Effect of admicellar properties on adsolubilization: column studies and solute transport

Mixtures of anionic and cationic surfactants exhibit synergistic behavior as evidenced by low critical micelle concentrations (CMC) of the mixed system, increased surface activity, and improved detergency performance. The adsorption of a single-head anionic surfactant, sodium dodecyl sulfate (SDS), in mixture with a twin-head cationic surfactant, pentamethyl-octadecyl-1,3-propane diammonium dichloride (PODD), showed synergism of adsorption onto silica when present at a mixing ratio of 1:3 (cationic-rich), and also demonstrated lower surfactant desorption with water flushing of columns packed with the surfactant-modified media. In addition, the proportion of the mixed surfactants in the admicelles moved from the initial ratio of 1:3 towards equimolar after rinsing the surfactant-modified silica absorbent. The retardation of organic solutes passing through columns packed with modified-silica adsorbent increased nominally three fold for silica modified with mixed surfactants versus single surfactants (retardation factors increase from 4.0 to 12.8 for styrene and from 32.1 to 90.2 for ethylcyclohexane for single and mixed surfactants, respectively). Thus, this study demonstrates that mixed surfactant systems more effectively modified the silica surface than single surfactant systems both in terms of enhanced retardation of organic solutes and in terms of reduced surfactant desorption.     

Micellar effect on the photolysis of hydrogen peroxide

Photolysis experiments were performed to quantify the effect of three anionic surfactants on the photolysis of hydrogen peroxide (H2O2) at the ambient laboratory temperature of 22+/-1 degrees C. H2O2 photolysis in water, methanol, and surfactant monomeric solution was also conducted to compare the photochemical reactivity of H2O2 in different media. Photolysis rates were highest for water, followed by micellar solutions, and lowest for methanol. The results show that the photochemical reactivity of H2O2 is less favorable in organic solvent than in water and surfactant micelles affect H2O2 photolysis. Retarded photolysis of H2O2 in micellar solutions implies that a fraction of H2O2 dissolved in water partitions into micellar pseudophase of surfactant. H2O2 partitioned into micelles has less photochemical reactivity and thus photolysis rate was retarded in the presence of micelles. Photolysis inhibitory level by micelles was shown to be dependent on the kinds of surfactants used in this study. In addition, the inhibitory effect by surfactant monomers was negligible due to the absence of micelles.     

Combination of surfactant solubilization with permanganate oxidation for DNAPL remediation

A combination of surfactant solubilization with permanganate oxidation of trichloroethylene (TCE) was studied in batch, flow-through column, and three-dimensional (3-D) tank tests. Batch results showed that chloride production, an indication of TCE degradation, followed a pseudo-first-order reaction kinetics with respect to KMnO4 in the presence of free-phase TCE. A higher chloride production rate was achieved when anionic surfactants were present. The observed pseudo-first-order reaction rate constant increased as the concentrations of anionic surfactants Ninate 411 and Calfax increased from 0% to 0.1%, 0.3%, and 1.0%. Column experiments on TCE reduction by permanganate in the presence and absence of surfactants were carried out using well-sorted coarse Ottawa sand. The peak effluent TCE concentration reached 1700 mg/L due to enhanced solubilization when both sodium dodecyl sulfate (SDS) and permanganate were used, in contrast to less than 300 mg/L when only permanganate solution was used. In addition, the effluent TCE concentration decreased much faster when SDS was present in the permanganate solution, compared with the case when SDS was absent. With an initial 1 mL of TCE emplaced in the columns, the effluent TCE concentration dropped to <5mg/L after 29-31h of flushing with 1% SDS and 0.1% KMnO4 solution in contrast to 37-73 h when only 0.1% KMnO4 was used. Furthermore, KMnO4 breakthrough occurred after 21-25 h of injection when SDS was present compared with 45-70 h later when SDS was absent. A slightly higher chloride concentration was observed in the earlier stage of the column experiment and the chloride concentration decreased quickly once KMnO4 was seen in the effluent. The 3-D tank test showed that the MnO2 precipitation front formed more quickly when 1% SDS was present, which further confirmed the observation from the column study.     

The growth inhibition of planktonic algae due to surfactants used in washing agents

A survey of inhibitory effects of nonionic and anionic surfactants, including a soap, used in washing agents, on the growth on three species of freshwater phytoplankton, Selenastrum capricornutum, Nitzschia fonticola and Microcystis aeruginosa was conducted. Based on the specific growth rate, μu estimated from a short period (2 or 3 days) cultivation of test algae, the growth inhibition was determined using EC₅₀ values where μu in the culture medium with surfactant decreased 50% of that without surfactant.The EC₅₀ values of nonionic and anionic surfactants tested here for S. capricornutum ranged from 2 to 50 mg l⁻¹ and from 10 to 100 mg l⁻¹, respectively. The tolerances of three species of algae tested with three surfactants, LAS, AE (EO:9) and soap, were different and the inhibitory effects were species specific. EC₅₀ values of LAS, AE (EO:9) and soap for S. capricornutum were 50–100, 4–8 and 10–50 mg l⁻¹, respectively. Those for N. fonticola were 20–50, 5–10 and 20–50 mg l⁻¹, and those for M. aeruginosa were 10–20, 10–50 and 10–20 mg l⁻¹, respectively.     

Partitioning of hydrophobic organic compounds within soil-water-surfactant systems

Understanding the partitioning of hydrophobic organic compounds (HOCs) within soil-water-surfactant systems is key to improving the use of surfactants for remediation. The overall objective of this study was to investigate the soil properties that influence the effectiveness of surfactants used to remediate soil contaminated with hydrophobic pesticides, as an example of a more general application for removing strongly sorbing HOCs from contaminated soils via in-situ enhanced sorption, or ex-situ soil washing. In this study, the partitioning of two commonly used pesticides, atrazine and diuron, within soil-water-surfactant systems was investigated. Five natural soils, one nonionic surfactant (Triton-100 (TX)) and one cationic surfactant (benzalkonium chloride (BC)) were used. The results showed that the cation exchange capacity (CEC) is the soil property that controls surfactant sorption onto the soils. Diuron showed much higher solubility enhancement than atrazine with the micelles of either surfactant. Within an ex-situ soil washing system, TX is more effective for soils with lower CEC than those with higher CEC. Within an in-situ enhanced sorption zone, BC works significantly better with more hydrophobic HOCs. The HOC sorption capacity of the sorbed surfactant (K(ss)) was a non-linear function of the amount of surfactant sorbed. For the cationic surfactant (BC), the maximal K(ss) occurred when around 40% of the total CEC sites in the various soils were occupied by sorbed surfactant. Below a sub-saturation sorption range (~20 g/kg), under the same amount of BC sorbed, a soil with lower CEC tends to have higher K(ss) than the one with higher CEC.     

Comprehensive modeling of mat density effect on duckweed (Lemna minor) growth under controlled eutrophication

The effect of mat density on duckweed (Lemna minor) growth was studied under controlled conditions: 12.5h a day light exposure and 342 mol m(-2) s(-1) light intensity at 20 degrees C. The plant growth was carried out in Hoagland medium for 7 days without harvesting. The results revealed a maximal biomass growth rate of 88 g-dry m(-2) (1,470 g-wet m(-2)) at an optimal initial mat density of 45 g-dry m(-2) (750 g-wet m(-2)), with removal rates for nitrogen (N) and phosphorus (P) of 483 mg-Nm(-2) d(-1) and 128 mg-Pm(-2) d(-1), respectively. A mathematical model that takes into account the mat density was developed in order to simulate the growth of Lemna minor under controlled eutrophication. Based on experiments carried out, the model exhibits a reliability of 89% . The model remains to be validated at the full-scale level.     

Use of surfactant modified ultrafiltration for perchlorate (Cl(O)(4-)) removal

Determinations of perchlorate anion (ClO(4)(-)) transport and rejection were performed using a surfactant modified ultrafiltration (UF) membrane. Perchlorate anion (at a concentration of 100 microg/L of ClO(4)(-), spiked with KClO(4)) was introduced to the membrane as a pure component, in binary mixtures with other salts, cationic and anionic surfactants, and at various ionic strength conditions (conductivity). Also, a natural source water was spiked with perchlorate in the presence of cationic and anionic surfactants and used to determine the effects of a complex mixture (including natural organic matter (NOM)) on the observed rejection. All filtration measurements were performed at approximately the same permeate flow rate in order to minimize artifacts from mass transfer at the membrane interface. The objective of this study was to modify a negatively charged UF membrane in terms of the fundamental mechanisms, steric/size exclusion and electrostatic exclusion and to enhance perchlorate rejection, with synthetic water and a blend of Colorado River water and State Project water (CRW/SPW). Previous work suggested that perchlorate was dominantly rejected by electrostatic exclusion for charged nanofiltration (NF) and UF membranes (Rejection of perchlorate by reverse osmosis, nanofiltration and ultrafiltration (UF) membranes: mechanism and modeling. Ph.D. dissertation, University of Colorado, Boulder, USA, 2001). In that research, perchlorate rejection capability was quickly lost in the presence of a sufficient amount of other ions. However, this study showed that ClO(4)(-) was excluded from a (negatively) charged UF membrane with pores large with respect to the size of the ion. Although perchlorate rejection capability due to apparent electrostatic force was reduced in the presence of a cationic surfactant, a desired amount of the ClO(4)(-) was excluded by steric exclusion. The steric exclusion was due to decreasing membrane pore size caused by the adsorption of the cationic surfactant.     

Metal extraction by Alyssum serpyllifolium ssp. lusitanicum on mine-spoil soils from Spain

The efficiency of Alyssum serpyllifolium ssp. lusitanicum (Brassicaceae) for use in phytoextraction of polymetallic contaminated soils was evaluated. A. serpyllifolium was grown on two mine-spoil soils (MS1 and MS2): MS1 is contaminated with Cr (283 mg kg(-1)) and MS2 is moderately contaminated with Cr (263 mg kg(-1)), Cu (264 mg kg(-1)), Pb (1433 mg kg(-1)) and Zn (377 mg kg(-1)). Soils were limed to about pH 6.0 (MS1/Ca and MS2/Ca) or limed and amended with NPK fertilisers (MS1/NPK and MS2/NPK). Biomass was reduced on MS2/Ca due to Cu phytotoxicity. Fertilisation increased biomass by 10-fold on MS1/NPK, but root growth was reduced by 7-fold compared with MS1/Ca. Plants accumulated Mn, Ni and Zn in shoots, and both metal content and transportation were generally greater in MS2 than in MS1. Zinc bioaccumulation factors (BF, shoot([metal])/soil([metal])) were significantly greater in MS2 than in MS1. However, metal yields were greatest in plants grown on MS1/NPK. Concentrations of EDTA-, NH(4)Cl- and Mehlich 3 (M3)-extractable Mn and Zn were greater after plant growth. Concentrations of M3-extractable Cr, Ni, Pb and Zn were increased at the rhizosphere. Sequential extractions showed changes in the metal distribution among different soil fractions after growth. This could reflect the buffering capacity of these soils or the plants' ability to mobilise metals from less plant-available soil pools. Results suggest that A. serpyllifolium could be suitable for phytoextraction uses in polymetallic-contaminated soils, provided Cu concentrations were not phytotoxic. However, further optimisation of growth and metal extraction are required.     

Photodegradation mechanism and rate improvement of chlorinated aromatic dye in non-ionic surfactant solutions

A typical insoluble chlorinated aromatic dye (CAD), disperse red (DR), was used to explore the reaction mechanism and kinetics of photodegradation in non-ionic surfactant solutions. The use of an additional hydrogen source and photosensitizer is also studied to improve the decay rates. The decay rate of dye in surfactants depends on the Km of surfactants and their ability to offering an effective hydrogen source. The photodegradation of CAD can be divided into three stages: the initial lag stage. the fast degradation stage and the final retardation stage. The lag stage will vanish and the decay rates of dye can be greatly improved by 2.5-3.6 times after adding an additional hydrogen source (NaBH4) or photosensitizer (acetone) to the surfactant micellar solution. However, the use of an additional hydrogen source or photosensitizer has dosage limitations in such applications. The photoreduction of DR is the main reaction mechanism, in which photodechlorination is observed first with the generation of HCI as the final product, then followed by photodecolorization by breaking the azo bond of the chromophore.     

Equilibrium partitioning of a non-ionic surfactant and pentachlorophenol between water and a non-aqueous phase liquid

The partitioning of the non-ionic surfactant Tergitol NP-10 (TNP10) and pentachlorophenol (PCP) into a mineral oil light non-aqueous phase liquid (NAPL) were quantified in batch tests. Due to the ionizable nature of PCP, the effects of pH and ionic strength (micro) on the equilibrium partitioning were evaluated. NAPL:water partition coefficients (K(n:w)) of TNP10 ranged from 3 to 7 l(water)/l(NAPL). Enhanced PCP dissolution into water from the NAPL was achieved at aqueous TNP10 concentrations > or =200mg/l. Surfactant addition of 1200 mg/l TNP10 increased the aqueous PCP concentrations by 14-fold at pH 5 versus 2 to 3-fold at pH 7 as compared to PCP aqueous solubility. The more significant response at the lower pH is likely due to the greater hydrophobicity of PCP at the lower pH, which is approaching PCP's pK(a) of 4.7. Higher ionic strength (micro 0.11 versus 0.001 M) increased K(n:w) of PCP by 10-33% without surfactant, compared to a more than 150% increase with a dose of 4000 mg/l TNP10. This work contributes information relevant to the application of surfactants to remediate sites contaminated with NAPLs.     

Control of denitrification in a septage-treating artificial wetland: the dual role of particulate organic carbon

We examined the factors controlling organic carbon (C) cycling and its control of nitrogen (N) removal via denitrification in an aerated artificial wetland treating highly concentrated wastewater to nutrient-removal standards. Processing of organic material by the septage-treating wetland affected the biological reactivity (half-life, or t1/2) of organic C pools through microbial degradation and gravity fractionation of the influent septage. Primary sedimentation fractionated the initial septage material (t1/2 = 8.4d) into recalcitrant waste solids (t1/2 = 16.7d) and highly labile supernatant (t1/2 = 5.0d), allowing this reactive fraction to be further degraded during treatment in aerobic wetland tanks until a less labile material (t1/2 = 7.3d) remained. Organic C contributions from in situ fixation by nitrifying bacteria or algae in these tanks were small, about 1% of the C degradation rate. In the aerated tanks, denitrification was correlated with particulate organic C loading rates, although the average C required (0.35 mg C L(-1)h(-1)) to support denitrification was only 12% of the total C respiration rate (2.9 mg C L(-1)h(-1)). Additions of plant litter (2.5g C L(-1)) to the aerated tanks under normal operating conditions doubled denitrification rates to 0.58 mg N L(-1)h(-1), and reduced effluent nitrate levels by half, from 12.7 to 6.4 mg N L(-1). However, C degradation within the plant litter (0.15mg C L(-1)h(-1)) was sufficient to have accounted for only 35% of the additional denitrification. Evidence from laboratory and full-scale plant litter additions as well as process monitoring indicates that the stimulation of denitrification is due to the respiration-driven formation of anaerobic microsites within particulate organic C. In this aerated highly C-loaded septage-treating wetland, anaerobic microsite, rather than C substrate availability limits denitrification.     

Examination of arsenic(III) and (V) uptake by the desert plant species mesquite (Prosopis spp.) using X-ray absorption spectroscopy

This study describes the effects of Arsenic(III) and (V) on the growth and their uptake by the desert plant mesquite (Prosopis spp.). Seedlings were sown in agar-based medium containing a modified Hoagland's nutrient solution. After 1 week, the seedlings were transplanted to arsenic (As) treated agar media that contained 5 mgL(-1) of As either As(III) (As(2)O(3)) or As(V) (As(2)O(5)). The plants were harvested after 14 days of growth and sectioned into roots, stems, and leaves. After digestion, As concentrations in the roots, stems, and leaves were determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES). Our results showed that the As concentrations from As(V) were significantly higher than the As concentrations from As(III) in all portions of the plant. Plants exposed to As(V) concentrated (mg As kg(-1) d wt) about 770+/-191, 326+/-94, and 119+/-18 in roots, stems, and leaves, respectively. X-ray absorption spectroscopy (XAS) showed that As(V) was reduced to As(III) inside the mesquite plant. In addition, greater than 90% of the As(III) found in the mesquite plants was bound to sulfur ligands in the roots, stems and leaves.     

Degradation of microcystin in sediments at oxic and anoxic, denitrifying conditions

The potent toxin microcystin is frequently released during cyanobacterial blooms in eutrophic waters and may impose a risk to human health, when surface water is used for drinking water. For removal of microcystin in surface waters, infiltration through sediment is commonly used. In the present study, mineralization of 14C-labelled microcystin (accumulation of 14CO(2)) and concentration changes (protein phosphatase inhibition assay) demonstrated that indigenous microorganisms in the sediment of a water recharge facility were capable of degrading microcystin. At oxic or microaerophilic (<2% O(2)) conditions, microcystin added to sediment slurries at 70 microg l(-1) was reduced to <20 microg l(-1) in 1-2 weeks, and less than 3 microg l(-1) after 7 weeks. At anoxic conditions (<0.3% O(2)) and with addition of nitrate, the degradation was significantly stimulated, reducing microcystin from 100 to <20 microg l(-1) within 1 day. The simultaneous production of N(2)O in the samples suggests that the microcystin degradation was coupled to dissimilative nitrate reduction (denitrification). Since aquifers and sediments beneath drinking water reservoirs often are anoxic, nitrate respiration may be an important process in removal and detoxification of microcystin.     

Anaerobic treatment of azo dye Acid Orange 7 under fed-batch and continuous conditions

Acid Orange 7 (AO7) was treated anaerobically under fed-batch and continuous conditions. Fed-batch assays carried out with and without cosubstrate showed that the removal rate of this dye is highly favourable when glucose is added as cosubstrate. In addition, some intermediates generated after the reductive breakdown of AO7, such as 1-amino-2-naphthol (1A2N), seem to play a significant role as redox mediators, thus increasing the degradation rate of the dye. This effect is evidenced by the fact that, during the first feeding, the maximum AO7 removal rate was achieved after a lag phase, whereas for further AO7 feedings this phase was not observed. This can be explained by the presence of 1-amino-2-naphthol in the medium. During the continuous treatment with UASB reactors, AO7 loading rates of 1.7 mM d(-1) (590 mg l(-1)d(-1)) were achieved, with 92% AO7 removal efficiencies, operating with an influent comprised of AO7 (0.58 mM) and glucose (2 gl(-1)). In addition, when the cosubstrate was limiting (AO7 0.3 mM and glucose 0.25 gl(-1)), AO7 removal was significantly lower (78%).     

Evaluation of an elevated non-ionic surfactant critical micelle concentration in a soil/aqueous system

In this study, an elevated non-ionic surfactant critical micelle concentration (CMC) in a soil/aqueous system was examined. Experimental measurements have been made of surfactant solubilization of polycyclic aromatic hydrocarbons (PAH) (i.e. fluoranthene and pyrene) in a 5-month aged PAH contaminated soil, as well as surfactant sorption onto soil. Fluoranthene and pyrene in the soil/aqueous system in the presence of three non-ionic surfactants (i.e. Tween 80, Triton X-100 and Brij 35) were extracted using dichloramethane and analyzed using GC-MS. Maximum sorption of non-ionic surfactant onto soil was evaluated using a surface tension technique. It was observed that PAH solubilization is proportional to surfactant dose after the elevated CMC, termed as the effective CMC (CMCeff), is achieved. The values of surfactant CMCeff assessed by the surface tension technique were found to be similar to those determined from surfactant PAH solublization, thereby proving the research hypothesis that surfactant sorption is the cause for the elevation of surfactant CMC in a soil/aqueous system.     

Degradation of soil-sorbed trichloroethylene by stabilized zero valent iron nanoparticles: effects of sorption, surfactants, and natural organic matter

Zero valent iron (ZVI) nanoparticles have been studied extensively for degradation of chlorinated solvents in the aqueous phase, and have been tested for in-situ remediation of contaminated soil and groundwater. However, little is known about its effectiveness for degrading soil-sorbed contaminants. This work studied reductive dechlorination of trichloroethylene (TCE) sorbed in two model soils (a potting soil and Smith Farm soil) using carboxymethyl cellulose (CMC) stabilized Fe-Pd bimetallic nanoparticles. Effects of sorption, surfactants and dissolved organic matter (DOC) were determined through batch kinetic experiments. While the nanoparticles can effectively degrade soil-sorbed TCE, the TCE degradation rate was strongly limited by desorption kinetics, especially for the potting soil which has a higher organic matter content of 8.2%. Under otherwise identical conditions, ∼44% of TCE sorbed in the potting soil was degraded in 30 h, compared to ∼82% for Smith Farm soil (organic matter content = 0.7%). DOC from the potting soil was found to inhibit TCE degradation. The presence of the extracted SOM at 40 ppm and 350 ppm as TOC reduced the degradation rate by 34% and 67%, respectively. Four prototype surfactants were tested for their effects on TCE desorption and degradation rates, including two anionic surfactants known as SDS (sodium dodecyl sulfate) and SDBS (sodium dodecyl benzene sulfonate), a cationic surfactant hexadecyltrimethylammonium (HDTMA) bromide, and a non-ionic surfactant Tween 80. All four surfactants were observed to enhance TCE desorption at concentrations below or above the critical micelle concentration (cmc), with the anionic surfactant SDS being most effective. Based on the pseudo-first-order reaction rate law, the presence of 1×cmc SDS increased the reaction rate by a factor of 2.5 when the nanoparticles were used for degrading TCE in a water solution. SDS was effective for enhancing degradation of TCE sorbed in Smith Farm soil, the presence of SDS at sub-cmc increased TCE degraded by ∼10%. However, effect of SDS on degradation of TCE in the potting soil was more complex. The presence of SDS at sub-cmc decreased TCE degradation by 5%, but increased degradation by 5% when SDS dosage was raised to 5×cmc. The opposing effects were attributed to combined effects of SDS on TCE desorption and degradation, release of soil organic matter and nanoparticle aggregation. The findings strongly suggest that effect of soil sorption on the effectiveness of Fe-Pd nanoparticles must be taken into account in process design, and soil organic content plays an important role in the overall degradation rate and in the effectiveness of surfactant uses.     

Geothermal environmental assessment behaviour of selected geothermal brine contaminants in plants and soils

The behaviour of selected elements found in geothermal fluids of the Roosevelt Hot Springs known geothermal resource area (KGRA) was investigated in plant and soil systems. The kinetics of these potential environmental contaminants were studied by using soil columns and selected cultivated and native plant species.The data collected indicate that, of the 26 elements examined, lithium is the best indicator of geothermal contamination. This element, which occurs in the fluids at concentrations exceeding 25.0 parts per million (ppm), was readily detected in and through a variety of different test soils.The plant species, which were exposed via a number of rooting media including soils, vermiculite, and hydroponic solution, absorbed and translocated lithium to all aerial plant parts. The greatest lithium concentration occurred in hydroponically grown tomatoes where the leaves, stems, and fruit contain 914.5±35.8 ppm, 106.5±3.2 ppm, and 35.7±4.8 ppm of this element, respectively.Two native species — four-winged saltbush, A triplex canescens, and bitterbush, Purshia tridentata — appear to be good biological indicators since they accumulated nearly twice as much lithium, 309.8±29.9 ppm and 226.0±5.8 ppm, respectively, as did other native species tested.     

A comparison of CSTR and SBR bioslurry reactor performance

A continuous-flow stirred tank reactor (CSTR) and a soil slurry-sequencing batch reactor (SS-SBR) were maintained in 8 l vessels for 180 days to treat a diesel fuel-contaminated soil. The SS-SBR provided markedly enhanced contaminant degradation relative to the CSTR. Diesel fuel removal efficiency was 96% in the SS-SBR, compared with 75% in the CSTR. Microbial growth was approximately 25% greater in the SS-SBR than the CSTR. However, significant biosurfactant production and foaming occurred in the SS-SBR, whereas none was observed in the CSTR. Surfactants were produced in the SS-SBR at concentrations up to 70 times the critical micelle concentration (CMC), but were biodegraded by the end of the cycle. Reactor operation was reversed after 80 days. The reactor converted from an SS-SBR to a CSTR lost surfactant production and showed reduced diesel fuel degradation. Converting the CSTR to an SS-SBR resulted in surfactant production and enhanced diesel fuel degradation. These results indicate that fill-and-draw operation selected for microbes with a greater ability to produce surfactants and degrade diesel fuel than the CSTR operation. Decreasing the diesel fuel addition rate in the SS-SBR by four times on day 160 reduced the maximum surfactant concentration and foam thickness by more than three times without affecting diesel fuel removal.     

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

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

Degradation of polyethoxylated nonylphenols in a sewage treatment plant. Quantitative analysis by isotopic dilution-HRGC/MS

Polyethoxylated alkylphenols (APnEO, where n is the number of ethylene oxide molecules), are non-ionic surfactants widely used for domestic and industrial purposes. Most of APnEO are polyethoxylated nonylphenols (NPnEO). NPnEO are widespread environmental pollutants with relatively low toxicity for mammals and higher toxicity for aquatic organisms. In addition, they have been described as endocrine disrupters in recent publications. One of the main problems related to these surfactants is their uncomplete degradation, even in the most effective sewage treatment plants. Usually, the final products, more toxic and resistant to biological degradation than NPnEO, are nonylphenol (NP), monoethoxylated nonylphenol (NP1EO), diethoxylated nonylphenol (NP2EO), nonylphenoxy acetic acid (NP1EC), and nonylphenoxyethoxy acetic acid (NP2EC). In this paper, the degradation of NPnEO was studied in the different processes of a sewage treatment plant. For this purpose, NP, NP1EO and NP2EO were analysed in composite samples collected at different points along the plant (influent, pre-treatment effluent, primary effluent, plant effluent). Analyses were carried out by isotopic dilution-HRGC/MS, using available labelled nonylphenols (13C6-NP, 13C6-NP1EO, 13C6-NP2EO) as internal standards. Extraction of NPnEO from aqueous samples, previous to analysis, was performed by the Likens-Nickerson method (simultaneous steam distillation/solvent extraction, SDE).