phytotoxicity and enhanced airborne formaldehyde removal of Z. zamiifolia whereas non-inoculated plants suffered from formaldehyde phytotoxicity because their natural shoot endophytic community was detrimentally affected by formaldehyde. In contrast, B. cereus ERBP inoculation into non-native E. milii deteriorated airborne formaldehyde removal of the non-native host (compared to a non-inoculated one) as B. cereus ERBP interfered with natural shoot endophytic community of E. milii, which caused stress symptoms and stimulated ethylene biosynthesis. Non-native host inoculation with PGP B. cereus ERBP could bear potentials and challenges for airborne formaldehyde removal.

A Novel Semi-Supervised Electronic Nose Learning Technique: M-Training.

When an electronic nose (E-nose) is used to distinguish different kinds of gases, the label information of the target gas could be lost due to some fault of the operators or some other reason, although this is not expected. Another fact is that the cost of getting the labeled samples is usually higher than for unlabeled ones. In most cases, the classification accuracy of an E-nose trained using labeled samples is higher than that of the E-nose trained by unlabeled ones, so gases without label information should not be used to train an E-nose, however, this wastes resources and can even delay the progress of research. In this work a novel multi-class semi-supervised learning technique called M-training is proposed to train E-noses with both labeled and unlabeled samples. We employ M-training to train the E-nose which is used to distinguish three indoor pollutant gases (benzene, toluene and formaldehyde). Data processing results prove that the classification accuracy of E-nose trained by semi-supervised techniques (tri-training and M-training) is higher than that of an E-nose trained only with labeled samples, and the performance of M-training is better than that of tri-training because more base classifiers can be employed by M-training.

Three-Dimensional Ordered Mesoporous MnO2-Supported Ag Nanoparticles for Catalytic Removal of Formaldehyde.

Three-dimensional (3D) ordered mesoporous Ag/MnO2 catalyst was prepared by impregnation method based on 3D-MnO2 and used for catalytic oxidation of HCHO. Ag nanoparticles are uniformly distributed on the polycrystalline wall of 3D-MnO2. The addition of Ag does not change the 3D ordered mesoporous structure of the Ag/MnO2, but does reduce the pore size and surface area. Ag nanoparticles provide sufficient active site for the oxidation reaction of HCHO, and Ag (111) crystal facets in the Ag/MnO2 are active faces. The 8.9% Ag/MnO2 catalyst shows a higher normalized rate (10.1 nmol·s(-1)·m(-2) at 110 °C) and TOF (0.007 s(-1) at 110 °C) under 1300 ppm of HCHO and 150 000 h(-1) of GHSV, and its apparent activation energy of the reaction is the lowest (39.1 kJ/mol). More Ag active sites, higher low-temperature reducibility, more abundant surface lattice oxygen species, oxygen vacancies, and lattice defects generated from interaction Ag with MnO2 are responsible for the excellent catalytic performance of HCHO oxidation on the 8.9% Ag/MnO2 catalyst. The 8.9% Ag/MnO2 catalyst remained highly active and stable under space velocity increasing from 60 000 to 150 000 h(-1), under initial HCHO concentration increasing from 500 to 1300 ppm, and under the presence of humidity, respectively.

A portable system for on-site quantification of formaldehyde in air based on G-quadruplex halves coupled with A smartphone reader.

A portable colorimetric determination system based on G-quadruplex DNAzyme integrated with a smartphone was developed to quantitatively detect formaldehyde (FA). The method is based on the oxidation of FA by H2O2, which prevents the 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS)­H2O2 reaction catalyzed by G-quadruplex halves. With the addition of FA, the amount of the blue-green-colored free-radical cation (ABTS+) was reduced. The concentration of FA can be determined by monitoring this competitive reaction with a UV-vis spectrometer. Response surface methodology (RSM) and Box-Behnken design (BBD) were applied for optimization of the colorimetric assay. A smartphone-based colorimetric reader was also developed, which could display FA responses and report the concentration in real-time. The system could detect FA as low as 0.01 µM with a linear range of 1-600 µM. Taking advantages of smartphone and DNAzyme, the assay provides great potential for its practical application as a home testing or on-site analysis with high sensitivity and selectivity.

A Short Review on Photocatalytic Degradation of Formaldehyde.

Nowadays, it is a great challenge to eliminate toxic and harmful organic pollutants from air and water. This paper reviews the role of TiO2 as a photocatalyst, light source and photoreactor in the particular case of removal of formaldehyde using the photocatalytic reaction by titanium dioxide (TiO2) in aqueous and gaseous systems. The reaction mechanisms of the photocatalytic oxidation of gaseous formaldehyde are given. We also present a detailed review of published articles on photocatalytic degradation of formaldehyde by modified titanium dioxide doped with foreign species such as metal and non-metal components. We point out the most prospective developments of the photocatalyst compositions for the future potential commercial applications.

Formaldehyde scavengers function as novel antigen retrieval agents.

Antigen retrieval agents improve the detection of formaldehyde-fixed proteins, but how they work is not well understood. We demonstrate that formaldehyde scavenging represents a key characteristic associated with effective antigen retrieval; under controlled temperature and pH conditions, scavenging improves the typical antigen retrieval process through reversal of formaldehyde-protein adduct formation. This approach provides a rational framework for the identification and development of more effective antigen retrieval agents.

Exploitation of pulsed flows for on-line dispersive liquid-liquid microextraction: Spectrophotometric determination of formaldehyde in milk.

Formaldehyde is often added to foods as a preservative, but it is highly toxic to humans, having been identified as a carcinogenic substance. It has also been used for the adulteration of milk in order to diminish the bacteria count and increase the shelf life of the product. Herein, we present a green dispersive liquid-liquid microextraction procedure in a flow-batch system for the determination of formaldehyde in milk. Pulsed flows were exploited for the first time to improve the dispersion of the extractant in the aqueous phase. The Hantzsch reaction was used for the derivatization of formaldehyde and the product was extracted with the ionic liquid (IL) trihexyltetradecylphosphonium chloride with methanol as the disperser. The flow-batch chamber was made of stainless steel with the facility for resistive heating to speed up the derivatization reaction. Spectrophotometric measurements were directly carried out in the organic phase using an optical fiber spectrophotometer. The limit of detection and coefficient of variation were 100 µg L(-1) and 3.1% (n=10), respectively, with a linear response from 0.5 to 5.0 mg L(-1), described by the equation A=0.088+0.116CF (mg L(-1)) in which A is absorbance and CF is formaldehyde concentration in mg L(-1). The estimated recoveries of formaldehyde from spiked milk samples ranged from 91% to 106% and the slopes of the analytical curves obtained with reference solutions in water or milk were in agreement, thus indicating the absence of matrix effects. Accuracy was demonstrated by the agreement of the results with those achieved by the reference fluorimetric procedure at the 95% confidence level. The proposed procedure allows for 10 extractions per hour, with minimized reagent consumption (120 µL of IL and 3.5 µL acetylacetone) and generation of only 6.7 mL waste per determination, which contribute to the eco-friendliness of the procedure.

Highly active mesoporous ferrihydrite supported pt catalyst for formaldehyde removal at room temperature.

Ferrihydrite (Fh) supported Pt (Pt/Fh) catalyst was first prepared by combining microemulsion and NaBH4 reduction methods and investigated for room-temperature removal of formaldehyde (HCHO). It was found that the order of addition of Pt precursor and ferrihydrite in the preparation process has an important effect on the microstructure and performance of the catalyst. Pt/Fh was shown to be an efficient catalyst for complete oxidation of HCHO at room temperature, featuring higher activity than magnetite supported Pt (Pt/Fe3O4). Pt/Fh and Pt/Fe3O4 exhibited much higher catalytic activity than Pt supported over calcined Fh and TiO2. The abundance of surface hydroxyls, high Pt dispersion and excellent adsorption performance of Fh are responsible for superior catalytic activity and stability of the Pt/Fh catalyst. This work provides some indications into the design and fabrication of the cost-effective and environmentally benign catalysts with excellent adsorption and catalytic oxidation performances for HCHO removal at room temperature.