A Simplified Method for the Measurement of Insoluble Solids in Pretreated Biomass Slurries

The biochemical conversion of cellulosic biomass to liquid transportation fuels includes the breakdown of biomass into its soluble, fermentable components. Pretreatment, the initial step in the conversion process, results in heterogeneous slurry comprised of both soluble and insoluble biomass components. For the purpose of tracking the progress of the conversion process, it is important to be able to accurately measure the fraction of insoluble biomass solids in the slurry. The current standard method involves separating the solids from the free liquor and then repeatedly washing the solids to remove the soluble fraction, a laborious and tedious process susceptible to operator variations. In this paper, we propose an alternative method for calculating the fraction of insoluble solids which does not require a washing step. The proposed method involves measuring the dry matter content of the whole slurry as well as the dry matter content in the isolated liquor fraction. We compared the two methods using three different pretreated biomass slurry samples and two oven-drying techniques for determining dry matter content, an important measurement for both methods. We also evaluated a large set of fraction insoluble solids data collected from previously analyzed pretreated samples. The proposed new method provided statistically equivalent results to the standard washing method when an infrared balance was used for determining dry matter content in the controlled measurement experiment. Similarly, in the large historical data set, there was no statistical difference shown between the wash and no-wash methods. The new method is offered as an alternative method for determining the fraction of insoluble solids.     

Use of physical and chemical properties of commercial tomato (Lycopersicon esculentum Mill.) products for monitoring their quality

Eighteen physical and chemical variables were determined in 25 samples of commercial tomato products: total solids, soluble solids, water activity, lycopene, 5-hydroxymethyl-2-furfural, CIE(L*a*b*) components (L*, a*, b*, a*/b*, C*, H degrees), total acidity, sodium chloride, wet-weight pulp percentage, alcohol insoluble solids, total pectic substances, ascorbic acid, and pH. In order to maximize the variability of products, samples included crushed tomato, tomato puree, tomato paste, and heavy concentrates and were taken from Italy, France, Spain, Portugal, the United States, Mexico, Colombia, and Chile. Correlation analysis and multidimensional data analysis techniques (principal component analysis and hierarchical classifications) were used to describe the products' variability and to study the relationships among variables. Three variables were selected, with the aim of classifying the collection of samples in a way consistent with the classification obtained with the first principal components. These variables were soluble solids content, the CIE(L*a*b*) lightness parameter L*, and total pectic substances content.     

Determining Yields in High Solids Enzymatic Hydrolysis of Biomass

As technologies for utilizing biomass for fuel and chemical production continue to improve, enzymatic hydrolysis can be run at still higher solids concentrations. For hydrolyses that initially contain little or no free water (10-40% total solids, w/w), the saccharification of insoluble polymers into soluble sugars involves changes of volume, density, and proportion of insoluble solids. This poses a new challenge when determining the degree of hydrolysis (conversion yield). Experiments have shown that calculating the yield from the resulting sugar concentration in the supernatant of the slurry and using the assumed initial volume leads to significant overestimations of the yield. By measuring the proportion of insoluble solids in the slurry as well as the sugar concentration and specific gravity of the aqueous phase, it is possible to precisely calculate the degree of conversion. The discrepancies between the different ways of calculating yields are demonstrated along with a nonlaborious method for approximating yields in high solids hydrolysis.     

Measurement of water by oven evaporation using a novel oven design.

Using an automated oven evaporation technique combined with the coulometric Karl Fischer method, the mass fraction of water has been measured in cement, coal, and refined oil samples. The accuracy of this method was established by using SRM 2890, water-saturated 1-octanol that was added to white oil. The samples were analyzed for total reactive Karl Fischer reagent (KFR) material, for interfering materials, and for material that does not react with the aldehyde–ketone KFR. All of the samples yielded volatile material that reacted with the standard KFR. None of the samples contained significant masses of material that reacted with iodine. The cement and coal SRMs contained no material that reacted with methanol and very little material that did not volatilize at 107°C. The refined oils contained some material that was volatile at 107°C and some at 160°C. However, none of this material reacted with the aldehyde–ketone reagent. These results show that the material in the solid samples is water and that the material in the refined oils is a material other than water which reacts with methanol to form water.     

Pollution potential reduction of cheese whey through yeast fermentation

Batch and continuous pilot-scale aerobic fermenters of 4.8 L operating volume were designed and constructed from plexiglass materials. The fermenters were used to study the kinetics of cheese whey fermentation using the yeast K. fragilis for pollution potential reduction and single cell protein production. Four retention times (6, 12, 18, and 24 h) were used in this study. The fermentation process was successful in reducing the total chemical oxygen demand (COD) by 42%, the soluble COD by 65%, the total solids by 53%, and the ammonium nitrogen by 90%. There were also gains in the suspended solids and the organic nitrogen of 60 and 17%, respectively. The reductions in the COD, total solids, and ammonium nitrogen, and the gains in the suspended solids and organic nitrogen were affected by the hydraulic retention time. More soluble material was converted to insoluble microbial cells at the 12-h hydraulic retention time, whereas greater pollution potential reduction was achieved at the 24-h hydraulic retention time for both batch and continuous operations.     

A new combination of the ring oven method with chromatography - the rotating ring oven

Chromatographic techniques have been used in combination with the ring oven method in various ways. The use of a rotating ring oven in combination with column chromatography is proposed. Separations are done on a chromatographic column fixed vertically above the rotating ring oven. Thus the various substances leaving the column are concentrated successively in sharply outlined distinct segments. The apparatus is described in detail. Its use is illustrated by the example of the separation of four amino acids (0.3 μg each).Other applications (dyes, gel chromatography on Sephadex) are mentioned briefly.     

Analysis by release of radioactivity by inorganic ion-exchange and ring oven technique-I Determination of copper

A sparingly soluble inorganic compound, fixed as a spot on filter paper, is used as an ion-exchanger in which the exchangeable ions are labelled with a radioactive isotope. These ions are replaced by the ions of the element to be determined but not by other accompanying ions. In this exchange an equivalent amount of the radioactive labelled ions is released from the ion-exchanger and separated from the spot by the ring oven technique. The activity of the ring is measured and compared with that of a standard processed in the same way. The determination of copper in amounts greater than 25 ng in the presence of a similar amount of lead and considerably greater amounts of cobalt, nickel, zinc, manganese and thallium is described.     

Neutral persulfate digestion at sub-boiling temperature in an oven for total dissolved phosphorus determination in natural waters

A simplified, easily performed persulfate digestion method has been developed to process a large number of water samples for routine determination of total dissolved phosphorus. A neutral potassium persulfate solution (5%, w/v, pH ∼6.5) is added to the samples (at 10 mg potassium persulfate per mL of sample), which are then digested at 90 °C in an oven for 16 h. This method does not require pH adjustment after digestion because neither an acid nor a base is added to the samples prior to digestion. The full color of phosphoantimonylmolybdenum blue from the digested samples develops within 8 min. Compared with the autoclave method, digestion at sub-boiling temperatures in an oven is safer, and a large number of samples can be heated overnight requiring no constant monitoring. The apparent molar absorptivity (?) of nine organic phosphorus compounds and two condensed inorganic phosphates ranged from 1.17 × 10⁴ to 1.82 × 10⁴ L mol⁻¹ cm⁻¹ in both distilled water and artificial seawater matrixes. The average recovery of these phosphorus compounds was 94 ± 11% for the DIW matrix and 90 ± 12% for the ASW matrix. No significant difference in molar absorptivity was observed between the undigested and digested phosphate, especially in the seawater matrix. It is, therefore, suggested that a phosphate solution be directly employed without digestion as the calibration standard for routine determination of total dissolved phosphorus. This method was used to study the spatial distribution of total dissolved phosphorus in the surface waters of Florida Bay.     

Rapid analysis of coke oven gas by capillary gas chromatography

A porous layer open tubular (PLOT) column has been used for monitoring the light hydrocarbons and permanent gases produced in coking plants. The method, which offers a simple alternative to traditional multi column techniques, entails a single injection on to a Carboplot 007 capillary column and simultaneous thermal conductivity and flame ionization detection. The simplified approach proposed is restricted to coke oven gas analysis: application to other gas mixtures has not been considered. The reliability of this procedure compares favorably with that of traditional methods; the technique is also much less time-consuming: seven individual gases can be determined on-line every fifteen minutes. Primary and secondary gas standards were used to determine response curves for the gases. The method also facilitates reliable calculation of heat values associated with the burning of the fuel gas mixtures.     

Action of Humicola lanuginosa lipase on long-chain lipid substrates: 2. Hydrolysis of diolein monolayers

The hydrolysis of 1,2-diolein (DO) monomolecular films by Humicola lanuginosa lipase (HLL) was studied by simultaneous measuring the decrease in the film area and the changes in the surface potential in the “zero-order trough” at constant surface pressure and in the presence of β-cyclodextrin (β-CD). The decrease with time in the film area reflects both the reduction in the area per molecule due to the transformation of substrate DO molecules into the products molecules of monoolein (MO) and oleic acid (OA) and the desorption of the soluble inclusion complexes β-CD–MO and β-CD–OA. The surface potential data were interpreted as an accumulation at the interface of negatively charged products of OA and insoluble β-CD–DO complexes. In the proposed kinetic model, the product solubilization rates in the presence of β-CD and the flux supplied progressively by the moving barrier from the reservoir to the reaction compartment in order to keep the constant surface pressure were taken into account. The surface concentrations of MO and OA transiently present at the interface were determined. The values of the global kinetic constant Q_m′ of hydrolysis of DO to MO were obtained. Comparison with the values of the global kinetic constant of hydrolysis of monoglyceride MO to OA shows that the rates of hydrolysis of diglyceride and monoglyceride by HLL are of the same order of magnitude.     

Through oven transfer adsorption-desorption interface for the analysis of methyl jasmonate in aromatic samples by on-line RPLC-GC

A fully automated method for the determination of medium volatility compounds in aromatic samples was developed. Specifically, the determination of methyl jasmonate in jasmine fragrances was performed by using the through oven transfer adsorption-desorption (TOTAD) interface for the on-line coupling between RPLC-GC. A study of the most relevant variables involved in the performance of the TOTAD interface for medium volatility compounds was carried out by testing different values of helium flow (100, 300, 400, and 500 mL/min), transfer speed (0.1, 0.3, 0.5, and 2.0 mL/min), and methanol/water percentages (86:14, 85:15, 83:17, 80:20, and 70:30). The method developed provided satisfactory repeatability (RSD for retention times of 0.15% and for peak areas of 9.4%) and recovery (71%) as well as excellent LOD (0.01 mg/L) for methyl jasmonate in commercial jasmine essence under the experimental conditions selected as optimum. Additional advantages of the automated RPLC-TOTAD-GC method proposed in the present work are its rapidness, reliability, and the possibility of directly introducing the sample with no further pretreatment.     

Fast capillary GC using a low thermal mass column oven for the determination of residual solvents in pharmaceuticals

A low thermal mass column oven was used for fast capillary GC analysis (high throughput) of residual solvents in pharmaceutical products. A dedicated capillary column, 20 m L x 180 microm ID x 1 microm DB-624 was programmed from 35 degrees C (30 s) to 150 degrees C at 100 degrees C/min and to 250 degrees C (30 s) at 200 degrees C/min, resulting in a total GC cycle time of less than 4 min. Complete separation of a target 20-component mixture was achieved, while method performance in terms of repeatability, sensitivity, and linearity was maintained in comparison to the generic method currently applied in our laboratories.     

Rubber aging in tires. Part 2: Accelerated oven aging tests

The kinetics of oxidation of wedge and skim rubber from tires aged at different oven temperatures with various fill gases have been measured for 5 different tires and compared to field results. We demonstrate that oven aging tires mounted on wheels and inflated to the maximum sidewall pressure closely reproduce the aging behavior measured for tires collected after customer use. Temperatures as high as 70 °C can be used to accelerate aging. Use of 50/50 blend of N₂/O₂ as a fill gas accelerates the oxidative aging by 30-40% relative to air. By combining elevated temperatures with oxygen enriched fill gas, it is possible to oven age tires to an age equivalent to 6 years in Phoenix in 8 weeks or less.     

Analysis of wax esters in edible oils by automated on-line coupling liquid chromatography-gas chromatography using the through oven transfer adsorption desorption (TOTAD) interface

An automated method for the direct analysis of wax esters in edible oils is presented. The proposed method uses the TOTAD (through oven transfer adsorption desorption) interface for the on-line coupling of normal phase liquid chromatography and gas chromatography. In this fully automated system, the oil with C32 wax ester as internal standard and diluted with heptane is injected directly with no sample pre-treatment step other than filtration. The proposed method allows analysis of different wax esters, and is simpler and faster than the European Union Official Method, which is tedious and time-consuming. The obtained results closely match the certified values obtained from the median of the analytical results of the inter-labs certification study. Relative standard deviations of the concentrations are less than 5%. The method is appropriate for routine analysis as it is totally automated.     

Evaluation of ammonia buffer containing EDTA as an extractant for Cr(VI) from solid samples

A novel procedure for the extraction of soluble, sparingly soluble and insoluble Cr(VI) from solid samples was presented. EDTA was added to an ammonia buffer commonly used only for the extraction of soluble and sparingly soluble Cr(VI). In the course of extraction in an ultrasonic bath cations which form insoluble chromates are complexed with EDTA while Cr(VI) is transferred to the solution. A concentration of EDTA equal to 0.01 mol L⁻¹ was chosen. The presence of EDTA in the extraction solution enables not only dissolution of insoluble Cr(VI) but also, as reported previously in literature, minimises oxidation of Cr(III) to Cr(VI). The extraction procedure was optimised and applied to Cr(VI) determination in the paint chips real sample. The results obtained were compared with the results obtained using two other extraction procedures. The results show that the novel extraction procedure can be used for the extraction of soluble, sparingly soluble and insoluble Cr(VI) from real solid samples.     

Digestion of plastic materials for the determination of toxic metals with a microwave oven for household use.

A rapid sample-digestion method for the determination of toxic metals, cadmium, chromium, and lead, in polyethylene and polyvinyl chloride has been developed by using a microwave oven for household use. An appropriate amount of the sample taken in a PTFE decomposition vessel was mixed with nitric acid or nitric and sulfuric acids. The vessel was heated in a microwave oven by a predetermined operating program. The digested sample was diluted to a definite volume with water after evaporating most of the nitric acid. The precipitate, if formed, was filtered off by a membrane filter. The metals were determined by ICP-AES. The sample digestion required 5 min (for 20-mg sample) to 25 min (for 60-mg sample). The analytical results obtained for cadmium, chromium, and lead in a polyethylene certified reference material, BCR-680, digested with nitric acid, were in good agreement with the certified values.     

An amperometric biosensor based on peroxidases from Brassica napus for the determination of the total polyphenolic content in wine and tea samples

An amperometric biosensor based on peroxidases from Brassica napus hairy roots (PBHR) used to determine the total polyphenolic content in wine and tea samples is proposed by the first time. The method employs carbon paste (CP) electrodes filled up with PBHR, ferrocene (Fc), and multi-walled carbon nanotubes embedded in a mineral oil (MWCNT + MO) at a given composition (PBHR-Fc-MWCNT + MO). The biosensor was covered externally with a dialysis membrane, which was fixed at the electrode body side part with a Teflon laboratory film and an O-ring. Calibration curves obtained from steady-state currents as a function of the concentration of a polyphenolic standard reference compound such as t-resveratrol (t-Res) or caffeic acid (CA) were then used to estimate the total polyphenolic content in real samples. The reproducibility and the repeatability were of 7.0% and 4.1% for t-Res (8.4% and 5.2% for CA), respectively, showing a good biosensor performance. The calibration curves were linear in a concentration range from 0.05 to 52 mg L⁻¹ and 0.06 to 69 mg L⁻¹ for t-Res and CA, respectively. The lowest polyphenolic compound concentration values measured experimentally for a signal to noise ratio of 3:1 were 0.023 mg L⁻¹ and 0.020 mg L⁻¹ for t-Res and CA, respectively.     

Electroanalytical determination of cadmium and lead in deciduous teeth after microwave oven digestion

A method using differential pulse anodic stripping voltammetry after microwave oven digestion was developed for the simultaneous determination of Cd(II) and Pb(II) in the deciduous teeth of children. Each tooth was weighed; deposited in a 120 mL capped Teflon vessel with 5 mL 65% nitric acid, Suprapur analytical grade; and digested in a 2-step microwave oven for 15 min. The detection limits for Cd(II) and Pb(II) in the final solution were 0.078 and 0.323 microg/L, and the quantitation limits 0.394 and 1.613 microg/L, respectively, with a linearity range of 2 microg/L for Cd(II) and 23.3 microg/L for Pb(II). The sensitivity was 2.51 nA/microg-L and 1.37 nA/microg-L, for Cd(II) and Pb(II). The main advantages of this technique are a complete and satisfactory dissolution of the tooth material with the proposed microwave oven digestion procedure, without sample pretreatments, such as drying, ashing, or powdering. The voltammetric procedure proved to be well designed because of significant goodness of fit to a linear model, and the accuracy of the method was established as compared with standard reference material. The methodology has enabled us to study Cd(II) and Pb(II) in 371 deciduous teeth from school children in Cartagena, Spain.     

Physicochemical characterization,thermal, and electrical conductivity studies of some transition metal complexes of bis-chelating Schiff base

Polychelates of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and VO(IV) with a new bis-chelating Schiff base derived from 5-acetyl-2,4-dihydroxyacetophenone and isonicotinic acidhydrazide have been synthesized. The resulting polychelates have been characterized by elemental analyses, IR and electronic spectral data, magnetic susceptibility measurements and thermogravimetric analysis. All the polychelates are dark coloured solids and insoluble in water and common organic solvents. Thermogravimetric analyses confirm coordination of water in complexes. Various kinetic and thermodynamic parameters have been evaluated from thermal data. The ligand acts as a bis-tridentate molecule coordinating through deprotonated phenolic/enolic oxygen atoms and azomethine nitrogen atoms. The solid-state conductivity of ligand and its polychelates have been measured in their compressed pellet form and all compounds were found to be semiconducting in nature.     

Gas-chromatographic determination of divalent sulphur compounds using the catalyzed iodine-azide reaction in non-aqueous media

Summary A new gas-chromatographic catalytic method is described for the determination of divalent sulphur compounds, which are soluble or insoluble in water, based on the iodine-azide reaction in non-aqueous solutions. An analytical column with molecular sieve 5A and thermal conductivity detector was used. The nitrogen produced in the catalyzed reaction was measured as amount directly proportional to the sulphur catalysator concentrations. The analysis was carried out in methanol, ethylene glycol, dimethylformamide, methylformamide, formamide and dimethylsulphoxide as well as in the mixture of these solvents. The method allows to determine microamounts of sodium sulphide, pyrrolidinedithiocarbamate, thiourea, dithiothreitol, cysteine, ergothioneine, glutathion and thioammeline. The time required for a single analysis does not exceed 3 min.

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Gas-chromatographische Bestimmung von Schwefel(II)-Verbindungen mit der katalysierten Iod-Azid-Reaktion in nichtwäßrigen Medien