挥发性有机物与阳离子表面活性剂溶液间气液平衡关系

研究了挥发性化合物(VOCs)甲苯与典型阳离子表面活性剂十六烷基三甲基溴化铵(CTMAB)溶液间气液平衡关系.结果表明,CTMAB对甲苯气液平衡影响显著,可明显降低甲苯表观亨利系数(Hc以),抑制甲苯挥发;Hc随CTMAB浓度的增加而降低,CTMAB浓度XCMC时,亨利系数随X降低较快,抑制甲苯挥发能力较强.推导并验证了Hc与X之间定量关系式:Hc=H/(1+K(X-CMC)),Hc计算值与实验值间相关系数R=0.91.温度对Hc影响显著,Hc随温度(T)的升高而增大,Hc与1/r呈线性关系.     

腐殖酸对蒽的增溶作用及其影响因素

对比研究了腐殖酸(HA)及3种非离子表面活性剂(Tween20,Tween80,TX100)对典型多环芳烃蒽的增溶性,并探讨了离子强度、共存有机物对HA增溶多环芳烃行为的影响,实验结果表明,当表面活性物质浓度大于临界胶束浓度(CMC)时,蒽的表观溶解度与表面活性物质浓度具有良好的线性关系,而且HA与非离子表面活性剂相比,其增溶效果明显优于非离子表面活性剂,增溶顺序为HA＞Tween20＞Tween80＞TX100;同时离子强度及共存有机物对HA增溶葸的程度均有较大的影响.     

不同类型表面活性剂对三氯乙烯的增溶作用

考察不同类型的表面活性剂对三氯乙烯(TCE)的增溶作用.选用阴离子型十二烷基硫酸钠(SDS)、非离子型聚氧乙烯辛基苯酚醚(TX100)、阳离子型十六烷基三甲基溴化铵(CTAB)及生物表面活性剂鼠李糖脂和脂肽,研究表面活性剂对三氯乙烯的增溶能力.结果表明,5种表面活性剂浓度在临界胶束浓度(CMC)以上时,TCE在水相中的表观溶解度随表面活性剂浓度的增大而线性增大.质量增溶比(WSR)和摩尔增溶比(MSR)为鼠李糖脂>脂肽>CTAB>TX100>SDS.在各表面活性剂溶液中,所用的各表面活性剂质量浓度顺序为SDS#TX100=CTAB#鼠李糖脂=脂肽,两种生物表面活性剂的质量浓度仅为SDS的1%,但生物表面活性剂对TCE的饱和增溶容量有更好的提高效果.因此,相比之下,生物表面活性剂对TCE的增溶能力较强,其中以鼠李糖脂为最佳,而在化学合成表面活性剂中阳离子表面活性剂CTAB增溶TCE的效果最优.     

混合表面活性剂吸附和分配损失减小的热力学机制

通过测定Triton X-100-十二烷基苯磺酸钠(TX100-SDBS)混合表面活性剂的表面张力和临界胶束浓度(CMC),运用非理想混合溶液理论和相分离模型,研究了TX100和SDBS的混合胶束化过程.TX100和SDBS在水相形成混合胶束,相互作用参数β的平均值为-3.35,标准混合胶束化自由能小于单一TX100.结果表明,在表面活性剂增效修复土壤和地下水的有机污染过程中,混合表面活性剂的胶束化过程是非离子表面活性剂吸附和分配损失减小的机制.     

表面活性剂对微黄分支杆菌CP13降解芘特性的影响

芘在环境中的累积已经对生态安全和人类健康造成严重威胁。研究了阳离子-十六烷基三甲基溴化铵(CTMAB),阴离子-十二烷基硫酸钠(SDS),非离子-聚山梨酯-80(Tween80)、聚乙二醇辛基苯基醚(TritonX-100)、聚氧乙烯月桂醚(Brij30)和生物型表面活性剂-皂素对微黄分支杆菌CP13细胞特性及降解芘的影响,可为增效修复PAHs应用中选择合适的表面活性剂提供理论依据。结果表明,表面活性剂对CP13降解芘起促进或抑制作用,会随其种类和添加浓度而发生变化。皂素添加量为0.2倍的临界胶束浓度(CMC)时,芘的降解率提高了10.7%;0.2和1CMC的Tween80使芘的降解率分别增强了4.8%和10.3%;0.2 CMC的TritonX-100轻微的促进了芘降解;较高浓度的皂素、Tween80和TritonX-100抑制了菌CP13对芘的降解;Brij30、SDS和CTMAB对芘的降解表现出显著抑制作用,大小顺序为CTMABSDSBrij30。菌落计数和流式细胞仪的检测结果显示皂素和Tween80能够促进CP13的生长和细胞活性,TritonX-100、Brij30、SDS和CTMAB抑制了CP13的生长,并导致降解体系中死亡细胞比例的增加。低浓度(0.2、1 CMC)的皂素、Tween80和TritonX-100提高了CP13的细胞表面疏水性(CSH),随着浓度的增加,CSH逐渐下降;Brij30、SDS和CTMAB降低了CP13的CSH,添加浓度越高,CSH的下降幅度越大。综上所述,皂素、Tween80、TritonX-100、Brij30、SDS和CTMAB影响菌CP13对芘的降解与其CSH的变化规律基本一致,它们可以通过改变CSH,改变菌体对芘的吸附和摄取。此外,表面活性剂对菌体细胞的毒性作用,也是影响芘降解效果的原因之一。     

表面活性剂对柴油在土壤中吸附的影响

通过静态吸附实验,研究土壤对十二烷基苯磺酸钠(LAS)和十六烷基三甲基溴化铵(CTAB)的吸附行为,探讨表面活性剂对柴油吸附的影响.结果表明,土壤对LAS和CTAB的吸附等温线均为非线性,其吸附能力的大小顺序为:轻壤土>轻粘土>中壤土>砂壤土>重壤土>紧砂土.同一土壤中,CTAB的吸附量大于LAS的吸附量.LAS和CTAB均利于柴油在土壤表面的解吸,且LAS的解吸效果更好.柴油的吸附量随LAS浓度的升高而降低.当CTAB的浓度小于临界胶束浓度CMC时,吸附量随CTAB浓度的升高而升高,当CTAB的浓度等于或大于临界胶束浓度(CMC)时,吸附量随CTAB浓度的升高而降低.     

生物表面活性剂胆酸钠对氯酚的增溶

胆酸钠是一种重要的生物表面活性剂,目前的研究主要集中在利胆药物研制方面,而有关其在增溶修复有机污染方面的应用研究较少.本文考察了胆酸钠(Na C)、脱氧胆酸钠(Na DC)、十二烷基硫酸钠(SDS)、曲拉通(TX-100)和十六烷基三甲基溴化铵(CTAB)对2,4,6-三氯苯酚(2,4,6-TCP)和2,4-二氯苯酚(2,4-DCP)的增溶作用,并探究了底物结构、温度和无机离子对Na C增溶氯酚的性能的影响.实验结果表明,当表面活性剂浓度大于临界胶束浓度(CMC)时,2,4,6-TCP和2,4-DCP的表观溶解度与表面活性剂浓度具有良好的线性关系.其中,相比于其它表面活性剂,当浓度高于0.05 mol·L-1时,Na C具有更良好的增溶性能.随苯环上氯原子个数从0增加到3,Na C的摩尔增溶比(MSR)值随氯酚疏水性(Kow)的增大而线性减小,Na C的胶束-水分配系数(Kmc)值则线性增大.在288—308 K的温度范围内,Na C增溶氯酚的性能逐渐增强.4种无机盐KCl、Na Cl、Na2SO4、Ca Cl2对Na C增溶2,4,6-TCP和2,4-DCP的影响不同.随着无机盐浓度的升高,Na C增溶2,4,6-TCP的能力先上升后下降,而增溶2,4-DCP的能力则迅速下降.     

非离子表面活性剂对有机磷农药在沉积物上吸附行为的影响

用振荡平衡方法,研究了非离子表面活性剂Brij35和Brij30在沉积物上的吸附行为及其对甲基对硫磷在三种沉积物上吸附的影响.结果表明:Brij35的吸附符合Langmuir型吸附等温线;Brij30的吸附符合S型吸附等温线.对于有机质含量高的沉积物,Brij35抑制甲基对硫磷的吸附,Brij30在加入浓度大于CMC时能促进甲基对硫磷的吸附,低于CMC时则抑制甲基对硫磷的吸附.对于有机质含量低的沉积物,Brij35和Brij30均能使甲基对硫磷的吸附量增加.表面活性剂对甲基对硫磷吸附行为的影响机理为吸附态和溶解态的表面活性剂对甲基对硫磷的吸附和增溶共同作用的结果,表面活性剂吸附态对甲基对硫磷吸附的贡献主要来自于吸附并集聚于沉积物表面的表面活性剂,通过分配作用进入沉积物有机质的表面活性剂吸附态贡献率小.     

鼠李糖脂生物表面活性剂对多环芳烃的增溶作用

考察了鼠李糖脂生物表面活性剂对多环芳烃类化合物(萘,菲和芘)的增溶特性以及温度、盐度、pH值等环境因子对增溶性能的影响,结果表明,鼠李糖脂浓度在临界胶束浓度(CMC)以上时,多环芳烃化合物在水相中的溶解度随表面活性剂浓度的增大而线性增大,摩尔增溶比(MSR)随被增溶物分子量的增大而减小,即萘＞菲＞芘;胶束/水分配系数(Km)随被增溶物疏水性增大而增大,即芘＞菲＞萘;IgKm与IgKow之间呈良好线性正相关性,鼠李糖脂对菲的增溶作用随温度升高略有增大,而随所添加NaCl浓度的增大显著增大,鼠李糖脂对菲的增溶作用在pH值为5.5时达到最大,然后随pH值的升高而不断下降,在pH值达7.5后基本保持不变.     

表面活性剂对土壤中多环芳烃(PAHs)纵向迁移的影响

选取山东省分布较广的3种类型土壤(潮土、褐土和棕壤)为研究对象,采用室内土柱淋滤实验,模拟多环芳烃(PAHs)在土壤中纵向迁移的过程.选用生物表面活性剂鼠李糖脂和非离子表面活性剂TX-100分别对3种土壤进行淋滤实验,分析淋滤后较清洁土层PAHs的含量和组成.结果表明,3种类型土壤中,潮土最有利于土壤中PAHs的纵向迁移,褐土和棕壤无显著差异(P0.05);不同淋滤处理下,PAHs均主要富集在土柱表层,占39.00%—60.00%;有无表面活性剂的添加,低环PAHs均较易向下迁移,在污染土壤中的残留率为14.33%—38.52%;不添加表面活性剂条件下高环PAHs在污染土中残留率较高,为79.67%—92.47%,在鼠李糖脂3倍(3 CMC)和TX-100 2倍(2 CMC)临界胶束浓度条件下淋滤效果有明显提高,污染土中高环PAHs残留率与去离子水淋滤时相比降低28.95%—35.31%;相同临界胶束浓度下,TX-100处理后PAHs淋滤率高于鼠李糖脂,淋滤效果更好.     

Behavior of aqueous stable colloidal nano-C60 aggregates exposed to TX100 micelles under different environmental conditions

C₆₀, as one of carbon nanomaterials widely used in various fields, could be released into the water environment thus exerting some potential health risks to human beings. This work examined the behavior of aqueous stable colloidal nano-C₆₀ (nC₆₀) aggregates under different environmental conditions including Polyethylene glycol octylphenol ether (TX100) micelles concentration, pH, and reaction time when exposed to TX100 micelles. Results show that the nC₆₀ aggregates became more dispersive and restored the capability of generating the singlet oxygen when exposed to TX100 micelles. With the increase of TX100 concentration, smaller average size of nC₆₀ aggregates was observed in dynamic light scattering (DLS) analysis, the fluorescence intensity of TX100 was more quenched by nC₆₀ aggregates, and the kinetic rate constant of generating the singlet oxygen for nC₆₀ aggregates was improved. The mean size of nC₆₀ aggregates in the presence of TX100 had no obvious variations when the pH ranged from 4 to 8. The longer reaction time between nC₆₀ aggregates and TX100 led to a higher kinetic rate constant of generating the singlet oxygen. Collective data suggest that variations in physicochemical properties of nC₆₀ aggregates are strongly dependent on the surrounding media under different environmental conditions and directly govern nC₆₀’s transport behavior and potential toxicity.     

Between-individual variation in haemocyanin concentrations in the Norway lobster<Emphasis Type="Italic"> Nephrops norvegicus</Emphasis> following exposure to hypoxia and manganese

Environmental hypoxia and the release of reduced manganese (Mn) are often combined stress factors in marine sediments. Previous investigations have shown that hypoxia induces variable responses in the concentration of the respiratory pigment haemocyanin (Hc) of crustaceans. A recent study demonstrated that the magnitude and direction of the changes was dependent on the initial level of Hc in individuals of the Norway lobster Nephrops norvegicus. The changes also took place within 24 h rather than days as suggested by previous studies. In this present study we investigated changes of Hc in individual N. norvegicus in uncontaminated sea water after exposure to and release from realistic hypoxic stress (PO ₂=6.0 kPa). Furthermore we investigated how concomitant exposure to realistic concentrations of manganese (20 mg l ^-1) modified the responses we observed. We confirmed a between-individual variation in response and a change in Hc towards an optimum level after hypoxia, but also showed that changes that took place post-hypoxic exposure occurred over a timescale similar to that of the hypoxic response itself. Manganese exposure resulted in no significant changes in Hc whereas Mn exposure combined with hypoxia resulted in a significant decrease (15%) in all individuals independent of initial Hc. N. norvegicus was thus unable to compensate for the effects of hypoxia by synthesis of Hc after exposure to naturally occurring Mn concentrations.     

Environmental hypoxia and haemocyanin between-individual variability in Norway lobsters Nephrops norvegicus (L.)

The extent to which exposure to environmental hypoxia (PO₂=8, 6, and 4 kPa, approximately 40%, 30%, and 20% saturation, respectively) resulted in an increase in the concentration of the respiratory pigment haemocyanin ([Hc]) in individuals of the Norway lobster Nephrops norvegicus depended crucially on the initial [Hc] as well as the intensity of the hypoxia itself. While mean [Hc] did increase with decreasing PO₂ (and the variation decreased), for individuals with relatively high initial [Hc] there was no change or even a decrease observed. The greatest hypoxia-related increases in [Hc] were observed in the individuals with the lowest initial [Hc]. Consequently the notion of an 'optimum' [Hc] for a given level of oxygenation was postulated. The changes in [Hc] recorded took place over a considerably shorter time scale (hours rather than days) than has been observed in previous studies. It was not possible to correlate environmental PO₂ and median [Hc] in the field. However, it was interesting that the [Hc] frequency distribution curve for lobsters collected from a site that had been markedly hypoxic (PO₂=8.0 kPa, approximately 40% saturation) until a few days before sampling was almost exactly the same shape (i.e. leptokurtic) and position (i.e. similar median) to that obtained when lobsters were exposed to PO₂=8.0 kPa in the laboratory. Although it would have been desirable to investigate the effect of hypoxia on the frequency distribution of a physiological trait, in this case [Hc], it was not possible due to insufficient sample size, even though the sample sizes employed were considerably larger than those normally used in physiological investigations.     

Natural variation in the concentrations of haemocyanin from three decapod crustaceans, Nephrops norvegicus, Liocarcinus depurator and Hyas aranaeus

Natural variation in the concentrations of haemocyanin ([Hc]) is examined for three decapod species collected from two different locations (Gullmarsfjord and Kattegat) off the west coast of Sweden (August to September 1998). Only one of the frequency distributions for [Hc] is normally distributed, and median values differ both between and within species. Differences in [Hc] cannot be attributed to sex, reproductive condition or moulting condition (over the limited range of moult stages examined) for any of the species. While body size did not scale with [Hc] for the Norway lobster Nephrops norvegicus or the swimming crab Liocarcinus depurator, it did for the spider crab Hyas araneus. To our knowledge this is the first time a negative relationship between body size and [Hc] has been reported for any crustacean. Thus the right-skewed frequency distribution of spider crab [Hc] could be accounted for by the right-skewed body size distribution recorded. The shape of the frequency distributions for [Hc] from the other two species could not be accounted for through differences in the factors examined here, although it is suggested that the amount of food consumed (or not) may be important. Received: 19 July 1999 / Accepted: 4 October 1999     

Comparative studies on toluene removal and pressure drop in biofilters using different packing materials

To select the best available packing material for malodorous organic gases such as toluene and benzene, biofilter performance was compared in biofilters employed different packing materials including porous ceramic (celite), Jeju scoria (lava), a mixture of granular activated carbon (GAC) and celite (GAC/celite), and cubic polyurethane foam (PU). A toluene-degrading bacterium, Stenotrophomonas maltophilia T3-c, was used as the inoculum. The maximum elimination capacities in the celite, lava, and GAC/celite biofilters were 100, 130, and 110 gm(-3) hr(-1), respectively. The elimination capacity for the PU biofilter was approximately 350 g m(-3) hr(-1) at an inlet loading of approximately 430 g m(-3) hr(-1), which was 2 to 3.5 times higher than for the other biofilters. The pressure drop gradually increased in the GAC/ celite, celite and lava biofilters after 23 day due to bacterial over-growth, and the toluene removal efficiency remarkably decreased with increasing pressure drop. Backwashing method was not effective for the control of biomass in these biofilters. In the PU biofilter however, backwashing allowed maintenance of a pressure drop of 1 to 3 mm H2O m(-1) and a removal efficiency of > 80%, indicating that the PU was the best packing material for toluene removal among the packing materials tested.     

Structural and functional heterogeneity of hemocyanin: intra- and inter-specific comparison in four species of portunid crabs (Crustacea: Portunidae)

This work is focused on hemocyanin (Hc) heterogeneity at population level and on the biochemical characterization of the different subunit patterns. Two different approaches have been used: we have characterized Hc subunit composition to describe the subunit polymorphism. Then, we have measured the Hc oxygen-binding affinity to disclose the physiological implications of such heterogeneity. In order to evaluate the intra- and inter-specific variability, different populations of Liocarcinus depurator, Liocarcinus marmoreus, Liocarcinus holsatus, Necora puber (Crustacea: Portunidae), from British Isles and Adriatic Sea, have been sampled. Results indicate that Hc polymorphism normally occurs at both intra- and inter-specific levels and involves the protein subunit type. These evidences extend to the portunid Hc the concept of molecular heterogeneity within species that have been previously reported for other decapod and amphipod crustaceans. Besides, the results support the view that subunit composition of crustacean Hcs is almost species-specific, but also that closely related species share a common pattern. Furthermore, this heterogeneity corresponds to different stability of the native oligomers quaternary structure and different oxygen affinity. The results are discussed in relation with the environmental regimes that characterize the different sampling areas. In addition to Hc, the hemolymph collected in specimens from different sampling areas contained also a non-respiratory pseudo-Hc. This paper reports for the first time the occurrence of pseudo-Hc at the level of population. Declaration: All the experiments comply with the current laws of Italy.     

Oxygen-binding by haemocyanins from an ecological series of amphipod crustaceans

The oxygen-binding properties of haemocyanins (Hc) from three species of gammaridean amphipods, Gammarus locusta (L.) (subtidal), Echinogammarus pirloti (Sexton and Spooner), (intertidal, marine) and E. marinus (Leach) (intertidal, estuarine), one species of hyalid amphipod Hyale nilsonni Rathke (high intertidal, marine) and the talitrid amphipod Orchestia gammarellus (Pallas) (semi-terrestrial) have been studied. All the species were collected from the Firth of Clyde, Scotland, during the spring of 1992. The oxygen-carrying capacity of haemolymph from each species was low, although variable, and was correlated with the low concentration of Hc present. The Hc oxygen-affinity of native gammarid haemolymph was relatively high [partial pressure of oxygen required for half-saturation, P₅₀=4 to 5 torr (0.53 to 0.67 kPa)] at their respective in vivo pH values. At equivalent pH, however, Hc from G. locusta displayed a lower O₂-affinity than either Echinogammarus species. Gammarid Hcs had a large Bohr effect ( log P₅₀/ pH=-1.16 to-1.47). Resuspended Hc isolated from whole H. nilsonni showed similar O₂-binding properties to those of the gammaridean amphipods [P₅₀=6.3 torr (1.44 kPa) at pH=8.0; log P₅₀/pH=-1.20]. Comparable data for haemolymph from O. gammarellus showed that the Hc had a lower affinity for O₂ [P₅₀=14.1 torr (1.87 kPa) at in vivo pH] and exhibited a more moderate Bohr effect ( log P₅₀/ pH=-0.79). To eliminate the possibility that these differences were due to the different haemolymph constituents, each of the Hcs were pelleted and resuspended in physiological saline. The differences noted above persisted, demonstrating that they were due to inherent O₂-binding properties of the Hc molecules themselves. An increase in L-lactate resulted in an increase in Hc oxygen-affinity for both Echinogammarus species but not for O. gammarellus. This study has confirmed that there is a clear difference between Hcs from aquatic and semi-terrestrial amphipod genera. The results lend further support to the hypothesis that the move on to land by amphipod crustaceans is accompanied by a decrease in Hc oxygen-affinity, a decrease in the Bohr effect and a decrease in effector (in this case L-lactate) sensitivity.     

助溶剂甲苯和二甲基亚砜对斑马鱼胚胎发育的复合毒性效应

研究了甲苯和二甲基亚砜(DMSO)对斑马鱼胚胎生长、发育的毒性效应.实验结果表明:低剂量的甲苯(0.05%)单一暴露对斑马鱼胚胎发育有一定毒性,DMSO(0.45%)对斑马鱼胚胎无明显毒性;但甲苯与DMSO具有较强的复合毒性效应,随着DMSO含量的增加,与甲苯单一暴露组相比,斑马鱼胚胎死亡率显著增加、胚胎孵化率下降、胚胎发育迟缓并生成大量畸形;但甲苯以及甲苯和DMSO复合物对人胚肾HEK-293细胞株和人胃癌SGC-7901细胞株的活力均没有明显效应.DMSO可通过提高甲苯在水中的分散性,增加甲苯的神经毒性,但对离体实验模型无显著效应,故在选择不同生物模型评估有机污染物毒性效应时,需考虑不同类型助溶剂所产生的复合效应,以减少实验误差.     

Population differences in how black-tailed prairie dogs deal with snakes

Summary This paper examines the antisnake behavior of a snake-experienced Texas (TX) population and a snake-naive South Dakota (SD) population of black-tailed prairie dogs (Cynomys ludovicianus). Animals in both populations were presented with tethered rattlesnakes and nonvenomous bullsnakes before and after the first emergence of pups from their natal burrows. SD and TX adults were more likely to actively harass snakes than were pups. There were no differences in the behavior of SD adult males vs females or fathers vs non-fathers, contrary to what was found in TX. However, SD mothers did call more and stayed closer to snakes than did SD non-mothers. All SD adult sex-parental classes spent less time dealing with snakes after the emergence of pups, which was not observed in TX. The primary difference between the two populations was the behavior of TX males who spent a great deal of time harassing snakes. SD adults behaved most like TX females in that these groups spent little time actively dealing with snakes. Pups in both populations behaved similarly. These results are interpreted in terms of the relationship between potential predator and potential prey.     

Degradation of toluene and benzene by Trametes versicolor

In this study, biological degradation of non-polar monoaromatic compounds, benzene and toluene, by one of the white rot fungi, namely Trametes versicolor was analyzed and the biomass formed was determined. The studies were carried out in mediums which contain basic nutrients in certain amounts, toluene and benzene at concentrations of 50, 100, 200, 250 and 350 mg/l, pH at 5, temperature at 28 degrees C and rpm at 150. Within an incubation period of 48 hours, it was observed that, removal was completed in 4 hours when toluene concentration was 50 mg/l and was completed in 36 hours when concentration was 300 mg/l. Biodegradation was completed at the end of 4th hour at benzene concentration of 50 mg/l while it continued for 42 hours at the concentration of 300 mg/l. With the addition of veratryl alcohol (3,4-Dimethoxybenzyl alcohol) to the basic feed medium, the operation of the enzyme system gained speed and biodegradation completed in a shorter time period.