Fate of linear alkylbenzene sulfonates in the environment: A review

The fate and risk of linear alkylbenzene sulfonates (LAS) in various compartments of the environment have been reviewed. Under aerobic conditions LAS degrade rapidly and concentration of LAS has been found very low in effluents from aerobic sewage treatment plants (STP). On the contrary, in anaerobic STPs effluents, LAS concentrations have been found very high. Anaerobic effluents containing high LAS concentrations have been found to pose risk to aquatic environment. Similarly, LAS concentrations have been found high in anaerobically treated sewage sludge's. LAS enter the soil as a result of sludge application to the land. Risk to aquatic and terrestrial ecosystems is increased when wastewaters and sludge's are treated anaerobically.     

Inhibition of the anaerobic digestion process by linear alkylbenzene sulfonates

Linear Alkylbenzene Sulfonates (LAS) are the most widely used synthetic anionicsurfactants. They are anthropogenic, toxic compounds and are found in the primarysludge generated in municipal wastewater treatment plants. Primary sludge is usuallystabilized anaerobically and therefore it is important to investigate the effect of thesexenobiotic compounds on an anaerobic environment. The inhibitory effect of LinearAlkylbenzene Sulfonates (LAS) on the acetogenic and methanogenic step of theanaerobic digestion process was studied. LAS inhibit both acetogenesis from propionate and methanogenesis from acetate and hydrogen and it is shown that the propionate-utilising bacteria are more sensitive to the presence of LAS than the acetoclastic methanogens. It has been proven that the inhibition intensity depends on the solids concentration and thus the term ``biomass specific LAS concentration' has been introduced in order to describe the phenomenon better. Conclusively, it is believed that the inhibitory effect of LAS is the main reason that anaerobic microbial enrichments on LAS have not been succeeded yet. Also, the inhibition caused by LAS on the acetogenic and methanogenic step of the anaerobic digestion process should be seriously taken into consideration when wastewater from a surfactant producing industry is to be treated biologically or enter a municipal wastewater treatment plant that employs anaerobic technology. The upper allowable biomass specific LAS concentration should be 14 mg LAS (gVSS)^-1.     

直链烷基苯磺酸钠对中国林蛙抗菌肽基因表达的影响

近年来由于生境丧失及环境污染等原因,中国林蛙野生种群急剧减少.为深入研究水体中普遍存在的阴离子表面活性剂直链烷基苯磺酸钠(linear alkylbenzene sulfonate,LAS)对中国林蛙生存的影响,通过急毒实验确定LAS对分别处于发育阶段26、32、42、46期的中国林蛙的半致死浓度.同时利用1、4、8 mg/L LAS处理不同发育阶段中国林蛙,研究LAS对中国林蛙存活率、发育状态的影响,并利用real-time PCR技术检测中国林蛙抗菌肽基因表达水平变化.结果表明,当处理时间为96 h,LAS浓度达到12.33 mg/L以上时会对不同发育阶段中国林蛙产生较为严重的致死效应.1~8 mg/L浓度范围的LAS虽然对中国林蛙存活和发育没有明显影响,但是改变了其抗菌肽基因表达模式.特别是中国林蛙胚后发育后期(32期)和变态期(42期),4~8 mg/L LAS会在不同程度上抑制prepropalustrin-2CE3、preprobrevinin-2CE1和preprotemporin-1CEd1抗菌肽基因表达.总体而言,高浓度LAS对中国林蛙免疫系统造成一定影响,可能使该物种更易受到致病菌的侵袭.研究结果为化学污染物对中国林蛙免疫系统影响积累了实验数据,同时为研究中国林蛙抗菌肽基因表达的调控通路提供一定的理论依据.     

Interactions between vascular actions of detergent and catecholamines in perfused gills of European eel, Anguilla anguilla L. and brown trout, Salmo trutta L.

Noradrenaline induced vasodilation in isolated perfused eel or trout gills was inhibited by propranolol, aβ-adrenergic blocking agent. The noradrenaline effect was much reduced in gills of fish which had been kept in 1 mg/l solutions of the detergent LAS (linear alkylate sulphonate; 12C chain length). LAS produced concentration-dependent vasodilation, which was inhibited by propranolol, in eel and trout gills. Noradrenaline produced additional vasodilation in eel and trout gills which had been dilated by 2.10⁻⁸ m LAS but had no effect on trout gills perfused with 2.10⁻⁷ m LAS. Gills from trout which had been kept in 0.1 mg l^-1 LAS responded to noradrenaline normally but the propranolol inhibition appeared to be potentiated.     

Inhibition of Biogas Production by Alkyl Benzene Sulfonates (LAS) in a Screening Test for Anaerobic Biodegradability

The effect of the inoculum source on the digestion of linear alkylbenzene sulfonates (LAS) under anaerobic conditions has been investigated. The potential for primary and ultimate LAS biodegradation of anaerobic sludge samples obtained from wastewater treatment plants (WWTPs) of different geographical locations was studied applying a batch test system. It was found that only 4–22% of the LAS added to the batch anaerobic digesters was primarily transformed suggesting a poor primary degradation of the LAS molecule in anaerobic discontinuous systems. Regarding ultimate biodegradation, the addition of LAS to the batch anaerobic digesters caused a reduction on the extent of biogas production. Significant differences in the inhibition extent of the biogas production were observed (4–26%) depending on the sludge used as inoculum. Effect of the surfactant on the anaerobic microorganisms was correlated with its concentration in the aqueous phase. Sorption of LAS on anaerobic sludge affects its toxicity by depletion of the available fraction of the surfactant. LAS content on sludge was related to the total amount of calcium and magnesium extractable ions. The presence of divalent cations promote the association of LAS with anaerobic sludge reducing its bioavailability and the extent of its inhibitory effect on the biogas production.     

How adaptation and mass transfer control the biodegradation of linear alkylbenzene sulfonate by activated sludge

We use a nonsteady-state model to evaluate the effects of community adaptation and sorption kinetics on the fate of linear alkylbenzene sulfonate (LAS) in batch experiments conducted with activated sludge that was continuously fed different concentrations of LAS. We observed a sharp decrease in the biodegradation rate between 30 and 60 minutes and the presence of an LAS residual at the end of the batch experiments. The modeling analysis indicates that these phenomena were caused by relatively slow inter-phase mass transport of LAS. The modeling analyses also showed that the amount of LAS-degrading biomass increased when the continuous activated sludge was fed a higher LAS concentration. Although community adaptation to LAS involved accumulation of more LAS degraders, the increase was not proportional to the feed concentration of LAS, which supports the concept that LAS degraders also utilized portions of the general biochemical oxygen demand (BOD) fed to the continuous activated sludge systems.     

Isolation and characterization of the yeast las21 mutants, which are sensitive to a local anestheticum, tetracaine.

We isolated and characterized yeast mutants whose growth is sensitive to a local anestheticum tetracaine and, at the same time, temperature sensitive. These mutants were collectively called las mutants (local anestheticum sensitive). The las21 mutants were analyzed in this study. The wild type LAS21 gene was cloned by exploiting temperature sensitivity of the las21 mutants and we found that LAS21 encodes ORF YJL062w which has not been analyzed before. Las21p is putative membrane protein belonging to the major facilitator super family containing plural membrane spanning domains. Complete elimination of the LAS21 ORF did not kill the cells but made their growth temperature sensitive. Interestingly, the complete loss of the LAS21 gene canceled the sensitivity to tetracaine. The ability of the las21 mutants to grow at a higher temperature was recovered in the various media containing an osmotic stabilizer or salts. Furthermore, temperature sensitivity of the las21 mutants was partially suppressed by introduction of PKC1, encoding protein kinase C, on a high copy vector. We found some genetic interactions between LAS21 and Ras/cAMP cascade genes. These results suggest that LAS21 defines unknown pathway regulating the stress response of yeast.     

Isolation of (S)-2,3-dichloro-1-propanol assimilating bacterium,its characterization,and its use in preparation of (R)-2,3-dichloro-1-propanol and (S)-epichlorohydrin

Summary Linear alkylbenzene sulfonate (LAS) is a widely used anionic surfactant. Although approximately 1 million metric tons of LAS are produced annually, relatively little is known about the bacteria or the genetic factors that control LAS degradation in the environment. The objectives of this research were to: i) compare bacterial populations in wastewater and pristine pond systems; ii) determine the frequency of plasmids in bacteria from these sites; and iii) compare the frequency of DNA sequences coding for aromatic catabolism in isolates from these two sites. Plate counts indicated that exposure to wastewater resulted in higher levels of both heterotrophic bacteria and bacteria capable of growing on LAS containing medium (LAS/YEPG). In addition to higher numbers, a higher proportion of heterotrophs from the wastewater system were capable of growth on LAS/YEPG medium. Thus, the high levels of LAS in the wastewater system apparently selected fro organisms that were able to tolerate and/or degrade, it. Mineralization of¹⁴C-ring labelled LAS in any habitat related to the presence of organisms that grew on LAS/YEPG. Although may of these isolates could carry out primary degradation, no isolate, could mineralize¹⁴C-ring LAS in pure culture. A higher incidence of plasmids was found in bacteria from the wastewater pond and among bacteria that grew on LAS containing medium. However, the presence of plasmid, DNA did not necessarily confer the ability to degrade LAS nor was the ability to degrade LAS dependent on the presence of a plasmid. The incidence of selected genotypes for aromatic catabolism was similar among isolates on LAS/YEPG at both sites, suggesting that LAS ring degradation may be present in other populations or encoded by alternative sequences. In conclusion, LAS mineralization is mediated by a consortium and the evidence that initial attack of LAS is plasmid mediated is inconclusive.     

Screening test for assessment of ultimate biodegradability: linear alkylbenzene sulfonates.

A relatively simple shake-flask system for determining CO2 evolution was developed to assess the ultimate biodegradability by soil and sewage micro-organisms of chemicals which enter the environment. Linear alkylbenzene sulfonates (LAS) were used as model compounds to evaluate the method and were found to undergo substantial biodegradation in this dilute system. At the 30 mg/liter test concentration, higher-molecular-weight LAS compounds were biodegraded at a slower rate and to a lesser extent than lower-molecular-weight LAS, an effect which was eliminated or greatly reduced upon incremental addition of the LAS to the test medium during the first week of incubation. LA35S was used to demonstrate rapid LAS desulfonation, and 14CO2 evolution studies with (14C) benzene ring-labeled LAS indicated concomitant biodegradation of the entire LAS molecule as well as the LAS aromatic component. The test can be employed to examine numerous compounds at the same time and is readily adapted to studies of the effect of variation in temperature and oxygen concentration on biodegradation.     

Toxic effects of linear alkylbenzene sulfonate on metabolic activity, growth rate, and microcolony formation of Nitrosomonas and Nitrosospira strains

Strong inhibitory effects of the anionic surfactant linear alkylbenzene sulfonate (LAS) on four strains of autotrophic ammonia-oxidizing bacteria (AOB) are reported. Two Nitrosospira strains were considerably more sensitive to LAS than two Nitrosomonas strains were. Interestingly, the two Nitrosospira strains showed a weak capacity to remove LAS from the medium. This could not be attributed to adsorption or any other known physical or chemical process, suggesting that biodegradation of LAS took place. In each strain, the metabolic activity (50% effective concentration [EC(50)], 6 to 38 mg liter(-1)) was affected much less by LAS than the growth rate and viability (EC(50), 3 to 14 mg liter(-1)) were. However, at LAS levels that inhibited growth, metabolic activity took place only for 1 to 5 days, after which metabolic activity also ceased. The potential for adaptation to LAS exposure was investigated with Nitrosomonas europaea grown at a sublethal LAS level (10 mg liter(-1)); compared to control cells, preexposed cells showed severely affected cell functions (cessation of growth, loss of viability, and reduced NH(4)(+) oxidation activity), demonstrating that long-term incubation at sublethal LAS levels was also detrimental. Our data strongly suggest that AOB are more sensitive to LAS than most heterotrophic bacteria are, and we hypothesize that thermodynamic constraints make AOB more susceptible to surfactant-induced stress than heterotrophic bacteria are. We further suggest that AOB may comprise a sensitive indicator group which can be used to determine the impact of LAS on microbial communities.     

Effects of process stability on anaerobic biodegradation of LAS in UASB reactors

Anaerobic biodegradation of linear alkylbenzene sulfonates (LAS) was studied in upflow anaerobic sludge blanket (UASB) reactors operated under mesophilic (37 degrees C) and thermophilic (55 degrees C) conditions. LAS C12 concentration in the influents was 10 mg.L(-1), and the hydraulic retention time in the reactors was 2 days. Adsorption of LAS C12 was assessed in an autoclaved control reactor and ceased after 115 days. The reactors were operated for a minimum of 267 days; 40-80% removal of LAS C12 was observed. A temperature reduction from 55 degrees C to 32 degrees C for 30 h resulted in process imbalance as indicated by increase of volatile fatty acids (VFA). The imbalance was much more intense in the LAS amended reactor compared with an unamended reactor. At the same time, the process imbalance resulted in discontinued LAS removal. This finding indicates that process stability is a key factor in anaerobic biological removal of LAS. After a recovery period, the removal of LAS resumed, providing evidence of biological anaerobic LAS degradation. The removal remained constant until termination of experiments in the reactor. Biodegradation of LAS in the mesophilic reactor was at the same level as in the thermophilic reactor under stable conditions.     

Degradation of linear alkylbenzene sulfonate by a bacterial consortium isolated from the aquatic environment of Argentina

Aims:  To isolate and identify linear alkylbenzene sulfonate (LAS)-degrading bacteria from Río de la Plata and adjacent waters, and to assay their degradation capability as a consortium and as single organisms.
Methods and Results:  A consortium consisting of four bacterial strains: Aeromonas caviae (two strains), Pseudomonas alcaliphila and Vibrio sp. was identified by 16S rRNA analysis. Isolates grown as a consortium produced higher biomass from LAS and CO₂ release (mineralization) than individual cultures, and degraded 86% of LAS (20 mg l⁻¹), whereas pure strains degraded between 21% and 60%. Bacterial desulfonation from LAS was evidenced in the consortium and A. caviae strains. A complete disappearance of LAS (10 mg l⁻¹) was accomplished, and LAS levels of 50 and 100 mg l⁻¹ led to a pronounced decrease in the biodegradation extent and inhibition of culture growth.
Conclusions:  A bacterial consortium capable of complete LAS degradation was isolated from the Río de la Plata and adjacent waters. This consortium was more efficient for LAS degradation than individual cultures, and was sensitive to high LAS concentrations.
Significance and Impact of the Study:  The autochthonous consortium with high effectiveness on LAS biodegradation is a useful tool for LAS depletion from these polluted ecosystems.     

Las1 Is an Essential Nuclear Protein Involved in Cell Morphogenesis and Cell Surface Growth

Saccharomyces cerevisiae mutations that cause a requirement for SSD1-v for viability were isolated, yielding one new gene, LAS1, and three previously identified genes, SIT4, BCK1/SLK1, and SMP3. Three of these genes, LAS1, SIT4, and BCK1/SLK1, encode proteins that have roles in bud formation or morphogenesis. LAS1 is essential and loss of LAS1 function causes the cells to arrest as 80% unbudded cells and 20% large budded cells that accumulate many vesicles at the mother-daughter neck. Overexpression of LAS1 results in extra cell surface projections in the mother cell, alterations in actin and SPA2 localization, and the accumulation of electron-dense structures along the periphery of both the mother cell and the bud. The nuclear localization of LAS1 suggests a role of LAS1 for regulating bud formation and morphogenesis via the expression of components that function directly in these processes.     

气单胞菌（Aeromonas sp．D-4）降解LAS的研究

Aeromonas sp.D-4不能以LAS作为唯一碳源,它对LAS的利用是通过共代谢来完成的。LAS对D-4具有毒害作用,而且,起始LAS浓度越高,毒害作用越大。LAS的最大去除串与起始LAS浓度呈负相关。当起始LAS在40-120mg/L之间时,去除串较高;如果起始LAS在40mg／L左右,则去除率可达s096以上。研究还表明,Aeromonas sp.D-4纯培养对LAS的去除率(最大值84．97%)大于混合菌(最大值78．57%)。耗氧呼吸测定证实了Aeromonas sp.D-4对于LAS的共代谢和LAS对细菌的毒性,同时也证实了培养基中LAS的消失是细菌作用的结果。     

DNA microarray mediated transcriptional profiling of Nitrosomonas europaea in response to linear alkylbenzene sulfonates

Linear alkylbenzene sulfonates (LAS) constitute, quantitatively, the most important group of synthetic surfactants used today. We studied the gene expression of Nitrosomonas europaea in response to LAS using a DNA microarray because ammonia-oxidizers are thought to be more sensitive to LAS than other microorganisms. Our objective was to elucidate which genes are expressed for N. europaea in response to LAS exposure. Microarray analysis and real-time PCR assay revealed that c. 30 genes were significantly expressed after LAS exposure, in particular genes associated with energy production and conversion. Our findings demonstrate that physical disruption of membrane structures, which contain enzymes associated with energy production and conversion, might be an important explanation for the high sensitivity of N. europaea to LAS exposure.     

Toxic Effects of Linear Alkylbenzene Sulfonate on Metabolic Activity, Growth Rate, and Microcolony Formation of Nitrosomonas and Nitrosospira Strains

Strong inhibitory effects of the anionic surfactant linear alkylbenzene sulfonate (LAS) on four strains of autotrophic ammonia-oxidizing bacteria (AOB) are reported. Two Nitrosospira strains were considerably more sensitive to LAS than two Nitrosomonas strains were. Interestingly, the two Nitrosospira strains showed a weak capacity to remove LAS from the medium. This could not be attributed to adsorption or any other known physical or chemical process, suggesting that biodegradation of LAS took place. In each strain, the metabolic activity (50% effective concentration [EC₅₀], 6 to 38 mg liter⁻¹) was affected much less by LAS than the growth rate and viability (EC₅₀, 3 to 14 mg liter⁻¹) were. However, at LAS levels that inhibited growth, metabolic activity took place only for 1 to 5 days, after which metabolic activity also ceased. The potential for adaptation to LAS exposure was investigated with Nitrosomonas europaea grown at a sublethal LAS level (10 mg liter⁻¹); compared to control cells, preexposed cells showed severely affected cell functions (cessation of growth, loss of viability, and reduced NH₄⁺ oxidation activity), demonstrating that long-term incubation at sublethal LAS levels was also detrimental. Our data strongly suggest that AOB are more sensitive to LAS than most heterotrophic bacteria are, and we hypothesize that thermodynamic constraints make AOB more susceptible to surfactant-induced stress than heterotrophic bacteria are. We further suggest that AOB may comprise a sensitive indicator group which can be used to determine the impact of LAS on microbial communities.     

Influence of linear alkylbenzene sulfonate and ethanol on the degradation kinetics of domestic sewage in co-digestion with commercial laundry wastewater

The influence of ethanol on the degradation kinetics of linear alkyl benzene sulfonate (LAS) and organic matter was investigated using batch experiments with different initial LAS concentrations (8.3 mg L⁻¹ to 66.9 mg L⁻¹) and biomass immobilized on sand. Data were fitted with a substrate inhibition model. Concentrations of 2.4 mg LAS L⁻¹ and 18.9 mg LAS L⁻¹ (without and with ethanol) provided the maximum LAS utilization rate by the biomass (S_bm). For LAS degradation, ethanol addition favored a lower decrease in the specific substrate utilization rate (r_obs), even at the LAS concentration usually reported as inhibitory (> 14.4 mg L⁻¹). For organic matter degradation, r_obs was higher with ethanol. Higher biomass differentiation was observed at higher LAS concentrations. With ethanol, microbial selection occurred at LAS concentrations near S_bm. At higher LAS concentrations, the dominance and diversity values did not change significantly with ethanol, whereas without ethanol, their behaviors were irregular.

     

Influence of posture on left ventricular long- and short-axis shortening

End-diastolic volume and left ventricular stroke volume are increased in the supine compared with upright position, but the contribution of long-axis (LAS) and short-axis shortening (SAS) to these changes with change in posture has not been established. We examined long- and short-axis motion and dimensions with echocardiography in 10 healthy subjects in the upright and supine position. Long-axis length at end diastole was almost identical, whereas the diastolic short-axis diameter was increased in the supine position. At end systole, there was a decreased long-axis length and increased short-axis length in the supine vs. upright position. Both LAS and SAS were enhanced in supine vs. upright positions [LAS: 9.3 +/- 2.2 vs. 15.1 +/- 3.1 mm (P < 0.001); SAS: 12.7 +/- 3.2 vs. 16.3 +/- 2.8 mm (P < 0.001)], presumably via Starling mechanisms. LAS increased more in the lateral part of the mitral annulus than in the septal part [7.7 +/- 2.6 vs. 4.0 +/- 2.8 mm (P < 0.006)], which implies that the more spherical form, in the supine position, induces more stretch at the lateral free wall than in the ventricular septum. These findings support the notion that Starling mechanisms affect systolic LAS.     

Enrichment of linear alkylbenzenesulphonate (LAS) degrading bacteria in continuous culture

Enrichment experiments were carried out in continuous-flow units using a mineral medium with commercial linear alkylbenzenesulphonate (LAS) as the limiting carbon- and energy-source. The mixed bacterial culture originating from the waste water of a detergent plant consisted of five strains belonging to the genus Pseudomonas and two strains each of the genera Achromobacter and Acinetobacter. The cultivation conditions corresponding to dilution rates of 0.025-0.1 h^-1 and LAS concentrations of 20–50 mg/1 were examined. During the experiments the composition of mixed cultures and the kinetics of LAS biodegradation were followed. Continuous-flow enrichment experiments resulted in the selection of six bacterial cultures with different compositions of individual species and capability to utilize LAS. From the original seven strains at lower dilution rates (0.025 and 0.05 h^-1) six were selected, excluding Pseudomonas sp. 3, while at the highest dilution rate (0.1/h^-1) five strains were selected after eliminating Pseudomonas sp. 5 and Achromobacter sp. 1. All enriched mixed cultures were more efficient in primary than in ultimate LAS degradation. Two of the culture strains were able to achieve primary LAS degradation ( Pseudomonas sp. 1 in mineral medium with LAS as the sole carbon- and energy-source and Acinetobacter sp. 3 in medium supplemented by yeast extract and nutrient broth).
None of the strains could degrade LAS completely, which indicates that many types of interactions based on combined metabolic attack as well as those based on provision of specific nutrients, may exist between culture members during the complete LAS bio-oxidation.     

Long-term experiment on Branchiura sowerbyi Beddard (Oligochaeta,Tubificidae) using sediment treated with LAS (Linear Alkylbenzene Sulphonate)

A long-term experiment was performed with Branchiura sowerbyi in order to assess possible effects of LAS sorbed to sediment on its reproductive cycle, using concentrations in sediment 2–5 times higher than those calculated for the LC50 values of LAS dissolved in water. No significant effects were observed during the whole experiment, so that we can confirm that LAS adsorbed on sediment has a much lower influence on the examined animals than LAS dissolved in water.