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The activity of supported noble metal (e.g., palladium (Pd)) catalysts is often governed by the combined effects of multiple factors (e.g., electronic and geometric properties of the support, surface chemistry of metal nanoparticles (NPs), and metal-support interactions). Pd/titanium dioxide (TiO 2 ) catalyst has been developed as a highly efficient photocatalytic degradation (PCD) system against gaseous toluene based on high-temperature pretreatment (300 and 450 °C) in a mixed stream of hydrogen (H 2 ) and (N 2 ). The interaction of Pd NPs with TiO 2 synergistically improves the PCD efficiency of toluene through the efficient adsorption and activation of toluene as well as molecular oxygen (O 2 ) and water (H 2 O) for the facile generation of reactive oxygen species (ROS (e.g., superoxide anion (•O 2 - ) and hydroxyl (•OH) radicals)). The PCD efficiency of the prepared sample against 5 ppm toluene (at 20% relative humidity (RH)) is 79.6% with the values of maximum reaction rate, quantum yield, space-time yield, and clean air delivery rate as 9.9 μmol g -1 h -1 , 1.68E-03 molecules photon -1 , 1.68E-02 molecules photon -1 g -1 , and 4.8 L h -1 , respectively. Based on this research, the PCD mechanism of gaseous toluene has been explored along with the dynamic behavior of O 2 and H 2 O for ROS generation and their relative contribution to the PCD of toluene. As such, this research offers a perspective for designing advanced photocatalysts through surface defect engineering., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

A prototype air purifier (AP) module has been constructed using bismuth-doped titanium dioxide (Bi x -P25: x(%) as Bi/Ti molar ratios of 1.1, 2.1, 3.3, 5.3, and 8.7). The reactive adsorption property of Bi x -P25 materials is evaluated against H 2 S gas at a recirculation rate of 160 L min -1 in a 17 L closed chamber. The AP (Bi 5.3 -P25) exhibits superior performance against 10 ppm H 2 S in dry air under dark conditions (i.e., without light irradiation), with a removal efficiency (X H2S )= 99% in 5 mins, reaction kinetic rate (r (at X = 10%))= 7.3 mmol h -1 g -1 , and partition coefficient= 0.18 mol kg -1 Pa -1 . As such, its superiority is evident over the reference AP (P25) filter with X H2S < 10%. The clean air delivery rate (CADR) of AP (Bi 5.3 -P25) increases noticeably from 9.9 to 17.8 L min -1 with increasing relative humidity (RH) from 0 to 80%, respectively. In contrast, the CADR decreases from 9.9 to 5.8 L min -1 as the H 2 S increases from 10 to 20 ppm. According to density functional theory (DFT), the presence of H 2 O vapor enhances the hydroxylation of Bi x -P25 surface to promote H 2 S mineralization through the formation of TiS 3 (i.e., thermodynamic reaction of S atom with the catalytic surface). Complete removal of H 2 S on the Bi 5.3 -P25 surface is also confirmed consistently through gas chromatography-mass spectrometry (GC-MS), in-situ diffuse reflection infrared spectroscopy (in-situ DRIFTS), and elemental analysis (EA). This work represents the first utilization of Bi x -P25 materials fabricated on an AP platform toward the desulfurization of H 2 S at room temperature (RT). The practical utility of Bi x -P25 is overall validated by its eminent role in reactive adsorption and catalytic oxidation (RACO) of H 2 S from the air., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The adsorption potential of activated carbon (AC) derived from macadamia nut shells (product code of Procarb-900: namely, AC-P) has been investigated using gaseous toluene as the target pollutant. The powder AC-P with high-microporosity (96%) and oxygen content (5.62%) exhibited very high adsorption capacity (214 mg·g -1 ) and partition coefficient (PC: 25 mol·kg -1 ·Pa -1 ) against 100 ppm (10 Pa) toluene at 99% breakthrough levels (1 atm dry N 2 ). The factors governing toluene adsorption were explored with respect to the key variables such as surface functional groups, pore size distribution, sorbent bed mass (50, 100, and 150 mg), and particle size (i.e., 0.212-0.6 mm (powder AC: PAC)) vs. 0.6-2.36 mm (granular AC: GAC)). Accordingly, the adsorption process was physical, mainly due to the non-polar interactions (i.e., π-π interactions) between the adsorbent and adsorbate molecules. The high affinity of AC-P at low breakthrough levels was obtained through a combination of smaller particle size (PAC) and larger adsorbent mass (i.e., 150 mg) with the appearance of a very pronounced retrograde phenomenon (e.g., at < 1% breakthrough level). As such, toluene adsorption appeared to be affected more sensitively by particle size and adsorbent mass (especially at low breakthrough levels) than by high microporosity. Most importantly, the oxygen content of AC emerges as one of the key factors governing the maximum capacity, as the changes in pore volume are not crucial to explain the observed adsorption patterns of toluene., Competing Interests: Declaration of competing interest Younes Ahmadi reports financial support was provided by National Research Foundation of Korea. Ki-Hyun Kim reports financial support was provided by Korea Ministry of Science and ICT., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The utility of nanomaterial adsorbents is often limited by their physical features, especially fine particle size. For example, a large bed-pressure drop is accompnied inevitably, if fine-particle sorbents are used in a packed bed system. To learn more about the effect of adsorbent morphology on uptake performance, we examined the adsorption efficiency of metal-organic framework 199 (MOF-199) in the pristine (fine powder) form and after its binding on to glass beads as an inert support. Most importantly, we investigated the effect of such coatings on adsorption of gaseous benzene (0.1-10 Pa) in a dry N 2 stream, particularly as a function of the amount of MOF-199 loaded on glass beads (MOF-199@GB) (i.e., 0,% 1%, 3%, 10%, and 20%, w/w) at near-ambient conditions (298 K and 1 atm). A 1% MOF-199 load gave optimal performance against a 0.1 Pa benzene vapor stream in 1 atm of N 2 , with a two-to five-fold improvement (e.g., in terms of 10% breakthrough volume [BTV] (46 L atm [g.MOF-199) -1 ], partition coefficient at 100% BTV (3 mol [kg.MOF-199] -1  Pa -1 ), and adsorption capacity at 100% BTV (20 mg [g.MOF-199] - 1 (areal capacity: 8.8 × 10 -7  mol m -2 ) compared with those of 3%, 10%, and 20% loading. The relative performance of benzene adsorption was closely associated with the content of MOF-199@GB (e.g., 1% > 3% > 10% > 20%) and the surface availability (m 2 [g.MOF-199] -1 ) such as 291 > 221 > 198 > 181, respectively. This study offers new insights into the strategies needed to expand the utility of finely powdered MOFs in various environmental applications., (Copyright © 2021. Published by Elsevier Inc.)

The utility of metal-organic frameworks (MOFs) such as the CUK family (CUK - Cambridge University-KRICT) has been explored intensively for adsorption/separation of airborne volatile organic compounds (VOCs). In this article, three M-CUK analogs (M = Mg, Co, or Ni) were synthesized hydrothermally under similar conditions to assess the effects of their isostructural properties and metal centers on adsorption of benzene vapor (0.05-1 Pa). A list of performance metrics (e.g., breakthrough volume (BTV) and partition coefficient (PC)) were used to assess the role of the metal type (in M-CUK-1s) in the adsorption of VOCs. Specifically, Co-CUK-1 (average pore size of 8.98 nm) showed 2-3 times greater performance (e.g., in terms of 10% BTV (2012 L atm g -1 ) and PC (6 mol kg -1 Pa -1 )) over other analogs when exposed up to 0.05 Pa benzene vapor. The superiority of mesoporous Co-CUK-1 (e.g., enhanced adsorption diffusion mechanism through favorable metal-π and π- π interactions) can be attributed to the presence of cobalt metal centers (e.g., in reference to Mg- or Ni-CUK-1)., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Considerable efforts have been undertaken in the domain of air quality management for the removal of hazardous volatile organic compounds, particularly carbonyl compounds (CCs). In this study, the competitive sorptive removal of six CCs (namely, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde) was assessed using selected metal-organic frameworks (MOFs: MOF-5, MOF-199, UiO-66, and UiO-66-NH 2 ) and inexpensive commercial activated carbon as a reference sorbent. The sorption experiments were conducted using a mixture of the six CCs (formaldehyde and acetaldehyde at ∼1 Pa and propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde at ∼0.2 Pa) together with 15 Pa water and 2.6 Pa methanol in 1 bar nitrogen. For all of the carbonyl compounds other than formaldehyde, MOF-199 showed the best 10% breakthrough performance ranging from 34 L g -1 and 0.14 mol kg -1 Pa -1 for acetaldehyde to 1870 L g -1 and 7.6 mol kg -1 Pa -1 for isovaleraldehyde. Among all the sorbents tested, UiO-66-NH 2 exhibited the best 10% breakthrough performance metrics towards the lightest formaldehyde which remains to be one of the most difficult targets for sorptive removal (breakthrough volume: 285 L g -1 and partition coefficient: 1.1 mol kg -1 Pa -1 ). Theoretical density functional theory (DFT)-based computations were also conducted to provide better insights into the adsorbate-adsorbent interactions. Accordingly, the magnitude of adsorption energy increased with an increase in the CC molar mass due to an enhancement in the synergetic interaction between C[double bond, length as m-dash]O groups (in adsorbate molecules) and the MOF active centers (open metallic centers and/or NH 2 functionality) as the adsorbent. Such interactions were observed to result in strong distortion of MOF structures. In contrast, weak van der Waals attraction between the hydrocarbon "tail" of CC molecules and MOF linkers were seen to play a stabilizing role for the sorbent structure. The presence of the NH 2 group in the MOF structure was suspected to play a key role in capturing lighter CCs, while such an effect was less prominent for heavier CCs. Overall, the results of this study provided a basis for the establishment of an effective strategy to enhance the sorption capacity of MOFs against diverse carbonyl species.

Various materials have been investigated for the adsorptive removal of volatile organic compounds (VOCs, such as benzene). However, most materials proposed for the adsorptive removal of gaseous benzene (and other VOCs) perform relatively poorly (e.g., an impractically low-service 10% breakthrough volume [BTV10] at < 100 ppm). The adsorbent uptake rate (mg g -1 min -1 ) can also be assessed as a function of the gas-stream flow rate (or space velocity). The main aim of this study is to explore the effect of two different gas-stream supply modes - stopped flow (at a fixed stream flow rate of 330 mL atm min -1 ) vs. continuous flow (a variable-stream flow rate of 100, 200, or 330 mL atm min -1 ) on the adsorption metrics of gaseous benzene on 5 mg of two types of - II covalent organic polymers (COPs: CBAP-1 [DETA], CD; or CBAP-1 [EDA], CE). The sorbent tube outlet stream was sampled by two respective sampling methods (i.e., a large-volume injector [LVI] for stopped flow vs. syringe injection [SI] for continuous flow) for sample quantitation by gas chromatography flame-ionization detection (GC-FID). The observed BTV10 values in the two sampling modes were similar when tested using 10 ppm benzene, irrespective of sorbents: 56/60 (CD) vs. 620/624 L atm g -1 (CE). BTV10 values increased systematically with decreasing stream-flow rates to reflect the importance of space velocity in adsorptive removal of benzene. The overall assessment of adsorption performance between stopped flow (LVI) and continuous flow (SI) revealed that the performance of the adsorbent is independent of flow mode (e.g., when performance was compared at flow rate of 330 mL min -1 )., Competing Interests: Declaration of competing interest There is no competing interests., (Copyright © 2019 Elsevier Inc. All rights reserved.)

In this research, the competitive adsorption characteristics between aromatic hydrocarbons were investigated. It is well-known that an industrial effluent may contain a mixture of pollutants. The composition of effluents is usually highly variable in nature to depend upon the feedstock. Hence, one of the pollutants that is present in larger amounts may have the potential to dominate the sorption processes. Although many studies have investigated the competitive adsorption of volatile organic compounds (VOCs) onto activated carbon (AC) in detail, little is known about how the overall process is influenced when a fresh incoming VOC molecule encounters a sorbent bed pre-loaded with other VOCs. Consequently, the objective of the present study was to investigate the stability of pre-adsorbed VOC molecules in the presence of other potentially competitive VOCs in the influent stream. In this regard, the sorbent bed of AC was first preloaded with benzene (50 ppm (0.16 mg L -1 )) and subsequently challenged by either high purity nitrogen or a stream of xylene (at 10, 50, or 100 ppm (0.043, 0.22, or 0.43 mg L -1 )). The desorption rate of preloaded benzene and uptake rate of challenger xylene were assessed simultaneously. The maximum desorption rates of benzene (R b ) against two challenge scenarios (e.g., 100 ppm (0.43 mg L -1 ) xylene and pure N 2 ) were very different from each other, i.e., 663 vs. 257 g kg -1 h -1 , and their final benzene recoveries were 84% and 42%, respectively. The initially high desorption rate for the former quickly decreased with decreasing benzene residual capacity (C, mg g -1 ). Interestingly, the adsorption capacity of xylene increased considerably after the preloading of benzene (relative to no preloading). As such, 10% breakthrough volumes (BTV10) of 100, 50, and 10 ppm (0.43, 0.22, and 0.043 mg L -1 ) xylene challenge scenarios increased significantly from 100 to 186, 43.4 to 694, and 600 to 1000 L atm g -1 , respectively. The prevalent mechanisms were analyzed using density functional theory (DFT)-based modelling approaches. The results demonstrated effective replacement of pre-adsorbed molecules with weaker affinity (e.g., benzene) when challenged by molecules with stronger affinity (e.g., xylene) toward the sorbent; this was accompanied by noticeable synergistic enhancement in the adsorption capacity of the latter., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The potential use of activated carbon (AC) as an inexpensive and effective alternative sorbent material in thermal desorption is presented and validated for the analysis of aromatic volatile organic compounds (VOCs) such as benzene, toluene, m-xylene, and styrene (BTXS) in air. The optimum desorption conditions of an AC sampling tube (2 mg AC bed) were determined and compared with a commercial three-bed (Carbopack; C + B + X) tube sampler as a reference. The AC sampler exhibited good linearity (R 2  > 0.99) and reproducibility (RSE of 2.38 ± 0.21%) for BTXS analysis. The AC tube sampler showed good storability (up to 3 d) and excellent recyclability (up to 50 cycles). An analysis of BTXS in ambient air showed excellent agreement between AC and CBX (bias < 5%). The 1% breakthrough volume values for 2 mg AC, when tested at 100 ppb of benzene as a sole component or in a BTXS mixture, were 10,000 or 5000 L g -1 , respectively. The results of this study support the performance of AC as a suitable medium for sampling VOCs as reliable as high-cost commercial sorbent products., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The adsorption dynamics of common solid sorbents against various pollutant species are yet poorly understood with respect to the retrograde phenomenon in which the relationship between breakthrough vs. pulled volume is characterized by an early unusual trend (initial increase followed by a decrease to a minimum) and by a normal trend of finally increasing to 100% (or equilibrium). If such trend is expressed in terms of the partition coefficient (PC), a reversed trend of adsorption processes becomes more evident. Retrograde has been previously observed in the initial breakthrough (<10%) isotherms in continuous flow gas-phase adsorption processes. However, retrograde has been neglected/overlooked and not discussed at all in the main stream literature even when it is explicitly observed from isotherm datasets. To properly describe the various aspects of such process, a stop-flow technique was developed to measure the adsorption isotherm of a model volatile organic compound (i.e., toluene in this study) onto a commercial low-cost sorbent (activated carbon: AC). Accordingly, a 10% breakthrough volume of 762 L atm g -1 (corresponding adsorption capacity of 142 mg g -1 ) was determined (at an inlet stream 5 Pa of toluene in 1 atm of N 2 and 5 mg of AC). This automated method was effective to generate a detailed breakthrough profile at high stream-flow rates (or high space velocities) to specifically detect the retrograde phenomenon at the breakthrough onset. This study offers a practical approach towards establishing an in-depth monitoring protocol for the rare retrograde phenomenon., (Copyright © 2019. Published by Elsevier Inc.)

Covalent-organic polymers (COPs) are recognized for their great potential for treating diverse pollutants via adsorption. In this study, the sorption behavior of benzene and toluene was investigated both individually and in a binary mixture against two types of COPs possessing different -NH 2 functionalities. Namely, the potential of COPs was tested against benzene and toluene in a low inlet partial pressure range (0.5-20 Pa) using carbonyl-incorporated aromatic polymer (CBAP)-1-based diethylenediamine (EDA) [CD] and ethylenetriamine (DETA) [CE]. The maximum adsorption capacity and breakthrough values of both COPs showed dynamic changes with increases in the partial pressures of benzene and toluene. The maximum adsorption capacities (A max ) of benzene (as the sole component in N 2 under atmospheric conditions) on CD and CE were in the range of 24-36 and 33-75 mg g -1 , respectively. In contrast, with benzene and toluene in a binary mixture, the benzene A max decreased more than two-fold (range of 2.7-15 and 6-39 mg g -1 , respectively) due to competition with toluene for sorption sites. In contrast, the toluene A max values remained consistent, reflecting its competitive dominance over benzene. The adsorption behavior of the targeted compounds (i.e., benzene and toluene) was explained by fitting the adsorption data by diverse isotherm models (e.g., Langmuir, Freundlich, Elovich, and Dubinin-Radushkevich). The current research would be helpful for acquiring a better understanding of the factors affecting competitive adsorption between different VOCs in relation to a given sorbent and across varying partial pressures., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The adsorption characteristics of four aromatic hydrocarbons (i.e., benzene, toluene, xylene, and styrene) onto ground-activated carbon were investigated both independently and as a mixture of the four at <10 Pa partial pressures (e.g., 0-100 ppm concentration range). The maximum sorption capacities for benzene, toluene, styrene, and xylene were measured both as a sole component and as a mixture (at 10 Pa). In the former, the values were approximately 123, 184, 272, and 238 mg g -1 , respectively. In contrast, the latter values were 5, 52, 222, and 248 mg g -1 respectively, showing dramatic reduction in lighter compounds (below C7) relative to heavier ones (above C8). The mechanistic detail of sorption has been explained in terms of Henry's law and Langmuir, Freundlich, Dubinin-Radushkevich, and Elovich isotherm models. The linearized Langmuir adsorption isotherm analysis showed three sorption pressure regions: low (<1 Pa, retrograde), intermediate (1-4 Pa), and high (4-10 Pa). As such, the outcome of this study offers a unique opportunity to acquire detailed information on the dramatic and dynamic effects of the sorptive interaction between competing sorbates, along with a common sorption process between sorbent and sorbate at 298 K., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The effective removal technique is necessary for the real world treatment of a hazardous pollutant (e.g., gaseous benzene). In an effort to develop such technique, the adsorption efficiency of benzene in a nitrogen stream (5 Pa (50 ppm) at 50 mL atm min -1 flow rate and 298 K) was assessed against 10 different metal oxide/GO composite materials (i.e., 1: graphene oxide Co (GO-Co (OH) 2 ), 2: graphene oxide Cu (GO-Cu(OH) 2 ), 3: graphene oxide Mn (GO-MnO), 4: graphene oxide Ni (GO-Ni(OH) 2 ), 5: graphene oxide Sn (GO-SnO 2 ), 6: reduced graphene oxide Co (rGO-Co(OH) 2 ), 7: reduced graphene oxide Cu (rGO-Cu(OH) 2 ), 8: reduced graphene oxide Mn (rGO-MnO), 9: reduced graphene oxide Ni (rGO-Ni(OH) 2 ), and 10: reduced graphene oxide Sn (rGO-SnO 2 )) in reference to their pristine forms of graphene oxide (GO) and reduced graphene oxide (rGO). The highest adsorption capacities (at 100% breakthrough) were observed as ~23 mg g -1 for both GO-Ni(OH) 2 and rGO-SnO 2 , followed by GO (~19.1 mg g -1 ) and GO-Co(OH) 2 (~18.8 mg g -1 ). Therefore, the GO-Ni(OH) 2 and rGO-SnO 2 composites exhibited considerably high capacities to treat streams containing >5 Pa of benzene. However, the lowest adsorption capacity was found for GO-MnO (0.05 mg g -1 ). Alternately, if expressed in terms of the 10% breakthrough volume (BTV), the five aforementioned materials showed values of 0.50, 0.46, 0.40, 0.44, and 0.39 L g -1 , respectively. The experimental data of target sorbents were fitted to linearized Langmuir, Freundlich, Elovich, and Dubinin-Radushkevich isotherm models. Accordingly, the non-linear Langmuir isotherm model revealed the presence of two or more distinct sorption profiles for several of the tested sorbents. Most of the sorbents showed type-III isotherm profiles where the sorption capacity proportional to the loaded volume., (Copyright © 2019 Elsevier Inc. All rights reserved.)

To effectively remove gaseous pollutants from air using sorbents, a thorough knowledge of the actual sorption performance is needed at ambient conditions rather than at unrealistically high-pressure conditions, as is commonly presented in the literature. To this end, the sorbent capacities of gaseous benzene were evaluated at a constant sorbent bed inlet pressure (50 ppm or ~5 Pa) in 1 atm of N 2 , room temperature (298 K), a fixed flow rate (50 mL min -1 ), and equal outlet sampling intervals (5 min). The benzene adsorption patterns were investigated against six sorbent types in a total of 17 different forms: 1- zeolite in five forms: beads (ZB), ground to 212 µm (ZG212), beads ground to 300 µm (ZG300), coarsely ground/washed zeolite (ZWc), and coarsely ground/washed/thermally treated zeolite (ZTc), 2- activated carbon in two forms: 212 µm (ACd212) and granular (ACdg), 3- Carbopack-X (CX), 4- Tenax TA (TA), 5- used black tea leaves of 150 or 300 µm in three forms: dry (TD150/TD300), wet (TW150/TW300), and wet dust (TWd), and 6- used ground coffee in either dry (CD) or wet forms (CW). Accordingly, the largest adsorption capacities at 5 Pa (e.g., >10 mg g -1 ) were observed for ACd212 (79.1) and ACdg (73.6). Moderate values (e.g., 5 < < 10 mg g -1 ) were obtained for ZG212 (7.98), CX (6.79), ZG300 (5.70), and ZB (5.58), while the remainder were far lower at < 5 mg g -1 (e.g., tea leaves, ground coffee, TA, ZWc, and ZTc). The experimental benzene capacities of the tested sorbents were further assessed by the Langmuir, Henry's law, Freundlich, Dubinin-Radushkevich, and Elovich isotherm models. The linearized Langmuir adsorption isotherms of ACd212, ACdg, and CX showed the presence of more than one adsorption site (i.e., retrograde at the lowest pressures and two others at higher pressures). However, TA, zeolite, tea leaves, and ground coffee exhibited a type-V isotherm, wherein the sorption capacity continued to increase with loaded volume (i.e., multilayer adsorption). Thus, ACd212 has the best figure-of-merit based on a high 10% breakthrough volume (BTV) and low cost for real-world applications., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The effect of flavors on carbonyl compound (CC) emission factors (EF) from electronic cigarettes (ECs) vaping was investigated at the default vaping (voltage) setting in all experiments using a total of 21 lab-made e-liquid samples (five different types of retail flavorant bases: beverage/dessert/fruit/mint/tobacco). Each flavorant base was added to a separate unflavored base composed of a 1:1 mixture of propylene glycol/vegetable glycerol (PG/VG) at four levels (5/10/30/50% (v/v)). The e-liquid CC levels increased linearly with flavorant base content, 1.3-10.5 times (R 2 : 0.762-0.999). The vaping CC EFs increased linearly with flavorant base content (if ≥ 10%) from 1.0 to 92 times (R 2 : 0.431-0.998). For flavorant base content of 0%, 5%, and 10%, the EFs ranged from undetected to 0.11 μg puff -1 (acetone). The 40-year cancer risk due to formaldehyde (70 kg EC user inhaling 5% flavorant base content e-liquid: 120 puffs day -1 ) is estimated to be 2.0E-06 (highest) compared to 1.0E-06 for the 1:1 PG:VG base. Most formaldehyde vaped from the fruit flavored e-liquid was the flavorant base. The CC concentrations in EC liquids (before vaping) were approximately linear with e-liquid flavorant base content. Retail e-liquid product information labels should be guided to provide a complete list of all ingredients, their concentrations, and carbonyl compound EFs., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The use of glass impinger is an important device for sampling and handling when measuring volatile organic compounds (SVOCs). Thus, it is important to check for possible analyte losses to the inner glass surface when carrying out sample analysis with the aid of impinger system. In this research, we evaluated the sorptive loss patterns of vapor-phase semi-volatile organic compounds [SVOCs (n = 10): acetic acid (ACA), propionic acid (PPA), i-butyric acid (IBA), n-butyric acid (BTA), i-valeric acid (IVA), n-valeric acid (VLA), phenol (PhAl), p-cresol (p-C), indole (ID), and skatole (SK)] on inert surfaces of an impinger in reference to sampling bags. The gaseous standard of these SVOCs (48-406 ppb) in polyester aluminum (PEA) bags was passed through an empty impinger in 1 L steps. The exiting SVOCs were collected on three-bed sorbent tubes for subsequent analysis by thermal desorption-gas chromatography-mass spectroscopy (TD-GC-MS). Impinger wall sorption capacities ranged from 2.0 to 21.0 ng cm -2 . The 10% breakthrough adsorption capacities on the impinger wall for acids, phenols, and indoles ranged from 1.21 ± 0.15 to 5.39 ± 0.79, 0.92 ± 0.12 to 13.4 ± 2.25, and 4.47 ± 0.42 to 5.23 ± 0.35 ng cm -2 , respectively. The observed sorptive patterns suggest that the sorptive losses of the volatile fatty acids, phenols, and indoles can occur very effectively at low ppb levels onto a glass surface.

In this study, we report a 2,4-dinitrophenylhydrazine (DNPH) derivatization HPLC/UV method to quantify carbonyl compounds (CCs) either in electronic cigarette (EC) refill solutions or in vaped aerosols. Vaped aerosol samples were entrained in a 1 L atm min -1 ambient lab air stream and pulled through an impinger containing a DNPH solution for derivatization. The mass change tracking (MCT) approach was used to check mass balance. Refill solution samples were diluted (2, 4, and 10 times) in a DNPH/acetonitrile solution for derivatization. EC vaping samples were collected for 5, 10, or 15 puffs (2-s puff duration) with a 10-s interpuff interval. The DNPH derivatization method was used successfully for the estimation of both EC liquid CCs concentrations and vaping emission factors. The results for formaldehyde (FA), acetaldehyde (AA), and butyraldehyde (BA) were determined as 10.4 ± 3.10 μg mL -1 (27.6 ± 7.43 ng puff -1 ), 1.9 ± 0.83 μg mL -1 (4.4 ± 1.98 ng puff -1 ), and 4.4 ± 2.82 μg mL -1 (12.0 ± 7.43 ng puff -1 ), respectively.

The concentrations of C 6 -C 10 volatile aromatic hydrocarbons (AHCs) in air were measured at an urban air quality monitoring station in Jong-Ro, Seoul, Korea, between 2013 and 2015. Their temporal patterns (e.g., diurnal, intraweek, daily) were assessed individually and collectively as groups of benzene, toluene, ethylbenzene, styrene, and xylene (BTESX); total aliphatic hydrocarbon (TALHC: C 2 -C 12 ); total aromatic hydrocarbon (TARHC: C 6 -C 10 ); and total hydrocarbon (THC: C 2 -C 12 ). The highest mean AHC concentrations over the 3-year study (in ppb (v/v)) were observed for toluene (6.0 ± 4.3), followed by the xylenes (1.5 ± 1.3), ethylbenzene (0.85 ± 0.93), benzene (0.73 ± 0.77), and styrene (0.16 ± 0.30) nL/L. The mean ppbC ((v/v), nL∙atm∙C/nL∙atm) values for BTESX, TALHC, TARHC, and THC were 65.8, 113, 77.7, and 191 ppbC, respectively. For most AHC species (e.g., toluene, styrene, and BTESX), only weak seasonal trends were observed in contrast to temporally varying species like nitric oxide (NO) (e.g., 26.3 ppb (January-February) vs. 8.5 ppb (July-August) during weekdays in 2013). Furthermore, toluene and NO concentrations were much higher (up to a factor 3) on weekdays than on Sunday for most weeks. This might reflect reduced anthropogenic activities on Sunday., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Atmospheric concentration of sulfur dioxide (SO 2 ) was intermittently measured at an air quality monitoring (AQM) station in the Yong-san district of Seoul, Korea, between 1987 and 2013. The SO 2 level was compared with other important pollutants concurrently measured, including methane (CH 4 ), carbon monoxide (CO), nitric oxide (NO), nitrogen dioxide (NO 2 ), ozone (O 3 ), and particulate matter (PM 10 ). If split into three different periods (period 1, 1987-1988, period 2, 1999-2000, and period 3, 2004-2013), the respective mean [SO 2 ] values (6.57 ± 4.29, 6.30 ± 2.44, and 5.29 ± 0.63 ppb) showed a slight reduction across the entire study period. The concentrations of SO 2 are found to be strongly correlated with other pollutants such as CO (r = 0.614, p = 0.02), which tracked reductions in reported emissions due to tighter emissions standards enacted by the South Korean government. There was also a clear seasonal trend in the SO 2 level, especially in periods 2 and 3, reflecting the combined effects of domestic heating by coal briquettes and meteorological conditions. Although only a 16% concentration reduction was achieved during the 27-year study duration, this is significant if one considers rapid urbanization, an 83.2% increase in population, and rapid industrialization that took place during that period., Implications: Since 1970, a network of air quality monitoring (AQM) stations has been operated by the Korean Ministry of Environment (KMOE) for routine nationwide monitoring of air pollutant concentrations in urban/suburban areas. To date, the information obtained from these stations has provided a platform for analyzing long-term trends of major pollutant species. In this study, we examined the long-term trends of SO 2 levels and relevant environmental parameters monitored continuously in the Yong-san district of Seoul between 1987 and 2013. The data were analyzed over various time scales (i.e., monthly, seasonal, and annual intervals). The results obtained from this study will allow us to assess the effectiveness of abatement strategy and to predict future concentrations trends in association with future abatement strategies and technologies.

High energy electron-impact ionizers have found applications mainly in industry to reduce off-gas emissions from waste gas streams at low cost and high efficiency because of their ability to oxidize many airborne organic pollutants (e.g., volatile organic compounds (VOCs)) to CO 2 and H 2 O. Applications of air ionizers in indoor air quality management are limited due to poor removal efficiency and production of noxious side products, e.g., ozone (O 3 ). In this paper, we provide a critical evaluation of the pollutant removal performance of air ionizing system through comprehensive review of the literature. In particular, we focus on removal of VOCs and odorants. We also discuss the generation of unwanted air ionization byproducts such as O 3 , NOx, and VOC oxidation intermediates that limit the use of air-ionizers in indoor air quality management., (Copyright © 2017. Published by Elsevier Ltd.)

Globally, modern mass transport systems whether by road, rail, water, or air generate airborne pollutants in both developing and developed nations. Air pollution is the primary human health concern originating from modern transportation, particularly in densely-populated urban areas. This review will specifically focus on the origin and the health impacts of carbonaceous traffic-related air pollutants (TRAP), including particulate matter (PM), volatile organic compounds (VOCs), and elemental carbon (EC). We conclude that the greatest current challenge regarding urban TRAP is understanding and evaluating the human health impacts well enough to set appropriate pollution control measures. Furthermore, we provide a detailed discussion regarding the effects of TRAP on local environments and pedestrian health in low and high traffic-density environments., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

In order to investigate possible foliar transfer of toxic heavy metals, concentrations of Cd, Pb, and Fe were measured in samples of: Cassia siamea leaves (a common tree) Cassia siamea foliar dust, nearby road dust, and soil (Cassia siamea tree roots) at six different sites in/around the Bilaspur industrial area and a control site on the university campus. Bilaspur is located in a subtropical central Indian region. The enrichment factor (EF) values of Pb and Cd, when derived using the crustal and measured soil Fe data as reference, indicated significant anthropogenic contributions to Pb and Cd regional pollution. Based on correlation analysis and scanning electron microscopy (SEM) observations, it was evident that Pb and Cd in foliar part of Cassia siamea were largely from airborne sources. The SEM studies of leaf confirmed that leaf morphology (epidermis, trichome, and stomata) of Cassia siamea helped accumulate the toxic metals from deposited particulate matter (PM). There is a line of evidence that the leaf of Cassia siamea was able to entrap PM in respirable suspended particulate matter (RSPM) range (i.e., both in fine and coarse fractions). The overall results of this study suggest that Cassia siamea can be a potential plant species to control the pollution of PM and PM-bound metals (Pb and Cd) in affected areas., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In recent years, research on metal organic frameworks (MOFs) has been extended to explore various issues regarding structural flexibility, toxicity, aqueous synthesis, biodegradability, regeneration, reuse, and easy disposal. Based on such efforts, highly-ordered porous MOF structures bound to organic resins (metal organic resins or MORs) have emerged as a new generation of materials with excellent properties feasible for diverse applications. Here, we describe the excellent features of MORs and demonstrate their potential applicability in environmental as well as other relevant fields., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Volatile organic compounds (VOCs) in automobile cabins were measured quantitatively to describe their emission characteristics in relation to various idling scenarios using three used automobiles (compact, intermediate sedan, and large sedan) under three different idling conditions ([1] cold engine off and ventilation off, [2] exterior air ventilation with idling warm engine, and [3] internal air recirculation with idling warm engine). The ambient air outside the vehicle was also analyzed as a reference. A total of 24 VOCs (with six functional groups) were selected as target compounds. Accordingly, the concentration of 24 VOC quantified as key target compounds averaged 4.58 ± 3.62 ppb (range: 0.05 (isobutyl alcohol) ∼ 38.2 ppb (formaldehyde)). Moreover, if their concentrations are compared between different automobile operational modes: the 'idling engine' levels (5.24 ± 4.07) was 1.3-5 times higher than the 'engine off' levels (4.09 ± 3.23) across all 3 automobile classes. In summary, automobile in-cabin VOC emissions are highly contingent on changes in engine and ventilation modes., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

In this research, we investigated the sorptive behavior of a mixture of 14 volatile and semi-volatile organic compounds (four aromatic hydrocarbons (benzene, toluene, p-xylene, and styrene), six C2-C5 volatile fatty acids (VFAs), two phenols, and two indoles) against three metal-organic frameworks (MOFs), i.e., MOF-5, Eu-MOF, and MOF-199 at 5 to 10 mPa VOC partial pressures (25 °C). The selected MOFs exhibited the strongest affinity for semi-volatile (polar) VOC molecules (skatole), whereas the weakest affinity toward was volatile (non-polar) VOC molecules (i.e., benzene). Our experimental results were also supported through simulation analysis in which polar molecules were bound most strongly to MOF-199, reflecting the presence of strong interactions of Cu(2+) with polar VOCs. In addition, the performance of selected MOFs was compared to three well-known commercial sorbents (Tenax TA, Carbopack X, and Carboxen 1000) under the same conditions. The estimated equilibrium adsorption capacity (mg.g(-1)) for the all target VOCs was in the order of; MOF-199 (71.7) >Carboxen-1000 (68.4) >Eu-MOF (27.9) >Carbopack X (24.3) >MOF-5 (12.7) >Tenax TA (10.6). Hopefully, outcome of this study are expected to open a new corridor to expand the practical application of MOFs for the treatment diverse VOC mixtures.

In this study, the distribution of airborne iron (Fe), one of the most abundant heavy metals in the Earth's crust was investigated to describe the basic features of i'ts pollution in various urban locations. The spatiotemporal distribution of Fe concentrations in seven major South Korean cities exhibited unique patterns to reflect differences as to Fe sources reflected in the relative enrichment in coastal relative to inland areas. In addition, the analysis of long-term trends of different metal species indicated that Fe levels maintained a fairly constant trend, while there had been a noticeable decline in concentrations of other metals (Cd, Cr, Cu, Mn, and Ni). The relative robustness of our correlation analysis was assessed by comparing (1) the Fe concentrations among cities, and (2) Fe with other metals at a given city. Fe concentrations were also partly explainable by the frequency of Asian dust events in most cities, with the observed spatial gradients in such relationships., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In this study, the odorant emission rates from excretory wastes collected in sealed containers from a large swine facility were determined offsite in a laboratory using both raw slurry from ([1] windowless pigpen (WP) and [2] open pigpen (OP)) and treated waste samples ([3] composting facility (CF) and [4] slurry treatment facility (SF)). The emission rates of up to 41 volatile odorants were measured for 100g waste samples (of all four types) in a 0.75L impinger with an air change rate of 8h(-1). The initial emission rates (mgkg(-1)·h(-1)) for the most dominant species from each waste type can be summarized as: (1) WP: NH3 (16.3) and H2S (0.54); (2) OP: H2S (1.78), NH3 (1.69), and p-cresol (0.36); (3) CF: NH3 (7.04), CH3SH (0.30), and DMS (0.12); and (4) SF: NH3 (11.7), H2S (11.7), and p-cresol (0.25). Accordingly, the emission factors for the key odorant (mE, kg·pig(-1))) for fattening pigs in the WP and OP facilities of S. Korea were extrapolated as 3.46 (NH3) and 0.38 (H2S), respectively. The emission factors were estimated assuming exponentially decaying emission rates and slurry production rates obtained from the literature., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Among the numerous sources of greenhouse gases, emissions of CO2 are considerably affected by changes in the extent and type of land use, e.g., intensive agriculture, deforestation, urbanization, soil erosion, or wetland drainage. As a feasible option to control emissions from the terrestrial ecosystems, the scientific community has explored the possibility of enhancing soil carbon (C) storage capacity. Thus, restoration of damaged lands through conservation tillage, crop rotation, cover cropping, reforestation, sub-soiling of compacted lands, sustainable water management practices, and organic manuring are the major antidotes against attenuation of soil organic C (SOC) stocks. In this research, we focused on the effect of various man-made activities on soil biotic organics (e.g., green-, farm-yard manure, and composts) to understand how C fluxes from various sources contribute to the establishment of a new equilibrium in the terrestrial ecosystems. Although such inputs substitute a portion of chemical fertilizers, they all undergo activities that augment the rate and extent of decay to deplete the SOC bank. Here, we provide perspectives on the balancing factors that control the mineralization rate of organic matter. Our arguments are placed in the background of different land use types and their impacts on forests, agriculture, urbanization, soil erosion, and wetland destruction., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

As emission rates of airborne pollutants are commonly measured from combusting substances placed inside small chambers, those values need to be re-evaluated for the possible significance under practical conditions. Here, a simple numerical procedure is investigated to extrapolate the chamber-based emission rates of formaldehyde that can be released from various combustible sources including e-cigarettes, conventional cigarettes, or scented candles to their concentration levels in a small room with relatively poor ventilation. This simple procedure relies on a mass balance approach by considering the masses of pollutants emitted from source and lost through ventilation under the assumption that mixing occurs instantaneously in the room without chemical reactions or surface sorption. The results of our study provide valuable insights into re-evaluation procedure of chamber data to allow comparison between extrapolated and recommended values to judge the safe use of various combustible products in confined spaces. If two scented candles with a formaldehyde emission rate of 310 µg h(-1) each were lit for 4 h in a small 20 m(3) room with an air change rate of 0.5 h(-1), then the 4-h (candle lit) and 8-h (up to 8 h after candle lighting) TWA [FA] were determined to be 28.5 and 23.5 ppb, respectively. This is clearly above the 8-h NIOSH recommended exposure limit (REL) time weighted average of 16 ppb., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The sorptive removal properties of a synthetic A4 zeolite were evaluated against sulfur dioxide (SO2) and four reference reduced sulfur compounds (RSC: hydrogen sulfide (H2S), methanethiol (CH3SH), dimethyl sulfide (DMS, (CH3)2S), and dimethyl disulfide (DMDS, CH3SSCH3). To this end, a sorbent bed of untreated (as-received) A4 zeolite was loaded with gaseous standards at four concentration levels (10-100 part-per-billion (ppb (v/v)) at four different volumes (0.1, 0.2, 0.5, and 1 L increments) in both increasing (IO: 0.1-1.0 L) and decreasing volume order (DO: 1.0 to 0.1 L). Morphological properties were characterized by PXRD, FTIR, and BET analysis. The removal efficiency of SO2 decreased from 100% for all concentrations at 0.1 L (initial sample volume) to ∼82% (100 ppb) or ∼96% (10 ppb) at 3.6 L. In contrast, removal efficiency of RSC was near 100% at small loading volumes but then fell sharply, irrespective of concentration (10-100 ppb) (e.g., 32% (DMS) to 52% (H2S) at 100 ppb). The adsorption capacity of zeolite, if expressed in terms of solid-gas partition coefficient (e.g., similar to the Henry's law constant (mmol kg(-1) Pa(-1))), showed moderate variabilities with the standard concentration levels and S compound types such as the minimum of 2.03 for CH3SH (at 20 ppb) to the maximum of 13.9 for SO2 (at 10 ppb). It clearly demonstrated a notable distinction in the removal efficiency of A4 zeolite among the different S species in a mixture with enhanced removal efficiency of SO2 compared to the RSCs., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Long-term trends in observed carbon monoxide (CO) concentrations were analyzed in seven major South Korean cities from 1989 to 2013. Temporal trends were evident on seasonal and annual timescales, as were spatial gradients between the cities. As CO levels in the most polluted cities decreased significantly until the early 2000s, the data were arbitrarily divided into two time periods (I: 1989-2000 and II: 2001-2013) for analysis. The mean CO concentration of period II was about 50% lower than that of period I. Long-term trends of annual mean CO concentrations, examined using the Mann-Kendall (MK) method, confirm a consistent reduction in CO levels from 1989 to 2000 (period I). The abrupt reduction in CO levels was attributed to a combination of technological improvements and government administrative/regulatory initiatives (e.g., emission mitigation strategies and a gradual shift in the fuel/energy consumption mix away from coal and oil to natural gas and nuclear power)., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In our recent study, we experimentally demonstrated the feasibility of an effective carbon number (ECN) approach for the prediction of the response factor (RF) values of 'compounds lacking authentic standards or surrogates' (CLASS) using a certified 54-mix containing 38 halogenated analytes as a pseudo-unknown. Although our recent analysis performed well in terms of RF predictive power for a 25-component learning set (for both Q-MS and TOF-MS detection), large physically unrealistic negative ECN and carbon number equivalent (CNE) values were noted for TOF-MS detection, e.g., ECN (acetic acid)=-16.96. Hence, to further improve the ECN-based quantitation procedure of CLASS, we re-challenged RF vs. ECN linear regression analysis with additional descriptors (i.e., Cl, Br, CC, and a group ECN offset (Ok)) using the 1-point RF values. With an Ok, all compound classes, e.g., halo-alkanes/-alkenes and aromatics can now be fitted to yield consistently positive set of ECN values for most analytes (e.g., 3 outliers out of 29, Q-MS detection). In this way, we were able to further refine our approach so that the absolute percentage difference (PD)±standard deviation (SD) between mass detected vs. mass loaded is reduced from 39.0±34.1% (previous work) to 13.1±12.0% (this work) for 29 C1C4 halocarbons (Q-MS detector)., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Many classes of odorants and volatile organic compounds that are deleterious to our wellbeing can be emitted from diverse cooking activities. Once emitted, they can persist in our living space for varying durations. In this study, various volatile organic compounds released prior to and during the pan frying of fish (mackerel) were analyzed at three different cooking stages (stage 1 = raw (R), stage 2 = well-done (W), and stage 3 = overcooked/charred (O)). Generally, most volatile organic compounds recorded their highest concentration levels at stage 3 (O), e.g., 465 (trimethylamine) and 106 ppb (acetic acid). In contrast, at stage 2 (W), the lowest volatile organic compounds emissions were observed. The overall results of this study confirm that trimethylamine is identified as the strongest odorous compound, especially prior to cooking (stage 1 (R)) and during overcooking leading to charring (stage 3 (O)). As there is a paucity of research effort to measure odor intensities from pan frying of mackerel, this study will provide valuable information regarding the management of indoor air quality.

The relative performance of different sorbent materials employed in the cryofocusing (e.g. in cold trap (CT) unit) stage was investigated at sub-ambient temperature by the thermal desorption (TD)-gas chromatography (GC)-pulsed flame photometric detector. To this end, the TD-based calibration of five reduced sulphur compounds (RSC: H2S, CH3SH, CS2, DMS and DMDS) and SO2 was carried out via the Peltier cooling system with five types of sorbent combinations such as two single-bed (Tenax TA and Silica gel) plus three multibed types (a combination of either two from the following three sorbents: Tenax TA, Silica gel and Carbopack B). Relative performance of each of all five CT options, if evaluated in terms of response factors for each compound, demonstrated that each CT composition acts as an important criterion to distinguish detection properties between light and heavy sulphur species. Although the relative response of H2S and CH3 SH was systematically distinguishable between the CT types, that of SO2 was the most complicated to interpret. According to this study, the two CT types consisting of Carbopack B and Silica gel (CS-0.4 and CS-0.6) were the optimum choices for sulphur gas analysis in terms of basic QA parameters (sensitivity, reproducibility and linearity).

The breakthrough (BT) properties of Tenax TA sorbent were challenged by gaseous standards containing a suite of 13 volatile organic compounds (VOC): (1) aromatic hydrocarbons: benzene (B), toluene (T), p-xylene (p-X), and styrene (S), (2) aldehydes: acetaldehyde (AA), propionaldehyde (PA), butyraldehyde (BA), isovaleraldehyde (IA), and valeraldehyde (VA), (3) ketones: methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), and (4) two others: isobutyl alcohol (i-BuAl) and butyl acetate (BuAc). To this end, 1-3 L of standards (10-50 ppb) were loaded on the two sorbent tubes (ST) connected in series at 100 mL min(-1). The front ST-1 was used for calibration purposes, while the ST-2 for breakthrough (recovery criterion of <1% with p-xylene as the key datum point). Although aromatic hydrocarbons generally met such criterion, benzene was readily distinguishable with the maximum BT. The BT for the aldehydes exhibited ~100% (AA) ≥ 85% (PA) ≥ 45% (BA) ≥ 30% (VA and IVA). There is good correlation between ST-2 recovery vs. carbon number for >CO entity (aldehydes, ester, and ketones). As such, BT is essentially concentration independent and relatively predictable across different functional groups and between the homologues. However, the BT behavior of ppb level VOCs is no longer consistent for certain species (like benzene or MEK) relative their ppm counterparts. This variation is explained by the Langmuir equation in which the 1/BTV is proportional to analyte gas-phase concentration, if the gas-phase/sorbent partition coefficient is large., (Copyright © 2014. Published by Elsevier B.V.)

Headspace (HS) analysis has been recommended as one of the most optimal methods for extracting and analyzing volatile organic compounds from samples in diverse media such as soil and water. Short-chain volatile fatty acids (VFA, C3-C7) with strong adsorptivity were selected as the target compounds to assess the basic characteristics of the HS analysis through simulation of HS conditions by in-vial vaporization of liquid-phase standards (VL) in 25 mL glass vials. The reliability of the VL approach was assessed by apportioning the in-vial VFA mass into three classes: (1) vaporized fraction, (2) dynamic adsorption on the vial walls (intermediate stage between vaporization and irreversible absorption), and (3) irreversible absorptive loss (on the vial wall). The dynamic adsorption partitioning inside the vial increased with n-VFA carbon number, e.g., 43% (C2: acetic acid, extrapolated value), 65% (C3: propanoic acid), and 98% (C7: heptanoic acid). The maximum irreversible losses for the studied n-VFAs exhibited a quadratic relationship with carbon number. If the detection threshold limit (DTL: the onset of mass detection after attaining the maximum irreversible loss) is estimated, the DTL values for target VFAs were in the range of 101 ng for i-valeric acid to 616 ng for propionic acid, which are larger than the method detection limit by about 3 orders of magnitude. Consequently, quantitation of VFAs using the VL approach should be critically assessed by simultaneously considering the DTL criterion and the initial VFA masses loaded into the vial.

For the quantitative analysis of 'compounds lacking authentic standards or surrogates' (CLASS) in environmental media, we previously introduced an effective carbon number (ECN) approach to develop an empirical equation for the prediction of their response factor (RF). In this research, a series of laboratory experiments were carried out to benchmark the reliability of an ECN approach for sorbent tube/thermal desorption/gas chromatography (GC)/mass spectrometry (MS) applications. First, the ECN values were determined using external calibration data from 25 reference volatile organic compounds (VOCs) using two MS dectectors (quadrupole (Q) and time-of-flight (TOF)). Then, a certified standard mixture of 54 VOCs was analyzed by each system as a simulated unknown sample. The analytical bias, assessed in terms of percentage difference (PD) between the certified and ECN-predicted mass values, averaged 19.2±16.1% (TOF-MS) and 28.2±27.6% (Q-MS). The bias using a more simplified carbon number (CN)-based prediction increased considerably, yielding 53.4±53.3% (TOF-MS) and 61.7±81.3% (Q-MS). However, the bias obtained using the ECN-based prediction decreased significantly to yield average PD values of 9.84±7.28% (TOF-MS) and 16.8±8.35% (Q-MS), if the comparison was limited to 26 (out of 54) VOCs with CN≥4 (i.e., 25 aromatics and hexachlorobutadiene)., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The production of short-chained volatile fatty acids (VFAs) by the anaerobic bacterial digestion of sewage (wastewater) affords an excellent opportunity to alternative greener viable bio-energy fuels (i.e., microbial fuel cell). VFAs in wastewater (sewage) samples are commonly quantified through direct injection (DI) into a gas chromatograph with a flame ionization detector (GC-FID). In this study, the reliability of VFA analysis by the DI-GC method has been examined against a thermal desorption (TD-GC) method. The results indicate that the VFA concentrations determined from an aliquot from each wastewater sample by the DI-GC method were generally underestimated, e.g., reductions of 7% (acetic acid) to 93.4% (hexanoic acid) relative to the TD-GC method. The observed differences between the two methods suggest the possibly important role of the matrix effect to give rise to the negative biases in DI-GC analysis. To further explore this possibility, an ancillary experiment was performed to examine bias patterns of three DI-GC approaches. For instance, the results of the standard addition (SA) method confirm the definite role of matrix effect when analyzing wastewater samples by DI-GC. More importantly, their biases tend to increase systematically with increasing molecular weight and decreasing VFA concentrations. As such, the use of DI-GC method, if applied for the analysis of samples with a complicated matrix, needs a thorough validation to improve the reliability in data acquisition., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The relative performance figure of merits was investigated for the two most common analytical methods employed for carbonyl compounds (CC), for example, between high performance liquid chromatography (HPLC)-UV detector (with 2,4-dinitrophenylhydrazine (DNPH) derivatization) and thermal desorption (TD)-gas chromatography (GC)-mass spectrometry (MS) (without derivatization). To this end, the suitability of each method is assessed by computing the relative recovery (RR) between the gas- and liquid-phase standards containing a suite of CC such as formaldehyde (FA), acetaldehyde (AA), propionaldehyde (PA), butyraldehyde (BA), isovaleraldehyde (IA), and valeraldehyde (VA) along with benzene (B) as a recovery reference for the GC method. The results confirm that a TD-GC-MS is advantageous to attain the maximum recovery for the heavier CCs (i.e., with molecular weights (MW) above BA-MW ≥ 74). On the other hand, the HPLC-UV is favorable for the lighter CCs (like FA and AA) with the least bias. Such compound-specific responses for each platform are validated by relative ordering of CCs as a function of response factor (RF), method detection limit (MDL), and recovery pattern. It is thus desirable to understand the advantages and limitations of each method to attain the CC data with the least experimental bias.

Rationale: Low-mass cut-off restrictions for injecting ions from external ion sources into high magnetic fields impose limitations for wide mass range analyses with Fourier transform ion cyclotron resonance (FTICR) instruments. Radio-frequency (RF)-only quadrupole ion guides (QIGs) with higher frequencies can be used to overcome low-mass cut-off in FTICR instruments., Methods: RF signals (1.0 MHz to 10.0 MHz) were applied to QIGs to transfer externally generated ions from either electron ionization (EI) or electrospray ionization (ESI) sources into ICR cells of 9.4 T FTICR mass spectrometers. Efficiencies of QIGs were evaluated using externally generated ions from: EI of acetone, air, and perfluorotributylamine mixture, EI of gas chromatography (GC)-separated components of a standard sample mixture, and ESI of complex mixtures such as petroleum and fulvic acid samples., Results: We were able to transfer ions with m/z as low as 26 from an external EI source into the ICR cell of a 9.4 T FTICR mass spectrometer and extend the operational low-mass range for ESI-FTICR analyses. High mass resolving power and mass measurement accuracy of GC/FTICR mass spectrometry were utilized to discriminate between oxygenated and non-oxygenated compounds in a 'Grob' sample. Ion losses based on SIMION ion trajectory predictions were consistent with experimental findings., Conclusions: We demonstrated that the use of high-frequency QIGs can extend the operational lower m/z range for both external EI- and ESI-FTICR mass spectrometers. By considering both ICR and Mathieu equations of motions to describe ion trajectories, theoretical ion ejection thresholds (consistent with our experimental findings) could be predicted., (Copyright © 2013 John Wiley & Sons, Ltd.)

The gas-liquid partitioning behavior of major odorants (acetic acid, propionic acid, isobutyric acid, n-butyric acid, i-valeric acid, n-valeric acid, hexanoic acid, phenol, p-cresol, indole, skatole, and toluene (as a reference)) commonly found in microbially digested wastewaters was investigated by two experimental approaches. Firstly, a simple vaporization method was applied to measure the target odorants dissolved in liquid samples with the aid of sorbent tube/thermal desorption/gas chromatography/mass spectrometry. As an alternative method, an impinger-based dynamic headspace sampling method was also explored to measure the partitioning of target odorants between the gas and liquid phases with the same detection system. The relative extraction efficiency (in percent) of the odorants by dynamic headspace sampling was estimated against the calibration results derived by the vaporization method. Finally, the concentrations of the major odorants in real digested wastewater samples were also analyzed using both analytical approaches. Through a parallel application of the two experimental methods, we intended to develop an experimental approach to be able to assess the liquid-to-gas phase partitioning behavior of major odorants in a complex wastewater system. The relative sensitivity of the two methods expressed in terms of response factor ratios (RFvap/RFimp) of liquid standard calibration between vaporization and impinger-based calibrations varied widely from 981 (skatole) to 6,022 (acetic acid). Comparison of this relative sensitivity thus highlights the rather low extraction efficiency of the highly soluble and more acidic odorants from wastewater samples in dynamic headspace sampling.

A procedure has been developed to estimate GC-MS response factors based on the theory of effective carbon number defined as the sum of the carbon number and carbon number equivalent for each selected molecular descriptor (multiplied by its number of occurrences) in each compound's molecular structure. As a means to validate the effective carbon number procedure for GC-MS analysis, a test suite of 19 volatile organic compounds was analyzed by the sorbent-tube thermal desorption method. In the effective carbon number procedure, the carbon number equivalent for each descriptor was determined to yield the optimal linear plots between response factor versus the effective carbon number with the maximum R(2) (>0.975) and the minimum mean absolute error (<5%). Effective carbon number analysis is validated as a potent approach to estimate response factor values for most compounds amenable to the sorbent-tube thermal desorption GC-MS method. Overall, it is concluded that the application of response factor versus effective carbon number relationship can produce fairly reliable prediction with reduced errors relative to other comparable procedures such as the response factor versus the carbon number approach., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The classes and concentrations of volatile organic compounds (VOC) released from fresh and decaying strawberries were investigated and compared. In this study, a total of 147 strawberry volatiles were quantified before and after nine days of storage to explore differences in the aroma profile between fresh strawberries (storage days (SRD) of 0, 1, and 3) and those that had started to decay (SRD = 6 and 9). In terms of concentration, seven compounds dominated the aroma profile of fresh strawberries (relative composition (RC) up to 97.4% by mass, sum concentration): (1) ethyl acetate = 518 mg∙m⁻³, (2) methyl acetate = 239 mg∙m⁻³, (3) ethyl butyrate = 13.5 mg∙m⁻³, (4) methyl butyrate = 11.1 mg∙m⁻³, (5) acetaldehyde = 24.9 mg∙m⁻³, (6) acetic acid = 15.2 mg∙m⁻³, and (7) acetone = 13.9 mg∙m⁻³. In contrast, two alcohols dominated the aroma profile of decayed samples (RC up to 98.6%): (1) ethyl alcohol = 94.2 mg∙m⁻³ and (2) isobutyl alcohol = 289 mg∙m⁻³. Alternatively; if the aroma profiles are re-evaluated by summing odor activity values (ΣOAV); four ester compounds ((1) ethyl butyrate (6,160); (2) ethyl hexanoate (3,608); (3) ethyl isovalerate (1,592); and (4) ethyl 2-methylbutyrate (942)) were identified as the key constituents of fresh strawberry aroma (SRD-0). As the strawberries began to decay; isobutyl alcohol recorded the maximum OAV of 114 (relative proportion (RP) (SRD = 6) = 58.3%). However, as the decay process continued, the total OAV dropped further by 3 to 4 orders of magnitude--decreasing to 196 on SRD = 6 to 7.37 on SRD = 9. The overall results of this study confirm dramatic changes in the aroma profile of strawberries over time, especially with the onset of decay.

Travelling wave ion mobility mass spectrometry (TWIM-MS) with post-TWIM and pre-TWIM collision-induced dissociation (CID) experiments were used to form, separate and characterize protomers sampled directly from solutions or generated in the gas phase via CID. When in solution equilibria, these species were transferred to the gas phase via electrospray ionization, and then separated by TWIM-MS. CID performed after TWIM separation (post-TWIM) allowed the characterization of both protomers via structurally diagnostic fragments. Protonated aniline (1) sampled from solution was found to be constituted of a ca. 5:1 mixture of two gaseous protomers, that is, the N-protonated (1a) and ring protonated (1b) molecules, respectively. When dissociated, 1a nearly exclusively loses NH(3) , whereas 1b displays a much diverse set of fragments. When formed via CID, varying populations of 1a and 1b were detected. Two co-existing protomers of two isomeric porphyrins were also separated and characterized via post-TWIM CID. A deprotonated porphyrin sampled from a basic methanolic solution was found to be constituted predominantly of the protomer arising from deprotonation at the carboxyl group, which dissociates promptly by CO(2) loss, but a CID-resistant protomer arising from deprotonation at a porphyrinic ring NH was also detected and characterized. The doubly deprotonated porphyrin was found to be constituted predominantly of a single protomer arising from deprotonation of two carboxyl groups., (Copyright © 2012 John Wiley & Sons, Ltd.)

The contributions of molecular and fragment ions toward the disparate self-chemical ionization (SCI) of alpha-pinene and camphene isomers were investigated. A kinetic model was constructed to predict the SCI outcomes for these two C(10)H(16) isomers. A major portion of the camphene molecular ions (isolated 500 ms after the 10 ms EI event at 24 eV) unimolecularly dissociated within 200 s of the ionization event. Conversely, under similar experimental conditions, the alpha-pinene molecular ions as well as the major fragment ions of alpha-pinene and camphene showed no unimolecular dissociation. The alpha-pinene and camphene molecular ions yielded product ions through two different reaction mechanisms (direct charge-transfer {CT} and indirect proton transfer {PT}). The isolated terpene fragment ions at m/z 93 and 121 reacted with their respective neutrals to produce [M + H](+). Proton affinity (PA) bracketing experiments, PA additivity schemes, and alkene PA versus adiabatic ionization energy (IE) linear correlation indicated that the PAs of camphene and alpha-pinene were comparable ( approximately 210 +/- 2 kcal x mol(-1)). The observed [M + H](+) SCI terpene ions were mainly the products of various fragment ion reactions.

The gas-phase basicities of a representative set of hydroxy- and methoxycarbonyl compounds (hydroxyacetone, 1, 3-hydroxybutanone, 2, 3-hydroxy-3-methylbutanone, 3, 1-hydroxy-2-butanone, 4, 4-hydroxy-2-butanone, 5, 5-hydroxy-2-pentanone, 6, methoxyacetone, 7, 3-methoxy-2-butanone, 8, 4-methoxy-2-butanone, 9, and 5-methoxy-2-pentanone, 10) were experimentally determined by the equilibrium method using Fourier transform ion cyclotron resonance and high-pressure mass spectrometry techniques. The latter method allows the measurement of proton transfer equilibrium constants at various temperatures and thus the estimate of both the proton affinities and the protonation entropies of the relevant species. Quantum chemical calculations at the G3 and the B3LYP/6-311+G(3df,2p)//6-31G(d) levels of theory were undertaken in order to find the most stable structures of the neutrals 1-10 and their protonated forms. Conformational and vibrational analyses have been done with the aim of obtaining a theoretical estimate of the protonation entropies.

Coupling of a cryogenic preconcentrator (PC) to a gas chromatograph/Fourier transform ion cyclotron resonance mass spectrometer (GC/FT-ICR MS) is reported. To demonstrate the analytical capabilities of the PC/GC/FT-ICR MS, headspace samples containing volatile organic compounds (VOCs) emitted from detached pine tree twigs were analyzed. Sub-ppm mass measurement accuracy (MMA) for highly resolved (m/Deltam(50%) > 150 k) terpene ions was achieved. Direct PC/GC/FT-ICR MS analyses revealed that detached twigs from pine trees emit acetone, camphor, and four detectable hydrocarbon isomers with C(10)H(16) empirical formula. The unknown analytes were identified based on accurate mass measurement and their mass spectral appearances. Authentic samples were used to confirm initially unknown identifications. Self-chemical-ionization (SCI) reactions furnished an additional dimension for rapid isomer differentiation of GC eluents in real time.

Details of interfacing a high-pressure gas chromatograph to the internal ion source of a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) are described. We present our preliminary results and potential analytical applications of GC/FT-ICR for analyzing complex biological and environmental sample matrixes, such as petroleum mixtures. Based on GC/FT-ICR data, rapid characterization of various automobile gasoline samples is possible. Comparison between acquired data from the GC/FT-ICR MS (in broadband mode) and a commercial GC quadrupole mass spectrometer (QMS) (over a wide mass range) indicates that sensitivity of the GC/FT-ICR MS is an order of magnitude lower. High mass resolution and mass measurement accuracy of FT-ICR MS can be utilized for unambiguous molecular formula identification of unknown analytes.

Metastable Ion (MI) and collision-induced dissociation (CID) mass spectra for all isomeric even-electron [C(4)H(12)Si - H](+) ions were recorded and compared. Deuterium labeling experiments indicated that most precursors give rise to silylium ions. Silylium ions with two or more methyl groups are found to lose C(2)H(4) after isomerization via a straightforward hydrogen transfer to the appropriate ethylsilylium ion. Similarly, all isomeric propyl- and butyl-containing silylium ions are found to lose C(2)H(4) by rearrangement preceding dissociation. In the CI source of the mass spectrometer many of the silylium ions are found to cluster with the parent neutral silane present in the source to give stable [M - H](+)+M adduct ions. The MI and CID spectra of these adduct ions were also obtained. In the MI spectra of all adducts, except i-BuSiH(3), only the starting silylium ion is observed. Under CID conditions generation of silylium ions dominates. Deuterium labeling studies show that this dissociation may be accompanied by some rearrangement, in particular for the adducts from i-BuSiH(3). High-pressure mass spectrometric clustering equilibrium measurements were also carried out to determine the enthalpies and entropies of binding of the silylium ions to the neutral silanes. These measurements yield insight into the effects of various alkyl group substitutions on the association thermochemistry in these adducts. Copyright 2000 John Wiley & Sons, Ltd.