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 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 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 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.     

Profiles and risk assessment of phthalate acid esters (PAEs) in drinking water sources and treatment plants,East China

This study is the first report describing the occurrence of 15 phthalate acid esters (PAEs) in the three typical water sources of YiXing City, Taihu Upper-River Basin, East China. The fate of target PAEs in the Jiubin drinking water treatment plant (JTP) was also analyzed. The amounts of Σ₁₅PAE in the Hengshan (HS), Youche (YC), and Xijiu (XJ) water sources were relatively moderate, with mean values of 360, 357, and 697 ng L⁻¹, respectively. Bis(2-ethylhexyl) phthalate (DEHP) dominated the PAE concentration, making up 80% of the 15 total PAEs. The highest levels of Σ₁₅PAE were found in HS, YC, and XJ in March 2015, January 2015, and July 2014, respectively. The occurrence and concentrations of these compounds were spatially dependent, and the mean concentrations of Σ₁₅PAE in HS, YC, and XJ samples increased from the surface layer to the bottom layer with varied percentage increases. The removal efficiency of the PAEs in the finished water varied markedly, and the removal of PAEs by the JTP ranged from 12.8 to 64.5%. The potential ecosystem risk assessment indicated that the risk of PAEs was relatively low in these three water sources. However, risks posed by PAEs due to drinking water still exist; therefore, special attention should be paid to source control in the JTP, and advanced treatment processes for drinking water supplies should be implemented.

     

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.     

Atmospheric distribution of particulate- and gas-phase phthalic esters (PAEs) in a Metropolitan City, Nanjing, East China

Phthalic acid esters (PAEs) are used in many branches of industry and are produced in huge amounts throughout the world. An investigation on particulate- and gas-phase distribution of PAEs has been conducted in Nanjing (China). The 12-h daily sampling program (from 8:00 am to 8:00 pm) for ten consecutive days was conducted in April, July and October 2005, and in January 2006 at about 1.5m above the ground level. For comparative purposes, sampling events were simultaneously conducted at two stations, one at the urban center and the other about 12 km from city center for suburban background monitoring. It was observed that the most abundant members of the PAE group were dimethyl phthalate (DMP) (10.1 ng m(-3), average), diethyl phthalate (DEP) (3.4 ng m(-3)), dibutyl phthalate (DBP) (58.8 ng m(-3)), butylbenzyl phthalate (BBP) (3.2 ng m(-3)), di-2-ethylhexyl phthalate (DEHP) (20.3 ng m(-3)) and di-n-octyl phthalate (DOP) (1.2 ng m(-3)). The average contribution of PAEs in the gas phase to the total PAE concentration (Sigma(6)PAE, sum of six PAE congeners) ranged from 75.0% to 89.2%. Both particulate- and gas-phase Sigma(6)PAE concentrations decreased with increasing temperature. Experimentally determined gas-particle partitioning (K(p)) of PAEs is well-correlated with their vapor pressure. The Sigma(6)PAE levels in the urban area are approximately 3.5 times as high as the levels found at the suburban station. The vertical profiles from 1.5 to 30.0m above the ground display slight height dependence.     

Current status and historical variations of phthalate ester (PAE) contamination in the sediments from a large Chinese lake (Lake Chaohu)

The residual levels of phthalate esters (PAEs) in the surface and two core sediments from Lake Chaohu were measured with a gas chromatograph–mass spectrometer (GC–MS). The temporal–spatial distributions, compositions of PAEs, and their effecting factors were investigated. The results indicated that di-n-butyl phthalate (DnBP), diisobutyl phthalate (DIBP), and di(2-ethylhexyl) phthalate (DEHP) were three dominant PAE components in both the surface and core sediments. The residual level of total detected PAEs (∑PAEs) in the surface sediments (2.146?±?2.255 μg/g dw) was lower than that in the western core sediments (10.615?±?9.733 μg/g) and in the eastern core sediments (5.109?±?4.741 μg/g). The average content of ∑PAEs in the surface sediments from the inflow rivers (4.128?±?1.738 μg/g dw) was an order of magnitude higher than those from the lake (0.323?±?0.093 μg/g dw), and there were similar PAE compositions between the lake and inflow rivers. This finding means that there were important effects of PAE input from the inflow rivers on the compositions and distributions of PAEs in the surface sediments. An increasing trend was found for the residual levels of ΣPAEs, DnBP, and DIBP from the bottom to the surface in both the western and eastern core sediments. Increasing PAE usage with the population growth, urbanization, and industrial and agricultural development in Lake Chaohu watershed would result in the increasing production of PAEs and their resulting presence in the sediments. The significant positive relationships were also found between the PAE contents and the percentage of sand particles, as well as TOC contents in the sediment cores.     

Rape (Brassica chinensis L.) seed germination, seedling growth, and physiology in soil polluted with di-n-butyl phthalate and bis(2-ethylhexyl) phthalate

Phthalic acid esters (PAEs) pollution in agricultural soils caused by widely employed plastic products is becoming more and more widespread in China. PAEs polluted soil can lead to phytotoxicity in higher plants and potential health risks to human being. We evaluated the individual toxicity of di-n-butyl phthalate (DnBP) and bis(2-ethylhexyl) phthalate (DEHP), two representative PAEs, to sown rape (Brassica chinensis L.) seeds within 72 h (as germination stage) and seedlings after germination for 14 days by monitoring responses and trends of different biological parameters. No significant effects of six concentrations of PAE ranging from 0 (not treated/NT) to 500 mg?kg^?1 on germination rate in soil were observed. However, root length, shoot length, and biomass (fresh weight) were inhibited by both pollutants (except root length and biomass under DEHP). Stimulatory effects of both target pollutants on malondialdehyde (MDA) content, superoxide dismutase (SODase) activity, ascorbate peroxidase (APXase) content, and polyphenoloxidase (PPOase) activity in shoots and roots (SODase activity in shoots excluded) were in the same trend with the promotion of proline (Pro) but differed with acetylcholinesterase activity (except in shoots under DnBP) for analyzed samples treated for 72 h and 14 days. Responses of representative storage compounds free amino acids (FAA) and total soluble sugar (TSS) under both PAEs were raised. Sensitivity of APXase and Pro in roots demonstrates their possibility in estimation of PAE phytotoxicity and the higher toxicity of DnBP, which has also been approved by the morphological photos of seedlings at day 14. Higher sensitivity of the roots was also observed. The recommended soil allowable concentration is 5 mg DnBP?kg^?1 soil for the development of rape. We still need to know the phytotoxicity of DEHP at whole seedling stage for both the growing and development; on the other hand, soil criteria for PAE compounds are urgently required in China.     

Sorption behavior of dibutyl phthalate and dioctyl phthalate by aged refuse

Sorption is a fundamental process controlling the transformation, fate, degradation, and biological activity of hydrophobic organic contaminants in the environment. We investigated the kinetics, isotherms, and potential mechanisms for the sorption of two phthalic acid esters (PAEs), dibutyl phthalate (DBP) and dioctyl phthalate (DOP), on aged refuse. A two-compartment first-order model performed better than a one-compartment first-order model in describing the kinetic sorption of PAEs, with a fast sorption process dominating. Both the Freundlich and Dubinin–Astakhov (DA) models fit the sorption isotherms of DBP and DOP, with the DA model being of a better fit over the range of apparent equilibrium concentrations. The values of the fitting parameters (n, b, E) of the PAEs suggest nonlinear sorption characteristics. Higher predicted partition coefficient values and saturated sorption capacity existed in refuse containing larger quantities of organic matter. The sorption capacity of DOP was significantly higher than that of DBP. PAE sorption was dependent on liquid phase pH. Desorption hysteresis occurred in PAE desorption experiments, especially for the long-chain DOP. PAEs may therefore be a potential environmental risk in landfill.     

Cadmium availability to wheat in five soil series from the Yonne district, Burgundy, France

Preliminary results from the French ASPITET programme demonstrated that Cd background levels in agricultural soils can vary greatly (0.02-6.9 mg Cd kg(-1)) depending on parent material and pedogenic processes (Baize, 1997). However, the total Cd content in soil is often not significantly related to the Cd concentration in edible plant parts. A field case study was undertaken across the southern part of the Yonne district, Burgundy, France. This area has various soil series with either low or high geochemical Cd content in the topsoil. Cd availability in soils sampled at 16 sites belonging to five soil series was investigated using single extractions. In addition, shoots (at stem elongation) and grains (at harvest) of field-grown wheat were collected at the same sites and analysed for macronutrients and trace elements. Cd concentrations in grain varied from 0.015 to 0.146 mg Cd kg(-1) DM depending on soil characteristics, soil series, and plant mineral composition. Cd grain concentrations did not reflect total Cd content in the surface soil layer; however, they were correlated with Cd extracted by a 0.1 M calcium nitrate unbuffered solution, and to a lesser extent with either soil pH or CEC. These three parameters may be useful guides to predict Cd in wheat grain harvested in the Yonne district. An inverse relationship was found between Cd and Cu contents in grain. The highest Cd concentrations in wheat grain occurred in plants grown on Aubues soils which had marginal Cu and Zn deficiencies in shoots. In order of Cd accumulation in wheat grain, soil series may be ranked as follows: Domérien < Carixien, Terres Noires < Sols Marron < Aubues.     

Phthalate esters (PAEs): emerging organic contaminants in agricultural soils in peri-urban areas around Guangzhou, China

This study reports the first data on the concentrations and distribution of phthalate esters (PAEs) in the agricultural soils from the peri-urban areas of Guangzhou city. Σ₁₆PAEs concentrations ranged from 0.195 to 33.6 μg g⁻¹-dry weight (dw). Elevated levels of PAEs were recorded in the vegetable fields located next to the urban districts, and a decreasing trend exists following the distance away from the urban center. Diisobutyl phthalate (DiBP), Di-n-butyl phthalate (DnBP), and Di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs in the agricultural soils. Significant relationship (correlation coefficient R² = 0.85, p < 0.01, n = 40) was present between the accumulation of PAEs and total organic carbons in agricultural soils. In addition, both pH and texture of soils are found to be important factors affecting the level of PAEs. This study shows that the agricultural soils in the peri-urban area of Guangzhou city were moderately polluted by PAEs.     

空气和土壤中酞酸酯的污染及其相关性分析

对天津市11个采样点的空气颗粒物和土壤样品进行采样调查,采用气相色谱/质谱联用仪分析样品中15种酞酸酯类化合物(PAEs)的含量。结果表明,11个采样点空气颗粒物样品中总酞酸酯类化合物(TPAEs)以体积计质量浓度为90.87～1355.70ng/m3,以质量计质量浓度为783.84～8712.37mg/kg;土壤中TPAEs质量浓度为0.53～2.53mg/kg。邻苯二甲酸二丁酯(DBP)与邻苯二甲酸二(2-乙基己基)酯(DEHP)是空气颗粒物和土壤样品中的主要污染物。土壤与空气颗粒物中TPAEs和DBP存在相关关系,Pearson相关系数分别为0.825和0.864(双尾检验,显著性水平0.01),且空气颗粒物中各种PAEs浓度为土壤PAEs浓度的数百至数万倍,说明空气沉降可能是土壤PAEs污染的主要原因之一。     

Evaluating the potential genotoxicity of phthalates esters (PAEs) in perfumes using in vitro assays

We previously reported high levels of phthalate esters (PAEs) added as solvents or fixatives in 47 brands of perfumes. Diethyl phthalate was the most abundant compound (0.232–23,649 ppm), and 83.3% of the perfumes had levels >1 ppm, the threshold limit cited by a Greenpeace investigation. All samples had dimethyl phthalate levels higher than its threshold limit of 0.1 ppm, and 88, 38, and 7% of the perfumes had benzyl butyl phthalate, di(2-ethylhexyl) phthalate, and dibutyl phthalate levels, respectively, above their threshold limits. The role of PAEs as endocrine disruptors has been well documented, but their effect on genotoxic behavior has received little attention. We used in vitro single-cell gel electrophoresis (comet) and micronucleus (MN) assays with human lymphoblastoid TK6 cells to evaluate the genotoxic potency of 42 of the same perfumes and to determine its association with PAEs. All perfumes induced more DNA damage than a negative control (NEG), ≥ 90% of the samples caused more damage than cells treated with the vehicles possibly used in perfume’s preparations such as methanol (ME) and ethanol (ET), and 11.6% of the perfumes caused more DNA damage than a positive control (hydrogen peroxide). Chromosome breakage expressed as MN frequency was higher in cells treated with 71.4, 64.3, 57.1, and 4.8% of the perfumes than in NEG, cells treated with ME or ET, and another positive control (x-rays), respectively. The genotoxic responses in the comet and MN assays were not correlated. The comet assay indicated that the damage in TK6 cells treated with five PAEs at concentrations of 0.05 and 0.2 ppm either individually or as a mixture did not differ significantly from the damage in cells treated with the perfumes. Unlike the comet assay, the sensitivity of the MN assay to PAEs was weak at both low and high concentrations, and MN frequencies were generally low. This study demonstrates for the first time the possible contribution of PAEs in perfumes to DNA damage and suggests that their use as solvents or fixatives should be regulated. Other ingredients with mutagenic/genotoxic properties, however, may also have contributed to the DNA damage. Future studies should focus on applying a series of assays that use different cellular models with various endpoints to identify the spectrum of genotoxic mechanisms involved.

     

Predictive statistical modelling of cadmium content in durum wheat grain based on soil parameters

Regulatory limits on cadmium (Cd) content in food products are tending to become stricter, especially in cereals, which are a major contributor to dietary intake of Cd by humans. This is of particular importance for durum wheat, which accumulates more Cd than bread wheat. The contamination of durum wheat grain by Cd depends not only on the genotype but also to a large extent on soil Cd availability. Assessing the phytoavailability of Cd for durum wheat is thus crucial, and appropriate methods are required. For this purpose, we propose a statistical model to predict Cd accumulation in durum wheat grain based on soil geochemical properties related to Cd availability in French agricultural soils with low Cd contents and neutral to alkaline pH (soils commonly used to grow durum wheat). The best model is based on the concentration of total Cd in the soil solution, the pH of a soil CaCl₂ extract, the cation exchange capacity (CEC), and the content of manganese oxides (Tamm’s extraction) in the soil. The model variables suggest a major influence of cadmium buffering power of the soil and of Cd speciation in solution. The model successfully explains 88% of Cd variability in grains with, generally, below 0.02 mg Cd kg^?1 prediction error in wheat grain. Monte Carlo cross-validation indicated that model accuracy will suffice for the European Community project to reduce the regulatory limit from 0.2 to 0.15 mg Cd kg^?1 grain, but not for the intermediate step at 0.175 mg Cd kg^?1. The model will help farmers assess the risk that the Cd content of their durum wheat grain will exceed regulatory limits, and help food safety authorities test different regulatory thresholds to find a trade-off between food safety and the negative impact a too strict regulation could have on farmers.

     

Biodegradation of endosulfan by Mortieralla sp. strain W8 in soil: Influence of different substrates on biodegradation

To examine the bioremediation potential of Mortierella sp. strain W8 in endosulfan contaminated soil, the fungus was inoculated into sterilized and unsterilized soil spiked with endosulfan. Wheat bran and cane molasses were used as substrates to understand the influence of different organic materials on the degradation of endosulfan in soil. Strain W8 degraded α- and β-endosulfan in both sterilized and unsterilized soil. In unsterilized soil with wheat bran+W8, α- and β- endosulfan were degraded by approximately 80% and 50%, respectively after 28 d incubation against the initial endosulfan concentration (3 mg kg(-1) dw). The corresponding values for α- and β-endosulfan degradation with wheat bran only were 50% and 3%. Endosulfan diol metabolite was detected after 14 d incubation in wheat bran+W8 whereas it was not found with wheat bran only. Production of endosulfan sulfate, the main metabolite of endosulfan, was suppressed with wheat bran+W8 treatment compared with wheat bran only. It was demonstrated that wheat bran is a more suitable substrate for strain W8 than cane molasses. Wheat bran+W8 is a superior fungus and substrate mix for bioremediation in soil contaminated with endosulfan.     

东莞地下水邻苯二甲酸酯分布特征及来源探讨

在广东东莞地区采集了59组地下水水样和9组地表水水样,采用气相色谱-质谱联用技术进行测定,结果表明,地下水中邻苯二甲酸酯(PAEs)的检出率为39.0％,6种PAEs的质量浓度在未检出～6.70 μg/L.其中,邻苯二甲酸双(2-乙基己基)酯(DEHP)检出率最高,为22.O％,最大值为6.20 μg/L;邻苯二甲酸二...     

Characteristics of heavy metals in soils and grains of wheat and maize from farmland irrigated with sewage

The farmland irrigation with the sewage is a common and better pathway to save the resource of groundwater in Northern China. The investigation was conducted in the farmland along the Fuhe River to explore characteristics of heavy metals in soils and grains of wheat and maize from a long-term sewage-irrigated area of Baoding region. The results showed that the topsoil with long-term sewage irrigation accumulated more Cd, Pb, and Hg compared with that of soil irrigated with groundwater and their corresponding natural background values. Cd concentrations in 48% of sewage-irrigated soil samples exceeded the Chinese safety limitation at 0.6 mg/kg, but less Cd accumulated in crop grains and did not pose the potential health risk. On the contrary, Pb levels in soils irrigated with sewage were lower than the safety limitation but Pb concentrations in 24% of wheat grain samples exceeded the Chinese national safety limit. Long-term sewage irrigation did not increase As, Cr, and Ni concentrations in soils or crop grains. The target hazard quotient (THQ) of heavy metals in edible grains of crops was selected to assess their risk to human health. Total THQ values were higher than 1.0 for the wheat samples from sewage-irrigated area and both sewage-irrigated and smelter-impacted areas, and As is the main contributor to the total THQ and posed the potential risk to human health. Therefore, the accumulation of Cd, Pb, Hg, and As in soils and crops in sewage-irrigated area should be monitored continuously to ensure food safety and security.

     

Distribution,transfer, and health risks of polycyclic aromatic hydrocarbons (PAHs) in soil-wheat systems of Henan Province,a typical agriculture province of China

In order to investigate the distribution, transfer, and human health risks of polycyclic aromatic hydrocarbons (PAHs) in the soil-wheat systems, soil samples from 20 farmlands and corresponding wheat tissues were collected from selected regions of Henan Province in June 2013 and were analyzed to estimate the concentration of PAHs. The total concentrations of 15 PAHs (∑₁₅ PAHs) in soils from Henan Province varied from 6.91 to 72.4 ng/g. Moreover, two-ring to three-ring PAHs (1.59–29.1 ng/g) were the major species in soils, occupying 56.2% of total PAHs. Principal component analysis (PCA)-multiple linear regression (MLR) revealed that fossil fuel burning dominated the input of PAHs in agricultural soils of Henan Province. The range of ∑₁₅ PAHs concentrations in wheat tissues was 13.9–50.9 ng/g, which decreased along the root-straw-grain. Positive correlation among PAHs of soil and wheat tissues showed that PAHs in wheat mainly came from soil and then migrated along root-straw-grain. Moreover, PAHs were accumulated highest in root and lowest in grain. Two-ring to three-ring PAHs were easier to transfer from soil to wheat than five-ring to six-ring PAHs. Consumption of wheat grain created potential risk of cancer in Henan Province.

     

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.