Biodegradation of mono-alkyl phthalate esters in natural sediments

Mono-alkyl phthalate esters (MPEs) are primary metabolites of di-alkyl phthalate esters (DPEs), a family of industrial chemicals widely used in the production of soft polyvinyl chloride and a large range of other products. To better understand the long term fate of DPEs in the environment, we measured the biodegradation kinetics of eight MPEs (-ethyl, -n-butyl, -benzyl, -i-hexyl, -2-ethyl-hexyl, -n-octyl, -i-nonyl, and -i-decyl monoesters) in marine and freshwater sediments collected from three locations in the Greater Vancouver area. After a lag period in which no apparent biodegradation occurred, all MPEs tested showed degradation rates in both marine and freshwater sediments at 22 °C with half-lives ranging between 16 and 39 h. Half-lives increased approximately 8-fold in incubations performed at 5 °C. Biodegradation rates did not differ between marine and freshwater sediments. Half-lives did not show a relationship with increasing alkyl chain length. We conclude that MPEs can be quickly degraded in natural sediments and that the similarity in MPE degradation kinetics among sediment types suggests a wide occurrence of nonspecific esterases in microorganisms from various locations, as has been reported previously.     

水环境中邻苯二甲酸酯的迁移转化研究

邻苯二甲酸酯(PAEs)是一类普遍使用的化学工业品,并广泛存在于环境中.已有研究表明,PAEs环境内分泌干扰物,对人类和自然环境有非常大的危害.总结了PAEs在地表水中的分布和在水体中迁移转化的主要途径,如水解、光降解、与颗粒物(沉积物或悬浮颗粒物)的作用以及生物转化作用,并指出对它们进一步研究的重要性和今后主要的研究方向.     

Anaerobic degradation of diethyl phthalate, di-n-butyl phthalate, and di-(2-ethylhexyl) phthalate from river sediment in Taiwan

We investigated anaerobic degradation rates for three phthalate esters (PAEs), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and di-(2-ethylhexyl) phthalate (DEHP), from river sediment in Taiwan. The respective anaerobic degradation rate constants for DEP, DBP, and DEHP were observed as 0.045, 0.074, and 0.027 1/day, with respective half-lives of 15.4, 9.4, and 25.7 days under optimal conditions of 30 °C and pH 7.0. Anaerobic degradation rates were enhanced by the addition of the surfactants brij 35 and triton N101 at a concentration of 1 critical micelle concentration (CMC), and by the addition of yeast extract. Degradation rates were inhibited by the addition of acetate, pyruvate, lactate, FeCl₃, MnO₂, NaCl, heavy metals, and nonylphenol. Our results indicate that methanogen, sulfate-reducing bacteria, and eubacteria are involved in the degradation of PAEs.     

粉煤灰对模拟河流中DMP的动态吸附

针对污染物泄露导致的河流污染问题,以邻苯二甲酸二甲酯(DMP)为研究对象,以粉煤灰作为吸附剂、有机玻璃反应槽作为反应装置,向其持续注入初始浓度相同的DMP溶液,将其所得实验数据拟合Logistic穿透模型,研究模拟河流条件下,粉煤灰对DMP的动态吸附规律;同时,分析了水流速度、DMP初始浓度及吸附剂投加方式3种因素对粉煤灰去除DMP性能的影响。结果表明：Logistic穿透模型能较好地拟合河流中粉煤灰动态吸附DMP的过程;提高溶液的进水流速,污染物更容易穿透吸附剂表面,单位时间内的最大吸附量由17.81 μg·g-1增加至27.78 μg·g-1,最大去除率由35.63%升高至55.57%,穿透时间提前;随着DMP溶液初始浓度的增加,粉煤灰与DMP分子之间的浓度差增大,相同时间内与粉煤灰接触的DMP污染物增多,达到饱和的时间由131 min缩短至119 min,穿透曲线上的穿透点左移,粉煤灰的吸附性能提高;将粉煤灰全部平铺在槽体底部时,吸附质能够充分地与其接触,传质阻力减小,吸附速率常数由0.003 9提高至0.004 7,粉煤灰的吸附率升高。该研究可为河流突发性污染的应急处理提供一定理论依据。     

Aerobic degradation of tetrabromobisphenol-A by microbes in river sediment

This study investigated the aerobic degradation of tetrabromobisphenol-A (TBBPA) and changes in the microbial community in river sediment from southern Taiwan. Aerobic degradation rate constants (k₁) and half-lives (t_1/2) for TBBPA (50 μg g⁻¹) ranged from 0.053 to 0.077 d⁻¹ and 9.0 to 13.1 d, respectively. The degradation of TBBPA (50 μg g⁻¹) was enhanced by adding yeast extract (5 mg L⁻¹), sodium chloride (10 ppt), cellulose (0.96 mg L⁻¹), humic acid (0.5 g L⁻¹), brij 30 (55 μM), brij 35 (91 μM), rhamnolipid (130 mg L⁻¹), or surfactin (43 mg L⁻¹), with rhamnolipid yielding a higher TBBPA degradation than the other additives. For different toxic chemicals in the sediment, the results showed the high-to-low order of degradation rates were bisphenol-A (BPA) (50 μg g⁻¹) > nonylphenol (NP) (50 μg g⁻¹) > 4,4′-dibrominated diphenyl ether (BDE-15) (50 μg g⁻¹) > TBBPA (50 μg g⁻¹) > 2,2′,3,3′,4,4′,5,5′,6,6′-decabromodiphenyl ether (BDE-209) (50 μg g⁻¹). The addition of various treatments changed the microbial community in river sediments. The results also showed that Bacillus pumilus and Rhodococcus ruber were the dominant bacteria in the process of TBBPA degradation in the river sediments.     

Potential mechanisms of phthalate ester embryotoxicity in the abalone Haliotis diversicolor supertexta

The effects and associated toxicological mechanisms of five phthalate esters (PAEs) on abalone embryonic development were investigated by exposing the embryos to a range of PAEs concentrations (0.05, 0.2, 2 and 10 μg/mL). The results showed that PAEs could significantly reduce embryo hatchability, increase developmental malformations, and suppress the metamorphosis of abalone larvae. The possible toxicological mechanisms of PAEs to abalone embryos included, affecting the Na⁺-K⁺-pump and Ca²⁺-Mg²⁺-pump activities, altering the peroxidase (POD) level and the malondialdehyde (MDA) production, damaging the extraembryonic membranes structure, as well as disrupting endocrine-related genes (gpx, cyp3a, and 17β-hsd 12) expression properties. Taken together, this work showed that PAEs adversely affected the embryonic ontogeny of abalone. The abilities of PAEs affecting the osmoregulation, inducing oxidative stress, damaging embryo envelope structure, and causing physiological homeostasis disorder, are likely to be a part of the common mechanisms responsible for their embryonic toxicity.     

微生物燃料电池降解邻苯二甲酸酯及同步产电特性

构建双室微生物燃料电池（MFC）装置,研究了分别以乙酸钠（NaAc）作单一燃料和乙酸钠+邻苯二甲酸酯（PAEs）作混合燃料条件下,MFC的产电性能及其对邻苯二甲酸酯的去除效果。结果显示,微生物燃料电池对邻苯二甲酸酯类废水的化学需氧量（COD）的总去除率可达89%~94%,对邻苯二甲酸酯的去除率均在70%以上。以2 g·L-1 NaAc+10 mg·L-1 PAEs作混合燃料时,MFC获得最大（面积）功率密度58.78 mW·m-2,电池内阻213.50 Ω。实验结果表明,MFC能够利用高浓度邻苯二甲酸酯作燃料,在实现高效降解的同时稳定地向外输出电能,这为环境激素类难降解有机物的高效低耗处理提供了一种新的研究思路。     

Anaerobic degradation of five polycyclic aromatic hydrocarbons from river sediment in Taiwan

This study investigated the anaerobic degradation of five polycyclic aromatic hydrocarbons (PAHs) from Erren River sediment in southern Taiwan. The degradation rates of PAH were in the order: acenaphthene > fluorene > phenanthrene > anthracene > pyrene. The degradation rate was enhanced when the five compounds were present simultaneously in river sediment. Comparison of the PAH degradation rates under three reducing conditions showed the following order: sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The addition of electron donors (acetate, lactate and pyruvate) enhanced PAH degradation under methanogenic and sulfate-reducing conditions. However, the addition of acetate, lactate or pyruvate inhibited PAH degradation under nitrate-reducing conditions. The addition of heavy metals, nonylphenol and phthalate esters (PAEs) inhibited PAH degradation. Our results show that sulfate-reducing bacteria, methanogen and eubacteria are involved in the degradation of PAH; sulfate-reducing bacteria constitute a major microbial component in PAH degradation. Of the microorganism strains isolated from the sediment samples, we found that strain ER9 expressed the greatest biodegrading ability.     

The lack of microbial degradation of polycyclic aromatic hydrocarbons from coal-rich soils

Analytical techniques used to assess the environmental risk of contamination from polycyclic aromatic hydrocarbons (PAHs) typically consider only abiotic sample parameters. Supercritical fluid extraction and sorption enthalpy experiments previously suggested slow desorption rates for PAH compounds in two coal-contaminated floodplain soils. In this study, the actual PAH availability for aerobic soil microorganisms was tested in two series of soil-slurry experiments. The experimental conditions supported microbial degradation of phenanthrene if it was weakly sorbed onto silica gel. Native coals and coal-derived particles in two soils effectively acted as very strong sorbents and prevented microbial PAH degradation. The long history of PAH exposure and degree of coal contamination apparently had no influence on the capability of the microbial soil community to overcome constraints of PAH availability. Within the context of the experimental conditions and the compounds chosen, our results confirm that coal-bound PAHs are not bioavailable and hence of low environmental concern.     

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.     

Phthalate exposure in pregnant women and their children in central Taiwan

Phthalate exposure was found to be associated with endocrine disruption, respiratory effects, reproductive and developmental toxicity. The intensive use of plastics may be increasing the exposure to phthalates in Taiwanese population, particularly for young children.We studied phthalate metabolites in pregnant women and their newborns in a prospective cohort from a medical center in Central Taiwan. One hundred maternal urine samples and 30 paired cord blood and milk samples were randomly selected from all of participants (430 pregnant women). Eleven phthalate metabolites (MEHP, 5OH-MEHP, 2cx-MEHP, 5cx-MEPP, 5oxo-MEHP, MiBP, MnBP, MBzP, OH-MiNP, oxo-MiNP, and cx-MiNP) representing the exposure to five commonly used phthalates (DEHP, di-isobutyl phthalate (DiBP), DnBP, BBP, DiNP) were measured in urine of pregnant women, cord serum and breast milk after delivery, and in urine of their children. Exposure was estimated with excretion factors and correlation among metabolites of the same parent compound. Thirty and 59 urinary samples from 2 and 5 years-old children were randomly selected from 185 children successfully followed.Total urinary phthalate metabolite concentration (geometric mean, μg L⁻¹) was found to be higher in 2-years-olds (398.6) and 5-years-olds (333.7) than pregnant women (205.2). Metabolites in urine are mainly from DEHP. The proportion of DiNP metabolites was higher in children urine (4.39 and 8.31%, ages 2 and 5) than in adults (0.83%) (p < 0.01). Compared to urinary levels, phthalate metabolite levels are low in cord blood (37.45) and milk (14.90). DEHP metabolite levels in women’s urine and their corresponding cord blood are significantly correlated. Compared to other populations in the world, DEHP derived metabolites in maternal urine were higher, while phthalate metabolite levels in milk and cord blood were similar. The level of phthalate metabolites in milk and cord blood were comparable to those found in other populations. Further studies of health effects related to DEHP and DiNP exposure are necessary for the children.     

Mg/Al水滑石对水中痕量邻苯二甲酸酯的吸附动力学和热力学

研究了Mg／A1水滑石对水中痕量邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二（2一乙基己基）酯（DEHP）和邻苯二甲酸二辛酯（DnOP）的吸附动力学和热力学特性。结果表明,在所研究的浓度范围内,3种邻苯二甲酸酯的吸附动力学曲线均符合准二级速率方程,DMP、DEHP和DnOP分别在600、200和200min基本达到吸附平衡;3种邻苯二甲酸酯的吸附等温线基本符合Langmuir和Freundlich吸附等温方程;在283～308K范围,pH=6．36,3种邻苯二甲酸酯初始浓度均为50μg／L时,吸附过程△H为负值且绝对值为5～12kJ／mol,表明吸附为放热过程,以表面物理吸附为主,邻苯二甲酸酯在Mg／Al水滑石上的吸附是色散力、诱导力、取向力和氢键力等多种作用力协同作用的结果。     

Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain

The occurrence of 43 pharmaceuticals belonging to predominant therapeutic classes and their distribution in surface water, suspended solids and sediments has been investigated in the Ebro river basin in the Northeast of Spain. WWTP effluents were found to be a main source of contamination and the spatial distribution was affected by the river flow at the sampling point and corresponding dilution factor, resulting in higher concentrations and higher loads in small tributary rivers than in the Ebro river. The study showed that some compounds are preferentially found bound to suspended solids and not detected in river water. Generally, compounds with basic characteristics (pKa > 7) showed higher tendency to bind to suspended solids. The sediment samples generally presented lower concentrations than suspended solids.     

不同处理技术对河流污染物降解系数影响的比较

以苏州官渎花园内河为研究背景,利用模拟河道分别考察了曝气复氧、人工水力循环、渗滤净化技术3种处理技术对受污河水中COD降解系数k COD、NH3-N降解系数k NH3-N变化规律的影响。实验表明,在无外源污染且河水滞留的天然情况下河道拥有一定自我净化的能力,并且3种处理技术对COD、NH3-N的降解系数都有一定提高,分别使k COD增加了34.3%、47.8%和57.8%,k NH3-N增加了8.35%、15.4%和52.8%,结果显示,渗滤净化技术对污染物降解系数的提高影响最大。     

受污染城市河道沉积物磷吸附特征及其影响因素

采集了典型受污染城市河道——陕西省新河不同季节的沉积物,研究其磷吸附特征及影响因素,并考察其缓冲外源污染的能力,评估其磷释放风险。结果显示,沉积物平均粒径在秋季小于夏季和春季,pH为7.64~8.88;沉积物总磷 (TP) 为870~2 173 mg·kg⁻¹;计算了沉积物磷富集系数,明确了新河部分点位为重度污染类型。吸附动力学研究结果表明：0~2 h沉积物对磷的吸附量在正负之间波动;2~4 h吸附量迅速增加,吸附速率也达到了峰值;之后吸附量增加趋势变缓,并在48 h达到平衡。绘制吸附等温线,可知沉积物的磷吸附-解吸平衡质量浓度 (EPC₀) 为0.39~2.21 mg·L⁻¹,高于同时段上覆水中磷的质量浓度,具有释放风险;磷最大缓冲容量MBC和Freundlich常数K_F呈现秋季>>夏季>春季的规律;经D-R模型拟合,绝大多数样品的吸附能为8.45~11.18 kJ·mol⁻¹,说明吸附机制为离子交换。相关性分析结果表明,沉积物的磷吸附速率常数与钙的相对含量呈显著相关 (P<0.05) 。EPC₀与沉积物的总磷和易释放态磷含量呈显著相关 (P<0.01) ,与沉积物平均粒径和有机质显著相关 (P<0.05) ,与pH显著相关 (P<0.05) 。本研究结果可为受污染城市河道治理提供参考。     

Occurrence of polycyclic aromatic hydrocarbons in surface sediments of a highly urbanized river system with special reference to energy consumption patterns

Sediment samples collected from downstream of the Dongjiang River, a highly urbanized river network within the Pearl River Delta of South China, were analyzed for 28 polycyclic aromatic hydrocarbons (PAHs). Total concentrations of 28 PAHs, 16 priority PAHs designated by the United States Environmental Protection Agency (USEPA) and the seven carcinogenic PAHs classified by the USEPA ranged from 480 to 4600, 100 to 3400 and 10 to 1700 ng/g dry weight, respectively. Principal component analysis-based stepwise multivariate linear regression showed that sediment PAHs were predominantly derived from coal combustion, refined fossil fuel combustion and oil spills, accounting for 37%, 32% and 23%, respectively, of the total loading. The levels of sediment PAHs remained steady from 2002 to 2008, during which fossil fuel consumption had doubled, probably reflecting efforts to control PAH emissions from fossil fuel combustion. Finally, use of natural gas and liquefied petroleum gas in automobiles should be encouraged to improve environmental quality.     

2,4,6-Trinitrotoluene mineralization and bacterial production rates of natural microbial assemblages from coastal sediments

The nitrogenous energetic constituent, 2,4,6-Trinitrotoluene (TNT), is widely reported to be resistant to bacterial mineralization (conversion to CO₂); however, these studies primarily involve bacterial isolates from freshwater where bacterial production is typically limited by phosphorus. This study involved six surveys of coastal waters adjacent to three biome types: temperate broadleaf, northern coniferous, and tropical. Capacity to catabolize and mineralize TNT ring carbon to CO₂ was a common feature of natural sediment assemblages from these coastal environments (ranging to 270+/−38 μg C kg⁻¹ d⁻¹). More importantly, these mineralization rates comprised a significant proportion of total heterotrophic production. The finding that most natural assemblages surveyed from these ecosystems can mineralize TNT ring carbon to CO₂ is consistent with recent reports that assemblage components can incorporate TNT ring carbon into bacterial biomass. These data counter the widely held contention that TNT is recalcitrant to bacterial catabolism of the ring carbon in natural environments.     

辉光放电等离子体氧化降解水中邻苯二甲酸二丁酯

研究了辉光放电等离子体降解水中典型的环境内分泌干扰物邻苯二甲酸二丁酯(DBP)及降解过程中过氧化氢(H2O2)的生成规律。考察了电解质种类、共存污染物(甲醇、叔丁醇)及催化剂等条件对DBP降解及H2O2生成的影响。结果表明,在硫酸钠溶液中DBP降解效率和H2O2生成速率最高;甲醇、叔丁醇等共存污染物对DBP降解和H2O2生成有抑制作用;Fe2+,Fe3+和Cu2+对DBP的降解有催化作用,其催化效果为Fe2+>Fe3+>Cu2+。用高效液相色谱、离子色谱及气质联用仪等仪器分析了降解中间产物,提出了可能的降解机理。     

Occurrence and profiles of organic sun-blocking agents in surface waters and sediments in Japanese rivers and lakes

Sun-blocking agents including eight UV filters (UVF) and 10 UV light stabilizers (UVLS) were measured in water and sediment collected from 22 rivers, four sewage treatment plant effluents (STPE) and three lakes in Japan. Total sun blocking agents levels ranged from N.D. to 4928 ng/L and from 2.0 to 3422 μg/kg dry wt in surface water and in sediment, respectively. Benzyl salicylate, benzophenone-3, 2-ethyl hexyl-4-methoxycinnamte (EHMC) and octyl salicylate were dominant in surface water receiving wastewater effluents and STPE, although UV-328, benzophenone and EHMC were dominant in other surface water except background sites. Three UVF and nine UVLS were observed from all sediment and their compositions showed similar patterns with UV-328 and UV-234 as the most prevalent compounds. Homosalate, octocrylene, UV-326, UV-327, UV-328 and UV-234 were significantly correlated with Galaxolide^® in sediments. Concentrations of UV-327 and UV-328 also had strong correlation between those of UV-326 in sediment.     

Alteration of sediment organic matter in sediment microbial fuel cells

The alteration of physico-chemical properties of sediment organic matter (SOM) incubated under current-harvesting conditions as well as no-current producing conditions over 120 days using sediment microbial fuel cell systems was examined. The SOM was microbially oxidized under anaerobic conditions with an electrode serving as a terminal electron acceptor. It was found that SOM around the electrochemically-active electrodes became more humified, aromatic, and polydispersed, and had a higher average molecular weight, along with its partial degradation and electricity generation compared to that for the original sediment. These changes in SOM properties were analogous to those commonly observed in the early stages of the SOM diagenetic process (i.e. humification). Such a humification-like process was evidently more stimulated when electrical current was produced than no-current condition. These new findings associated with microbially-catalyzed electricity generation may present a potential for the energy-efficient remediation, monitoring, and/or management of the geo-environment.