不同点火模式下软质聚氨酯泡沫燃烧的实验研究

为研究软质聚氨酯泡沫(FPUF)的燃烧行为对火灾的影响,采用锥形量热仪(CONE)分析FPUF在强制点火和非强制点火模式下的燃烧行为、热释放速率HRR、质量损失速率MLR和燃烧效率η。研究结果表明：当外部辐射≥40 kW/m²时,FPUF在2种点火模式下燃烧的HRR和MLR均出现2个明显的峰值且η约为88%;当外部辐射<40 kW/m²时,FPUF在非强制点火模式下燃烧的HRR和MLR曲线趋于单峰形式;FPUF在强制点火模式下燃烧前期为异氰酸酯(TDI)和多元醇的混合燃烧,在非强制点火模式下为TDI的挥发。根据研究结果修正现有燃料组分的热值计算方法,获得FPUF和多元醇的热值分别为(20±2),(28±3) kJ/g。     

Comprehensive assessment of toxic metals in urban and suburban street deposited sediments (SDSs) in the biggest metropolitan area of China

A set of toxic metals, i.e. As, Hg, Pb, Cd, Cu, Zn, Ni and Cr, in urban and suburban SDSs were investigated comparatively in the biggest metropolitan area of China, Shanghai. Results showed that all of the metals except As were accumulated greatly, much higher than background values. Geo-accumulation index indicated that metal contamination in urban SDSs was generally heavier than that in suburban SDSs. Potential ecological risk index demonstrated that overall risks caused by metals were considerable. Cd contributed 52% to the overall risk. Multivariate statistical analysis revealed that in urban SDSs, Zn, Ni, Cd, Pb, Cu and Cr were related to traffic and industry; coal combustion led to elevated levels of Hg; soil parent materials controlled As contents. In suburban SDSs, Pb, Cu, As and Cd largely originated from traffic pollution; Zn, Ni and Cr were associated with industrial contaminants; Hg was mainly from domestic solid waste.     

Toxic masking and synergistic modulation of the estrogenic activity of chemical mixtures in a yeast estrogen screen (YES)

Background, aim and scope

Estrogenic and non-estrogenic chemicals typically co-occur in the environment. Interference by non-estrogenic chemicals may confound the assessment of the actual estrogenic activity of complex environmental samples. The aim of the present study was to investigate whether, in which way and how seriously the estrogenic activity of single estrogens and the observed and predicted joint action of estrogenic mixtures is influenced by toxic masking and synergistic modulation caused by non-estrogenic chemical confounders.

Materials and methods

The yeast estrogen screen (YES) was adapted so that toxicity and estrogenicity could be quantified simultaneously in one experimental run. Mercury, two organic solvents (dimethyl sulfoxide (DMSO) and 2,4-dinitroaniline), a surfactant (LAS-12) and the antibiotic cycloheximide were selected as toxic but non-estrogenic test chemicals. The confounding impact of selected concentrations of these toxicants on the estrogenic activity of the hormone 17ß-estradiol was determined by co-incubation experiments. In a second step, the impact of toxic masking and synergistic modulation on the predictability of the joint action of 17ß-estradiol, estrone and estriol mixtures by concentration addition was analysed.

Results

Each of the non-estrogenic chemicals reduced the apparent estrogenicity of both single estrogens and their mixtures if applied at high, toxic concentrations. Besides this common pattern, a highly substance- and concentration-dependent impact of the non-estrogenic toxicants was observable. The activity of 17ß-estradiol was still reduced in the presence of only low or non-toxic concentrations of 2,4-dinitroaniline and cycloheximide, which was not the case for mercury and DMSO. A clear synergistic modulation, i.e. an enhanced estrogenic activity, was induced by the presence of slightly toxic concentrations of LAS-12. The joint estrogenic activity of the mixture of estrogens was affected by toxic masking and synergistic modulation in direct proportion to the single estrogens, which allowed for an adequate adaptation of concentration addition and thus unaffected predictability of the joint estrogenicity in the presence of non-estrogenic confounders.

Discussion

The modified YES proved to be a reliable system for the simultaneous quantification of yeast toxicity and estrogen receptor activation. Experimental results substantiate the available evidence for toxic masking as a relevant phenomenon in estrogenicity assessment of complex environmental samples. Synergistic modulation of estrogenic activity by non-estrogenic confounders might be of lower importance. The concept of concentration addition is discussed as a valuable tool for estrogenicity assessment of complex mixtures, with deviations of the measured joint estrogenicity from predictions indicating the need for refined analyses.

Conclusions

Two major challenges are to be considered simultaneously for a reliable analysis of the estrogenic activity of complex mixtures: the identification of known and suspected estrogenic compounds in the sample as well as the substance- and effect-level-dependent confounding impact of non-estrogenic toxicants.

Recommendations and perspectives

The application of screening assays such as the YES to complex mixtures should be accompanied by measures that safeguard against false negative results which may be caused by non-estrogenic but toxic confounders. Simultaneous assessments of estrogenicity and toxicity are generally advisable.     

富营养化水体内源磷释放和稳定化研究进展

水体富营养化是当今世界面临的一个严峻的环境问题,很多研究表明:水体沉积物中磷的释放是引起富营养化的主要因素,因此国内外很多学者对水体沉积物中磷形态,磷释放的影响因素和控制技术进行了研究。研究发现:pH、温度、溶解氧、氧化还原电位和扰动等环境因子对沉积物中磷的释放均有影响,但其影响程度不同。国外关于水体沉积物中磷的控制技术的研究比较多,其中包括供氧技术、原位控制技术和覆盖技术等,还有近几年发现的水生植物控制技术,但国内对沉积物污染控制技术的研究还停留在实验探索阶段,应用的很少。     

有机质对三峡库区消落区沉积物磷释放的影响

以三峡库区丰都消落区沉积物为研究对象,通过分析沉积物中磷的赋存形态,以及去除轻组有机质沉积物和沉积物矿物质对磷的吸附等温曲线,揭示了磷的赋存形态及释放与有机质的关系. 结果表明:消落区本底土壤较沉积物w(总磷),w(有机磷)及w(活性磷)更高,首次覆水时更具潜在释磷风险,夏季出露期有利于沉积物有机质和有机磷积累,沉积物有机质矿化分解对磷释放起促进作用,沉积物中w(有机质)与w(有机磷)呈显著正相关,与w(无机磷)呈负相关.      

pH和有机酸对氟溶出砖红壤中铝离子的影响

研究砖红壤对F-的吸附反应尤其是随后Al3+的释放过程,有助于增进对土壤酸化过程及其环境影响的理解. 在初步揭示出F-吸附反应以及Al3+释放反应的动力学特征基础上,重点考察了pH和有机酸对上述反应的影响. 结果表明:土壤对F-的吸附反应十分迅速,2 min内吸附量即可达到24 h内总吸附量95%,而土壤中不同含铝矿物的溶解度差异使Al3+的释放过程在前15 min十分迅速,释放量可达24 h内总释放量的80%,随后则逐渐减缓. 降低反应体系pH可促进Al3+释放,但会使F-吸附量减少,这是因为伴随Al3+的释放,部分F-又可以AlF络合物的形态重新进入溶液,尽管在低pH条件下,土壤表面以带正电荷为主而有利于F-吸附. 草酸和抗坏血酸对土壤吸附F-均有抑制作用,但对F-溶出土壤Al3+有促进作用. 此外,草酸对土壤铁氧化物的选择性溶解作用,可使更多F-吸附在土壤铝氧化物位点,并导致Al3+释放量增加.      

过硫酸钠缓释材料的释放性能及其对2, 4-二硝基甲苯的降解效果

针对原位化学氧化技术修复土壤和地下水时氧化剂因释放过快而导致的利用率低等问题,通过熔化成型法制备过硫酸钠缓释材料,分析石蜡、硅砂和过硫酸钠不同配比对材料成型度和释放性能的影响,研究缓释过程中溶液pH的变化,探讨其在水溶液中的缓释行为及其对2,4-二硝基甲苯（2,4-DNT）的降解效果.结果表明:当固定过硫酸钠质量为6 g、硅砂质量为18 g、蜡砂比（石蜡、硅砂质量之比）为1:4~1:8时,过硫酸钠缓释材料成型度适中,且过硫酸钠的累积缓释量随着时间的延长而逐渐增大,第31天时过硫酸钠累积释放百分比为74.67%~88.40%,可实现过硫酸钠的持续可控释放.当硅砂质量为18 g、蜡砂比为1:1~1:6时,过硫酸钠累积释放百分比随着过硫酸钠质量的增加而增大,且溶液中的pH呈先降低后上升的变化规律.缓释材料缓释前后实物图和显微镜分析结果显示,过硫酸钠缓释材料的释放是一个由外到内、速率由快变慢最终趋于平稳的过程.过硫酸钠质量为12 g、硅砂质量为18 g、蜡砂比为1:4的缓释材料对2,4-DNT具有较好的降解效果,第16次置换浓度为0.2 mg/L的2,4-DNT水溶液时,2,4-DNT的降解率为56.38%.研究显示,改变制备材料的配比可有效实现缓释材料中过硫酸钠的缓慢释放及对污染物的有效降解,可为原位化学氧化修复土壤和地下水提供理论支撑.      

水稻秸秆生物炭中铜和镉的形态分布及释放特性

由于目前缺乏对生物质原料来源的管控办法,极有可能用产自受污染农田土壤的秸秆制备出具有高重金属含量的生物炭,因此,研究生物炭中重金属的形态分布及其释放特性对于防控生物炭应用产生的环境风险具有重要意义.基于此,分别采集江西省贵溪铜冶炼厂周边九牛岗污染区和中国科学院鹰潭红壤生态实验站清洁区种植的水稻秸秆制备生物炭（分别记为“九牛岗生物炭”和“红壤站生物炭”）,分析两种生物炭中Cu、Cd的含量及其化学形态分布,考察不同固液比及pH对生物炭中Cu、Cd浸出的影响.结果表明:九牛岗生物炭中Cu、Cd的总量（以w计）分别为119.99、3.83 mg/kg,显著高于红壤站生物炭（19.50、0.96 mg/kg）.尽管九牛岗生物炭中w（酸溶态Cu）、w（酸溶态Cd）显著高于红壤站生物炭,但在形态分布上,九牛岗生物炭中Cu、Cd主要为相对稳定态（可氧化态和残渣态）,二者占比分别为80.3%、76.7%,高于红壤站生物炭（二者占比分别为53.2%、48.0%）.高固液比和低pH可有效增加两种生物炭中Cu、Cd的浸出毒性,其中,九牛岗生物炭在固液比为1:20和1:60时,浸出液中ρ（Cu）、ρ（Cd）均超过GB/T 14848—2017《地下水质量标准》中Ⅱ类标准限值.动力学及累积释放试验表明,两种生物炭中的部分Cu、Cd可在短时间内迅速释放而后逐渐平稳并有上升趋势,且九牛岗生物炭中Cu、Cd释放量显著高于红壤站生物炭.研究显示,来自污染区水稻秸秆生物炭中的Cu、Cd活性显著高于清洁区生物炭,具有更高的环境风险.      

外源有机酸添加对风化煤矸石污染释放及重金属有效性的影响

为评价不同类型有机酸对风化煤矸石污染释放的影响,通过在风化煤矸石中添加不同种类的外源有机酸(腐殖酸、柠檬酸、草酸、水杨酸)进行处理,分析稳定7d后煤矸石浸出液的特征污染组分及TCLP提取态重金属含量。结果表明:对照处理组的风化煤矸石浸出液具有典型的酸性矿山废水特征。添加少量柠檬酸、草酸和水杨酸能显著(p0.05)降低风化煤矸石浸出液的pH和Eh值、明显增加浸出液的盐度、亚铁、总铁和硫酸盐含量,然而腐殖酸处理对浸出液pH、EC、Eh无明显影响,且可降低浸出液硫酸盐含量。少量外源有机酸添加均能不同程度促进风化煤矸石中Fe、Mn、Cu、Zn元素溶出,其中水杨酸处理对4种金属元素的溶出量较大。然而4种外源有机酸处理则能有效抑制Pb溶出,其中柠檬酸、水杨酸处理抑制效果最明显。有机酸添加对风化煤矸石的重金属有效性影响表现为4种外源有机酸处理均能明显增加风化煤矸石中Mn元素的有效性,降低Zn元素的有效性,但对Fe元素的有效性影响不明显。4种外源有机酸添加对煤矸石中Cu元素有效性具有不同程度的影响,其中腐殖酸、草酸处理能明显降低Cu元素有效性,而柠檬酸和水杨酸处理则明显增加Cu的有效性。     

苯胺类化合物在不同pH值下对大型蚤的急性毒性及QSAR研究

测定了13种苯胺类化合物在不同pH下（6．0，7．8，9．0）对大型蚤（Daphnia magna)的24h半数活动抑制浓度24h-1C50，应用三种理化参数logP,TSA和pKa，对毒性数据进行了定量构效关系（QSARs)研究，并在此基础上初步探讨了苯胺类化合物的毒性机制。