Biodegradability and toxicity of sulphonate-based surfactants in aerobic and anaerobic aquatic environments

Four types of commonly used sulphonate-based surfactants (alkane sulphonates, alpha-olefin sulphonates, sulphosuccinates and methyl ester sulphonates) were tested for their aerobic and anaerobic biodegradability as well as for their toxicity to Daphnia magna and Photobacterium phosphoreum to assess the effect of the surfactant structure on those properties. Aerobic biodegradation was evaluated by means of the CO₂ headspace test and anaerobic biodegradation was assessed by a method based on the ECETOC test. All the surfactants tested were readily biodegraded under aerobic conditions. No clear effect of the surfactant structures on the toxicity to the aquatic organisms tested was found. The most significant differences in the surfactants studied were observed in their behaviour under anaerobic conditions. Alkane sulphonates, alpha-olefin sulphonates and methyl ester sulphonates were not mineralized in lab anaerobic digesters despite the fact that the last one showed a certain degree of primary degradation. Nevertheless, these surfactants did not significantly inhibit methanogenic activity at concentrations up to 15 g surfactant/kg dry sludge, a concentration that is much higher than the expected concentrations of these surfactants in real anaerobic digesters. Sulphosuccinates showed a high level of primary biodegradation in anaerobic conditions. However, linear alkyl sulphosuccinates were completely mineralized whereas branched alkyl sulphosuccinates achieved percentages of ultimate biodegradation ≤50%.     

Effect of anionic and nonionic surfactants on the kinetics of the aerobic heterotrophic biodegradation of organic matter in industrial wastewater

While using the contemporary mathematical models for activated sludge systems, it is necessary to describe quantitatively the kinetics of microbiological processes and to characterise substrate (wastewater components in the influent) as well as biomass (activated sludge). In this paper, the kinetic parameters of the aerobic biodegradation of organic matter in wastewater containing synthetic surfactants in an activated sludge system were determined and discussed. Also, the composition of the tested wastewater was estimated and expressed as COD fractions. Five synthetic surfactants, three anionic and two nonionic, of different chemical structure were investigated. Each of them was tested separately and dissolved in wastewater to obtain a concentration of 50 mgl(-1), which can be found in some industrial wastewater. The presence of the elevated amount of synthetic surfactants in wastewater decreased the affinity of biomass to substrate. Nevertheless, maximum specific growth rates (micromax) of heterotrophic biomass exposed to wastewater containing surfactants were high but usually lower than micromax estimated for wastewater without surfactant. Surfactants, which contain a benzene ring, were the most likely to deteriorate wastewater treatment processes in the activated sludge systems.     

Anaerobic degradation of nonionic and anionic surfactants in enrichment cultures and fixed-bed reactors

Anaerobic biodegradation and inhibitory effects of nonionic and anionic surfactants on methanogenic fermentation were tested in incubation experiments with anoxic sediment samples and sewage sludge. Alkylsulfonates and alkylbenzenesulfonates were not degraded but inhibited methanogenesis from sludge constituents at concentrations ≥10 mgl⁻¹. Sodium dodecylsulfate was at least partly degraded after adaptation at concentrations 100 mgl⁻¹ and the sulfate group was reduced to sulfide. The polyethyleneglycol moiety of alkylphenolethoxylates was fermented to methane at concentrations 500 mgl⁻¹ whereas the alkylphenol residue probably remained unchanged. Alkylethoxylates were completely degraded to methane and CO₂ at concentrations up to 1.0 gl⁻¹. Complete anaerobic degradation of this surfactant type to methane, CO₂, and traces of acetate and propionate was demonstrated in a lab scale anaerobic fixed-bed reactor, either with prereduced mineral salts medium or with air-saturated artificial wastewater. This process lends itself as a suited, inexpensive means for treatment of wastewaters containing enhanced loads of nonionic surfactants, e.g. from the surfactant manufacturing or processing industry.     

Direct spectrophotometric determination of alkylphenol polyethoxylate nonionic surfactants in wastewater

A new spectrophotometric method is proposed for direct determination of alkylphenol polyethoxylate, RO(CH(2)CH(2)O)(n)H (where R is alkylphenyl and n is the degree of polymerization), in wastewater. The method is based on the formation of ternary complex, Pb(II)-meso-tetra-(3,5-dibromo-4-hydrooxyphenyl)-Porphyrin (T(DBHP)P)-alkylphenol polyethoxylate (APE). Under optimum reaction conditions, T(DBHP)P reacts with lead(II) and APE to form a yellow ternary complex with the maximum absorption peak at 479 nm. The color reaction is rapidly completed and the absorbance remains stable for at least 24h under room temperature. The apparent molar absorption coefficients were 0.4-4.3 x 10(4) L mol(-1) cm(-1) for n=5-50. As little as 0.02 microg mL(-1) of APE can be detected. The effects of various substances on the determination of APE were also investigated in detail. It was found that all the studied co-existing substances, especially cationic and anionic surfactants, which always seriously interfere in some reported methods, could be tolerated in considerable amounts. The method offered the advantages of simplicity, rapidity, sensitivity and selectivity without any prior separation or extraction.     

Biokinetics of biodegradation of surfactants under aerobic, anoxic and anaerobic conditions

The present investigation aims at estimating the biodegradation coefficients of surfactants. The biodegradabilities of Triton X-100 and Rhamnolipid were tested under aerobic, nitrate reducing, sulphate reducing and anaerobic conditions using a respirometer. The results indicated that in terms of biodegradability, Rhamnolipid is superior to Triton X-100, since it is biodegradable under all conditions, whereas Triton X-100 is partially biodegradable under aerobic conditions and non-biodegradable under anaerobic, nitrate reducing and sulphate reducing conditions.     

Transformation and characterisation of dissolved organic matter during the thermophilic aerobic biodegradation of faeces

We conducted a comparison of the characteristics of dissolved organic matter (DOM) taken from the bio-toilet and other sources. A characterisation of DOM was carried out to assess the stability of the compost generated during the thermophilic and aerobic biodegradation of faeces. In addition, levels of soluble microbial products generated in the bio-toilet composting reactor were compared with those taken from other sources. The results showed that (i) the main component of DOM from the bio-toilet are solutes with molecular weight (MW)>30,000 Da (40%), whereas micromolecules (MW< 1000 Da) constituted more than 60% of the DOM from other solid samples, while liquid samples reached even more than 90%; (ii) the DOM stabilisation level in the composting reactor of the bio-toilet system was greater than that shown by DOM from other sources; (iii) stabilisation of DOM in the bio-toilet system was characterised by an increasing amount of macromolecules (MW>30,000 Da) after a decreasing trend was observed in the early stages of the biodegradation process; and (iv) net production of lipopolysaccharide (LPS) in wastewater treatment plants is greater than in the bio-toilet.     

Modeling of aerobic biodegradation of feces using sawdust as a matrix

Composting in the bio-toilet system is a continuous thermophilic-aerobic biodegradation process. Unlike to the traditional composting systems, biodegradation rates of organic matter are very important because feces are daily added into the composting reactor of the bio-toilet and an accelerated decomposition is aimed. The models developed for conventional composting processes include simple formulations of biodegradation kinetics and deal mainly with energy and water balances. Therefore, formulation of kinetics that can reasonably describe the biodegradation process in the bio-toilet system is required for better modeling predictions. In this work, a bio-kinetic model was introduced to describe the aerobic biodegradation of feces in the bio-toilet system. This model includes three processes for carbonaceous material degradation and is prepared by using the activated sludge modeling techniques and formulations. Stoichiometric parameters were adopted from literature on activated sludge processes. Kinetic parameters were estimated by conducting batch tests for several organic loadings and by using respirometry, curve-fitting techniques, and sensitivity analysis. Feasibility and applicability of these parameters were assessed by conducting feces intermittent-feeding tests and by simulating the experimental respiration rates. Model, stoichiometric and kinetic parameters proved to be affordable for describing the biodegradation of feces in the bio-toilet system.     

Development of enzyme-linked immunosorbent assay for detection of alkylphenol polyethoxylates and their biodegradation products

An enzyme-linked immunosorbent assay (ELISA) was developed for the quantitative analysis of alkylphenol polyethoxylates (APnEOs) and their biodegradation products. To generate a specific monoclonal antibody (mAb) for the ELISA, hybridoma cells were produced by the fusion of mouse myeloma cells and spleen cells from mice immunized with nonylphenol polyethoxylate (NPnEO) derivatives coupled to bovine serum albumin. The developed ELISA showed the detection limits of 16 and 30 μg/L NP10EO when 10% and 60% (v/v) methanol solutions were used as assay diluent. The mAb was shown to be specific to APnEOs and their metabolites, such as short-ethoxy-chain APnEOs and alkylphenoxy carboxylic acids, except for nonylphenol. Moreover, no response was observed with non-APnEO surfactants as well as other compounds structurally similar to APnEOs. The percentage river water recoveries of 85–118% were obtained for 10 μg/L NP10EO fortification after preconcentration by C18 solid-phase extraction. The ELISA was also validated by comparing it with high-performance liquid chromatography for the analysis of APnEOs and their metabolites in river samples; the correlation coefficient between the values obtained by these assays was 0.96.     

Temperature effect on aerobic biodegradation of feces using sawdust as a matrix

Temperature is one of the most important factors affecting microbial growth and biological reactions. In this study, the effect of temperature on aerobic biodegradation of feces is described through the comparison and analysis of experimental oxygen utilization rates (OUR) profiles obtained from batch tests conducted at several temperatures covering mainly mesophilic and thermophilic ranges. Additionally, the temperature effect was incorporated into the bio-kinetic model introduced by Lopez Zavala et al. (Water Res 38(5) (2004) 1327) and simulation of experimental OUR profiles was conducted. Results show that mesophilic and thermophilic microorganisms behaved differently to temperature; additionally, results suggest that the optimum temperature from the viewpoint of feces biodegradability is within the thermophilic range, nearly 60 degrees C. The enzymatic activity of microorganisms at 70 degrees C was remarkably diminished. For better predictions in the mesophilic range, two fractions of slowly biodegradable organic matter were identified, easily hydrolyzable organic matter (X(Se)) and slowly hydrolyzable organic matter (X(Ss)).     

Phenol biodegradation and its effect on the nitrification process

Phenol biodegradation under aerobic conditions and its effect on the nitrification process were studied, first in batch assays and then in an activated sludge reactor. In batch assays, phenol was completely biodegraded at concentrations ranging from 100 to 2500 mg l(-1). Phenol was inhibitory to the nitrification process, showing more inhibition at higher initial phenol concentrations. At initial phenol concentrations above 1000 mg l(-1), the level of nitrification decreased. In the activated sludge reactor, the applied ammonium loading rate was maintained at 140 mg N-NH(4)(+)l(-1)d(-1) (350 mg N-NH(4)(+)l(-1)) during the operation time. However, the applied organic loading rate was increased stepwise from 30 to 2700 mg COD l(-1)d(-1) by increasing the phenol concentration from 35 up to 2800 mg l(-1). High phenol removal efficiencies, above 99.9%, were maintained at all the applied organic loading rates. Ammonium removal was also very high during the operation period, around 99.8%, indicating that there was no inhibition of nitrification by phenol.     

The biodegradability of two primary alcohol ethoxylate nonionic surfactants under practical conditions,and the toxicity of the biodegradation products to rainbow trout

A field trial has been performed to measure the biodegradability of two typical alcohol ethoxylate nonionic surfactants, “Dobanol” 45-7 and “Dobanol” 45-11, by dosing them to biological filters in a mixture with domestic sewage. Influent levels were 10 and 25 mg l^?1 of each surfactant and 96–98% degradation was achieved within a temperature range of 5–10°C. The surfactants had no adverse effects on the filters in terms of the usual sanitary parameters (BOD, COD, TOC and ammoniacal nitrogen). Tests on the effluents indicated no residual acute lethal toxicity to rainbow trout Salmo gairdneri).     

Inhibition of aerobic metabolic cis-1,2-di-chloroethene biodegradation by other chloroethenes

The presence of other chloroethenes influences aerobic metabolic biodegradation of cis-1,2-dichloroethene (cDCE). A new metabolically cDCE degrading enrichment culture was identified as also being capable of degrading vinyl chloride (VC), but not 1,1-dichloroethene (1,1DCE), trans-1,2-dichloroethene (tDCE), trichloroethene (TCE), or tetrachloroethene (PCE). The fastest degradation of cDCE was observed in the absence of any other chloroethene. In the presence of a second chloroethene (40-90 μM), the rate of cDCE (60 μM) degradation decreased in the following order: cDCE (+PCE) > cDCE (+tDCE) > cDCE (+VC)> cDCE (+1,1DCE) ≈ cDCE (+TCE). With increasing concentrations of VC, ranging from 10 to 110 μM, the rate of cDCE (60 μM) degradation decreased. This study demonstrates that the inhibiting effects of chloroethene mixtures have to be considered during laboratory studies and bioremediation approaches based on metabolic cDCE degradation.     

聚氧乙烯型非离子表面活性剂在细水雾灭火中的应用

以几种O系列聚氧乙烯型非离子表面活性剂为添加剂,利用表面张力仪、激光粒度分析仪、乳化性能实验等详细研究了它们对水的物理性质(表面张力、喷雾粒径、乳化性能)的影响.根据测试结果,以O-8为细水雾添加剂,利用灭汽油油盆火实验研究了含O-8细水雾的灭火性能,并用烟气分析仪分析了灭火过程中的烟气(氧气、一氧化碳和二氧化碳)浓度.实验结果表明:O系列聚氧乙烯型非离子表面活性剂的加入能显著降低水的表面张力、减小细水雾的粒径分布、增强水的乳化性能.与纯水细水雾相比,含O-8的细水雾具有更好的灭火性能,并有利于抑制汽油燃烧过程中一氧化碳和二氧化碳的产生.     

Aerobic biodegradation of polyethylene glycols of different molecular weights in wastewater and seawater

In order to distinguish between aerobic biodegradation of synthetic polymers in fresh and seawater, polyethylene glycols (PEGs) were systematically and comparatively investigated in inocula from municipal wastewater and seawater aquarium filters for the first time. The molecular weight (MW) of the PEGs, (HO(CH(2)CH(2)O)(n)H, n=3-1350) as representatives of water-soluble polymers, ranged from 250 to 57,800Da. The biodegradation was observed by removal of dissolved organic carbon and carbon dioxide production by applying standardized ISO and OECD test methods. Specific analyses using liquid chromatography mass spectrometry (LC-MS) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) were performed. All PEGs selected were completely biodegradable in freshwater media within 65d. PEGs with an MW up to 14,600Da have a similar degradation pathway which is characterized by gradual splitting of C(2)-units off the chain resulting in formation of short-chain PEGs. In artificial seawater media, full biodegradation of PEGs up to 7400Da required more time than in freshwater. PEGs with MW 10,300 and 14,600Da were only partially degraded whereas PEGs with MW 26,600 and 57,800Da were not degraded for a period of 135d. The biodegradation pathway of PEG 250 and PEG 970 in seawater is similar to that for freshwater. For PEGs having an MW from 2000 to 10,300Da, the degradation pathway in seawater differs from the pathway of the shorter PEGs.     

Selection and evaluation of adsorbents for the removal of anionic surfactants from laundry rinsing water

Low-cost adsorbents were tested to remove anionic surfactants from laundry rinsing water to allow re-use of water. Adsorbents were selected corresponding to the different surfactant adsorption mechanisms. Equilibrium adsorption studies of linear alkyl benzene sulfonate (LAS) show that ionic interaction results in a high maximum adsorption capacity on positively charged adsorbents of 0.6-1.7 gLAS/g. Non-ionic interactions, such as hydrophobic interactions of LAS with non-ionic resins or activated carbons, result in a lower adsorption capacity of 0.02-0.6 gLAS/g. Negatively charged materials, such as cation exchange resins or bentonite clay, have negligible adsorption capacities for LAS. Similar results are obtained for alpha olefin sulfonate (AOS). Cost comparison of different adsorbents shows that an inorganic anion exchange material (layered double hydroxide) and activated carbons are the most cost-effective materials in terms of the amount of surfactant adsorbed per dollar worth of adsorbent.     

UV-TiO2联用去除饮用水中阴离子表面活性剂的研究

采用UV-TiO2催化氧化联用工艺去除饮用水中低含量阴离子表面活性剂LAS.试验考察了玻璃纤维网膜数目、涂敷次数和LAS的初始浓度对LAS去除效果的影响,在LAS浓度为1 mg/L,紫外光强度为4 mw/cm2,3张玻璃纤维网膜分别涂敷3次条件下,反应100 min后,LAS的去除率超过90%.并建立了UV-TiO2催化氧化联用工艺降解LAS的动力学方程.     

Effects of alcohols, anionic and nonionic surfactants on the reduction of PCE and TCE by zero-valent iron

The effects of surfactants, sodium dodecyl sulfate (SDS) and Triton X-a00 (TX), and alcohols (methanol, ethanol, and propanol) on the dehalogenation of TCE and PCE by zero-valent iron were examined. Surface concentrations of PCE and TCE on the iron were dependent on aqueous surfactant concentrations. At concentrations above the CMC, sorbed halocarbon concentrations declined and concentrations associated with solution phase micelles increased. The anionic surfactant SDS ([SDS] < CMC) did not affect reduction rates, until the CMC was exceeded after which reactivity decreased, possibly due to sequestering of the TCE and PCE in mobile micelles. The nonionic TX showed a mixed effect on reactivity, increasing the PCE reduction rate, but not affecting TCE removal. Production of TCE from PCE increased in the presence of TX. Similar experiments showed that methanol, ethanol, and propanol inhibited reduction of TCE and PCE by metallic iron. Zero-valent iron may be useful in recycling soil washing effluents contaminated with TCE and PCE.     

Distribution and geochemical behaviour of anionic surfactants determined as ethyl violet active substances in Lake Biwa,Japan

The distribution and geochemical behaviour of anionic surfactants (AS) determined as ethyl violet active substances (EVAS) were studied in Lake Biwa, Japan. We determined the vertical distributions of dissolved EVAS (DEVAS), suspended particulate EVAS (PEVAS), particulate organic carbon (POC) and the PEVAS/POC ratio. Statistical analyses conducted using plots of PEVAS versus POC and PEVAS/ Chlorophyll‐a (Chl‐a) versus POC/Chl‐a revealed that the distributions of DEVAS and PEVAS were affected by the concentrations of freshly produced POC and aged POC and by the pH of the lake water. Adsorption and desorption of EVAS onto the POC phase were found to be important mechanisms regulating the distribution and environmental/geochemical behaviour of EVAS in the lake. The organic carbon‐normalized particle–water‐partitioning coefficient, K_oc, for EVAS was also estimated and compared with that for nonylphenol.     

Determination of non-ionic surfactants and their biotransformation by-products adsorbed on alive activated sludge

A procedure has been developed for the determination of non-ionic surfactants (NS) adsorbed on particles of alive and dead activated sludge. The procedure also enables the determination of adsorption of major biodegradation by-products: short-chained ethoxylates, long- and short-chained PEG. The basis of measurement is the determination of NS concentration in a slurry of activated sludge and in a solution phase. The difference between these two concentrations represents the NS adsorbed on activated sludge. Separation of NS and their biotransformation by-products from samples and then on narrower fractions was performed by a sequential liquid-liquid extraction and precipitation with modified Dragendorff reagent. The indirect tensammetric technique (ITT) was applied for the final determination. The developed method was checked using the example of the treatment of the surfactant C12E10 (oxyethylated fatty alcohol) (C12E10) in the continuous flow activated sludge facility. No statistically significant accumulation of C12E10 on the alive activated sludge was detected, probably because of faster C12E10 fission than its adsorption. However, significant adsorption of the short-chained ethoxylates (including free alcohol) on the alive activated sludge was found, as well as statistically significant adsorption of long- and short-chained PEG. The adsorption of surfactant C12E10 and its biodegradation by-products on dead activated sludge was found to be higher than the species adsorption on alive activated sludge.     

水体沉积物中石油污染物的生物降解试验研究

研究了高效石油降解茵(邻单胞菌属)对水体沉积物中石油污染物的处理效果,以及微生物接种量、石油烃初始浓度和上层水体中溶解氧浓度对其降解效果的影响.结果表明,微生物接种量越多,石油烃去除率越高,加入30 mL浓度为105CFU/mL的菌悬液时,沉积物中石油烃的去除率为34.94%;沉积物中石油烃初始浓度过高或过低均不利于石油烃降解,当试验土样中石油烃浓度为107.15 mg/kg时,石油烃的去除率为77.30%;水中溶解氧浓度的提高可以加速石油烃的降解,密闭曝气状态下水中DO为7.09 mg/L时,石油烃的去除率为64.95%.