Development of Solid Ceramic Dosimeters for the Time-Integrative Passive Sampling of Volatile Organic Compounds in Waters.

Time-integrative passive sampling of volatile organic compounds (VOCs) in water can now be accomplished using a solid ceramic dosimeter. A nonporous ceramic, which excludes the permeation of water, allowing only gas-phase diffusion of VOCs into the resin inside the dosimeter, effectively captured the VOCs. The mass accumulation of 11 VOCs linearly increased with time over a wide range of aqueous-phase concentrations (16.9 to 1100 µg L-1), and the linearity was dependent upon the Henry's constant (H). The average diffusivity of the VOCs in the solid ceramic was 1.46 × 10-10 m2 s-1 at 25 °C, which was 4 orders of magnitude lower than that in air (8.09 × 10-6 m2 s-1). This value was 60% greater than that in the water-permeable porous ceramic (0.92 × 10-10 m2 s-1), suggesting that its mass accumulation could be more effective than that of porous ceramic dosimeters. The mass accumulation of the VOCs in the solid ceramic dosimeter increased in the presence of salt (≥0.1 M) and with increasing temperature (4 to 40 °C) but varied only slightly with dissolved organic matter concentration. The solid ceramic dosimeter was suitable for the field testing and measurement of time-weighted average concentrations of VOC-contaminated waters.

Interaction Studies of Greenly Synthesized Gold Nanoparticles with Bovine Serum Albumin (BSA) Using Fluorescence Spectroscopy.

In the present study, gold nanoparticles (AuNPs) with an average particle size of -41.23 nm were synthesized using eco-friendly reducing material (i.e., aqueous Nelumbo nucifera root extract). Rapid reduction results in the formation of polydispersed nanoparticles. The formation of AuNPs was characterized by surface plasmon resonance (SPR) which was determined by UV-Vis spectra (band at 544 nm), FTIR, SEM-EDX, TEM, HR-TEM, and XRD. This study aims to investigate the interaction between AuNPs and Bovine Serum Albumin (BSA) using fluorescence spectroscopy. The analysis of fluorescence spectra and intensity at physiological pH in an aqueous solution indicates that AuNPs have a potent ability to quench the BSA fluorescence by both quenching mechanisms. Resonance light scattering spectra indicated the formation of BSA-AuNPs complex. The number of binding sites and binding constants were determined based on fluorescence quenching at different temperatures. The thermodynamic parameters were also calculated at various temperatures that indicate that hydrophobic forces are abundant in the AuNPs-BSA complex. Negative ΔG degrees values suggest that the binding process is spontaneous. Synchronous fluorescence spectra showed a blue shift and CD spectra showed an increase in a-helicity content which is an indication of increasing hydrophobicity.

Efficient ethanol production from dried oil palm trunk treated by hydrothermolysis and subsequent enzymatic hydrolysis.

BACKGROUND: Oil palm trunk (OPT) is a valuable bioresource for the biorefinery industry producing biofuels and biochemicals. It has the distinct feature of containing a large amount of starch, which, unlike cellulose, can be easily solubilized by water when heated and hydrolyzed to glucose by amylolytic enzymes without pretreatment for breaking down the biomass recalcitrance. Therefore, it is suggested as beneficial to extract most of the starch from OPT through autoclaving and subsequent amylolytic hydrolysis prior to pretreatment. However, this treatment requires high capital and operational costs, and there could be a high probability of microbial contamination during starch processing. In terms of biochemical conversion of OPT, this study aimed to develop a simple and efficient ethanol conversion process without any chemical use such as acids and bases or detoxification. RESULTS: For comparison with the proposed efficient ethanol conversion process, OPT was subjected to hydrothermal treatment at 180 °C for 30 min. After enzymatic hydrolysis of PWS, 43.5 g of glucose per 100 g dry biomass was obtained, which corresponds to 81.3 % of the theoretical glucose yield. Through subsequent alcohol fermentation, 81.4 % ethanol yield of the theoretical ethanol yield was achieved. To conduct the proposed new process, starch in OPT was converted to ethanol through enzymatic hydrolysis and subsequent fermentation prior to hydrothermal treatment, and the resulting slurry was subjected to identical processes that were applied to control. Consequently, a high-glucose yield of 96.3 % was achieved, and the resulting ethanol yield was 93.5 %. CONCLUSIONS: The proposed new process was a simple method for minimizing the loss of starch during biochemical conversion and maximizing ethanol production as well as fermentable sugars from OPT. In addition, this methodology offers the advantage of reducing operational and capital costs due to minimizing the process for ethanol production by excluding expensive processes related to detoxification prior to enzymatic hydrolysis and fermentation such as washing/conditioning and solid-liquid separation of pretreated slurry. The potential future use of xylose-digestible microorganisms could further increase the ethanol yield from the proposed process, thereby increasing its effectiveness for the conversion of OPT into biofuels and biochemicals.

Fermentative l-lactic acid production from pretreated whole slurry of oil palm trunk treated by hydrothermolysis and subsequent enzymatic hydrolysis.

A simple and cost-effective biochemical conversion process consisting of hydrothermal treatment, enzymatic hydrolysis and fermentation of pretreated whole slurry (PWS) was developed for producing l-lactic acid (L-LA) from oil palm trunk (OPT). When OPT was hydrothermally treated at optimal condition capable of achieving maximum yield of hemicellulosic sugars after enzymatic hydrolysis, the enzymatic digestibility of the PWS afforded a yield of 81.4% of the theoretical glucose yield (TGY). However, glucose yield from washed pretreated solid (WPS) was only 43.5% of TGY. The use of two hydrolysates from PWS and WPS for fermentation by Lactobacillus paracasei engineered to selectively produce L-LA afforded yields of 89.5% and 45.8% of the theoretical LA yield (TLY), respectively. This study confirmed the inevitable extensive sugar loss during washing of pretreated slurry due to loss of soluble starch. Alternatively, the proposed design process is considered suitable for converting OPT to L-LA without such starch loss.

Green synthesized silver nanoparticles using Nelumbonucifera root extract for efficient protein binding, antioxidant and cytotoxicity activities.

Silver nanoparticles (AgNPs) with a mean particle size of ∼ 16.7 nm were synthesized using an eco-friendly reducing material, aqueous Nelumbo nucifera root extract. Rapid reduction resulted in the formation of polydispersed nanoparticles. The formation of AgNPs was characterized by surface plasmon resonance, which was determined by ultraviolet-visible (UV-Vis) spectroscopy (band at 412 nm), Fourier transform infrared spectroscopy, scanning electron microscopy-energy dispersive X-ray spectroscopy, transmission electron microscopy and X-ray diffraction. The interaction of the green synthesized AgNPs with Bovine Serum Albumin (BSA) at various temperatures was investigated. Fluorescence quenching, synchronous and resonance light scattering spectroscopy along with UV-Vis absorption studies revealed the efficient binding between BSA and the AgNPs. In addition, the AgNPs exhibited moderate antioxidant and cytotoxicity activities against HeLa cell lines.

Development of syringe pump assisted headspace sampler.

This report describes a new platform for headspace sampling technique, i.e. a syringe pump assisted headspace sampler (SPHS). The stand type pump's syringe itself was used as a sealed sample vial and a needle trap device (NTD) was adopted as a miniaturized sorbent tube. The NTD was directly used to inject trapped VOCs into a gas chromatograph. The proposed sampler was designed to take a whole headspace volume instead of a portion of it so as to enhance easily the extraction efficiency. The performance of the SPHS-NTD system was evaluated and compared with the solid-phase microextraction (SPME) with a static headspace (HS) sampling technique. Calibration curves were obtained for aqueous TEX (toluene, ethylbenzene, and o-xylene) solutions in the concentration range of ∼0.1-45 ng/mL. The calculated limit of detections (LOD, S/N=3) for TEX were 0.13 ng/mL or less. This SPHS-NTD was successfully applied to analyze aqueous TEX in river water samples and showed highly good recovery ranged from 97.2% to 105.8% for all tested VOCs.

Sugar yields from sunflower stalks treated by hydrothermolysis and subsequent enzymatic hydrolysis.

To produce fermentable sugar with fewer microbial inhibitors via few processes, batch-type hydrothermal treatments of sunflower stalks were performed, followed by enzymatic hydrolysis of pretreatment slurries with Cellic CTec2 and Cellic HTec2 (9:1, v/v, 0.1 ml/g dry biomass, 8.1FPU). The yields of hemicellulosic sugars were maximized at the pretreatment condition of 180°C for 30 min, while the furfural and 5-hydroxymethyl-2-furaldehyde (HMF) concentrations remained low. The glucose yield, however, was only 67.0% of the theoretical glucose yield (TGY). Either the treatment of raw biomass prior to pretreatment or the post-treatment of pretreated residue prior to enzymatic hydrolysis increased the glucose yield as follows: washing the pretreated solid with solvents (90% TGY)>partial removal of liquid fraction from the pretreatment slurry (PS, 83%)>removal of hot-water extractives from the biomass prior to pretreatment (77%)>prewetting of the biomass (70%).

Comparison of pyrolytic products produced from inorganic-rich and demineralized rice straw (Oryza sativa L.) by fluidized bed pyrolyzer for future biorefinery approach.

The objectives of this study were to investigate the effects of inorganic constituents on the fast pyrolysis of the biomass and to determine the yields as well as physicochemical properties of pyrolytic products. The pyrolytic products were obtained from raw and demineralized rice straw using a fluidized bed type pyrolyzer at different temperatures. As pyrolysis temperature increased, total biooil yield gradually decreased from 46.6 to 29.6 wt.% for the raw-straw, and from 55.4 to 35.3 wt.% for the demineralized rice straw. For demineralized rice straw, higher pyrolysis temperatures promoted gasification reactions but reduced char formations. However, char yield for the raw-straw was relatively unaffected by temperature due to an increase in carbonization reactions that were catalyzed by some inorganics. Certain inorganic constituents in the biomass were distinctively distributed in the biooil, and ICP-ES and GC/MS analysis indicated that some inorganics may be chemically bound to cell wall components.

Characterization of pyrolytic products obtained from fast pyrolysis of chromated copper arsenate (CCA)- and alkaline copper quaternary compounds (ACQ)-treated wood biomasses.

In this study, chromated copper arsenate-treated wood (CCA-W) and alkaline copper quaternary compounds-treated wood (ACQ-W) were subjected to fast pyrolysis at 500°C for ca. 2s to produce bio-oil and char. The physicochemical properties of the pyrolytic products as well as the distribution of heavy metals - arsenic, copper and chrome - during fast pyrolysis were investigated. The water content, viscosity, pH and higher heating value (HHV) of bio-oil from CCA-W were 24.8 wt%, 13.5 cSt, 2.1 and 16 MJ/kg, respectively, whereas those of bio-oil from ACQ-W were 27.9 wt%, 16 cSt, 3.0 and 14.1 MJ/kg, respectively. The yields of bio-oil from CCA-W and ACQ-W were 43.3% and 46.6%, respectively, significantly lower than that of control (61.6%). In the pyrolytic products of CCA-W, the concentrations of arsenic, copper and chromium were determined to be 36.4 wt%, 74.0 wt% and 75.4 wt% in char, respectively, 34.5 wt%, 10.3 wt% and 9.0 wt% in bio-oil, respectively, and 29.0 wt%, 15.7 wt% and 15.5 wt% in gas, respectively. In addition, most of the copper appeared in the char (98.8 wt%) and only a trace amount of copper was detected in the bio-oil (0.2 wt%) produced by ACQ-W.

Simultaneous sampling and analysis of indoor air infested with Cimex lectularius L. (Hemiptera: Cimicidae) by solid phase microextraction, thin film microextraction and needle trap device.

Air in a room infested by Cimex lectularius L. (Hemiptera: Cimicidae) was sampled simultaneously by three different sampling devices including solid phase microextraction (SPME) fiber coatings, thin film microextraction (TFME) devices, and needle trap devices (NTDs) and then analyzed by gas chromatography-mass spectrometry (GC-MS). The main focus of this study was to fully characterize indoor air by identifying compounds extracted by three different microextraction formats and, therefore, perform both the device comparison and more complete characterization of C. lectularius pheromone. The NTD technique was capable of extracting both (E)-2-hexenal and (E)-2-octenal, which were previously identified as alarm pheromones of bedbugs, and superior NTD recoveries for these two components allowed reliable identification based on mass spectral library searching and linear temperature programmed retention index (LTPRI) technique. While the use of DVB/CAR/PDMS SPME fiber coatings provided complementary sample fingerprinting and profiling results, TFME sampling devices provided discriminative extraction coverage toward highly volatile analytes. In addition to two alarm pheromones, relative abundances of all other analytes were recorded for all three devices and aligned across all examined samples, namely, highly infested area, less infested area, and control samples which were characterized by different bedbug populations. The results presented in the current study illustrate comprehensive characterization of infested indoor air samples through the use of three different non-invasive SPME formats and identification of novel components comprising C. lectularius pheromone, therefore, promising future alternatives for use of potential synthetic pheromones for detection of infestations.

Effect of essential inorganic metals on primary thermal degradation of lignocellulosic biomass.

This study employed thermogravimetric analysis (TGA) and analytical Py-GC/MS in order to examine the catalytic effect of main inorganic metals (K, Mg and Ca) on the thermal degradation and the formation of pyrolytic products in lignocellulosic biomass. In addition, potential mechanisms of the primary pyrolysis in presence of the inorganic metals were derived. TG analysis showed that when potassium content increased in the biomass, char formation increased from 10.5 wt.% to 19.6 wt.% at 550 °C, and temperatures at which the maximum degradation rate was achieved shifted from 367 °C to 333 °C. With increasing magnesium content, the maximum degradation rate increased from 1.21 wt.%/°C to 1.43 wt.%/°C. Analytical Py-GC/MS revealed that potassium had a distinguished catalytic effect promoting the formation of low molecular weight compounds and suppressing the formation of levoglucosan. An increase in the yield of C6 and C2C6 lignin derivatives with increasing potassium content was also observed.

Structural features of lignin macromolecules extracted with ionic liquid from poplar wood.

1-Ethyl-3-methylimidazolium acetate ([Emim][CH3COO]) was used for the extraction of lignin from poplar wood (Populus albaglandulosa), which was called to ionic liquid lignin (ILL) and structural features of ILL were compared with the corresponding milled wood lignin (MWL). Yields of ILL and MWL were 5.8±0.3% and 4.4±0.4%, respectively. The maximum decomposition rate (V(M)) and temperature (T(M)) corresponding to V(M) were 0.25%/ °C and 308.2 °C for ILL and 0.30%/ °C and 381.3 °C for MWL. The amounts of functional groups (OMe and phenolic OH) appeared to be similar for both lignins; approximately 15.5% and 6.7% for ILL and 14.4% and 6.3% for MWL. However, the weight average molecular weight (M(w)) of ILL (6347 Da) was determined to be 2/3-fold of that of MWL (10,002 Da) and polydispersity index (PDI: M(w)/M(n)) suggested that the lignin fragments were more uniform in the ILL (PDI 1.62) than in the MWL (PDI 2.64).

Characterization of lignin-rich residues remaining after continuous super-critical water hydrolysis of poplar wood (Populus albaglandulosa) for conversion to fermentable sugars.

Poplar wood flour (Populous albaglandulosa) was treated with sub- and super-critical water (subcritical: 325, 350°C; super-critical: 380, 400, 425°C) for 60s at 220 ± 10 atm. Hydrochloric acid (0.05%v/v) was added to samples as acidic catalyst. The final products were separated into water soluble fraction and undegraded solids. The yields of undegraded solids were thoroughly dependent on temperature severity and mainly composed of lignin fragments. Average molecular weights of the lignins were between 1500 and 4400 Da, which was only 1/3-1/8-fold of poplar milled wood lignin (13,250 Da). DFRC (Derivatization Followed by Reductive Cleavage) analysis revealed that C6C3 phenols (coniferyl and sinapyl alcohol) were rarely detected in the lignins, indicating occurrence of two probable lignin reactions during SCW hydrolysis: lignin fragmentation via splitting of ß-O-4 linkage and loss of propane side chains. These results were also confirmed by (1)H and (13)C NMR spectroscopic analysis.

Characterization of primary thermal degradation features of lignocellulosic biomass after removal of inorganic metals by diverse solvents.

Poplar wood powders were treated with distilled water, tap water, HCl and HF, respectively, to remove inorganics from the biomass and to investigate effect of demineralization processes on pyrolysis behavior of the biomass. TG and DTG revealed that maximum degradation temperatures rose slightly from 362°C for control to 372°C, 366°C and 368°C after demineralization with distilled water, HCl and HF, respectively. Maximum degradation rates also increased from 0.96%/°C for control to 1.15%/°C for HF-biomass, 1.23%/°C for DI-H(2)O-biomass, and 1.55%/°C for HCl-biomass. Analytical pyrolysis-GC/MS of demineralized biomasses produced approximately 45 pyrolysis compounds. Total amount of low molecular weight compounds, such as acetic acid, acetol, and 3-hydroxypropanal, was significantly lowered in the demineralized biomasses. But levoglucosan increased 2-10-folds in the demineralized biomasses. One of the features regarding lignin derivatives was the reduction of the amount of C6-type phenols, such as phenol, guaiacol, and syringol after demineralization.

Sampling free and particle-bound chemicals using solid-phase microextraction and needle trap device simultaneously.

The possibility of sampling the free and particle-bound concentrations of organic compounds was studied using two different sampling techniques at the same time: needle trap device (NTD) and solid-phase microextraction (SPME). In this study, a mosquito coil was used to produce gaseous (free) and particle-bound compounds. Allethrin, the active ingredient in mosquito coils, was chosen as the target analyte. Under the same sampling conditions, the amount of allethrin extracted from the mosquito-coil smoke was higher for the NTD compared to the SPME fiber, while the extracted amounts were almost the same for both devices when sampling gaseous samples of allethrin. These results can be explained by the fact that the SPME fiber can only extract free molecules (based on diffusion), whereas the NTD, an exhaustive sampling device, collects both free and particle-bound allethrin. Breakthrough for NTD and carryover for both NTD and SPME were negligible under the given sampling and desorption conditions.

Development and application of a needle trap device for time-weighted average diffusive sampling.

A simple, cost-effective analysis combining solventless extraction, thermal desorption, and determination of volatile organic compounds (VOCs) was developed and validated. A needle trap device (NTD) packed with the sorbent Carboxen1000 was used as a time-weighted average (TWA) diffusive sampler to collect target compounds by molecular diffusion and adsorption to the packed sorbent. This process can be described with derivations of Fick's first law of diffusion, which expresses the relation between the TWA concentrations to which the passive sampler is exposed and the mass of analytes adsorbed to the packed sorbent in the sampler. The effects of experimental factors such as temperature, pressure, humidity, and face velocity were taken into account in applying diffusive sampling under nonideal conditions. This study demonstrates that NTD is effective for air analysis of benzene, toluene, ethylbenzene, and o-xylene (BTEX), due to the good adsorption/desorption quality of Carboxen 1000 and to the special geometric shape of the needle with a small cross section avoiding the need for calibration. Storage tests showed good storage stability for BTEX. Verification of the theoretical model showed good agreement between theoretical and experimental sampling rates. Method validation done against NIOSH method 1501, SPME, and NTD active sampling revealed good agreement between those methods. Automated NTD sample introduction to a gas chromatograph facilitates the use of this technology for industrial hygiene applications.

Simple sample transfer technique by internally expanded desorptive flow for needle trap devices.

Needle trap devices (NTDs) are improving in simplicity and usefulness for sampling volatile organic compounds (VOCs) since their first introduction in early 2000s. Three different sample transfer methods have been reported for NTDs to date. All methods use thermal desorption and simultaneously provide desorptive flow to transfer desorbed VOCs into a GC separation column. For NTDs having 'side holes', GC carrier gas enters a 'side hole' and passes through sorbent particles to carry desorbed VOCs, while for NTD not having a 'side hole', clean air as desorptive flow can be provided through a needle head by a air tight syringe to sweep out desorbed VOCs or water vapor has been reported recently to be used as desorptive flow. We report here a new simple sample transfer technique for NTDs, in which no side holes and an external desorptive flow are required. When an NTD enriched by a mixture of benzene, toluene, ethylbenzene, and xylene (BTEX) or n-alkane mixture (C6-C15) is exposed to the hot zone of GC injector, the expanding air above the packed sorbent transfers the desorbed compounds from the sorbent to the GC column. This internal air expansion results in clean and sharp desorption profiles for BTEX and n-alkane mixture with no carryover. The effect of desorption temperature, desorption time, and overhead volumes was studied. Decane having vapor pressure of approximately 1 Torr at 20 degrees C showed approximately 1% carryover at the moderate thermal desorption condition (0.5 min at 250 degrees C).

Development of a syringe pump assisted dynamic headspace sampling technique for needle trap device.

This paper describes a new approach that combines needle trap devices (NTDs) with a dynamic headspace sampling technique (purge and trap) using a bidirectional syringe pump. The needle trap device is a 22-G stainless steel needle 3.5-in. long packed with divinylbenzene sorbent particles. The same sized needle, without packing, was used for purging purposes. We chose an aqueous mixture of benzene, toluene, ethylbenzene, and p-xylene (BTEX) and developed a sequential purge and trap (SPNT) method, in which sampling (trapping) and purging cycles were performed sequentially by the use of syringe pump with different distribution channels. In this technique, a certain volume (1 mL) of headspace was sequentially sampled using the needle trap; afterwards, the same volume of air was purged into the solution at a high flow rate. The proposed technique showed an effective extraction compared to the continuous purge and trap technique, with a minimal dilution effect. Method evaluation was also performed by obtaining the calibration graphs for aqueous BTEX solutions in the concentration range of 1-250 ng/mL. The developed technique was compared to the headspace solid-phase microextraction method for the analysis of aqueous BTEX samples. Detection limits as low as 1 ng/mL were obtained for BTEX by NTD-SPNT.

Development and application of needle trap devices.

Needle trap devices (NTDs), like solid-phase microextraction (SPME) fibers, represent a new approach to one-step, solvent-free sample preparation and injection. New NTDs, packed with divinylbenzene (DVB) or Carboxen 1000 particles, are prepared, characterized, and used for benzene, toluene, ethylbenzne, and xylene (BTEX) sampling in our laboratory. This paper describes optimization parameters, performance evaluation, and application of NTDs for the analysis of a BTEX mixture from air. For active sampling, a sampling flow rate is an essential optimization parameter. Using a very small amount of sorbent particles (less than 1mg DVB or Carboxen), 1.9 mL/min was the highest sampling flow rate that could be used with no breakthrough of any BTEX components. A single NTD was used to study breakthrough volumes (BTVs) and the breakthrough volume was proportional to the quantity of sorbent packed inside the needle. The Carboxen-packed NTD showed higher BTVs for all BTEX compared to the DVB-packed NTD. The performance of home-made NTDs was evaluated at different sampling flow rates, storage times, and for reusability. Finally, DVB packed NTDs were used to sample and analyze a BTEX mixture from permanent marker fumes, mosquito coil smoke, and at various points in the interior of a house. A very low concentration (10 pg/mL) of toluene was detected in the garage.

Robust hybrid flow analyzer for formaldehyde.

We report fully automated self-calibrating formaldehyde analyzers relying on a hybrid flow format and include operational scheme and design details. Long-term operation is made possible with the use of syringe pumps. Four identical analyzers were built and showed low LODs of 120 pptv or better (S/N = 3) and good linearity over 0-50 ppbv HCHO concentration range (r2 > 0.9960), all concentrations refer to 10 min averaging times. The analyzer can resume normal operation after shortterm power failure with at most two cycles of data loss following restart. Good agreement between analyzers was observed for either indoor or outdoor measurements. The use of an integrated HCHO calibration source and full control by the host computer via a graphical user interface program enables the instrument to switch between zero, calibration, and sampling modes in a programmed automated manner. Detailed field data from deployment in three urban Texas locations from the summer of 2006 are presented. Features of the data, including an episode in which the HCHO concentration exceeded 50 ppbv, the highest reported ambient HCHO concentration in North America to our knowledge, are discussed in some detail.