Abstract  The tandem mass spectrometry (MS/MS) characterization of cyclodextrin derivatives, namely randomly esterified 6-O-(3-hydroxybutyril)-beta-cyclodextrin (HBCD) and triacetyl-beta-cyclodextrin (TABCD) is described. The chosen compounds share certain structural similarities which are exploited in order to establish a general approach in their tandem MS characterization. The TABCD commercial product is fully esterified and presents in single stage MS a single peak while HBCD presents a molecular weight distribution due to the variation of the substitution degree. HBCD product was obtained via ring opening of beta-butyrolactone in the presence of beta-cyclodextrin (CD). First, the specific fragmentation pathways are established for protonated and sodiated TABCD parent ions and, based on the established fragmentation behaviour, HBCD compounds are analyzed. Our findings indicate that in MS/MS analysis of esterified cyclodextrins the cleavage of the substituents can be selectively induced thus offering information on the substitution patterns. Moreover, we demonstrate, using tandem MS technique, that beta-butyrolactone monomer units are attached to the CD molecule not as oligomer chains but as singly esterified molecules.

Abstract  For a poly(ethylene terephthalate) (PET)/cotton blended fabric, a reactive-type flame retardant 2, 3-dibromo-succinic anhydride (DBSA) was used to endow durable flame retardancy via the pad-dry-cure method. DBSA was synthesized via the addition reaction of maleic anhydride and bromine in ethyl acetate solution and extracted by solventing-out crystallization. DBSA was used to finish a cotton fabric firstly with sodium hypophosphite as the catalyst. Thermal behaviors and amount of DBSA that esterified with the cotton was determined. Pyrovatex CP new was applied as a comparison. It was speculated from the thermogravimetric analysis result that esterification of cellulose with DBSA worked similar to phosphate-ester at the initial stage of thermal decomposition. DBSA was also applied to PET and PET/cotton blended fabrics. Flame retardancy, thermal behaviors and durability of the finished fabrics were investigated. Evidence of the condensed phase effect of DBSA was also observed on PET and PET/cotton.

Abstract  To fulfill national and international fire safety standards, flame retardants (FRs) are being added to a wide range of consumer products and building materials consisting of flammable materials like plastic, wood and textiles. While the FR composition of some products and materials has been identified in recent years, the limited global coverage of the data and the large diversity in consumer products necessitates more information for an overall picture of the FR composition in common products/materials. To address this issue, 137 individual samples of various consumer products, building materials and wastes were collected. To identify and characterize potential sources of FRs in indoor environment, all samples were analyzed for content of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and novel flame retardants (NFRs). The most frequently detected were HBCDDs (85%), with the highest median concentration of Σ4HBCDDs of 300 mg kg(-1) in polystyrenes. The highest median concentration of Σ10PBDEs was found in recycled plastic materials, reaching 4 mg kg(-1). The lowest concentrations were observed for NFRs, where the median of Σ12NFRs reached 0.4 mg kg(-1) in the group of electrical & electronic equipment wastes. This suggests that for consumer products and building materials that are currently in-use, legacy compounds still contribute to the overall burden of FRs. Additionally, contrasting patterns of FR composition in recycled and virgin plastics, revealed using principle component analysis (PCA), suggest that legacy flame retardants are reentering the market through recycled products, perpetuating the potential for emissions to indoor environments and thus for human exposure.

Abstract  Non-durable and semi-durable flame retardants based mostly on phosphate or phosphonate salts continue to be used on infrequently washed or disposable goods, and recent improvements have been made to impart better 'hand' or some limited wash resistance. Backcoating with insoluble ammonium polyphosphate, usually with additives and binders to provide intumescence, has been found effective on charrable fabrics. However, the leading backcoating effective on a wider range of fabrics, including synthetics and blends, is decabromodiphenyl. ether plus antimony oxide. Newer candidates in development for textile coating are polymers and copolymers of pentabromobenzyl acrylate. The leading durable finish for cellulosic fibers, in use for about 50 years, continues to be based on tetrakis(hydroxymethyl)phosphonium salts reacted with urea and cured with gaseous ammonia. Softer versions have been recently developed using chemical or process modifications, or using selected fiber blends. Somewhat less durable phosphonic ester methylolamide finishes, not requiring gaseous curing, are used on cellulosic fabrics, especially overseas. Other competitive wash-durable phosphorus-based finishes for cellulosics and blends are in development. Polyesters continue to be flame retarded using a phosphonate or hexabromocyclododecane in a 'thermosol' process. Polyesters with built-in phosphinate structures are available as specialty fabrics. A dialkylphosphinate salt has been recently introduced as a melt spinning additive in polyester. A tribromoneopentyl phosphate melt spinning additive has been developed for polypropylene fiber. A number of inherently flame retardant synthetic fibers recently achieving increased usage include melamine-based fiber, viscose rayon containing silicic acid, aramides, oxidized polyacrylonitrile, and polyphenylene sulfide fibers. Some of these are used in protective clothing. The recent California and Federal mattress open-flame test standards have brought barrier fabrics into prominence. Some of these barriers use boric acid on cotton batting, others are proprietary composites and blends, both woven and nonwoven, comprising inherently flame retarded fibers combined with lower cost non-flame-retardant fibers. Upholstered furniture open-flame standards are pending.

Abstract  Molecular beam mass spectrometry (MBMS) and optical diagnostic techniques, two common combustion science diagnostic tools for studying the impact of material on flames, Lire evaluated as tools for estimating the gas-phase potential of polymer-flame retardant additives. The gas-phase activity of hexabromocyclododecane (HBCD), it widely used commercial flame retardant, was studied and compared via the two combustion diagnostic techniques. MBMS data for HBCD were reviewed and provided identification of gas-phase active species as well its quantitative information on the degree of effectiveness based upon reduction of OH in a premixed CH(4)/air/N(2) flame. In contrast, optical chemiluminescence detection of OH* and CH* provided it simpler technique for monitoring the gas-phase potential of flame retardants. Studies of CH* and OH* levels after addition of pyrolyzed products from polystyrene/HBCD blends into a diffusion flame system are compared with MBMS experiments of flames doped with pure HBCD. Comparison of chemiluminescence data with similar data from it small-scale heat release test, the pyrolysis combustion flow calorimeter, indicated that CH* and OH* activity relate to the heat release rate for flaming combustion. (c) 2009 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Abstract  In the present research, bioremediation of sediment contaminated with decabromodiphenyl ether (BDE-209) at 2 mg/kg (dw) using composting technology under four treatments was investigated. After 78 days, 87.9 +/- 4.3%, 96.3 +/- 3.3%, 95.7 +/- 1.6%, and 95.5 +/- 3.1% of the BDE-209 had been removed in treatments of sediment plus cabbage (treatment A); sediment plus cabbage, activated sludge, and sawdust (treatment B); sediment plus cabbage, co-metabolizable substances, and sawdust (treatment C); and sediment plus cabbage and sawdust (treatment D), respectively. Adding sawdust as an ameliorant slightly improved the BDE-209 degradation efficiency relative to adding only cabbage. The addition of TBBPA/HBCD (as co-metabolizable substances), and activated sludge (to provide exogenous microbes) did not significantly enhance the bioremediation process. A total of 15 additional less-brominated PBDEs congeners were detected demonstrated that BDE-209 was debrominated during the composting process. The results suggest that composting is an effective way of bioremediating sediment containing B DE-209.

Abstract  Polybrominated diphenyl ether (PBDE) concentrations were measured in surficial sediments from coastal sediments receiving industrial and municipal effluents in Kuwait. The summation PBDE concentrations varied by two orders of magnitude ranging from 80 to 3800 pg g(-1)dw. The congener distribution was dominated by BDE 183, with minor contributions from BDEs 154 and 153. The similarity between the congener profile to that of the technical octa formulation (Bromkal 79-8DE) suggests a source of this product in Kuwait. The observed gradient in concentration distribution, with high summation PBDE concentrations near the shore and an exponential decrease seaward, indicates that wastewater discharge from industrial activities in the study area is the primary source of these compounds in the sediments.

Abstract  The thermal degradation and combustion of ultra-high-molecular-weight polyethylene (UHMWPE) doped with triphenyl phosphate (TPP) at atmospheric pressure was studied by molecular beam mass spectrometry, dynamic mass spectrometric thermal analysis, microthermocouples, thermogravimetry, gas chromatography/mass spectrometry. The kinetics of thermal degradation of pure UHMWPE and that mixed with TPP at high (a parts per thousand 150 K/s) and low (0.17 K/s) heating rates was investigated. The effective values of the rate constant and activation energy of the thermal degradation reaction were determined. Burning velocity and temperature profiles in UHMWPE and UHMWPE + TPP flames were measured. The composition of the combustion products in a flame zone adjacent to the burning surface of the sample was determined. TPP vapor in the flame was detected. The addition of TPP to UHMWPE was found to reduce the flammability of the polymer. It is shown that TPP acts as a fire retardant in both the condensed and gas phases.

Abstract  Treatment of cotton fabric with etherified methylolated melamine (MM) alone or in admixture with dimethylodihydroxy ethylene urea (DMDHEU) along with Pyrovatex Cp was investigated to render the cotton fabric crease resistant and flame retardant. The treatment was carried out under different conditions including nature of catalyst, ratios of EMM and DMDHEU in their binary mixture and incorporation of silicon-elastomers, other polymeric products, as well as pre-polymerized EMM in the treating solution. Of all several catalysts examined, ammonium sulphate proved to be the best one for combined easy-care and flame retardancy finishing using EMM/Pyrovatex Cp mixture. The use of EMM/DMDHEU at different ratios, along with Pyrovatex Cp, did not perturb the individual contribution of EMM and DMDHEU in nitrogen content, crease recovery and strength losses of the fabric. Flame retardancy was greater at higher ratios of EMM in the EMM/DMDHEU mixture. Incorporation of certain silicon elastomers in the EMM/Pyrovatex Cp treating solution enhanced the easy-care and flame retardancy properties of the finished fabric without adversely affecting strength properties. On the other hand, incorporation of pre-polymerized EMM in a treating solution containing EMM and Pyrovatex Cp caused substantial changes in easy-care and flame retarding properties of the finished fabric, depending upon the pH of both pre-polymerization and treating solution. The use of EMM pre-polymerization at pH 6 brought about a finished fabric with significant flame retardancy beside a crease recovery of 250-degrees and retained strength of ca. 77 %.

Abstract  The technical feasibility of multifinishing of cotton fabric through conducting easy-care, flame retardancy and grafting treatments in one-stage process using the pad-dry-cure method was studied. In essence, the treating formulation consisted of etherified methylolated melamine (EMM), Pyrovatex Cp and acrylamide along with ammonium sulphate (catalyst for reactions involving EMM and Pyrovatex (p) and potassium persulphate (initiator for acrylamide grafting). The multifinishing treatment was carried out under different conditions including concentrations of EMM, Pyrovatex Cp, acrylamide, ammonium sulphate and potassium persulphate, as well as curing temperature and time. Results obtained indicated that increasing the acrylamide concentration in the multifinishing formulation caused enhancement in the percent add-on, nitrogen content and flame retarding properties of the multifinished fabric, while decreasing the crease recovery, tensile strength and elongation at break. Similar effects were obtained upon increasing the concentration of EMM, Pyrovatex Cp and ammonium sulphate. Raising the curing temperature from 120-degrees to 200-degrees was accompanied by increased add-on and decreased tensile strength and elongation at break. The nitrogen content and crease recovery increased by increasing the temperature upto 160-degrees and 140-degrees, respectively, then decreased. Maximum flame retardancy was obtained at a curing temperature of 160-degrees. Increasing the curing time from 1 to 5 minutes increased the add-on and decreased the tensile strength and elongation at break. Nitrogen content and flame retardancy increased with curing time up to 3 minutes, then decreased. The highest crease recovery was achieved after 1 minute curing. Explanation of these findings was reported.

Abstract  Product information sheet, MSDS, and Toxicity Data Summaries: acute oral rats, acute dermal rabbits, primary skin irritation rabbits, eye irritation rabbits, acute inhalation rats, Ames test, acute fish toxicity test, pilot cataractogenic study in chicks, cataractogenic study in chicks, biodegradation, hydrolysis, partition coefficient, solubility,

Abstract  Notice of initiation of 28-day repeated dose oral toxicity study of HBCD in rats

Abstract  Notice of initiation of 7 studies on HBCD: acute fish test, acute daphnid test, algal toxicity test, analytical method verification for the determination of HBCD in well water, determination of water solubility, determination of n-octanol/water partition coefficient, evaluation of hydrolysis as a function of pH

Abstract  Notice of initiation of a flow-through life-cycle toxicity test with the Cladoceran (Daphnia magna)