Degradation Of Nonylphenol Research Articles

Modeling of nonylphenol degradation by photo-nanocatalytic process via multivariate approach

Modeling of photocatalytic degradation of nonylphenol (NP), an endocrine disrupter and toxic compound, has been investigated in synthetic aqueous solutions containing ZnO nanoparticles as semiconductor using multivariate approach. In this regard, a full factorial experimental design was performed in order to study the main variables affecting the degradation process as well as their most significant interactions. Initial NP concentrations ([NP] 0) of 0.454–9.08 μM, were treated with UV–vis/ZnO using different pH and nanocatalyst loading rates. Effect of experimental parameters on the NP degradation rate constant was established by the response surface plots. The degradation rate constant decreased with an increase in the initial concentration of NP, while it increased with ZnO loading until a concentration of 0.5 g L −1. The rate constant increases with increase in pH up to 10, after which a significant decrease is observed. The results showed that most influential factors on NP degradation constant are the [NP] 0, pH of reaction media, and ZnO loading rate, and the most significant interaction is [NP]-pH. Finally, two mathematical models have been proposed to estimate NP degradation rate constant ( k) on the basis of the significant variables and interactions. Predicted results of models showed good agreement with the experimental data ( R 2 = 0.83 and 0.93).

Fate and effects of nonylphenol in the presence of the cyanobacterium Microcystis aeruginosa

Interactions of nonylphenol (NP), a toxic and oestrogenic degradation product of widely used non-ionic surfactants, with the cyanobacterium Microcystis aeruginosa were studied. Batch cultures were incubated for 10 days with NP concentrations between 10 and 570 nM. NP was removed more quickly in the presence of M. aeruginosa (half-life 2.7–5.2 days) than in its absence (half-life 6.7–10.2 days) at all concentrations tested. At the end of the experiment, NP could not be found in the biomass, so the biotic removal is due to uptake and chemical transformation, and not to physical binding on the cells. The observed effective concentrations, EC50 and EC20, were 0.45 and 0.25 μ M, respectively. Therefore, NP is expected to have toxic effects on M. aeruginosa only in very contaminated surface waters. However, for concentrations that go far beyond environmental levels, cyanobacteria are able to cope with NP toxicity by internalising the compound in a less toxic form. Therefore, the presence of cyanobacteria may increase the rate of NP removal from the aquatic environment.

Degradation of 4-n-nonylphenol under nitrate reducing conditions

Nonylphenol (NP) is an endocrine disruptor present as a pollutant in river sediment. Biodegradation of NP can reduce its toxicological risk. As sediments are mainly anaerobic, degradation of linear (4-n-NP) and branched nonylphenol (tNP) was studied under methanogenic, sulphate reducing and denitrifying conditions in NP polluted river sediment. Anaerobic bioconversion was observed only for linear NP under denitrifying conditions. The microbial population involved herein was further studied by enrichment and molecular characterization. The largest change in diversity was observed between the enrichments of the third and fourth generation, and further enrichment did not affect the diversity. This implies that different microorganisms are involved in the degradation of 4-n-NP in the sediment. The major degrading bacteria were most closely related to denitrifying hexadecane degraders and linear alkyl benzene sulphonate (LAS) degraders. The molecular structures of alkanes and LAS are similar to the linear chain of 4-n-NP, this might indicate that the biodegradation of linear NP under denitrifying conditions starts at the nonyl chain. Initiation of anaerobic NP degradation was further tested using phenol as a structure analogue. Phenol was chosen instead of an aliphatic analogue, because phenol is the common structure present in all NP isomers while the structure of the aliphatic chain differs per isomer. Phenol was degraded in all cases, but did not affect the linear NP degradation under denitrifying conditions and did not initiate the degradation of tNP and linear NP under the other tested conditions.

Aerobic nonylphenol degradation and nitro-nonylphenol formation by microbial cultures from sediments

Nonylphenol (NP) is an estrogenic pollutant which is widely present in the aquatic environment. Biodegradation of NP can reduce the toxicological risk. In this study, aerobic biodegradation of NP in river sediment was investigated. The sediment used for the microcosm experiments was aged polluted with NP. The biodegradation of NP in the sediment occurred within 8 days with a lag phase of 2 days at 30°C. During the biodegradation, nitro-nonylphenol metabolites were formed, which were further degraded to unknown compounds. The attached nitro-group originated from the ammonium in the medium. Five subsequent transfers were performed from original sediment and yielded a final stable population. In this NP-degrading culture, the microorganisms possibly involved in the biotransformation of NP to nitro-nonylphenol were related to ammonium-oxidizing bacteria. Besides the degradation of NP via nitro-nonylphenol, bacteria related to phenol-degrading species, which degrade phenol via ring cleavage, are abundantly present.

Impact of bio-augmentation with Sphingomonas sp. strain TTNP3 in membrane bioreactors degrading nonylphenol

This study evaluates the potential of bio-augmentation to improve the degradation of recalcitrant nonylphenol during the wastewater treatment in membrane bioreactors (MBR). One MBR containing activated sludge was bio-augmented using multistep inoculation with freeze dried Sphingomonas sp. strain TTNP3, whereas a second control reactor contained activated sludge solely. The (14)C-labeled-nonylphenol isomer (4-[1-ethyl-1,3-dimethylpentyl]phenol) was applied as a single pulse. Bio-augmentation resulted in an immediate increase of dissolved radioactivity in the effluent in comparison to the control reactor (13% and 2% of initially applied radioactivity after 1 day, respectively). After 5 days of operation, the retentate of the bio-augmented reactor contained only 7% of the initial radioactivity in contrast to 50% in the control reactor. The radioactivity associated to the mixed liquor suspended solids, i.e., the suspension of biomass and other solids on the retentate side of the membrane, was mainly found as non-extractable residues that were increasingly formed during prolonged reactor operation, especially for the control MBR. HPLC-LSC and GC-MS(n) analyses revealed that the bio-augmented reactor produced more polar hydroquinone as main degradation intermediate, whereas the control reactor effluent contained a complex mixture of apolar compounds with shortened oxidized alkyl chains. Thus, the apparent differences in the behavior of nonylphenol between the reactors were due to the catabolism of nonylphenol conferred by bio-augmentation with Sphingomonas sp. strain TTNP3.

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 (AP nEO) – 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.

Anaerobic degradation of nonylphenol in subtropical mangrove sediments

Nonylphenol (NP) is known as an endocrine disruptor and has consequently drawn much environmental concern. We investigated the effects of various factors on the anaerobic degradation of NP and characterized the structures of microbial communities in mangrove sediments collected at five sites along the Tanshui River in northern Taiwan. NP anaerobic degradation rate constants ( k 1) and half-lives ( t 1/2) ranged from 0.008 to 0.013 1/day and 53.3 to 86.6 days, respectively. The addition of NaCl (1%, 2%), zero-valent iron (10 g/L), humic acid (0.5 g/L), cellulose (0.96 mg/L), brij 30 (55 μM) and brij 35 (91 μM) enhanced NP anaerobic degradation. However, the addition of NaCl (3%), acetate (20 mM), lactate (20 mM), pyruvate (20 mM), and humic acid (5 g/L) inhibited NP anaerobic degradation. Sulfate-reducing bacteria, methanogen, and eubacteria are involved in the degradation of NP, sulfate-reducing bacteria being a major component of the sediment. Our results also show that the addition of various substrates changed the microbial community in mangrove sediments. Also noted was the presence of 2-butyl-1-octanol, an intermediate product resulting from the anaerobic degradation of NP accumulated in the sediments.

Isomer-Specific Degradation and Endocrine Disrupting Activity of Nonylphenols

Degradation of technical nonylphenol by Sphingobium xenophagum Bayram led to a significant shift in the isomers composition of the mixture. By means of gas chromatography-mass spectrometry, we could observe a strong correlation between transformation of individual isomers and their alpha-substitution pattern, as expressed by their assignment to one of six mass spectrometric groups. As a rule, isomers with less bulkiness at the alpha-carbon and those with an optimally sized main alkyl chain (4-6 carbon atoms) were degraded more efficiently. By mass spectrometric analysis, we identified the two most recalcitrant main isomers of the technical mixture (Group 4) as 4-(1,2-dimethyl-1-propylbutyl)phenols (NP193a and NP193b), which are diastereomers with a bulky alpha-CH3, alpha-CH(CH3)C2H5 substitution. Our experiments with strain Bayram show that the selective enrichment of isomers with bulky alpha-substitutions observed in nonylphenol fingerprints of natural systems can be caused by microbial ipso-hydroxylation. Based on the yeast estrogen assay (YES), we established an estrogenicity ranking with a variety of single isomers and compared it to rankings obtained with different reporter cell systems. Structure-activity relationships derived from these data suggest that Group 4 isomers have a high estrogenic potency. This indicates a substantial risk that enrichment of highly estrogenic isomers during microbial degradation by ipso-substitution will increase the specific estrogenicity of aging material.

Degradation and plant uptake of nonylphenol (NP) and nonylphenol-12-ethoxylate (NP12EO) in four contrasting agricultural soils

Nonylphenol polyethoxylates (NPEOs) are surfactants found ubiquitously in the environment due to widespread industrial and domestic use. Biodegradation of NPEOs produces nonylphenol (NP), an endocrine disruptor. Sewage sludge application introduces NPEOs and NP into soils, potentially leading to accumulation in soils and crops. We examined degradation of NP and nonylphenol-12-ethoxylate (NP12EO) in four soils. NP12EO degraded rapidly (initial half time 0.3-5 days). Concentrations became undetectable within 70-90 days, with a small increase in NP concentrations after 30 days. NP initially degraded quickly (mean half time 11.5 days), but in three soils a recalcitrant fraction of 26-35% remained: the non-degrading fraction may consist of branched isomers, resistant to biodegradation. Uptake of NP by bean plants was also examined. Mean bioconcentration factors for shoots and seeds were 0.71 and 0.58, respectively. Removal of NP from the soil by plant uptake was negligible (0.01-0.02% of initial NP). Root concentrations were substantially higher than shoot and seed concentrations.

Measurement of the free concentrations of alkyl phenols and bisphenol A to determine their biodegradation kinetics by activated sludge

A negligible depletion-solid phase microextraction (nd-SPME) method is developed to measure free concentrations of two alkyl phenols (4-t-octylphenol, nonylphenol) and bisphenol A in activated sludge, with which aerobic biodegradation kinetics of three pollutants was determined. For the degradation of octylphenol, nonylphenol and bisphenol A, the apparent rate constant based on total concentration is 0.02, 0.01 and 0.03 h−1, respectively; with the half life being 34.9, 54.3 and 22.3 h correspondingly. Meanwhile, real rate constants based on free concentration are 0.74, 0.60 and 1.03 h−1, respectively; with the half life being 0.9, 1.2 and 0.7 h accordingly. Differences between two constants revealed that desorption of targeted pollutants from activated sludge should be the rate-limiting step. Compared to the rapid biodegradation of alkyl phenols and bisphenol A in free state, the desorption of pollutants from the sludge is relatively slow, which made the apparent biodegradation rate constants much lower.

Temporal trends of nonylphenol and bisphenol A contamination in the Pearl River Estuary and the adjacent South China Sea recorded by dated sedimentary cores

Three dated sedimentary cores were collected for the investigation of temporal trends and the environmental loadings of nonylphenol (NP) and bisphenol A (BPA) in recent decades in the Pearl River Estuary (PRE), South China and the adjacent South China Sea (SCS). The peak fluxes of NP and BPA occurred in the mid-1980s in the PRE, coincident with the rapid economic growth in China. The decline of NP and BPA fluxes is attributable to the implementation of sewage treatment in the late 1980s in the Pearl River Delta (PRD). Multi-model distributions were observed for the fluxes of NP and BPA in the SCS with the peak fluxes occurring in the late 1950s and the mid-1970s respectively. The fluxes of NP and BPA have increased since the 1990s due to the lack of adequate wastewater treatment facilities and the constant economic growth. Nonylphenol was quantifiably detected in sediments predating its widespread application (1940s), suggesting the downward penetration of NP in the sediment columns. The characterization results revealed that NP and BPA were preserved well and the isomer-selective degradation of NP did not occur significantly in the sediment cores. The environmental loadings of NP and BPA in the PRE sediments were roughly estimated to be 124 t and 1.7 t respectively over the past 30 years.

Degradation of bisphenol A and nonylphenol by nitrifying activated sludge

Nitrifier-enriched activated sludge was used in batch degradation of bisphenol A (BPA) and nonylphenol (NP) to verify if ammonium-oxidizing activity within nitrifiers is responsible for the biodegradation of those compounds. Decreases in both BPA and NP concentrations occurred simultaneously with ammonium (NH 4 +) oxidation into nitrate (NO 3 −) by nitrifying sludge. However, when ammonium was replaced by nitrite (NO 2 −) in the medium, an acclimation period was required prior onset of significant degradation of BPA and NP. In the presence of inhibitors such as allylthiourea or Hg 2SO 4, BPA and/or NP reduction decreased significantly, implying that removal of BPA and NP was mostly mediated by biological activity rather than by physicochemical adsorption onto sludge flocs.

Degradation pathway of bisphenol A: does ipso substitution apply to phenols containing a quaternary alpha-carbon structure in the para position?

The degradation of bisphenol A and nonylphenol involves the unusual rearrangement of stable carbon-carbon bonds. Some nonylphenol isomers and bisphenol A possess a quaternary alpha-carbon atom as a common structural feature. The degradation of nonylphenol in Sphingomonas sp. strain TTNP3 occurs via a type II ipso substitution with the presence of a quaternary alpha-carbon as a prerequisite. We report here a new degradation pathway of bisphenol A. Consequent to the hydroxylation at position C-4, according to a type II ipso substitution mechanism, the C-C bond between the phenolic moiety and the isopropyl group of bisphenol A is broken. Besides the formation of hydroquinone and 4-(2-hydroxypropan-2-yl)phenol as the main metabolites, further compounds resulting from molecular rearrangements consistent with a carbocationic intermediate were identified. Assays with resting cells or cell extracts of Sphingomonas sp. strain TTNP3 under an (18)O(2) atmosphere were performed. One atom of (18)O(2) was present in hydroquinone, resulting from the monooxygenation of bisphenol A and nonylphenol. The monooxygenase activity was dependent on both NADPH and flavin adenine dinucleotide. Various cytochrome P450 inhibitors had identical inhibition effects on the conversion of both xenobiotics. Using a mutant of Sphingomonas sp. strain TTNP3, which is defective for growth on nonylphenol, we demonstrated that the reaction is catalyzed by the same enzymatic system. In conclusion, the degradation of bisphenol A and nonylphenol is initiated by the same monooxygenase, which may also lead to ipso substitution in other xenobiotics containing phenol with a quaternary alpha-carbon.

Degradation of octylphenol and nonylphenol by ozone – Part II: Indirect reaction

The indirect reaction of octylphenol (OP) and nonylphenol (NP) with hydroxyl radicals (*OH) during ozonation was investigated at pH values ranging from 6 to 9. A parameter Rct, representing the ratio of the *OH-exposure to the ozone-exposure, was measured using a method involving a low concentration of p-chlorobenzoic acid as a *OH-probe compound during the ozonation. By assuming that Rct is a constant value at a given pH, the second order rate constants of the alkylphenol reaction with hydroxyl radicals were determined as 1.4(+/-0.2) x 10(10) and 1.1(+/-0.2) x 10(10) M(-1) s(-1) for OP and NP, respectively. The proportions of each alkylphenol degraded by direct molecular ozone reaction and indirect hydroxyl radical reaction were predicted at different pH values. The contribution of indirect *OH reactions with each AP was found to represent over 50% of the total degradation for pH approximately 7, and the contribution increases substantially with pH>7.

Anaerobic degradation of nonylphenol in soil

This study investigated the effects of various factors on the anaerobic degradation of nonylphenol (NP) in soil. The results show that the optimal pH for NP degradation was 7.0 and that the degradation rate was enhanced when the temperature was increased. The addition of compost enhanced NP degradation. The individual addition of the electron donors lactate, acetate, and pyruvate inhibited NP degradation. The high-to-low order of NP degradation rates under three anaerobic conditions was sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The results show that sulfate-reducing bacteria, methanogen, and eubacteria are involved in the anaerobic degradation of NP, with sulfate-reducing bacteria being a major component of the soil. Of the anaerobic strains isolated from the soil samples, strain AT3 expressed the best ability to biodegrade NP.

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.

Degradation of octylphenol and nonylphenol by ozone – Part I: Direct reaction

This aqueous reaction between ozone and two alkylphenols (APs), namely octylphenol (OP) and nonylphenol (NP), has been investigated. Both compounds are important endocrine disrupting chemicals, which arise from the biodegradation of alkylphenol ethoxylates and are often found at relatively high concentrations in wastewater effluents. In this paper the results of an experimental study are presented which provide values for the reaction rate constants between molecular ozone and undissociated OP and NP, and overall reaction rate constants for the degradation of the two APs at pH values in the range of 7-9. The kinetic rate constants for OP and NP degradation by molecular ozone were 4.33(+/-0.18) x 10(4) and 3.90(+/-0.10) x 10(4) M(-1) s(-1), and the reaction stoichiometry was similar in both cases and equal to approximately 1.3:1 ([O3]:[AP]). The overall second order reaction rate constants for the two APs increased significantly with increasing pH, which is believed to be mainly due to the increasing influence of indirect radical reaction with increasing pH; this aspect is considered in more detail in a companion paper. A preliminary investigation of the reaction mechanism suggests that an initial product of ozonation is hydroxyl-alkyl phenol.

Biodegradation of nonylphenol in soil

We investigated the effects of various factors (brij 30, brij 35, yeast extract, hydrogen peroxide and compost) on the aerobic degradation of nonylphenol (NP) in soil and characterized the structure of the microbial community in that soil. Residues of NP were measured using gas chromatography–mass spectrometry (GC–MS) and a change of microbial communities was demonstrated using denaturing gradient gel electrophoresis (DGGE). The results showed that Taichung sandy clay loam had higher NP degradation rate than Kaoshiung silty clay. The addition of compost, yeast extract (0.5 mg/l), brij 30 (55 μM), or brij 35 (91 μM) enhanced NP degradation, while the addition of hydrogen peroxide (1.0 mg/l) inhibited its degradation. We also found that the addition of various substrates changed the microbial community in the soils. Cytophaga sp. and Ochrobactrum sp. were constantly dominant bacteria under various conditions in the soil.

Cyclodextrin-linked alginate beads as supporting materials for Sphingomonas cloacae, a nonylphenol degrading bacteria

Calcium alginate beads covalently linked with α-cyclodextrin (α-CD–alginate beads) were prepared and examined for their ability to serve as a supporting matrix for bacterial degradation of nonylphenol, an endocrine disruptor. Column chromatographic experiment using α-CD–alginate beads with diameter of 657 ± 82 μm and with degree of CD substitution of 0.16 showed a strong affinity for nonylphenol adsorption. Although addition of α-CD (2.7–27 mM) to the culture broth of Sphingomonas cloacae retarded nonylphenol degradation, the immobilized bacteria on the CD–alginate beads were effective for the degradation. Batch degradation tests using the immobilized bacteria on α-CD–alginate-beads showed 46% nonylphenol recovery after 10-day incubation at 25 ± 2 °C, and the recovery reached to about 17% when wide and shallow incubation tubes were used to facilitate uptake of the viscous liquid of nonylphenol on the surface of the medium. Scanning electron microscopic photographs revealed that multiplicated bacteria was present both on the surface and inside the beads and the matrix of CD–alginate was stable and suitable during 10-day incubation.

Microbial degradation of nonylphenol and other alkylphenols—our evolving view

Because the endocrine disrupting effects of nonylphenol (NP) and octylphenol became evident, the degradation of long-chain alkylphenols (AP) by microorganisms was intensively studied. Most NP-degrading bacteria belong to the sphingomonads and closely related genera, while NP metabolism is not restricted to defined fungal taxa. Growth on NP and its mineralization was demonstrated for bacterial isolates, whereas ultimate degradation by fungi still remains unclear. While both bacterial and fungal degradation of short-chain AP, such as cresols, and the bacterial degradation of long-chain branched AP involves aromatic ring hydroxylation, alkyl chain oxidation and the formation of phenolic polymers seem to be preferential elimination pathways of long-chain branched AP in fungi, whereby both intracellular and extracellular oxidative enzymes may be involved. The degradation of NP by sphingomonads does not proceed via the common degradation mechanisms reported for short-chain AP, rather, via an unusual ipso-substitution mechanism. This fact underlies the peculiarity of long-chain AP such as NP isomers, which possess highly branched alkyl groups mostly containing a quaternary alpha-carbon. In addition to physicochemical parameters influencing degradation rates, this structural characteristic confers to branched isomers of NP a biodegradability different to that of the widely used linear isomer of NP. Potential biotechnological applications for the removal of AP from contaminated media and the difficulties of analysis and application inherent to the hydrophobic NP, in particular, are also discussed. The combination of bacteria and fungi, attacking NP at both the phenolic and alkylic moiety, represents a promising perspective.