全氟辛烷磺酸盐(PFOS)替代品对家蚕大造的生态毒性

以中国本地家蚕品种大造作为受试生物,实现实验室规模化饲料饲养和初步实验动物化;建立家蚕大造环境危害评价急性毒性测试方法;对4种PFOS替代品包括:50%的全氟丁基有机铵盐阳离子表面活性剂、用调聚法合成的织物三防整理剂(含固率23.7%)、用电解氟化法合成的C4和C6织物三防整理剂,进行了急性接触毒性、急性饲喂毒性及慢性饲喂毒性的安全风险评价。实验使用的4种PFOS替代品试验急性饲喂浓度均达到或超过2000mg·L-1,家蚕未出现明显死亡;在接触实验浓度达到10g·L-1时,家蚕未出现明显死亡,以上结果证明,4种PFOS替代品对大造蚕种的急性饲喂毒性和接触毒性均为低毒。较低浓度的表面活性剂会严重影响到大造蚕种的结茧率,当表面活性剂浓度为0.4g·kg-1时,蚕种不能结茧,其余3种化学品在浓度大于0.004g·kg-1,对大造蚕种的结茧率产生一定的影响作用,但抑制作用相对较为平缓。替代品均会降低家蚕茧层率,表面活性剂在浓度为0.04g·kg-1时,茧层率剧烈下降,其他3种替代品抑制作用相对平缓。织物三防整理剂、C4和C6织物三防整理剂几乎不会影响蚕卵孵化,但表面活性剂会造成家蚕孵化率降低,在0.04g·kg-1后孵化率为0。     

Effect of dye auxiliaries on chemical oxygen demand and colour competitive removal from textile effluents using Posidonia oceanica

The use of an abundant and widely distributed seagrass species, Posidonia oceanica, as a biosorbent for the direct dye Yellow 44 was successfully shown. The studies were performed on the single dyestuff dissolved in water and in a dyebath containing agents commonly used in the textile industry, i.e. a surfactant (Lavotan TBU), a sequestring agent (Meropan DPE), a softening agent (Eurosoft CI10) and a salt (NaCl). The colour reduction results showed that P. oceanica was found to be more efficient for removal of Yellow 44 from an aqueous solution (162 mg g^?1) than from a dyebath solution (135 mg g^?1), according to the Langmuir isotherm model. For the single dyestuff sorption, Fourier transform infrared and X-ray photoelectron spectroscopy studies highlighted chemical sorption between the dye alcohol function and the sorbent acid function. The chemical oxygen demand removal percentages were found to be 54.9 and 76.6% for Yellow 44 dissolved in aqueous solution and in dyebath solution, respectively. This confirmed the both sorption of the chemical auxiliaries and the dye on P. oceanica.     

全氟辛烷磺酸盐(PFOS)替代品对4种本土水生生物的生态毒性

本文选择了紫背浮萍、四尾栅藻、蚤状溞和稀有鮈鲫4种本土水生生物,开展了阳离子表面活性剂、织物三防整理剂、C4三防整理剂和C6三防整理剂4种全氟辛烷磺酸盐(PFOS)替代品的安全性评估,为筛选理想PFOS化学替代品提供科学依据。急性毒性结果发现阳离子表面活性剂对4种水生生物均未显示出急性毒性;织物三防整理剂、C4三防整理剂和C6三防整理剂对蚤状溞的LC50值分别为17.97、64.61和85.58 mg·L-1,显示出低的急性毒性。另外,织物三防整理剂对四尾栅藻的半数抑制浓度(EC50)值为88.32 mg·L-1,而对稀有鮈鲫半致死浓度(LC50)值为14.79 mg·L-1,均存在急性毒性。短期生长抑制试验结果发现阳离子表面活性剂、织物三防整理剂、C4三防整理剂和C6三防整理剂对稀有鮈鲫生长抑制最低可见效应浓度(LOEC)值分别为20、1.5、100和50 mg·L-1,表明4种PFOS替代品均显示低慢性毒性。急慢性综合分析可知C4和C6三防整理剂相对较安全,可能成为理想的PFOS替代品。     

全氟辛烷磺酸盐(PFOS)替代品对中国白羽鹌鹑的生态毒性

为研究全氟辛烷磺酸盐(perfluorooctane sulfonate,PFOS)替代品对环境生物的毒害效应,选用中国白羽鹌鹑作为受试生物,建立其环境危害评价毒性测试方法,并对PFOS替代化学品进行了急性经口、急性饲喂及繁殖毒性的风险评价。结果表明,全氟丁基有机铵盐阳离子表面活性剂急性经口毒性实验的LD50为500.44mg·kg-1,其余3种替代化学品在上限浓度2000mg·kg-1,白羽鹌鹑均未出现明显死亡,4种PFOS替代品对中国白羽鹌鹑的急性经口毒性均为低毒。全氟丁基有机铵盐阳离子表面活性剂急性饲喂毒性实验的LC50为970.50mg.kg-1,对白羽鹌鹑的饲喂毒性为中毒,而其余3种替代化学品在上限浓度5000mg·kg-1,白羽鹌鹑均未出现明显死亡,对中国白羽鹌鹑的急性饲喂毒性为低毒。在长期饲喂过程中,织物三防整理剂和C6织物三防整理剂会表现出一定的生殖毒性,造成中国白羽鹌鹑的孵化率降低,胚胎死亡率及未受精率升高;全氟丁基有机铵盐阳离子表面活性剂会影响到中国白羽鹌鹑的未受精率,C4织物三防整理剂未表现出明显的生殖毒性。     

氧化石墨烯遗传毒性的实验研究

研究氧化石墨烯(GO)的遗传毒性,考察其致突变作用,为GO在生物领域的安全应用提供依据。采用Ames试验、体外CHL细胞染色体畸变试验和小鼠体内染色体畸变试验,分别在细菌水平、细胞水平及整体动物水平研究GO的遗传毒性。GO各剂量组的Ames试验结果为阴性。CHL试验中,CHL细胞染色体畸变率随GO浓度的增加而升高,其中1.000 mg·mL~(-1)剂量组(+S_9)和0.500 mg·mL~(-1)剂量组(-S_9)畸变率显著升高(P 0.05)。小鼠骨髓细胞染色体畸变试验中,骨髓细胞染色体畸变率同样随GO浓度的增加而升高,1.000和0.500 mg·kg~(-1)剂量组的畸变率显著提高(P 0.05)。虽然Ames试验结果没有反映出GO的遗传毒性,但在体外及体内染色体畸变试验中,GO均表现出对哺乳动物细胞染色体有潜在的遗传毒性。     

Effects of microbial inoculations and surfactant levels on biologically- and chemically-assisted phytoremediation of lead-contaminated soil by maize (Zea Mays L.)

Assisted phytoremediation has been widely used for decontamination of potentially toxic elements contaminated soils. A greenhouse experiment was conducted to evaluate the effectiveness of different microbial inoculations and surfactant levels on the phytoremediation of a Pb-polluted calcareous soil by maize. The results showed that application of surfactant increased both root and shoot dry matter yields. Microbial inoculations, however, had no significant effect on the root or shoot dry matter yield. Mean Pb uptake in maize root or shoot increased only following the application of some surfactant levels. Inoculation with microorganisms significantly increased both mean Pb concentration and uptake in maize root but not in maize shoot. Application of 4?mmol surfactant kg?1 along with inoculation with Priformospora indica was effective in increasing Pb phytostabilisation potential. While the application of 2?mmol surfactant kg^?1 along with inoculation with Pseudomonas fluorescens was effective in increasing Pb phytoextraction potential. The fact that the values of translocation efficiencies were low in all treatments, demonstrated the low capability of maize for translocation of Pb from root to shoot. Inoculation with P. fluorescens was the most effective treatment in increasing metal micronutrient uptake. Microbial inoculation and surfactant levels enhanced Pb phytoremediation mostly through phytostabilisation of this metal by maize.     

Utilization of fly ash in adsorption of heavy metals from wastewater

The aim of this study was to assess the toxicity reduction of wastewaster after treatment with fly ash. Fly ash is a waste material which is formed as a result of coal burning in power plants, but has the potential to adsorb heavy metal ions. The present study examined the adsorption capacity of fly ash to adsorb Pb²⁺, Cu²⁺, and Zn²⁺ from waste water under different conditions of contact time, pH, and temperature. Uptake of metal ions by fly ash generally rose with increasing pH. At lower temperatures the uptake of heavy metal adsorption were enhanced. Significant reduction in Pb²⁺ (79%), Cu²⁺ (53%), and Zn²⁺ (80%) content was found after treatment with fly ash of waste water treatment. Using the microtox test toxicity of the effluent was reduced by 75% due to removal of Pb²⁺ ion by the fly ash. Data indicated that fly ash generated by power plants may be used beneficially to remove metals from waste water.     

Removal of malachite green from water samples by cloud point extraction using Triton X-100 as non-ionic surfactant

A surfactant mediated cloud point extraction (CPE) procedure has been developed to remove color from wastewater containing malachite green using Triton X-100 as non-ionic surfactant. The effects of the concentration of the surfactant, temperature and salt concentration on the different concentrations of dye have been studied and optimum conditions were obtained for the removal of malachite green. The concentration of malachite green in the dilute phase was measured using UV–Vis spectrophotometer. It was found that the separation of phases was complete and the recovery of malachite green was very effective in the presence of NaCl as an electrolyte. The results showed that up to 500 ppm of malachite green can quantitatively be removed (>95%) by CPE procedure in a single extraction using optimum conditions.     

Transport of antibiotic resistance plasmids in porous media and the influence of surfactants

Transport of engineered antibiotic resistance plasmids in porous media has been reported to potentially cause significant spreading of antibiotic resistance in the environment. In this work, transport of an indigenous resistance plasmid pK5 in porous media was investigated through packed column experiments. At identical ionic strengths in CaCl₂ solutions, the breakthroughs of pK5 from soil columns were very close to those from quartz sand columns, indicating that transport of pK5 in quartz sand and soil was similar. A similarity in transport behavior was also found between pK5 and an engineered plasmid pBR322 that has approximately the same number of base pairs as pK5. The influence of surfactants, a major group of constituents in soil solutions, was examined using an engineered plasmid pcDNA3.1(+)/myc-His A. The impact of an anionic surfactant, sodium dodecyl sulfate (SDS), was negligible at concentrations up to 200 mg·L^–1. Cetyltrimethyl ammonium bromide (CTAB), a cationic surfactant, was found to significantly enhance plasmid adsorption at high concentrations. However, at environmentally relevant concentrations (<1 mg·L^–1), the effect of this surfactant was also minimal. The negligible impact of surfactants and the similarity between the transport of engineered and indigenous plasmids indicate that under environmentally relevant conditions, indigenous plasmids in soil also have the potential to transport over long distances and lead to the spreading of antibiotic resistance.

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Ligand-less in situ surfactant-based solid phase extraction for preconcentration of silver from natural water samples prior to its determination by atomic absorption spectroscopy

A simple and rapid ligand-less in situ surfactant-based solid phase extraction method for preconcentration of silver from water samples is developed. In this method, a cationic surfactant containing a proper alkyl group (n-dodecyltrimethylammonium bromide) is dissolved in the aqueous sample and then a proper ion-pairing agent (ClO₄^?) is added. Due to the interaction between surfactant and ion-pairing agent, solid particles are formed and used for adsorption of silver carbonate. After centrifugation, the sediment is dissolved in 2.0 mL 1 M HNO₃ in ethanol and then aspirated directly into the flame atomic absorption spectrometer. Variables affecting the extraction efficiencies such as pH, concentrations of surfactant and CO₃^2?, ion pair concentration, and extraction time, are optimized. Under such conditions, the calibration curve is linear from 3 to 700 μg L^?1. Detection limit is 1.1 μg L^?1 with an enrichment factor of 37. The relative standard deviation for eight replicate measurements of 100 μg L^?1 is 2.1%. The method has been applied for the determination of silver in water samples.     

Selenium speciation in wheat grain varies in the presence of nitrogen and sulphur fertilisers

This study investigated whether selenium species in wheat grains could be altered by exposure to different combinations of nitrogen (N) and sulphur (S) fertilisers in an agronomic biofortification experiment. Four Australian wheat cultivars (Mace, Janz, Emu Rock and Magenta) were grown in a glasshouse experiment and exposed to 3 mg Se kg^?1 soil as selenate (Se^VI). Plants were also exposed to 60 mg N kg^?1 soil as urea and 20 mg S kg^?1 soil as gypsum in a factorial design (N + S + Se; N + Se; S + Se; Se only). Plants were grown to maturity with grain analysed for total Se concentrations via ICP-MS and Se species determined via HPLC-ICP-MS. Grain Se concentrations ranged from 22 to 70 µg Se g^?1 grain (dry mass). Selenomethionine (SeMet), Se-methylselenocystine (MeSeCys), selenohomolanthionine (SeHLan), plus a large concentration of uncharacterised Se species were found in the extracts from grains. SeMet was the major Se species identified accounting for between 9 and 24 µg Se g^?1 grain. Exposure to different N and S fertiliser combinations altered the SeMet content of Mace, Janz and Emu Rock grain, but not that of Magenta. MeSeCys and SeHLan were found in far lower concentrations (<4 µg Se g^?1 grain). A large component of the total grain Se was uncharacterisable (>30 % of total grain Se) in all samples. When N fertiliser was applied (with or without S), the proportion of uncharacterisable Se increased between 60 and 70 % of the total grain Se. The data presented here indicate that it is possible to alter the content of individual Se species in wheat grains via biofortification combined with manipulation of N and S fertiliser regimes. This has potential significance in alleviating or combating both Se deficiency and Se toxicity effects in humans.     

Enhanced performances in catalytic oxidation of <Emphasis Type="Italic">o</Emphasis>-xylene over hierarchical macro-/mesoporous silica-supported palladium catalysts

A series of hierarchical macro-/mesoporous silica supports (MMSs) were successfully synthesized using dual-templating technique employing polystyrene (PS) spheres and the Pluronic P123 surfactant. Pd was next loaded on the hierarchical silica supports via colloids precipitation method. Physicochemical properties of the synthesized samples were characterized by various techniques and all catalysts were tested for the total oxidation of o-xylene. Among them, the Pd/MMS-b catalyst with tetraethoxysilane/polystyrene weight ratio of 1.0 exhibited superior catalytic activity, and under a higher gas hourly space velocity (GHSV) of 70000 h^–1, the 90% conversion of o-xylene has been obtained at around 200°C. The BET and SEM results indicated that Pd/MMSb catalyst possesses high surface area and large pore volume, and well-ordered, interconnected macropores and 2D hexagonally mesopores hybrid network. This novel ordered hierarchical porous structure was highly beneficial to the dispersion of active sites Pd nanoparticles with less aggregation, and facilitates diffusion of reactants and products. Furthermore, the Pd/MMS-b catalyst possessed good stability and durability.     

Adsorption of cationic and anionic surfactants onto organic polymer resin Lewatit VPOC 1064 MD PH

The adsorption of a cationic (CTAB, cetyl trimethylammonium bromide) and an anionic surfactant (SLES, sodium dodecylethersulfate) from aqueous solution onto organic polymer resin (Lewatit VPOC 1064 MD PH) was studied. A series of batch experiments were performed to determine the sorption isotherms of surfactants to organic polymer resin. The experimental studies were analyzed by Langmuir and Freundlich isotherms. Furthermore, the isotherm parameters, average percentage errors (ε) of model data, and separation factor (R _L) were calculated. Other factors influencing the adsorption capacity (contact time, adsorbent amount, and initial surfactant concentration) were also discussed. The experimental data fitted very well to the Langmuir equilibrium model in the studied concentration range. The calculated R _L values showed that the adsorption of both surfactants were favorable. Among the surfactants, CTAB showed higher adsorption capacity onto organic polymer resin compared to SLES (Q ⁰ = 250 and 34.36 mg g⁻¹, respectively).     

Mikrobieller PAK-Abbau

The biodegradation of the five ring PAH benzo[a]pyrene (BaP) is assumed to be limited by the low water solubility of this compound. A mixed culture of microorganisms — isolated from a PAH-contaminated soil — was able to degrade¹⁴C labelled BaP in mineral medium by cometabolism with phenanthrene, fluoranthene, anthracene and pyrene as sources of carbon and energy. The mineralisation of these compounds to low levels resulted in an inhibition of the degradation of BaP. After the new addition of the four PAH compounds to the culture medium the mineralisation of BaP started again. A non-ionic surfactant of the alkylpolyglycoside type (Plantacare 2000 UP) increased the concentration of BaP in the culture medium because of solubilization. At high Plantacare concentrations, the degradation of BaP was completely inhibited above the critical micelle concentration (cmc). The degradation of the three and four ring PAHs was also inhibited. If the surfactant was metabolised to concentrations below the cmc, an increase of mineralisation of BaP could occur up to 24% in 384 days.     

Bioaccessibility of arsenic in soils developed over Jurassic ironstones in eastern England

Jurassic ironstones outcropping over parts of eastern England give rise to soils with arsenic concentrations in excess of the UK soil guideline value of 20 mg kg⁻¹ for residential areas. Total arsenic concentrations were determined for 73 ironstone derived soils and bioaccessible arsenic determined using an in vitro physiologically based extraction test. The bioaccessible arsenic concentration for these soils was found to be well below the soil guideline value with a mean concentration of 4 mg kg⁻¹ and a range of 2–17 mg kg⁻¹. The bioaccessible fraction ranges from 1.2 to 33%. Data from a sequential extraction test based on the use of aqua regia as the main extractant is presented for a subset of 20 of the soils. Chemometric data reduction is used to demonstrate that the bioaccessible arsenic is mainly contained within calcium iron carbonate (sideritic) assemblages and only partially iron aluminosilicates, probably berthierine, and iron oxyhydroxide phases, probably goethite. It is suggested that the bulk of the non-bioaccessible arsenic is bound up with less reactive iron oxide phases.     

十二烷基苯磺酸钠(SDBS)及消油剂对刺参幼参的急性毒性

为探究表面活性剂对海洋棘皮动物的影响,测定了十二烷基苯磺酸钠(SDBS)和消油剂对刺参(Stichopus japonicas )幼参的急性毒性。结果显示,SDBS对刺参幼参的72 h-LC₅₀和96 h-LC₅₀分别为2.50和1.71 mg·L^-1;消油剂对刺参幼参的96 h-LC₅₀为7 498.94 mg·L^-1。刺参幼参相对于多刺裸腹溞(Moina macrocopa )和脊尾白虾仔虾(Palaemon carincauda )对SDBS的敏感性较高,相对于安氏伪镖水蚤(Pseudodiaptomus annandalei )对SDBS的敏感性则较低,SDBS对刺参幼参的毒性明显大于十二烷基磺酸钠(SDS),消油剂的96 h-LC₅₀ 远远大于SDBS和SDS,毒性非常小,但这仅是对刺参幼参而言,大多数研究忽视了消油剂自身对生物体存在的影响,因此这方面的研究工作还需要继续开展。     

Degradation of benzyldimethyl hexadecylammonium chloride by Bacillus niabensis and Thalassospira sp. isolated from marine sediments

Following enrichment in its presence, two strains of bacteria, isolated from marine sediments, were shown to degrade the quaternary ammonium surfactant benzyldimethyl hexadecylammonium chloride (BDHAC) in a minimal salts medium. The bacteria identified by 16S ribosomal deoxyribonucleic acid sequencing were shown to belong to several genera and determined to be Bacillus niabensis and Thalassospira sp. Initial investigations demonstrated that the bacteria were capable of degrading BDHAC when it was present at concentrations in the range 2–4 mg mL^?1. In media containing BDHAC, up to 90% was degraded within 7 days, but limited growth of the strain was observed at 2 and 4 mg mL^?1 BDHAC. Preliminary analysis of samples after degradation experiment by electrospray ionization mass spectrometry/mass spectrometry produced a peak with a parent–daughter ion transition of 136 → 91, corresponding to N,N-dimethylbenzylamine. The presence of this potential metabolite suggests the cleavage of the C-alkyl-N bond as a step in BDHAC catabolism.     

Microwave and Fenton's reagent oxidation of wastewater

We compared two H₂O₂ oxidation methods for the treatment of industrial wastewater: oxidation using Fenton's reagent [H₂O₂/Fe(II)] and microwave irradiation. Both methods were applied to the treatment of synthetic phenol solutions (100 mg L⁻¹) and of an industrial effluent containing a mixture of ionic and non-ionic surfactants at high load (20 g L⁻¹ of COD). The effects of initial pH, initial H₂O₂ concentration, Fenton catalyst amount and irradiation time were assessed. According to the oxidation of phenol, it has been found that the oxidation by Fenton's reagent is dependent on the pH, contrary to the microwave system, which is not influenced by this parameter. For both systems, a limiting amount of oxidant has been found; above this point the oxidation of phenol is not improved by a further addition of peroxide. The oxidation of the industrial surfactant effluent has only been successful with the Fenton's reagent. In this case, large amounts of ferrous ions are necessary for the precipitation of the ionic surfactants of the effluent, followed by the oxidation of the non-ionic constituents of the solution. Electronic Publication     

全氟烷基磺酸盐(PFOS)及其替代品对两栖类胚胎的发育毒性

用非洲爪蟾胚胎致畸实验和黑斑蛙胚胎发育毒性实验,比较研究了PFOS及其4种替代品对两栖动物胚胎的发育毒性。结果发现,用调聚法合成的织物三防整理剂和50%的全氟丁基有机铵盐阳离子表面活性剂同PFOS一样对非洲爪蟾胚胎有明显毒性,且织物三防整理剂和表面活性剂的毒性强于PFOS;电解氟化法合成的C4织物及C6织物三防整理剂(以下简称C4及C6织物三防整理剂)对非洲爪蟾胚胎没有明显毒性。与非洲爪蟾不同,PFOS和4种替代品对黑斑蛙胚胎没有明显毒性。结果显示,从生物安全性的角度分析,C4和C6织物三防整理剂可作为PFOS的替代品使用,而织物三防整理剂和表面活性剂的毒性比PFOS大,作为PFOS替代品使用需要慎重考虑。     

Sensitized photooxygenation of mononitrophenols in micellar media

The singlet molecular oxygen‐mediated photooxidation of simple nitrophenols was studied in micellar (CTAB) alkaline solutions.

A different behaviour for the values of the overall rate constant (K_t ) and the reactive rate constant (K_t ) in the interaction nitrophenol‐singlet molecular oxygen was observed as a function of surfactant concentration. The former decreases as [CTAB] increases, from values of 1–3 × 10⁹ M^–1 s^–1 in the absence of surfactant to values at least one order of magnitude lower at [CTAB] ～0.1 M. Parallel, k_t remains practically unaffected, in values of the order of 10⁶ — 10⁷ M^–l s^–1, depending on the particular nitrophenol, within the same [CTAB] range. The quantum yield of nitrophenols photooxidation reaches a maximum at [CTAB] ～0.1 M.

The results are discussed in terms of a combination of causes, the polarity of the nitrophenolic microenvironment being the driving effect. The implication of the results on environmental decontamination are also analyzed.