Recertification of Standard Reference Material (SRM) 1649, Urban Dust,for the Determination of Polycyclic Aromatic Hydrocarbons (PAHs)

The National Institute of Standards and Technology (NIST) recently issued SRM 1649a, Urban Dust, with certified and reference values for 44 polycyclic aromatic hydrocarbons (PAHs). This material is a recertification of SRM 1649 which was issued in 1982 with certified values for only five PAHs. The PAHs were determined using the following analytical techniques: (1) reversed-phase liquid chromatography with fluorescence detection (LC-FL) for analysis of the total PAH fraction, (2) reversed-phase LC-FL for analysis of isomeric PAH fractions isolated by normal-phase LC (i.e., multidimensional LC), and (3) gas chromatography/mass spectrometry (GC/MS) for analysis of the PAH fraction using three different stationary phases, each with different selectivity for PAH separations. The results from the different techniques are compared and discussed. SRM 1649a is currently the most extensively characterized environmental matrix SRM with respect to PAH constituents.     

Effect of process distillation on the distribution of amino polycyclic aromatic hydrocarbons in refined coal-derived liquids

After fractional distillation of SRC-I process solvent, 3- and 4-ring amino polycyclic aromatic hydrocarbons (amino PAH) are essentially absent from fractions boiling at < ≈ 400 °C. Amino PAH determine the mutagenicity of SRC-I process solvent and also that of several other coal-derived liquids, hence these studies indicate that distillation may be optimized so as to confine mutagenic activity to heavy products, while recovering the material distilling at < ≈ 400 °C as a mutagenically inactive fuel or feedstock.     

Effect of sonication assisted by titanium dioxide and ferrous ions on polyaromatic hydrocarbons (PAHs) and toxicity removals from a petrochemical industry wastewater in Turkey

BACKGROUND: In Izmir (Turkey) polyaromatic hydracarbon (PAH) removal efficiencies are low in petrochemical industry aerobic biological wastewater treatment plants because bacteria are not able to overcome the inhibition of these toxic and refractory organics. In order to increase PAHs removal, sonication process was chosen among other advanced treatment processes include sonication processes. The effects of ambient conditions, increasing sonication time, sonication temperature, TiO₂ and Fe⁺² concentrations on sonication at a petrochemical industry wastewater treatment plant in Izmir (Turkey) was investigated in a 650 W sonicator, at a frequency of 35 kHz and a 500 mL glass reactor. RESULTS: Increasing the temperature improved PAH removal after 150 min sonication at 30 °C and 60 °C. The maximum total PAH removal efficiencies were the same in a reactor containing 20 mg L^?1 TiO₂ and in a TiO₂‐free reactor at 30 °C and 60 °C after 150 min sonication. Maximum 91% and 97% total PAH removals were obtained in a control reactor and a reactor containing 20 mg L^?1 Fe⁺² at 30 °C and 60 °C, respectively, after 150 min sonication. The PAH concentration was toxic to Daphnia magna, so that the EC₅₀ value decreased significantly from 342.56 ng mL^?1 to EC₅₀ = 9.88 ng mL^?1 and to EC₅₀ = 3.35 ng mL^?1, at the lowest TiO₂ (0.1 mg L^?1) and Fe⁺² (2 mg L^?1) concentrations, respectively, after 150 min sonication at 30 °C. CONCLUSION: PAHs and the acute toxicity in a petrochemical industry wastewater were removed efficiently through sonication. Copyright © 2010 Society of Chemical Industry     

Standard Reference Materials (SRMs) for the Determination of Polycyclic Aromatic Compounds--Twenty Years of Progress

In 1981 the National Bureau of Standards, now the National Institute of Standards and Technology (NIST), issued the first natural matrix Standard Reference Material (SRM) for the determination of polycyclic aromatic compounds (PACs), SRM 1580 Organics in Shale Oil. In the next 10 years, additional natural matrix SRMs were developed including air and diesel particulate matter, petroleum crude oil, coal tar, sediment, and mussel tissue. The SRMs represented the "first generation" of natural matrix SRMs for the determination of PACs. The SRMs had "certified" values for only 5 to 12 PACs; however, their development established the foundation for the implementation of the "two or more independent analytical techniques" approach for certification of individual PACs in environmental matrices. The requirement for use of different analytical techniques spurred the development of both gas chromatography (GC) and liquid chromatography (LC) approaches for the determination of PACs. Since the mid-1990s, the "second generation" of natural matrix SRMs has been issued by NIST with certified values for over 20 PACs in each material. The greater number of certified values in these SRMs was the result of the combination of measurements using reversed-phase LC with fluorescence detection, multidimensional LC, and GC with mass spectrometric detection using two or more stationary phases with different selectivity for polycyclic aromatic hydrocarbon (PAH) separations. This article discusses the significant developments in analytical methods and chromatographic separation of PAHs during the past 20 years that have resulted in the certification of over 25 SRMs, which are now used worldwide for the validation of analytical methods for the measurement of PACs in environmental matrices.     

Temperature stability of vitamin D2 and color changes during drying of UVB-treated mushrooms

The study investigates the effect of drying temperature on vitamin D₂ content and color changes of UVB-treated shiitake (Lentinula edodes), oyster (Pleurotus ostreatus), and white and brown button mushrooms (Agaricus bisporus). Fresh samples were UVB treated up to 1.5?J/cm² for 20?min at 25°C and either dried in a high precision dryer (temperatures: 40, 60, 80°C, specific humidity: 10?g/kg, air velocity: 0.6?m/s) or frozen at ?25°C, and then freeze-dried (pressure: 0.28?mbar). Vitamin D₂ content was not negatively affected by the increased temperatures of the drying air. The highest content of vitamin D₂ was detected in freeze-dried (171.84?µg/g) and hot-air dried shiitake at 60°C (169?µg/g), followed by oyster (121.96?µg/g), whereas the lowest amount was observed in brown button mushrooms at 40°C (34.65?µg/g). Although vitamin D₂ indicated a remarkable stability even at 80°C, the dried samples were characterized by intensive tissue darkening.     

Influence of Temperature Stress on Lipid Stability of Atlantic Herring (<Emphasis Type="Italic">Clupea harengus</Emphasis>) Muscle During Frozen Storage

Unstable conditions are commonly encountered during industrial storage and transportation of frozen fish. Temperature stress and fluctuations may increase the amount of unfrozen water in the muscle and enzymatic activity and lipid oxidation can thus still take place during frozen storage. The aim of this study was to investigate the changes of characteristics of different muscle types of herring at unstable modelled conditions during storage and transportation. Compositional changes, lipid oxidation and lipid hydrolysis were monitored in light and dark muscle of Atlantic herring (Clupea harengus), during frozen storage, as affected by temperature stress (samples were stored at ? 25 °C for 2 months, then stressed at ? 12 °C for 1 month, followed by storage at a stable ? 25 °C for the remaining storage duration), and compared to samples stored at a stable ? 25 °C for 14 months. The dark muscle was more sensitive to lipid oxidation than the light muscle, leading to faster degradation. Increased lipid oxidation and lipid hydrolysis were observed in temperature‐stressed samples of both muscle types. The study demonstrated the importance of avoiding temperature stress during industrial frozen storage and transportation to improve the quality and shelf life of frozen herring products. Removal of dark muscle by deep skinning could benefit both processors and customers regarding the shelf life and nutritional value of the light herring muscle.     

Mechanochemical synthesis and cold sintering of mussel shell-derived hydroxyapatite nano-powders for bone tissue regeneration

According to the circular economy principles, processing routes aiming at reducing the natural resources consumption and the energy demand can be addressed as ‘green’. In this framework, mussel shells, a natural feedstock of calcium carbonate, were successfully transformed into nano-crystalline hydroxyapatite by mechanochemical synthesis at room temperature after mixing with a phosphoric acid solution. The as-synthesized powder was then consolidated up to 82 % relative density by cold sintering (600 MPa, 200 °C). The materials were fully investigated by physical, chemical and thermal characterization techniques. Cold-sintered samples were also subjected to biaxial flexural strength test, showing a flexural resistance of 23 MPa. Cell viability assessment revealed that cold sintered hydroxyapatite derived from mussel shells promotes faster adhesion and spreading of human bone marrow-derived mesenchymal stem cells, in comparison to a commercial hydroxyapatite sintered at 1050 °C. Therefore, cold-sintered mussel shells-derived hydroxyapatite can be a promising future candidate scaffold for bone tissue regeneration.     

Physical Properties of Isotactic Poly(propylene)/Silver Nanocomposites: Dynamic Crystallization Behavior and Resultant Morphology

Summary: The presence of silver nanoparticles (0.01–5 wt.‐%) increased the crystallization temperature of isotactic poly(propylene) (iPP) (e.g., a 5 wt.‐% content increases the temperature by ca. 7 °C) and produced a sharper crystalline peak. It had little effect on the melt rheology of the nanocomposites. The shear‐induced crystallization behavior of iPP was accelerated with increasing Ag content and imposed frequency. In addition, the promoting effect of Ag nanoparticles on the overall crystallization behavior was more notable at 140 °C than at 130 °C. The wide‐angle X‐ray diffraction scans of iPP nanocomposites with 5 wt.‐% Ag crystallized at 130 °C clearly presented another peak at a 2θ value of 15.8°, which corresponded to a β‐form crystal. The nanocomposites with 5 wt.‐% Ag crystallized at 130 °C gave double melting peaks at 154 and 166 °C. On the other hand, the samples crystallized at 140 °C produced two melting peaks at 166 and 172 °C. The introduction of as much as 0.1 wt.‐% of Ag nanoparticles increased both the tensile strength and elongation at break, but subsequent further addition caused a decrease. In addition, iPP nanocomposites with more than 1 wt.‐% Ag exhibited a higher modulus than pure iPP.

Time dependence of G′ of iPP and iPP/Ag nanocomposites at 130 °C at ω = 1 rad · s^?1.     

Effect of olive fruit freezing on oxidative stability of virgin olive oil

Several studies have suggested that the phenolic fraction plays an important role during storage and therefore in the shelf life of virgin olive oil. This investigation examines the effect of freezing olives (–18 °C) before processing into oil on the transfer of the phenolic compounds into the subsequent oil, and the consequential changes in oxidative stability. Oil samples obtained from frozen olives (24 h at –18 °C), crushed with and without preliminary thawing, were compared to a control sample; both oils were obtained using a two‐phase low‐scale mill. The oxidative stability in different samples was assessed in terms of primary and secondary oxidation products as measured by peroxide values and oxidative stability index times, respectively. The quality of the oil samples was also checked through the percentage of free acidity and the phenolic content. Phenols were determined by both spectrophotometric assays (total phenols and o‐diphenols) and HPLC‐DAD/MSD. The antiradical capacity of the phenolic fraction was determined by DPPH and ABTS spectrophotometric tests. These analyses showed that thawing of olives before oil extraction led to a significant loss of oxidative stability and phenols; in contrast, samples obtained from frozen olives that were not thawed before crushing showed qualitative characteristics similar to control samples.     

Rheological investigation of a random copolymer of polyacrylamide and polyacryloyl hydrazide (PAM‐ran‐PAH) for oil recovery applications

In this article, we synthesize and investigate the rheological properties of a random copolymer PAM‐ran‐PAH of polyacrylamide (PAM) and polyacryloyl hydrazide (PAH) and compare with the results of PAM at different temperature (30 and 80 °C) and salinity (0 and 1.0 wt %). At 30 °C, both PAM and PAM‐ran‐PAH exhibited non‐Newtonian rheology with both shear thinning and shear thickening responses. The rheological properties such as viscosity and moduli (G′ and G″) of PAM significantly deformed at elevated temperature (80 °C) and salinity (1.0 wt %), resulting no recovery in viscosity and moduli. On the other hand, the effect of temperature and salinity was found to be least on PAM‐ran‐PAH and showed better stability with the possibility of recovering its original rheological properties. The performance of PAM and PAM‐ran‐PAH was also characterized by enhanced oil recovery tests. The use of PAM‐ran‐PAH for polymer flooding, due to its stable rheology, resulted in an increase in the oil recovery than PAM. In general, the rheological behavior of PAM‐ran‐PAH as a chemical agent proved to be thermally stable than PAM, which clearly supports its use for saline environment and high temperature applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44648.     

Effect of natural and synthetic tackifiers on viscosities,adhesion properties and thermal stability of SNR and DPNR solution adhesives

Styrene-grafted natural rubber (SNR) and deproteinized natural rubber (DPNR) latexes were formulated with coumarone-indene (CI), gum rosin and petro resin (PR) tackifiers into solution adhesives with toluene as a solvent. The solution viscosities were evaluated by a Brookfield viscometer DV-II Plus with spindle No. 3. Pressure sensitive adhesives (PSAs) films were made and the adhesion properties were evaluated with loop tack, peel strength and shear strength tests. Thermal stability of the film was evaluated via Perkin-Elmer Pyris 6^TM thermogravimetric analysis at temperatures ranging from 30 to 600?°C at a heating rate of 10?°C per minute in nitrogen environment. Results indicate that as the tackifiers content increased, the solution viscosities increased with SNR/PR and DPNR/PR formulations showing the highest viscosities. Adhesion test also indicates that loop tack and peel strength of the adhesive solution increased but their shear strength decreased; increase of CI tackifier loadings conferred the highest peel strength for both SNR- and DPNR-based PSAs. Thermal analyses show that the addition of 40 phr CI tackifiers improved thermal stability of SNR adhesives based on their higher T_max and integral procedural decomposition temperature properties.     

Study of the electrical properties of flame retardant poly(vinylchloride) using positron annihilation lifetime spectroscopy

Since the large fire at the Brown Ferry cable plant which occurred at noon on March 22, 1975 in Alabama, attention has been given to the use of flame retardant cable in buildings to meet fire safety requirements. Flame retardants are used in wire and cable applications to prevent the conversion of an electric spark into fire and subsequently to prevent the spread of fire throughout a structure along the wiring. There are many substances used as flame retardants in wires and cables. In Egypt, Multi‐Purpose Reactor insulation and jacket cables have been constructed from a flame retardant substance, poly(vinylchloride) (PVC). In the present work, elemental and X‐ray fluorescence analyses have been performed to determine the composition of PVC in the jacket cable samples. In addition, the conductivity (σ), permittivity (?′), and dielectric loss (?″) as well as positron annihilation lifetime (PAL) are measured in the temperature range 30 to 140 °C. It is found that the amount of chlorine in the flame‐retardant PVC (FRPVC) jacket cable is significantly higher (5%) than the conventional PVC jacket cable. Inverse relationships between σ and free volume size and fractions (V, f) through the temperature range are obtained. However, a distinct positive relationship between σ and I₂ above 100°C is found. The results of PAL and electrical measurements indicate that FRPVC has good electrical insulation properties below 100°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 638–644, 2005     

Effects of supercritical carbon dioxide treatment on the morphology of poly(l‐lactide)

Synthetic l ‐lactide random copolymers can be employed as controlled release materials when prepared using supercritical carbon dioxide (scCO₂), since they are biodegradable via hydrolysis. To determine the effects of thermal properties on polymer performance following scCO₂ processing, three types of poly(l ‐lactide) having different properties were assessed. The T_m of one poly(l ‐lactide) sample (H‐100) was found to be approximately 170 °C over the processing pressure range from 8 to 18 MPa, while a second sample (H‐440) also showed a constant value of approximately 152 °C. In contrast, the poly(l ‐lactide) REVODE exhibited a T_m of 146 °C prior to processing but a higher value of 147 °C following treatment at 8 MPa. Unlike the H‐100 and H‐440, the T_m value of the REVODE tended to decrease with increasing pressure. The T_g values increased greatly under mild conditions of 8 MPa pressure and a temperature of 40 °C. In particular, the T_g values for the H‐440 and REVODE increased by 4 °C and 5 °C, respectively. All T_g values were lowest at 12 MPa and increased with increasing processing pressure, although the effect of processing temperature was minimal. The Χ_{c DSC} of the H‐100 was 18% initially but increased to 20% upon scCO₂ processing at 40 °C and 14 MPa, and showed further increases at higher processing temperatures. Although the relationship between processing temperature and Χ_{c DSC} values for the H‐440 showed the same trend as observed with the H‐100, a different trend was seen for the REVODE. The Χ_{c XRD} values obtained from the XRD analyses differed from the values generated by DSC analysis, and showed a maximum degree of crystallinity following processing at 80 °C both with and without scCO₂ treatment. ATR FT‐IR analyses identified peaks due to semicrystalline regions in poly(l ‐lactide) samples treated with scCO₂, even when applying low temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44006.     

Synthesis and properties of organosoluble poly(ether imide)s containing 4,4′(octahydro-4,7-methano-5H-inden-5-ylidene) cardo group

A series of organosoluble aromatic poly(ether imide)s (PEIs) VIIa-k were synthesized from 4,4′-[(octahydro-4,7-methano-5H-inden-5-ylidene)bis(1,4-phenylene)dioxy] diphthalic dianhydride (IV) and various aromatic diamines. PEIs synthesized through two-stage polymerization had inherent viscosities of 0.51–0.64 dL/g. This series of polymers could also be synthesized from IV and diamines in a small amount of refluxing m-cresol in a one-step process and had inherent viscosities of 0.65–0.87 dL/g. For the low melting point diamines (Vj and Vk), polymers could be obtained by bulk polymerization and had inherent viscosities of 0.36 and 0.41 dL/g. Polymers showed good organosolubility and could be cast into transparent, flexible, and tough polyimide films with good tensile properties. These PEIs had glass transition temperatures among 203–281°C. Thermogravimetric analyses established that these polymers were fairly stable up to 430°C, and the 10% weight loss temperatures were recorded in the range of 473–503°C in nitrogen and 481–512°C in air atmosphere. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 987–996, 1999     

CYCLOPENT[bc]ACENAPHTHYLENE: A PUTATIVE INTERMEDIATE ON THE PATHWAY FOR THERMAL CYCLODEHYDROGENATION OF PHENANTHRENE

Phenanthrene, the archetypal “bay region” polycyclic aromatic hydrocarbon (PAH), loses two hydrogen atoms when subjected to flash vacuum pyrolysis (FVP) at 1100 °C and suffers a major skeletal rearrangement to form pyracylene (1), along with 1-, 3-, and 4-ethynylacenaphthylene (2, 3, and 4, respectively). Evidence is presented that implicates cyclopenta[bc]acenaphthylene (7) as a key intermediate on the reaction pathway from phenanthrene to these four C₁₄H₈ products.     

Effect of vacuum‐packaging on the changes of Russian sturgeon muscle lipids during frozen storage

The changes in fatty acid composition, non‐polar (triglycerols) and polar lipids (phospholipids), total free fatty acids and total cholesterol of Russian sturgeon (Acipenser gueldenstaedtii) were studied during 360 days of storage at ?18°C. It was established that total neutral lipids and phospholipids content decreased and total free fatty acids concentration increased significantly during the frozen storage. Lower non‐polar and polar lipids content and higher free fatty acids concentration of vacuum‐packaged samples in comparison with air‐packaged samples were found. The changes in total cholesterol concentration and phospholipid classes of frozen stored sturgeon were not influenced by the frozen storage period and the type of packaging. It was established that the sturgeon polar lipids consisted mainly of phosphatidylcholine – 54.98 ± 0.85%, phosphatidylethanolamine – 28.42 ± 0.61%, and phosphatidylserine – 8.64 ± 0.45%. The increase of the total free fatty acids concentration was associated with the free n ? 3 PUFA accumulation as a result of hydrolysis of non‐polar and polar lipids. During the frozen storage DHA percentage of non‐polar lipids and phospholipids decreased approximately 3 and 1.75%, respectively. After 360 days of storage at ?18°C the n ? 3/n ? 6 PUFA ratio of total lipids decreased 4.9%.     

Morphology and crystallization of poly(ethylene terephthalate)

The melting behaviour and the morphology of poly(ethylene terephthalate) crystallized from the melt are reported. In general, dual or triple melting endotherms are seen, and single endotherms are seen when the samples are crystallized above 215°C for long times. The location of the uppermost endotherm was found to be constant below T_c = 230°C, and above that temperature the location depends on T_c. Therefore, we have shown that samples of PET which are crystallized above T_c = 230°C contain perfect crystals only; below T_c = 230°C, they contain perfect and imperfect crystals. Scanning electron microscopy showed that the perfect crystals are the dominant lamellae in the spherulitic structure, while the imperfect crystals are the subsidiary lamellae in the spherulitic structure, The amorphous regions are located between individual lamellae.     

Solid‐state characterization and the thermal properties of stereoregular poly(vinyl chloride) prepared by urea clathrate polymerization

The solid‐state characterization of highly stereoregular poly(vinyl chloride) (PVC) prepared by urea clathrate polymerization was carried out by using various instrumental analyses. The structural differences of PVC appeared most remarkably in solubility to organic solvents, IR, WAXD, and solid‐state ¹³C‐NMR spectra. The value of the glass transition temperature (T_g) was about 90°C, not as high as expected, although its detection was quite difficult. The thermal stability was poor, as evidenced by the easy discoloration of this polymer by heat treatment, which was related to the absence of a termination reaction. Dynamic ESR spectra in the solid state clearly indicate that the radical formation occurs at such a low temperature as 160°C in the initial degradation stage. The degradation characteristics of urea clathrate PVC were critically discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2820–2825, 1999     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and poly(DL-lactide)-co-poly(ethylene glycol)

The melting and crystallization behavior and phase morphology of poly(3-hydroxybutyrate) (PHB) and poly(DL-lactide)-co-poly(ethylene glycol) (PELA) blends were studied by DSC, SEM, and polarizing optical microscopy. The melting temperatures of PHB in the blends showed a slight shift, and the melting enthalpy of the blends decreased linearly with the increase of PELA content. The glass transition temperatures of PHB/PELA (60/40), (40/60), and (20/80) blends were found at about 30°C, close to that of the pure PELA component, during DSC heating runs for the original samples and samples after cooling from the melt at a rate of 20°C/min. After a DSC cooling run at a rate of 100°C/min, the blends showed glass transitions in the range of 10–30°C. Uniform distribution of two phases in the blends was observed by SEM. The crystallization of PHB in the blends from both the melt and the glassy state was affected by the PELA component. When crystallized from the melt during the DSC nonisothermal crystallization run at a rate of 20°C/min, the temperatures of crystallization decreased with the increase of PELA content. Compared with pure PHB, the cold crystallization peaks of PHB in the blends shifted to higher temperatures. Well-defined spherulites of PHB were found in both pure PHB and the blends with PHB content of 80 or 60%. The growth of spherulites of PHB in the blends was affected significantly by 60% PELA content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1849–1856, 1997     

Synthesis and characterization of copolyimides with high solubility

A series of copolyimides were prepared from various diamines (polysiloxane and isophorone units) with aromatic tetracarboxylic dianhydrides via a two‐step (thermal imidization) method. The monomers and polymers were produced in high yields, and the copolyimides containing Si? O? C bonds and asymmetric meta catenation in the polymer backbone exhibited good solubility. The glass‐transition temperatures (T_g's) of all the copolyimides were found to be 201–262 and 215–258°C by differential scanning calorimetry (DSC) and dynamic mechanical analysis, respectively. Thermogravimetric analyses indicated that the polymers were fairly stable up to 502–578°C (10 wt % loss in N2) and 490–574°C (10 wt % loss in air). The char yields at 800°C in N2 and air atmospheres were 26–59 and 20–53%, respectively. The copolymerization results, determined with 1H‐NMR and DSC, indicated a random copolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1963–1970, 2003