Effect of the alkyl chain length on the anaerobic biodegradability and toxicity of quaternary ammonium based surfactants

The anaerobic biodegradability and toxicity to methanogenic gas production of different alkyl chain length homologs of quaternary ammonium based surfactants were examinated. Two series of these cationic surfactants were selected: alkyl trimethyl ammonium and alkyl benzyl dimethyl ammonium compounds. A simple anaerobic gas production test containing municipal digester solids as a source of anaerobic bacteria was used. Under the applied methanogenic conditions, the cationic surfactants tested showed a very poor primary biodegradation and no evidence of any extent of ultimate biodegradation was observed. The toxicity of quaternary ammonium based surfactants to methanogenic gas production decreased with increasing the alkyl chain length.     

Pesticide adsorption on a calcareous soil modified with sewage sludge and quaternary alkyl-ammonium cationic surfactants

BACKGROUND, AIM AND SCOPE: Pesticides are often found in soil as a result of their application to control pests. They can be transported on soil particles to surface waters or they can lixiviate and reach other environmental compartments. Soil modification with amendments, such as sewage sludge, and with surfactants, h been proposed to reduce pesticide environmental fate. METHODS: The sorption of atrazine, methidathion and diazinon using the batch technique has been studied on non-modified soil and soil modified with sewage sludge and cationic surfactants, as well as the effect of their addition on soil properties such as organic carbon (OC) content and exchange cations. RESULTS AND DISCUSSION: The OC content of the surfactant modified soils was the highest with the surfactant with the longest hydrocarbon chain (hexadecyltrimethyl ammonium bromide, HDTMA). The results of the OC content run in parallel with the increase in pesticide retention. When the sorption was n malized to soil OC content, the retention induced by addition of HDTMA was still the highest, which is an indication that the organic matter derived from the organic cations is a more effective medium to retain dissolved contaminants, than organic matter from native soil. The addition of sewage sludge to the soil did only result in a slight increase of the soil CEC and, hence, moderately affected the ability of the cationic surfactant to retain the pesticides. CONCLUSIONS: The addition of cationic surfactants to soil would possibly reduce the movement to groundwater of atrazine, methidathion and diazinon. In the case of HDTMA, the decrease in sorption at high surfactant loadings was very slow, being that the surfactant was able to retain the pesticides at concentration values which clearly exceeded the monolayer coverage. RECOMMENDATIONS AND PERSPECTIVES: Contamination by pesticides, which are present in the soil due to their direct input in this medium or to spills or illegal tipping, may be hindered from migration to groundwater by application of a cationic surfactant.     

Bioaccumulation and toxicity of a cationic surfactant (DODMAC) in sediment dwelling freshwater invertebrates

Dimethyldioctadecylammonium chloride (DODMAC, CAS No. 107-64-2) is the principal active component of Di(hydrogenated tallow alkyl) dimethylammonium chloride (DHTDMAC, CAS No. 61789-80-8), a cationic surfactant formerly used principally in laundry fabric softeners. After discharge to water, DODMAC partitions strongly to sediment, therefore the assessment of the effects of DODMAC to benthic organisms is essential in any risk assessment. Chronic toxicity studies were conducted with Lumbriculus variegatus (Oligochaete), Tubifex tubifex (Oligochaete) and Caenorhabditis elegans (Nematode). NOECs were greater than 5738, 1515 and 1351 mg/kg dw, respectively, even for sub-lethal effects. Measurement of the route of uptake of DODMAC by L. variegatus demonstrated the relative importance of uptake via ingestion (86%) compared with direct contact with the sediment and via pore water (14%). The overall tendency of DODMAC to bioaccumulate, however, was low with measured accumulation factors of 0.22 and 0.78 for L. variegatus and T. tubifex, respectively.     

4种表面活性剂及其混合物对p,p'-DDT污染土壤洗脱效果

为了研究表面活性剂对p,p'-DDT污染土壤的淋洗效果,选取了4种阴、非离子表面活性剂,对人工p,p'-DDT污染土壤进行单一和复配洗脱实验。结果表明,对于人工p,p'-DDT污染土壤,阴离子表面活性剂洗脱效果优于非离子表面活性剂,其中阴离子表面活性剂十二烷基硫酸钠（SDS）和鼠李糖脂（RL）的洗脱效果较好,添加量为15 000 mg·L-1时洗脱率分别达到44.5%和36.5%,均优于非离子表面活性剂吐温80（TW80）（30.4%）和曲拉通100（TR100）（20.3%）;研究还表明非离子表面活性剂在添加量达到10 000 mg·L-1后,继续增加表面活性剂浓度,洗脱效果提升不明显。混合表面活性剂体系中,总添加量为10 000 mg·L-1时,SDS-TW80混合体系对p,p'-DDT的洗脱率为42%,高于SDS-TR100（34.9%）、RL-TW80（33.4%）和RL-TR100（37.4%）,表面活性剂混合体系对于p,p'-DDT的淋洗有明显的协同作用。     

阳离子聚丙烯酰胺类絮凝剂PAD的合成及优化

为了提高阳离子絮凝剂的絮凝性能,选用阳离子疏水表面活性单体DBC和亲水单体AM,以EDTA-2Na为络合剂,以AIBN和APS-NaHSO₃为复合引发剂,采用水溶液聚合法制得一种新型阳离子聚丙烯酰胺类絮凝剂P(AM-DBC) (PAD)。此方法具有工艺操作简单、无需添加其他模板和表面活性剂、产物的相对分子质量高和转化率高等优势。单因素实验结果表明,当总单体质量分数为40%、单体摩尔比n(AM)∶n(DBC)=7∶3、pH=4.0、反应温度为60 ℃、EDTA-2Na的浓度为0.5%时,产物PAD的特性黏数为1 018.7 mL·g⁻¹,转化率可达97.2%。采用响应曲面法的Box-Behnken模型对实验参数进行了优化,根据预测出的实验参数,修正后进行了平行实验。当总单体质量分数为42%、EDTA-2Na的浓度为0.56%、pH=4、反应温度为60 ℃时,合成的PAD的特性黏数为1 027.1 mL·g⁻¹,预测值与实验值的误差仅为0.497%,可以较好地吻合,从而得到PAD的最优制备方法。制备的PAD性能优良,为工业化生产提供了依据,可以广泛应用于含油废水的处理。     

Isolation and characteristics of sulfentrazone-degrading bacteria

This study aimed to isolate and characterize bacteria able to use sulfentrazone in the commercial formulation as their sole carbon source. The isolation of the potential sulfentrazone-degrading bacteria was made from soil samples with a recent history of herbicide application and from isolates identified through rDNA sequencing. Subsequently, we assessed the growth of the isolates and their sulfentrazone degradation ability using high-performance liquid chromatography. Twenty-six potential sulfentrazone-degrading bacterial isolates were obtained in pure culture. Through analysis of the rDNA sequences, the predominance of bacterial species of the genus Pseudomonas was found. The isolates presented a differentiated ability of sulfentrazone degradation. The presence of herbicide in the culture medium reduced the log phase of four isolates. Pseudomonas putida, Pseudomonas lutea, Pseudomonas plecoglossicida and three isolates of Pseudomonas sp. showed higher sulfentrazone degradation capacity, which varied from 4 to 15%. This is the first report of the Pseudomonas genre capable of sulfentrazone degradation. The isolates obtained present potential use in bioremediation programs for soil contaminated with sulfentrazone.     

离子液体对三种农作物发芽和生长的毒性研究

为了考察离子液体的生态毒性,研究了5种离子液体及其浓度变化对3种农作物发芽及生长状况的影响。结果表明：就种子发芽这一生态毒理指标而言,不同作物对离子液体毒性的敏感程度不同,其次序为黄瓜>玉米>白菜;在一定浓度下,离子液体对白菜、黄瓜和玉米均具有一定的毒害作用;对于所考察的5种离子液体,阴离子为卤素的［EMIM］Br和［BMIM］Cl对植物发芽和生长的抑制作用远大于阴离子为烷基硫酸酯和烷基磷酸酯的同类离子液体 ［EMIM］［ES］、［EMIM］［DEP］和［MMIM］［DMP］。这种毒性顺序可能与卤素离子对细胞膜较强的穿透能力和由于离子液体的稳定性所造成的阴阳“离子对”的共迁移有关。     

不同表面活性剂存在下Ga2O3的水热合成及其光催化性能

以氯代十六烷基吡啶(CPC)、聚乙二醇6000(PEG6000)和十二烷基磺酸钠(SDS)为模板剂,采用水热法合成宽禁带Ga2O3纳米晶(Ga2O3CPC、Ga2O3PEG6000和Ga2O3SDS)。利用X射线衍射法(XRD)、扫描电镜(SEM)、紫外可见漫反射(UV-Vis DRS)、比表面积测定仪(BET)对催化剂晶相结构、形貌、比表面积以及其带隙进行了表征。其中Ga2O3CPC为单相α- Ga2O3,棒状形貌,Ga2O3PEG6000和Ga2O3SDS都为α和β相共存的多相Ga2O3。在紫外光(λ=254 nm)照射下,分别以罗丹明B(rhodamine B,RhB)和水杨酸(salicylic acid,SA)为目标降解物,发现Ga2O3CPC活性最好,反应4 h RhB基本降解完全,45 min对SA的降解率达到94.92%。通过测定降解过程中产生的活性物种及RhB降解过程中红外吸收光谱的变化,指出Ga2O3CPC对RhB的深度氧化矿化过程是涉及·OH自由基的氧化历程。     

Sources, transport and reactivity of anionic and non-ionic surfactants in several aquatic ecosystems in SW Spain: a comparative study

Presence, distribution and transport mechanisms of the four major synthetic surfactants -linear alkylbenzene sulfonates (LAS), alkyl ethoxysulfates (AES), nonylphenol ethoxylates (NPEOs) and alcohol ethoxylates (AEOs)- have been simultaneously studied in different aquatic ecosystems. Urban wastewater discharges and industrial activities were identified as the main sources for these compounds and their metabolites. LAS, AES and carboxylic metabolites remained in the dissolved form (87–99%). However, NPEOs and AEOs were mostly associated with particulate matter (65–86%), so their degradation in the water column was limited due to their lower bioavailability. It was also observed that sorption to the particulate phase was more intense for longer homologs/ethoxymers for all surfactants. With respect to surface sediments, AES levels were considerably below (<0.25 mg/kg) the values detected for LAS and NPEOs. Concentrations of AEOs, however, were occasionally higher (several tens of ppm) than those found for the rest of the target compounds in several sampling stations.     

Voltammetric detection of trifluralin in tap water,fruit juice,and vegetable extracts in the presence of surfactants

This study describes a novel electrochemical method to determine the herbicide trifluralin in samples of water, fruit juice, and vegetable extracts in the presence of surfactants, using a glassy carbon electrode (GCE). In acidic media, trifluralin was irreversible on the glassy carbon electrode surface at ?0.5 V vs. Ag/AgCl. Surfactant presence on the electrode–solution interface modified current intensities and shifted the reduction peak potential of trifluralin. Different types of surfactant and their concentrations were investigated. The anionic surfactant significantly enhanced the peak current intensity of trifluralin. Under optimal analytical conditions, an analytical curve was obtained in the concentration range of 0.48–32.20 µM. The limits of detection and quantification were estimated at 0.031 and 0.104 µM, respectively. The method was successfully applied to quantify trifluralin in samples of water, orange and tomato juice, and green pepper, carrot, and onion extracts, with recovery rates of 97.9–102.1%. The results were in good agreement with those obtained using high-performance liquid chromatography, indicating that the proposed electrochemical method can be employed to quantify trifluralin in various types foods, with sensitivity, specificity, selectivity and reproducibility.     

疫情背景下污水中的表面活性剂对污水处理效果的影响与机理

新冠疫情使人们洗手消毒的频次增加,导致比平日更多的表面活性剂进入污水处理厂,这可能会影响污水、污泥的处理过程。市政污水中表面活性剂的质量浓度一般为5~20 mg·L⁻¹,而在疫情期间可达10~30 mg·L⁻¹。污水经处理后,其中的表面活性剂仅1%随出水外流,约10%~20%则进入剩余污泥。尽管污水中表面活性剂的宏观含量并不高,但其特殊两性分子结构会降低氧传质效率、破坏污泥絮体结构,并影响脱氮除磷微生物的活性与丰度。在污泥处理方面,表面活性剂似乎会对污泥絮体脱水、解体与增溶产生正面效果,甚至还能促进污泥厌氧消化水解酸化。因此,有必要首先对表面活性剂来源、结构及其迁移转化进行梳理,进而阐述其对污水处理过程的负面影响与污水处理厂的应对措施,以及表面活性剂对污泥处理过程产生的积极影响,以期对污水处理厂在疫情背景下的运行措施调整提供参考。     

Effect of cationic and anionic surfactants on the sorption and desorption of perfluorooctane sulfonate (PFOS) on natural sediments

Sorption and desorption of PFOS at water-sediment interfaces were investigated in the presence of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), and an anionic surfactant, sodium dodecylbenzene sulfonate (SDBS). CTAB remarkably enhanced the sorption of PFOS on the sediment. In contrast, the influence of SDBS to the sorption of PFOS was concentration dependent. Two contrasting factors were responsible for the phenomenon. One was the sorption of the surfactant itself to the sediment, which enhanced the sorption of PFOS. The other was the increase in solubility of PFOS caused by the adding of surfactants, which decreased the sorption of PFOS. SDBS had a much lower sorption capacity, but rather strong ability to increase the solubility of PFOS. High levels of SDBS remarkably reduced the sorption of PFOS on the sediment. These results imply that cationic and anionic surfactants may have contrast impacts on the distribution and transport of PFOS in the environment.     

Biodegradation of Methoxychlor and Its Metabolites by the White Rot Fungus Stereum hirsutum Related to the Inactivation of Estrogenic Activity

The white rot fungus Stereum hirsutum was used to degrade methoxychlor [2,2,2-trichloro-1,1-bis(4-methoxyphenyl)ethane] in culture and the degraded products were extensively determined. The estrogenic activity of the degraded products of methoxychlor was examined using cell proliferation and pS2 gene expression assays in MCF-7 cells. S. hirsutum showed high resistance to methoxychlor 100 ppm, and the mycelial growth was fully completed within 8 days of incubation at 30°C. Methoxychlor in liquid culture medium was gradually converted into 2,2-dichloro-1,1-bis(4-methoxyphenyl)ethane, 2,2-dichloro-1,1-bis(4-methoxyphenyl)ethylene, 2-chloro-1,1-bis(4-methoxyphenyl) ethane, 2-chloro-1,1-bis(4-methoxyphenyl) ethylene, and 1,1-bis(4-methoxyphenyl)ethylene, indicating that methoxychlor is dominantly degraded by dechlorination and dehydrogenation. MCF-7 cells were demonstrated to proliferate actively at the 10^?5 M concentration of methoxychlor. However, cell proliferation was significantly inhibited by the incubation with methoxychlor culture media containing S. hirsutum. In addition, the expression level of pS2 mRNA was increased at the concentration (10^?5 M) of methoxychlor. The reductive effect of S. hirsutum for methoxychlor was clear but not significant as in the proliferation assay.     

Influence of anionic, cationic and nonionic surfactants on adsorption and desorption of oxytetracycline by ultrasonically treated and non-treated multiwalled carbon nanotubes

High adsorption capacity of carbon nanotubes (CNTs) may greatly determine the bioavailability and mobility of organic contaminants. The fate of contaminants adsorbed by CNTs may be substantially influenced by surfactants used both in the synthesis and dispersion of CNTs. The aim of this research was to determine the influence of surfactants (nonionic - TX100, cationic - CTAB and anionic - SDBS) on adsorption and desorption of oxytetracycline (OTC) by multiwalled carbon nanotubes (MWCNTs). The surfactants used had a substantial influence on both adsorption and desorption of OTC. The direction of changes depended clearly on the type of surfactant. In case of anionic SDBS, increased adsorption of OTC by MWCNTs was observed. The presence of TX100 and CTAB decreased the adsorption of OTC by MWCNTs significantly. The increase of OTC adsorption after ultrasonic treatment was observed in case of MWCNTs alone and MWCNTs with SDBS and TX100. However, ultrasonic treatment caused OTC adsorption decrease in the presence of CTAB. The change of pH had also an important effect on OTC adsorption in the presence of surfactants. Depending on the surfactant and pH, an increase or decrease of OTC adsorption was observed. The presence of surfactants increased OTC desorption from MWCNTs significantly as follows: SDBS = CTAB < TX100. The results obtained suggest new potential threats and constitute a basis for further research considering the bioavailability and toxicity of antibiotics in the presence of MWCNTs and surfactants.     

Photolysis of Enrofloxacin in aqueous systems under simulated sunlight irradiation: Kinetics, mechanism and toxicity of photolysis products

Photolysis of Enro in water was investigated under simulated sunlight irradiation using a Xenon lamp. The results showed that Enro photolysis followed apparent first-order kinetics. Increasing Enro concentration from 5.0 to 40.0 mg L⁻¹ led to the decrease of the photolysis rate constant from 1.6 × 10⁻² to 3.0 × 10⁻³ min⁻¹. Compared with the acidic and basic conditions, the photolysis rate was faster at neutral condition. Both of nitrate and humic acid can markedly decrease the photolysis rate of Enro because they can competitively absorb photons with Enro. The electron spin resonance and reactive oxygen species scavenging experiments indicated that Enro underwent self-sensitized photooxidation via OH and ¹O₂. After irradiation for 90 min, only 13.1% reduction of TOC occurred in spite of fast photolysis of 58.9% of Enro, indicating that Enro was transformed into intermediates without complete mineralization. The photolysis of Enro involved three main pathways: decarboxylation, defluorination, and piperazinyl N⁴-dealkylation. The bioluminescence inhibition rate using Vibrio fischeri increased to 67.2% at 60 min and then decreased to 56.9% at 90 min, indicative of the generation of some more toxic intermediates than Enro and then the degradation of the intermediates. The results will help us understand fundamental mechanisms of Enro photolysis and provide insight into the potential fate and transformation of Enro in surface waters.     

微量NO2对氨氧化过程中产物的影响

在无O2条件下,氨氧化速率越高,氨氧化过程中产生的NO-2-N、NO-3-N浓度和氮损失越大;NO2为25×10-6 mg/L时氮损失率最大,约为20.93%.在相同浓度的O2条件下,氮损失与氨氧化速率相关,氨氧化速率增加时,氮损失增大.在O2的体积分数为2%时,50×10-6 mg/L NO2时的氮损失率最大,为27.57%;在O2的体积分数为21%时,100×10-6 mg/L NO2时的氮损失率最大,为34.19%.     

微量NO2对厌氧氨氧化甲烷化反硝化耦合影响的动力学分析

采用批试验方法,研究微量NO2对颗粒污泥厌氧氨氧化、甲烷化和反硝化耦合的影响。基于Haldane模型建立了厌氧氨氧化的NO2强化函数,估计了强化函数中的最大强化系数（30.55）、NO2半饱和常数（1.96 mg/L）、NO2抑制常数（0.0082 mg/L）和基础速率系数（0.0314）。微量NO2对甲烷化和反硝化动力学可用反竞争性抑制动力学方程进行描述。甲烷化的最大比乙酸盐去除速率为0.15 mg COD/（mg VSS·h）,乙酸盐半饱和常数为395 mg COD/L,NO2抑制系数为0.623 mg/L。反硝化的亚硝酸盐氮最大去除速率0.00685 h-1,亚硝酸盐氮半饱和常数 0.214 mg/L,NO2抑制系数为22.4 mg/L。试验中大部分的NOx气体物质出现损失。     

Phenolic content,antioxidant and antibacterial activity of selected natural sweeteners available on the Polish market

Seventeen natural sweeteners available on the Polish market were screened for total phenolic content, by the Folin-Ciocalteu method, and for antioxidant activity, using the ferric reducing antioxidant power (FRAP) assay and the 2,2′-Azinobis (3-ethylbenzthiazoline-6-sulphonic acid) radical cation decolorization assay (ABTS^·+). In addition, we analyzed antibacterial activities against Staphylococcus aureus strains: both those susceptible and those resistant to methicillin (MRSA). The results of the study showed that total phenolic content, antioxidant activity and antibacterial activity differ widely among different samples of sweeteners. Phenolic content, expressed as a gallic acid equivalent, ranged from 0 mg kg^?1 in white, refined sugar, xylitol and wheat malt syrup to 11.4 g kg^?1 in sugarcane molasses. Antioxidant activity was lowest in refined white sugar, xylitol, brown beet sugar, liquid fructose, and rape honey; it was average in spelt syrup and corn syrup, and highest in sugar cane, beet molasses, date and barley syrups. Despite the great variety of sweeteners, a strong correlation was noted between the concentration of phenolics and antioxidant properties, as determined by the ABTS^·+ method (r = 0.97) and the FRAP assay (r = 0.77). The strongest antibacterial activity was observed in sugarcane molasses, which was lethal to S. aureus strains at 2 and 4% concentrations in medium for susceptible and MRSA strains respectively. Other sweeteners kill bacteria in 6–15% solutions, whereas some did not show any antibacterial activities against S. aureus strains, even at 20% concentrations. Due to their high antioxidant and antibacterial activities, some of the tested sweeteners have potential therapeutic value as supporting agents in antibiotic therapy.     

Genotoxicity of water from the Songhua River, China, in 1994-1995 and 2002-2003: Potential risks for human health

A previous study showed that the cancer mortalities are higher for residents who lived nearby the Songhua River heavily polluted by organic contamination. It is important to determine its risk of carcinogenic potential. Short-term genotoxic bio-assays using Salmonella, Sister Chromatid Exchange (SCE), and Micronuclei (MN) assays were employed to examine the genotoxic activity of ether extracts of water samples taken from the Songhua River. The results of the Salmonella bioassay indicated that there were indirect frame-shift mutagens in the water samples. A dose-response relationship for the SCE and MN assays was obtained. These results showed that organic extracts of water samples have genotoxic activity and the risk of carcinogenic potential to human health. The mutagenesis of water samples had changed compared to the results in 1994-1995. An increasing trend of risk of carcinogenic potential in the Songhua River after ten years should be noted and needs to be studied further.