Occurrence and migration of microplastics and plasticizers in different wastewater and sludge treatment units in municipal wastewater treatment plant

● Reduce the quantifying MPs time by using Nile red staining. ● The removal rate of MPs and PAEs in wastewater and sludge were investigated. ● MPs and PAEs were firstly analyzed during thermal hydrolysis treatment. ● The removal of PAEs from wastewater and sludge was mainly biodegradation. Microplastics (MPs) and plasticizers, such as phthalate esters (PAEs), were frequently detected in municipal wastewater treatment plants (MWTP). Previous research mainly studied the removal of MPs and PAEs in wastewater. However, the occurrence of MPs and PAEs in the sludge was generally ignored. To comprehensively investigate the occurrence and the migration behaviors of MPs and PAEs in MWTP, a series of representative parameters including the number, size, color, shape of MPs, and the concentrations of PAEs in wastewater and sludge were systematically investigated. In this study, the concentrations of MPs in the influent and effluent were 15.46±0.37 and 0.30±0.14 particles/L. The MP removal efficiency of 98.1% was achieved and about 73.8% of MPs were accumulated in the sludge in the MWTP. The numbers of MPs in the sludge before and after digestion were 4.40±0.14 and 0.31±0.01 particles/g (dry sludge), respectively. Fourier Transform Infrared Spectroscopy (ATR FT-IR) analysis showed that the main types of MPs were polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), and polystyrene (PS). Six PAEs, including phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), ortho dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), and bis(2-ethyl) hexyl phthalate (DEHP), were detected in the MWTP. The concentrations of total PAEs (ΣPAEs) in the influent and effluent were 76.66 and 6.28 µg/L, respectively. The concentrations of ΣPAEs in the sludge before and after digestion were 152.64 and 31.70 µg/g, respectively. In the process of thermal hydrolysis, the number and size of MPs decreased accompanied by the increase of the plasticizer concentration.     

Phenanthrene adsorption by soils treated with humic substances under different pH and temperature conditions

The mobility of phenanthrene (PHE) in soils depends on its sorption and is influenced by either the existing soil humus or exogenous humic substances. Exogenous humic acids (HAs) were added to soil to enhance the amount of soil organic carbon (SOC) by 2.5, 5.0, and 10.0 g kg⁻¹. PHE desorption of the treated soils was determined at two pH levels (3.0 and 6.0) and temperatures (15 and 25 °C). Soil PHE adsorption was related to pH and the type and quantity of added HAs. Humic acid (HA) and fulvic acid (FA) derived from peat had different effects on adsorption of PHE. Adsorption increased at first and then decreased with increasing quantity of exogenous FA. When the soil solution pH (in 0.005 M CaCl₂) was 4.5 or 3.0, the turning points were 2.5 g FA kg⁻¹ at pH 3.0 and 5 g FA kg⁻¹ at pH 4.5. When soil solution pH was 6, the amount of adsorbed PHE was enhanced with increasing exogenous HAs (HA or FA) and amount of adsorption by soil treated with FA was higher than with HA. Adsorption of PHE in the FA treatment at 10.0 g kg⁻¹ was lower than the controls (untreated soil or treatment with HAs at 0 g kg⁻¹) when the soil solution pH was 3.0. This suggests that FA adsorbed by soil was desorbed at low pH and would then increase PHE solubility, and PHE then combined with FA. PHE adsorption was usually higher under lower pH and/or lower temperature conditions. PHE sorption fitted the Freundlich isotherm, indicating that exogenous humic substances influenced adsorption of phenanthrene, which in turn was affected by environmental conditions such as pH and temperature. Thus, exogenous humic substances can be used to control the mobility of soil PAHs under appropriate conditions to decrease PAH contamination.     

The distribution of phthalate esters in indoor dust of Palermo (Italy)

In this work, phthalic acid esters (PAEs): dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate, benzyl butyl phthalate, bis(2-ethylhexyl) phthalate, and di-n-octyl phthalate in indoor dust (used as passive sampler) were investigated. The settled dust samples were collected from thirteen indoor environments from Palermo city. A fast and simple method using Soxhlet and GC–MS analysis has been optimized to identify and quantify the phthalates. Total phthalates concentrations in indoor dusts ranged from 269 to 4,831 mg/kg d.w. (d.w. = dry weight). The data show a linear correlation between total PAEs concentration and a single compound content, with the exclusion of the two most volatile components (DMP and DEP) that are present in appreciable amounts only in two samples. These results suggest that most of the PAEs identified in the samples of settled dust originate from the same type of material. This evidence indicates that, in a specific indoor environment, generally is not present only one compound but a mixture having over time comparable percentages of PAEs. Consequently, for routine analyses of a specific indoor environment, only a smaller number of compounds could be determined to value the contamination of that environment. We also note differences in phthalate concentrations between buildings from different construction periods; the total concentration of PAEs was higher in ancient homes compared to those constructed later. This is due to a trend to reduce or remove certain hazardous compounds from building materials and consumer goods. A linear correlation between total PAEs concentration and age of the building was observed (R = 0.71).     

Adsorptive behaviors of humic acid onto freshly prepared hydrous manganese dioxides

This study focused on the adsorptive behaviors of humic acid onto freshly prepared hydrous MnO₂(s) (δMnO₂), and investigated the feasibility of employing δMnO₂ for humic acid removal from drinking water. Effects of such parameters as molecular mass of humic acid, kinds of divalent cations on adsorptive behaviors and possible mechanisms involved were investigated. This study indicated that humic acid with higher molecular mass exhibited more tendency of adsorbing onto δMnO₂ than that with lower molecular mass. Ca²⁺ facilitated more humic acid adsorption than Mg²⁺; UV-Vis spectra analysis indicated higher capabilities of Ca²⁺ coordinating with acidic functional groups of humic acid than that of Mg²⁺. Additionally, ζ potential characterization indicated that Ca²⁺ showed higher potential of increasing gz potential of δMnO₂ than Mg²⁺. Ca²⁺ of 1.0 mmol/L increased ζ potential of δMnO₂ from ?37 mV (pH 7.9) to +7 mV (pH 7.2), while 1.0 mmol/L Mg²⁺ increased to lower value as ?9 mV (pH 6.5), correspondingly. Fourier transform infrared (FTIR) spectra demonstrated the adsorption of humic acid onto δMnO₂, showing the important roles of-COO^? functional groups and surface Mn-OH in the adsorption of humic acid onto δMnO₂.     

城市污泥中邻苯二甲酸酯的好氧降解规律研究

为评价邻苯二甲酸酯类环境激素在环境中的滞留情况,妥善解决城市污泥的处理处置问题,对城市污泥中6种邻苯二甲酸酯的好氧生物降解规律进行了研究。结果表明,邻苯二甲酸酯的好氧生物降解性随烷基链含碳数的增加而降低;其好氧降解过程可用一级动力学模型描述;其好氧生物降解速率常数与烷基链含碳数、降解半衰期与烷基链含碳数、降解速率常数与正辛醇—水分配系数之间存在良好的相关性。     

Application of ultra-sonication,acid precipitation and membrane filtration for co-recovery of protein and humic acid from sewage sludge

A novel method was applied to co-recover proteins and humic acid from the dewatered sewage sludge for liquid fertilizer and animal feed. The proteins in sewage sludge were first extracted using the processes of ultra-sonication and acid precipitation, and then the humic acid was recovered via membrane filtration. The extraction efficiency was 125.9 mg humic acid?g⁻¹VSS volatile suspended solids (VSS) and 123.9 mg proteins?g⁻¹ VSS at the optimal ultrasonic density of 1.5 W?mL⁻¹. FT-IR spectrum results indicated that the recovered proteins and humic acid showed similar chemical characteristic to the natural proteins and humic acid. The acidic solution (pH 2) could be recycled and used more than 10 times during the co-recovery processes. In addition, the dewatered sludge could be easily biodegraded when the humic acid and proteins are extracted, which was essential for further utilization. These findings are of great significance for recovering valuable nutrient from sewage sludge.     

不同填埋年龄的矿化垃圾中胡敏酸的分子荧光光谱研究

对上海市老港填埋场封场6-10年矿化垃圾中的胡敏酸(HA)进行荧光光谱分析,结果表明,不同封场时间的矿化垃圾中HA的荧光光谱均为宽带峰型,pH值对HA荧光光谱的影响较小.而且随着矿化垃圾封场时间的加长,荧光特征峰波长缓慢增加.     

溶解性有机碳的主要组成对青鳉鱼铜急性毒性的影响

为揭示溶解性有机碳(DOC)的组成对生物配体模型(BLM)预测铜的生物毒性准确性的影响,研究了不同浓度黄腐酸(FA)、腐殖酸(HA)和两者不同浓度比例混合物影响铜对青鳉急性毒性。结果表明:在相同水质条件下,黄腐酸或腐殖酸浓度增加时,铜对青鳉的LC50均增加;两者共存时,当腐殖酸质量百分比从10%增至90%时,铜对青鳉的LC50也增加。当天然水中DOC的组成不确定时,可假设HA和FA的组成比例为1∶1,此时BLM预测铜对青鳉的LC50的偏差最小。     

Investigating into composition,distribution, sources and health risk of phthalic acid esters in street dust of Xi’an City,Northwest China

Phthalic acid esters (PAEs) are widely used as plasticizers and in consumer products, which may enter the environment and present risks to human health. U.S. EPA classifies six PAEs as priority pollutants, which could be accumulated in street dust at the interface of atmosphere, biosphere and geosphere. This study collected a total of 58 street dust samples from Xi’an City in Northwest China and analyzed for concentrations of the priority PAEs. Composition, distribution, sources and health risk of the PAEs were further examined. All the priority PAEs were detected in the street dust. The concentrations of individual PAEs varied between not detected and 183.19 mg/kg. The sum of the 6 priority PAEs (∑6PAEs) ranged from 0.87 to 250.30 mg/kg with a mean of 40.48 mg/kg. The most abundant PAEs in the street dust were di-n-butyl phthalate and di (2-ethylhexyl) phthalate (DEHP). Higher concentrations of ∑6PAEs in the street dust were found in the south and west parts of Xi’an City as well as its urban center, which were possibly attributed to the prevailing northerly Asian winter monsoon. The PAEs in the street dust originated mainly from wide application of plasticizers as well as cosmetics and personal care products. The main pathways of human exposure to PAEs in the street dust were ingestion and dermal adsorption of dust particles. The non-cancer risk of human exposure to PAEs in the street dust was relatively low, while the risk to children was higher than that to adults. The cancer risk of human exposure to DEHP in the street dust was lower than the standard limit value of 10^?6.     

Unwanted metals and hydrophobic contaminants in bioreactor effluents are associated with the presence of humic substances

Biological treatment of landfill leachate is challenging due to the presence of complex compounds. Here, we treated an old landfill leachate using a membrane bioreactor under the following conditions: 24 h for hydraulic retention, 65 days of sludge retention and an average organic load rate of 1.71 ± 0.16 g/L/day. We observed a high removal of ammonia, phosphorous and some metals. However, removal of organic carbon was incomplete. Despite a major removal of suspended solids, hydrophobic and volatile hydrophilic compounds, high concentration of fulvic acid and hydrophilic contaminants was found in the effluent. Overally, we demonstrate that the presence of humic substances in the effluent is associated with the detection of arsenic, copper and chromium and di(2-ethylhexyl) phthalate.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

最大累积率识别中国地表水中邻苯二甲酸酯类关键污染物和复合污染生态风险

邻苯二甲酸酯类物质(phthalic acid esters,PAEs)环境存在量大,研究表明其能对水生生物造成寿命减少、发育不良、细胞受损等负效应.因此,为保护水生生物,我国地表水中PAEs的生态风险需要科学评估.本文利用了风险商法(risk quotient,RQ)、最大累积率法(maximum cumulative ratio,MCR)、联合概率曲线法(joint probability curve,JPC)结合毒性当量的概念构建了三层级生态风险评价体系,借此评估了我国地表水中PAEs的分布情况与生态风险.结果显示,我国地表水中共检出19种PAEs,浓度范围为ND—5616.80μg·L^-1.邻苯二甲酸二(2-乙基)己酯(di(2-ethylhexyl)phthalate,DEHP)和邻苯二甲酸二丁酯(dibutyl phthalate,DBP)环境存在量最高,且DEHP为PAEs风险的主要贡献者.以DEHP为参照物,JPC的结果显示我国PAEs对5%生物造成急性影响的概率为6.25%—24.02%,造成慢性影响的概率为8.05%—27.79%.PAEs对我国水生生态系统,尤其是西北、东北、中部及华东地区存在较高的生态风险.     

Characterization of humic substances in bio-treated municipal solid waste landfill leachate

Considerable organic matter remains in municipal solid waste landfill leachate after biological treatments. Humic substances (HSs) dominate the organic matter in bio-treated landfill leachate. In this study, the HSs from landfill leachate treated by membrane bioreactor (MBR-HSs) were analyzed via elemental analysis, ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, and charge polarized magic-angle spinning-¹³C-nuclear magnetic resonance. The characteristic absorption in the UV wavelength range indicated the presence of high C=C and C=O double bonds within the MBR-HSs. Compared with commercial HSs, MBR-HSs had lower carbon content [48.14% for fulvic acids (FA) and 49.52% for humic acids (HA)], higher nitrogen content (4.31% for FA and 6.16% for HA), lower aromatic structure content, and higher carbohydrate and carboxylic atoms of carbon content. FA predominantly had an aliphatic structure, and HA had less condensed or substituted aromatic ring structures than natural HA. The aromatic carbon content of MBR-HSs was lower than that of humus-derived HSs but higher than that of waste-derived HSs, indicating that MBR-HSs appeared to be more similar to humus-derived HSs than waste-derived HA.     

Interaction between Humic Acid and p-Arsanilic Acid Using Fluorescence Quenching Approach

P-arsanilic acid(p-ASA),as a kind of organoarsenic feed additive,has been widely used in poultry and swine breeding.However,it has caused the arsenic pollution around the farm.Currently data shows humic acid(HA)is closely to the migration and transformation of p-ASA.Therefore,the interaction between p-ASA and HA was investigated by using the method of fluorescence quenching titration.The association constant changed from2.74 to 4.88 L·mol-1at a p H varying from 5 to 9 and reached the maximum at p H 7.In addition,log K varied from4.15 to 5.02 L·mol-1when the temperature increased from 15℃to 35℃.The log K increased with an increase in the concentration of HA.The dominant mechanism between p-ASA and HA is static quenching.The primary interaction force was likely the hydrogen bond,and the binding behavior occurred on the As-O stretch of p-ASA and the carboxylic acid C=O stretch of HA.The results showed that dissolved organic matters could affect the fate and biogeochemical cycling of organoarsenic pharmaceuticals in aquatic ecosystems.     

The influences of different organic fractions in refuse on the sorption and bioavailability of dibutyl phthalate

The structure and composition of the organic matter in landfilled refuse might have an influence on the migration and transformation of dibutyl phthalate (DBP). Humic acid (HA) and humin (HU) were separated from aged-refuse to determine the influences of different organic fractions in the refuse on the sorption and bioavailability of DBP. The sorption kinetics and isotherms for the sorption of DBP to HA, HU, and whole refuse were determined. The results showed that the sorption constants (K) and nonlinearities decreased in the order HU?>?whole refuse?>?HA. The HA had lower K values than did the other refuse fractions, and it retarded the biodegradation of DBP over a short degradation period (48?h). Increasing the amount of HA present caused the amount of DBP that was biodegraded to decrease significantly, 81.3% of the DBP sorbed to HA being degraded in the original experiments after 48?h but 21.8% of the DBP being degraded when three times as much HA was used. Similar results were not observed when the amount of HU used was changed. These findings suggest that HA plays an important role in the biodegradation of DBP adsorbed by refuse.     

邻苯二甲酸酯类对水生食物链的影响研究进展

邻苯二甲酸酯类(PAEs)增塑剂被普遍用于塑料制品中,在大气、水等环境中广泛存在,其潜在危害受到关注。水环境中的PAEs,从藻类等初级生产者吸收,到浮游动物、游泳动物等通过鳃和皮肤直接接触或捕食摄取,在水生生物之间转化和传递。笔者总结了PAEs在水生食物链中不同营养级生物体的含量,分析了PAEs在食物链中富集和转化的影响因素(辛醇-水分配系数Kow、代谢转化、生长阶段等)。目前的研究表明PAEs可能在食物链中传递,最终在较高营养级生物体中富集。同时总结了5种PAEs(邻苯二甲酸二丁酯、邻苯二甲酸二乙酯、邻苯二甲酯丁苄酯、邻苯二甲酸二(2-乙基)己酯和邻苯二甲酸二甲酯)对水生生物的毒性效应的研究进展,已有研究表明PAEs对藻类的细胞器和抗氧化体系,对鱼类的生殖系统、内分泌系统和抗氧化体系都有一定程度损伤。PAEs在食物链中传递和富集现象的存在会对高营养级水生生物产生潜在危害。针对目前PAEs在食物链中传递的研究数量较少、结构简单等问题,对未来研究方向做了简要分析和展望。     

Adsorption of humic acid from aqueous solution on bilayer hexadecyltrimethyl ammonium bromide-modified zeolite

Surfactant-modified natural zeolites (SMNZ) with different coverage types were prepared by loading hexadecyltrimethyl ammonium bromide (HTAB) onto the surface of a natural zeolite. The adsorption behavior of humic acid (HA) on SMNZ was investigated. Results indicate that the adsorbent SMNZ exhibited a higher affinity toward HA than the natural zeolite. HA removal efficiency by SMNZ increased with HTAB loading. Coexisting Ca²⁺ in solution favored HA adsorption onto SMNZ. Adsorption capacity decreased with an increasing solution pH. For typical SMNZ with bilayer HTAB coverage, HA adsorption process is well described by a pseudo-second-order kinetic model. The experimental isotherm data fitted well with the Langmuir model. Calculated maximum HA adsorption capacities for SMNZ with bilayer HTAB coverage at pH 5.5 and 7.5 were 63 and 41 mg·g^-1, respectively. E2/E3 (absorbance at 250 nm to that at 365 nm) and E4/E6 (absorbance at 465 nm to that at 665 nm) ratios of the residual HA in solution were lower than that of the original HA solution. This indicates that the HA fractions with high polar functional groups, low molecular weight (MW), and aromaticity had a stronger tendency for adsorption onto SMNZ with bilayer HTAB coverage. Results show that HTAB-modified natural zeolite is a promising adsorbent for removal of HA from aqueous solution.     

Degradation of bisphenol A by photo-fenton processes

The photo-Fenton reactions, which could yield hydroxyl radicals via the catalytic degradation of H₂O₂ by Fe(II), were focused as one of the abiotic degradation processes of bisphenol A (BPA) in surface waters. At pH 6, in the presence of H₂O₂ only, 32% of BPA was degraded after 120?min of irradiation. However, 97% of BPA was degraded in the presence of both H₂O₂ and Fe(II). Without light irradiation, no BPA degradation was observed even in the presence of Fe(II) and H₂O₂. These results show that photo-Fenton processes are effective in the natural attenuation of BPA in surface water. In addition, the presence of humic acids (HAs), which were of more aliphatic nature, resulted in enhancing BPA degradation via the photo-Fenton processes. Therefore, HAs can be one of the important factors in enhancing the degradation of BPA in surface water via the photo-Fenton processes.     

Influence of humic acid on the sorption of uranium(IV) to kaolin

Safety assessments for radioactive waste disposal require estimations of the migration of radionuclides in soils. The influence of humic acid (HA) on the sorption of uranium in its +4 oxidation state to kaolin has been examined from pH 4 to 8, with HA concentrations of 15–200 ppm. In the absence of HA, 20–40% of the U(IV) was in solution, with more sorption occurring at higher pH. The presence of HA solubilised up to 90% of the uranium with higher solubilities at higher HA concentrations and higher pH values. Uranium sorption was mapped against HA sorption, and it was found that there was a lower level of U(IV) sorption than can be accounted for by just measuring HA sorption. However, this effect got less marked as the pH rose. Sensitivity analysis indicated that the fraction of surface-bound HA is the controlling parameter for modelling in these systems.     

Degradation of pentachlorophenol in a contaminated soil suspension using hybrid catalysts prepared via urea�Cformaldehyde polycondensation between iron(III)-tetrakis(p-hydroxyphenyl)porphyrin and humic acid

Hybrid catalysts were synthesized by attaching iron(III)-tetrakis(p-hydroxyphenyl)porphyrin (FeTPP(OH)₄) to humic acid (HA) via urea–formaldehyde polycondensation. FTIR spectra of the prepared catalysts indicated that the catalysts prepared via urea–formaldehyde polycondensation contained cross-links between the phenolic groups of FeTPP(OH)₄ and HA, which contains aliphatic amine functional groups. The prepared catalysts were examined for their ability to catalyze the oxidative degradation of pentachlorophenol (PCP) in a contaminated soil suspension. The levels of PCP degradation and dechlorination for the hybrid catalysts were significantly higher than those for the non-modified catalyst, FeTPP(OH)₄.