Sorption Of Volatile Organic Compounds Research Articles

Sorption and attenuation of petroleum VOCs in five unsaturated soils: Microcosms and column experiments

The fate of volatile organic compounds (VOC) vapors in the unsaturated zone is the basis for evaluating the natural attenuation potential and vapor intrusion risk. Microcosm and column experiments were conducted to study the effects chemical speciation and soil types/properties on the fate of petroleum VOCs in unsaturated zone. The biodegradation and total attenuation rates of the seven VOCs obtained by microcosm experiments in black soil and yellow earth were also generally higher than those in floodplain soil, lateritic red earth, and quartz sand. The VOC vapors in floodplain soil, lateritic red earth, and quartz sand showed slow total attenuation rates (<0.3 d−1). N-pentane, methylcyclopentane, and methylcyclohexane showed lower biodegradation rates than octane and three monoaromatic hydrocarbons. Volatilization into the atmosphere and biodegradation are two important natural attenuation paths for VOCs in unsaturated soil columns. The volatilization loss fractions of different volatile hydrocarbons in all five unsaturated soils were generally in the order: n-pentane (93.5%–97.8%) > methylcyclopentane (77.2%–85.5%) > methylcyclohexane (53.5%–69.2%) > benzene (17.1%–73.3%) > toluene (0–45.7%) > octane (1.9%–34.2%) > m-xylene (0–5.7%). The fractions by volatilization into the atmosphere of all seven hydrocarbons in quartz sand, lateritic red earth, and floodplain soil were close and higher compared to the yellow earth and black soil. Overall, this study illustrated the important roles chemical speciation and soil properties in determining the vapor-phase transport and natural attenuation of VOCs in the unsaturated zone.

Co-Adsorption of Alcohols and Water in JUK-8 Studied Using Quasi-Equilibrated Thermodesorption.

JUK-8 ([Zn(oba)(pip)]n, oba2- = 4,4'-oxybis(benzenedicarboxylate), pip = 4-pyridyl-functionalized benzene-1,3-dicarbohydrazide) is a hydrolytically stable flexible metal-organic framework. Owing to its unusual adsorptive properties, JUK-8 can be considered as a promising sensing material for construction of detectors of volatile organic compounds (VOCs) in air. Quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) is a versatile method dedicated to characterization of porous materials. In this work, QE-TPDA was employed to study co-adsorption of water and selected alcohols in JUK-8. For the first time an infrared detector sensitive to organic compounds was used in the QE-TPDA measurements, allowing the study of the influence of water vapor on sorption of VOCs. The QE-TPDA profiles of the studied alcohols, exhibiting two desorption maxima and two adsorption minima, are consistent with the standard sorption isotherms, revealing a two-step adsorption-desorption mechanism. The profiles recorded in the presence of water are noticeably changed in different ways for different alcohols. While at low relative humidity (RH) (ca. 20%) the low temperature adsorption states of ethanol and 1-propanol were only slightly destabilized, for 2-propanol almost complete suppression of adsorption was observed. The results found for moderate RH levels (ca. 50%) indicated that the opening of the JUK-8 structure, responsible for its breathing behavior, was followed by the filling of the just generated pores with a water-alcohol mixture.

Micro- and Mesoporous Structural Effects of Beta Zeolites for Volatile Organic Compound Sorption.

To fully exploit pore engineering in the design of more efficient zeolite adsorbents for volatile organic compound (VOC) treatment, the roles of meso- and micropores need to be clarified to provide the theoretical basis and feasible measures. In this work, the three VOC sorption properties of conventional and hierarchical porous beta zeolites were comparatively investigated to study the roles of meso- and micropores. There is a division of functions between micro- and mesopores, with micropores being the main VOC adsorption sites and mesopores greatly enhancing VOC diffusion and adsorbent reusability. On the one hand, micropores should be preserved as much as possible because obtaining mesopores by sacrificing micropores (i.e., alkali treatment) results in 28-60% decreases in adsorption capacities. On the other hand, mesopore introduction is highly desirable, which results in an enhancement of VOC intraparticle diffusion rates by 1.3-2.3 times (at the VOC concentration of 600 ppm) and chlorobenzene adsorption capacity on the 20th cycle increasing from 78% of the initial value to 89 and 93%. The findings may provide valuable information about zeolite-based adsorbents for adsorption removal or recovery of VOCs.

Preparation of nano-MFI zeolites doped with Al/Ti and their performance in VOC sorption.

Highly crystalline nano-MFI-type zeolites containing different elements were synthesized, and the sorption effects of the elements on volatile organic compounds (VOCs) were investigated. The results showed that the optimal toluene and acetone breakthrough time of the synthesized zeolites was 2.1 and 1.9 times as long as that of the commercial zeolite, respectively. For a weakly polar toluene molecule, MFI zeolites (aluminum-free) showed better adsorption properties than aluminum-containing zeolites. For the highly polar acetone molecule, zeolites with a Si/Al ratio of 87 showed the highest adsorption capacity, which was 7% higher than that of the all-silica zeolite and 1.4 times that of the commercial zeolite. Furthermore, MFI zeolites with Ti replacing part of Al proved to have better performance for highly polar molecules. In the adsorption process of VOCs, in addition to internal diffusion, diffusion on the external surface of the zeolite also played a remarkable role, and the adsorption data of all samples fitted better with the pseudo-first-order model. This study may provide a reliable structure-performance relationship for the synthesis of nanosized zeolite-based adsorbents and their use in the industrial recovery/treatment of VOCs.

Synthesis of graphene oxide from biomass waste: Characterization and volatile organic compounds removal

This research study focuses on analyzing the effects of graphene oxide (GO) synthesized from subabul, pine, and copperpod biomass waste for the adsorption of volatile organic compounds (VOCs). Five different VOCs i.e., benzene, xylene, carbon tetrachloride, n-hexane, and toluene were utilized for the sorption experiment. A modified Hummers process was carried out for the successful GO production from biomass waste and the obtained GO was confirmed using SEM, Raman spectroscopy, FTIR, and XRD. The existence of 2D-mode and G-mode in Raman spectroscopy as well as O-H and C=O groups in the FTIR confirmed the GO synthesis. The sorption efficiency of SGO, PGO, and CGO for different VOCs was in the range 82–146, 74–144, and 126–166 mg g−1, respectively. The sorption of VOCs was also affected by feedstock type, contact time, and dose of GO. The sorption efficiency of GO increased with a long contact time and higher surface area. Furthermore, for statistical analysis, ANOVA was used. For the kinetics of VOCs sorption, the pseudo-second-order model was utilized, which well fitted with the findings of this research study. The excellent sorption performance of GO produced from biomass waste made it a potential adsorbent for the sorption of VOCs.

Functionalization of metal organic frameworks by [BMIM][CH3COO] ionic liquid for toluene capture

Indoor exposure to volatile organic compounds (VOCs) is detrimental to the health of the occupants, and their removal is crucial in maintaining good air quality. Novel adsorbents prepared by modifying Metal-Organic Frameworks (MOFs), MIL101 (Cr), UiO-66, and UiO-66-NH2 with [BMIM][CH3COO] ionic liquid, were characterized and tested for toluene adsorption. [BMIM][CH3COO]/MIL101 performed best with a fast sorption rate, large sorption capacity, and good regenerability. It displays synergistic interactions between the IL and MOF. Adding one weight percent [BMIM][CH3COO] to UiO-66 and UiO-66-NH2 has a synergistic effect with respective 14% and 5% enhancements sorption over calculated values. The strong interactions between IL and UiO-66 and UiO-66-NH2, as observed in their thermogravimetric data, results in poor toluene sorption for 10 wt% [BMIM][CH3COO] loadings. This work provides a basis for IL modification of MOFs for enhanced sorption of VOCs for air treatment.

Adsorption properties and gas chromatographic application of a composite surface-layer sorbent with Terephthalic acid-based metal-organic framework

In this paper, we report on the fabrication of a new material SiO2@MIL-101(Cr), which synthesis is based on the metal-organic framework MIL-101(Cr) and the silica support Chromosorb W. The obtained surface-layer sorbent was analyzed by powder X-ray diffraction analysis, Raman spectroscopy and porosity measurement. The retention regularities and the thermodynamic characteristics of the sorption of volatile organic compounds from the gas phase were studied for the packed column with the surface-layer sorbent SiO2@MIL-101(Cr). The results indicated that the adsorbent-adsorbate interaction in the mesoporous structure of SiO2@MIL-101(Cr) depends not only on the dispersion attractive forces but also on π-π-stacking and specific interactions with hydroxyl groups and metal cations’ open coordination sites on the pore surface. In this work, we gave examples of gas chromatograms of isomers of alkanes, arenes, and chlorine derivatives of methane on a packed column with the obtained sorbent. Examples of gas chromatograms of isomers of alkanes, arenes, and chlorine derivatives of methane on a packed column with the obtained sorbent are presented.

Nanoporous-Crystalline Poly(2,6-dimethyl-1,4-phenylene)oxide Aerogels with Selectively Sulfonated Amorphous Phase for Fast VOC Sorption from Water.

This paper describes the preparation and characterization of poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) highly porous monolithic aerogels with a hydrophobic nanoporous–crystalline phase and a hydrophilic sulfonated amorphous phase. The sulfonated aerogels were obtained by the sulfonation of PPO physical gels, followed by the supercritical CO2 extraction of solvents. WAXD and FTIR analysis showed that the nanoporous–crystalline phase was preserved for a degree of sulfonation up to c.a. 35%, allowing a highly volatile organic compound (VOC) sorption capacity. The sulfonated PPO aerogels exhibited a high water sorption capacity, with a water uptake of up to 500 wt%, and faster VOC sorption kinetics from water with respect to unsulfonated aerogels.

Adsorption of trichloroethylene on common indoor materials studied using a combined inverse gas chromatography and frequency response technique

Building materials can act as sinks and sources of volatile organic compounds (VOCs) which are indoor air contaminants. A knowledge of the dynamics of VOC sorption processes on building materials is needed in order to fully understand how these compounds can influence indoor air quality, and thus, their potential for influencing human health. In the current work, a combination of classical inverse gas chromatography (IGC) and frequency response (FR) technique was used to investigate the sorptive partition and diffusion coefficients of trichloroethylene (TCE) on building materials. This is a compound of considerable interest in many indoor air environments, particularly those impacted by vapor intrusion processes, and the TCE also serves as a model VOC for demonstrating the method. Six typical indoor materials (carpet, cotton, cinderblock, printer paper, polyethylene, drywall) were selected to demonstrate the technique. A selected building material was packed into a stainless-steel column and exposed to a low-concentration TCE flow applied in a sinusoidal temporal pattern at room temperature (22 ℃). In this case, cinderblock showed the highest sorption uptakes (6209 ng TCE/g material-ppbv TCE) and the slowest sorption rates (7.3 × 10−10 m2/s) among tested materials. The results from the FR-IGC method are compared to other conventionally obtained results and agree well.

Microwave biochars produced with activated carbon catalyst: Characterization and sorption of volatile organic compounds (VOCs)

A series of microwave biochars derived from wheat straw in the presence of a granulated activated carbon (GAC) catalyst, using a range of microwave conditions, were produced, characterized and tested as sorbents of three benzene series volatile organic compounds (VOCs). The microwave biochar with the greatest specific surface area (SSA), total pore volume (TPV), and micropore volume (312.62 m2 g−1, 0.2218 cm3 g−1, and 0.1380 cm3 g−1, respectively), were produced with 1:3 biomass:GAC catalyst mass ratio, 10 min microwave irradiation time, and at 500 W power level (WB500). Maximum adsorption capacities of WB500 to benzene, toluene and o-xylene were 53.9 mg g−1, 75.8 mg g−1 and 63.0 mg g−1, respectively, and were directly correlated to microwave biochar properties such as SSA, TPV or micropore volume, but were also influenced by VOC properties such as molecular polarity and boiling point. Kinetic modeling suggested that adsorption was governed by both physical partitioning and chemisorption mechanisms. In addition, microwave biochars maintained 79% to 92% of their initial adsorption capacity after ten adsorption/desorption cycles. These results suggest that microwave biochars produced with an GAC catalyst have excellent potential for efficient use in the removal of VOCs from waste gas.

MIL-100(Fe)/Diatomite Composite with Hierarchical Porous Structure for Sorption of Volatile Organic Compounds

MIL-100(Fe)/Diatomite Composite with Hierarchical Porous Structure for Sorption of Volatile Organic Compounds

Application of carbon monolith based on exfoliated graphite for sorption and subsequent chromatographic determination of volatile organic compounds in soil air

The possibility of using a new graphene-based carbon monolith for searching new oil deposits or branches adjacent to the already registered oilfields by areal geochemical survey is demonstrated. The material has been developed at the Faculty of Chemistry of M. V. Lomonosov Moscow State University. Sorption of volatile organic compounds (VOCs) from soil air at the oilfield was carried out using two sorbents (carbon adsorbent and Tenax-TA traditionally used for such analyses) with subsequent determination by gas chromatography with mass spectrometric detection and thermal desorption as a way of sample injection (TD/GC/MS). The new material absorbs more hydrocarbons (n-alkanes and monoaromatics) in the range from C8 to C16 than Tenax-TA, the intensities of the chromatographic peaks of the compounds also being higher. The phenomenon of irreversible sorption from carbon materials is observed for VOCs from C17 and more. However, the concentration of such substances in the soil air is rather low due to the low pressure of saturated vapors of these compounds under normal conditions. Hence, the chromatogram of carbon monolith reflects the macro-characteristics of this oil deposit better than Tenax-TA. To increase the sensitivity of the determination, a preliminary optimization of thermal desorption conditions was carried out. The values of the helium flow rate through the sorbent sample and the desorption time of the compounds are chosen to get the largest peak area. The regeneration of sorbent samples is carried out to provide the possibility of their reusage. Tenax-TA decomposes at lower temperatures compared to carbon sorbent and thus cannot be purified completely unlike the new monolith. The graphene-based sorbent is reusable and much cheaper in the manufacture than imported polymer Tenax-TA since it is made of domestic materials.

Competitive adsorption of multicomponent volatile organic compounds on biochar

Crude oil contaminated lands are recognised to have significant contributions to airborne volatile organic compounds (VOCs) with adverse effects on human health and tropospheric ozone. Soil capping systems for controlling harmful emissions are critical engineering solutions where advanced soil remediation techniques are neither available nor feasible. Studies on the adsorption of single VOC species in biochar have shown promising results as a potential capping material; however, current understanding of mixed gas system and multi-component adsorption of VOCs on biochar which would represent more realistic in situ conditions is very limited. We present, for the first time, the results of a study on competitive adsorption of mixed VOCs, including aromatic and non-aromatic VOCs commonly emitted from crude oil contaminated sites on two types of biochar pyrolysed at 500°C from wheat straw and bagasse as feedstock. The kinetics of sorption of multicomponent VOCs including acetone, hexane, toluene and p-xylene in biochar are studied based on the results of an extensive experimental investigation using a bespoke laboratory setup. Both biochar types used in this study presented a high sorption capacity for VOC compounds when tested individually (51–110 mg/g). For the multicomponent mixture, the competition for occupying sorption sites on biochar surface resulted in a lower absolute sorption capacity for each species, however, the overall sorption capacity of biochar remained more or less similar to that observed in the single gas experiments (50–109 mg/g). The chemical interactions via hydrogen bonds, electrostatic attraction, and pore-filling were found to be the main mechanisms of adsorption of VOC in the biochar studied. The efficiency of biochar regeneration was assessed through five cycles of adsorption-desorption tests and was found to be between 88% and 96%. The incomplete desorption observed confirm the formation of likely permanent bonds and heel build-ups during the sorption process.

Gas Chromatographic Study of a Composite Sorbent Based on Metal-Organic Framework MIL-53(Al)

The retention regularities and the thermodynamic characteristics of the sorption of volatile organic compounds from the gas phase were studied for the chromatography columns packed with composite sorbents based on the MIL-53(Al) metal-organic framework and polydiphenyldimethylsiloxane (PPMS). It was shown that with an increase in the content of MIL-53(Al) in the binary sorbent to 73 wt %, retention is predominantly associated with adsorption in the microporous structure of MIL-53(Al) rather than dissolution in the PFMS film. It has been shown that the adsorbate–adsorbent interaction in the orthorhombic channels of MIL-53(Al) depends to a greater extent on the dispersion attractive forces than the dipole–dipole and specific interactions.

The Application of Essential Oil Vapors at the End of Vacuum Cooling of Fresh Culinary Herbs Promotes Aromatic Recovery.

Aroma is an important quality parameter of fresh culinary herbs that may be highly affected after postharvest treatments. The innovative technology of vapor essential oil (EO) application under vacuum conditions may recover aroma lost during the postharvest processing of plant products like aromatic herbs. Hence, this study assessed the aroma recovery effect of vapor EOs applied during vacuum cooling on curly parsley and dill. The volatile organic compounds (VOCs) profiles of these aromatic herbs were studied by static headspace solid-phase microextraction (SPME), and the VOCs sorption kinetics onto the SPME stir-bar coating were modeled by the Baranyi model. At the pilot plant scale, the total VOCs contents of parsley and dill (whose extractability was increased by 10–20% after a single vacuum process) were enhanced by 4.5- and 2-fold, respectively, when vapor EOs were applied. In particular, 1,3,8-p-menthatriene and carvone (parsley) increased by 18.7- and 7.3-fold, respectively, while dill ether (the characteristic VOC of dill) augmented by 2.4-fold after vapor EOs were applied under vacuum conditions. The aroma recovery of culinary herbs was successfully validated at an industrial level in an installation developed by our group to apply vapor EOs within a vacuum cooling system, reaching total VOC recoveries of 4.9- and 2.3-fold in parsley and dill, respectively.

Superior Monitoring of Chemical Exposure Using Nanoconfinement Technology.

Military personnel are exposed to a broad range of potentially toxic compounds that can affect their health. These hazards are unpredictable because military service occurs in a wide array of uncontrolled environments. Therefore, a novel sorbent was developed that allows the fabrication of lightweight personal samplers that are both capable of sorbing an extremely wide range of organic chemical types and able to stabilize reactive compounds. OSU-6, a nanoporous silica, was provided by XploSafe LLC. The sorption capacity for several volatile organic compounds, the temperatures required for thermal desorption of adsorbed compounds, and the sampling rates for targeted analytes were determined. The uptake capacity was found to be on average 1.5 g/g of sorbent. Analytes were not only held tightly but also could be desorbed upon heating the sorbate to temperatures below 150°C. Sampling rates for volatile organic compound by an OSU-6 sampler badge were on average, 5.7 times higher than those for a commercially available activated carbon badge. Theoretical calculations showed that sorption of volatile organic compounds on the surface of the tightly curved pore walls in OSU-6 is because of exceptionally strong cumulative addition of Van der Waals forces. Analytes could readily be analyzed by either solvent extraction or thermal desorption gas chromatography/mass spectrometry techniques. Excellent sampling rates, high concentrations of analytes in the OSU-6 sorbent matrix, and high desorption efficiencies (recoveries) were obtained using the thermal desorption method. The performance of the OSU-6 sorbent makes it highly capable of meeting the need for personal samplers that enable Individual Longitudinal Exposure Records development. It can adsorb an extremely wide array of different volatile organic compounds, it can stabilize reactive compounds, it has high sampling rates coupled with high capacity that provide both sensitivity and resistance to saturation, and it is unique in being very amenable to thermal desorption in combination with having strong sorbate binding and high capacity and surface area.

Use of biochar for the sorption of volatile organic compounds (VOCs) emitted from cattle manure.

The ability of biochar to be used as filter or as additive for the adsorption of volatile organic compounds (VOCs) emitted from cattle manure is investigated. The employed biochar was produced from cattle manure after slow pyrolysis at 550 °C (under nitrogen). Towards this, in-house-made glass emission reactors were filled with fresh cattle manure samples and a thin layer of biochar (10% w/w) was placed on the top of the manure layer. The mixture was left for 24 h to equilibrate and air samples were collected from the headspace air. The samples were then analyzed using the headspace solid-phase micro-extraction gas chromatography-mass spectrometry (HS-SPME-GC-MS) method. Cattle manure emissions are considered unpleasant and odoriferous. The respective changes in the emitted cattle manure VOCs were reported; these included mainly reduction in sulfur- (thiols and sulfides) and oxygen-containing VOCs (alcohols, ketones, phenolics), showing a promising application of biochar for the removal of such compounds from manure wastes. Also, five VOCs were selected as sorbents for further laboratory studies: hexane, dimethyl trisulfide, phenol, p-cresol, and 2-methyl-3-pentanone. The results of cattle manure-derived biochar, revealed a reduction in their emitted concentrations (low ppbv). The present application highlights a straightforward example of cyclic economy, where a waste product is reused after being processed; its re-usage as odor adsorbent serves again the agriculture sector.

Sorption of volatile organic compounds on non-activated biochar

This work dealt with the determination of the suitability of sorption of Volatile Organic Compounds (VOCs) on biochars prepared from neem, sugarcane and bamboo feedstocks. Six different VOCs namely benzene, toluene, methyl chloride, xylene, chloroform and carbon tetrachloride were used in a laboratory-scale set-up on non-activated biochars prepared via slow pyrolysis (350–550 °C). Although all the chars showed considerable sorption but amongst them N3 (neem-based biochar) showed the maximum removal efficiency (65.5 mg g−1 for toluene). Variation in pyrolysis temperature and feedstock type showed significant change in the porosity and specific surface area of the biochar, which is favorable for VOC sorption efficiency. With higher surface area and contact time, the sorption capacity of char enhanced. However, the extent of sorption capacity of biochars differed with changing VOC type. Pseudo-Second-Order model fitted well with the results obtained from VOC sorption kinetics.

Solvatochromism and Selective Sorption of Volatile Organic Solvents in Pyridylbenzoate Metal-Organic Frameworks

Using cobalt(II) as a metal centre with different solvent systems afforded the crystallization of isomorphous metal-organic frameworks {[Co(34pba)(44pba)]·DMF}n (1) and {[Co(34pba)(44pba)]·(C3H6O)}n (2) from mixed 4-(4-pyridyl)benzoate (44pba) and 3-(4-pyridyl)benzoate (34pba) ligands. Zinc(II) under the same reaction conditions that led to the formation of 1 formed an isostructural {[Zn(34pba)(44pba)]·DMF}n framework (3). Crystal structures of all three MOFs were elucidated and their thermal stabilities were determined. The frameworks of 1, 2, and 3 were activated under vacuum to form the desolvated forms 1d, 2d, and 3d, respectively. PXRD results showed that 1d and 2d were identical, consequently, 1d and 3d were then investigated for sorption of volatile organic compounds (VOCs) containing either chloro or amine moieties. Thermogravimetric analysis (TGA) and nuclear magnetic resonance (NMR) were used to determine the sorption capacity and selectivity for the VOCs. Some sorption products of 1d with amines became amorphous, but the crystalline framework could be recovered on desorption of the amines. Investigation of the sorption of water (H2O) and ammonia (NH3) in 1d gave rise to new phases identifiable by means of a colour change (solvatochromism). The kinetics of desorption of DMF, water and ammonia from frameworks 1d and 3d were studied using non-isothermal TGA. Activation energies for both cobalt(II) and zinc(II) frameworks are in the order NH3 &lt; H2O &lt; DMF, with values for the 1d analogue always higher than those for 3d.

Impact of material emissions and sorption of volatile organic compounds on indoor air quality in a low energy building: Field measurements and modeling.

The assessment of VOC emission rates and sorption coefficients was performed for ten surfaces present within a classroom, using field and laboratory emission cells (FLEC) coupled to online and off-line VOC quantification techniques. A total of 21 identified VOCs were emitted by the different surfaces. VOC emission rates measured using PTR-ToF-MS were compared to gas chromatographic measurements. The results showed that the two methods are complementary to one another. Sorption parameters were also successfully measured for a mixture of 14 VOCs within a few hours (<17hours per surface). A study of the spatial and temporal variability of the measured parameters was also carried out on the two surfaces that presented the most potential for interaction with VOCs, accounting for the largest surface areas within the room. The dataset of emission rates and sorption parameters was used in the INCA-Indoor model to predict indoor air concentrations of VOCs that are compared to experimental values measured in the room. Modeling results showed that sorption processes had a limited effect on indoor concentrations of VOCs for these field campaigns. Modeled daily profiles show good agreement with the experimental observations for VOCs such as toluene (indoor source) and xylenes (outdoor source) but underestimate concentrations of methanol (both indoor and outdoor sources).