The role of black carbon as a catalyst for environmental redox transformation

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983–6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC—graphite, activated carbon, and diesel soot—to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H₂S. All three types of BC enhanced DNT and DBP reduction. H₂S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.     

The role of black carbon as a catalyst for environmental redox transformation

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983–6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC—graphite, activated carbon, and diesel soot—to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H₂S. All three types of BC enhanced DNT and DBP reduction. H₂S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.

     

Contribution of black carbon to nonlinearity of sorption and desorption of acetochlor on sediment

In order to investigate the contribution of various black carbon (BC) contents to nonlinearity of sorption and desorption isotherms for acetochlor on sediment, equilibrium sorption and desorption isotherms were determined to measure sorption and desorption of acetochlor in sediment amended with various amounts of BC. In this paper, two types of BC referred to as BC400 and BC500 were prepared at 400°C and 500°C, respectively. Higher preparation temperature facilitated the formation of micropores on BC to enhance its sorption capacity. Increase of the BC content obviously increased the sorption amount and reduced the desorption amount for acetochlor. When the BC500 contents in total organic carbon (TOC) increased from 0 to 60%, Freundlich sorption coefficient (K _f) increased from 4.07 to 35.74, and desorption hysteresis became gradually obvious.When the content of BC in TOC was lower than 23%, the sorption isotherm had a significant linear correlation (p = 50.05). In case of desorption, a significant nonlinear change could be observed when the content of BC was up to 13%. Increase of BC content in the sediment would result in shifting the sorption-desorption isotherms from linearity to nonlinearity, which indicated that contribution of BC to nonlinear adsorption fraction became gradually remarkable.     

土壤和沉积物中非水解有机碳对菲的吸附

采用改进的酸水解方法对土壤和沉积物中的有机质组分进行了分离和提取,用固体13C核磁共振（13CNMR）表征了非水解有机碳（NHC）,同时研究了不同有机质组分对菲的吸附行为,结果表明,菲的吸附等温线都呈现出明显的非线性,能很好地拟合Freundlich方程;而且NHC和碳黑（BC）比其原始和去矿样品的吸附容量都有明显提高.这些结果揭示了NHC和BC主要控制着菲在土壤和沉积物中的吸附行为.沉积物及其NHC对菲的吸附容量要高于土壤及其NHC,这与土壤和沉积物中有机质的不同来源有关.     

超临界流体萃取在研究土壤和沉积物结合态残留中的应用

许多有机污染物在土壤和沉积物中形成持久稳定的结合态残留；结合态残留对土壤和沉积物的解毒过程、污染物长期分配行为、生物可用性和生物毒性都具有重要影响。为了揭示结合态残留的形成机制及其对污染物环境行为和毒理学参数的影响，从土壤或沉积物中提取出不同结合状态的有机污染物就显得非常重要。超临界流体萃取(SFE)可以实现选择性萃取，从而得到有关污染物一基体间相互作用的信息。文章介绍了SFE应用类型、超临界流体种类以及影响SFE萃取率的因素，对SFE模拟有机污染物长期吸附／解吸行为和生物可用性研究进行了论述，并认为SFE势必发展成为土壤或沉积物中结合态残留形成机理研究、土壤修复和生态风险评价的一种强有力的技术。     

Phenanthrene sorption to environmental black carbon in sediments from the Song-Liao watershed (China)

Black carbon (BC) in ten contaminated sediments from the Song-Liao watershed, NE China, was isolated upon treatments using a combustion method at 375°C, and the isolates’ sorption isotherms for phenanthrene (Phen) were determined. All sorption isotherms were nonlinear and fitted well by the Freundlich model. A negative relation was found between Freundlich sorption nonlinearity parameter (n values) and BC/total organic carbon (TOC) content of the original sediments (r²=0.687, p<0.01), indicating the dominance of BC in Phen sorption nonlinearity. The BC isolates from this industrialized region had n values of 0.342 to 0.505 and logK_FOC values of 6.02 to 6.42(μg·kg⁻¹·OC⁻¹)/(μg·L⁻¹) ⁿ for Phen. At a given C_e, the BC had higher K_oc value than the original sediments, revealing a higher sorption capacity for BC. BC was responsible for 50.0% to 87.3% of the total sorption at C_e=0.05 S_w, clearly indicating the dominance of BC particles in overall sorption of Phen by sediments.     

土壤和沉积物中有机质对双酚A和17α-乙炔基雌二醇的吸附行为

研究了土壤和沉积物原始样品bulk及其有机质组分(非水解性有机质NHC、碳黑BC和腐殖酸HA)对17α-乙炔基雌二醇(EE2)和双酚A(BPA)的吸附行为.所有的吸附等温线都很好地拟合了Freundlich模型,除HA和bulk外,所有的吸附等温线都为显著的非线性(n值为0.46—0.76).对于EE2和BPA的吸附非线性因子n值都存在这样的关系:HA>NHC>BC.EE2以有机碳归一化的Freundlich吸附能力(lgKOC)有BC>NHC>bulk>HA的关系,说明有机质成熟度越高,对EE2或者BPA的吸附能力越高.在土壤和沉积物有机质SOM(NHC、BC和HA)对吸附BPA和EE2的贡献上,NHC、BC和HA对沉积物和土壤对BPA总吸附贡献上要明显弱于它们对EE2的贡献.除了内分泌干扰物(EDCs)的疏水性影响EE2和BPA的吸附能力的差异外,分子大小和带电子苯环数也影响它们的吸附能力差异.     

Sorption of DDTs on biofilms, suspended particles and river sediments: effects of heavy metals

The sorption by solid materials is one of the most important processes that affect the fate of hydrophobic organic pollutants in aquatic systems. Current studies focus on the sorption of hydrophobic pollutants by single natural solid material, whereas few studies compared the sorption behaviors of different solids. Furthermore, natural aquatic environment is a complex system where hydrophobic pollutants coexist with many other pollutants, but only limited studies reported the effects of coexisting components on the sorption. Here we studied the sorption of dichlorodiphenyltrichloroethanes (DDTs) by three common solids in natural water, i.e., biofilms, suspended particles and sediments. The effects of typical coexisting heavy metals on the sorption were also examined. The results show that the sorption is described by a dual-mode sorption model. Compared with sediments, more DDTs were sorbed by biofilms and suspended particles. Coexisting Pb, Cd and Cu increased the sorption of DDTs on sediments while decreasing the sorption on biofilms slightly, with little effect on the sorption on suspended particles. The different sorption behaviors of the solids were mainly determined by the composition of the solids: more organics were observed in biofilms and suspended particles.     

Evidence for a mutual effect of biofilms, suspended particles and sediments on DDT sorption

This report shows that biofilms and suspended particles double DDT sorption capacity on surface sediments. Sorption of pollutants by solid materials, such as biofilms, suspended particles and sediments, is a major process controlling the fate of hydrophobic pollutants in natural waters. Most previous studies focused on the sorption of hydrophobic pollutants by single-solid material, whereas few studies considered the mutual effect of different solids on the sorption. Various solid materials often interact with each other when they coexist in the same system. Therefore, pollutants sorption could be different from that in the single-solid sorption system. Here we studied the mutual effect of biofilms, suspended particles and surface sediments on the sorption of dichlorodiphenyltrichloroethane (DDT). Results showed that biofilms and suspended particles double DDT sorption capacity on surface sediments. The different effects were mainly determined by distinct components and structures of the three solid materials, particularly by organic components. Here we show the mutual effect of biofilms, suspended particles and sediments on DDT sorption.     

沼泽产甲烷能力和途径差异的机制

土壤中甲烷的形成有 2条途径 :乙酸发酵和H2 /CO2 还原。比较而言 ,乙酸发酵产甲烷的能力强于H2 /CO2 还原。在特定环境中 ,何种产甲烷途径占优势取决于底物尤其是活性有机碳含量 ,而新形成的有机碳尤为重要。活性有机碳含量丰富的沼泽 ,甲烷主要由乙酸发酵形成 ,因此产甲烷能力较强。导致沼泽产甲烷能力异同的原因就是有效底物含量差异 ,从而使不同类型沼泽环境中产甲烷菌菌种不同 ,正是底物含量的高低和由此引起的产甲烷菌菌种的不同决定了不同类型沼泽产甲烷潜能的差异     

Carbon nanotubes and cyclodextrin polymers for removing organic pollutants from water

Some organic compounds are major water pollutants. They can be toxic or carcinogenic even at low concentrations. Current technologies, however, fail to remove these contaminants to parts per billion (ppb) levels. Here we report on the removal of organic pollutants from water using cross-linked nanoporous polymers that have been copolymerized with previously functionalized carbon nanotubes. These novel polymers can remove model organic species such as p-nitrophenol by as much as 99% from a 10 mg/L spiked water sample compared to granular activated carbon and native cyclodextrin polymer that removed only 47 and 58%, respectively. These polymers have also demonstrated the ability to remove trichloroethylene (10 mg/L spiked sample) to non-detectable levels (detection limit <0.01 ppb) compared to 55 and 70% for activated carbon and native cyclodextrin polymers, respectively.     

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.     

PM2.5: global progress in controlling the motor vehicle contribution

It is well established that ambient particles in the size range of 2.5 microns or less case a wide variety of adverse health effects. According to a recent study from the World Health Organization, in 2010 these effects resulted in approximately 3.2million premature deaths with vehicles being one of the significant contributors. Diesel vehicle particulate emissions which are virtually all smaller than 2.5 microns raise additional special concerns due to their carcinogenicity and high ratio of black carbon （BC） to organic carbon; black carbon has recently been found to be the second most important contributor to climate change after carbon dioxide. Other pollutants emitted by diesels and other vehicles such as the oxides of nitrogen and volatile organic compounds also contribute to ambient particulate matter smaller than 2.5 microns in size （PM2.5） after undergoing secondary transformations in the atrno- sphere. Technologies have dramatically reduce vehicle been developed that can emissions when clean, low sulfur fuels are available and these technologies are being phased in throughout the industrialized world resulting in a global decrease in particulate matter （PM） and BC emissions from vehicles. However the vehicle population is growing rapidly in the developing world, leading to increases in emissions in many countries. Unless these rapidly industrializing countries move to state of the art vehicles and clean fuels, global PM, BC and NOx emissions from road vehicles will start to turn up over the next 10 to 15 years.     

Antioxidant enzyme activities of <Emphasis Type="Italic">Microcystis aeruginosa</Emphasis> in response to nonylphenols and degradation of nonylphenols by <Emphasis Type="Italic">M. aeruginosa</Emphasis>

The aim of this study was to examine the effects of chemical nonylphenols (NPs) on the antioxidant system of Microcystis aeruginosa strains. The degradation and sorption of NPs by M. aeruginosa were also evaluated. High concentrations of NPs (1 and 2 mg/l) were found to cause increases in superoxidase dismutase (SOD) and glutathione-S-transferase (GST) activities and in glutathione (GSH) levels. These results suggest that toxic stress manifested by elevated SOD and GST levels and GSH contents may be responsible for the toxicity of NPs to M. aeruginosa and that the algal cells could improve their antioxidant and detoxification ability through the enhancement of enzymatic and nonenzymatic prevention substances. The observed elevations in GSH levels and GST activities were relatively higher than those in SOD activities, indicating that GSH and GST contributed more in eliminating toxic effects than SOD. Low concentrations of NPs (0.05–0.2 mg/l) enhanced cell growth and decreased GST activity in algal cells of M. aeruginosa, suggesting that NPs may have acted as a protecting factor, such as an antioxidant. The larger portion of the NPs (>60%) disappeared after 12 days of incubation, indicating the strong ability of M. aeruginosa to degrade the moderate persistent NP compounds. The sorption ratio of M. aeruginosa after a 12-day exposure to low nominal concentrations of NPs (0.02–0.5 mg/l) was relatively high (>30%). The fact that M. aeruginosa effectively resisted the toxic effects of NPs and strongly degraded these pollutants indicate that M. aeruginosa cells have a strong ability to adapt to variations in environmental conditions and that low and moderate concentrations of organic compounds may favor its survival. Further studies are needed to provide detailed information on the fate of persistent organic pollutants and the survival of algae and to determine the possible role of organic pollutants in the occurrence of water blooms in eutrophic lakes.     

Control strategies for disinfection byproducts by ion exchange resin,nanofiltration and their sequential combination

● Effects of AER adsorption and NF on DBP precursors, DBPs, and TOX were examined. ● A treatment approach of resin adsorption followed by nanofiltration was developed. ● Both DOC and Br⁻ could be effectively removed by the sequential approach. ● DBPs, TOX, and cytotoxicity were significantly reduced by the sequential approach. Disinfection byproducts (DBPs) are emerging pollutants in drinking water with high health risks. Precursor reduction before disinfection is an effective strategy to control the formation of DBPs. In this study, three types of anion exchange resins (AERs) and two types of nanofiltration (NF) membranes were tested for their control effects on DBP precursors, DBPs, and total organic halogen (TOX). The results showed that, for AER adsorption, the removal efficiencies of DBP precursors, DBPs, and TOX increased with the increase of resin dose, and the strong basic macroporous anion exchange resin (M500MB) had the highest removal efficiencies. For NF, the highest removal efficiencies were achieved at an operating pressure of 4 bar, and the membrane (NF90) with a smaller molecular weight cut-off, had a better control efficiency. However, AER adsorption was inefficient in removing dissolved organic carbon (DOC); NF was inefficient in removing Br⁻ resulting in insufficient control of Br-DBPs. Accordingly, a sequential approach of AER (M500MB) adsorption followed by NF (NF90) was developed to enhance the control efficiency of DBPs. Compared with single AER adsorption and single NF, the sequential approach further increased the removal efficiencies of DOC by 19.4%–101.9%, coupled with the high Br⁻ removal efficiency of 92%, and thus improved the reduction of cyclic DBPs and TOX by 3.5%–4.9%, and 2.4%–8.4%, respectively; the sequential approach also reduced the cytotoxicity of the water sample by 66.4%.     

对硝基苯酚在阴-阳离子有机膨润土/水间的界面行为研究

用阴、阳离子表面活性剂改性制得一系列阴-阳离子有机膨润土,表征了有机膨润土的结构特征,研究了对硝基苯酚在阴-阳离子有机膨润土/水间的界面行为,并探讨了其吸附机理.结果表明:阴-阳离子有机膨润土的层间距和有机碳含量与改性时阴、阳离子表面活性剂的组成和配比有关;阴-阳离子表面活性剂在有机膨润土中形成了增溶(分配)作用较强的有机相,在一定配比下对水中有机污染物产生协同效应.     

多环芳烃在全土及其碱提残余物上的吸附行为

以菲和芘为代表性化合物,采用8种有机质含量不同的天然全土样品及其碱提残余物进行吸附实验,并利用不同吸附模型进行数据拟合,藉以探讨有机质含量对土壤吸附行为的影响.结果表明,Freundlich吸附模型的非线性指数n都小于1,显示全土和碱提残余物在多环芳烃的吸附过程中表现出非线性特征.菲和芘的吸附行为随土壤有机质含量不同而变化,碱提残余物的吸附能力强于全土,两者吸附行为的差异主要归因于土壤有机质含量和性状的区别.     

几类有机污染物的微塑料/水分配系数的线性溶解能关系模型

水体中的微塑料会吸附其中的有机污染物,影响有机污染物和微塑料的环境归趋和生态毒性。研究微塑料对有机污染物的吸附行为,对于评价有机污染物和微塑料的环境赋存、迁移及生物有效性有重要意义。污染物在微塑料与水之间的平衡分配系数(Kd),是表征微塑料对有机污染物吸附能力的重要参数。实验方法难以逐个测定众多有机污染物的Kd值,有必要发展其预测模型。本研究搜集了有机污染物的线性溶解能关系(LSER)参数及Kd值,构建了可预测有机污染物在聚丙烯微塑料与海水、聚乙烯微塑料与海水、聚乙烯微塑料与淡水之间Kd值的LSER模型。模型具有良好的拟合优度(R2adj介于0.794~0.903)、稳健性(Q2LOO和Q2BOOT分别介于0.763~0.863和0.720~0.804)和预测能力(R2ext和Q2ext分别介于0.886~0.971和0.825~0.954),能够用于预测多氯联苯、多环芳烃、六氯环已烷和氯苯类有机污染物的Kd值。     

土壤有机碳对磺胺甲噁唑吸附的影响

以从云南元阳采集的1个水稻土和1个非耕作土,按颗粒大小分组作为模型吸附剂,探讨磺胺甲噁唑在土壤上的吸附行为与土壤有机质的关系.结果表明,梯田水稻土对磺胺甲噁唑的吸附(Kd:1.33—5.08)明显高于非耕作土(Kd:0.27—1.53).吸附强度与土壤C含量和O+N+S含量呈正相关,相关系数分别为0.953、0.917和0.769、0.809,说明土壤有机碳可能控制了磺胺甲噁唑的吸附,以有机碳为代表的憎水性吸附点位对吸附有较高的影响,憎水性作用为主导机理.     

水体中悬浮颗粒物对酞酸酯的吸附和解吸特性

选择水体中的悬浮颗粒物(SPM)--沉积颗粒物和浮游植物颗粒(铜绿微囊藻和普通小球藻),研究它们对邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异辛酯(DEHP)的吸附和解吸行为.结果表明,SPM对DBP 和DEHP的吸附在很短的时间内即可达到平衡,沉积颗粒物约为2h,浮游植物颗粒约为0.5h;SPM对DEHP的吸附能力明显大于DBP;不同SPM对同一种化合物的吸附能力差异较大,这与颗粒物中有机质的类型和结构有关;在实验浓度范围内,SPM对DBP和DEHP的吸附和解吸等温线具有较好的线性关系,解吸过程存在明显的迟滞现象,且沉积颗粒物比浮游植物颗粒物具有明显的迟滞效应,DBP比DEHP具有较大程度的迟滞效应.