Aerosolization of an anionic surfactant (LAS) and dissolved organic carbon (DOC) under laboratory conditions.

Aerosolization of natural salt and brackish waters under laboratory conditions is responsible for the transfer of synthetic surfactants such as linear alkylbenzene sulphonate (LAS) from water to the atmosphere. Excluded the lagoon sample which stands apart, on the average ca. 45% of the LAS present at concentrations between 0.1 and 4.1 microg l(-1) in the tested coastal and offshore marine and lagoon waters was transferred to the aerosol extract. The distribution of the individual LAS homologs in the aerosol is very similar to that in water, which indicates no preferential removal from the bulk water of any LAS homolog. The fraction of dissolved organic carbon (DOC) undergoing aerosolization under the same conditions for each tested sample was on an average ca. 3.3%, corresponding to ca. 5.6 mg l(-1). On the average, the enrichment factor of the sea samples, resulting from the changing of the LAS/DOC ratio before and after aerosolization, was ca. 20.     

Toxicity of lead on Ceriodaphnia dubia in the presence of nano-CeO(2) and nano-TiO(2)

Although engineered nanoparticles (NPs) could negatively impact environmental organisms, the synergistic effect of NPs and other toxic substances, which could be more significant than that of NP alone, have seldom been examined. The effect of two common NPs, nano-CeO₂ and nano-TiO₂, on the toxicity of Pb was evaluated using Ceriodaphnia dubia (C. dubia) as the model organism. Standard EPA procedures were followed in the toxicity evaluation. The toxicity of bare NPs (without Pb) was first evaluated and safe doses (levels without causing lethal effect) of NPs were used in the synergistic studies. It was found that the overall toxicity of Pb in the system containing NPs was greater than that of Pb alone, as indicted by the reduced median lethal concentration (LC₅₀) of soluble Pb. The sorption of Pb onto the NP, and the uptake of NPs in the gastrointestinal tract of C. dubia were validated. Therefore, the uptake of Pb-loaded NPs increased the exposure of C. dubia to Pb, resulting in the enhanced toxicity. Reducing the solution pH could shift Pb speciation and enhance the overall toxicity of Pb, with or without the presence of NPs.     

Solubilization and biodegradation of phenanthrene in mixed anionic-nonionic surfactant solutions

The effects of mixed anionic-nonionic surfactants, sodium dodecyl sulfate (SDS) mixed with Tween80 (TW80), Triton X-100 (TX100) and Brij35 respectively on the solubility enhancement and biodegradation of phenanthrene in the aqueous phase were investigated. The efficiency of solubilization and biodegradation of phenanthrene in single-, and mixed-surfactant solutions were also compared. The critical micellar concentrations (CMCs) of mixed surfactants were sharply lower than that of sole SDS. The degree of solubility enhancements by the mixed surfactants followed the order of SDS-TW80>SDS-Brij35>SDS-TX100. Synergistic solubilization was observed in the mixed surfactant solutions, in which the molar ratios of SDS to nonionic surfactant were 1:0, 9:1, 7:3, 5:5, 3:7, 1:9 and 0:1 while the total concentration of surfactants was kept at 5.0 and 10.0 mM, respectively. SDS-Brij35 exhibited more significant degree of synergistic solubility enhancement for phenanthrene. The mixed surfactants exhibited no inhibitory effect on biodegradation of phenanthrene. Substantial amounts of the solubilized phenanthrene by mixed surfactants were completely degraded by phenanthrene-degrading microorganisms within 96 h. The results suggested that anionic-nonionic surfactants would improve the performance of remediation of PAH-contaminated soils.     

Influence of microbial and synthetic surfactant on the biodegradation of atrazine

The present study reports the effect of surfactants (rhamnolipids and triton X-100) on biodegradation of atrazine herbicide by strain A6, belonging to the genus Acinetobacter. The strain A6 was able to degrade nearly 80 % of the 250-ppm atrazine after 6 days of growth. The bacterium degraded atrazine by de-alkylation process. Bacterial cell surface hydrophobicity as well as atrazine solubility increased in the presence of surfactant. However, addition of surfactant to the mineral salt media reduced the rate and extent of atrazine degradation by decreasing the bioavailability of herbicide. On the contrary, addition of surfactant to atrazine-contaminated soil increased the rate and extent of biodegradation by increasing the bioavailability of herbicide. As compared to triton X-100, rhamnolipids were more efficient in enhancing microbial degradation of atrazine as a significant amount of atrazine was removed from the soil by rhamnolipids. Surfactants added for the purpose of hastening microbial degradation may have an unintended inhibitory effect on herbicide degradation depending upon contiguous condition, thus highlighting the fact that surfactant must be judiciously used in bioremediation of herbicides.     

Transformation and biodegradation of 1,2,3-trichloropropane (TCP)

PURPOSE: 1,2,3-Trichloropropane (TCP) is a persistent groundwater pollutant and a suspected human carcinogen. It is also is an industrial chemical waste that has been formed in large amounts during epichlorohydrin manufacture. In view of the spread of TCP via groundwater and its toxicity, there is a need for cheap and efficient technologies for the cleanup of TCP-contaminated sites. In situ or on-site bioremediation of TCP is an option if biodegradation can be achieved and stimulated. This paper presents an overview of methods for the remediation of TCP-contaminated water with an emphasis on the possibilities of biodegradation. CONCLUSIONS: Although TCP is a xenobiotic chlorinated compound of high chemical stability, a number of abiotic and biotic conversions have been demonstrated, including abiotic oxidative conversion in the presence of a strong oxidant and reductive conversion by zero-valent zinc. Biotransformations that have been observed include reductive dechlorination, monooxygenase-mediated cometabolism, and enzymatic hydrolysis. No natural organisms are known that can use TCP as a carbon source for growth under aerobic conditions, but anaerobically TCP may serve as electron acceptor. The application of biodegradation is hindered by low degradation rates and incomplete mineralization. Protein engineering and genetic modification can be used to obtain microorganisms with enhanced TCP degradation potential.     

Biosynthesis of (S)-1-(1-naphthyl) ethanol by microbial ketoreductase

Environmental Science and Pollution Research - (S)-1-(1-naphthyl) ethanol (SNE) is a chiral drug intermediate for the production of mevinic acid analog, a potent cholesterol agent. It acts as an...     

Nonionic surfactant enhanced biodegradation of m-xylene by mixed bacteria and its application in biotrickling filter

In this study, m-xylene biodegradation was examined in bacteria-water mixed solution and biotrickling filter (BTF) systems amended with the nonionic surfactant Tween 80. The mixed bacteria were obtained from the activated sludge of a coking plant through a multisubstrate acclimatization process. High-throughput sequencing analysis revealed that Rhodanobacter sp. was the dominant species among the mixed bacteria. In the bacteria-water mixed solution, the bacterial density increased with increasing Tween 80 concentration. Hence, Tween 80 could be utilized as substrate by the mixed bacteria. Tween 80, with concentrations of 50–100 mg L^?1, could enhance the bioavailability of m-xylene and consequently improve the degradation efficiency of m-xylene. However, further increasing the initial concentration of Tween 80 would decrease the degradation efficiency of m-xylene. At concentrations exceeding 100 mg L^?1, Tween 80 was preferentially degraded by the mixed bacteria over m-xylene. In BTF systems, when the m-xylene inlet concentration was 1200 mg m^?3 and the empty bed residence time was 20 sec, the removal efficiency and elimination capacity of BTF1 with Tween 80 addition were at most 20% and 24% higher than those of BTF2 without Tween 80 addition. Overall, the integrated application of the mixed bacteria and surfactant was demonstrated to be a highly effective strategy for m-xylene waste gas treatment.

Implications: The integrated application of mixed bacteria and surfactant was demonstrated to be a promising approach for the highly efficient removal of m-xylene. Surfactant can activate mixed bacteria to degrade m-xylene by increasing its bioavailability. Besides, surfactant can be utilized as carbon source by the mixed bacteria so that the growth of mixed bacteria can be promoted. It is expected that the integrated application of both technologies will become more common in future chemical industry.     

Influence of water hardness on the bioavailability and toxicity of linear alkylbenzene sulphonate (LAS)

In the present work, the influence of Ca²⁺ concentration on the toxicity of single cut linear alkylbenzene sulfonate (LAS) homologues was studied. Precipitation boundary diagrams for each homologue were obtained, indicating turbid and clear zones depending on the LAS and Ca²⁺ concentrations. The separation between transparent and turbid zones is given by the so-called precipitation line. LAS toxicity to Daphnia magna was determined at concentrations close to this precipitation line. It was observed that when Ca(LAS)₂ precipitation progresses, LAS bioavailability decreases for test animals, and the toxicity diminishes even at high nominal LAS concentrations. According to the “free ion activity model” (FIAM), the toxicity of a given chemical compound is mainly due to the ionic species (Ca²⁺–LAS⁻) and not due to the precipitated molecule, Ca(LAS)₂. The significance of the present study is in connection with the assessment of LAS sorption/precipitation studies in soils and sediments, where in situ toxicity is strongly influenced by Ca²⁺/Mg²⁺ ions, according to the results presented in this work.     

Partitioning of hydrogen peroxide between the gas and liquid phases in the presence of surfactant

Gas-liquid phase partitioning is a key physical property that can predict the environmental fate of a compound between two phases. Several environmental factors have been known to affect the gas-liquid phase partitioning. We investigated the influence of surfactant on the gas-liquid phase partitioning of hydrogen peroxide (H(2)O(2)). The surfactant used was ammonium perfluorooctanoate (APFO). H(2)O(2) solution containing the surfactant was equilibrated in a closed system and gas phase H(2)O(2) concentration was measured by the peroxyoxalate chemiluminescence (PO-CL) method. Gas phase H(2)O(2) concentrations remained constant below the critical micelle concentration (CMC) and increased linearly with surfactant concentration above the CMC, which indicated that surfactant micelles influenced the gas-liquid phase partitioning of H(2)O(2). This result showed that H(2)O(2)-micelle interactions are less favorable than H(2)O(2)-H(2)O interactions. Surfactant monomers did not affect the gas-liquid phase partitioning of H(2)O(2) due to the absence of micelles. Solvent (methanol) effect was also investigated and showed that gas phase H(2)O(2) concentrations increased with the addition of solvent. This indicated the unfavorable interaction of H(2)O(2) with hydrophobic medium compared to hydrophilic one. It is consistent with the result that H(2)O(2)-micelles has a weaker interaction than H(2)O(2)-water because surfactant micelles are hydrocarbon-like organic phase rather than aqueous phase.     

Toxicity of atrazine and its bioaccumulation and biodegradation in a green microalga,Chlamydomonas mexicana

This study evaluated the toxicity of herbicide atrazine, along with its bioaccumulation and biodegradation in the green microalga Chlamydomonas mexicana. At low concentration (10 μg L^?1), atrazine had no profound effect on the microalga, while higher concentrations (25, 50, and 100 μg L^?1) imposed toxicity, leading to inhibition of cell growth and chlorophyll a accumulation by 22 %, 33 %, and 36 %, and 13 %, 24 %, and 27 %, respectively. Atrazine 96-h EC50 for C. mexicana was estimated to be 33 μg L^?1. Microalga showed a capability to accumulate atrazine in the cell and to biodegrade the cell-accumulated atrazine resulting in 14–36 % atrazine degradation at 10–100 μg L^?1. Increasing atrazine concentration decreased the total fatty acids (from 102 to 75 mg g^?1) and increased the unsaturated fatty acid content in the microalga. Carbohydrate content increased gradually with the increase in atrazine concentration up to 15 %. This study shows that C. mexicana has the capability to degrade atrazine and can be employed for the remediation of atrazine-contaminated streams.     

Reduction of surfactant concentrations in static fish tests compared with biodegradation rates in the OECD screening test

The loss of chemicals in static fish tests due to biodegradation has been studied with eight model surfactants whose biodegradabilities in the OECD Screening Test range from 0 to 99 % BiAS removal. There was a good correlation between biodegradation in the fish test and in the OECD Screening Test. Only surfactants with a very high BiAS removal of above 93 % were also degraded quickly in the fish test. Surfactants with less than 80 % BiAS removal incurred losses of less than 20 % in the fish test. These results indicate that those substances which are not lost by volatility or adsorption will be maintained to at least 80 % of their nominal concentration during a 96 hour static fish test.     

Influence of hydroxypropyl-beta-cyclodextrin (HPCD) on the bioavailability and biodegradation of pyrene

It is well known that the limited aqueous solubilities of polycyclic aromatic hydrocarbons (PAH) often reduce their bioavailability to bacterial populations. The objective of this study was to test the impact of a solubility-enhancement reagent, hydroxypropyl-beta-cyclodextrin (HPCD), on the bioavailability and biodegradation of pyrene. No measurable loss of pyrene occurred for the control vials throughout the first 22 weeks of the experiment, indicating the absence of mass loss via abiotic transformation and volatilization. The vials containing pyrene and the degrader isolate (Burkholderia CRE 7), but no HPCD, also exhibited no measurable loss of pyrene throughout the experiment. Conversely, biodegradation of pyrene appears to have been initiated after approximately 15 weeks for the vials containing 10(4) mg l(-1) HPCD. By the end of the experiment, approximately 14% (w/w) of the pyrene was biodegraded in the presence of HPCD. These results indicate that HPCD may be useful for enhancing the bioavailability and biodegradation of pyrene and other PAHs.     

Nonylphenols, nonylphenol-ethoxylates, linear alkylbenzenesulfonates (LAS) and bis (4-chlorophenyl)-sulfone in the German Bight of the North Sea.

Nonylphenols and nonylphenol-ethoxylates were detected in the water and sediment samples from the German Bight of the North Sea. Additionally bis (4-chlorophenyl)-sulfone and linear alkylbenzenesulfonates (LAS) were detected in marine waters. Proof of identification is given by comparison of spectral and chromatographic data from the compounds in sample extracts to those obtained from pure standards. In extracts obtained from water samples taken in 1990 and 1995 the concentrations of nonylphenols and bis-(4-chlorophenyl)-sulfone were compared for each year. The concentrations of nonylphenols in seawater varied from 0.7 to 4.4 ng/l while in the Elbe estuary about 33 ng/l were found. In water samples taken in 1998 nonylphenol-polyethoxylates could not be determined, whereas LAS concentrations of 30 ng/l were confirmed by HPLC-MS/MS. The concentrations of bis (4-chlorophenyl)-sulfone ranged from 0.18 to 2.2 ng/l. In sediment samples LAS concentrations of 39-109 ng/g dry weight were determined.     

In vivo and in vitro metabolism of tobacco-specific nitrosamine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), by the freshwater planarian, Dugesia japonica

Cigarette smoke is a risk factor for human health, and many studies were conducted to investigate its adverse effects on humans and other mammals. However, since large amounts of cigarette products are produced and consumed, it is possible that tobacco chemicals can end up in aquatic environments through several routes, thus influencing aquatic organisms. In this study, the presence of tobacco-specific nitrosamine (TSNA), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), in aquatic environment was demonstrated. Since toxic effects on and distribution patterns of tobacco chemicals in aquatic organisms were rarely studied, after results of an acute toxicity pretest were obtained, experiment was conducted to investigate the bioaccumulation pattern of NNK and distribution patterns of its metabolites, mainly 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), in NNK-treated freshwater planarians, Dugesia japonica. Results from in vivo and in vitro studies showed that NNK was readily converted to NNAL through the carbonyl reduction in bodies of NNK-treated planarians. Tissue concentrations of both chemicals increased in time- and dose-dependent manners. Furthermore, we examined the end products of NNK/NNAL α-hydroxylation in NNK-treated planarians, but only 1-(3-pyridyl)-1,4-butanediol was detected, suggesting that NNK metabolism in planarians partially differs from that in mammalian systems. This is the first report on NNK metabolism in an aquatic organism and can be used as a foundation for developing freshwater planarians as a new in vivo model for the study of NNK toxicology in the future.     

Effect of linear alkylbenzene sulphonate (LAS) on the mineralization, metabolism and uptake of 14C-phenanthrene in a model ecosystem (water-lava-plant-air)

The aim of this work was to evaluate the effect of linear alkylbenzene sulfonate (LAS, 200 mg l(-1)) on the fate of phenanthrene in a model ecosystem "water-lava-hydrophytes-air". The experiments were conducted using two closed cultivation chamber systems. Rushes (Juncus effesus) were selected as a representative hydrophyte. Five hundred micrograms per liter of phenanthrene in a culture solution containing a 14C-activity of 75 microCi per chamber was applied (i) to investigate the degradation of the labeled test substance and the transfer processes within the system; (ii) to determine the mass-balance possible and (iii) to detect the occurrence of volatile test substances, their volatile metabolites and the degradation end-product CO2 in the gas phase. Most of the applied 14C-activity was found in the plant (41-45%), in which approximately 95% was associated with plant roots and approximately 5% with shoots. The 14C-activity recovered in the form of VOCs and CO2 was measured in lava (18-29%, 8-11%), and in the culture solution (10-14% and 1%), respectively. Majority of the applied 14C-activity existed in two forms, i.e. (1) polar metabolites (26%), of which 91% were found in plant roots, and (2) un-extractable residues (23%), most of which were in plant roots (40%) and bounded to lava (58%). The presence of LAS significantly increased the volatilization of phenanthrene and its metabolites, inhibited its mineralization and decreased the level of 14C-activity in lava. Moreover, LAS reduced the phenanthrene level in plant roots.     

Enhancement of ozone oxidation and its associated processes in the presence of surfactant: degradation of atrazine

In this study, the degradation of atrazine (ATZ) by ozone (O3) oxidation and its associated processes (i.e. UV, UV/O3) in the presence and absence of surfactant was investigated and compared. A non-ionic surfactant, Brij 35, was selected. It was found that the presence of a low concentration of surfactant could improve the removal of ATZ by increasing the dissolution of ozone and the indirect generation of hydroxyl radicals. The saturated ozone level and the reaction rate constants were increased with increasing the concentration of surfactant and then decreased at higher surfactant doses at pH level of 2.5. A similar trend was observed at pH level of 7.0 in the presence of bicarbonate ion, because it is capable of deactivating the hydroxyl radicals generating at higher pH level. However, when the radical reactions become dominant in the ozonation (at pH 7.0 without bicarbonate), the saturated ozone level was higher than that with bicarbonate and the kinetic rate constants were increased first and levelled off with increasing of the dose of surfactant. Through the examining of a proposed unit performance index, the low concentration of surfactant is surely beneficial to the ozonation process. Besides, the direct photolysis and photo-assisted ozonation were compared to the ozonation. A significant enhancement on the decay rate of ATZ was resulted exclusively by adding the surfactant. An enhancement index for quantifying the improvement of the various processes was developed.     

Degradation and photodegradation of tetraacetylethylenediamine (TAED) in the presence of iron (III) in aqueous solution

The dark degradation of tetraacetylethylenediamine (TAED) was investigated. It is a slow process which is favored in acidic medium. There is a hydrolysis of an imide group with the scission of the C---N bond giving rise to the triacetyl derivative (TAED'). When allowed to stand for longer times a second acetyl group is eliminated with the formation of the symetric diacetyl derivative (DAED). The degradation of TAED photoinduced by iron (III) was also investigated. It appears a faster degradation which does not lead to the same products. The process only involves ^•OH radicals formed upon photolysis of aquocomplex of iron (III). They preferentially abstract a hydrogen from the methylene group. The degradation is then assisted by oxygen and leads to the formation of carbonylated oxidation products.     

Fate of mutagenicity produced during anaerobic biodegradation of the herbicide chlornitrofen (CNP)

The mutagenicity of chlornitrofen (CNP)-containing solutions has been reported to increase during anaerobic biodegradation. In the present study, the fate of this increased mutagenicity under subsequent aerobic and anaerobic incubation conditions was investigated using two Salmonella tester strains, YG 1024 (a frameshift-detecting strain) and YG 1029 (a base-pair-substitution-detecting strain). Mutagenicity for both YG 1024 and YG 1029 strains increased during nine-day anaerobic biodegradation. During subsequent anaerobic incubation, the increased mutagenicity decreased gradually for YG 1029 but did not change significantly for YG 1024. By contrast, the increased mutagenicity decreased rapidly after the conversion to aerobic incubation for both YG 1024 and YG 1029 strains. The rapid decrease in mutagenicity during aerobic incubation was due to decreases, not only in an identified mutagenic metabolite (CNP-amino) but also in unidentified mutagenic metabolites.     

Synthesis of the DDT metabolite 2,4-dichloro-1-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene (o-Cl-DDMU) and its detection in abiotic and biotic samples

Environmental Science and Pollution Research - Technical dichlorodiphenyltrichloroethane (DDT) has been used worldwide as a pesticide since the beginning of the 1940s. Due to its persistence, DDT...