Removal of linear alkylbenzene sulfonates and their degradation intermediates at low temperatures during activated sludge treatment

The degradation of linear alkylbenzene sulfonates and their degradation intermediates (sulfophenylcarboxylic acids) has been characterized at 9 degrees C in an activated sludge pilot plant. After an adequate adaptation period (20 days), LAS primary degradation exceeds 99% and takes place preferentially for long alkyl chain homologues and external isomers. LAS homologues in the reactor are preferentially sorbed onto particulate matter, while sulfophenylcarboxylic acids (SPCs) are present predominantly in solution, due to their lower hydrophobicity. During the adaptation period the most abundant LAS biodegradation intermediates were long chain sulfophenylcarboxylic acids (SPCs) (C(9)-C(13)SPC). However once this system is fully adapted, the microorganisms are capable of degrading SPCs efficiently. SPCs with 7-9 carbon atoms in the carboxylic chain predominate due to their degradation being slower than for the rest of the SPCs. The presence of C(13)SPC confirms that LAS degradation in wastewater starts with a omega-oxidation on the alkylic chain. A preferential degradation of SPC isomers of the types 2phiC(n)SPC to 6phiC(n)SPC was also detected, as shown by the relatively higher SPC concentrations of the remaining ones.     

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

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

Predicting diffuse-source transfers of surfactants to surface waters using SWAT

Chemicals present in domestic wastewater can adsorb to solid phase materials during sewage treatment. If biosolids (or sewage sludge) are applied to land, these chemicals can be transferred to soil. Under some circumstances they can also be transferred to surface waters during storm events either in solution or attached to sediment. In this paper we describe the utility of the SWAT 2000 model to estimate diffuse-source surface water exposure to "down-the-drain" chemicals. The model was applied hypothetically to predict the behaviour of linear alkylbenzene sulphonate (LAS), an anionic surfactant commonly used in household detergents, in a small catchment in Bedfordshire, UK, where it has previously been successfully validated for stream flow, sediments and pesticides. LAS transfers were estimated for two scenarios: (1) realistic and (2) reasonable worst case, based on assumptions on sludge application rates and the concentration of LAS in sludge. In addition, the sensitivity of the model output to the proportion of the catchment to which sludge is applied was established. Soil wetness and the total quantity of biosolids applied were the biggest determinants of chemical transport from the catchment. The potential of SWAT as a higher-tier tool in environmental risk assessments is discussed.     

Effect of sediment properties on the sorption of C12-2-LAS in marine and estuarine sediments

Linear alkylbenzene sulfonates (LAS) are anionic high production volume surfactants used in the manufacture of cleaning products. Here, we have studied the effect of the characteristics of marine and estuarine sediments on the sorption of LAS. Sorption experiments were performed with single sediment materials (pure clays and sea sand), with sediments treated to reduce their organic carbon content, and with field marine and estuarine sediments. C₁₂-2-LAS was used as a model compound. Sorption to the clays montmorillonite and kaolinite resulted in non-linear isotherms very similar for both clays. When reducing the organic content, sorption coefficients decreased proportionally to the fraction removed in fine grain sediments but this was not the case for the sandy sediment. The correlation of the sediment characteristics with the sorption coefficients at different surfactant concentrations showed that at concentrations below 10 μg C₁₂-2-LAS/L, the clay content correlated better with sorption, while the organic fraction became more significant at higher concentrations.     

Radiolytic decomposition of multi-class surfactants and their biotransformation products in sewage treatment plant effluents

Electron beam irradiation (EBI), as one of the most efficient advanced oxidation processes, was applied to the treatment of sewage treatment plant (STP) effluent, with the objective of evaluating the effectiveness of radiolytic decomposition of multi-class surfactants. Target compounds, included several high-volume surfactant groups, such as alkylphenol ethoxylates (APEOs) and their biotransformation products, linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylether sulfates (AES), coconut diethanol amides (CDEA), alcohol ethoxylates (AEO) and polyethylene glycols (PEGs). EBI treatment of STP effluent (total concentration of APEO-derived compounds 265mugl(-1), being APE(2)C the most abundant by-degradation products) resulted in efficient decomposition of all alkylphenolic compounds; elimination of 94% longer ethoxy chain nonylphenol ethoxylates (NPEO, n(EO)=3-15) was obtained when 3kGy were applied. Slightly less efficient decomposition of short ethoxy chain oligomers (NPEO(1) and NPEO(2)) was observed, resulting in disappearance of about 80% of the initially present compounds. LC-MS analysis of treated wastewater suggested that the mechanism of EBI degradation of APEOs is a combination of two parallel pathways: a progressive shortening and oxidation of the ethoxy chain, which resulted in a formation of short ethoxy chain oligomers and APECs and central fission that resulted in formation of PEGs. Decomposition of APECs at 1kGy initially yielded APs, which were subsequently eliminated applying higher radiation doses. With a radiation dose of 2kGy about 95% of NPE(1)C and 97% of NPE(2)C were decomposed. Similar elimination rates were obtained for octylphenolic compounds. Radiolytic treatment applied was also very effective in removing PEGs formed as by-products from APEO degradation, as well as in decomposing other surfactants, such as linear LAS, AS and AES.     

Sorption comparison between phenanthrene and its degradation intermediates, 9,10-phenanthrenequinone and 9-phenanthrol in soils/sediments

The degradation intermediates of phenanthrene (PHE) may have increased health risks to organisms than PHE. Therefore, environmental fate and risk assessment studies should take into considerations of PHE degradation products. This study compared the sorption properties of PHE and its degradation intermediates, 9,10-phenanthrenequinone (PQN) and 9-phenanthrol (PTR) in soils, sediments and soil components. A relationship between organic carbon content (f_OC) and single-point sorption coefficient (log K_d) was observed for all three chemicals in 10 soils/sediments. The large intercept in the log f_OC − log K_d regression for PTR indicated that inorganic fractions control PTR sorption in soils/sediments. No relationship between specific surface area and K_d was observed. This result indicated that determination of surface area based on gas sorption could not identify surface properties for PHE, PQN, and PTR sorption and thus provide limit information on sorption mechanisms. The high sorption and strong nonlinearity (low n values) of PTR in comparison to PHE suggested that the mobility of PTR could be lower than PHE. Increased mobility of PQN compared with PHE may be expected in soils/sediments because of PQN lower sorption. The varied sorption properties of the three chemicals suggested that their environmental risks should be assessed differently.     

Biodegradation of linear alkylbenzene sulfonates in sulfate-leached soil mesocosms

Aromatic sulfonates (R-SO(3)(-)) can be used as sulfur sources by sulfate-starved bacteria in laboratory cultures and the corresponding phenols are excreted from the cells. The present study was conducted to demonstrate whether such desulfonation reactions also occur in sulfate-leached agricultural soil, where desulfonation of organic sulfur compounds may have agronomic importance as a S source for plants. Xenobiotic linear alkylbenzene sulfonates (LAS) were added to nominal concentrations of 0, 10 and 100 mgkg(-1) dry weight in a sandy soil that was depleted in sulfate by leaching the soil with water (sulfate depletion, approximately 75%). The soil was incubated at 20 degrees C in duplicate 3-dm(3) mesocosms for 8 weeks. Primary degradation of LAS was rapid with half-lives of 1-4 days. Sulfophenylcarboxylates were identified and quantified as intermediates, whereas linear alkylphenols (the expected primary desulfonation products) were not detected by high-pressure liquid chromatography coupled with both fluorescence and electrospray ionization-mass spectrometry. Thus, LAS was used by the bacteria as a source of energy and carbon, rather than as a source of sulfur. Measurements of soil pH, fluorescein diacetate (FDA) hydrolysis and arylsulfatase activity showed that stable microbial conditions prevailed in the soil mesocosms. FDA hydrolysis (a measure of total microbial activity) was transiently inhibited at the highest LAS concentrations. Arylsulfatase activity (i.e., hydrolysis of aromatic sulfate esters) was not significantly affected by the soil incubation, although arylsulfatases may be upregulated in sulfate-starved bacteria. However, an increased production of arylsulfatase may be difficult to detect due to the background of extracellular arylsulfatases stabilised in the soil. Therefore, the present data does not exclude a regulatory response to sulfate depletion by the soil microorganisms. However, the importance of desulfonation reactions in natural environments still needs to be demonstrated.     

Biodegradation of undecylbenzenesulphonate by mixed methane-oxidizing culture

Biodegradation of undecylbenzenesulphonate (C(11)LAS) was performed in shake flasks at 21 degrees C by using a mixed methanotrophic-heterotrophic culture containing type II methanotrophs. Concentrations of C(11)LAS and aromatic intermediates were determined by reversed-phase high-performance liquid chromatography (RP-HPLC). Methane and carbon dioxide concentrations were measured in headspace samples by using gas chromatography. RP-HPLC analyses of aqueous samples show that the culture MM1 expresses the capability of C(11)LAS transformation in the presence or absence of methane. Simultaneous methane oxidation and C(11)LAS degradation, and the inhibition of both transformation processes by acetylene were observed. This suggests the possibility that C(11)LAS transformation is catalyzed by methane monooxygenase (MMO). Comparable affinity of culture MM1 for both methane and C(11)LAS ( [Formula: see text], respectively), and more than four times higher maximum transformation rate for methane than for C(11)LAS ( [Formula: see text] (dry weight) cells day(-1), respectively), were determined. This further supports the involvement of MMO enzyme system in transformation and suggests a pronounced competitive inhibition of C(11)LAS degradation by methane.     

Anaerobic digestion of linear alkyl benzene sulfonates: biodegradation kinetics and metabolite analysis

In the present work the effect of the alkyl chain length and the position of the sulfophenyl substituent of the linear alkylbenzene sulfonates (LAS) on their anaerobic biodegradability have been investigated. Degradation kinetics of the linear alkyl benzene sulfonates homologues, 2C₁₀LAS, 2C₁₂LAS and 2C₁₄LAS, have been studied. It has been also investigated the effect of the isomer type on the degradation rate of the LAS molecule through the comparative study of the 2C₁₀LAS and 5C₁₀LAS isomers. Batch anaerobic biodegradation tests were performed using sludge from the anaerobic digester of a wastewater treatment plant as microorganisms source. Ultimate biodegradation was evaluated from the biogas production whereas primary biodegradation was determined by specific analysis of the surfactant. LAS homologues and isomers showed a negligible primary biodegradation under anaerobic conditions. Furthermore, analysis of sulfophenyl carboxilates (SPC) by LC–MS indicated a low and constant level of these LAS degradation metabolites over the test period. These data are consistent with a minimal transformation of the LAS parent molecule in the anaerobic digesters. On the other hand, the addition of the shortest alkyl chain length homologues, decyl and dodecylbenzene sulfonates, reduces the biogas production whereas the most hydrophobic homologue, the tetradecylbenzene sulfonate, enhances the biogas production. This LAS homologue seems to increase the availability of organic compounds sorbed on the anaerobic sludge promoting their biodegradation.     

Influence of water hardness on the bioavailability and toxicity of linear alkylbenzene sulphonate (LAS)

In the present work, the influence of Ca²⁺ concentration on the toxicity of single cut linear alkylbenzene sulfonate (LAS) homologues was studied. Precipitation boundary diagrams for each homologue were obtained, indicating turbid and clear zones depending on the LAS and Ca²⁺ concentrations. The separation between transparent and turbid zones is given by the so-called precipitation line. LAS toxicity to Daphnia magna was determined at concentrations close to this precipitation line. It was observed that when Ca(LAS)₂ precipitation progresses, LAS bioavailability decreases for test animals, and the toxicity diminishes even at high nominal LAS concentrations. According to the “free ion activity model” (FIAM), the toxicity of a given chemical compound is mainly due to the ionic species (Ca²⁺–LAS⁻) and not due to the precipitated molecule, Ca(LAS)₂. The significance of the present study is in connection with the assessment of LAS sorption/precipitation studies in soils and sediments, where in situ toxicity is strongly influenced by Ca²⁺/Mg²⁺ ions, according to the results presented in this work.     

European risk assessment of LAS in agricultural soil revisited: species sensitivity distribution and risk estimates

Linear alkylbenzene sulphonate (LAS) is used at a rate of approximately 430,000 tons/y in Western Europe, mainly in laundry detergents. It is present in sewage sludge (70-5,600 mg/kg; 5-95th percentile) because of its high usage per capita, its sorption and precipitation in primary settlers, and its lack of degradation in anaerobic digesters. Immediately after amendment, calculated and measured concentrations are <1 to 60 mg LAS/kg soil. LAS biodegrades rapidly in soil with primary and ultimate half-lives of up to 7 and 30 days, respectively. Calculated residual concentrations after the averaging time (30 days) are 0.24-18 mg LAS/kg soil. The long-term ecotoxicity to soil microbiota is relatively low (EC10 >or=26 mg sludge-associated LAS/kg soil). An extensive review of the invertebrate and plant ecotoxicological data, combined with a probabilistic assessment approach, led to a PNEC value of 35 mg LAS/kg soil, i.e. the 5th percentile (HC5) of the species sensitivity distribution (lognormal distribution of the EC10 and NOEC values). Risk ratios were identified to fall within a range of 0.01 (median LAS concentration in sludge) to 0.1 (95th percentile) and always below 0.5 (maximum LAS concentration measured in sludge) according to various scenarios covering different factors such as local sewage influent concentration, water hardness, and sewage sludge stabilisation process. Based on the present information, it can be concluded that LAS does not represent an ecological risk in Western Europe when applied via normal sludge amendment to agricultural soil.     

Adsorption and transformation of selected human-used macrolide antibacterial agents with iron(III) and manganese(IV) oxides

The adsorption/transformation of two members (clarithromycin and roxithromycin) of the macrolide (ML) antibacterial agents on the surface of three environmental subsurface sorbents (clay, iron(III) and manganese(IV) oxy-hydroxides) was investigated. The adsorption fitted well to the Freundlich model with a high sorption capacity. Adsorption probably occurred through a surface complexation mechanism and was accompanied by slow degradation of the selected MLs. Transformation proceeded through two parallel pathways: a major pathway was the hydrolysis of the cladinose sugar, and to a lesser extent the hydrolysis of the lactone ring. A minor pathway was the N-dealkylation of the amino sugar. This study indicates that Fe(III) and Mn(IV) oxy-hydroxides in aquatic sediments may play an important role in the natural attenuation of MLs. Such an attenuation route yields a range of intermediates that might retain some of their biological activity.     

Relationship among parameters of lake polluted sediments evaluated by multivariate statistical analysis

In the attempt to assess the relationship and interdependency among sediment toxic pollutants, in particular heavy metals, polycyclic aromatic hydrocarbons (PAH), and linear alkyl sulfonates (LAS) and some of the sediment typical components: inorganic carbon (IC), organic material (OM) and acid volatile sulphides (AVS), multivariate techniques of statistical analysis have been applied to a set of chemical data obtained by the analysis of the sediments of the Trasimeno Lake, a central Italy lake characterized by a large surface (128 km(2)) and a low mean depth (about 4.5 m). The results of principal component analysis (PCA) show interrelationships between: OM content and PAH, Pb, and Cu concentrations of the sediments, LAS and AVS, and AVS and IC. The effect of the different sampling periods on sediment composition and contamination level, and the clustering of the sampling sites as a consequence of pollutant load are also shown. The principal component bi-plot of the variables and samples indicates that PAH have the greatest influence on the separation of samples in the different sampling periods.     

Environmental monitoring of alcohol sulfates and alcohol ethoxysulfates in marine sediments

The study describes the environmental monitoring of anionic surfactants―alcohol sulfates (AS) and alcohol ethoxysulfates (AES)—in marine sediments. Concentration values were obtained after pressurised liquid extraction (PLE) and liquid chromatography–tandem mass spectrometry analysis (LC–MS/MS). Samples were collected from a range of wastewater discharge points along the coast of the provinces of Huelva, Málaga, Granada and Almería. Urban, agricultural and industrial wastewaters are discharged at the selected 38 sampling sites. Principal component analysis was carried out in order to evaluate the distribution and behaviour of these compounds in these coastal environments. Evaluation of the data revealed that the behaviour and sources of AS and AES in marine sediments are different, and that the distribution of AES depends on the length of the alkyl chain, while the number of ethoxylated units is not relevant. Additionally, the 38 sampling sites can be grouped into only two types of outfalls according to their AS distribution. The concentration of compounds in sediment samples ranged from 7.52 to 13.50 mg kg^?1 for AS, from 3.04 to 10.68 mg kg^?1 for AES–C₁₂E_x and from 3.83 to 11.56 mg kg^?1 for AES–C₁₄E_x.     

Seasonality of contamination, toxicity, and quality values in sediments from littoral ecosystems in the Gulf of Cádiz (SW Spain)

To seasonally evaluate littoral contamination, toxicity and quality values of sediments from the Gulf of Cádiz, we measured chemical concentrations and conducted toxicity tests in winter and summer and linked these results by means of multivariate analysis. Sediment samples were subjected to two separate, replicated sediment toxicity tests (Microdeutopus gryllotalpa amphipod survival, and Ruditapes philippinarum clam reburial), and to comprehensive sediment chemistry analyses (grain size, organic carbon, 14 heavy metals, and the surfactant linear alkylbenzenesulfonate (LAS)). Only sediments associated with an untreated urban discharge were toxic and related to high levels of surfactant LAS, Ag, and Pb. Multivariate analysis indicated that variables and chemicals associated with geochemical matrix and background levels (specific surface, Fe, Zn, Cu, V, Ni, and Co), chemicals associated with untreated urban discharge sources, and toxicity effects showed no seasonal variability. Only copper concentrations showed seasonal differences, being toxic during the winter and not toxic during summer. Multivariate analysis permits us to derive sediment quality values (SQVs); in terms of concentrations at or below which biological effects were not measured (mg kg(-1) dry sediment), are: LAS, 2.6; lead, 66.8; silver, 0.78; copper, 69.6.     

Degradation mechanisms of 4-chlorophenol in a novel gas-liquid hybrid discharge reactor by pulsed high voltage system with oxygen or nitrogen bubbling

The effect of gas bubbling on the removal efficiency of 4-chlorophenol (4-CP) in aqueous solution has been investigated using a novel pulsed high voltage gas-liquid hybrid discharge reactor, which generates gas-phase discharge above the water surface simultaneously with the spark discharge directly in the liquid. The time for 100% of 4-CP degradation in the case of oxygen bubbling (7 min) was much shorter than that in the case of nitrogen bubbling (25 min) as plenty of hydrogen peroxide and ozone formed in oxygen atmosphere enhanced the removal efficiency of 4-CP. Except for the main similar intermediates (4-chlorocatechol, hydroquinone and 1,4-benzoquinone) produced in the both cases of oxygen and nitrogen bubbling, special intermediates (5-chloro-3-nitropyrocatechol, 4-chloro-2-nitrophenol, nitrate and nitrite ions) were produced in nitrogen atmosphere. The reaction pathway of 4-CP in the case of oxygen bubbling was oxygen/ozone attack on the radical hydroxylated derivatives of 4-CP. However, in the case of nitrogen bubbling, hydroxylation was the main reaction pathway with effect of N atom on degradation of 4-CP.     

酒店废水中LAS的强化生物处理研究

本文主要研究在生长有成熟生物膜的填料上强化LAS生物降解作用,提高生物接触氧化系统的LAS降解能力。试验结果表明,经强化LAS降解作用的二段生物接触氧化系统LAS去除率可由65％提高到80％以上。其中第二段接触氧化的LAS去除率高于第一段接触氧化。     

Degradation of the herbicide dichlobenil and its metabolite BAM in soils and subsurface sediments

The worldwide used herbicide dichlobenil (2,6-dichlorobenzonitrile) has resulted in widespread presence of its metabolite 2,6-dichlorobenzamide (BAM) in surface water and groundwater. To evaluate the potential for natural attenuation of this BAM pollution in groundwater, we studied the degradation of BAM and dichlobenil in 16 samples of clayey till, unconsolidated sand and limestone, including sediments from both oxidized and reduced conditions. The degradation of dichlobenil occurred primarily in the upper few meters below surface, although dichlobenil was strongly sorbed to these sediments. However, the degradation of dichlobenil to BAM could not be correlated to either sorption, water chemistry, composition of soils or sediments. Degradation of dichlobenil to BAM was limited (<2% degraded) in the deeper unsaturated zones, and no degradation was observed in aquifer sediments. This illustrates, that dichlobenil transported to aquifers does not contribute to the BAM-contamination in aquifers. A small, but significant degradation of BAM was observed in the upper part of the unsaturated zones in sandy sediments, but no degradation was observed in the clayey till sediment or in the deeper unsaturated zones. The insignificant degradation of BAM in aquifer systems shows that BAM pollution detected in aquifers will appear for a long time; and consequently the potential for natural attenuation of BAM in aquifer systems is limited.     

Movement and fate of detergents in groundwater: a field study

The major cations, anions, and detergents in a plume of contaminated groundwater at Otis Air Base on Cape Cod (Mass., U.S.A.) have moved approximately 3.5 km down gradient from the disposal beds. We hypothesize that the detergents form two distinct plumes, which consist of alkyl benzene sulfonates (ABS) detergents and linear alkyl sulfonates (LAS) and sodium dodecyl sulfate (NaLS) detergents. The ABS detergents were deposited from approximately 1940 through 1965, when ABS detergents were banned. From 1965 to the present, LAS and NaLS detergents were in the sewage. The ABS detergents appear to be transported in the aquifer at the same rate as the specific conductance (major cations and anions) and boron, which are currently used as conservative tracers of the plume of contaminated groundwater. There appears to be little or no biological degradation of the ABS detergents in the aquifer, based on their concentration in the plume. On the other hand, the LAS and NaLS detergents have degraded rapidly and have been detected only 0.6 km down gradient. The roleof the detergents in the transport of other organic compounds in the plume is nuclear. There is a separation of the ABS detergent plume and the volatile organic compound plume; however, the time of entry of the detergents and the volatile organic compounds is unknown. Therefore, it is not possible to conclude on the interaction of these two classes of compounds.     

Increased persistence of antifouling paint biocides when associated with paint particles

Current regulatory risk assessment procedures only assess the impact of antifouling paint biocides that are released through leaching from a painted surface. Hull cleaning activities can lead to particles of antifouling paint containing biocides to enter the environment. Comparative pseudo-first order anaerobic degradation rate constants and half-lives were determined for a selection of common antifouling paint booster biocides, their degradation products, and associated with paint particles. Anaerobic half-lives of <0.5 days were calculated for chlorothalonil, dichlofluanid, and SeaNine 211, between 1 and 3 days for DCPMU and DCPU, between 14 and 35 days for diuron and CPDU, and over 226 days for GS26575 and Irgarol 1051. Increased persistence was observed when the compounds were introduced to sediments associated with antifouling paint particles. When present as antifouling paint particles, an increased half-life of 9.9 days for SeaNine 211 and 1.4 days was calculated for dichlofluanid, no significant degradation was observed for diuron. It is suspected that this is due to much of the biocide being initially bound within the matrix of the paint particle that is slowly released through dissolution processes into the sediment pore water prior to degradation. The release of booster biocides associated with paint particles into marinas has the potential to lead to their accumulation unless activities such as hull cleaning are strictly regulated.