Removal of micropollutants and NOM in carbon nanotube-UF membrane system from seawater

One of the main problems for seawater reverse osmosis desalination is membrane fouling associated with natural organic matter. Bisphenol-A (BPA) and 17alpha-ethinylestradiol (EE2) are well-known endocrine-disrupting compounds that have been detected in wastewater and seawater. In this study, the contribution of carbon nanotubes (CNTs, single-walled carbon nanotubes) to membrane fouling control and the potential adsorption mechanisms of BPA and EE2 were investigated using artificial seawater (ASW) in a bench scale ultrafiltration (UF) membrane coupled with CNTs. For high ionic strength ASW, UVA254 nm is a good alternative for highly aromatic dissolved organic carbon (DOC) determination, with a very strong linear relationship (R2 > or = 0.99) with increasing DOC concentrations. Approximately 80% of DOC in ASW was rejected by the CNT-UF system where 31% of DOC was removed due to adsorption by CNTs. The presence of CNTs shows a 20% increase in membrane flux in ASW. A strong linear correlation between retention and adsorption of BPA and EE2 was obtained. The percentage of adsorption/retention of BPA and EE2 in UF-CNTs follows the order: 94.0/96.6 (DI + CNTs, EE2) > 86.2/90.0 (ASW + CNTs, EE2) > 73.6/78.9 (DI + CNTS, BPA) > or = 74.1/77.3 (ASW + CNTS, BPA) > 29.8/29.8 (ASW, EE2) approximately equal to 27.3/27.3 (ASW, BPA) > or = 25.3/25.3 (DI, EE2) approximately equal to 24.8/24.8 (DI, BPA). This indicates that retention by the UF-CNT system is mainly due to adsorption. Overall, EE2 adsorption was greater than BPA during the UF-CNT experiments, presumably due to the higher hydrophobicity of EE2 than BPA.     

Fate of oestrogens during anaerobic blackwater treatment with micro-aerobic post-treatment.

The fate of oestrone (E1), 17beta-oestradiol (E2) and 17alpha-ethynyloestradiol (EE2) was investigated in a concentrated blackwater treatment system consisting of an UASB septic tank, with micro-aerobic post-treatment. In UASB septic tank effluent a (natural) total concentration of 4.02 microg/L E1 and 18.69 microg/L E2, comprising the sum of conjugated (>70% for E1 and >80% for E2) and unconjugated forms, was measured. During post-treatment the unconjugated oestrogens were removed to below 1 microg/L. A percentage of 77% of the measured unconjugated E1 and 82% of E2 was associated with particles >1.2 microm in the final effluent implying high sorption affinity of both compounds. When spiking the UASB septic tank effluent with E1, E2, EE2 and the sulphate conjugate of E2, removal in the micro-aerobic post-treatment was >99% for both E2 and EE2 and 83% for E1. The lower removal value for E1 was a result of (slow) deconjugation during the treatment, and in the final effluent still 40% of E1 and 99% of E2 was present in conjugated form. The latter was the result of incomplete deconjugation of the spiked E2(3S) in the post-treatment system.     

Removal of typical endocrine disrupting chemicals by membrane bioreactor: in comparison with sequencing batch reactor

The removal of endocrine disrupting chemicals (EDCs) by a laboratory-scale membrane bioreactor (MBR) fed with synthetic sewage was evaluated and moreover, compared with that by a sequencing batch reactor (SBR) operated under same conditions in parallel. Eight kinds of typical EDCs, including 17β-estradiol (E2), estrone (E1), estriol (E3), 17α-ethynilestradiol (EE2), 4-octylphenol (4-OP), 4-nonylphenol (4-NP), bisphenol A (BPA) and nonylphenol ethoxylates (NPnEO), were spiked into the feed. Their concentrations in influent, effluent and supernatant were determined by gas chromatography-mass spectrometry method. The overall estrogenecity was evaluated as 17β-estradiol equivalent quantity (EEQ), determined via yeast estrogen screen (YES) assay. E2, E3, BPA and 4-OP were well removed by both MBR and SBR, with removal rates more than 95% and no significant differences between the two reactors. However, with regard to the other four EDCs, of which the removal rates were lower, MBR performed better. Comparison between supernatant and effluent of the two reactors indicated that membrane separation of sludge and effluent, compared with sedimentation, can relatively improve elimination of target EDCs and total estrogenecity. By applying different solids retention times (SRTs) (5, 10, 20 and 40 d) to the MBR, 10 and 5 d were found to be the lower critical SRTs for efficient target EDCs and EEQ removal, respectively.     

Distribution of estrogen, nonylphenol and its derivatives in the sediments of a shallow lake.

To determine the distribution of endocrine disruptors (EDs) in lake water and sediments, field investigation was conducted in Lake Teganuma, which is a shallow eutrophic lake, highly affected by human activities. Concentration profiles with sediment depths were obtained for estrogens, nonylphenol (NP), nonylphenol ethoxylates (NPnEO), and nonylphenoxy acetic acids (NPnEC). 17beta-Estradiol (E2) was rarely detected, and 17alpha-ethynylestradiol (EE2) and estriol (E3) were undetected at all depths (0-98 cm) in any of the sediment core samples. The sediment concentrations of estrone (E1) ranging from <0.05 to 3.5 microg/kg-dry wt. and NP from 11.8 microg/kg-dry wt. to 21 mg/kg-dry wt. were obtained. The maximum concentrations of NPnEO and NPnEC in the core sediments were 2.5 mg/kg-dry wt. and 1.4 mg/kg-dry wt., respectively. The EDs concentrations are higher at the inlet than at the outlet (except for NP) in the sediments near the surface. The longitudinal distributions of E1, NPnEO and NPnEC in the benthic sediments show that the concentrations are highest at the inlet, and are fairly constant at lower levels towards the downstream. The obtained results also indicate that NP tends to be adsorbed to the organic particulates produced by algae, followed by sedimentation near the outlet of the lake.     

The case of the nonionic alkylphenol ethoxylates in the Mediterranean Sea region: is there a problem?

The concentration profiles of the potential endocrine disrupting nonionic alkylphenol ethoxylate (APEO) surfactants in Israel's rivers, groundwaters and coastal water of the eastern Mediterranean Sea, were found to be within the range of 12.5-74.6, trace - 20.2 and 4.2-25.0 microg/L respectively. Determination of the APEO's homologic distribution revealed "skewing" towards the more toxic shorter-chain ethoxylates. Egg production of zebrafish, Danio rerio, exposed to these actually found the environmental concentrations range of the APEOs decreased, after 20 days, to 89.6+/-2.1, 84.7+/-3.9 and 76.9+/-2.2% of the baseline levels, compared with control, in concentrations of 10, 25 and 75 microg/L respectively. These results suggest that, (a) there is a potential health problem, particularly in countries in which the "hard"/environmentally persistent APEOs are still in use; and (b) the related health-risk is seasonally-dependent, particularly in semi-arid regions where the fluctuations in the water quantities in surface- and groundwater are substantial.     

Anaerobic biodegradation of estrogens--hard to digest.

Although many publications are available on the fate of estrone (E1), 17beta-estradiol (E2) and 17alpha-ethynylestradiol (EE2) during aerobic wastewater treatment, little is published on their fate under strictly anaerobic conditions. Present research investigated the digestibility of E1 and EE2, using digested pig manure, granular UASB sludge, UASB-septic tank sludge and activated sludge as inocula. Besides, actual concentrations were measured in a UASB septic tank treating black water. Under anaerobic conditions E1 is reduced to E2 but the extent of this reduction depends on type of inoculum. No significant loss of the sum of E1 and E2 and of EE2 was observed. Adsorption was responsible for a 32-35% loss of E1 and E2 from the liquid phase in the UASB septic tank and the effluent still contained considerable concentrations of respectively 4.02 microg/l and 18.79 microg/l for E1 and E2 with a large fraction present in conjugated form. No EE2 was detected in the UASB effluent.     

The effect of bisphenol A and chlorinated derivatives of bisphenol A on the level of serum vitellogenin in Japanese medaka (Oryzias latipes).

2,2-bis (4-hydroxyphenyl) propane or Bisphenol A (BPA), has been reported to behave as an endocrine disrupter below acute toxic levels, and is widely present in the water environment. Although BPA is easily chlorinated, very little is reported on the effect of chlorinated BPA to the aquatic organisms. In this study, the estrogenic activities of BPA and its chlorinated derivatives were evaluated by the induction of vitellogenin (VTG) in the serum of mature male Japanese medaka. In addition, the effect of sodium hypochlorite on the decomposition of BPA was tested. The relative potencies of estrogenic activities of chlorinated BPA descended in the order 3,3'-diCIBPA>BPA> or =3-CIBPA>3,3',5-triCIBPA, and no estrogenic activity was observed in 3,3',5,5'-tetraCIBPA. Lowest Observed Effect Concentration (LOEC) and No Observed Effect Concentration (NOEC) for both 3-CIBPA and 3,3'-diCIBPA were 500 microg/L and 200 microg/L, respectively. LOEC for 3,3',5-triCIBPA was >500 microg/L. When BPA was reacted with sodium hypochlorite (24 hours; residual chlorine at 1 ppm), however, complete decomposition of BPA and its chlorinated derivatives was observed. The decrease in BPA and its chlorinated derivatives paralleled the decrease in estrogenic potency evaluated by the induction of vitellogenin (VTG) in the serum of mature male Japanese medaka.     

Removal of endocrine disrupting chemicals in a large scale membrane bioreactor plant combined with anaerobic-anoxic-oxic process for municipal wastewater reclamation

The removal of eight typical endocrine disrupting compounds (EDCs) in a full scale membrane bioreactor combined with anaerobic-anoxic-oxic process (A(2)/O-MBR) for municipal wastewater reclamation located in Beijing was investigated. These EDCs, including 4-octylphenol (4-OP), 4-n-nonylphenol (4-n-NP), bisphenol A (BPA), estrone (E1), 17α-estradiol (17α-E2), 17β-estradiol (17β-E2), estriol (E3) and 17α-ethinylestradiol (EE2), were simultaneously analyzed by gas chromatography/mass spectrometry after derivatization. The concentrations of eight EDCs were also measured in sludge of anaerobic, anoxic, oxic and membrane tanks to measure sludge-water distribution coefficients (K(d) values) as the indicator of adsorption propensity of target compound to sludge. The removal efficiencies of EDCs reached above 97%, except for 4-n-NP removal efficiency of 72%, 4-OP removal efficiency of 75% and EE2 removal efficiency of 87% in the A(2)/O-MBR process. The high K(d) values indicated that the sludge had a large adsorption capacity for these EDCs, and significantly contributed to removal of EDCs. Yeast estrogen screen assay was performed on samples to assess the total estrogenic activity by measuring the 17β-E2 equivalent quantity (EEQ), expressed in ng-EEQ/L. The measured EEQ value was markedly reduced from 72.1 ng-EEQ/L in the influent to 4.9 ng-EEQ/L in the effluent. Anoxic tank and anaerobic tank contributed to 80% and 37% in total EEQ removal, respectively.     

Characteristics of estrogen decomposition by ozonation.

Since the natural estrogens 17 beta-estradiol (E2) and estron (E1), and the synthetic estrogen 17 alpha-ethynyl estradiol (EE2) have strong endocrine disrupting effects and the tendency to persist in effluent from wastewater treatment plants, effective measures are needed to remove them from wastewater. In this research, to gain an understanding of the characteristics of estrogen decomposition by ozonation, experiments were conducted using effluent from an actual wastewater treatment plant. In this experiment, estrogen was added to effluent at a concentration of 200 ng/l and 20 ng/l before the ozonation experiments. The results showed 90% or more of estrogen concentration and estrogenic activity of E2, El and EE2 to be removed at an ozone dose of 1 mg/l. At an ozone dose of 3 mg/l, the estrogen concentration and estrogenic activity of E2, El and EE2 in the treated water fell below the detection limit. The removal rate was not influenced by the kind of estrogen. No generation of byproducts with estrogenic activity was observed. The authors conclude that estrogen in secondary treated wastewater can be almost entirely removed at the practical ozone dose rate applied for the purpose of disinfection, which is up to about 5 mg/l.     

Comparison of Fenton's oxidation and ozonation for removal of estrogens

This study compares efficiency of Fenton's oxidation and ozonation of 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) as two possible processes for removal of estrogens from aqueous solutions. The effectiveness of Fenton's oxidative removal was studied at different ratios of reagents Fe2+:H2O2 (1:0.5; 1:10; 1:20; 1:33), where with some molar ratios up to 100% removal of E2 and EE2 was achieved in the first few minutes of reaction. The best molar ratio for E2 (17beta-estradiol) removal was 1:33, while in the case of EE2 the most efficient one was 1:20 ratio. Ozonation was much faster, because complete removal of estrogens was achieved in 30 seconds (pH approximately eaqual 6), but the time of ozonation was extended up to 60 minutes trying to decompose formed by-products, expressing estrogenic activity, detected by YES (Yeast Estrogen Screening) assay. The obtained results showed that the removal efficiency of estrogens from waters should be assessed by a combination of chemical analyses and bioassay.     

城市污水中EDCs的活性污泥法去除特性研究

以4种(壬基酚(4-n-NP),双酚A(BPA),雌二醇(E2)、乙炔基雌二醇(EE2))内分泌干扰物(EDCs)为目标物,针对其在城市污水处理厂工艺流程中的分布与去除进行了研究,并进一步实验研究了其去除机理。所有EDCs在城市污水厂进出水中均被检出,进水中平均浓度分别为E2:64.8 ng/L,EE2:171.5 ng/L,4-n-NP:115.4 ng/L,BPA:920.7ng/L;出水中平均浓度分别为E2:22.8 ng/L,EE2:49.9 ng/L,4-n-NP:50.9 ng/L,BPA:84.3 ng/L。污水中EDCs目标物的去除主要来自于生物处理阶段,其去除机理主要是生物降解,生物降解速率与EDCs种类及污泥类型有关。污泥吸附对EDCs的去除可产生一定的影响。     

Decontamination of wastewater contaminated by polychlorinated biphenyls (PCBs).

Wastewater contaminated by PCBs obtained from three different sources was treated at both laboratory and pilot plant scale conditions by ultraviolet oxidation of organics at the presence of hydrogen peroxide after partial adsorption of impurities and PCBs on activated carbon and/or activated bentonite. The procedure was conducted both with and without a Fe(II) catalyst and considerable reduction of PCB concentration was achieved in both cases. In pilot plant scale experiments, activated carbon polishing step followed UV oxidation. The following three types of contaminated waste water were examined: a) aqueous extracts originated in the course of clean-up of contaminated soil by extraction with aqueous solvents. Concentrations of PCBs in extracts were between 1 microg/L to 3,000 microg/L; b) wastewater condensates originated in the process of thermal desorption of PCB from soils. Concentrations of PCBs in condensates were between 300 microg/L and 5,000 microg/L. c) underground water contaminated by PCBs extracted from the sites of old contamination. The content of PCBs was up to 50,000 ng/L. Biodegradation of PCBs with a mixture of indigenous soil bacteria (selected strains of Pseudomonas and Acitenotobacter) was also tested. It was carried out in a reactor with volume of 1.5 m3 by application of the bacteria in a slurry of bentonite with adsorbed PCBs.     

LAS in urban rivers and factors contributing to reduction of their concentrations.

LC/MS analysis with improved SPE preparation was applied to determine trace amounts of LAS in river waters. By using this procedure, the distribution of LAS was investigated and compared with the previous concentration level measured by HPLC in the Akashi River flowing through urbanized coastal areas in Hyogo Prefecture, western Japan. Detected LAS were in the range of 0.6-11 microg/L and considerably lower than those in 1985. This indicated that LAS concentration levels reduced to 1/10 and below during the past 18 years. From the model analysis, major factors contributing to the reduction of their concentrations were estimated to be the sewerage development and the decrease of consumption of anionic surfactants. Statistical analysis of MBAS monitoring data suggested that over 90% of sewerage diffusion rate was needed in order to reduce LAS to the concentration level of the order of 10 microg/L in river waters.     

The Niagara River mussel biomonitoring program (Elliptio complanata): 1983-2009

The Ontario Ministry of the Environment has monitored the concentrations of contaminants in mussel (Elliptio complanata) tissue and bottom sediments at sites in the Niagara River since 1983 to describe the general contamination of the river and identify contaminant sources. More recently, the data have been used to document the effectiveness of remedial actions implemented at identified sources along the river. Results from Canadian sites and five U.S. sites at which remedial actions have been implemented [Bloody Run Creek (Hyde Park Hazardous Waste Site); Gill Creek; Occidental Chemical Company (Buffalo Avenue Plant); 102nd Street Hazardous Waste Site; and Pettit Flume Cove] are discussed. p,p′-DDE, PCBs and dioxins were the only contaminants detected at Canadian sites at concentrations probably representative of background. Results from the five sites showed the effectiveness of implemented remedial actions in reducing the flow of contaminants to the river ranged between very effective (Gill Creek: PCBs; and 102nd Street, CBs) to no effect (Bloody Run Creek: PCBs, CBs, and dioxins). Remedial actions at the Pettit Flume Cove (for dioxins/furans) initially appeared to be effective, but were subsequently shown to have missed a source to the cove. The effectiveness of the actions taken at these sites in improving contaminant conditions in the Niagara River since the 1980s as demonstrated by our mussel and sediment results is corroborated by the data from other fish and water quality monitoring programs. Additional remedial efforts are still required at these sites and other known sources of contaminants to the river.     

Biodegradation of bisphenol A and 4-alkylphenols by Novosphingobium sp. strain TYA-1 and its potential for treatment of polluted water

We investigated the use of Novosphingobium sp. strain TYA-1 for the simultaneous removal of bisphenol A (BPA) and 4-alkylphenols (4-APs) from complex polluted waters. Strain TYA-1 degraded BPA and utilized it as a sole carbon and energy source via oxidative skeletal rearrangement involving the cytochrome p450 monooxygenase system. Strain TYA-1 also degraded 4-APs with branched side alkyl chains (4-tert-butylphenol [4-tert-BP], 4-sec-butylphenol, 4-tert-pentylphenol, 4-tert-octylphenol [4-tert-OP], and branched nonylphenol mixture) via 4-alkylcatechols but could not degrade 4-APs with linear side alkyl chains. Degradation of 4-APs, like that of BPA, involved the cytochrome p450 monooxygenase system in strain TYA-1. A sequencing batch bioreactor (100 mL of polluted water [50 mg/L BPA, 50 mg/L 4-tert-BP, and 5 mg/L 4-tert-OP]; 6 h of reaction time/cycle; 12 cycles in total) containing alginate-immobilized TYA-1 cells (15 mg dry cells) simultaneously removed BPA, 4-tert-BP, and 4-tert-OP from complex polluted waters. These immobilized TYA-1 cells could be reused for a total of 9 cycles without any loss of degradation activity. Our results support the potential of using immobilized TYA-1 cells for the simultaneous removal of BPA and 4-APs from complex polluted waters.     

High performance liquid chromatography-tandem mass spectrometry for rapid and sensitive analysis of six polycyclic aromatic hydrocarbons in wastewater

A sensitive and fast method was developed to quantitatively analyse the six polycyclic aromatic hydrocarbons (fluoranthene (FLT), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a] pyrene (Bap), benzo[ghi]perylene (BghiP) and indeno[1,2,3-cd]pyrene (INPY)) by high performance liquid chromatography (UPLC) coupling with tandem mass spectrometry (MS/MS). Chromatographic separation was performed on a Waters Acquity UPLC BEHC18 column (1.7 microm, 2.1 mm x 50 mm). A 0.2 microm precolumn filter was used to protect the analytical column. Mobile phase Awas acetonitrile containing 0.5% toluene. Mobile phase B was water. Linearity of detection was in the range of 1-100 microg L(-1); LOD of 5 PAHs were lower than 0.1 microg L(-1); LOQ were 0.2 microg L(-1) except for benzo[k]fluoranthene. The LOD and the LOQ of benzo[k]fluoranthene were respectively 0.1 microg L(-1) and 0.8 microg L(-1). Wastewater samples collected from two wastewater treatment plants were determined using this method respectively. Recovery of all compounds varied from 67.8 +/- 10.6% to 113.2 +/- 7.2%. In comparison with the existing methods, this rapid method saves time and solvent and improves instrument sample throughput by 2-5 fold.     

Microbial degradation of estrogens using activated sludge and night soil-composting microorganisms.

In order to investigate the potential for microbial degradation of estrogens, and the products formed, activated sludge collected from Korea (ASK) and night soil-composting microorganisms (NSCM) were used to degrade estrogens. Results showed that both ASK and NSCM degraded almost 100% of the natural estrogens estrone (E1), 17beta-estradiol (E2), and estriol (E3) from initial concentrations of 20-25 mg/L, while synthetic estrogen, ethynylestradiol (EE2), was not degraded. Analysis of degradation products of E2 by using HPLC-ECD and a consecutive first-order reaction calculation confirmed that E2 was sequentially degraded to E1, which was further degraded to other unknown compounds by ASK and NSCM. We then used the yeast two-hybrid assay to show that the unknown degradation products did not appear to possess estrogenic activity when E1, E2 or E3 were degraded to below the detection limit after 14 days of incubation, indicating that ASK and NSCM not only degrade natural estrogens, but also remove their estrogenic activities.     

Elimination of aromatic surfactants from municipal wastewaters: comparison of conventional activated sludge treatment and membrane biological reactor.

Behaviour of anionic surfactants of linear alkylbenzene sulphonates (LAS) type and non-ionic surfactants of nonylphenol polyethoxylate (NPnEO) type was studied in the conventional mechanical/biological sewage treatment plant (STP) as well as using a membrane biological reactor (MBR). LAS and NPnEO were determined using high performance liquid chromatography (HPLC) equipped with spectrofluorimetric detection. Liquid chromatography/tandem mass spectrometry (LC/MS/MS) was used for identification and quantification of stable metabolites, including nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO) and nonylphenoxy carboxylic acids (NPnEC). The study showed that aromatic surfactants belong to the most prominent constituents in the examined municipal wastewaters with typical LAS and NPnEO concentrations of 2-10 mg/L and 0.1-0.5 mg/L, respectively. The removal of aromatic surfactants in conventional STP showed well-known features reported in the literature, including an efficient microbial transformation of the parent molecules and formation of stable metabolic products. The elimination efficiency of aromatic surfactants using the MBR unit was higher than that in the conventional STP, while the composition of recalcitrant nonylphenolic residues in the effluent seems to be ecotoxicologically more favourable due to the lower contributions of the lipophilic metabolites.     

Degradation of bisphenol A using electrochemical assistant Fe(II)-activated peroxydisulfate process

Degradation of bisphenol A(BPA) in aqueous solution using sulfate radicals was investigated using the Fe(II)-activated peroxydisulfate(PDS) process, electrochemical process, electrochemical process with 2.5 mmol/L Na2S2O8 without Fe(II), and electrochemical assistant Fe(II)-activated PDS process. It was found that the electrochemical assistant Fe(II)-activated PDS process performed best in the degradation of BPA.The variables considered to influence the degradation efficiency of BPA were the initial concentration of Fe2 t, the initial concentration of Na2S2O8, and the current density. More than 97% of the BPA removals were achieved within 120 min under the optimum operational condition.The degradation of BPA was accompanied by the formation of phenol, hydroquinone, and small-molecule compounds such as succinic acid. The electron transfer was the principal step in the oxidation of BPA.     

Removal mechanisms of 17β-estradiol and 17α-ethinylestradiol in membrane bioreactors

The fate and behavior of natural and synthetic estrogens in wastewater treatment processes is currently of increasing concern all over the world. In this study, the removal mechanisms of a natural estrogen, 17β-estradiol (E2), and a synthetic estrogen, 17α-ethinylestradiol (EE2) were investigated in membrane bioreactors (MBRs) with and without powdered activated carbon (PAC) addition. The experimental results showed that the average removal rates of E2 and EE2 by the MBR without PAC addition were 89.0 and 70.9%; PAC addition in the MBR increased the removal rate of E2 and EE2 by 3.4 and 15.8%, respectively. The greater impact of PAC dosing on EE2 removal was due to its greater hydrophobic property. Adsorption played a more important role in the removal mechanisms of EE2 than E2. Biodegradation was the dominant mechanism for the removal of E2 and EE2 in MBRs. Unlike their adsorption behavior, the biodegradation rates of both E2 and EE2 were not significantly different between the MBRs with and without PAC addition.