Biodegradation of four phthalate esters in sludge

This study investigated the effects of ultrasonic pretreatment and various treatments on the aerobic degradation of four phthalic acid esters (PAEs) such as diethyl phthalate (DEP), benzyl butyl phthalate (BBP), di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl)phthalate (DEHP) in sludge. The effect on PAE degradation of treating sludge with a 20 min sonication period at a power level of 0.1 W ml(-1) was evaluated. The degradation rates of the four PAEs were DBP>BBP>DEP>DEHP. Degradation rate constants (k(1)) and half-lives (t(1/2)) for the four PAEs (50 mg kg(-1)) ranged from 0.182 to 0.379 day(-1) and 1.8 to 3.8 days, respectively. The optimal pH for PAE degradation in sludge was 7.0 at 30 degrees C. PAE degradation was enhanced by the addition of yeast extract, brij 30 or brij 35 and inhibited by the addition of hydrogen peroxide. Our results show that a combination of ultrasonic pretreatment and biodegradation can effectively remove PAE from sludge.     

Biodegradation of mono-alkyl phthalate esters in natural sediments

Mono-alkyl phthalate esters (MPEs) are primary metabolites of di-alkyl phthalate esters (DPEs), a family of industrial chemicals widely used in the production of soft polyvinyl chloride and a large range of other products. To better understand the long term fate of DPEs in the environment, we measured the biodegradation kinetics of eight MPEs (-ethyl, -n-butyl, -benzyl, -i-hexyl, -2-ethyl-hexyl, -n-octyl, -i-nonyl, and -i-decyl monoesters) in marine and freshwater sediments collected from three locations in the Greater Vancouver area. After a lag period in which no apparent biodegradation occurred, all MPEs tested showed degradation rates in both marine and freshwater sediments at 22 °C with half-lives ranging between 16 and 39 h. Half-lives increased approximately 8-fold in incubations performed at 5 °C. Biodegradation rates did not differ between marine and freshwater sediments. Half-lives did not show a relationship with increasing alkyl chain length. We conclude that MPEs can be quickly degraded in natural sediments and that the similarity in MPE degradation kinetics among sediment types suggests a wide occurrence of nonspecific esterases in microorganisms from various locations, as has been reported previously.     

Biodegradation of phthalate esters in polluted soil by using organic amendment

This study investigated the biodegradation of the phthalate esters (PAEs) di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl) phthalate (DEHP) in sludge and sludge-amended soil. DBP (100 mg kg^?1) and DEHP (100 mg kg^?1) were added to sewage sludge, which was subsequently added to soil. The results showed that sewage sludge can degrade PAEs and the addition of sewage sludge to soil enhanced PAE degradation. Sludge samples were separated into fractions with various particle size ranges, which spanned 0.1–0.45 μm to 500–2000 μm. The sludge fractions with smaller particle sizes demonstrated higher PAE degradation rates. However, when the different sludge fractions were added to soil, particle size had no significant effect on the rate of PAE degradation. The results from this study showed that microbial strains F4 (Rhodococcus sp.) and F8 (Microbacterium sp.) were constantly dominant in the mixtures of soil and sludge.     

Biodegradation of phthalate esters in polluted soil by using organic amendment

This study investigated the biodegradation of the phthalate esters (PAEs) di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl) phthalate (DEHP) in sludge and sludge-amended soil. DBP (100 mg kg(-1)) and DEHP (100 mg kg(-1)) were added to sewage sludge, which was subsequently added to soil. The results showed that sewage sludge can degrade PAEs and the addition of sewage sludge to soil enhanced PAE degradation. Sludge samples were separated into fractions with various particle size ranges, which spanned 0.1-0.45 μm to 500-2000 μm. The sludge fractions with smaller particle sizes demonstrated higher PAE degradation rates. However, when the different sludge fractions were added to soil, particle size had no significant effect on the rate of PAE degradation. The results from this study showed that microbial strains F4 (Rhodococcus sp.) and F8 (Microbacterium sp.) were constantly dominant in the mixtures of soil and sludge.     

Biodegradation of phthalate esters during the mesophilic anaerobic digestion of sludge

Phthalic acid esters (PAE) are commonly found in the sludge generated in the wastewater treatment plants. Anaerobic digestion followed by land application is a common treatment and disposal practice of sludge. To date, many studies exist on the anaerobic biodegradation rates of PAE, especially of the easily biodegradable ones, whereas the higher molecular weight PAE have reported to be non-biodegradable under methanogenic conditions. Furthermore, there is no information on the effect of the PAE on the performance of the anaerobic digesters treating sludge. In this study, the anaerobic biodegradation of di-n-butyl phthalate (DBP), di-ethyl phthalate (DEP) and di-ethylhexyl phthalate (DEHP) was investigated and their relative rates of anaerobic degradation were calculated. Also, the biological removal of PAE during the anaerobic digestion of sludge in bench-scale digesters was investigated using DBP and DEHP as model compounds of one biodegradable and one recalcitrant PAE respectively. The degradation of all the PAE tested in this study (DEP, DBP and DEHP) is adequately described by first-order kinetics. Batch and continuous experiments showed that DEP and DBP present in sludge are rapidly degraded under mesophilic anaerobic conditions (a first-order kinetic constant of 8.04 x 10(-2) and 13.69 x 10(-2)-4.35 day(-1) respectively) while DEHP is degraded at a rate between one to two orders of magnitude lower (0.35 x 10(-2)-3.59 x 10(-2) day(-1)). It is of high significance that experiments with anaerobic sludge of different origin (US and Europe) showed that degradation of DEHP occurs under methanogenic conditions. Accumulation of high levels of DEHP (more than 60 mg/l) in the anaerobic digester has a negative effect on DBP and DEHP removal rates as well as on the biogas production.     

环境内分泌干扰物--邻苯二甲酸酯的研究

介绍了环境内分泌干扰物的生殖毒性，综述了不同环境样品中邻苯二甲酸酯类内分泌干扰物的前处理技术和分析测试技术，并指出环境中邻苯二甲酸酯的污染状况。     

降解菌对堆肥中多环芳烃降解作用的研究

通过在堆肥中加入经过驯化的降解菌这种土壤有机污染生物修复技术 ,对堆肥中多环芳烃的浓度变化进行监测 ,从而了解降解菌对堆肥中多环芳烃的降解作用。实验结果表明 ,降解菌的加入能明显地提高多环芳烃的降解率 ,本次实验中 ,菲、芴的去除率提高了 2 5 %左右 ,芘的去除率提高了约 4 5 %。     

Biodegradation capacity of tributyltin by two Chlorella species

Two microalgal species, Chlorella vulgaris and Chlorella sp., which showed high tributyltin (TBT) tolerant ability were investigated for their capabilities in degrading TBT at sublethal concentration. The distribution of TBT and its degraded products dibutyltin (DBT) and monobutyltin (MBT) in the incubation medium, extracellular surface and intracellular fraction were monitored during an exposure period of 14 days. Results showed that biosorption of TBT by the algal cell wall was the major mechanism in reducing 40% of the initial TBT from the medium in the first 2 days. The half-life of TBT incubated with C. vulgaris was 60 h while that of Chlorella sp. was 80 h. The occurrence of DBT at Day 1 in the culture medium provided direct evidence to the biodegradation of TBT by both Chlorella species. At the end of the experimental period, 27 and 41% of the original TBT were recovered as DBT and MBT in cultures of C. vulgaris, respectively. In contrast, DBT appeared to be the only degradation product of Chlorella sp. and only 26% of the original TBT was transformed to DBT. Despite the same genus, TBT was debutylated to a greater extent to MBT by C. vulgaris, while DBT was the end degradation product by Chlorella sp. The capability of such debutylating process therefore accounted for the higher tolerant ability of C. vulgaris than Chlorella sp.     

Biodegradation of polyaromatic hydrocarbons by recombinant bacteria containing Alasan gene

Alasan, the bioemulsifier of Acinetobacter radioresistens KA53, is a high molecular-mass complex of an alanine-containing polysaccharide and three proteins. This gene was isolated from the A. radioresistens using PCR and the amplified product (850 bp) was cloned using PGEMT cloning kit. DNA sequence was carried out for the amplification and sequence analysis showed that the PCR product was highly similar to the OMPA precursor protein which called Alan. Subcloning was carried out into pTRAC expression vector and the purified protein was used in mineralisation of the polyaromatic hydrocarbon. As well as the recombinant E. coli cells were cultured directly on MSM containing four polyaromatic hydrocarbon using real time method (phenol, naphthalene, phenantherene and antherathene). The obtained results showed that no difference between the purified protein and the using of the recombinant cells directly with the presence of the inducer like IPTG. Both of the purified protein and the recombinant cells showed high degradation rates for (anthrathene and phenantherene).     

Atmospheric deposition of phthalate esters in a subtropical city

In Chinese cities, air pollution has become a serious and aggravating environmental problem undermining the sustainability of urban ecosystems and the quality of urban life. Bulk atmospheric deposition samples were collected two-weekly, from February 2007 to January 2008, at three representative areas, one suburban and two urbanized, in the subtropical city, Guangzhou, China, to assess the deposition fluxes and seasonal variations of phthalate esters (PAEs). Sixteen PAE congeners in bulk deposition samples were measured and the depositional fluxes of ∑₁₆PAEs ranged from 3.41 to 190 μg m^?2 day^?1, and were highly affected by local anthropogenic activities. The significant relationship between PAEs and particulate depositional fluxes (correlation coefficient R² = 0.72, P < 0.001) showed PAEs are associated primarily with particles. Temporal flux variations of PAEs were influenced by seasonal changes in meteorological parameters, and the deposition fluxes of PAEs were obviously higher in wet season than in dry season. Diisobutyl phthalate (DiBP), Di-n-butyl phthalate (DnBP), and Di(2-ethylhexyl) phthalate (DEHP) dominated the PAE pattern in bulk depositions, which is consistent with a high consumption of the plasticizer market in China. PAE profiles in bulk deposition showed similarities exhibited in both time and space, and a weak increase of high molecular weight PAE (HMW PAE) contribution in the wet season compared to those in the dry season. Average atmospheric deposition fluxes of PAEs in the present study were significantly higher than those from other studies, reflecting strong anthropogenic inputs as a consequence of rapid industrial and urban development in the region.     

水环境中邻苯二甲酸酯的迁移转化研究

邻苯二甲酸酯(PAEs)是一类普遍使用的化学工业品,并广泛存在于环境中.已有研究表明,PAEs环境内分泌干扰物,对人类和自然环境有非常大的危害.总结了PAEs在地表水中的分布和在水体中迁移转化的主要途径,如水解、光降解、与颗粒物(沉积物或悬浮颗粒物)的作用以及生物转化作用,并指出对它们进一步研究的重要性和今后主要的研究方向.     

Biodegradation of sucrose poly fatty acid esters in soils

Sucrose polyesters (SPEs) were applied to soil at rates equivalent to 1062 to 1293 kg per hectare and incubated over periods of 100 to 403 days at 20 ± 2°C in darkness and at a soil moisture of 40 % of the maximum water holding capacity. All applied forms of SPEs were aerobically biodegraded to some degree in both American and German soil. However, the mineralization rates varied considerably and were dependent on both SPE and soil type. For example, sucrose octaoleate underwent slow and limited mineralization in the German soils Speyer and Borstel as well as in the American soil Madera, reaching only 6.9 – 18.4 % mineralisation after over 400 days incubation. The same material in the American soils Hollande, Thermal and Uvalde as well as in the German soil Speicherkoog, reached 35–52 % after the same incubation period. Of the SPEs most realistic for use in food products, the more liquid (i.e. with the least saturated fatty acids) underwent the most rapid and extensive mineralization. However, the mineralization rates for these materials were distinctly lower than the corresponding ones for sucrose octaoleate. In all cases the extent of mineralization of the SPEs in soil was significantly lower than that of a control fat (synthetic triglyceride mixture HB307), which typically underwent over 50 % mineralization in 60 days.

As field conditions would be considerably different to those in the laboratory (due to the presence of microbially acclimatised sewage sludge, fluctuations in soil temperature and moisture, and contamination by ecotoxic pollutants) it is difficult to predict accurately, on the basis of laboratory results, the likely rate of mineralization of SPEs in the field. However, this study does suggest that the more solid the SPE, the more likely it is to persist, and possibly accumulate, following application to soil.     

Trace phthalate and adipate esters contaminated in packaged food

A method for trace analysis of two plasticizers, di-2-ethylhexyl phthalate (DEHP) and di-2-ethylhexyl adipate (DEHA), contaminated in packaged curry paste were investigated by gas chromatography with flame ionization detector (GC-FID). Curry paste samples were extracted by ultrasonic and solid phase extraction using Florisil® cartridge. Analysis by the GC-FID system provided limits of detection for DEHA and DEHP at 12 and 25 μ g L^{? 1} and a linear dynamic range between 25 μ g L^{? 1} to 60 mg L^{? 1} with a coefficient of determination (R²) greater than 0.99. High recoveries were obtained, ranged from 91 to 99% and 88 to 98% for DEHP and DEHA with RSD lower than 7 and 10% respectively. The method detection limit and limits of quantitation were ranged from 27 to 30 and 90 to 100 μ g L^{? 1}. The analysis of curry paste samples showed concentrations of DEHP and DEHA in the range of 4.0 ng g^{? 1} to 0.61 μg g^{? 1}.     

Trace phthalate and adipate esters contaminated in packaged food

A method for trace analysis of two plasticizers, di-2-ethylhexyl phthalate (DEHP) and di-2-ethylhexyl adipate (DEHA), contaminated in packaged curry paste were investigated by gas chromatography with flame ionization detector (GC-FID). Curry paste samples were extracted by ultrasonic and solid phase extraction using Florisil(R) cartridge. Analysis by the GC-FID system provided limits of detection for DEHA and DEHP at 12 and 25 microg L(- 1) and a linear dynamic range between 25 microg L(- 1) to 60 mg L(- 1) with a coefficient of determination (R(2)) greater than 0.99. High recoveries were obtained, ranged from 91 to 99% and 88 to 98% for DEHP and DEHA with RSD lower than 7 and 10% respectively. The method detection limit and limits of quantitation were ranged from 27 to 30 and 90 to 100 microg L(- 1). The analysis of curry paste samples showed concentrations of DEHP and DEHA in the range of 4.0 ng g(- 1) to 0.61 microg g(- 1).     

Biodegradation of dimethylphenols by bacteria with different ring-cleavage pathways of phenolic compounds

The biodegradation of 3,4, 2,4, 2,3, 2,6 and 3,5-di-methylphenol in combination with phenol andp-cresol by axenic and mixed cultures of bacteria was investigated. The strains, which degrade phenol andp-cresol through different catabolic pathways, were isolated from river water continuously polluted with phenolic compounds of leachate of oil shale semicoke ash heaps. The proper research of degradation of 2,4 and 3,4-di-methylphenol in multinutrient environments was performed. The degradation of phenolic compounds from mixtures indicated a flux of substrates into different catabolic pathways. Catechol 2,3-dioxygenase activity was induced by dimethylphenols inPseudomonas mendocina PC1, wheremeta cleavage pathway was functional during the degradation ofp-cresol. In the case of strains PC18 and PC24 ofP. fluorescens, the degradation ofp-cresol occurred via the protocatechuateortho pathway and the key enzyme of this pathway,p-cresol methylhydroxylase, was also induced by dimethylphenols. 2,4 and 3,4-dimethylphenols were converted into the dead-end products 4-hydroxy-3-methylbenzoic acid and 4-hydroxy-2-methylbenzoic acid. In the degradation of 3,4-dimethylphenol, the transient accumulation of 4-hydroxy-2-methylbenzaldehyde repressed the consumption of phenol from substrate mixtures. A mixed culture of strains with different catabolic types made it possible to overcome the incompatibilities at degradation of studied substrate mixtures.     

Chemodynamic properties of phthalate esters: Partitioning and soil migration

Phthalate esters (PEs) form a class of organic pollutants whose chemical and physical properties relevant to their environmental transport and distribution are not completely known. Three PEs encompassing a wide range of molecular weights were studied as model compounds. Soil-water partition coefficients and rates of migration through river sand in laboratory column experiments were determined. Diethyl phthalate (DEP) has a low K_p and is fairly mobile, while di-(2-ethylhexyl) phthalate (DEHP) is strongly adsorbed and relatively immobile. Di-n-butyl phthalate (DBP), with an intermediate K_p, has a moderate mobility and exhibits a distinct flow rate dependence related to the mechanism of the adsorption and/or desorption process.     

粘土矿物材料吸附去除水中痕量邻苯二甲酸酯

研究了天然沸石、2种有机改性沸石及Mg/Al水滑石对水中痕量邻苯二甲酸二甲酯、邻苯二甲酸二(2-乙基己基)酯和邻苯二甲酸二辛酯的等温吸附情况和吸附机理,并与活性炭的吸附性能进行了比较。结果表明,Freundlich和Langmuir吸附等温方程均可以很好地描述天然沸石和Mg/Al水滑石对邻苯二甲酸酯的吸附,2种有机改性沸石对邻苯二甲酸酯的吸附更符合Linear吸附等温方程。与活性炭相比,天然沸石对邻苯二甲酸酯的吸附效果较差;2种有机改性沸石和Mg/Al水滑石对分子尺寸较小的邻苯二甲酸酯物质邻苯二甲酸二甲酯的去除率较低,分别低31.8%、31.4%和19.8%,但对分子较大的邻苯二甲酸酯物质邻苯二甲酸二(2-乙基己基)酯和邻苯二甲酸二辛酯的去除效果相差不大。     

环境中邻苯酸酯类化合物污染研究概况

邻苯酸酯类化合物在工农业及人们日常生活中均有广泛应用。近来它已被确认为环境激素。本文介绍该领域的研究概况，着重在北美和西欧地区对这类化合物的风险评价、雌激素活性体内和体外的测定结果以及对它的安全性看法。     

Occurrence and microbial degradation of phthalate esters in Taiwan river sediments

Concentrations and microbial degradation rates were measured for eight phthalate esters (PAEs) found in 14 surface water and six sediment samples taken from rivers in Taiwan. The tested PAEs were diethyl phthalate (DEP), dipropyl phthalate (DPP), di-n-butyl phthalate (DBP), diphenyl phthalate (DPhP), benzylbutyl phthalate (BBP), dihexyl phthalate (DHP), dicyclohexyl phthalate (DCP), and di-(2-ethylhexyl) phthalate (DEHP). In all samples, concentrations of DEHP and DBP were found to be higher than the other six PAEs. DEHP concentrations in the water and sediment samples ranged from ND to 18.5 μg/l and 0.5 to 23.9 μg/g, respectively; for DBP the concentration ranges were 1.0–13.5 μg/l and 0.3–30.3 μg/g, respectively. Concentrations of DHP, BBP, DCP and DPhP were below detection limits. Under aerobic conditions, average degradation half-lives for DEP, DPP, DBP, DPhP, BBP, DHP, DCP and DEHP were measured as 2.5, 2.8, 2.9, 2.6, 3.1, 9.7, 11.1 and 14.8 days, respectively; under anaerobic conditions, respective average half-lives were measured as 33.6, 25.7, 14.4, 14.6, 19.3, 24.1, 26.4 and 34.7 days. In other words, under aerobic conditions we found that DEP, DPP, DBP, DPhP and BBP were easily degraded, but DEHP was difficult to degrade; under anaerobic conditions, DBP, DPhP and BBP were easily degraded, but DEP and DEHP were difficult to degrade. Aerobic degradation rates were up to 10 times faster than anaerobic degradation rates.