Development of a solid-phase microextraction GC-NPD procedure for the determination of free volatile amines in wastewater and sewage-polluted waters.

An analytical procedure for the determination of free volatile C1-C6 amines in aqueous matrixes has been developed and applied to their determination in waste-water, primary and secondary effluents, and sewage-polluted river samples. The developed analytical procedure involves headspace sampling using solid-phase microextraction with a poly(dimethylpolysiloxane) coating (100 microns) followed by GC-NPD determination and GC/MS confirmation using a tailor-made PoraPLOT amines capillary GC column for volatile amines. Procedural detection limits were compound dependent but ranged from 3 to 56 micrograms L-1, being close to or lower than the odor threshold concentration, and the reproducibility was ca. 15% (N = 5) in real water samples. The developed analytical procedure is solvent free, cost-effective (no cryogenic trap needed), and faster than existing methods because no derivatization step is involved in the determination. Linearity was compound dependent but ranged at least from 50 to 600 micrograms L-1.     

The biodegradation of a biopolymeric additive in building materials

A summary is given of a series of studies performed in order to explain one cause of bad odour and spoilage of floor covering materials (‘sick building syndrome’). Bad odours as well as spoilage of floor covering materials, i.e. blackening etc., inside buildings with self-levelling concrete containing casein are due to the biodegradation of the protein molecule by different species ofClostridia, which have adapted themselves to the extreme environment, i.e. a high pH and a relatively low temperature (pH 12 and 17°C). These new characteristics ofClostridia make it possible, under these extreme conditions, for theClostridia to degrade the casein molecule to volatile organic acids and monoamines. Organic acids such as propionic acid, butyric acid etc, and monoamines such as triethylamine, di-iso-butylamine etc. have been detected in biodegraded concrete. The monoamines are odorous and contribute strongly to the bad odour experienced inside some buildings constructed between 1979 and 1982. The acids are chemically bound in the concrete and can therefore not be observed as bad odour. A simulation of the biodegradative attack on concrete showed that the same acids were produced in the laboratory (in vitro) as the one detected in the floor covered with concrete.

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Résumé On résume une série d'études destinées à déterminer la cause de l'odeur désagréable et de la détérioration de matériaux de revêtements de sols (‘sick building syndrome”). Les odeurs désagréables et la détérioration des revêtements de sols, c'est-à-dire le noircissement, etc... dans des batiments où pour la confection de chapes on s'est servi d'un béton contenant de la caséine sont imputables à la biodégradation de la molécule de protéine par différentes espèces deClostridia, qui se sont adaptées aux conditions extrêmes (haut pH: 12 et températures relativement basses: 17°C). Ces nouvelles propriétés desClostridia leur permenttent dans ces conditions extrêmes de transformer la molécule de caséine en acides organiques volatiles et en monoamines. On a discerné des acides organiques, tels que l'acide propionique, butyrique, etc... et des monoamines comme la triéthylène et di-iso-butylamine dans le béton biodétérioré. Les monoamines sont odorigènes et contribuent largement à l'odeur désagréable qui se dégage dans certains batiments construits entre 1979 et 1982. Les acides se trouvent chimiquement liés dans le béton. On ne peut donc les déceler par leur odeur désagréable. Une simulation de l'attaque du béton par une action biodégradante a montré qu'on obtenait en laboratoire (in vitro) les mêmes acides que ceux dont la présence avait été détectée dans un sol recouvert de béton.

     

Development of an automated method for simultaneous determination of low molecular weight aliphatic amines and ammonia in ambient air by diffusion scrubber coupled to ion chromatography

A method has been developed for the simultaneous determination of low molecular weight aliphatic amines and ammonia in the atmosphere. Analyte gases are collected quantitatively in high-purity deionized water of a planar diffusion scrubber, and the resultant solution is analyzed by ion chromatography. A 1-h cycle analysis could be continuously repeated. The calibrations for the amines are linear between 5 and 500 pptv. The detection limits are a few pptv with RSD of less than 3%. The calibration for ammonia shows severe curvature at high concentrations so that second-order fitting is required for accurate determination. This method was successfully applied to the environmental air analyses. The major amines in the atmosphere were trimethylamine, dimethylamine, and methylamine, and the temporal variations were closely correlated with that of ammonia, implying their identical emission sources.     

Membrane extraction with a sorbent interface for headspace monitoring of aqueous samples using a cap sampling device

A cap-shaped device was employed for headspace sampling. This sampling device coupled to membrane extraction with a sorbent interface (MESI) is intended to perform on-site and on-line aqueous sample monitoring. A laboratory sampling testwas performed both at the water surface and under water, and it showed some advantages in underwater monitoring. A group of volatile organic compounds (VOCs), varying in PDMS/gas and gas/water distribution constants, benzene, toluene, ethylbenzene, o-xylene, and trichloroethylene (TCE), was used for the sampling study. Magnetic stirring of the sample and circulation of the headspace air with a microfan were used for the enhancement of mass transfer between sample matrix and membrane to obtain higher extraction rate and efficiency. The agitation approaches were investigated individually and compared. The results showed that simultaneous agitation in water and air could greatly improve the extraction efficiency. Good linearity and precision and low detection limits were obtained for water-surface monitoring. The study demonstrated that Cap-MESI is a useful tool for field headspace monitoring of volatile organic compounds.     

An Environmentally Assisted Cracking Evaluation of UNS C64200 (Al–Si–Bronze) and UNS C63200 (Ni–Al–Bronze)

A recent failure of a union nut, UNS C64200, made of Al–Si–Bronze (ASB) in a breathing air system of a marine platform has highlighted the need for environmentally assisted cracking (EAC) data for both ASB and Ni–Al–Bronze UNS C63200 (NAB) components in environments relevant to marine use. In addition, the possibility of exposure to ammonia environments via cleaning agents or biological processes warrants consideration because of the known susceptibility of bronze to EAC in ammonia environments. A displacement-controlled, rising step load (RSL) technique was employed on precracked compact tension specimens to quantify and compare the threshold stress intensities for EAC in air, seawater (SW), and SW + ammonia environments for wrought ASB and NAB materials. These results are compared to calculations of the stress intensity in service to determine the probability of EAC initiation. ASB was found to be susceptible to subcritical intergranular EAC initiation in laboratory air, SW, and SW + ammonia environments. NAB was immune to EAC under the conditions tested in laboratory air and SW, but was susceptible to intergranular EAC in SW + ammonia solution. The threshold stress intensity in SW + ammonia was found to be similar for both ASB and NAB; however, the subcritical crack growth rate for NAB was found to be 2–3 times faster than ASB. Calculations of stress intensity indicate that, in the air system applications where the installation torques are higher, the likelihood of subcritical cracking in ammonia environments is high. Stress intensities approach the ASB threshold values for subcritical intergranular cracking in air when the defect depth approaches half the wall thickness of the nut.     

高强度聚硫密封腻子的制备及粘接性能研究

以液态聚硫橡胶为主体材料、二氧化锰为固化剂研究了不同牌号聚硫橡胶配比、二氧化锰用量对密封腻子力学性能的影响以及橡胶粘接面处理形式对密封腻子粘接性能的影响.结果显示,当不同分子量的液体聚硫橡胶以质量比30∶55∶15复配使用、二氧化锰用量为12份时,聚硫密封腻子具有较好的力学性能,砂带打磨结合等离子处理橡胶粘接面可以大幅...     

Design and validation of portable SPME devices for rapid field air sampling and diffusion-based calibration

The use of SPME fibers coated with porous polymer solid phases for quantitative purposes is limited due to effects such as interanalyte displacement and competitive adsorption. For air analysis, these problems can be averted by employing short exposure times to air samples flowing around the fiber. In these conditions, a simple mathematical model allows quantification without the need of calibration curves. This work describes two portable dynamic air sampling (PDAS) devices designed for application of this approach to nonequilibrium SPME sampling and determination of airborne volatile organic compounds (VOCs). The use of a PDAS device resulted in greater adsorbed VOC mass compared to the conventional SPME extraction in static air for qualitative screening of live plant aromas and contaminants in indoor air. For all studied air samples, an increase in the number of detected compounds and sensitivity was also observed. Quantification of aromatic VOCs in indoor air was also carried out using this approach and the PDAS/SPME device. Measured VOC concentrations were in low parts-per-billion by volume range using only 30-s SPME fiber exposure and were comparable to those obtained with a standard NIOSH method 1501. The use of PDAS/SPME devices reduced the total air sampling and analysis time by several orders of magnitude compared to the NIOSH 1501 method.     

The association of hydrogel and biphasic calcium phosphate in the treatment of dehiscence-type peri-implant defects: an experimental study in dogs

Hydrogel polymers have many applications in regenerative medicine. The aim of this study in dogs was to investigate bone regeneration in dehiscence-type peri-implant defects created surgically and treated with (i) biphasic calcium phosphate (BCP) granules alone; (ii) a composite putty hydroxypropyl methylcellulose (HPMC)/BCP (MBCP/putty); and (iii) a polymer crosslinked membrane of silanized-HPMC (Si-HPMC/BCP) compared with empty controls. At 3 months, new bone formation was significantly more important in defects filled with HPMC/BCP or Si-HPMC/BCP compared with spontaneous healing in control (P = 0.032 and P = 0.046 respectively) and more substantial compared with BCP alone. Furthermore, new bone formation in direct contact with the implant surface was observed in all three groups treated with BCP. The addition of HPMC to the BCP granules may have enhanced the initial stability of the material within the blood clot in these large and complex osseous defects. The Si-HPMC hydrogel may also act as an occlusive membrane covering the BCP, which could improve the stability of the granules in the defect area. However, the crosslinking time of the Si-HPMC is too long for easy handling and the mechanical properties remain to be improved. The composite MBCP/putty appears to be a valuable bone-graft material in complex defects in periodontology and implantology. These encouraging results should now be confirmed in clinical studies.     

Sorbent-impregnated polyurethane foam disk for passive air sampling of volatile fluorinated chemicals

A passive air sampler comprising a polyurethane foam (PUF) disk impregnated with XAD-4 powder has been developed. This sorbent-impregnated PUF (SIP) disk builds on previous work using PUF disk passive air samplers that have been effective in spatial air mapping studies of nonpolar hydrophobic chemicals, without the need of electricity or expensive air sampling equipment. In this study, PUF disks and SIP disks are calibrated for sampling volatile polyfluorinated chemicals--specifically, the fluorotelomer alcohols (FTOHs) and perfluoroalkyl sulfonamides (PFASs). Results demonstrate the low sorptive capacity of the PUF disk samplers, particularly for the FTOHs, with PUF disks reaching equilibrium within 1 day, after collecting approximately 0.4 and 1.2 m3 of air for 8:2 FTOH and 10:2 FTOH, respectively. This limits their use for these target compounds when time-weighted, linear-phase sampling is desired. The presence of just 0.4 g of XAD powder in the SIP disks greatly increases the sorptive capacity (by approximately 2 orders of magnitude for the FTOHs) and provides linear-phase sampling for a period of several weeks. PUF-air partition coefficients, KPUF-A, calculated for the FTOHs and PFASs are considerably lower than values predicted using previously established correlations against the octanol-air partition coefficient, KOA, demonstrating the unique partitioning behavior of the polyfluorinated chemicals. Using results from these calibration tests, air concentrations of FTOHs were derived from PUF disk samples that were deployed in 52 homes in Ottawa, Canada, during 2002/2003. These represent the first comprehensive measurements of FTOHs in indoor air in North America. Range and (geometric mean) air concentrations (pg m-3) were 261-28 900 (2070) for 8:2 FTOH and 104-9210 (890) for 10:2 FTOH. These air concentrations are orders of magnitude higher than observed for outdoor air, establishing indoor environments as important for human exposure and also as potential sources to the larger environment.     

Characterization of Polymers Used as Pharmaceutical Excipients by Dynamic Headspace Gas Chromatography — Mass Spectrometry

Abstract

The use of dynamic headspace, a continuous gas extraction technique, for the analysis of volatile compounds in polymers is discussed. The present work presents the principles of dynamic headspace and its use in combination with capillary gas chromatography - mass spectrometry. The merits of dynamic headspace sampling in comparison to static headspace, the predominantly used headspace sampling method, are also discussed. To illustrate the technique, analyses of volatile compounds in three different carbohydrate polymers, commonly used as pharmaceutical excipients, are carried out.     

Sampling of trace volatile metal(loid) compounds in ambient air using polymer bags: a convenient method

The sampling of volatile metal(loid) compounds (VOMs) such as hydrides, methylated, and permethylated species of arsenic, antimony, and tin is described using Tedlar bags. Advantages as well as limitations and constraints are discussed and compared to other widely used sampling techniques within this area, namely, stainless steel canisters, cryotrapping, and solid adsorbent cartridges. To prove the suitability of Tedlar bags for the sampling of volatile metal(loid) compounds, series of stability tests have been run using both laboratory synthetic and real samples analyzed periodically after increasing periods of storage. The samples have been stored in the dark at 20 degrees C and at 50 degrees C. Various volatile arsenic species (AsH3, MeAsH2, Me2AsH, Me3As), tin species (SnH4, MeSnH3, Me2SnH2, Me3SnH, Me4Sn, BuSnH3), and antimony species (SbH3, MeSbH2, Me2SbH, Me3Sb) have been generated using hydride generation methodology and mixed with moisturized air. Three static gaseous atmospheres with concentrations of 0.3-18 ng/L for the various compounds have been generated in Tedlar bags, and the stability of the VOMs has been monitored over a period of 5 weeks. Sewage sludge digester gas samples have been stored only at 20 degrees C for a period of 48 h. Cryotrapping GC/ICPMS has been used for the determination of the VOMs with a relative standard deviation of 5% for 100 pg. After 8 h, the recovery rate of all the compounds in the air atmospheres was better than 95% at 20 and 50 degrees C, whereas the recovery after 24 h was found to be between 81 and 99% for all VOMs at 20 and 50 degrees C except for Me3Sb and Me3As. These species show a loss between 48 and 73% at both temperatures. After 5 weeks at 20 degrees C, a loss of only 25-50% for arsine and stibine and the above-mentioned tin compounds was determined. Only Me3Sb, Me3Bi, and Me2Te were present in the digester gas sample. After 24 h, losses of 44, 10, and 12%, respectively, could be determined. Given these results, Tedlar bags could even be used, with some limitations, for long-term sampling of air containing traces of VOMs. The loss is more pronounced at higher temperatures.     

Effect of heat treatment on the properties of erbium-doped silicon

The effect of thermal treatment on the electrical properties of n-Si doped with the rare-earth element erbium during growth was studied for the first time. Annealing of the erbium-doped samples in air at 900–1200°C for 1–2 h, followed by quenching or slow cooling, leads to inhibition of the high-temperature defects.     

噪声敏感建筑隔声与声舒适性要求

住宅声学性能将在心理、生理和社会上影响住户,声学舒适性是高要求敏感建筑设计和施工中的重要考虑因素。文章对比分析了中国和欧美等国家隔声指标和要求的差异,发现国内住宅空气声隔声指标比国外的指标要求低4～10 dB;楼板撞击声压级比国外的要求高3～25 dB,最大偏差达到-25 dB。考虑到城市化进程的不断推进,城镇居住密度和容积率的不断增大,以及多高层居住建筑的大量应用,以预期满意度50%～67%为目标,建议住宅声学设计标准在现有的标准和规范基础上提高5 dB左右,以期改善住宅的声学品质和住户的声学满意度,而后期开展相应的声学社会调查,改善居住声学环境是十分必要的。     

Placement of effective work-in-progress limits in route-specific unit-based pull systems

Unit-based pull systems control the throughput time of orders in a production system by limiting the number of orders on the shop floor. In production systems where orders can follow different routings on the shop floor, route-specific pull systems that control the progress of orders on the shop floor by placing limits on the number of orders in (parts of) a routing, have shown to be effective in controlling throughput times. This is because route-specific pull systems are able to create a balanced distribution of the amount of work on the shop floor, which leads to shorter and more reliable throughput times. The placement of limits on work-in-progress in a route-specific pull system determines to a large extent the workload balancing capability of such a system. This paper shows how the placement of work-in-progress limits affects the workload balancing capability and thereby the throughput time performance of a route-specific unit-based pull system, namely POLCA.     

Helical sorbent microtrap for continuous sampling by a membrane and trap interface for on-line gas chromatographic monitoring of volatile organic compounds

A helical sorbent microtrap consisting of a helical sorbent fixed inside a silicosteel capillary tube is presented. The main parameters that affect the safe sampling time of the helical sorbent microtrap in continuous sampling by a membrane and trap interface for on-line gas chromatographic monitoring of organic volatiles in gaseous samples are examined, taking into account the helical configuration of the sorbent, the presence of the membrane in system, and the properties of the analytes. Thermal desorption of analytes from the helical sorbent trap was also examined having regard to the influence of the turbulent flow generated by the helical sorbent in the heat transfer and the effect of thermal backward flow on the peak shape. The practical application of the helical sorbent microtrap in a membrane and trap interface was demonstrated by on-line gas chromatographic monitoring of four volatile organic compounds in the fume hood air and of volatile organic compounds from a diesel engine exhaust. The limit of detection was in the picogram per milliliter range, depending on the time of trapping and the parameters that affect the permeation through the membrane.     

建筑隔声研究的进展

论文对近年来建筑隔声在研究和实践的几个主要方面进展,作一评述。所讨论的问题包括:质量定律与单值评价、轻钢龙骨板墙的隔声、楼板隔声的评价、侧向传声、声屏障及绿化降噪、窗的隔声和通风、敞开办公室的私密性。     

Experimental upgrades of membrane introduction mass spectrometry for water and air analysis

Some improvements to the membrane introduction mass spectrometry (MIMS) technique, resulting in low-ppt detection limits for volatile organohalogen compounds (CX) in water (namely, chloroform, bromoform, bromodichloromethane, chlorodibromomethane, tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane, and carbon tetrachloride) and low-microgram per cubic meter detection limits for benzene, toluene, ethylbenzene, and xylenes (BTEX) in gaseous samples, are shown. A static MIMS configuration was compared to a dynamic one, the former requiring longer time to obtain the analytical response. A cryotrapping preconcentration step is introduced and linearity of response, mixture effects, and detection limits are presented. The instrumental setup consists of a hollow fiber silicone membrane, a water or air container, a cryofocusing trap based on Tenax adsorbent, a Peltier cell, and a Varian ion trap benchtop mass spectrometer is described. This instrumental setup, which we named membrane extraction trap focusing mass spectrometry, allowed the detection of CX in water at a concentration as low as 8 ppt and of benzene in air at 0.1 microg/m3. The whole assembly shows great potential for on-site routine monitoring of drinking water resources and urban and indoor air under current EU and Italian regulations.     

Evaluation of an osteostimulative putty in the sheep spine

The objective of this study is to evaluate local response to a bioactive glass based composite putty (NovaBone Putty) in a vertebral body defect model in sheep, as compared to NovaBone, a bioactive glass particulate. Two time periods were used for the study, 6 and 12 weeks. Empty defects were also used as a control. In comparing the three test groups, the relative amount of new bone for both grafted defects was substantially greater than for the empty controls (P < 0.05). At 6 weeks, the bone formation was 42% for NovaBone Putty, 27% for NovaBone and 1.2% for the ungrafted empty defect. At 12 weeks, the bone formation was 51.4% for NovaBone Putty, 47.3% for NovaBone and 5.1% for the empty defect. NovaBone Putty, the test material, had greater bone content than the NovaBone, both of which were significantly greater than the empty control.     

北京市居室几种常见有害气体全年污染水平调查

通过全年两月一次随机选择北京市共34处办公室和35处家居作为样点,按照国家标准方法采集氨、苯、甲醛、总挥发性有机化合物和氡几种常见有害气体,并进行浓度水平的分析,调查其污染水平及季节变化情况。结果表明:北京市室内环境中氨、甲醛和总挥发性有机化合物的超标现象严重,苯属轻度污染,氡完全符合室内环境质量标准。不同季节污染物水平表现出差异:甲醛浓度在7月最高,氨、苯浓度在9月最高,氡浓度在春季左右达到最高,总挥发性有机化合物成分复杂,随时间变化规律性不明显。     

Combined effect of chill storage and modified atmosphere packaging on mussels (Mytilus galloprovincialis) preservation

Changes in biochemical indices, microbial growth, headspace and sensory quality of mussels which had been packaged in two modified atmospheres [Modified atmosphere packaging (MAP) 1: 60% CO₂/20% N₂/20% O₂ and MAP 2: 60% CO₂/40% N₂] and under vacuum (VP) were studied for 14 days. The results showed better quality retention and greater shelf life of mussels packaged under MAP 1 as compared to MAP 2 and VP samples. Increase in total volatile basic nitrogen followed the order: MAP 1 < MAP 2, VP < air (control) samples while increase in trimethylamine nitrogen followed the order: MAP 1 < air < MAP 2 < VP. The 2‐thiobarbituric acid (TBA) values of MAP 1 and air samples were significantly higher (p < 0.05) than the TBA values of VP and MAP 2 samples. MAP 1 showed a greater (p < 0.05) inhibition effect on total viable count of mussel samples than all other packaging conditions. Based primarily on odour scores, the MAP 1 samples remained acceptable up to ca. 10–11 days, the MAP 2 and VP up to ca. 7–8 days while the air‐packaged samples up to ca. 5–6 days of storage. Copyright © 2007 John Wiley & Sons, Ltd.