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.     

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。     

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 phthalate esters by two bacteria strains

In this study two aerobic phthalic acid ester (PAE) degrading bacteria strains, DK4 and O18, were isolated from river sediment and petrochemical sludge, respectively. The two strains were found to rapidly degrade PAE with shorter alkyl-chains such diethyl phthalate (DEP), dipropyl phthalate (DPrP), di-n-butyl phthalate (DBP), benzylbutyl phthalate (BBP) and diphenyl phthalate (DPP) are very easily biodegraded, while PAE with longer alkyl-chains such as dicyclohexyl phthalate (DCP) and dihexyl phthalate (DHP) and di-(2-ethylhexyl) phthalate (DEHP) are poorly degraded. The degradation rates of the eight PAEs were higher for strain DK4 than for strain O18. In the simultaneous presence of strains DK4 and O18, the degradation rates of the eight PAEs examined were enhanced. When the eight PAEs were present simultaneously, degradation rates were also enhanced. We also found that PAE degradation was delayed by the addition of nonylphenol or selected polycyclic aromatic hydrocarbons (PAHs) at a concentration of 1 microg/g in the sediment. The bacteria strains isolated, DK4 and O18, were identified as Sphigomonas sp. and Corynebacterium sp., respectively.     

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).     

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。     

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.     

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.     

Atmospheric deposition to the edge of a spruce forest in Denmark

Atmospheric deposition was measured during 1 year at the forest edge of a Norway spruce stand in Denmark. Inside the forest the deposition of H(+), Ca(2+), Mg(2+), Na(+), K(+), Cl(-), NO(3)(-), NH(4)(2) and SO(4)(2-) with canopy throughfall varies with the distance from the forest edge. The deposition at the edge is found to be 10-20 times as high as deposition to an open field and 2-8 times as high as deposition inside the stand. An exponential decrease in deposition as a function of the distance from the forest edge is found. Increased deposition of K(+) and non-sea salt Mg(2+), which mainly originates as a result of leaching from the needles may be explained by a larger leaf area index (LAI) at the forest edge. Deposition of particulate substances, especially Na(+), Cl(-), Mg(2+) and to some extent SO(4)(2-), NH(4)(+) and NO(3)(-) is increased much more than the LAI, which we believe to be caused by changes in wind movements at the forest edge.     

Atmospheric deposition of organochlorine pesticides by precipitation in a coastal area

Wet deposition fluxes of organochlorine pesticides (OCPs) were determined for rain samples collected in a coastal area of Turkey. Seventeen precipitation samples were collected over a 1-year period from 2008 to 2009. Rainwater was accumulated at the beginning of rain events using real time monitoring. Atmospheric concentrations were also measured in parallel with deposition samples. Both atmospheric concentrations and deposition fluxes were determined as particle and gas phases. The particle phase and dissolved phase deposition fluxes were 794.26?±?756.70 ngm^?2 day^?1 and 800.77?±?672.63 ngm^?2 day^?1, respectively. The washout ratios for OCP compounds were calculated separately for the particle and dissolved phases using the atmospheric concentrations and rain concentrations. The minimum washout ratio for the particle phase was 2339.47 for Endrin aldehyde, whereas the maximum washout ratio was 497593.34 for Methoxychlor. The maximum washout ratio for the dissolved phase was 247523.89 for Endosulfan beta, whereas the minimum washout ratio was 10169.69 for p,p′-DDT. The dry deposition velocities ranged from 0.01 to 1.67 cms^?1. The partitioning of wet deposition between the particle and dissolved phases was 50 % in terms of total OCP deposition.     

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.     

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.     

Preliminary toxicological assessment of phthalate esters from drinking water consumed in Portugal

This paper reports, for the first time, the concentrations of selected phthalates in drinking water consumed in Portugal. The use of bottled water in Portugal has increased in recent years. The main material for bottles is polyethylene terephthalate (PET). Its plasticizer components can contaminate water by leaching, and several scientific studies have evidenced potential health risks of phthalates to humans of all ages. With water being one of the most essential elements to human health and because it is consumed by ingestion, the evaluation of drinking water quality, with respect to phthalate contents, is important. This study tested seven commercial brands of bottled water consumed in Portugal, six PET and one glass (the most consumed) bottled water. Furthermore, tap water from Lisbon and three small neighbor cities was analyzed. Phthalates (di-n-butyl phthalate ester (DnBP), bis(2-ethylhexyl) phthalate ester (DEHP), and di-i-butyl phthalate ester (DIBP)) in water samples were quantified (PET and glass) by means of direct immersion solid-phase microextraction and ionic liquid gas chromatography associated with flame ionization detection or mass spectrometry due to their high boiling points and water solubility. The method utilized in this study showed a linear range for target phthalates between 0.02 and 6.5 μg L^?1, good precision and low limits of detection that were between 0.01 and 0.06 μg L^?1, and quantitation between 0.04 and 0.19 μg L^?1. Only three phthalates were detected in Portuguese drinking waters: dibutyl (DnBP), diisobutyl (DIBP), and di(ethylhexyl) phthalate (DEHP). Concentrations ranged between 0.06 and 6.5 μg L^?1 for DnBP, between 0.02 and 0.16 μg L^?1 for DEHP, and between 0.1 and 1.89 μg L^?1 for DIBP. The concentration of DEHP was found to be up to five times higher in PET than in glass bottled water. Surprisingly, all the three phthalates were detected in glass bottled water with the amount of DnBP being higher (6.5 μg L^?1) than in PET bottled water. These concentrations do not represent direct risk to human health. Regarding potable tap water, only DIBP and DEHP were detected. Two of the cities showed concentration of all three phthalates in their water below the limits of detection of the method. All the samples showed phthalate concentrations below 6 μg L^?1, the maximum admissible concentration in water established by the US Environmental Protection Agency. The concentrations measured in Portuguese bottled waters do not represent any risk for adult's health.     

Monitoring the sonochemical degradation of phthalate esters in water using solid-phase microextraction

The sonochemical degradation of aqueous solutions containing low concentrations of six phthalate esters at an ultrasonic frequency of 80 kHz has been investigated. Ultrasonic treatment was found capable of removing the four higher molecular mass phthalates (di-n-butyl phthalate, butylbenzyl phthalate, di-(2-ethylhexyl) phthalate and di-n-octyl phthalate) within 30-60 min of irradiation. The rest (dimethyl phthalate and diethyl phthalate) were more recalcitrant and nearly complete removal could be achieved only after prolonged irradiation times. The relative reactivity of phthalates was explained in terms of their hydrophobicity. Experiments were carried out at an overall initial phthalate concentration of 240 microg l(-1), values of electric power of 75 and 150 W, temperatures of 21 and 50 degrees C and in the presence of NaCl to study the effect of various operating conditions on degradation. Solid-phase microextraction (SPME) coupled with GC-MS proved to be a powerful analytical tool to monitor the sonochemical degradation of phthalate esters at low microg l(-1) concentration levels, minimising the risk of secondary contamination during sample preparation, a major parameter to consider during phthalates analysis. The advantages as well as disadvantages of using SPME are also highlighted.     

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.     

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。