New Carvone-Based Deep Eutectic Solvents for Siloxanes Capture from Biogas.

During biogas combustion, siloxanes form deposits of SiO2 on engine components, thus shortening the lifespan of the installation. Therefore, the development of new methods for the purification of biogas is receiving increasing attention. One of the most effective methods is physical absorption with the use of appropriate solvents. According to the principles of green engineering, solvents should be biodegradable, non-toxic, and have a high absorption capacity. Deep eutectic solvents (DES) possess such characteristics. In the literature, due to the very large number of DES combinations, conductor-like screening models for real solvents (COSMO-RS), based on the comparison of siloxane activity coefficient of 90 DESs of various types, were studied. DESs, which have the highest affinity to siloxanes, were synthesized. The most important physicochemical properties of DESs were carefully studied. In order to explain of the mechanism of DES formation, and the interaction between DES and siloxanes, the theoretical studies based on σ-profiles, and experimental studies including the 1H NMR, 13C NMR, and FT-IR spectra, were applied. The obtained results indicated that the new DESs, which were composed of carvone and carboxylic acids, were characterized by the highest affinity to siloxanes. It was shown that the hydrogen bonds between the active ketone group (=O) and the carboxyl group (-COOH) determined the formation of stable DESs with a melting point much lower than those of the individual components. On the other hand, non-bonded interactions mainly determined the effective capture of siloxanes with DES.

The elimination of siloxanes from the biogas of a wastewater treatment plant by means of an adsorption process.

Siloxanes present in the biogas produced during anaerobic digestion in wastewater treatment plants (WWTPs) can damage the mechanism of cogeneration heat engines and obstruct the process of energy valorization. The objective of this research is to detect the presence of siloxanes in the biogas and evaluate a procedure for their elimination. A breakthrough curve of a synthetic decamethylcyclopentasiloxane on an experimental bed of activated carbon was modeled and the theoretical mathematical model of the adsorption process was adjusted. As a result, the constants of the model were obtained: the mass transfer constant, Henry's equilibrium constant, and the Eddy diffusion. The procedure developed allows the adsorption equilibrium of siloxanes on activated carbon to be predicted, and makes it possible to lay the basis for the design of an appropriate activated carbon module for the elimination of siloxanes in a WWTP.

Volatile methylsiloxanes in personal care products - Using QuEChERS as a "green" analytical approach.

Organosiloxanes, namely volatile methylsiloxanes (VMSs) are one of the most relevant classes of ingredients incorporated in personal care products (PCPs), such as creams and lotions, bath soaps and hair care products. Their use has caused concern among the scientific community due to their potential toxic behaviour to human health and environment. This manuscript reports the first application of QuEChERS ("Quick, Easy, Cheap, Effective, Rugged and Safe") extraction followed by gas chromatography - mass spectrometry analysis to determine VMSs in cosmetics and personal care products. Eight VMSs, four linear (L2-L5) and four cyclic (D3-D6) were investigated in 36 samples. The validated method was able to remove the interfering matrix components, conducting to high recovery percentages (74-104%) and low relative standard deviations (<18%). A linear behaviour was observed in the range of 0.005-2.50mgL(-1) (correlation coefficient, R(2)>0.996) and limits of detection ranged from 0.17ngg(-1) (L2) to 3.75ngg(-1) (L5). Matrix effects were also investigated for all analysed compounds and matrices and showed not to be significant. Global uncertainty of the proposed methodology was also estimated using a bottom-up approach being between 5% and 35% (on average). Finally, the method was satisfactorily applied to the analysis of 36 personal care products. As expected, results showed the existence of VMSs in all analysed samples in concentrations up to 754µgg(-1). D4 and D5 were more frequently detected while body moisturizers, facial creams and shampoos showed the highest levels of VMSs.

Insights into siloxane removal from biogas in biotrickling filters via process mapping-based analysis.

Data process mapping using response surface methodology (RSM)-based computational techniques is performed in this study for the diagnosis of a laboratory-scale biotrickling filter applied for siloxane (i.e. octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5)) removal from biogas. A mathematical model describing the process performance (i.e. Si removal efficiency, %) was obtained as a function of key operating parameters (e.g biogas flowrate, D4 and D5 concentration). The contour plots and the response surfaces generated for the obtained objective function indicate a minimization trend in siloxane removal performance, however a maximum performance of approximately 60% Si removal efficiency was recorded. Analysis of the process mapping results provides indicators of improvement to biological system performance.

Characterization of full-scale carbon contactors for siloxane removal from biogas using online Fourier transform infrared spectroscopy.

In this study, online Fourier transform infrared (FTIR) spectroscopy has been used to generate the first comprehensive characterization of full-scale carbon contactors for siloxane removal from biogas. Using FTIR, two clear operational regions within the exhaustion cycle were evidenced: an initial period of pseudo-steady state where the outlet siloxane concentration was consistently below the proposed siloxane limits; and a second period characterized by a progressive rise in outlet siloxane concentration during and after breakthrough. Due to the sharp breakthrough front identified, existing detection methods (which comprise field sampling coupled with laboratory-based chromatographic determination) are insufficiently responsive to define breakthrough, thus carbon contactors currently remain in service while providing limited protection to the combined heat and power engine. Integration of the exhaustion cycle to breakthrough identified average specific media capacities of 8.5-21.5 gsiloxane kg(-1)GAC, which are lower than that has been reported for vapour phase granular activated carbon (GAC). Further speciation of the biogas phase identified co-separation of organic compounds (alkanes and aromatics), which will inevitably reduce siloxane capacity. However, comparison of the five full-scale contactors identified that greater media capacity was accessible through operating contactors at velocities sufficient to diminish axial dispersion effects. In addition to enabling significant insight into gas phase GAC contactors, the use of FTIR for online control of GAC for siloxane removal is also presented.

Contribution of siloxanes to COD loading at wastewater treatment plants: phase transfer, removal, and fate at different treatment units.

Cyclic volatile methylsiloxanes (cVMSs) are entering to waste stream in increasing quantities due to their increasing use in personal care products (i.e., shampoos, creams). The cVMSs have high vapor pressures and low solubilities and are mostly transferred into the gaseous phase via volatilization; however, some are sorbed onto biosolids. The purpose of this study was to track and estimate the phase transfer (water, solids, gas), fate, and contribution to COD loading of selected siloxanes (D4, D5 and D6) which are the most commonly found cVMSs in the wastewater systems. Removal efficiencies of the wastewater treatment units were evaluated based on the partitioning characteristics of the cVMSs in gas, liquid, and biosolids phases. The contributions of the siloxanes present in the influent and effluent were estimated in terms of COD levels based on the theoretical oxygen demand (ThOD) of the siloxanes. Siloxanes constitute approximately 39 and 0.001mgL(-1) of the COD in the influents and effluent. Oxidation systems showed higher removal efficiencies based COD loading in comparison to the removal efficiencies achieved aeration tanks and filtration systems. Treatment systems effectively remove the siloxanes from the aqueous phase with over 94% efficiency. About 50% of the siloxanes entering to the wastewater treatment plant accumulate in biosolids.

Biogas upgrading: optimal activated carbon properties for siloxane removal.

A total of 12 commercial activated carbons (ACs) have been tested for the removal of octamethylcyclotetrasiloxane (D4) in dynamic adsorption experiments using different carrier gases and D4 concentrations. Characterization of the ACs included several physical and chemical techniques. The D4 adsorption capacities were strongly related with the textural development of the ACs. Results showed that the optimum adsorbent for D4 is a wood-based chemically activated carbon, which rendered an adsorption capacity of 1732 ± 93 mg g(-1) using 1000 ppm (v/v) of D4 with dry N2 as the carrier gas. When the concentration of D4 was lowered to typical values found in biogas, the adsorption capacity was halved. The presence of major biogas compounds (i.e., CH4 and CO2) and humidity further reduced the D4 adsorption capacity. The polymerization of D4 over the surface of all ACs was found to be relevant after prolonged contact times. The extent of this phenomenon, which may negatively affect the thermal regeneration of the AC, correlated reasonably well with the presence of phenolic and carboxylic groups on the carbon surfaces.

Relevance of an organic solvent for absorption of siloxanes.

A wide range of siloxanes exist but the most abundant in biogas are Hexamethyldisiloxane (L2) and Octamethyltrisiloxane (L3) as linear siloxanes and Octamethylcyclotetrasiloxane (D4) as a cyclic siloxane. In order to remove volatile organic compound from biogas, different processes can be used. A promising process for siloxane removal is their absorption in an organic solvent. In this work, three oils were tested to absorb the selected siloxanes: silicone oil 47V20, Seriola 1510 and Polyalphaolefin. Initially, the characterization of these oils was realized by measuring their viscosities and densities, depending on temperature. The second time, the absorption capacity of the siloxanes by selected oils was characterized through the determination of their Henry's constants, but also owing to the implementation of a wet-wall column. Both Henry's constants and removal efficiencies in continuous regime revealed that silicone oil (47V20) can be considered as the most efficient oil among the three selected siloxanes. Moreover, the cyclic siloxane (D4) showed more affinity with oils than linear siloxanes. Silicone oil 47V20 appeared to be the best oil (intermediate price 14 euro/L, low viscosity, low volatility, chemical inertness (no corrosion) and resistance to high and low temperatures).

Siloxanes removal from biogas by high surface area adsorbents.

Biogas utilized for energy production needs to be free from organic silicon compounds, as their burning has damaging effects on turbines and engines; organic silicon compounds in the form of siloxanes can be found in biogas produced from urban wastes, due to their massive industrial use in synthetic product, such as cosmetics, detergents and paints. Siloxanes removal from biogas can be carried out by various methods (Mona, 2009; Ajhar et al., 2010 May; Schweigkofler and Niessner, 2001); aim of the present work is to find a single practical and economic way to drastically and simultaneously reduce both the hydrogen sulphide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleone et al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing the most volatile siloxane (hexamethyldisiloxane or L2) in a nitrogen stream, typically 100-200 ppm L2 over N2, through an activated carbon powder bed; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best activated carbon shows an adsorption capacity of 0.1g L2 per gram of carbon. The next thermogravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests. The capacity results depend on L2 concentration. A regenerative carbon process is then carried out by heating the carbon bed up to 200 °C and flushing out the adsorbed L2 samples in a nitrogen stream in a three step heating procedure up to 200 °C. The adsorption capacity is observed to degrade after cycling the samples through several adsorption-desorption cycles.

Evaluation of adsorbents for volatile methyl siloxanes sampling based on the determination of their breakthrough volume.

Volatile methyl siloxanes (VMS) have been detected in many different atmospheres such as biogas, sewage sludge, landfill gas, gasoline and ambient air. In these different atmospheres, their presence can involve several contamination problems and negative effects in industrial processes, their identification and quantification become a real challenge. Up to now there is no standardized procedure for VMS quantification, the sampling step remaining the major obstacle. Sampling gas through sorbent tube followed by analysis on TD-GC-MS is one of the reliable possibilities. It gathers sampling and preconcentration in one step and allows discrimination between all VMS, despite the difficulty to choose the appropriate adsorbent in order to avoid loss of analytes during sampling. In this context, this work deals with the comparison of different types of adsorbents based on the determination of the VMS breakthrough volume (BV). Although Tenax TA is the most widely used adsorbent, experiments show low BV values for the lightest VMS. At 25°C, the BV of TMS and L2 are, respectively, 0.2 and 0.44 L g(-1) which can contribute to an underestimation in concentration during their quantification. Carbosieve SIII usually used for C2-C5, did not adsorb light VMS as it was expected, and breakthrough volume obtained for VMS are more than ten times less than the values obtained for Tenax. On other hand, Chromosorb 106 and Carboxen 1000 in association with Carbotrap C and Carbotrap proved to be appropriated for VMS sampling, due to the high breakthrough volumes obtained for the lightest compounds comparing to the other adsorbents. The BVs of TMS for Carboxen 1000 and Chromosorb 106 are 1.2 × 10(4) and 39 L g(-1), respectively, and 49 × 10(4) and 1142 L g(-1) for L2, respectively.

Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test.

Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane.

Absorption of a linear (L2) and a cyclic (D4) siloxane using different oils: application to biogas treatment.

Hydrophobic volatile methyl siloxanes (VMS), such as hexamethyldisiloxane (L2) and octamethylcyclotetrasiloxane (D4), present a low solubility in water. An alternative treatment by absorption into hydrophobic absorbents was therefore studied. For this purpose, three different absorbents, motor oil, cutting oil and a water-cutting oil mixture, were selected with the aim of re-using a waste product. The set of experiments was carried out in a bubble column, where parameters such as inlet concentration, residence time and temperature were studied. The best performance for the removal of both siloxanes, in terms of absorption capacity, was observed for motor oil, particularly for D4. In fact, motor oil removal efficiency for D 4 was 80%, whereas for L2 it was 60%, indicating that D 4 is more easily absorbed than L2. In the case of water-cutting oil, this showed a mass transfer enhancement from the gas phase to the liquid phase compared with water alone. Furthermore, a removal efficiency of 70% was observed for D 4, showing that the addition of an oil fraction to a water system improves the absorption of VMS. These results show that VMS absorption into oils could be a promising way to achieve their abatement.

Development of a liquid chromatography tandem mass spectrometry method for trace analysis of trisiloxane surfactants in the aqueous environment: an alternative strategy for quantification of ethoxylated surfactants.

Trisiloxane surfactants, often referred to as superspreaders or superwetters, are added to pesticides to enhance the activity and the rainfastness of the active substance by promoting rapid spreading over hydrophobic surfaces. To fill the lack of data on the environmental occurrence of these compounds, we have developed and validated a method for their trace analysis in the aqueous environment. The method is based on liquid-liquid extraction followed by liquid chromatography and tandem mass spectrometry. The oligomeric distribution of trisiloxane surfactant in a reference solution was determined by a theoretical calculation and by experimental measurements. Based on these results, the quantification was performed by comparison with a calibration made with a single homologue instead of a mixture of homologues. This approach avoids a time-consuming synthesis of pure homologues and reduces the risk of wrong estimation of the concentration because of different response factors of the sample and the standard. Such an approach could be applied to the quantification of other ethoxylated surfactants following a similar distribution. The validation was performed from 2 to 250 ng/L (total surfactant concentration) in deionized water, tap water, and river water (Rhine water). Knowing the oligomeric distribution of the polymer in the reference solution, the corresponding calibration ranges were estimated for individual homologues. Limits of quantification were found to be between 0.37 ng/L and 15 ng/L. The total recovery of sample preparation was between 77% and 116%. Matrix effects were lower than 10% with river water and the relative standard deviation evaluated over ten identical samples of spiked river water was below 12%.

Determination of cyclic volatile methylsiloxanes in biota with a purge and trap method.

The three cyclic volatile methylsiloxanes (cVMS), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), are recently identified environmental contaminants. Methods for the trace analysis of these chemicals in environmental matrices are required. A purge and trap method to prepare highly purified sample extracts with a low risk of sample contamination is presented. Without prior homogenization, the sample is heated in water, and the cVMS are purged from the slurry and trapped on an Isolute ENV+ cartridge. They are subsequently eluted with n-hexane and analyzed with GC/MS. The method was tested for eight different matrices including ragworms, muscle tissue from lean and lipid-rich fish, cod liver, and seal blubber. Analyte recoveries were consistent within and between matrices, averaging 79%, 68%, and 56% for D4, D5, and D6, respectively. Good control of blank levels resulted in limits of quantification of 1.5, 0.6, and 0.6 ng/g wet weight. The repeatability was 12% (D5) and 15% (D6) at concentrations 9 and 2 times above the LOQ. The method was applied to analyze cVMS in fish from Swedish lakes, demonstrating that contamination in fish as a result of long-range atmospheric transport is low as compared to contamination from local sources.

Dynamic multi-phase partitioning of decamethylcyclopentasiloxane (D5) in river water.

The behaviour of decamethylcyclopentasiloxane (D5) in river water was evaluated by measuring concentration changes in open beakers. Effective values for the partition coefficient between organic carbon and water (K(OC)) were derived by least-squares optimisation of a dynamic model which accounted for partitioning between the sorbed and dissolved phases of D5, and for losses via volatilisation and hydrolysis. Partial mass transfer coefficients for volatilisation were derived from model fits to controls containing deionised water. Effective values of log (K(OC)) were between 5.8 and 6.33 (mean 6.16). These figures are higher than some other experimentally-derived values but much lower than those estimated from the octanol: water partition coefficient using single-parameter linear free energy relationships (LFERs). A poly-parameter LFER gave a predicted log (K(OC)) of 5.5. Differences in partitioning are believed to be due to the nature of the organic matter present. The new value for effective K(OC) was employed in a simple model of D5 behaviour in rivers to ascertain the extent to which a higher affinity for organic carbon would depress volatility. The results suggest that despite the revised K(OC) value, volatilisation of D5 remains a significant removal mechanism in surface waters.

Behaviour and adsorptive removal of siloxanes in sewage sludge biogas.

We investigated the behaviour of siloxanes, which adversely affect biogas engines, as well as their concentration levels in sewage sludge biogas in Japan. We also performed experiments on the absorptive removal of siloxanes using various adsorbents and determined the main adsorbent characteristics required for the removal of siloxanes. The results of our study on the concentration and composition of siloxanes in biogas were similar to previous reports. Moreover, we found that the concentration of siloxanes changes in relation to the outside air temperature based on real-time measurements of siloxanes using a continuous analyser. We further speculated that the continuous analyser would accurately indicate the siloxane concentration in model biogas but overestimate the siloxane concentration in actual biogas because of positive interference by VOCs and other biogas components. In the siloxane adsorption experiment, the equilibrium uptake of both cyclic siloxanes, D4 and D5, was positively related to the BET-specific surface area of the adsorbents and the fraction of the external surface area taken up by relatively large diameter pores. We attributed the adsorption results to the fact that the siloxane molecules are generally larger than micropores; therefore, they are less susceptible to adsorption to micropores. Based on these results, we concluded that adsorbents with large BET-specific surface areas, especially those with a high external specific surface area and pores of relatively large diameters, are desired for the removal of siloxanes.

Optimization of solid-phase microextraction sampling for analysis of volatile compounds emitted from oestrous urine of mares.

The solid-phase microextraction (SPME) technique was applied and optimized for collection of volatile compounds emitted from oestrous urine of mares Equs cabalus L. (Perissodactyla, Equidae) for GC-MS analyses. Variables such as type of SPME fibre, collection time of volatiles, and addition of salt were optimized to improve the sampling efficiency in two aspects: extent and selectivity of absorption/adsorption of urine volatiles onto SPME fibres. The data revealed that the number of volatiles and the total amount represented as quantitative peak areas of the compounds trapped on fibres coated either with polydimethylsiloxane-divinylbenzene or with divinylbenzene-carboxen-polydimethylsiloxane were significantly higher compared to those coated with polydimethylsiloxane, polyacrylate, and carbowax-divinylbenzene. The polydimethylsiloxane-divinylbenzene-type of fibre coating was chosen for optimization of sampling time and effect of salt addition. Sampling periods lasted for 15, 30, 60, 120, and 240 min. The optimal collection time of volatiles from urine maintained at about 36 degrees C was 60 min, as the number of compounds detected with amounts sufficient for quantification did not differ significantly from those trapped during longer collection periods. No significant increase in total amount of volatiles trapped was registered after 120 min of sampling. Addition of 0.3 g NaCl to the 2-ml of samples shortened the collection period from 60 to 15 min during which almost all compounds were trapped. Addition of salt has a significant effect at all sampling periods taking into consideration the total amounts of volatiles trapped. The total intensities increased about 8, 5, 3, 3, and 2 times at collection periods of 15, 30, 60, 120, and 240 min, respectively, when compare with the ones obtained from the urine samples with no salt addition. In oestrous mare's urine, 139 +/- 4 (average number +/- standard deviation) volatile compounds suitable for quantitative analyses were detected compared to 45 compounds collected by the gas-tight syringe method.

Siloxane removal from landfill and digester gas - a technology overview.

This paper reviews technologies for the removal of volatile methyl siloxanes (VMS) from biogas. More than 20 years after identifying silicon dioxide in gas engines running on landfill and sewage gas, three technologies are commercially available to remove siloxanes today: adsorption, absorption and deep chilling. Newer concepts based on technologies other than sorption or condensation have not yet gained access to commercial biogas purification. These emerging siloxane removal concepts include biotrickling filters, catalysts, membranes, and in the case of sewage gas, sludge stripping, peroxidation and filtration at point inlet source. This work introduces the main principles of commercial siloxane removal systems and reviews scientific progress in the field over the last decade.

[Analysis of the volatile oils chemical constituents of roots of Actinidia deliciosa].

OBJECTIVE: To analyze the volatile oils chemical constituents of roots of Actinidia deliciosa. METHODS: The volatile oils fraction of roots of Actinidia deliciosa. were extracted by water vapor distilling, and then the constituents were separated and identified, by GC-MS. RESULTS: 16 compounds were identified, accounting for 89.37% of all quantity. CONCLUSION: The principal volatile oils chemical constituents are Phenol, 2,4-bis(1,1-dimethylethl)-; 2-Propenoic acid, 3-(4-methox yphenyl)-, ethyl ester; 9-Octadecenoic acid (Z)-, methyl ester; Cyclotetrasiloxane, octamethyl-.

Stability studies of stationary phases from poly(methyltetradecylsiloxane) sorbed and immobilized onto metalized and unmodified silicas.

Stationary phases for RP-HPLC were prepared from metalized (titanized and zirconized) and unmodified silica particles using sorbed and immobilized poly(methyltetradecylsiloxane) (PMTDS). Different immobilization procedures, such as gamma irradiation and thermal treatments, were used for the preparation of the immobilized PMTDS phases. The stabilities of these stationary phases were evaluated by passing alkaline (pH 10) mobile phase through 60 mm x 3.9 mm columns of the different phases, with periodic tests to evaluate chromatographic performance. The results show that higher stabilities were obtained with stationary phases based on PMTDS immobilized on zirconized silica, these phases being 50% more stable than their titanized silica counterparts and 400% more stable than those based on unmodified silica. These supports provide higher chemical stability to the laboratory-made stationary phases, when compared with chemically bonded silica-based phases.