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.     

Biodegradation of nonylphenol polyethoxylates by denitrifying activated sludge

Biodegradation of nonylphenol polyethoxylates (NPEOs) by denitrifying activated sludge was investigated. The results showed that NPEOs were readily degraded in the denitrifying activated sludge process. Organic substance, initial concentration, and temperature had great influence on biodegradation of NPEOs in the denitrifying activated sludge process while the influence of biodegradation intermediates such as nonylphenol (NP) could be neglected. Biodegradation of NPEOs was severely inhibited in the presence of organic substances. Different organic substances had different inhibition ability on the biodegradation of NPEOs. The maximum biodegradation rate increased 2.51 microM d(-1) for each 10 microM increase in initial concentration of NPEOs. This linear relationship was maintained even at relatively high initial concentration. The decrease in temperature caused a sharp decrease in the removal efficiency of NPEOs. The temperature coefficient (Phi) for the biodegradation of NPEOs in the denitrifying activated sludge process was 0.011 degrees C(-1). NPEOs were biodegraded through a nonoxidative pathway, through which NPEOs were degraded via sequential removal of ethoxyl units (as acetaldehyde) to NP. Compared to anaerobic activated sludge treatment, denitrifying activated sludge treatment had much higher removal efficiency of NPEO contaminants. To our knowledge, it is the first report on the biodegradation of NPEOs in denitrifying activated sludge process.     

Removal of the endocrine disrupter nonylphenol and its estrogenic activity in sludge treatment processes

The estrogenic compound nonylphenol (NP) is frequently found in sludge from sewage treatment works. Hence, when sewage sludge is spread on the land, endocrine-disrupting compounds may get into the soil. The goal of this study was to investigate the extent to which aerobic mesophilic treatment in continuous reactors permits the removal of NP from sludge and how this process may be useful for treating anaerobically stabilised sludge. We also report on the behaviour of NP during the anaerobic treatment of sludge. The reduction in sludge estrogenic activity observed in the different types of treatment, as measured using estrogen-responsive reporter cells lines (MELN bioassay), was compared with NP removal rates. Under anaerobic conditions, no degradation of NP and its estrogenic activity was observed. Indeed, an accumulation of the compound occurred. In contrast, high removal of NP was achieved in aerobic conditions as well as in aerobic Post-treatment of anaerobically pre-digested sludge, with a concomitant reduction of the sludge's estrogenic potency.     

Biodegradation of nonylphenoxy carboxylates mixtures in two microcosms

The environmental fate of nonylphenoxy carboxylates (NPECs), a representative class of aerobic biodegradation intermediates of nonylphenol ethoxylates (NPEOs), is still unclear. In this study, two NPEC mixtures with the ethoxy chain units ranging from 2 to 9 and from 5 to 18, respectively, were synthesized and applied for studying their aerobic biodegradation behaviors in a modified OECD 301 biodegradation test using two kinds of microcosms, a fresh secondary effluent from a sewage treatment plant and a NPEOs enriched consortium. The determination of NPECs and their related compounds were performed by LC/MS. Degradation of NPECs occurred 4-7 days after the start up of tests with producing a concomitant of shorter chain NPECs. The long-chain NPECs mixture demonstrated a higher degradation rate than that of shorter ones. In comparison with the fresh secondary effluent system, the NPEOs enriched one showed a much slower NPECs degradation. No nonylphenol or NPEOs was detected during our survey. The results in this study could provide some useful information for the comprehensive understanding of the environmental fate of NPEOs.     

3-nitrobenzenesulfonic acid and 3-aminobenzesulfonic acid in a laboratory trickling filter: Biodegradability with different activated sludges

The biodegradation of 3-nitrobenzenesulfonate (3-NBS) or 3-aminobenzenesulfonate (3-ABS) was examined in a laboratory trickling filter device containing one of six activated sludges as the biocatalyst. No activated sludge from four communal treatment plants could degrade 3-NBS or 3-ABS. In contrast, each of the sludges from two plants treating wastes from the textile industry was able to completely degrade 3-NBS or 3-ABS. Under certain conditions, communal activated sludge could acclimate to degrade 3-NBS, even though inoculation with a degradative sludge was a more efficient process. In the absence of a carbon source, the degradative ability of trickling filters was retained for at least 1 week; thereafter, an adaptation phase was required before rapid and extensive degradation of recovered 3-NBS. Degradation was monitored by global parameters (DOC and release of CO₂) and specific determinations of substrate (HPLC). The global parameters indicated incomplete metabolism of 3-NBS, but this effect was found to be due to the presence of a non-degraded impurity (5%), 4-NBS, found in most commercial preparations of 3-NBS.     

Ultrasonic waste activated sludge disintegration for improving anaerobic stabilization

The pretreatment of waste activated sludge by ultrasonic disintegration was studied in order to improve the anaerobic sludge stabilization. The ultrasound frequency was varied within a range from 41 to 3217 kHz. The impact of different ultrasound intensities and treatment times was examined. Sludge disintegration was most significant at low frequencies. Low-frequency ultrasound creates large cavitation bubbles which upon collapse initiate powerful jet streams exerting strong shear forces in the liquid. The decreasing sludge disintegration efficiency observed at higher frequencies was attributed to smaller cavitation bubbles which do not allow the initiation of such strong shear forces. Short sonication times resulted in sludge floc deagglomeration without the destruction of bacteria cells. Longer sonication brought about the break-up of cell walls, the sludge solids were distintegrated and dissolved organic compounds were released. The anaerobic digestion of waste activated sludge following ultrasonic pretreatment causing microbial cell lysis was significantly improved. There was an increase in the volatile solids degradation as well as an increase in the biogas production. The increase in digestion efficiency was proportional to the degree of sludge disintegration. To a lesser degree the deagglomeration of sludge flocs also augmented the anaerobic volatile solids degradation.     

Fate and removal of selected endocrine‐disrupting compounds in sewage using activated sludge treatment

The variation and fate of four endocrine‐disrupting compounds (EDCs) composed of 4‐n‐nonylphenol (4‐n‐NP), bisphenol A (BPA), 17β‐estradiol (E2) and 17α‐ethinylestradiol (EE2) were investigated along treatment units in a sewage treatment plant (STP), China with anaerobic, anoxic and aerobic activated sludge processes. The mean concentrations were 64.8 ng/L (E2), 115.3 ng/L (4‐n‐NP), 171.5 ng/L (EE2), and 920.7 ng/L (BPA) in the influents, and 22.8 ng/L (E2), 50.9 ng/L (4‐n‐NP), 49.9 ng/L (EE2), and 84.3 ng/L (BPA) in the effluents. The biological treatment was more effective in removing NP, BPA and E2 from the aqueous phase than the primary treatment, while the latter could effectively remove EE2. Their possible removal mechanisms during the biological treatment with activated sludge were further explored through spiked batch experiments under three oxygen‐supplying conditions (anaerobic, anoxic and aerobic). The batch experiments showed that 4‐n‐NP, E2 and BPA were removed from the aqueous phase through biodegradation. The combination of sludge sorption and biodegradation accounted for the removal of EE2. Anoxic activated sludge showed the most rapid degradation of 4‐n‐NP, while E2 could be removed most effectively by aerobic activated sludge, and sludge sorption had a remarkable effect on its removal within the initial 15 min of the experiments under three oxygen‐supplying conditions.     

Reduction of endocrine disruptor emissions in the environment: The benefit of wastewater treatment

The occurrence and fate of four estrogens and five alkylphenolic compounds were studied in thirteen plants with various treatment processes, sizes and countries. Complete load mass balance, including water and sludge phases, has shown a high reduction of the total load of hormones, around 90%. The removal of alkylphenols was more variable, due to the degradation of nonylphenol (NP) precursors - alkylphenol polyethoxylates (APnEO) - during the treatment, resulting in significant production of shorter and toxic alkylphenols (NP and short polyethoxylates) that concentrate in the sludges. Under anaerobic conditions, such as anaerobic digestion process, the load of NP was in most cases observed to increase. When considering the environmental impact, the high reduction of endocrine disrupting compounds (EDC) concentrations between raw wastewater and effluent enables to satisfy the requirements of the Water Framework Directive for NP except in very critical situations where the dilution factor of the effluent in the river would be lower than 7. For sludges, the pending European Directive on spreading of sludge on land would be complied with in all cases.     

The influence of key chemical constituents in activated sludge on surface and flocculating properties

This paper examines the influence of the chemical constituents of activated sludge and extracted extracellular polymeric substances (EPS) on the surface properties, hydrophobicity, surface charge (SC) and flocculating ability (FA) of activated sludge flocs. Activated sludge samples from 7 different full-scale wastewater treatment plants were examined. Protein and humic substances were found to be the dominant polymeric compounds in the activated sludges and the extracted EPS, and they significantly affected the FA and surface properties, hydrophobicity and SC, of the sludge flocs. The polymeric compounds proteins, humic substances and carbohydrates in the sludge flocs and the extracted EPS contributed to the negative SC, but correlated negatively to the hydrophobicity of sludge flocs. The quantity of protein and carbohydrate within the sludge and the extracted EPS was correlated positively to the FA of the sludge flocs, while increased amounts of humic substances resulted in lower FA. In contrast, increased amounts of total extracted EPS had a negative correlation to FA. The results reveal that the quality and quantity of the polymeric compounds within the sludge flocs is more informative, with respect to understanding the mechanisms involved in flocculation, than if only the extracted EPS are considered. This is an important finding as it indicates that extracting EPS may be insufficient to characterise the EPS. This is due to the low extraction efficiency and difficulties involved in the separation of EPS from other organic compounds. Correlations were observed between the surface properties and FA of the sludge flocs. This confirms that the surface properties of the sludge flocs play an important role in the bioflocculation process but that also other interactions like polymer entanglement are important.     

Removal and degradation characteristics of natural and synthetic estrogens by activated sludge in batch experiments

The removal and degradation characteristics of natural and synthetic estrogens by activated sludge were investigated by a series of batch experiments using the activated sludge samples of four actual wastewater treatment plants and synthetic wastewater spiked with estrogen. The rapid removal and degradation of 17β-estradiol (E2) and estrone (E1) were observed by the activated sludge samples of the oxidation ditch process which operated at higher solids retention time (SRT). On the other hand, E1 tended to remain both in the water phase and the sludge phase in the activated sludge samples of the conventional activated sludge process which operated at lower SRT. The anoxic condition was considered to be not favorable to the effective removal of estrogens as compared with the aerobic condition. The removal and degradation of EE2 showed the lag phase, which neither E2 nor E1 showed, but EE2 was finally removed and degraded completely after 24 h. The removal of estrogens in the water phase did not follow the first-order-rate reaction because a large part of the spiked estrogen was immediately removed from the water phase to the sludge phase by adsorption.     

Biodegradation of a cationic surfactant in activated sludge

The biodegradation of DTDMAC (ditallowdimethylammonium chloride, a fabric softening agent) was established in semi-batch activated sludge reactors. Three ¹⁴C-forms of DTDMAC were studied separately under the simulated organic loading rates of conventional and extended aeration activated sludge treatment. Primary biodegradation was shown by means of a specific analytical technique in combination with radiochemical procedures. Ultimate biodegradation for each carbon position in the DTDMAC molecule was established by the detection of ¹⁴CO₂. Intermediate metabolites were followed throughout the study by both radio thin-layer chromatography and radiochemical procedures. Each carbon position of the DTDMAC molecule was equally accessible to metabolism and ultimate degradation by acclimated microorganisms. Degradation occurred more rapidly under extended aeration conditions and was influenced by the strong tendency of DTDMAC to associate with the microbial population. The low levels of metabolites observed were not of a single classification or characteristic and they did not persist in the activated sludge. This study suggests that DTDMAC removal in an activated sludge plant is a result of both sorption/precipitation and biodegradation mechanisms.     

Effect of biological and chemical oxidation on the removal of estrogenic compounds (NP and BPA) from wastewater: an integrated assessment procedure

A major source of the wide presence of EDCs (Endocrine Disrupting Compounds) in water bodies is represented by direct/indirect discharge of sewage. Recent scientific literature reports data about their trace concentration in water, sediments and aquatic organisms, as well as removal efficiencies of different wastewater treatment schemes. Despite the availability of a huge amount of data, some doubts still persist due to the difficulty in evaluating synergistic effects of trace pollutants in complex matrices. In this paper, an integrated assessment procedure was used, based on chemical and biological analyses, in order to compare the performance of two full scale biological wastewater treatment plants (either equipped with conventional settling tanks or with an ultrafiltration membrane unit) and tertiary ozonation (pilot scale).Nonylphenol and bisphenol A were chosen as model EDCs, together with the parent compounds mono- and di-ethoxylated nonylphenol (quantified by means of GC-MS). Water estrogenic activity was evaluated by applying the human breast cancer MCF-7 based reporter gene assay. Process parameters (e.g., sludge age, temperature) and conventional pollutants (e.g., COD, suspended solids) were also measured during monitoring campaigns.Conventional activated sludge achieved satisfactory removal of both analytes and estrogenicity. A further reduction of biological activity was exerted by MBR (Membrane Biological Reactor) as well as ozonation; the latter contributed also to decrease EDC concentrations.     

Activated sludge treatment of abattoir wastewater—II : Influence of dissolved oxygen concentration

Performance of laboratory scale completely mixed activated sludge reactors fed with abattoir wastewater was measured at different dissolved oxygen (DO) concentrations. Degradation of fat present in the influent was inhibited at DO concentrations below about 0.5 mg l⁻¹, leading to sludges with high fat content which settled poorly due to excessive numbers of filamentous microorganisms. Fat was degraded rapidly at higher DO concentrations (up to 4.0 mg l⁻¹) and the sludge contained few filamentous microorganisms, a low fat content and settled readily. However, effluent quality was highest at low DO concentrations due to lower levels of soluble breakdown products from the fat.When wastewater was fed intermittently at constant aeration rate, sludge with a low fat content and good settleability resulted, even though the DO concentration was about 0.2 mg l⁻¹ for more than 30% of the time. Effluent quality was also high. Thus it is concluded that for full-scale abattoir treatment plants where wastewater flow is intermittent, DO concentration may be low during periods of high loading without adversely affecting effluent quality or sludge settleability.     

低强度超声波辐射活性污泥处理高浓度污水

在采用高负荷活性污泥法处理高浓度污水的工艺中引入超声波辐射活性污泥的预处理单元，考察了低强度超声波辐射对污泥活性及其降解有机物的影响。结果表明，活性污泥经21kHz、20W的低强度超声波辐射10min后，其活性得到了提高，对有机物的降解效率也有所提高。本试验所采用的低强度超声波辐射活性污泥的预处理方法，在提高污泥活性及其对有机物降解效率的同时也降低了能耗。     

Biological hydrolysis and acidification of sludge under anaerobic conditions: the effect of sludge type and origin on the production and composition of volatile fatty acids

New wastewater treatment processes resulting in considerably reduced sludge production and more effective treatment are needed. This is due to the more stringent legislations controlling discharges of wastewater treatment plants (WWTPs) and existing problems such as high sludge production. In this study, the feasibility of implementing biological hydrolysis and acidification process on different types of municipal sludge was investigated by batch and semi-continuous experiments. The municipal sludge originated from six major treatment plants located in Denmark were used. The results showed that fermentation of primary sludge produced the highest amount of volatile fatty acids (VFAs) and generated significantly higher COD- and VFA-yields compared to the other sludge types regardless of which WWTP the sludge originated from. Fermentation of activated and primary sludge resulted in 1.9-5.6% and 8.1-12.6% COD-yields, soluble COD (SCOD)/total COD (TCOD), in batch experiments, respectively. The COD-yields for primary, activated and mixed sludge were 19.1%, 6.5% and 21.37%, respectively, in semi-continuous experiments operated at solids retention time (SRT) of 5d and temperature of 37 degrees C. The benefit of fermentation for full-scale application was roughly estimated based on the experiments performed in semi-continuous reactors. The results revealed that even though the VFA production of primary sludge was higher compared to activated sludge, substantial amounts of VFA could be produced by fermentation of activated sludge due to the substantially higher production of activated sludge in WWTPs.     

Bacterial community shifts in nonylphenol polyethoxylates-enriched activated sludge

A molecular approach was used to evaluate the effect of nonylphenol ethoxylate surfactants on the bacterial diversity in lab-scale activated sludge reactors. Separate bench-scale units were fed synthetic wastewater with and without addition of branched nonylphenol ethoxylates (NPnEO). The performance of the reactors, in terms of carbonaceous removal was largely unaffected by the presence of NP10EO in the feeding solution. However, addition of NP10EO exerted a pronounced shift in bacterial community composition. In situ hybridization analyzing larger phylogenetic groups of bacteria with ribosomal RNA-targeted oligonucleotide probes revealed the dominance of clusters composed of Betaproteobacteria, accounting for up to one-third of 4',6-diamidino-2-phenylindol-dihydrochloride (DAPI)-stained cells in NP10EO amended reactors and only 5% of DAPI-stained cells in the controls. These shifts in populations of larger phylogenetic groups were confirmed by dot-blot analysis of rRNA. Members of gamma subclass of Proteobacteria were present in low numbers in all activated sludge samples examined, suggesting that only bacteria affiliated with the beta subclass of Proteobacteria may have a specific role in NP10EO degradation.     

The influence of sludge age on heavy metal removal in the activated sludge process

In a laboratory simulation of the activated sludge process ten heavy metals were added continuously to the system which was allowed to equilibrate at six sludge ages between 3 and 18d. Cobalt, manganese and molybdenum removals were poor and were unaffected by changes in the sludge age. The highest removal efficiencies for the other metals occurred at the 15d sludge age. Chromium (trivalent) and cadmium had the highest removal efficiencies, typically greater than 50%. The behaviour of the majority of the metals which were removed to a significant extent was related to one of the parameters influenced by sludge age, i.e. mixed liquor suspended solids, effluent suspended solids or effluent chemical oxygen demand. The metals which were poorly removed showed little affinity for the activated sludge, while most metals exhibited maximum specific uptake by the mixed liquor at a sludge age of 9–12d. However, the affinity of silver for the mixed liquor continued to increase as the sludge age increased to 18d. An affinity series, based on an arbitrary measure of the specific accumulation of metals by the mixed liquor, indicated that chromium, cadmium and silver were most readily adsorbed by the activated sludge.     

Fate of nonylphenol polyethoxylates and their metabolites in four Beijing wastewater treatment plants

Four Beijing wastewater treatment plants (WWTPs) were selected to investigate behaviours of nonylphenol polyethoxylates and their metabolites in different wastewater treatment processes. The results showed that the total concentrations of nonylphenolic compounds in the influents of the four WWTPs ranged from 0.115 to 0.347 μmol/L, as well as their removal efficiencies ranging from 75.7% to 90.8%. Both influent concentrations and removal efficiencies of nonylphenol polyethoxylates were correlated to seasons as follows: higher in the summer than in the winter, and influent concentrations were lower during the rain weather. The analysis revealed that 21.8-47.6% of nonylphenol polyethoxylates and their metabolites entering WWTPs were released via effluents and excess sludge, leaving a great part of them for biodegradation. Nonylphenol and short-chain nonylphenol polyethoxylates were disposed to the environment mainly via sewage sludge, while carboxylated nonylphenol polyethoxylates were the most abundant group of nonylphenol polyethoxylates in effluents.     

Phthalates,nonylphenols and LAS in an alternately operated wastewater treatment plant--fate modelling based on measured concentrations in wastewater and sludge

The performance of an alternately operated activated sludge wastewater treatment plant (WWTP) has been investigated with respect to six phthalates, nonylphenol (NP) and nonylphenol diethoxylate (NPDE) and linear alkylbenzene sulphonates (LAS). Samples of raw sewage, primary and secondary sludge and treated water were collected during an 8-day period in May 1999 and analysed for dissolved and sorbed substances. To evaluate the system performance with respect to substance removal through biodegradation and sorption to sludge the measured data were applied in a model describing the different bioreactors as one single reactor, corresponding to the concepts of, e.g. SimpleTreat. The most abundant of the investigated phthalates was di-(2-ethylhexyl)-phthalate (DEHP) with a measured mean inlet flow of 240g/day. Two percent of this amount was found in the treated water, 70% was biodegraded and 28% was found in the sludge. For LAS the mean inlet flow was 20,300g/day, of which less than 1% was found in the treated water, 84% was biodegraded and 15% was found in the sludge. The mean inlet flow of NP and NPDE was 44 and 590g/day, of which 4% and 2% was found in the treated water, 80% was biodegraded for both substances, and 16% and 18% was found in the sludge, respectively. The WWTP removal of the investigated substances was thus high compared to other studies of conventional activated sludge WWTPs. The simple model set-up presents a strong tool for predicting substance removal and system sensitivity related to changes in the inlet conditions, such as concentrations and flow. Furthermore, it allows the inclusion of complex alternately operated WWTPs in risk assessment tools such as e.g. SimpleTreat.     

Relationships between organic loading and zone settling velocity in the activated sludge process

The performance of the activated sludge process is functionally dependent on the settling and compaction properties of the activated sludge. The settling properties of activated sludges vary markedly depending on the presence or absence of filamentous organisms and on the process operating conditions. In this study the process was operated to minimize the presence of filamentous organisms and to investigate the effects of operating process variables, mainly organic loading. It was found that over the range of organic loadings tested, the ZSV increased with organic loading due to the size of the sludge floc which was also directly proportional to the organic loading. The ZSV in aerobically digested sludge was found to decrease with sludge age.