Ozonation catalyzed by homogeneous and heterogeneous catalysts for degradation of DEHP in aqueous phase

Di-(2-ethyl hexyl) phthalate (DEHP), a recalcitrant and an endocrine disrupting chemical, was studied for its removal from wastewater by advanced oxidation process. The effects of pH, transition metal ions, and granular activated carbon (GAC) were investigated. Removal of DEHP increased with increase in pH and among metal ions Cr(III) was found to be the most active catalyst to remove DEHP. In the case of GAC, original carbon (G0) and GAC pre-ozonated in gas phase for 10 min (G10) were tested as catalysts in catalytic ozonation and found G0 to be more active than G10. This is because, during pre-ozonation, basic groups like chromene, pyrones and also graphene layers were oxidized to acidic surface oxygen groups. These basic surface groups are reported to be active catalytic centres for ozone decomposition into .OH which is a strong oxidant. According to kinetic manipulations, DEHP degradation rate constant due to .OH was affected by the catalyst while that due to direct ozonation is same in all cases with or without catalyst. G0 was doped with chromia gels (G0/CrA) to combine the benefits of homogeneous and heterogeneous catalysis. G0/CrA showed lower catalytic efficiency than that of only G0. This might be because of changes in surface structure of GAC caused by doping of chromia gel and changes in chemical nature of Cr(III) during formation of gel. A good correlation was found between the rate constants of ozone decay and DEHP degradation (R2=0.96). This correlation confirms that ozone decomposition into .OH is a critical factor for the activity of a catalyst during ozonation.     

Impact of transverse and longitudinal dispersion on first-order degradation rate constant estimation

A two-dimensional analytical model is employed for estimating the first-order degradation rate constant of hydrophobic organic compounds (HOCs) in contaminated groundwater under steady-state conditions. The model may utilize all aqueous concentration data collected downgradient of a source area, but does not require that any data be collected along the plume centerline. Using a least squares fit of the model to aqueous concentrations measured in monitoring wells, degradation rate constants were estimated at a former manufactured gas plant (FMGP) site in the Midwest U.S. The estimated degradation rate constants are 0.0014, 0.0034, 0.0031, 0.0019, and 0.0053 day(-1) for acenaphthene, naphthalene, benzene, ethylbenzene, and toluene, respectively. These estimated rate constants were as low as one-half those estimated with the one-dimensional (centerline) approach of Buscheck and Alcantar [Buscheck, T.E., Alcantar, C.M., 1995. Regression techniques and analytical solutions to demonstrate intrinsic bioremediation. In: Hinchee, R.E., Wilson, J.T., Downey, D.C. (Eds.), Intrinsic Bioremediation, Battelle Press, Columbus, OH, pp. 109-116] which does not account for transverse dispersivity. Varying the transverse and longitudinal dispersivity values over one order of magnitude for toluene data obtained from the FMGP site resulted in nearly a threefold variation in the estimated degradation rate constant-highlighting the importance of reliable estimates of the dispersion coefficients for obtaining reasonable estimates of the degradation rate constants. These results have significant implications for decision making and site management where overestimation of a degradation rate may result in remediation times and bioconversion factors that exceed expectations. For a complex source area or non-steady-state plume, a superposition of analytical models that incorporate longitudinal and transverse dispersion and time may be used at sites where the centerline method would not be applicable.     

Monod kinetics rather than a first-order degradation model explains atrazine fate in soil mini-columns: Implications for pesticide fate modelling

Pesticide transport models commonly assume first-order pesticide degradation kinetics for describing reactive transport in soil. This assumption was assessed in mini-column studies with associated batch degradation tests. Soil mini-columns were irrigated with atrazine in two intermittent steps of about 30 days separated by 161 days application of artificial rain water. Atrazine concentration in the effluent peaked to that of the influent concentration after initial break-through but sharply decreased while influx was sustained, suggesting a degradation lag phase. The same pattern was displayed in the second step but peak height and percentage of atrazine recovered in the effluent were lower. A Monod model with biomass decay was successfully calibrated to this data. The model was successfully evaluated against batch degradation data and mini-column experiments at lower flow rate. The study suggested that first-order degradation models may underestimate risk of pesticide leaching if the pesticide degradation potential needs amplification during degradation.     

A combined first-order closure/gaussian dispersion model

A dispersion model incorporating a large wind direction shear has been developed for an industrialized coastal area with an indented coastline and rough terrain. The model is based on a first-order closure solution for the vertical spread and a Gaussian profile for the lateral spread. Lateral spread is obtained by numerical integration of turbulent energy spectra. The model is verified against a large number of tracer experiments with near surface release within industrial complexes. The model is shown to correctly simulate shear-enhanced spread out to a distance of 10 km from the source. Part of the observed scatter is believed to be the result of an oversimplified plume rise calculation.     

餐厨垃圾及其组分一级水解动力学模型研究

基于一级水解模型推导出含有单位可挥发性有机物理论沼气产量(ym,mg/L)与水解常数(k,d-1)组合项的动力学模型,将其应用于餐厨垃圾及其组分在厌氧消化过程中产沼气的特性规律分析,为研究厌氧消化机制提供理论基础。结果表明,除了脂肪厌氧消化拟合的R2为0.899 0,其余的均大于0.9,其中餐厨垃圾的R2为0.992 5,淀粉的R2为0.972 4。说明该模型能很好地反映厌氧消化的实际效果。厌氧消化水解速率依次为淀粉餐厨垃圾纤维素蛋白质脂肪。淀粉、餐厨垃圾、纤维素的k分别为0.198 3、0.089 7、0.013 9d-1,蛋白质、脂肪的k都小于零。单组分中淀粉lnym+lnk为4.983 6,表现出最好的产沼气特性;其次是蛋白质和纤维素,其值分别为2.157 8、2.046 6;脂肪产沼气特性最差,其值仅为0.902 4,与淀粉相比降低了81.89%;餐厨垃圾lnym+lnk为4.329 6,是淀粉的86.88%,产气特性仅次于淀粉。     

Integrated toxicity assessment of DEHP and DBP toward aquatic ecosystem based on multiple trophic model assays

Environmental Science and Pollution Research - To comprehensively understand the toxic risks of phthalates to aquatic ecosystems, we examined the acute toxicity of di-(2-ethylhexyl) phthalate...     

危险废物中有机物热降解动力学模型

为研究有机危险废物在高温工业窑炉中的协同处置效果,对典型有机物苯和氯乙烯进行热降解实验。将定量的气态苯、氯乙烯和空气的混合物分别通入高温管式炉中煅烧,用气相色谱质谱仪检测尾气中有机物浓度,确定其热降解动力学特性。结果表明：低温阶段苯和、氯乙烯的热降解率随温度较快速增加,高温阶段缓慢增加,1 000℃以上可完全热降解;延长煅烧时间促进苯和氯乙烯的热降解。最终得到苯和氯乙烯的热降解动力学模型,模型可以用于预测危险废物中有机物高温热降解率。     

Bacterial degradation of acetone in an outdoor model stream

Diurnal variations of the acetone concentration in an outdoor model stream were measured with and without a nitrate supplement to determine if the nitrate supplement would stimulate bacterial degradation of the acetone. Acetone loss coefficients were computed from the diurnal data using a fitting procedure based on a Lagrangian particle model. The coefficients indicated that bacterial degradation of the acetone was occurring in the downstream part of the stream during the nitrate addition. However, the acetone concentrations stabilized at values considerably above the limit of detection for acetone determination, in contrast to laboratory respirometer studies where the acetone concentration decreased rapidly to less than the detection limit, once bacterial acclimation to the acetone had occurred. One possible explanation for the difference in behavior was the limited 6-hour residence time of the acetone in the model stream.     

有机物降解产气率模型研究

根据重庆市生活垃圾的组成特点,自配垃圾试样进行有机物降解实验,根据实验期间试样的质量变化,结合降解反应方程式,计算试样的产气量,并建立产气率模型.实验结果表明,试样质量随时间逐渐降低,呈指数型衰减规律.试样在实验初期产气率增加较快,达到产气高峰后逐渐降低.用建立的产气率模型进行计算,计算结果与实测数据比较接近,说明该产...     

Persistence and degradation of coumaphos in model cattle dipping vats

The stability of coumaphos [O,O-diethyl O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7 yl)phosphorothioatel was studied in model dipping vats under field conditions using 14C-labelled and unlabelled coumaphos, with or without additives. The stability of coumaphos in model vats increased significantly by maintaining a pH of 5 by addition of superphosphate. Copper sulphate amendment did not seem to have any additional effect on stability. Potasan was the major metabolite in addition to chlorferon and 4-methylumbelliferone. Coumaphos concentration was doubled in the sediment of vat treated with copper sulphate as compared to the control vat as a result of emulsion breakdown. Chlorferon was the only metabolite detected in the sediment of the former vat indicating inhibition of the anaerobic degradation.     

Effect of introduced phthalate-degrading bacteria on the diversity of indigenous bacterial communities during di-(2-ethylhexyl) phthalate (DEHP) degradation in a soil microcosm

Four previously isolated di-butyl-phthalate (DBP) degraders were tested for their abilities to degrade di-(2-ethylhexyl) phthalate (DEHP). In aqueous medium supplemented with 100mg/l of DEHP, both isolate G1 and Rhodococcus rhodochrous G2 showed excellent degradative activity; in three days they were able to degrade more than 97% of the added DEHP. Rhodococcus rhodochrous G7 degraded 32.5% of the added DEHP and Corynebacterium nitrilophilus G11 showed the least amount of DEHP degradation. The addition of surfactant Brij 30 at 0.1x critical micelle concentration (2mg/l) significantly improved DEHP degradation by Rhodococcus rhodochrous G2 (more than 90% of the added DEHP was degraded within 24 hours), but slightly inhibited the degradation of DEHP by the isolate G1 and Rhodococcus rhodochrous G7. Based on the 16S rDNA sequence data, isolate G1 was identified as Gordonia polyisoprenivorans. Soil inhibited DEHP degradation by G. polyisoprenivorans G1; fourteen days after a second addition of DEHP, 11.5% of the total added DEHP (i.e., 243.4 microg/g soil) remained detectable. Changes in the bacterial community were monitored using denaturing gradient gel electrophoresis (DGGE) and respective dendrogram analysis. It is clear that DEHP and DEHP plus G. polyisoprenivorans G1 substantially affected the bacterial community structure in the soils. However, as the population of indigenous DEHP degraders increased in the DEPH-treated soil, its bacterial communities resembled those in the DEHP plus G. polyisoprenivorans G1-inoculated soil by Day 17.     

Removal of DEHP in composting and aeration of sewage sludge

The potential of composting and aeration to remove bis(2-ethylhexyl) phthalate (DEHP) from municipal sewage sludge was studied with two dewatered sludges: raw sludge and anaerobically digested sludge. Composting removed 58% of the DEHP content of the raw sludge and 34% of that of the anaerobically digested sludge during 85 days stabilisation in compost bins. A similar removal for the anaerobically digested sludge was achieved in a rotary drum in 28 days. Less than 1% of DEHP was removed with the compost leachate. Although DEHP removal was greater from raw sludge compost than anaerobically digested sludge compost, the total and volatile solids removals were on the same level in the two composts. In the aeration of raw sludge at 20 degrees C the DEHP removals were 33-41% and 50-62% in 7 and 28 days, respectively. Both composting and aeration are concluded to have the potential to reduce the DEHP contents typically found in sewage sludges to levels acceptable for agricultural use.     

粉末活性炭对水溶液中邻苯二甲酸二(2-乙基己基)酯的吸附

采用静态吸附法研究了邻苯二甲酸二(2-乙基己基)酯(DEHP)在粉末活性炭上的吸附性能,探讨了粉末活性炭对DEHP的吸附等温线、吸附动力学和吸附热力学特征。结果表明,粉末活性炭对DEHP吸附等温线符合Langmuir吸附等温式;分别采用拟一级反应、拟二级反应和颗粒内扩散反应模型对吸附动力学过程进行了拟合,实验数据遵循颗粒内扩散模型;在20、30、40和50℃下,对应的吉布斯自由能(ΔG0)分別为-2.014、-1.441、-0.868和-0.296 kJ/mol,表明该反应自发进行;焓变(ΔH0)<0,证实该反应为放热反应;熵变(ΔS0)<0,说明该吸附反应是熵值减小的过程;吸附活化能Ea=7.234 kJ/mol和粘附概率S*=0.036分别介于5～40 kJ/mol和0～1范围内,表明该吸附过程主要为物理吸附;活性炭吸附前后红外谱图分析,也验证物理吸附为PAC吸附DEHP之主要机制。     

组合工艺去除垃圾渗滤液中的DBP和DEHP

探讨了采用实验室规模的生物处理组合工艺(上流式厌氧污泥床+曝气生物滤池+缺氧反应器+膜生物反应器,UASB+BAF+ANO+MBR)处理垃圾渗滤液过程中,邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DE-HP)两种内分泌干扰物在各工艺段的去除效率和机理。测定结果表明,对于DBP和DEHP浓度分别为164.4μg/L和215.0μg/L的原水,总出水浓度分别降至11.8μg/L和10.4μg/L,去除率分别达到92.9%和95.2%,处理效果良好。其中DBP在处理工艺中逐级降解,主要是微生物的降解作用。MBR是DEHP的主要去除工艺段,去除比例达到56.6%,膜截留效果明显。采用生物处理组合工艺可实现对垃圾渗滤液中DBP和DEHP的同时高效去除。     

Leaching and degradation of 21 pesticides in a full-scale model biobed

Filling and cleaning of pesticide sprayers presents a potential risk of pollution of soil and water. Three different solutions for handling sprayers have been suggested: Filling and cleaning in the field, filling and cleaning on hard surfaces with collection of the waste water, and filling and cleaning on a biobed, which is an excavation lined with clay and filled with a mixture of chopped straw, sphagnum and soil with turf on top, and with increased sorption capacity and microbial activity for degradation of the pesticides. In the present study the degradation and leaching of 21 pesticides (5 g of each) was followed in an established full-scale model biobed. Percolate was collected and analysed for pesticide residues, and the biobed material was sampled at three different depths and analysed by liquid chromatography double mass spectrometry (LC-MSMS). During the total study period of 563 days, no traces of 10 out of 21 applied pesticides were detected in the percolate (detection limits between 0.02 and 0.9 μg l⁻¹) and three pesticides were only detected once and at concentrations below 2 μg l⁻¹. During the first 198 days before second application, 14% of the applied herbicide bentazone was detected in the leachate with maximum and mean concentrations of 445 and 172 μg l⁻¹, respectively. About 2% of the initial mecoprop and fluazifop dose was detected in the percolate, with mean concentrations of 23 μg l⁻¹, while MCPA and dimethoate had mean concentrations of 3.5 and 4.7 μg l⁻¹, respectively. Leachate concentrations for the remaining pesticides were generally below the detection limit (0.02–0.9 μg l⁻¹, below 1% of applied). Sorption studies of five pesticides showed that compounds with a low K_d value appeared in the leachate. After 169 days, all pesticides in the biobed profile were degraded to a level below 50% of the calculated initial dose. Pesticides with K_oc values above 100 were primarily found in the uppermost 10 cm and degraded slowest due to the low bioavailability. The 11 most degradable pesticides were all degraded such that less than 3% remained in the biobed after 169 days.

Following second pesticide application of the biobed, leachate was sampled 215 and 365 days after the treatment. This showed the same pesticides to be leached out and at concentrations comparable to those of the first treatment. The same pesticides as after the first treatment were retained in the biobed.     

分散固相萃取法萃取再生水中DBP与DEHP

为定量分析再生水中邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)痕量环境激素,考察了分散固相萃取(DSPE)预处理方法的萃取条件,并用于实际再生水样的预处理分析。结果表明,当萃取剂(HC-C18)用量为0.20 g、洗脱剂为6 mL乙酸乙酯、萃取时间为20 min、摇床振荡速度为200 r·min-1、萃取温度为50 ℃时,DBP与DEHP回收率分别为96.91%和101.82%。2种物质在0.50~50.00 μg·L-1范围内线性良好,相关系数(R2)分别为0.998 6和0.998 8,检出限分别是0.05和0.008 μg·L-1,加标回收率平均为96.58%和97.23%,相对标准偏差分别为3.37%~8.29%和4.91%~5.74%。该方法无需过滤水样,能够减少目标物在过滤过程中的损失,预处理时间短,且不会造成萃取小柱堵塞,适用于水质变化大、悬浮物含量高的再生水分析。采用DSPE-GC-MS方法对再生水中DBP、DEHP检测分析,方法的准确度和精密度满足痕量物质分析要求。     

The influence of aerosol dynamics on indoor exposure to airborne DEHP

A mass-balance model was extended to investigate the influence of aerosol particles on the accumulation of indoor airborne DEHP, which allows the consideration of a variable particle concentration. The calculated gas-phase di-2-ethylhexyl phthalate (DEHP) concentration is consistent with those measured within residences in both the United States and Europe. Model predictions suggest that there are differences of more than 10% of particle-phase DEHP concentrations between the variable-particle-concentration case and the constant one for over half (578 days) within the calculation time of 1000 days. Airborne DEHP consists primarily of a particle phase. The exposure data indicate that the influence of particle dynamics remains significant throughout the calculation period, and the size fraction of 0–0.5 μm contributes the most, at 39.1%, to the total exposure to particle-phase DEHP as a result of a strong “source” effect which brings particles into the indoor air and a weak “sink” effect which removes particles from the indoor air. The sensitivity analysis indicates that deposition exhibits the most apparent influence, and particle emission from cooking is a significant factor, as cooking is the main source of particles in the size fraction of 0–0.5 μm. The sensitivity analysis also shows that particle penetration has a less obvious influence on the exposure to airborne DEHP because air exchange rate caused penetration introduces and removes particles simultaneously, thus having a limited influence on the airborne DEHP; while resuspension exhibits the weakest influence because it contributes little to the small particles which are the main component of aerosol particles indoors. Strategies for enhancing deposition and reducing particle emissions from cooking and penetration may be helpful to reduce residents’ exposure to airborne SVOCs.     

光源对光催化降解甲醛效果的影响及预测模型

利用环境测试舱模拟不同光源种类和光照强度下的室内环境,以甲醛溶液的光催化降解为探针反应,分析Ce-TiO2光催化降解甲醛溶液效果与光源的关系。并且采用指数平滑法中的3次指数平滑模型,建立Ce—TiO2光催化降解甲醛溶液效果的预测模型,预测结果表明实测值与预测值误差小,预测值精确度高,这为光催化降解甲醛溶液的研究,提供了一个新的思路。     

建立数学模型分析UV-Fenton对金属切削液废水的降解

采用UV/Fenton技术处理金属切削液废水,并通过正交实验和单因素实验得到了最佳工作条件为:pH=2.5,H2O2(浓度30%)投加量=127.5 mL/L,Fe2+投加量=24.8 mmol/L,总反应时间=3 h,投加次数6次,此条件下金属切削液废水COD去除率达到95%。最后,通过正交实验数据和单因素模型方程利用1st Opt进行多元非线性拟合建立UV/Fen-ton对金属切削液废水COD降解率的数学模型方程,然后进行分析讨论。     

Including degradation products of persistent organic pollutants in a global multi-media box model

GOAL, SCOPE AND BACKGROUND: Global multi-media box models are used to calculate the fate of persistent organic chemicals in a global environment and assess long-range transport or arctic contamination. Currently, such models assume substances to degrade in one single step. In reality, however, intermediate degradation products are formed. If those degradation products have a high persistence, bioaccumulation potential and / or toxicity, they should be included in environmental fate models. The goal of this project was to gain an overview of the general importance of degradation products for environmental fate models, and to expand existing, exposure-based hazard indicators to take degradation products into account. METHODS: The environmental fate model CliMoChem was modified to simultaneously calculate a parent compound and several degradation products. The three established hazard indicators of persistence, spatial range and arctic contamination potential were extended to include degradation products. Five well-known pesticides were selected as example chemicals. For those substances, degradation pathways were calculated with CATABOL, and partition coefficients and half-lives were compiled from literature. RESULTS: Including degradation products yields a joint persistence value that is significantly higher than the persistence of the parent compound alone: in the case of heptachlor an increase of the persistence by a factor of 58 can be observed. For other substances, the increase is much smaller (4% for alpha-HCH). The spatial range and the arctic contamination potential (ACP) can increase significantly, too: for 2,4-D and heptachlor, an increase by a factor of 2.4 and 3.5 is seen for the spatial range. However, an important increase of the persistence does not always lead to a corresponding increase in the spatial range: the spatial range of aldrin increases by less than 50%, although the persistence increases by a factor of 20 if the degradation products are included in the assessment. Finally, the arctic contamination potential can increase by a factor of more than 100 in some cases. DISCUSSION: Influences of parent compounds and degradation products on persistence, spatial range and ACP are discussed. Joint persistence and joint ACP reflect similar characteristics of the total environmental exposure of a substance family (i.e., parent compound and all its degradation products). CONCLUSIONS: The present work emphasizes the importance of degradation products for exposure-based hazard indicators. It shows that the hazard of some substances is underestimated if the degradation products of these substances are not included in the assessment. The selected hazard indicators are useful to assess the importance of degradation products. RECOMMENDATIONS AND PERSPECTIVES: It is suggested that degradation products be included in hazard assessments to gain a more accurate insight into the environmental hazard of chemicals. The findings of this project could also be combined with information on the toxicity of degradation products. This would provide further insight into the importance of degradation products for environmental risk assessments.