An improved microdesulphonation/gas liquid chromatography procedure for the determination of linear alkylbenzene sulphonates in U.K. rivers

An improved microdesulphonation/gas liquid chromatography (GLC) procedure is described for the specific determination of μg l⁻¹ levels of linear alkylbenzene sulphonates (LAS) in aqueous environmental samples including sewage, sewage effluent and surface waters. The LAS is concentrated from samples as its methylene blue complex by a large-scale solvent extraction and is then freed from potential interferences by a series of clean-up steps, i.e. ion-exchange chromatography, hydrolysis and solvent extraction, prior to its desulphonation with a concentrated phosphoric acid reagent. The resulting alkylbenzene hydrocarbons are recovered and quantitatively determined by a capillary GLC technique with the aid of internal standards (primary and secondary alkylbenzene sulphonate isomers) added at the initial concentration stage.The introduction of the clean-up stages, particularly a selective extraction of the LAS as the l-methylheptyl amine salt into hexane, has resulted in GLC traces that are free from major interferences and in which it is possible to readily identify LAS isomers on the basis of the relative retention times. The procedure has a limit of detection of less than 10 μg l⁻¹ LAS in a sample and allows the quantification of sub-μg l⁻¹ levels of individual isomers (C₉–C₁₅ homologues). The mean recovery of a C₁₂ LAS internal standard through the complete procedure is 91% for the environmental samples analysed.This procedure, together with a non-specific methylene blue colorimetric method (for determining anion surface active material), has been used in a monitoring exercise to establish the levels of LAS and methylene blue active substances (MBAS) in U.K. rivers and the River Rhine. A mean MBAS level of 0.15 mg l⁻¹ was found at the U.K. river sites selected (35 samples), of which only 26% on average was attributable to LAS by microdesulphonation/GLC analysis. However, the levels of LAS and its contribution to the total MBAS in rivers was found to vary with the nature of the sampling location, i.e. depending whether it was above, below or in the vicinity of a sewage effluent discharge. The distribution of the LAS isomers at these sites also showed differences that could be explained in terms of their relative biodegradabilities.     

Acetoacetic acid as a potential trihalomethane precursor in the biodegradation intermediates produced by sewage bacteria

When sodium linear dodecylbenzenesulfonate (LAS), sodium dodecylsulfate (AS) and glucose were incubated with sewage bacteria, a high level of chloroform was produced on chlorination in the course of biodegradation. In addition to LAS, AS and glucose, the primary biodegradation intermediates of LAS and AS were not able to produce high level of chloroform. Acetoacetic acid was found to produce a large quantity of chloroform on chlorination amounting to 55.5% on a molar basis. The formation of acetoacetic acid in the course of biodegradation was determined and it was found that from 51 to 87% of the total chloroform produced could be explained to be derived from acetoacetic acid. These results indicate that acetoacetic acid functions as a potential chloroform precursor in the biodegradation of organic materials by sewage bacteria.     

Investigations into the scope and limitations of the bismuth active substances procedure (Wickbold) for the determination of nonionic surfactants in environmental samples

In Europe, the bismuth active substances (BiAS) procedure of Wickbold has been officially adopted as the means for determining alkoxylated nonionic surfactants in biodegradation test liquors. Less satisfactory has been its use for routine environmental monitoring of nonionic surfactants-particularly in sewage. The scope and limitations of the BiAS procedure in this application have been demonstrated in a series of experiments in which the influence of procedural variables such as sample pretreatment, number and duration of solvent sublation steps and the ion-exchange clean-up of BiAS extracts prior to their analysis, have been examined.As a result, it is recommended that when BiAS procedures are used to determine nonionic surfactant in environmental samples, whole samples should be used and the procedure should include four 10-min sublation steps and a cation/anion exchange clean-up of the sublation extracts.BiAS procedures in which the variables are not suitably chosen can result in BiAS levels being more seriously under-estimated in raw-sewage samples than in samples of the corresponding effluents. Their use could therefore lead to the belief that removal of nonionic surfactant by the sewage treatment process is less efficient than it is in practice.     

Effect of linear alkylbenzene sulphonates (LAS) on the anaerobic digestion of sewage sludge

Batch anaerobic biodegradation tests with different alkylbenzene sulphonates (LAS) at increasing concentrations were performed in order to investigate the effect of LAS homologues on the anaerobic digestion process of sewage sludge. Addition of LAS homologues to the anaerobic digesters increased the biogas production at surfactant concentrations 5-10 g/kg dry sludge and gave rise to a partial or total inhibition of the methanogenic activity at higher surfactant loads. Therefore, at the usual LAS concentration range in sewage sludge, no adverse effects on the anaerobic digesters functioning of a wastewater treatment plant (WWTP) can be expected. The increase of biogas production at low surfactant concentrations was attributed to an increase of the bioavailability and subsequent biodegradation of organic pollutants associated with the sludge, promoted by the surfactant adsorption at the solid/liquid interface. When the available surfactant fraction in the aqueous phase instead of the nominal surfactant concentration was used to evaluate the toxicity of LAS homologues, a highly significant relationship between toxicity and alkyl chain length was obtained. Taking into account the homologue distribution of commercial LAS in the liquid phase of the anaerobic digesters of a WWTP, an EC(50) value of 14 mg/L can be considered for LAS toxicity on the anaerobic microorganisms.     

Determination of trace levels of linear alkylbenzenesulfonates in the marine environment by high-performance liquid chromatography

The widespread and increasing use of linear alkylbenzenesulfonates (LAS) has shown the need for analytical procedure of LAS. A method has been developed to isolate, concentrate and determine trace levels of LAS from marine environmental samples. LAS were extracted with Bond Elut C₁₈ reversed-phase minicolumn and quantified by high-performance liquid chromatography with fluorophotometric detection. This method can determine trace levels of LAS, simply, rapidly, specifically and sensitively and minimize the risk of contamination. This method showed the limit of determination for each LAS component of approx. 0.1 μg l⁻¹ for water, 0.03 μg g⁻¹ (dry basis) for bottom sediment or 0.3 μg g⁻¹ (wet basis) for fish sample, the recovery of 80% for water, 87% for sediment or 86% for fish sample, and the reproduceability of 3–4% relative standard deviation for five-replicated analysis of sea water or sea sediment.This proposed method was employed for the determination of LAS in marine environmental samples of Tokyo bay, Japan. A concentration range between 0.8 and 30 μg l⁻¹ of LAS was found in Tokyo bay water. The highest concentration was detected in the coastal areas.     

The behaviour of linear alkyl benzene sulphonate under direct discharge conditions in Vientiane, Lao PDR

Direct discharge of untreated sewage to surface waters is a common practice in many parts of the world. However, relatively little is known about the behaviour of synthetic organic pollutants under these conditions. This paper describes a sampling campaign designed to track changes in water quality in a surface water system in Vientiane (Lao PDR) receiving significant quantities of untreated waste water. The study was based on following in-channel transport using a fluorescent tracer injected as a pulse, with a focus on the anionic surfactant linear alkylbenzene sulphonate (LAS) and ammonia. Water samples were collected at a number of stations with sampling times estimated to coincide with solute time-of-travel. The reduction in LAS concentration with flow-time could be approximated by first-order kinetics with a half life of about 7 h. Free ammonia concentrations decreased more slowly than LAS and remained above the level believed to be toxic for sensitive aquatic species along the entire channel. Changes in the ratios of LAS alkyl chain homologues to total LAS concentrations suggest a preferential removal of longer chain lengths. The role of biodegradation in the removal of LAS was confirmed by the presence of LAS metabolites (sulphophenylcarboxylates, SPCs) which increased systematically (as a fraction of LAS remaining) with flow-time.     

Occurrence and behaviour of linear alkylbenzenesulphonates, nonylphenol, nonylphenol mono- and nonylphenol diethoxylates in sewage and sewage sludge treatment

The fluxes of linear alkylbenzenesulphonates (LAS), nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) through sewage and sludge treatment of 29 Swiss sewage treatment plants were investigated. Reversed-phase high-performance liquid chromatography (HPLC) was used to determine LAS. Normal-phase HPLC was employed to measure NP, NP1EO and NP2EO which are metabolites of the nonionic surfactants of the nonylphenol polyethoxylate type (NPnEO). Quantitative determinations were performed of raw sewage, primary and secondary effluents and of sewage sludge. Under normal conditions of sewage and sludge treatment, LAS were efficiently removed from the raw wastewater (> 99% w/w) and were partly transferred to the sewage sludge (15–20% w/w). About 50% (molar base) of NPnEO in the sewage were transformed to NP and accumulated in the digested sludge. Large variations existed among different sewage treatment plants. It was estimated that 1.0 g m⁻² y⁻¹ of LAS and 0.3 g m⁻² y⁻¹ of NP are applied with sewage sludge to Swiss soils.     

Determination of 1-aminopropan-2-one, a dissolved sewage component, in water samples

A new method for the determination of 1-aminopropan-2-one (APR) in water samples was developed. APR was synthesised as its hydrochloride and derivatized with 2,4-dinitrophenylhydrazine (DNPH) for determination by high-pressure liquid chromatography with ultraviolet detection (UV-HPLC). APR was determined in water samples at pH 12 using a gas-stripping chamber, connected to a cartridge containing DNPH. Acidified water samples were injected into the gas-stripping chamber and a solution of NaOH added to bring the solution to pH 12. APR was volatilised and stripped from solution and passed onto the cartridge under a constant stream of nitrogen gas. Gas flow rates were carefully controlled to allow maximum contact of APR with DNPH on the cartridge. When the reaction time had elapsed, the cartridge was disconnected and the derivative eluted with a fixed volume of acetonitrile and injected onto the HPLC, where the APR hydrazone was resolved isocratically with a mobile phase consisting of acetonitrile and water (60:40). The HPLC was calibrated using standard solutions of the APR hydrazone. Recoveries of APR from standard samples were 90-100% at the 10 microM level and the detection limit for the method was calculated as 18 nM. Detection of APR in urine and primary-treated sewage samples (41 nM and 1.225 microM, respectively) confirmed the applicability of the technique to analysis of environmental samples.     

Fate and effects of linear alkylbenzene sulphonates (LAS) in the terrestrial environment

Linear alkylbenzene sulphonates (LAS) are a group of anionic surfactants, characterised by having both a hydrophobic and a hydrophilic group. LAS is one of the major ingredients of synthetic detergents and surfactants and is used world-wide for both domestic and industrial applications. LAS is relatively rapidly aerobically degraded, but only very slowly or not at all degraded under anaerobic conditions. Therefore, LAS can be found in very high concentrations in most sewage sludge and enter the soil compartment as a result of sludge application. LAS can be found in elevated concentrations in soil immediately after sludge amendment, but a half-life of approximately 1-3 weeks will generally prevent accumulation in soil and biota. The concentration in soils that have not received sewage sludge recently, is generally less than 1 mg kg-1 and not more than 5 mg LAS kg-1. This is below the lowest concentration of LAS where effects have been observed in the laboratory. The laboratory data is in accordance with field studies using aqueous solutions of the sodium salt of LAS. However, observations of the ecological impact of sewage sludge applications or application of LAS spiked into sludge indicates a lower toxicity of LAS when applied in sludge. On the basis of the information reviewed in this paper, it is concluded that LAS can be found in high concentrations in sewage sludge, but that the relatively rapid aerobic degradation and the reduced bioavailability when applied via sludge, most likely will prevent LAS from posing a threat to terrestrial ecosystems on a long term basis.     

Levels Of Linear Alkylbenzenesulfonates (LAS) In Sediments Of The Berre Lagoon (FRANCE)

A method is described to extract, concentrate and determine trace levels of linear alkylbenzenesulfonates (LAS) (a major anionic surfactant) from sediment samples. It consists of an ultrasonic extraction, followed by clean up and enrichment with C18 mini-columns cartridges and determination by HPLC. Both efficiency and accuracy of the method are high, i.e. mean recovery of 85% and repeatability of 2.8% relative standard deviation for five-replicate LAS analyses. The spatial distribution of LAS and their composition of homologues in sediments of the Berre lagoon, the widest lagoon of the Mediterranean littoral, have been studied. The levels of total LAS in sediments range from 0.21 to 5.00?mg=g (dry weight). Results show that LAS principally associated with solids in suspension, and originating from industrial and urban wastewaters, are principally discharged into the Arc and Cadière Rivers then decant in the mouths of these rivers. The maximum concentrations have been monitored in three zones of the site: the Bolmon lagoon, the Vaine lagoon and the northeast part of the Berre lagoon. The distribution of the LAS homologues in the sediments is not the same as that of the commercial LAS. A great percentage of C13-LAS has been observed (>50%).     

Influence of the hydrophilic moiety of anionic and nonionic surfactants on their aerobic biodegradation in seawater

The extent and kinetics of the primary biodegradation have been characterized for the most commonly-used surfactants, employing four homologues with the same alkyl chain: dodecyl ethoxy sulfate (C₁₂AES), sodium dodecyl sulfate (SDS), dodecyl alcohol ethoxylate (C₁₂AEO) and dodecyl benzenesulfonate (C₁₂LAS). A brief acclimatization period has been required to enable an effective degradation of C₁₂LAS and C₁₂AES to take place, but this lag phase has not been detected for SDS and C₁₂AEO. Primary biodegradation percentages at the end of these experiments were higher than 99%, showing a fast degradation rate in all cases (average half-life lower than 2 days). The secondary biodegradation of C₁₂LAS was also monitored. C₁₂LAS external isomers, which are predominant, are preferentially degraded by successive β-oxidations, generating significant amounts of external even isomers of sulfophenylcarboxylic acid (SPC) (mainly 2,3ΦC_4,6SPCs). In ontrast, internal isomers are converted into internal odd isomers of SPC (mostly 4,5ΦC_5,7SPCs) by ω-oxidation followed by α-oxidation and/or β-oxidations.     

HPLC detection of linear alkylbenzenesulfonates surfactants (LAS) in marine sediments of the urban sewage area of Cortiou (Marseille,France)

An improved selective method for determining linear alkylbenzenesulfonates surfactants (LASs) in marine sediments using solid‐phase extraction and RP‐HPLC with UV detection is described. The complete analytical method is used on surface sediments from the creek of Cortiou, France. This site is affected by the sewage from the urban area of Marseille. The total LAS concentrations in the sediment range from 12.19?µg/g near the existing outlet to 0.47?µg/g beyond Maire Island. The flux of pollution provided by the outfall is preferentially oriented from east to west by the Liguro‐Provençal current. The significant values are mainly confined on a perimeter of 2.5?km around the outfall. The particule size observations concerning the sediments show that oxygenated sandy zones, where eliminating mechanisms (desorption, biodegradation) particularly occur, are mainly located on the Chèvres plateau and around Jarre, Plane and Riou Islands.     

Reduction of aquatic toxicity of linear alkylbenzene sulfonate (LAS) by biodegradation

Partial biodegradation of LAS is shown to significantly reduce the specific toxicity (i.e. per unit weight) of the remaining LAS to Daphnia magna (water fleas) and Pimephales promelas (fathead minnows). This results from the fact that the longer homologs and more terminal isomers, which are the more toxic, are also the more rapidly degraded under bacterial action. The acute aquatic LC₅₀ of LAS may range from 0.5 to 50 mg/l depending mainly upon the chain length of the particular homolog. A high molecular weight commercial type LAS with LC₅₀ around 2 mg/l before biodegradation may show Daphnia LC₅₀'s of 30–40 mg/l. for the LAS remaining after 80–85% degradation.A further contribution to this toxicity reduction may occur if the methylene blue analytical method is used to determine the amount of LAS remaining, since some of the biodegradation intermediates show methylene blue activity but no significant toxicity. For example, sulfophenylundecanoate, a model of early intermediates, shows Daphnia and fathead lc₅₀'s 200 and 75 mg/l., respectively. Sulfophenylbutyrate, modeling somewhat later intermediates, gives lc₅₀ values around 5000–10,000 mg/l. Dialkyl tetralin/indane sulfonates (the major non-linear components in commercial LAS) exhibit 1/2–1/10 the toxicity of the corresponding LAS homologs.These results re-emphasize that analysis simply for methylene blue active substances (MBAS) gives no basis for predicting the aquatic toxicity of an environmental sample. And furthermore, that meaningful water quality criteria and standards cannot be established in terms of MBAS content while based on toxicity studies on intact, undegraded LAS.     

A REVIEW OF THE EFFECTS OF SEWER LEAKAGE ON GROUNDWATER QUALITY

Exfiltration (of sewage into the ground from faults in ageing sewerage networks) has been recognised for many years but has never been quantified. It was considered that this leakage did not pose a groundwater-contamination threat because it was assumed that pathogens in sewage would either die off or be attenuated before reaching the groundwater level.
This paper identifies why sewers have faults that could allow sewage exfiltration where the sewer is above a groundwater resource. Because of a lack of UK data on sewage exfiltration, research work in Germany is discussed and analogies are made between the sewerage networks of the two countries.
Until recently, it has not been possible to positively identify sewage contamination of groundwater because of other pollutants and potential sources within an urban environment. The development of sewage-fingerprinting techniques has overcome these difficulties and provides conclusive evidence of sewage contamination of shallow and deep groundwater resources in researched areas. Studies of groundwater recharge and total solute loadings allow quantification of sewage exfiltration reaching the groundwater within the Midlands conurbation. The paper concludes that urban aquifers are potentially more vulnerable to microbiological contamination from leaking sewers than has previously been assumed.     

A preliminary study on the occurrence and behavior of sulfonamides, ofloxacin and chloramphenicol antimicrobials in wastewaters of two sewage treatment plants in Guangzhou, China

Wastewater samples collected from two sewage treatment plants (STPs) in Guangzhou, China were acidified, solid-phase extracted (SPE) with Oasis HLB cartridges, followed by instrumental measurement by high performance liquid chromatography (HPLC) coupled with a diode array UV detector (DAD) and a fluorescence detector (FLD) for the occurrence and fate of antimicrobial compounds sulfadiazine (SDZ), sulfamethoxazole (SMX), ofloxacin (OFX) and chloramphenicol (CAP). Antimicrobials have been detected at 5.10-5.15, 5.45-7.91, 3.52-5.56 and 1.73-2.43 microg L(-1) for SDZ, SMX, OFX and CAP in the raw sewages of the two STPs, respectively. The concentrations of antimicrobials do not show substantial changes after preliminary mechanical sedimentation. No quantifiable sulfonamides and chloramphenicol have been identified, and >85% of ofloxacin has been removed in the effluents after activated sludge treatment in the two STPs, indicating that activated sludge treatment is effective and necessary to remove antimicrobial substances in municipal sewage.     

Field evidence of biodegradation of N-Nitrosodimethylamine (NDMA) in groundwater with incidental and active recycled water recharge

Biodegradation of N-Nitrosodimethylamine (NDMA) has been found through laboratory incubation in unsaturated and saturated soil samples under both aerobic and anaerobic conditions. However, direct field evidence of in situ biodegradation in groundwater is very limited. This research aimed to evaluate biodegradation of NDMA in a large-scale groundwater system receiving recycled water as incidental and active recharge. NDMA concentrations in 32 monitoring and production wells with different screen intervals were monitored over a period of seven years. Groundwater monitoring was used to characterize changes in the magnitude and extent of NDMA in groundwater in response to seasonal hydrogeologic conditions and, more importantly, to significant concentration variations in effluent from water reclamation plants (associated with treatment-process changes). Extensive monitoring of NDMA concentrations and flow rates at effluent discharge locations and surface-water stations was also conducted to reasonably estimate mass loading through unlined river reaches to underlying groundwater. Monitoring results indicate that significant biodegradation of NDMA occurred in groundwater, accounting for an estimated 90% mass reduction over the seven-year monitoring period. In addition, a discrete effluent-discharge and groundwater-extraction event was extensively monitored in a well-characterized, localized groundwater subsystem for 626 days. Analysis of the associated NDMA fate and transport in the subsystem indicated that an estimated 80% of the recharged mass was biodegraded. The observed field evidence of NDMA biodegradation is supported by groundwater transport modeling accounting for various dilution mechanisms and first-order decay for biodegradation, and by a previous laboratory study on soil samples collected from the study site [Bradley, P.M., Carr, S.A., Baird, R.B., Chapelle, F.H., 2005. Biodegradation of N-Nitrosodimethylamine in soil from a water reclamation facility. Bioremediat. J. 9 (2), 115-120.].     

Development of a sensitive E-screen assay for quantitative analysis of estrogenic activity in municipal sewage plant effluents

A simplified proliferation test with human estrogen receptor-positive MCF-7 breast cancer cells (E-screen assay) was optimized and validated for the sensitive quantitative determination of total estrogenic activity in effluent samples from municipal sewage plants. After solid phase extraction of 1 l sewage on either 0.2 g polystyrene copolymer (ENV+) or 1 g RP-C18 material and removal of the solvent, analysis of the extracts in the E-screen assay could be performed without any clean-up step. This was even possible with untreated sewage. Parallel extraction of four sewage samples on both different solid phase materials gave comparable quantitative results in the E-screen. A blank sample did not induce cell proliferation. As additive behaviour of the estrogenic response of single compounds was proven for two different mixtures each containing three xenoestrogens, total estrogenic activity in the sewage samples, expressed as 17 beta-estradiol equivalent concentration (EEQ), could be calculated comparing the EC50 values of the samples with those of the positive control 17 beta-estradiol. The detection limit of the E-screen method was 0.05 pmol EEQ/l (0.014 ng EEQ/l), the limit of quantification 0.25-0.5 pmol EEQ/l (0.07-0.14 ng EEQ/l). In total, extracts of nine effluent and one influent sample from five different municipal sewage plants in South Germany were analyzed in the E-screen. All samples strongly induced cell proliferation in a dose-dependent manner which was completely inhibited by coincubation with 5 nM of the estrogen receptor-antagonist ICI 182,780. The proliferative effect relative to the positive control 17 beta-estradiol (RPE) was between 30 and 101%. 17 beta-Estradiol equivalent concentrations were between 2.5 and 25 ng/l indicating a significant input of estrogenic substances via sewage treatment plants into rivers.     

Occurrence of selected surfactants in untreated and treated sewage

Several surfactants were monitored in treated and untreated sewage in nine municipal wastewater treatment plants (WWTPs) in western Austria. The nine sampled WWTPs cover a wide variety referring to size and applied treatment technology. The investigation focused on linear alkylbenzene sulphonate (LAS), quaternary ammonia compounds (QAC), nonylphenol (NP), octylphenol (OP), nonylphenolmono- (NP(1)EO) and -diethoxylates (NP(2)EO). Whereas LAS, NP, OP and NP(1,2)EO were analysed separately in the liquid phase and in the solid phase, the QACs were measured in the total sample. Total influent concentrations of LAS varied between 2.4 mg l(-1) up to 6.7 mg l(-1) whereas total effluent concentrations were in the lower microg l(-1) range (11-50 microg l(-1)). Whichever the type of treatment, a clear removal during treatment was observed. Solid liquid distribution coefficients K(d) were calculated for untreated sewage. The calculated K(d) values varied between 1300 and 3900 l kg(-1). OP was of minor importance with total influent concentrations below 1microg l(-1). NP and NP(1,2)EO were present in all analysed influents in concentrations between 1 and 35microg l(-1). Effluent concentrations were notably lower than the measured influent concentrations. K(d) values for NP varied between 500 and 6600 l kg(-1), for NP(1)EO between 800 and 2700 l kg(-1) and for NP(2)EO between 100 and 1800 l kg(-1). From the QACs several alkyl benzyl (BAC), dialkyl (DDAC) and trialkyl (ATAC) ammonium chlorides with varying alkyl chain lengths were analysed. Highest total concentrations in the influents to the WWTPs were observed for the BAC-C12 and the ATAC-C16 homologues. Effluent concentrations were notably lower compared to influent concentrations, indicating removal by adsorption and/or biodegradation. The influence of the removal by adsorption increased with increasing alkyl chain length.     

Chemical treatment of an anionic surfactant wastewater: Electrospray-MS studies of intermediates and effect on aerobic biodegradability

The effect of wet air oxidation on the aerobic biodegradability of a model wastewater containing 1000 mg L(-1) of linear alkylbenzene sulfonate (LAS) has been investigated. Semibatch oxidation experiments were performed temperature of 473 K, oxygen partial pressure of 1.3 MPa and residence times varying from 40 to 390 min, while continuous oxidation experiments were performed at a residence time of 120 min. Oxygen uptake tests were performed to assess the aerobic biodegradability of both the oxidised and the original LAS solutions using cultures that had been adapted to both LAS and oxidation intermediates. The concentration of total organic carbon, chemical oxygen demand and active detergent were followed throughout the wet oxidation and biodegradation experiments, while the main intermediates formed during wet oxidation were identified by means of Electrospray-MS and high performance liquid chromatography. It was found that LAS could be easily oxidised at 473 K to yield a group of molecules with short alkyl chains which do not behave as active detergents. Sulfonated aromatics are produced as intermediates which have had the alkyl chains shortened. The segments of alkyl chains broken off the intermediate compounds appear primarily as short chain organic acids. The original unoxidised 1000 mg L(-1) LAS solution was found to be readily biodegradable in the laboratory aerobic reactors operating at low organic loadings and substrate to microorganism concentration ratios. However, wet oxidation resulted in effluents that were less readily biodegradable than the original LAS with biodegradability decreasing with increasing degree of oxidation. These results suggest that, at the conditions under consideration, a combined chemical pre-oxidations and biological post-treatment process may be less effective in removing LAS than a single-stage biological or chemical process.     

Occurrence and distribution of linear alkylbenzene sulfonates and sulfophenylcarboxylic acids in several Iberian littoral ecosystems

The distribution of linear alkylbenzene sulfonates (LAS) and sulfophenylcarboxylic acids (SPC) has been characterized in water and sediment of five Iberian estuaries and a saltmarsh channel. The highest concentrations of LAS and SPC were detected in shallow zones close to discharge points of untreated urban effluent, and decreased sharply with increasing distance from these. SPC homologues of between 3 and 12 carbon atoms were detected, although their concentrations were several orders of magnitude lower than the corresponding LAS. The highest SPC concentrations found were of medium carboxylic chain lengths (C6-C8) in water, and of longer chain lengths (C9-C11) in particulate material. LAS homologues were associated preferentially with the particulate material. The vertical distribution of LAS in the water column was not homogeneous, in contrast to that presented by the SPC homologues. In the case of the Sancti Petri Channel, there was a net flow of LAS exportation into the Bay of Cádiz, of -38.6 kg day(-1), and a net flow for SPC of -6.0 kg day(-1). The daily mass input of LAS and their biodegradation intermediates from the Sancti Petri Channel to Cadiz Bay was 44.6 kg.