Adsorption of Phthalic Acid Esters by Humic Acid and Its Research Progress

Humic acid is rich in highly electronegative oxygen-containing organic functional groups,so it has high reactivity and can adsorb phthalic acid ester(PAEs)in the environment to reduce the risk of environmental pollution from PAEs.In this paper,the extraction,characterization and adsorption models of humic acid were reviewed,and the research status of adsorption of PAEs by humic acid was further summarized.Based on these,the feasibility and observable application prospect of humic acid as a cheap adsorbent were analyzed.

Abiotic degradation of four phthalic acid esters in aqueous phase under natural sunlight irradiation

Abiotic degradability of four phthalic acid esters （PAEs） in the aquatic phase was evaluated over a wide pH range 5-9. The PAE solutions in glass test tubes were placed either in the dark and under the natural sunlight irradiation for evaluating the degradation rate via hydrolysis or photolysis plus hydrolysis, respectively, at ambient temperature for 140 d from autumn to winter in Osaka, Japan. The efficiency of abiotic degradation of the PAEs with relatively short alkyl chains, such as butylbenzyl phthalate （BBP） and di-nbutyl phthalate （DBP）, at neutral pH was significantly lower than that in the acidic or alkaline condition. Photolysis was considered to contribute mainly to the total abiotic degradation at all pH. Neither hydrolysis nor photolysis of di-ethylhexyl phthalate （DEHP） proceeded significantly at any pH, especially hydrolysis at neutral pH was negligible. On the other hand, the degradation rate of di- isononyl phthalate （DINP） catalyzed mainly by photolysis was much higher than those of the other PAEs, and was almost completely removed during the experimental period at pH 5 and 9. As a whole, according to the half-life （t1/2） obtained in the experiments, the abiotic degradability of the PAEs was in the sequence： DINP （32-140 d） 〉 DBP （50-360 d）, BBP （58-480 d） 〉 DEHP （390-1600 d） under sunlight irradiation （via photolysis plus hydrolysis）. Although the abiotic degradation rates for BBP, DBP, and DEHP are much lower than the biodegradation rates reported, the photolysis rate for DINP is comparable to its biodegradation rate in the acidic or alkaline condition.

Biodegradability of four phthalic acid esters under anaerobic condition assessed using natural sediment

Biodegradability of di-n-butyl phthalate （DBP）, butylbenzyl phthalate （BBP）, di-ethylhexyl phthalate （DEHP）, and di-isononyl phthalate （DINP） under an anaerobic condition was evaluated using three natural sediment microcosms obtained from ponds in Osaka, which had not been significantly polluted by the chemicals. The degradabilities of the four phthalic acid esters（PAEs） were analyzed by a first-order kinetic model with a lag phase and ranked as DBP〉BBP〉〉DEHP〉DINP. The PAEs with shorter alkyl-chains, DBP and BBP, were degraded with quite short lag phases near to zero and short half-lives of a few days. The PAEs with longer alkyl-chains, DEHP and DINP, were degraded with lag phases of 5-30 d and the quite long half-lives of a couple of hundred days. Although no data was available on the anaerobic biodegradability of D1NP before this study, it was clarified that DINP can be degraded with slow degradation rates. The fact that all the three intact sediments were capable of biodegradation of the PAEs suggests that potential of anaerobic biodegradation of PAEs is widespread in the aquatic environment.

QSPR Analysis of the Physicochemical Properties for Phthalic Acid Esters

Based on quantitative structure-property relationship （QSPR） of organic compounds, the molecular connectivity indices of 21 phthalic acid ester compounds were extracted. Relationship between the physicochemical properties （n-octanol/air partition coefficient, vapor pressure, water solubility） and the molecular connectivity indices of phthalic acid ester compounds have been established by multiple linear regression （MLR） method. The results showed that the zero-order valence connectivity index （0Xu） is the topology parameter which affects octanol/water partition coefficient and water solubility, and the topology parameter which affects vapor pressure is the first-order connectivity index （1X）. This indicated to a certain extent_that the molecular connectivity indices can be well used to express the quantitative relationship between the physicochemical properties and structure descriptions of phthalic acid ester compounds. The models constructed have good robustness and highly predictive capability.

Screening of Degrading Bacteria for Phthalic Acid Esters Under Cadmium Stress and Its Application

In order to enrich the degrading microbial resources for phthalic acid esters(PAEs)under cadmium stress,a degrading bacterium B-7 for di(2-ethylhexyl)phthalate(DEHP)was screened from the strains stored in the laboratory by means of inorganic salt liquid medium containing DEHP and cadmium,and the characteristics of the strain were studied.Strain B-7 was Bacillus amyloliquefaciens,which had high biosafety and excellent degradability to DEHP.The optimum temperature for degradation was 25–40℃,and the optimum pH value was 6–8.Strain B-7 was cultured in inorganic salt medium(MSM)with an initial DEHP concentration of 400 mg/L and cadmium content of 10 mmol/L for 4 d,and its degradation rate of DEHP was up to 93.1%.In addition,the strain had a strong degradation ability to dimethyl phthalate(DMP),diethyl phthalate(DEP),and dibutyl phthalate(DBP).In soil contaminated by cadmium and DEHP,the synergic degradation of B-7 and indigenous microorganisms in soil significantly increased the degradation rate of DEHP,indicating that this strain had potential application value in the field of microbial remediation of soil contaminated by cadmium and PAEs.

Concentration and source identification of polycyclic aromatic hydrocarbons and phthalic acid esters in the surface water of the Yangtze River Delta,China

The pollution from polycyclic aromatic hydrocarbons（PAHs） and phthalic acid esters（PAEs） in the surface water of the rapidly urbanized Yangtze River Delta region was investigated.Fourteen surface water samples were collected in June 2010.Water samples were liquid-liquid extracted using methylene chloride and analyzed by gas chromatography-mass spectrometry.Concentrations of PAHs and PAEs ranged 12.9-638.1 ng/L and 61-28550 ng/L,respectively.Fluoranthene,naphthalene,pyrene,phenanthrene,di-2ethylhexyl phthalate,and di-n-butyl phthalate were the most abundant compounds in the samples.The water samples were moderately polluted with benzo[a]pyrene according to China＇s environmental quality standard for surface water.The two highest concentrations of PAHs and PAEs occurred in samples from Taihu Lake,Wuxi City and the western section of Yangchenghu Lake.Potential sources of pollution at S7 were petroleum combustion and the plastics industry,and at Yangchenghu Lake were petroleum combustion and domestic waste.Pollution in samples from the Beijing-Hangzhou Grand Canal originated from diesel engines.There were no obvious sources of pollution for the other water samples.These results can be used as reference levels for future monitoring programs of pollution from PAHs and PAEs.

Distribution and sources of polycyclic aromatic hydrocarbons and phthalic acid esters in water and surface sediment from the Three Gorges Reservoir

After the impoundment of the Three Gorges Reservoir（TGR）, the hydrological situation of the reservoir has changed greatly. The concentration and distribution of typical persistent organic pollutants in water and sediment have also changed accordingly. In this study, the concentration, distribution and potential sources of 16 polycyclic aromatic hydrocarbons（PAHs） and 6 phthalic acid esters（PAEs） during the water drawdown and impoundment periods were investigated in water and sediment from the TGR. According to our results, PAHs and PAEs showed temporal and spatial variations. The mean ΣPAH and ΣPAE concentrations in water and sediment were both higher during the water impoundment period than during the water drawdown period. The water samples from the main stream showed larger ΣPAH concentration fluctuations than those from tributaries. Both the PAH and PAE concentrations meet the Chinese national water environmental quality standard（GB 3838-2002）. PAH monomers with 2–3 rings and 4 rings were dominant in water, and 4-ring and 5–6-ring PAHs were dominant in sediment. Di-n-butyl phthalate（DBP） and di-2-ethylhexyl phthalate（DEHP）were the dominant PAE pollutants in the TGR. DBP and DEHP had the highest concentrations in water and sediment, respectively. The main source of PAHs in water from the TGR was petroleum and emissions from coal and biomass combustion, whereas the main sources of PAHs in sediments included coal and biomass combustion, petroleum, and petroleum combustion. The main source of PAEs in water was domestic waste, and the plastics and heavy chemical industries were the main sources of PAEs in sediment.

Abiotic association of phthalic acid esters with humic acid of a sludge landfill

The abiotic association between phthalic acid esters （PAEs） and humic substances （HS） in sludge landfill plays an important role in the fate and stability of PAEs. An equilibrium dialysis combined with 14C-labeling was used to study the abiotic association of two abundant PAEs （diethyl phthalate and di-n-butyl phthalate） with humic acid （HA） isolated from a sludge landfill with different stabilization times and different molecular weights. Ele- mental analysis and Fourier Transform Infrared Spectro- photometer （FTIR） suggested that high KA value of HA was related to the high aromatic content and large molecular weight of HA. The results indicated that the association strength of PAEs with HA depended on both the properties of the PAEs and the characteristics of HA. The KA values of the association were strongly dependent on solution pH, and decreased dramatically as the pH was increased from 3.0 to 9.0. The results suggested that non- specific hydrophobic interaction between PAEs and HA was the main contributor to the association of the PAEs with HA. The interactive hydrogen-bonds between the HA and the PAEs molecules may also be involved in the association.

Ultrasonic wave extraction and simultaneous analysis of polycyclic aromatic hydrocarbons (PAHs) and phthalic esters in soil

A method is developed for detection of polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil samples. Ultrasonic Wave Extraction under airtight circumstances is adopted to extract the analytes in soil samples with n-hexane–acetone(V:V=1:1) as extraction solvent. This method has several advantages, including high extraction efficiency, short time, convenience and simplicity. It can be used to detect polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil.

Unveiling the Nexus the link between water quality index and phthalic acid ester concentrations in Tigris River

Monitoring water quality in an aquatic system is a crucial objective in pursuing sustainable development,despite the challenges posed by water scarcity and the impact of climate change.The objective of the present study was to examine the water quality of the Tigris River along its course from the point of entry into Baghdad city to its exit,particularly in the presence of Phthalic Acid Esters(PAEs).In both dry and wet seasons and from five sites of the river,nine environmental factors(Turbidity,Total dissolved solids,pH,dissolved oxygen,Chloride,nitrate,phosphate,sulfate,and Biological oxygen demand)and three PAEs(di-n-butyl phthalate(DBP),di-isononyl phthalate(DiNP),and di-2-ethyl hexyl phthalate(DEHP))were investigated.Results revealed that the river has high levels of turbidity and Total dissolved solids,slightly alkaline,and well-aerated(dissolved oxygen>7 mg/L).Chloride,nitrate,phosphate,and sulfate values varied between seasons,as high values were recorded in the wet season.Biochemical oxygen demand levels were higher during the dry season.The highest value of total PAEs(2.20μg/L)was observed during the dry season,and the lowest value was in the wet season(1.16μg/L).The HQ results revealed that the river was ranked as a moderate risk area.However the water quality index and environmental risk index classified the water quality as a poor category,with a high-risk score in the study sites within Baghdad city.Therefore,despite the acceptable limit of PAEs in the river's water(<3μg/L),its presence is an early alarm to withdraw attention to its environmental risk.These findings highlight the need for appropriate measures to control and remove pollutants to ensure a safe and healthy water supply in the Tigris River.

Comparison of Di-n-methyl Phthalate Biodegradation by Free and Immobilized Microbial Cells

To compare the biodegradation of di-n-methyl pathalate by free and immobilized microbial cells. Methods The enrichment and isolation technique was used to isolate the microorganism. The PAV-entrapment method was utilized to immobilize the microorganisms. The scanning electron microscophy (SEM) was used to observe the growth and distribution of microbial cells immobilized inside the PVA bead gels. The GC/MS method was used to identify the main intermediates of DMP degradation. Results The microbial cells could grow quite well in PVA gel. The metabolic pathway did not change before and after immobilization of the microbial cells. The degradation rate of immobilized cells was higher than that of free cells. Conclusion The immobilized microbial cells possess advantages than free cells when applied to the biodegradation of toxic organic pollutants.

Removal of Di-n-butyl Phthalate Using Immobilized Microbial Cells

The biodegradation of di-n-butyl phthalate （DBP） using immobilized microbial cells was carded out in an internal airlift loop reactor with ceramic honeycomb supports. A strain that is capable of degrading DBP was isolated from the activated sludge and identified as Bacillus sp. using 16S rDNA sequential analysis. Bacillus sp. could be rapidly attached onto the ceramic honeycomb supports. The immobilized cells could effectively degrade DBP in batch and continuous experiments. When the influent concentration of DBP was 50mg·L^-1, the effluent DBP reached less than lmg.L i with 6h hydraulic retention time （HRT） in continuous experiment. The immobilized microbial cells could grow and accumulate through the biodegradation of DBP, and the rate of degradation is accordingly increased. The possible pathway of DBP biodegradation using immobilized cells was tentatively proposed.

Maternal Thyroid Hormones as Mediators between Phthalate Exposure and Neonatal Birth Weight:A Cross-Sectional Study from the Zunyi Birth Cohort

Studies have shown that exposure to phthalates can affect neonatal birth weight.However,epidemiological evidence on the mediating role of maternal thyroid hormones is limited.Therefore,this study,based on the Compliance Birth Cohort,aimed to reveal the potential mediating function of maternal thyroid hormones during pregnancy between phthalic acid ester(PAE)exposure and neonatal birth weight.The study included 1274 mother−infant pairs.Linear regression analysis revealed a negative association between MIBP and neonatal birth weight(β=−62.236;95%CI:−118.842,−5.631).Bayesian kernel-machine regression(BKMR)indicated a nonlinear negative association between PAE metabolites(PAEs)and birth weight.Linear regression analysis revealed a positive association between neonatal birth weight and FT3(β=41.605;95%CI:2.631,80.380).The BKMR model also found a positive association between thyroid hormones and birth weight but in a nonlinear manner.Additionally,linear regression analyses showed that TSH,TT3,TT4,FT3,and FT4 were associated with PAEs.The BKMR model revealed an inverted U-shaped association of PAEs with TT3 and FT3 and a nonlinear association with TSH,TT4,and FT4.Structural equation modeling revealed that MMP,MIBP,MBP,MEHP,MOP,MBZP,and MEOHP contributed to a net reduction in neonatal birth weight of 32 g through the TT3,FT3,TT4,and FT4 pathways.The findings suggest that exposure to PAEs during pregnancy leads to a reduction in neonatal birth weight,possibly due to the involvement of maternal thyroid hormones as mediators.Controlling maternal thyroid hormone levels during pregnancy may be a viable method to reduce the harmful effects of phthalate exposure on the developing fetus.

Resource utilization of typical biomass wastes as biochars in removing plasticizer diethyl phthalate from water: characterization and adsorption mechanisms

Plastic pollution as a global environmental issue has become a research hotspot,among which the removal of inherent plasticizer(e.g.,phthalic acid esters,PAEs)received increasing attention.However,the effects of biochars derived from different feedstocks on the adsorption of PAEs are poorly understood.Thus,the characteristics of biochars derived from six largely produced biomass wastes in China at 400°C,as well as their performance in adsorption of diethyl phthalate(DEP),one of frequently detected PAEs in aqueous environment,were investigated.The results indicated that the variation in feedstock type showed significant changes in the properties(e.g.,porosity,specific surface area,surface functional groups)of biochars,which affected DEP adsorption and desorption.Pseudosecond order and Freundlich models fitted the adsorption data well,and adsorption mechanisms mainly included hydrophobic effect,followed by micropore filling,hydrogen bonding,andπ-πEDA interactions.Adsorption thermodynamics revealed that the adsorption was a spontaneous and exothermic the adsorption capacities of DEP on these biochars slightly decreased with the increasing pH but increased with the increasing ionic strength.Among these biochars,the giant reed biochar with relatively higher DEP adsorption and low desorption exhibited the great efficiency for DEP removal as an environment-friendly sorbent.These results highlighted the significant roles of micropore filling and hydrogen bond in determining adsorption capacity of designed biochars prepared from selecting suitable agricultural straws and wetland plant waste to typical plasticizer.The findings are useful for producing designed biochars from different biomass wastes for plasticizer pollution control.

Occurrence and fate of endogenous steroid hormones,alkylphenol ethoxylates, bisphenol A and phthalates in municipal sewage treatment systems

Steroid hormones, alkylphenol ethoxylates（APEOs） and phthalic acid esters（PAEs） are emerging endocrine disrupting chemicals（EDCs） that can interfere with the endocrine function in organisms at low concentrations. The occurrence, distribution behavior, removal rate and the fate of 31 target EDCs in sewage treatment plants, which consist of various treatment facilities and receiving water in Hong Kong, were investigated. Estrone,nonylphenol-di-ethoxylate and diethyl phthalate were found to be dominant in each group of influent samples with concentrations ranging from 11–33, 747–3945 and 445–4635 ng/L,respectively. Conversely, progesterone, nonylphenol-mono-ethoxylate and bis（2-ethylhexyl）phthalate were the most abundant in dewatered sludge, with concentrations ranging from 0.9–237, 75–19,743 and 4310–37,016 ng/g（dry weight）. The removal rates of primary sedimentation and disinfection approaches were lower than 30% for most of the chemicals,while those of activated sludge and reverse osmosis were greater than 80% for more than two-thirds of the compounds, noticeably decreasing the estrogenic risk of sewage discharged into the environment. Steroid hormones were removed via biological degradation, while some APEOs and PAEs adsorbed to the sludge. Victoria Harbor poses a low to medium estrogenic risk mainly contributed by estrone and estradiol and deserves attention.