Linking PBDEs in house dust to consumer products using X-ray fluorescence

The indoor environment is an important source of exposure to polybrominated diphenyl ethers (PBDEs), a class of fire retardants used in many household products. Previous attempts to link PBDE concentrations in house dust to consumer products have been hampered by the inability to determine the presence of PBDEs in otherwise similar products. We used a portable X-rayfluorescence (XRF) analyzer to nondestructively quantify bromine concentrations in consumer goods. In the validation phase, XRF-measured bromine was highly correlated with GC/MS-measured bromine for furniture foam and plastic from electronics (n = 29, r = 0.93, p < 0.0001). In the field study phase, the XRF-measured bromine in room furniture was associated with pentaBDE concentrations in room dust in the bedroom (r = 0.68, p = 0.001) and main living area (r = 0.51, p = 0.02). We also found an association between XRF-measured bromine levels in electronics and decaBDE levels in dust, largely driven by the high levels in televisions (r = 0.64, p = 0.003 for bedrooms). For the main living area, predicting decaBDE in dust improved when we included an interaction effect between the bromine content of televisions and the number of persons in the house (p < 0.005), a potential surrogate for television usage.     

基于2种磷系阻燃剂的复鞣加脂工艺设计与优化

在阻燃性铬鞣黄牛家具革的研发中,选用2种常见的磷系阻燃剂CU003与TX01,分别在复鞣、加脂工序中加入,研究这2种阻燃剂加入的最佳工序设置、最佳工艺条件及最佳用量,并对各工艺方案所得坯革进行物理性能表征。结果表明:加脂工序中加入阻燃剂的坯革的阻燃效果,远优于复鞣工序中加入阻燃剂的效果。随着阻燃剂CU003用量的增加,皮革的阻燃效果会随之增强,尤其能大大缩短有焰燃烧时间,但用量达到一定量后,其阻燃效果没有明显改善。阻燃剂TX01用量的增加对有焰燃烧时间影响不大,但可显著缩短无焰燃烧时间,同样地,当用量达到一定量以后,无焰燃烧时间也不会继续降低。在6种复配用量及用量比中,当CU003∶TX01=10%∶20%时,阻燃效率最高,且对皮革的基本性能影响不大。     

废旧聚对苯二甲酸乙二醇酯纤维醇解制备阻燃水性聚氨酯及其应用

为解决废旧聚对苯二甲酸乙二醇酯(PET)纺织品日益增多,造成巨大的能源和资源浪费问题,采用醇解法对PET纤维进行解聚,优化其解聚工艺;并以醇解产物为原料合成磷硅协同阻燃改性水性聚氨酯,探究了异佛尔酮二异氰酸酯中NCO基团与对苯二甲酸双羟乙酯中OH基团的量比(n(NCO)/n(OH))、阻燃剂三羟甲基氧膦(THPO)和二氧化硅(SiO₂)质量分数对阻燃改性水性聚氨酯形态和稳定性的影响;然后将得到的阻燃改性水性聚氨酯通过后整理的方法改性PET织物,并表征其阻燃性能。结果表明：在乙二醇(EG)为解聚剂,酯酸锌和氯化胆碱为催化剂的条件下,最佳解聚工艺为EG与PET质量比为4∶1、氯化胆碱与酯酸锌量比为1∶1、反应温度为185℃、反应时间为4 h,解聚产物对苯二甲酸双羟乙酯的产率可达87.6%;当THPO质量分数小于24%,SiO₂质量分数小于6%,n(NCO)/n(OH)在3～7时,阻燃改性水性聚氨酯呈均匀稳定的乳液形态;当THPO质量分数为24%,SiO₂质量分数为4%,n(NCO)/n(OH)为6时,阻燃改性PET织物具有较...     

Serum levels of polybrominated diphenyl ethers (PBDEs) in foam recyclers and carpet installers working in the United States

Increased exposure to the flame retardants known as polybrominated diphenyl ethers (PBDEs) may be expected to occur during the recycling of polyurethane foam containing these chemicals. To date, no studies in the United States have investigated occupational exposure to these flame retardants during recycling processes. The objective of the present study was to determine if individuals working in foam recycling facilities, and/or carpet installers who may install carpet padding manufactured from recycled foam, possess significantly higher PBDE serum levels relative to that of the general U.S. population. As a control group, serum was collected from four spouses and one clerical worker. In addition, levels in workers were also compared to the recently published national health and nutrition examination survey (NHANES) data set on PBDEs in the general U.S. population. Serum samples were collected in duplicate and analyzed by two different laboratories as quality control. Total PBDE levels were found to be significantly higher (p < 0.05) in the individuals recycling foam and installing carpet (n = 15) relative to the control group (n = 5). Median sigmaPBDE levels in the foam recyclers, carpet layers, and control group were 160, 178, and 19 ng/g lipid, respectively. In contrast, concentrations of a polybrominated biphenyl (BB-153) and a polychlorinated biphenyl (CB-153) were equivalent among all groups tested. The PBDE congeners BDE-47, 99, 100, and 153 contributed 90% of the sigmaPBDE concentration in serum and no differences in congener patterns were apparent among the different groups. Relative to concentrations measured in the NHANES, foam recyclers and carpet layers have body burdens that are an order of magnitude higher. These data suggest individuals recycling foam-containing products, and/ or using products manufactured from recycled foam (i.e., carpet padding), have higher body burdens of PBDEs, and thus may be at higher risk from adverse health effects associated with brominated flame retardant exposure.     

一种磷酸酯阻燃剂的合成

采用POCl3过两步法合成了一种磷酸酯类阻燃剂,讨论了影响合成工艺的主要因素如温度、时间和真空度等,确定了最佳的工艺条件,并将其应用于聚氨酯泡沫的阻燃,通过发泡实验表征了阻燃剂对聚氨酯泡沫的阻燃性能。实验表明,合成产物对聚氨酯泡沫有较好的阻燃效果。     

PBCDD and PBCDF from incineration of waste-containing brominated flame retardants

Brominated organic flame retardants comprise a large, heterogeneous group of compounds that are useful but also potentially damaging to the environment. In this investigation, three common brominated flame retardants were co-combusted with an artificial municipal solid waste in a pilot-scale fluidized bed incinerator. Combustion conditions ensured degradation of the flame retardants, but stable brominated organic compounds such as polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans were formed in the cooling flue gases. The incineration of fuels that contain both chlorine and bromine leads to the formation of a complex mixture of polybrominated/chlorinated dibenzo-p-dioxins and dibenzofurans. More bromination than chlorination was observed in these experiments, and the chlorination levels increased when bromine was added to the fuel. The most favored reactions led to the formation of dibromodichlorodibenzo-p-dioxin and dibromodichlorodibenzofuran. Theoretical calculations show that there is more Br2 than Cl2 in the flue gas when the two halogens are present at equimolar levels, because chlorine is mainly found in the form of HCl. This may explain the higher bromination level. BrCl is also present, which drives the chlorination observed when bromine is added.     

皮革阻燃处理技术的发展与展望

对卤系、磷系、膨胀型阻燃剂的类型、阻燃机理及应用进行了较全面的总结,指出了阻燃处理在皮革加工的重要作用,讨论了影响皮革阻燃性能的因素,并对阻燃剂在皮革领域的应用进行了展望.     

木质素生物质阻燃剂及其应用研究进展

针对木质素作为生物质阻燃材料化学结构复杂、阻燃效率较低等问题,对国内外木质素在阻燃材料中的研究现状进行了综述,主要介绍了常见的4类木质素阻燃剂:单组分木质素阻燃剂、复配型木质素阻燃剂、化学改性木质素阻燃剂和纳米木质素阻燃剂,分析了木质素在阻燃体系中发挥的作用以及存在的问题;对各类阻燃剂的特点和阻燃机制进行阐述,以及木质素作为生物质阻燃材料的发展方向进行总结和展望;最后指出在4类阻燃剂中,复配型木质素阻燃剂和化学改性木质素阻燃剂阻燃性能比较优异,将木质素与其他物质复配以及对木质素进行结构改性将成为未来研究的重点。     

有机磷酸酯阻燃剂健康危害研究进展

随着有机溴系阻燃剂在全球范围内被限制使用,作为其替代品的有机磷酸酯阻燃剂(organophosphate flame retardants, OPFRs)的使用量逐年增加,在各种环境介质、野生动物样品以及孕期妇女、儿童等危害敏感人群的生物样品中已广泛检出OPFRs及其代谢物,OPFRs污染可能引发的生态风险以及健康危害值得高度关注。针对OPFRs的早期暴露风险,本文系统综述了关于传统OPFRs生殖发育毒性、脑发育毒性与神经毒性、骨发育毒性、心脏发育毒性、内分泌毒性和代谢毒性的相关研究,并对近年来发现的新型OPFRs毒理学研究进行总结。目前OPFRs的毒理学研究多针对单一OPFR展开,应关注不同OPFRs的联合毒性效应;几种新型OPFRs的动物实验以及人群调查也十分缺乏。本文分析了目前研究存在的问题以及亟待解决的科学问题,以期促进开展OPFRs环境风险和人体健康风险的研究。     

阻燃纤维素气凝胶研究进展

为提高纤维素气凝胶的阻燃性,拓宽其应用领域,首先介绍了纤维素气凝胶的分类及其制备方法;然后综述了当前应用较为广泛的无机阻燃剂、有机阻燃剂和有机/无机复合阻燃剂等阻燃改性纤维素气凝胶的研究进展,并对比分析了各类阻燃剂的优缺点.其中,有机/无机复合阻燃剂兼具无机和有机阻燃剂的优点,表现出高效的阻燃效率,但也存在与纤维素基体...     

皮革阻燃处理及技术的探讨

对卤系、磷系、膨胀型阻燃剂的类型、阻燃机理及应用进行了较全面的总结,指出了阻燃处理在皮革加工的重要作用,讨论了影响皮革阻燃性能的因素,并对阻燃剂在皮革领域的应用进行了展望。     

RoHS regulated substances in mixed plastics from waste electrical and electronic equipment

The disposal and recovery of plastics from waste electrical and electronic equipment (WEEE) are of considerable importance, both from an environmental and an economic perspective. This paper presents the results of a study investigating current concentrations of hazardous substances in mixed plastics from WEEE and their implications for an environmentally sound recovery. The study included 53 sampling campaigns for mixed plastics from WEEE. The samples were analyzed with regard to heavy metals (cadmium, chromium, mercury, and lead) and flame retardants (PentaBDE, OctaBDE, DecaBDE, DecaBB) regulated in the RoHS Directive. Besides these substances, other brominated flame retardants known to occur in electronics (HBCD, TBBPA) as well as the total bromine and phosphorus contents were considered. Results show that no mixed plastics fraction from WEEE is completely free from substances regulated in the RoHS Directive. The lowest number and average concentrations were found in flat screen monitors. The highest concentrations were found in mixed plastics from CRT monitors and TVs. Mixed plastics fractions with high average concentrations of heavy metals originate from the treatment of small household appliances (cadmium), ICT equipment (lead), and consumer equipment (lead). Mixed plastics fractions with high average concentrations of brominated flame retardants mainly originate from the treatment of small household appliances for high temperature applications (DecaBDE), CRT monitors (OctaBDE and DecaBDE) and consumer equipment (DecaBDE), in particular CRT TVs (DecaBDE). To avoid a dissipation of hazardous substances into plastics and the environment, it is recommended that mixed plastics from WEEE are subject to a strict quality management.     

涤棉混纺织物的阻燃整理

采用涤纶阻燃剂DFR、棉用阻燃剂Pyrovatex CP new及阻燃剂SFR对纯棉、纯涤纶、涤棉混纺织物进行整理,比较整理品的燃烧性能,并采用热重分析（TGA）探讨不同阻燃剂的阻燃机理.试验结果表明,DFR/CP两步法整理涤棉织物的限氧指数（LOI）值为25.0%,阻燃效果并不理想.CP对棉的阻燃作用主要是凝聚相机理;DFR对涤纶主要是气相机理.SFR整理棉、涤纶和涤棉织物的LOI值分别高达47.1%、51.3%和39.2%,阻燃效果显著.SFR对棉主要在凝聚相起作用,对涤纶主要在气相起作用.     

阻燃技术在制浆造纸工业中的应用研究进展

综述了近年来阻燃技术在制浆造纸工业中的应用研究进展,介绍了阻燃剂在造纸行业中的发展过程、阻燃纸类的应用、阻燃剂的作用机理和阻燃评价方法。从纤维的阻燃改性、难燃纤维阻燃、填料阻燃和涂料阻燃等方面论述了阻燃技术在制浆造纸工业中的应用,并对以上方法进行分析与比较。     

磷酸改性芳纶对聚氨酯硬质泡沫阻燃抑烟性能的影响

为提高聚氨酯泡沫的阻燃性能,采用磷酸改性芳纶对聚氨酯硬质泡沫进行阻燃改性,借助氧指数仪、烟密度仪、锥形量热仪、热重分析仪等对改性前后聚氨酯硬质泡沫的阻燃性能、产烟行为、燃烧行为、热稳定性和力学性能进行表征。结果表明:添加改性芳纶的聚氨酯泡沫具有更好的阻燃、抑烟和力学性能;相对于纯聚氨酯泡沫,添加质量分数为5%改性芳纶的聚氨酯泡沫的极限氧指数提高了15.8%,最大烟密度、最大燃烧热释放速率、热释放量、最大生烟速率、产烟量分别降低了25%、25.3%、10%、35.7%、47.3%;改性芳纶的添加有利于改善聚氨酯硬质泡沫的热稳定性,使其在700 ℃时的残炭率增加为14.5%。     

聚丙烯腈无卤阻燃及其抑烟技术研究进展

为推进聚丙烯腈无卤阻燃技术的进一步发展,同时为聚丙烯腈无卤阻燃技术的科学研究与产业化应用提供参考,阐述了聚丙烯腈纤维及其织物的主要阻燃技术,常用无卤阻燃剂的类别及不同无卤阻燃剂的主要抑烟机制。综述了国内外聚丙烯腈无卤阻燃及抑烟技术的发展概况和最新研究进展。针对不同无卤阻燃剂的缺点提出了对应的解决方案和发展要求。分析了国内外聚丙烯腈无卤阻燃技术的发展差异,并提出了相应建议。展望了未来聚丙烯腈阻燃技术的发展,指出高效、抑烟、环保的阻燃整理技术将会成为未来阻燃聚丙烯腈研究领域的重要发展方向。     

超高效液相色谱-串联质谱法检测婴儿米粉中11种有机磷阻燃剂

采用超高效液相色谱-串联质谱技术,建立婴儿米粉中11种有机磷阻燃剂的检测方法。样品用0.5%甲酸乙腈溶液超声提取,提取液经分散固相萃取吸附剂净化,聚四氟乙烯滤膜过滤后上机检测,5 mmol/L甲酸铵的水溶液和乙腈为流动相梯度洗脱,目标化合物在ACQUITY UPLC? BEH C₁₈ 色谱柱（100 mm×2.1 mm,1.7 μm）上实现分离,在电喷雾正离子扫描模式下进行多反应监测（MRM）,外标法定量。通过优化色谱条件,11种有机磷阻燃剂均达到了基线分离。11种有机磷阻燃剂在0.5~100 μg/L（磷酸三辛酯0.05~10 μg/L）范围内线性关系良好,相关系数r均大于0.994。检出限（3S/N）为0.003~0.926 μg/kg,定量限（10S/N）为0.01~2.78 μg/kg。婴儿米粉中低、中、高3个添加浓度水平的加标回收率为63.2%~113.4%,相对标准偏差（n=6）均小于10%。运用建立的方法分析了4种婴儿米粉,磷酸三苯酯的检出率高达100%,其中一份米粉检出了磷酸三正丁酯和磷酸三（2-氯丙基）酯。该方法简单可靠、灵敏度高、重现性好,覆盖的有机磷阻燃剂种类多,适用于婴儿米粉中痕量有机磷阻燃剂的检测。     

CPSC及CPSA中家具法规的解读及影响

近年来,美国消费品安全协会(CPSC)及《消费产品安全法案》(CPSA)针对中国出口家具,提出多项新的安全政策,而且其条款实施方法更为严格,实施力度不断加强,这些强制法规和召回行为使中国家具出口企业面临成本提高,订单取消,甚至是破产等多种风险。介绍分析了CPSC关于家具方面的法规要求、警示以及召回公告,以此希望家具出口企业及时改进产品质量,规避出口风险。     

丙纶织物发泡阻燃涂层工艺

采用稳泡的阻燃涂层胶对丙纶织物进行泡沫阻燃涂层整理。探讨了涂层的工艺条件（涂层机和发泡机的各项参数）；分析了涂层刀距、阻燃胶密度和上胶量对涂层织物阻燃性能的影响，以及泡沫密度、压泡压力与织物透气性和涂层膜的关系。综合考虑产品质量和成本，选择的工艺参数为：泡沫密度150-200g／L，压泡压力58．9—68．7N／cm^2。     

涤纶织物的涂层阻燃整理

以甲基三甲氧基硅烷和聚磷酸铵(APPⅡ)为原料制备硅氧烷包覆聚磷酸铵协同阻燃剂,并通过正交实验确定了磷/硅的最佳配比.将该阻燃剂与水性聚氨酯复合制成环保阻燃涂层剂并用于涤纶织物的阻燃涂层整理,探讨了阻燃剂与水性聚氨酯的配比以及涂层量对织物阻燃性能及其他性能的影响.结果表明,随着阻燃剂与水性聚氨酯配比的增加,织物阻燃效果提高,其强力及静水压下降;当涂层整理的涂层量为20g/m2时,涂层涤纶织物既具有优异的阻燃效果,又能保证织物的手感.通过对比实验表明,该阻燃剂相对APPⅡ而言,能赋予织物优异的阻燃、高强力及防"霜化"等效果.