Anaerobic degradation and toxicity of commercial cationic surfactants in anaerobic screening tests

Anaerobic biodegradability and toxicity on anaerobic bacteria of di(hydrogenated tallow) dimethyl ammonium chloride (DHTDMAC) and two esterquats have been investigated. A batch test system containing municipal digester solids as a source of anaerobic bacteria, based on the method proposed by the ECETOC, has been applied. To evaluate the potential toxicity of such surfactants on anaerobic sludge, a co-substrate, an easily biodegradable compound in anaerobic conditions, has been added to the samples to test and the effects on biogas production have been determined. For the esterquats studied high biodegradation levels were obtained and no toxic effects on anaerobic bacteria were observed even at the highest concentrations tested, 100 and 200 mg C/l, respectively. On the contrary, DHTDMAC was not degradated at the same test conditions. However, no inhibitory effects on the biogas production were detected for this surfactant at concentrations <100 mg C/l.     

Biodegradation of polylactide in aerobic and anaerobic thermophilic conditions

Biodegradable polymers are designed to resist a number of environmental factors during use, but to be biodegradable under disposal conditions. The biodegradation of polylactide (PLLA) was studied at different elevated temperatures in both aerobic and anaerobic, aquatic and solid state conditions. In the aerobic aquatic headspace test the mineralisation of PLLA was very slow at room temperature, but faster under thermophilic conditions. The clear effect of temperature on the biodegradability of PLLA in the aquatic tests indicates that its polymer structure has to be hydrolysed before microorganisms can utilise it as a nutrient source. At similar elevated temperatures, the biodegradation of PLLA was much faster in anaerobic solid state conditions than in aerobic aquatic conditions. The behaviour of PLLA in the natural composting process was similar to that in the aquatic biodegradation tests, biodegradation starting only after the beginning of the thermophilic phase. These results indicate that PLLA can be considered as a compostable material, being stable during use at mesophilic temperatures, but degrading rapidly during waste disposal in compost or anaerobic treatment facilities.     

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.     

Fate and effect of monoalkyl quaternary ammonium surfactants in the aquatic environment

The effect of the alkyl chain of quaternary ammonium-based surfactants on their aquatic toxicity and aerobic biodegradability has been studied. Two families of monoalkylquats surfactants were selected: alkyl trimethyl ammonium and alkyl benzyl dimethyl ammonium halides. Acute toxicity tests on Daphnia magna and Photobacterium phosphoreum were carried out and EC50 values in the range of 0.1-1 mg/l were obtained for the two series of cationic surfactants. Although the substitution of a benzyl group for a methyl group increases the toxicity, an incremental difference in toxicity between homologs of different chain length were not observed. Biodegradability of the different homologs was determined not only in standard conditions but also in coastal water, both tests yielding similar results. An increase in the alkyl chain length or the substitution of a benzyl group for a methyl group reduces the biodegradation rate. The degradation of these compounds in coastal waters was associated with an increase in bacterioplankton density, suggesting that the degradation takes place because the compound is used as a growth substrate.     

Ecotoxicity and biodegradation of phthalate monoesters

Little is known about the fate and the effects of phthalic acid monoesters. Various of these monoesters ranging from n-butyl to isononyl monoester have been evaluated in respect to their biodegradation behaviour and their acute aquatic toxicity. All esters are readily biodegradable, achieving degradation rates of 90% and more. The acute toxicity values strongly depend on the carbon chain length of the alcohol moiety. The short chain specimen have LC/EC50 around and above 100 mg/l, with values levelling off to around 30 mg/l for the isononyl monoester.     

Acute toxicity and genotoxicity of five selected anionic and nonionic surfactants

The results of four toxicity bioassays of selected anionic and nonionic surface active agents were presented. Three widely used anionic surfactants that belong to alkyl sulphates (AS), alkylbenzene sulphonates (LAS) and alkylpolyoxyethylene sulphates (AES) as well as nonionic surfactants: polyoxyethylene alkyl ethers (AE) and polyoxylethylene alkylphenyl ethers (APE) were tested. Three different toxicity assays to aquatic organisms: Physa acuta Draparnaud, Artemia salina and Raphidocelis subcapitata were applied. Additionally, the genotoxicity test with Bacillus subtilis M45 Rec- and H17 Rec+ strains was performed. The obtained results showed that none of the surfactants studied was genotoxic at the concentration 1000 mg l(-1). On the basis of toxicity tests to aquatic organisms all tested anionic surfactants were harmful (LC50 between 10 and 100 mg l(-1)), whereas nonionic ones were toxic (LC50 between 1 and 10 mg l(-1)) or even highly toxic (LC50 below 1 mg l(-1)). Moreover, the bigger was the molecular weight of the tested compound, the higher toxicity was observed.     

Fate, effects and potential environmental risks of ethylene glycol: a review

The fate, effects, and potential environmental risks of ethylene glycol (EG) in the environment were examined. EG undergoes rapid biodegradation in aerobic and anaerobic environments (approximately 100% removal of EG within 24 h to 28 days). In air, EG reacts with photo-chemically produced hydroxyl radicals with a resulting atmospheric half-life of 2 days. Acute toxicity values (LC(50)s and EC(50)s) were generally >10,000 mg/l for fish and aquatic invertebrates. The data collectively show that EG is not persistent in air, surface water, soil, or groundwater, is practically non-toxic to aquatic organisms, and does not bioaccumulate in aquatic organisms. Potential long-term, quasi-steady state regional concentrations of EG estimated with a multi-media model for air, water, soil, and sediment were all less than predicted no effect concentrations (PNECs).     

Kinetic study of the anaerobic biodegradation of alkyl polyglucosides and the influence of their structural parameters

This paper reports a study of the anaerobic biodegradation of non-ionic surfactants alkyl polyglucosides applying the method by measurement of the biogas production in digested sludge. Three alkyl polyglucosides with different length alkyl chain and degree of polymerization of the glucose units were tested. The influence of their structural parameters was evaluated, and the characteristics parameters of the anaerobic biodegradation were determined. Results show that alkyl polyglucosides, at the standard initial concentration of 100 mgC L^?1, are not completely biodegradable in anaerobic conditions because they inhibit the biogas production. The alkyl polyglucoside having the shortest alkyl chain showed the fastest biodegradability and reached the higher percentage of final mineralization. The anaerobic process was well adjusted to a pseudo first-order equation using the carbon produced as gas during the test; also, kinetics parameters and a global rate constant for all the involved metabolic process were determined. This modeling is helpful to evaluate the biodegradation or the persistence of alkyl polyglucosides under anaerobic conditions in the environment and in the wastewater treatment.     

Toxic effect of surfactants and probable products of their biodegradation on methanogenesis in an anaerobic microbial community.

Surfactants used in household and various industries, are rather toxic; therefore, the accumulation of these compounds in the environment through wastewaters has challenged the problem of their biodegradation. In this research, an attempt was made to assess the toxic effect of various surfactants and the likely products of their biodegradation on the acetoclastic methanogens of an anaerobic microbial community. Among the substances investigated, cationic surfactants were found to be most toxic to methanogens: 154 mg/l alkamon DS and 345 mg/l catamin AB induced a 50% inhibition of methanogenesis. Toxicity studies of some aromatic and cyclic compounds, as the probable products of biodegradation of alkylbenzene sulfonate surfactants, showed that methanogenesis in the microbial community under study are rather tolerant to high concentrations of these compounds.     

Biodegradability of surfactants and inhibition of surfactants to biodegradation of other pollutants

Changes of BOD/TOD and DOC with time were obtained for solutions of 9 synthetic surfactants and 2 fatty acid salts under various conditions. The cationic surfactants, ABM and ABDM, were not biodegraded at all and inhibited the biodegradation of a synthetic sewage. LAS was not biodegraded at concentration of 30 mg/l and higher and inhibited the biodegradation of the sewage.     

Xenobiotic benzotriazoles—biodegradation under meso- and oligotrophic conditions as well as denitrifying,sulfate-reducing,and anaerobic conditions

The intensive use of benzotriazoles as corrosion inhibitors for various applications and their application in dishwasher detergents result in an almost omnipresence of benzotriazole (BTri), 4-methyl- and 5-methyl-benzotriazole (4-TTri and 5-TTri, respectively) in aquatic systems. This study aims on the evaluation of the biodegradation potential of activated sludge communities (ASCs) toward the three benzotriazoles regarding aerobic, anoxic, and anaerobic conditions and different nutrients. ASCs were taken from three wastewater treatment plants with different technologies, namely, a membrane bioreactor (MBR-MH), a conventional activated sludge plant CAS-E (intermittent nitrification/denitrification), and CAS-M (two-stage activated sludge treatment) and used for inoculation of biodegradation setups. All ASCs eliminated up to 30 mg L^?1 5-TTri and BTri under aerobic conditions within 2–7 and 21–49 days, respectively, but not under anoxic or anaerobic conditions. 4-TTri was refractory at all conditions tested. Significant differences were observed for BTri biodegradation with non-acclimated ASCs from MBR-MH with 21 days, CAS-E with 41 days, and CAS-M with 49 days. Acclimated ASCs removed BTri within 7 days. Furthermore, different carbon and nitrogen concentrations revealed that nitrogen was implicitly required for biodegradation while carbon showed no such effect. The fastest biodegradation occurred for 5-TTri with no need for acclimatization, followed by BTri. BTri showed sludge-specific biodegradation patterns, but, after sludge acclimation, was removed with the same pattern, regardless of the sludge used. Under anaerobic conditions in the presence of different electron acceptors, none of the three compounds showed biological removal. Thus, presumably, aerobic biodegradation is the major removal mechanism in aquatic systems.     

The assessment of the energetic compound 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-Hexaazaisowurtzitane (CL-20) degradability in soil

CL-20 is a relatively new energetic compound with applications in explosive and propellant formulations. Currently, information about the fate of CL-20 in ecological systems is scarce. The aim of this study is to evaluate the biodegradability of CL-20 in soil environments. Four soils were used where initial CL-20 concentrations (above water solubility) ranged from 125 to 1500 mg of CL-20 per kg dry soil (corresponding to the concentrations derived from unexploded ordnance, low order detonation, or manufacturing spills). CL-20 appears to be biodegradable in soil under anaerobic conditions, and additions of organic substrates can substantially accelerate this process. However, CL-20 is not degraded in soil under aerobic conditions kept in the dark at temperatures up to 30 degrees C without organic amendments. Additions of starch or cellulose promote the biodegradation of CL-20 under aerobic conditions. Soil microbial community mediated biodegradation and plant uptake appears to enhance CL-20 biodegradation, the latter suggesting a possible route for CL-20 to entry in the food chain.     

Mutagenicity of anaerobic fenitrothion metabolites after aerobic biodegradation

Previous studies have revealed that the mutagenicity of fenitrothion increases during anaerobic biodegradation, suggesting that this insecticide's mutagenicity could effectively increase after it pollutes anaerobic environments such as lake sediments. To investigate possible changes to the mutagenicity of fenitrothion under aerobic conditions after it had already been increased by anaerobic biodegradation, batch incubation cultures were maintained under aerobic conditions. The mutagenicity, which had increased during anaerobic biodegradation, decreased under aerobic conditions with aerobic or facultative bacteria, but did not disappear completely in 22 days. In contrast, it did not change under aerobic conditions without bacteria or under continued anaerobic conditions. These observations suggest that the mutagenicity of anaerobically metabolized fenitrothion would not necessarily decrease after it arrives in an aerobic environment: this would depend on the presence of suitable bacteria. Therefore, fenitrothion-derived mutagenic compounds may pollute the water environment, including our drinking water sources, after accidental pollution of aerobic waters. Although amino-fenitrothion generated during anaerobic biodegradation of fenitrothion was the principal mutagen, non-trivial contributions of other, unidentified metabolites to the mutagenicity were also observed.     

絮凝剂对高速厌氧反应器污泥颗粒化的强化作用

以考察絮凝剂对厌氧反应器中活性污泥性能的影响为目的,将聚合氯化铝(PAC)、聚丙稀酰胺(PAM)、聚季铵盐3种不同类型絮凝剂以不同投加量添加到反应器中,采用生物化学甲烷势(BMP)和厌氧毒性测定(ATA)分析方法,评价了3种絮凝剂的厌氧生物可降解性以及3种絮凝剂对厌氧污泥产甲烷活性、沉降性能等方面的促进或抑制作用。确定以聚季铵盐作为厌氧污泥颗粒化促进剂,建议采用多次投加方式,反应器中聚季铵盐质量浓度以10-50mg／L为宜。     

4种脂肪酸浮选捕收剂的生物降解性能研究

在好氧的条件下,以活性污泥为接种体,使用改良斯特姆法测试脂肪酸浮选捕收剂(油酸钠、9-羟基硬脂酸钠、硬脂酸钠、蓖麻油酸钠)的生物降解性能,并与利用BOD5/COD进行的可生化评价方法进行比较。结果表明:(1)油酸钠、蓖麻油酸钠的BOD5/COD分别为0.54、0.63,属易生物降解物质;9-羟基硬脂酸钠、硬脂酸钠的BOD5/COD分别为0.36、0.37,属可生物降解物质。(2)油酸钠、9-羟基硬脂酸钠、蓖麻油酸钠28d的生物降解率分别为88.6%、62.2%、100.0%,达到了经济合作与发展组织的OECD-301B生物降解性能实验标准,属于易生物降解物质;硬脂酸钠28d的生物降解率为49.8%,没有达到OECD-301B生物降解性能实验标准,属难生物降解物质。4种脂肪酸浮选捕收剂的生物降解性能依次为:蓖麻油酸钠油酸钠9-羟基硬脂酸钠硬脂酸钠。(3)当有机酸中存在碳碳双键和羟基时,有机酸的生物降解性能都会提高,并且碳碳双键的影响要大于羟基的影响;当二者同时存在时,生物降解性能会大幅度提高。     

Biodegradation of phthalate esters during the mesophilic anaerobic digestion of sludge

Phthalic acid esters (PAE) are commonly found in the sludge generated in the wastewater treatment plants. Anaerobic digestion followed by land application is a common treatment and disposal practice of sludge. To date, many studies exist on the anaerobic biodegradation rates of PAE, especially of the easily biodegradable ones, whereas the higher molecular weight PAE have reported to be non-biodegradable under methanogenic conditions. Furthermore, there is no information on the effect of the PAE on the performance of the anaerobic digesters treating sludge. In this study, the anaerobic biodegradation of di-n-butyl phthalate (DBP), di-ethyl phthalate (DEP) and di-ethylhexyl phthalate (DEHP) was investigated and their relative rates of anaerobic degradation were calculated. Also, the biological removal of PAE during the anaerobic digestion of sludge in bench-scale digesters was investigated using DBP and DEHP as model compounds of one biodegradable and one recalcitrant PAE respectively. The degradation of all the PAE tested in this study (DEP, DBP and DEHP) is adequately described by first-order kinetics. Batch and continuous experiments showed that DEP and DBP present in sludge are rapidly degraded under mesophilic anaerobic conditions (a first-order kinetic constant of 8.04 x 10(-2) and 13.69 x 10(-2)-4.35 day(-1) respectively) while DEHP is degraded at a rate between one to two orders of magnitude lower (0.35 x 10(-2)-3.59 x 10(-2) day(-1)). It is of high significance that experiments with anaerobic sludge of different origin (US and Europe) showed that degradation of DEHP occurs under methanogenic conditions. Accumulation of high levels of DEHP (more than 60 mg/l) in the anaerobic digester has a negative effect on DBP and DEHP removal rates as well as on the biogas production.     

Modeling of vapor intrusion from hydrocarbon-contaminated sources accounting for aerobic and anaerobic biodegradation

A one-dimensional steady state vapor intrusion model including both anaerobic and oxygen-limited aerobic biodegradation was developed. The aerobic and anaerobic layer thickness are calculated by stoichiometrically coupling the reactive transport of vapors with oxygen transport and consumption. The model accounts for the different oxygen demand in the subsurface required to sustain the aerobic biodegradation of the compound(s) of concern and for the baseline soil oxygen respiration. In the case of anaerobic reaction under methanogenic conditions, the model accounts for the generation of methane which leads to a further oxygen demand, due to methane oxidation, in the aerobic zone. The model was solved analytically and applied, using representative parameter ranges and values, to identify under which site conditions the attenuation of hydrocarbons migrating into indoor environments is likely to be significant. Simulations were performed assuming a soil contaminated by toluene only, by a BTEX mixture, by Fresh Gasoline and by Weathered Gasoline. The obtained results have shown that for several site conditions oxygen concentration below the building is sufficient to sustain aerobic biodegradation. For these scenarios the aerobic biodegradation is the primary mechanism of attenuation, i.e. anaerobic contribution is negligible and a model accounting just for aerobic biodegradation can be used. On the contrary, in all cases where oxygen is not sufficient to sustain aerobic biodegradation alone (e.g. highly contaminated sources), anaerobic biodegradation can significantly contribute to the overall attenuation depending on the site specific conditions.     

Effects of nano-copper(II) oxide and nanomagnesium oxide particles on activated sludge

Effects of nano-copper(II) oxide (nano-CuO) and nanomagnesium oxide (nano-MgO) particles on activated sludge endogenous respiration (aerobic digestion), biochemical oxygen demand (BOD) biodegradation, and nitrification were investigated through respiration rate measurement. For comparison, the effects of Cu(II) and Mg(II) ions on activated sludge were also studied. Results indicated that soluble Cu(II) has half maximum inhibitory concentration (IC50) values of 19, 5.5, 53, and 117 mg Cu/L for endogenous respiration, BOD biodegradation, ammonium oxidation, and nitrite oxidation, respectively. However, nano-CuO only inhibited BOD biodegradation at 240 mg Cu/L or more, and its associated toxicity was primarily caused by soluble Cu(II). In contrast, soluble Mg(II) was not toxic to activated sludge in the experimental concentration range, but nano-MgO inhibited BOD biodegradation and nitrification with IC50 values of 70 and 143 mg Mg/L, respectively. Further study indicated that the toxicity of nano-MgO resulted primarily from increased pH following MgO hydrolysis.     

Primary biodegradation of veterinary antibiotics in aerobic and anaerobic surface water simulation systems

The primary aerobic and anaerobic biodegradability at intermediate concentrations (50-5000 microg/l) of the antibiotics olaquindox (OLA), metronidazole (MET), tylosin (TYL) and oxytetracycline (OTC) was studied in a simple shake flask system simulating the conditions in surface waters. The purpose of the study was to provide rate data for primary biodegradation in the scenario where antibiotics pollute surface waters as a result of run-off from arable land. The source of antibiotics may be application of manure as fertilizer or excreta of grazing animals. Assuming first-order degradation kinetics, ranges of half-lives for aerobic degradation of the four antibiotics studied were 4-8 days (OLA), 9.5-40 days (TYL), 14-104 days (MET) and 42-46 days (OTC). OLA and OTC were degraded with no initial lag phase whereas lag phases from 2 to 34 days (MET) and 31 to 40 days (TYL) were observed for other substances. The biodegradation behaviour was influenced by neither the concentrations of antibiotics nor the time of the year and location for sampling of surface water. Addition of 1 g/l of sediment or 3 mg/l of activated sludge from wastewater treatment increased the biodegradation potential which is believed to be the result of increased bacterial concentration in the test solution. Biodegradation was significantly slower in tests conducted in absence of oxygen. Assessments of the toxic properties of antibiotics by studying the influence on the biodegradation rates of 14C-aniline at different concentrations of antibiotics showed that no tests were conducted at toxic concentrations.     

Adaptation of the CAS test system and synthetic sewage for biological nutrient removal. Part II: design and validation of test units

A global increase in biological nutrient removal (BNR) applications in wastewater treatment and concern for potential effects of anthropogenic substances on BNR processes resulted in the adaptation of the Continuous Activated Sludge (CAS) laboratory test system (cf. guideline OECD 303A or ISO 11733). In this paper two novel systems are compared to the standard CAS unit: the Behrotest KLD4 and a University of Cape Town system (CAS-UCT). Both are 'single sludge' systems with an anoxic/aerobic and an anaerobic/anoxic/aerobic configuration, respectively. They both can simulate the essential processes of full-scale BNR installations. The units where fed with a specially designed synthetic sewage, Syntho (cf. Part I of this study), or its precursor BSR3 medium. The performance of the two new units was benchmarked against the standard CAS system in terms of carbon/nitrogen/phosphorus (C/N/P) removal, as well as primary biodegradation of the surfactants linear alkylbenzene sulfonate (LAS) and glucose amide (GA). Both systems allow to easily achieve stable excess N- and P-removal. Experimental C/N/P removal data compared closely with simulations obtained with the IAWQ Activated Sludge Model No. 2 (ASM2), and with full scale BNR plants with a similar configuration. In both units the effluent concentrations of the surfactants tested were significantly reduced in comparison to the standard CAS system (up to 50% less). No adverse effects on BNR were noted for the test surfactants dosed at 400 microg/l together with an overall surfactant background concentration in the feed of ca. 20 mg/l. The proposed systems hold potential to complement the standard CAS system for situations where advanced sewage treatment plants with BNR need to be simulated in the laboratory with minimum effort.