Phosphate Capture Enhancement Using Designed Iron Oxide-Based Nanostructures.

Phosphates in high concentrations are harmful pollutants for the environment, and new and cheap solutions are currently needed for phosphate removal from polluted liquid media. Iron oxide nanoparticles show a promising capacity for removing phosphates from polluted media and can be easily separated from polluted media under an external magnetic field. However, they have to display a high surface area allowing high removal pollutant capacity while preserving their magnetic properties. In that context, the reproducible synthesis of magnetic iron oxide raspberry-shaped nanostructures (RSNs) by a modified polyol solvothermal method has been optimized, and the conditions to dope the latter with cobalt, zinc, and aluminum to improve the phosphate adsorption have been determined. These RSNs consist of oriented aggregates of iron oxide nanocrystals, providing a very high saturation magnetization and a superparamagnetic behavior that favor colloidal stability. Finally, the adsorption of phosphates as a function of pH, time, and phosphate concentration has been studied. The undoped and especially aluminum-doped RSNs were demonstrated to be very effective phosphate adsorbents, and they can be extracted from the media by applying a magnet.

Experimental Validation of a Novel Generator of Gas Mixtures Based on Axial Gas Pulses Coupled to a Micromixer.

In this work, a novel generator of gas mixtures previously numerically investigated and based on axial gas pulses coupled to a micromixer has been conceived, manufactured, and validated. Standard gaseous pollutant mixtures and pure nitrogen or pure air were introduced in a microdevice designed to generate alternating axial gas pulses which were downstream homogenized by means of a multi-stage modular micromixer. The dilution, and therefore the final pollutant concentration, was controlled by two parameters: the ratio between the times of each of the two gas pulses and the partial pressure of the pollutant(s) mixture added to the device. The gas mixture generator was coupled to an analyzer to monitor the concentration of aromatic pollutants. The response time was optimized to be lower than 2 min in accordance with the analytical instrument. The quantity of pollutants measured at the micromixer's outlet increased linearly with the expected gas concentration of 3.7-100 ppb generated by this novel microfluidic generator and fitted perfectly with those obtained by a reference gas dilution bench. At 5 ppb, the precision on the concentration generated is close to that obtained with the conventional gas mixing bench, i.e., around 10%.

Low-volume PEEK gas cell for BTEX detection using portable deep-UV absorption spectrophotometry.

Monitoring of indoor air quality by detecting individual airborne pollutant is essential for maintaining a healthy indoor environment. UV absorption spectrophotometry coupled with gas chromatography offers a reliable, self-referenced and non-destructive technique for the identification and detection of gas molecules. This paper presents a deep-UV absorption spectrophotometer coupled with a micro gas-chromatography (µGC) for the detection of benzene, toluene, ethylbenzene and xylenes (BTEX). The spectrophotometer was developed using a low-volume gas cell made of PolyEther Ether Ketone (PEEK) polymer tube, connected with a portable deep-UV LED and photomultiplier tube. The performance of the detection unit was evaluated with different concentrations of toluene (5-100 ppm) in nitrogen and a sensitivity of 107.1 µAU/ppm with a limit of detection of 1.41 ppm was obtained. The detector was incorporated into a micro gas-chromatography setup and high quality chromatograms, having all the peaks separated with good repeatability were obtained for BTEX molecules. The deep-UV absorption spectrophotometer has low-volume, low-cost, and ease of development and integration. While demonstrated for BTEX in a nitrogen carrier gas, the spectrometer has the potential to be applied to chromatographic analysis of different analytes in gas or liquid media.

Optofluidic Formaldehyde Sensing: Towards On-Chip Integration.

Formaldehyde (HCHO), a chemical compound used in the fabrication process of a broad range of household products, is present indoors as an airborne pollutant due to its high volatility caused by its low boiling point ( T = - 19 °C). Miniaturization of analytical systems towards palm-held devices has the potential to provide more efficient and more sensitive tools for real-time monitoring of this hazardous air pollutant. This work presents the initial steps and results of the prototyping process towards on-chip integration of HCHO sensing, based on the Hantzsch reaction coupled to the fluorescence optical sensing methodology. This challenge was divided into two individually addressed problems: (1) efficient airborne HCHO trapping into a microfluidic context and (2) 3,5-diacetyl-1,4-dihydrolutidine (DDL) molecular sensing in low interrogation volumes. Part (2) was addressed in this paper by proposing, fabricating, and testing a fluorescence detection system based on an ultra-low light Complementary metal-oxide-semiconductor (CMOS) image sensor. Two three-layer fluidic cell configurations (quartz-SU-8-quartz and silicon-SU-8-quartz) were tested, with both possessing a 3.5 µL interrogation volume. Finally, the CMOS-based fluorescence system proved the capability to detect an initial 10 µg/L formaldehyde concentration fully derivatized into DDL for both the quartz and silicon fluidic cells, but with a higher signal-to-noise ratio (SNR) for the silicon fluidic cell ( S N R s i l i c o n = 6.1 ) when compared to the quartz fluidic cell ( S N R q u a r t z = 4.9 ). The signal intensity enhancement in the silicon fluidic cell was mainly due to the silicon absorption coefficient at the excitation wavelength,   a ( λ a b s = 420   nm ) = 5 × 10 4   cm - 1 , which is approximately five times higher than the absorption coefficient at the fluorescence emission wavelength, a ( λ e m = 515   nm ) = 9.25 × 10 3   cm - 1 .

Gas Detection Using Portable Deep-UV Absorption Spectrophotometry: A Review.

Several gas molecules of environmental and domestic significance exhibit a strong deep-UV absorption. Therefore, a sensitive and a selective gas detector based on this unique molecular property (i.e., absorption at a specific wavelength) can be developed using deep-UV absorption spectrophotometry. UV absorption spectrometry provides a highly sensitive, reliable, self-referenced, and selective approach for gas sensing. This review article addresses the recent progress in the application of deep-UV absorption for gas sensing owing to its inherent features and tremendous potentials. Applications, advancements, and challenges related to UV emission sources, gas cells, and UV photodetectors are assessed and compared. We present the relevant theoretical aspects and challenges associated with the development of portable sensitive spectrophotometer. Finally, the applications of UV absorption spectrometry for ozone, NO2, SO2, and aromatic organic compounds during the last decades are discussed and compared. A portable UV absorption spectrophotometer can be developed by using LEDs, hollow core waveguides (HCW), and UV photodetectors (i.e., photodiodes). LED provides a portable UV emission source with low power input, low-intensity drifts, low cost, and ease of alignment. It is a quasi-chromatic UV source and covers the absorption band of molecules without optical filters for absorbance measurement of a target analyte. HCWs can be applied as a miniature gas cell for guiding UV radiation for measurement of low gas concentrations. Photodiodes, on the other hand, offer a portable UV photodetector with excellent spectral selectivity with visible rejection, minimal dark current, linearity, and resistance against UV-aging.

Development and Optimization of an Airborne Formaldehyde Microfluidic Analytical Device Based on Passive Uptake through a Microporous Tube.

This paper describes a compact microfluidic analytical device developed for the detection of low airborne formaldehyde concentrations. This microdevice was based on a three-step analysis, i.e., the passive gaseous formaldehyde uptake using a microporous membrane into an acetylacetone solution, the derivatization with acetylacetone to form 3,5-diacetyl-1,4-dihydrolutidine, and the quantification of the latter using fluorescence detection. For a rapid and easier implementation, a cylindrical geometry of the microporous element was considered to perform laboratory-controlled experiments with known formaldehyde concentrations and to establish the proof of concept. This work reports the evaluation of the uptake performance according to the microporous tube length, the liquid flow rate inside the tube, the gas flow rate outside the tube, and the gaseous formaldehyde concentration. A 10.0 cm microporous tube combined with a gas flow rate of 250 NmL/min (normal milliliters per minute) and a liquid flow rate of 17 µL/min were found to be the optimized conditions. In these experimental conditions, the fluorescence signal increased linearly with the gaseous formaldehyde concentration in the range 0-118 µg/m3, with the detection limit being estimated as 0.13 µg/m3 when considering a signal-to-noise ratio of 3.

Micro Milled Microfluidic Photoionization Detector for Volatile Organic Compounds.

Government regulations and environmental conditions are pushing the development of improved miniaturized gas analyzers for volatile organic compounds. One of the many detectors used for gas analysis is the photoionization detector (PID). This paper presents the design and characterization of a microfluidic photoionization detector (or µPID) fabricated using micro milling and electrical discharge machining techniques. This device has no glue and facilitates easy replacement of components. Two materials and fabrication techniques are proposed to produce a layer on the electrodes to protect from ultraviolet (UV) light and possible signal noise generation. Three different microchannels are tested experimentally and their results are compared. The channel with highest electrode area (31.17 mm²) and higher volume (6.47 µL) produces the highest raw signal and the corresponding estimated detection limit is 0.6 ppm for toluene without any amplification unit.

Development of a Toluene Detector Based on Deep UV Absorption Spectrophotometry Using Glass and Aluminum Capillary Tube Gas Cells with a LED Source.

A simple deep-ultraviolet (UV) absorption spectrophotometer based on ultraviolet light-emitting diode (UV LED) was developed for the detection of air-borne toluene with a good sensitivity. A fiber-coupled deep UV-LED was employed as a light source, and a spectrometer was used as a detector with a gas cell in between. 3D printed opto-fluidics connectors were designed to integrate the gas flow with UV light. Two types of hollow core waveguides (HCW) were tested as gas cells: a glass capillary tube with aluminum-coated inner walls and an aluminum capillary tube. The setup was tested for different toluene concentrations (10⁻100 ppm), and a linear relationship was observed with sensitivities of 0.20 mA·U/ppm and 0.32 mA·U/ppm for the glass and aluminum HCWs, respectively. The corresponding limits of detection were found to be 8.1 ppm and 12.4 ppm, respectively.

Design of a Novel Axial Gas Pulses Micromixer and Simulations of its Mixing Abilities via Computational Fluid Dynamics.

Following the fast development of microfluidics over the last decade, the need for methods for mixing two gases in flow at an overall flow rate ranging from 1 to 100 NmL·min-1 with programmable mixing ratios has been quickly increasing in many fields of application, especially in the calibration of analytical devices such as air pollution sensors. This work investigates numerically the mixing of pure gas pulses at flow rates in the range 1⁻100 NmL·min-1 in a newly designed multi-stage and modular micromixer composed of 4 buffer tanks of 300 µL each per stage. Results indicate that, for a 1 s pulse of pure gas (formaldehyde) followed by a 9 s pulse of pure carrier gas (air), that is a pulses ratio of 1/10, an effective mixing up to 94⁻96% can be readily obtained at the exit of the micromixer. This is achieved in less than 20 s for any flow rate ranging from 1 to 100 NmL·min-1 simply by adjusting the number of stages, 1 to 16 respectively. By using an already diluted gas bottle containing 100 ppm of a given compound in an inert gas same as the carrier gas, concentrations ranging from 10 to 90 ppm should be obtained by adjusting the pulses ratio between 1/10 and 9/10 respectively.

Sub-ppb Level Detection of BTEX Gaseous Mixtures with a Compact Prototype GC Equipped with a Preconcentration Unit.

In this work, a compact gas chromatograph prototype for near real-time benzene, toluene, ethylbenzene and xylenes (BTEX) detection at sub-ppb levels has been developed. The system is composed of an aluminium preconcentrator (PC) filled with Basolite C300, a 20 m long Rxi-624 capillary column and a photoionization detector. The performance of the device has been evaluated in terms of adsorption capacity, linearity and sensitivity. Initially, PC breakthrough time for an equimolar 1 ppm BTEX mixture has been determined showing a remarkable capacity of the adsorbent to quantitatively trap BTEX even at high concentrations. Then, a highly linear relationship between sample volume and peak area has been obtained for all compounds by injecting 100-ppb samples with volumes ranging from 5⁻80 mL. Linear plots were also observed when calibration was conducted in the range 0⁻100 ppb using a 20 mL sampling volume implying a total analysis time of 19 min. Corresponding detection limits of 0.20, 0.26, 0.49, 0.80 and 1.70 ppb have been determined for benzene, toluene, ethylbenzene, m/p-xylenes and o-xylene, respectively. These experimental results highlight the potential applications of our device to monitor indoor or outdoor air quality.

On-line gaseous formaldehyde detection by a microfluidic analytical method based on simultaneous uptake and derivatization in a temperature controlled annular flow.

This paper is focused on the improvement of a microfluidic analytical method for the detection of low airborne formaldehyde concentrations, based on only two distinct steps permitting to reduce the response time and to improve the compactness of the device. First, gaseous formaldehyde is trapped into an acetylacetone solution at 65°C through an annular liquid/gas flow and reacts immediately to form 3,5-Diacetyl-1,4-dihydrolutidine which is then quantified by colorimetry using a liquid core waveguide (LCW). To obtain an annular flow, 3 different hydrophilic silica capillaries of 320, 450 and 530µm ID were tested and the corresponding phase diagrams were obtained in the ranges of liquid and gas flows of 5-35µLmin-1 and 5-35mLmin-1 respectively. Finally, the analytical performances were determined using the lowest flow values of 5µLmin-1 and 5NmLmin-1, ensuring an annular flow and increasing the microdevice autonomy. If the uptake yield of gaseous formaldehyde into the solution was close to 100%, only the 530µm ID capillary permits to obtain a reaction time long enough for a full conversion of formaldehyde into 3,5-Diacetyl-1,4-dihydrolutidine. With a LCW pathlength of 5cm, the microdevice response was perfectly linear in the range 0-154µgm-3 with a detection limit of 1.8µgm-3.

Data on comparison between FLEC and CLIMPAQ methods used for fast sorption measurements of VOCs on building materials.

A test emission chamber called CLIMPAQ has been coupled to a chromatography analyzer GC to measure volatile organic compounds (VOC) concentration during a sorption experiments (Fast sorption measurements of VOCs on building materials: Part 2 - Comparison between FLEC and CLIMPAQ methods, (Rizk et al., In press) [1]). The equations used to calculate the mass transfer coefficient and the thickness of the boundary layer developed on the surface of a material are presented. In addition, the experimental profiles obtained using the CLIMPAQ chamber is also presented in the presence and the absence of a building material. Finally, the impact of chamber size on the obtained concentration profile using different chambers is shown using 3 types of chambers having different volumes, 1 m(3), 30 m(3) and a micro chamber of 40 mL.

Photoinduced proton transfer promoted by peripheral subunits for some Hantzsch esters.

It is noted that, for a small series of 3,5-diacetyl-1,4-dihydrolutidine (DDL) derivatives and the corresponding Hantzsch esters, the presence of methyl groups at the 2,6-positions serves to extinguish fluorescence in solution but not in the solid state. Emission is weakly activated and affected by changes in solvent polarity. The latter situation arises because the optical transition involves intramolecular charge transfer. Calculations, both semiempirical and DFT, indicate that, in all cases, rotation of the carbonyl function is facile and that the dihydropyridine ring is planar. These calculations also indicate that the 2,6-methyl groups do not affect the generic structure of the molecule. It is proposed that illumination increases the molecular dipole moment and pushes electron density toward the carbonyl oxygen atom. Proton transfer can now occur from one of the methyl groups, leading to formation of a relatively low-energy, neutral intermediate, followed by a second proton transfer step that forms the enol. Reaction profiles computed for the ground-state species indicate that this route is highly favored relative to hydrogen transfer from the 4-position. The barriers for light-induced proton transfer are greatly reduced relative to the ground-state process but such large-scale structural transformations are hindered in the solid state. A rigid analogue that cannot form an enol is highly emissive in solution, supporting the conclusion that proton transfer is in competition to fluorescence in solution.

An analytical method coupling accelerated solvent extraction and HPLC-fluorescence for the quantification of particle-bound PAHs in indoor air sampled with a 3-stages cascade impactor.

Most of Polycyclic Aromatic Hydrocarbons (PAHs) are associated to airborne particles and their health impact depends on the particle size where they are bound. This work aims to develop a high sensitive analytical technique to quantify particulate PAHs sampled with a 3-stages cascade impactor in order to derive simultaneously their individual concentration in PM1, PM2.5 and PM10. Three key steps of the method were evaluated separately in order to avoid any PAHs loss during the global sample preparation procedure: (1) the accelerated solvent extraction of PAHs from the filter; (2) the primary concentration of the extract until 1 mL by means of a rotary evaporator at 45°C and 220 mbar and (3) the final concentration of the pre-concentrated extract to about 100-150 µL under a gentle nitrogen stream. Each recovery experiment was realized in triplicates. All these steps evaluated independently show that the overall PAHs loss, even for those with a low molecular weight, should not exceed more than a few percent. Extracts were then analyzed by using a HPLC coupled to fluorescence and Diode Array Detectors with the external standard method. The resulting calibration curves containing between 9 and 12 points were plotted in the concentration range of 0.05-45 µg L(-1) for most of the 16 US-EPA priority PAHs and were fully linear (R(2)>0.999). Limits Of Quantification were in the range 0.05-0.47 µg L(-1) corresponding to 0.75-7.05 pg m(-3) for 20 m(3) of pumped air. Finally, taking into account the average PAHs concentrations previously reported in typical European indoor environments, and considering the use of a 3-stages cascade impactor to collect simultaneously PM>10 µm, 2.5 µm

Particle-bound PAHs quantification using a 3-stages cascade impactor in French indoor environments.

Cascade Impactor is a powerful sampling method to collect airborne particles as a function of their size. The 3-stages Cascade Impactor used in this study allowed to sample simultaneously particles with aerodynamic diameter Dae>10 µm, 2.5 µm

A dynamic system for single and repeated exposure of airway epithelial cells to gaseous pollutants.

In vitro models are promising approaches to investigate the adverse effects and the mode of action of air pollutants on the respiratory tract. We designed a dynamic system that allows the single or repeated exposure of cultured cells to two major indoor air gaseous pollutants, formaldehyde (HCHO) and nitrogen dioxide (NO2), alone or as a mixture. In this system, the Calu-3 human bronchial epithelial cell line was exposed at the air-liquid interface (ALI) or submerged by culture medium to synthetic air or to target concentrations of HCHO and/or NO2 once or on 4 consecutive days before assessment of cell viability and necrosis, IL-6 and IL-8 release and trans-epithelial electrical resistance. Our data showed that whereas the ALI method can be used for single short-term exposures only, the submerged method provides the possibility to expose Calu-3 cells in a repeated manner. As well, we found that repeated exposures of the cells to HCHO and NO2 at concentrations that can be found indoors triggered a significant decrease in cell metabolism and an increase in IL-8 release that were not evoked by a single exposure. Thus, our work highlights the fact that the development of systems and methods that allow repeated exposures of cultured cells to gaseous compounds in mixtures is of major interest to evaluate the impact of air pollution on the respiratory tract.

Adsorption of hydroxyacetone on pure ice surfaces.

The adsorption of hydroxyacetone molecules at the surface of ice is investigated by means of flow-tube reactor measurements in the temperature range: 213-253 K. The number of molecules adsorbed per surface unit is conventionally plotted as a function of the absolute gas concentration of hydroxyacetone and is compared to that previously obtained for acetone and ethanol. The enthalpy of adsorption and the monolayer capacity at the ice surface are determined. In addition, molecular dynamics simulations are performed to support the experimental results. However, it is shown that the available interaction potential between hydroxyacetone and ice is not accurate enough to allow a robust detailed analysis of the adsorption process. Finally, a rapid estimation of the hydroxyacetone partitioning between the gas phase and ice shows that in the densest ice clouds, up to 29% of hydroxyacetone could be adsorbed on pure ice surfaces at 203 K.

In-cloud multiphase behaviour of acetone in the troposphere: gas uptake, Henry's law equilibrium and aqueous phase photooxidation.

Acetone is ubiquitous in the troposphere. Several papers have focused in the past on its gas phase reactivity and its impact on tropospheric chemistry. However, acetone is also present in atmospheric water droplets where its behaviour is still relatively unknown. In this work, we present its gas/aqueous phase transfer and its aqueous phase photooxidation. The uptake coefficient of acetone on water droplets was measured between 268 and 281K (γ=0.7 x 10(-2)-1.4 x 10(-2)), using the droplet train technique coupled to a mass spectrometer. The mass accommodation coefficient α (derived from γ) was found in the range (1.0-3.0±0.25) x 10(-2). Henry's law constant of acetone was directly measured between 283 and 298K using a dynamic equilibrium system (H((298K))=(29±5)Matm(-1)), with the Van't Hoff expression lnH(T)=(5100±1100)/T-(13.4±3.9). A recommended value of H was suggested according to comparison with literature. The OH-oxidation of acetone in the aqueous phase was carried out at 298K, under two different pH conditions: at pH=2, and under unbuffered conditions. In both cases, the formation of methylglyoxal, formaldehyde, hydroxyacetone, acetic acid/acetate and formic acid/formate was observed. The formation of small amounts of four hydroperoxides was also detected, and one of them was identified as peroxyacetic acid. A drastic effect of pH was observed on the yields of formaldehyde, one hydroperoxide, and, (to a lesser extent) acetic acid/acetate. Based on the experimental observations, a chemical mechanism of OH-oxidation of acetone in the aqueous phase was proposed and discussed. Atmospheric implications of these findings were finally discussed.

Adsorption of benzaldehyde at the surface of ice, studied by experimental method and computer simulation.

Adsorption study of benzaldehyde on ice surfaces is performed by combining experimental and theoretical approaches. The experiments are conducted over the temperature range 233-253 K using a coated wall flow tube coupled to a mass spectrometric detector. Besides the experimental way, the adsorption isotherm is also determined by performing a set of grand canonical Monte Carlo simulations at 233 K. The experimental and calculated adsorption isotherms show a very good agreement within the corresponding errors. Besides, both experimental and theoretical studies permit us to derive the enthalpy of adsorption of benzaldehyde on ice surfaces DeltaH(ads), which are in excellent agreement: DeltaH(ads) = -61.4 +/- 9.7 kJ/mol (experimental) and DeltaH(ads) = -59.4 +/- 5.1 kJ/mol (simulation). The obtained results indicate a much stronger ability of benzaldehyde of being adsorbed at the surface of ice than that of small aliphatic aldehydes, such as formaldehyde or acetaldehyde. At low surface coverages the adsorbed molecules exclusively lie parallel with the ice surface. With increasing surface coverage, however, the increasing competition of the adsorbed molecules for the surface area to be occupied leads to the appearance of two different perpendicular orientations relative to the surface. In the first orientation, the benzaldehyde molecule turns its aldehyde group toward the ice phase, and, similarly to the molecules in the lying orientation, forms a hydrogen bond with a surface water molecule. In the other perpendicular orientation the aldehyde group turns to the vapor phase, and its O atom interacts with the delocalized pi system of the benzene ring of a nearby lying benzaldehyde molecule of the second molecular layer. In accordance with this observed scenario, the saturated adsorption layer, being stable in a roughly 1 kJ/mol broad range of chemical potentials, contains, besides the first molecular layer, also traces of the second molecular layer of adsorbed benzaldehyde.

Tropospheric multiphase chemistry of 2,5- and 2,6-dimethylphenols: determination of the mass accommodation coefficients and the Henry's law constants.

The uptake of 2,5-dimethylphenol and 2,6-dimethylphenol on aqueous surfaces was measured between 279 and 293 K, using the wetted-wall flow tube technique coupled with UV absorption spectroscopic detection. For both compounds, the uptake coefficients gamma were found to be independent of the KOH scavenger concentration in the range of 0.01 to 1 M (pH > pK(a)) and of the liquid-gas contact times. In addition, the uptake coefficients and the derived mass accommodation coefficients alpha show a negative temperature dependence in the investigated temperature range. The mass accommodation coefficients decrease from 1.1 x 10(-3) to 1.1 x 10(-4), and from 5.4 x 10(-4) to 6.4 x 10(-5) for 2,5-dimethylphenol and 2,6-dimethylphenol, respectively. These results are used to discuss the incorporation of these species into the liquid using the nucleation theory. Henry's law constants (HLC) of both compounds were directly measured using a dynamic equilibrium system based on the water/air equilibrium at the interface within the length of a microporous tube. The measurements were conducted over the range 278-293 K in both deionized water and 35 g L(-1) solution of NaCl. At 293 K and in pure water, HLC were found to be equal to (in units of M atm(-1)): 2,5-dimethylphenol, HLC = (1270 +/- 240); 2,6-dimethylphenol, HLC = (250 +/- 80). All of the values for HLC in 35 g L(-1) salt solution were 5-55% lower than the corresponding values in deionized water, depending on the compound and the temperature. These data (mass accommodation coefficients and Henry's law constants) were then used to estimate the partitioning of these phenolic compounds between gaseous and aqueous phases and the corresponding atmospheric lifetimes under clear sky (tau(gas)) and cloudy conditions (tau(multiphase)) have then been derived. The calculated multiphase lifetimes (in units of hours) are lower than those in gas phase at a cumulus temperature of 283 K (in parentheses): 2,5-dimethylphenol, 2.2 (3.5); 2,6-dimethylphenol, 3.8 (4.2).