Effects of perfluorooctanoic acid (PFOA) on activated sludge microbial community under aerobic and anaerobic conditions

Environmental Science and Pollution Research - Per- and polyfluoroalkyl substances (PFASs) have received increasing attention due to their widespread presence in diverse environments including...     

Adsorption of anionic and nonionic surfactant mixtures from synthetic detergents on soils

Adsorption of anionic surfactant (sodium dodecylbenzenesulfonate, SDBS) and nonionic surfactant (an alcohol ethoxylates with 12 carbons and 9 oxyethyl groups, A12E9) mixtures, widely used as the major constituents of synthetic detergents in China and become the most common pollutants in the environment, on soils was conducted to investigate the behavior of mixed surfactants in soils. The effects of addition order and mixing ratios of two surfactants, associated with pH and ion strength in solutions, on adsorptions were considered. The results show that saturated adsorption amount of SDBS and A12E9 on soils decreased respectively when A12E9 was added into soils firstly compared with that secondly, possibly resulting from the screening of A12E9 to part adsorption sites on soils and the hydrocarbon chain-chain interactions between SDBS and A12E9. The adsorption of SDBS and A12E9 on soils was enhanced each other at pre-plateau region of isotherms. At plateau region of isotherms, the adsorption of SDBS on soils decreased with the increase of molar fraction of A12E9 in mixed surfactant solutions, while that of A12E9 increased except the molar ratio of SDBS to A12E9 0.0:1.0. With the increase of pH in mixed surfactant solutions, adsorption amount of SDBS and A12E9 on soils decreased, respectively. The reduction of ion strength in soils resulted in the decrease of adsorption amount of SDBS and A12E9 on soils, respectively.     

A comparative study of adsorption of an anionic and a non-ionic surfactant by soils based on physicochemical and mineralogical properties of soils

In the present work we performed a comparative study on the adsorption of the surfactants sodium dodecyl sulphate (SDS) (anionic), and octylphenoxypolyethoxyethanol (Triton X-100) (non-ionic) to 18 soils with organic matter (OM) and clay fraction contents varying over a broad range. The objective of the study was to gain further insight into the influence of the physicochemical and mineralogical properties of soils on the adsorption of surfactants by soils. Adsorption isotherms were obtained using concentrations below the critical micellar concentration (cmc) of the surfactants. The adsorption coefficients, Kf, determined from the Freundlich equation were lower for SDS (range 1.77-82.1, mean value 36.3) than for Triton X-100 (range 0.01-913, mean value 257). Simple and multiple correlation coefficients were obtained between Kf values and soil characteristics. The results obtained indicate the influence of the OM content on the adsorption of SDS (r=0.64, p<0.01) and of the clay fraction content on that of Triton X-100 (r=0.83, p<0.001). Additionally, we observed a preferential adsorption of SDS by the 1:1 mineral kaolinite (r=0.54, p<0.05), while Triton X-100 was adsorbed mainly by the 2:1 minerals, montmorillonite (r=0.66, p<0.01) and illite (r=0.87, p<0.001). According to the influence of different soil parameters on adsorption, different mechanisms of adsorption are proposed for each surfactant. Our findings point to the interest of considering the physicochemical properties of soils and also the mineralogy of the soil clay fraction when selecting a surfactant in technologies involving enhanced solubilization and removal of contaminants from soils and sediments.     

Perfluorooctanoic acid (PFOA) acts as a tumor promoter on Syrian hamster embryo (SHE) cells

Perfluorooctane sulfonate (PFOS) (C(8)F(17)SO(3)) and perfluorooctanoic acid (PFOA) (C(8)HF(15)O(2)) are synthetic chemicals widely used in industrial applications for their hydrophobic and oleophobic properties. They are persistent, bioaccumulative, and toxic to mammalian species. Their widespread distribution on earth and contamination of human serum raised concerns about long-term side effects. They are suspected to be carcinogenic through a nongenotoxic mode of action, a mechanism supported by recent findings that PFOS induced cell transformation but no genotoxicity in Syrian hamster embryo (SHE) cells. In the present study, we evaluated carcinogenic potential of PFOA using the cell transformation assay on SHE cells. The chemical was applied alone or in combination with a nontransformant concentration of benzo[a]pyrene (BaP, 0.4?μM) in order to detect PFOA ability to act as tumor initiator or tumor promoter. The results showed that PFOA tested alone in the range 3.7?×?10(-5) to 300?μM did not induce SHE cell transformation frequency in a 7-day treatment. On the other side, the combination BaP/PFOA induced cell transformation at all PFOA concentrations tested, which revealed synergistic effects. No genotoxicity of PFOA on SHE cells was detected using the comet assay after 5 and 24?h of exposure. No significant increase in DNA breakage was found in BaP-initiated cells exposed to PFOA in a 7-day treatment. The whole results showed that PFOA acts as a tumor promoter and a nongenotoxic carcinogen. Cell transformation in initiated cells was observed at concentrations equivalent to the ones found in human serum of nonoccupationally and occupationally exposed populations. An involvement of PFOA in increased incidence of cancer recorded in occupationally exposed population cannot be ruled out.     

Aerosolization of an anionic surfactant (LAS) and dissolved organic carbon (DOC) under laboratory conditions.

Aerosolization of natural salt and brackish waters under laboratory conditions is responsible for the transfer of synthetic surfactants such as linear alkylbenzene sulphonate (LAS) from water to the atmosphere. Excluded the lagoon sample which stands apart, on the average ca. 45% of the LAS present at concentrations between 0.1 and 4.1 microg l(-1) in the tested coastal and offshore marine and lagoon waters was transferred to the aerosol extract. The distribution of the individual LAS homologs in the aerosol is very similar to that in water, which indicates no preferential removal from the bulk water of any LAS homolog. The fraction of dissolved organic carbon (DOC) undergoing aerosolization under the same conditions for each tested sample was on an average ca. 3.3%, corresponding to ca. 5.6 mg l(-1). On the average, the enrichment factor of the sea samples, resulting from the changing of the LAS/DOC ratio before and after aerosolization, was ca. 20.     

Effects of SOM, surfactant and pH on the sorption-desorption and mobility of prometryne in soils

Sorption and desorption of the herbicide prometryne in two types of soil subjected to the changes of pH and soil organic matter and surfactant were investigated. The sorption and desorption isotherms were expressed by the Freundlich equation. Freundlich K_f and n values indicate that soil organic matter was the major factor affecting prometryne behavior in the test soils. We also quantified the prometryne sorption and desorption behavior in soils, which arose from the application of Triton X-100 (TX100), a nonionic surfactant and change in pH. Application of TX100 led to a general decrease in prometryne sorption to the soils and an increase in desorption from the soils when applied in dosages of the critical micella concentration (CMC) 0.5, 1 and 2. At the concentration below the CMC, the non-ionic surfactant showed a tendency to decrease prometryne sorption and desorption. It appeared that TX100 dosages above CMC were required to effectively mobilize prometryne. Results indicate that the maximum prometryne sorption and minimum prometryne desorption in soils were achieved when the solution pH was near its pK_a. Finally, the influence of TX100 on the mobility of prometryne in soils using soil thin-layer chromatography was examined.     

Adsorption behavior of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) on boehmite

Understanding the interaction of perfluorochemicals, persistent pollutants with known human health effects, with mineral compounds in surface water and groundwater environments is essential to determining their fate and transport. Kinetic experiments showed that adsorption equilibrium can be achieved within 48 h and the boehmite (AlOOH) surface is receptive to perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorption. The adsorption isotherms estimated the maximum adsorption capacities of PFOS and PFOA on boehmite as 0.877 μg m⁻² and 0.633 μg m⁻², respectively. Compared to the adsorption capacity on γ-alumina, the abundant hydroxyl groups on boehmite surfaces resulted in the 2-3 times higher adsorption of PFOS and PFOA. Increasing solution pH led to a moderate decrease in PFOS and PFOA adsorption, owing to an increase in ligand exchange reactions and the decrease of electrostatic interactions. The presence of NaCl and CaCl₂ in solution demonstrated negative effects for PFOS and PFOA adsorption on boehmite surfaces, with potential mechanisms being electrical double layer compression, competitive adsorption of chloride, and the Ca²⁺ bridging effect between perfluorochemicals.     

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.     

生物与化学表面活性剂协同洗脱土壤中PCBs的研究

通过序批实验和土柱淋洗实验研究了由生物表面活性剂鼠李糖脂(RL)与非离子化学表面活性剂十二烷基醇聚氧乙烯(6)醚(POE(6))混合得到的复配试剂洗脱污染土壤中多氯联苯(PCBs)的作用效果及其作用机理。结果表明,同一土样中,从批实验得到的PCBs洗脱率略高于土柱淋洗实验。RL与POE(6)两种单一试剂对人工污染土样中的PCBs洗脱率均大于60%,而对陈化土样中的洗脱率均不到20%,且土壤中的TOC含量越高,PCBs的洗脱率越低。在质量浓度为301 mg/L(10 CMC)及1 505 mg/L(50 CMC)的RL-POE(6)复配试剂中,RL与POE(6)对人工污染土壤中PCBs的洗脱具有一定的协同作用。当复配试剂的浓度为301 mg/L时,RL与POE(6)对陈化土样中PCBs的洗脱没有协同作用;但当RL-POE(6)的浓度增加到1 505 mg/L时,RL与POE(6)对陈化土样中PCBs的洗脱具有明显的协同作用。     

Effect of nitrogen amendment on respiration and respiratory quotient (RQ) in three hydrocarbon contaminated soils of different type

Three soil types (sandy gravel, silty clay and sandy loam) from sites historically contaminated with total petroleum hydrocarbon (TPH) were amended with NH(4)NO(3) at concentrations ranging from 16 to 2133 mg/kg soil(dry weight). Microbial activity was measured as O(2) consumption and CO(2) production in order to assess nitrogen limitation. Although activity was stimulated in all three soils under NH(4)NO(3) amendment (after 72 h), the level of nitrogen required was soil specific. For the sandy gravel and silty clay soils, O(2) consumption and CO(2) production both showed enhanced microbial activity when amended with 16 mg/kg soil(dry weight) NH(4)NO(3), whereas, these two parameters gave differing results for the sandy loam soil. Specifically, CO(2) production and O(2) consumption were stimulated with 66 mg/kg and 133 mg/kg soil(dry weight) of NH(4)NO(3) respectively. In addition, respiratory quotient kinetic analysis suggested different decomposition processes occurring in this soil under different NH(4)NO(3) amendment concentrations.     

Effects of iron(III)chelates on the solubility of heavy metals in calcareous soils

In this study I evaluated the effects of complexing agents on the solubility of heavy metals in an incubation experiment up to 56 days when complexing agents were applied as Fe-chelates (Fe-EDDS(S,S), Fe-EDDS(mix), Fe-EDTA and Fe-EDDHA) on calcareous soils at a level sufficient to correct Fe chlorosis (0.1 mmol kg⁻¹). Of these ligands, EDDHA was the most efficient in keeping Fe in water-soluble form, and EDDS increased the solubility of Cu and Zn most, and only EDTA increased the solubility of Cd and Pb. EDTA increased the solubility of Ni steadily during the incubation period, equalling about 5-8% of the added EDTA concentration. [S,S]-EDDS was biodegraded within 56 days, whereas EDDS(mix) was less biodegradable. Ni-chelates were the most recalcitrant against biodegradation. The study shows that even a moderate input of chelates to soil increases the solubility of toxic heavy metals and their risk of leaching.     

Equilibrium partitioning theory to predict the sediment toxicity of the anionic surfactant C(12)-2-LAS to Corophium volutator

The study of the effect of the sorption of linear alkylbenzene sulfonates (LAS) on the bioavailability to marine benthic organisms is essential to refine the environmental risk assessment of these compounds. According to the equilibrium partitioning theory (EqP), the effect concentration in water-only exposure will be similar to the effect concentration in the sediment pore water. In this work, sorption and desorption experiments with two marine sediments were carried out using the compound C₁₂-2-LAS. The effect of the sediment sorption on the toxicity of benthic organisms was studied in water-only and in sediment bioassays with the marine mud shrimp Corophium volutator. In addition, three common spiking methods were tested for its application in the toxicity tests, as well as the stability of the surfactant during the water-only and sediment-water test duration. LC50 values obtained from water-only exposure showed a good correspondence with the pore water concentrations calculated from the sorption and desorption isotherms in the spiked sediments.     

Fate and transport of carbamazepine in soil aquifer treatment (SAT) infiltration basin soils

The transport and fate of the pharmaceutical carbamazepine (CBZ) were investigated in the Dan Region Reclamation Project (SHAFDAN), Tel-Aviv, Israel. Soil samples were taken from seven subsections of soil profiles (150 cm) in infiltration basins of a soil aquifer treatment (SAT) system. The transport characteristics were studied from the release dynamics of soil-resident CBZ and, subsequently, from applying a pulse input of wastewater containing CBZ. In addition, a monitoring study was performed to evaluate the fate of CBZ after the SAT. Results of this study indicate adsorption, and consequently retardation, in CBZ transport through the top soil layer (0-5 cm) and to a lesser extent in the second layer (5-25 cm), but not in deeper soil layers (25-150 cm). The soluble and adsorbed fractions of CBZ obtained from the two upper soil layers comprised 45% of the total CBZ content in the entire soil profile. This behavior correlated to the higher organic matter content observed in the upper soil layers (0-25 cm). It is therefore deduced that when accounting for the full flow path of CBZ through the vadose zone to the groundwater region, the overall transport of CBZ in the SAT system is essentially conservative. The monitoring study revealed that the average concentration of CBZ decreased from 1094 ± 166 ng L⁻¹ in the recharged wastewater to 560 ± 175 ng L⁻¹ after the SAT. This reduction is explained by dilution of the recharged wastewater with resident groundwater, which may occur as it flows to active reclamation wells.     

Influence of surfactant sorption on the removal of phenanthrene from contaminated soils

Laboratory column flushing experiments were conducted to remove phenanthrene from contaminated soils by Triton X-100 (TX100) with an aim to investigating the effect of surfactant sorption on the performance of surfactant-enhanced remediation process. The effluent concentration of phenanthrene from soil columns showed strong dependence on the sorption breakthrough curves of TX100. The removal of phenanthrene from contaminated soils was enhanced only when the sorption breakthrough of TX100 occurred and the influent concentration of TX100 was greater than the critical enhanced flushing concentration (CEFC). The sorption of surfactant onto soils and the subsequent partitioning of contaminants into soil-sorbed surfactant had a significant effect on the solute equilibrium distribution coefficient (KD) and thus the flushing efficiency for phenanthrene. A model was developed to predict KD and CEFC values for simulating the performance of surfactant-enhanced flushing for contaminated soils. These results are of practical interest in developing effective and safe surfactant-enhanced remediation technologies.     

Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy

C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).     

The relationship between surface adsorption and the hydrolysis of amitraz in anionic surfactant solutions

The adsorption of amitraz to various adsorbents was studied in terms of the amount and rate of adsorption and the effect that adsorption had on the stability of amitraz in an aqueous environment. Adsorption results showed that in terms of their ability to adsorb amitraz from solution the adsorbents tested in this study can be ordered as follows: coarse carbon > cation exchange resin > or = anion exchange resin > fine carbon. Amitraz was not adsorbed on sand and potassium oxihumate. Adding sodium lauryl sulfate and potassium oxihumate to aqueous suspensions of suspended adsorbents containing adsorbed amitraz showed that both these anionic surfactants significantly increased the hydrolysis rate because the half-lives for amitraz was reduced from 27 days for a suspension to only 8 hours for amitraz adsorbed to a cation exchange resin and suspended in an aqueous buffer pH 5.8 containing 0.5% of the anionic surfactant sodium lauryl sulfate and 12 hours when 1% potassium oxihumate was added.     

石油烃在不同土壤中的气相自然衰减规律

挥发性有机物 (VOCs) 在包气带中的迁移扩散是土壤和地下水中可挥发污染物自然衰减的重要机制,也与蒸气入侵暴露和风险评估密切相关。采用微宇宙实验对12种挥发性石油烃 (正戊烷、正己烷、正庚烷、正辛烷、环戊烷、环己烷、环庚烷、环辛烷、苯、甲苯、乙苯、对二甲苯) 在4种土壤 (黑土、黄土、红土、石英砂) 中的气相自然衰减机制和气态生物降解动力学规律进行了研究。结果表明,正构烷烃、环烷烃和苯系物蒸气在4种土壤中的气相自然衰减去除率都遵循黑土>黄土>红土>石英砂的规律;黑土中生物降解对污染物去除率的贡献高于黄土,而红土和石英砂中的生物降解速率极低;4种苯系物的自然衰减和生物降解潜力远高于正构烷烃和环烷烃;苯系物气相生物降解速率排序为：甲苯>苯>乙苯>对二甲苯。本研究结果可为蒸气入侵定量风险评估和石油污染场地自然衰减速率定量评估提供参考。     

Impact of dilution on the transport of poly(acrylic acid) supported magnetite nanoparticles in porous media

This paper investigates the impact of dilution on the mobility of magnetite nanoparticles surface coated with poly(acrylic acid) (PAA). Transport experiments were conducted in a water-saturated sand-packed column for input nanoparticle solutions with total Fe concentrations ranging from 100 to 600mg/L. Particle size analysis of the synthesized nanoparticle solutions showed that PAA provides good size stability for Fe concentrations as low as about 1mg/L. Time-moment analysis of the nanoparticle breakthrough curves, on the other hand, revealed that nanoparticle mass recovery from the column decreased consistently with dilution, with greater attenuation, sharper fronts and longer tails compared to that of the tracer. Particle size analysis of the eluted solutions shows that the nanoparticle size is negatively correlated with nanoparticle concentration. Modeling results suggest that the decrease in nanoparticle mobility with input concentration can be represented using a kinetic time-dependent deposition term with finite deposition capacity and a kinetic detachment term. For field applications, the increase in particle size and detachment resulting from dilution means reduced transport efficiency of nanoparticles and reaction potential with travel distance.     

表面活性剂淋滤对土壤中邻苯二甲酸酯纵向迁移的影响

以无表面活性剂的去离子水为对照、设置1倍(1 CMC)和2倍临界胶束浓度(2 CMC)浓度,研究了单一和混合表面活性剂,包括十六烷基三甲基溴化铵(CTAB)、十二烷基苯磺酸钠(SDBS)和曲拉通X-100(TX-100)对人工污染土壤中邻苯二甲酸酯(PAEs)纵向迁移的影响,土柱中上层为PAEs污染土(3 cm),下层为清洁土(20 cm)。CTAB和SDBS在2 CMC时、TX-100为1 CMC时可增强污染土中PAEs的纵向迁移,其中DMP和DEP有无表面活性剂均可发生迁移,在相同表面活性剂条件下,延长老化时间对污染土中PAEs的迁移产生一定的影响。CTAB和SDBS在2 CMC时,清洁土中PAEs总含量较低,但TX-100在1 CMC时较低。清洁土中PAEs总含量均随土层深度的增加而降低。当老化时间较短时,土壤有机质对PAEs在清洁土柱的迁移影响较小,老化时间的延长对清洁土中的PAEs迁移影响较大。3种表面活性剂均可有效促进清洁土中DMP和DEP的迁移,CTAB和SDBS在2 CMC、TX-100在1 CMC时可促进DNBP和BBP的迁移,但3种表面活性剂对清洁土中DNOP迁移的影响较小。与单一表面活性剂相比,混合表面活性剂有助于污染土中PAEs的迁移,且随着浓度的升高,清洁土中PAEs的含量呈现降低的趋势。就整个土柱而言,单一表面活性剂CTAB和SDBS在较高浓度时、TX-100较低的浓度时对PAEs的淋滤效果更好;在较短老化时间下,土壤有机质含量的高低对淋滤率没有显著影响;老化时间延长有效降低了淋滤率;而混合表面活性剂的淋滤率有明显提高,更有助于PAEs的迁移。     

磺化蓖麻油胶束强化超滤特性研究

采用一种由天然油脂蓖麻油磺化制得的磺化蓖麻油作为阴离子表面活性剂,与超滤膜相结合处理含微量Cr3＋废水。探讨了膜过程的超滤特性及影响Cr3＋去除效果的因素,并对该表面活性剂的回收再利用问题做了初步实验。实验表明,溶液中加入Cr3＋,磺化蓖麻油截留率明显增大,可见磺化蓖麻油胶束在水溶液中与Cr3＋作用可形成比纯磺化蓖麻油胶束更大的胶束或胶束聚集体。经过超滤膜过程处理,透过液中Cr3＋浓度〈0.254 mg/L,用于含Cr3＋废水处理,可达到国家废水排放标准或装置回用要求。初步回收实验表明,磺化蓖麻油在酸性条件下析出,通过离心法可将其从浓缩液中分离出来。