Contribution to advances in waste-to-energy technologies

This paper presents a number of recent advances in technologies and improvements in units for the thermal processing of municipal solid waste (MSW) and various other types of waste. The focus is on the ‘waste-to-energy’ approach; various criteria for this approach are discussed, as well as the inconsistent attitudes about waste management approaches that are present in various countries in the European Union. The presented achievements include low-NO_x burners, improved efficiency, heat exchangers, waste heat recovery systems, newly developed equipment for wet scrubbing, dioxin filters and systems for the treatment of sewage sludge.A new concept for a regional Waste-to-Energy Centre (WTEC) is outlined, the design of which is based on a combination of experience, know-how and a sophisticated approach. The proposed WTEC will use up-to-date technologies and will provide an adequate response to the growing population and rising standards of living as well to increasingly stringent environmental regulatory standards.Utilization of computational methods such as Computational Fluid Dynamics (CFD) for design optimisation and/or for troubleshooting is demonstrated with examples (flue gas duct, burner, combustion chamber). Several examples from industrial applications are summarized.     

Quantifying the electron-donating and -accepting capacities of wastewater for evaluating and optimizing biological wastewater treatment processes

Biological processes have been widely used for the treatment of both domestic and industrial wastewaters. In such biological processes, pollutants are converted into pollution-free substances by microorganisms through oxidation-reduction reactions. Thus, how to quantify the internal oxidation-reduction properties wastewaters and seek out targeted countermeasures is essential to understand, operate, and optimize biological wastewater treatment systems. So far, no such approach is available yet. In this work, a novel concept of electron neutralization-based evaluation is proposed to describe the internal oxidation-reduction properties of wastewater. Pollutants in wastewater are defined as electron donor substances (EDSs) or electron acceptor substances (EASs), which could give or accept electrons, respectively. With such an electron neutralization concept, several parameters, i.e., electron residual concentration (R), economy-related index (E and E_r), and economical evaluation index (Y and Y_r), are defined. Then, these parameters are used to evaluate the performance and economic aspects of currently applied wastewater treatment processes and even optimize systems. Three case studies demonstrate that the proposed concept could be effectively used to reduce wastewater treatment costs, assess energy recovery, and evaluate process performance. Therefore, a new, simple, and reliable methodology is established to describe the oxidation-reduction properties of wastewater and assess the biological wastewater treatment processes.     

Statistical regression modeling for energy consumption in wastewater treatment

Wastewater treatment is one of critical issues faced by water utilities, and receives more and more attentions recently. The energy consumption modeling in biochemical wastewater treatment was investigated in the study via a general and robust approach based on Bayesian semi-parametric quantile regression. The dataset was derived from a municipal wastewater treatment plant, where the energy consumption of unit chemical oxygen demand (COD) reduction was the response variable of interest. Via the proposed approach, the comprehensive regression pictures of the energy consumption and truly influencing factors, i.e., the regression relationships at lower, median and higher energy consumption levels were characterized respectively. Meanwhile, the proposals for energy saving in different cases were also facilitated specifically. First, the lower level of energy consumption was closely associated with the temperature of influent wastewater, and the chroma-rich wastewater also showed helpful in the execution of energy saving. Second, at median energy consumption level, the COD-rich wastewater played a determinative role in the reduction of energy consumption, while the higher quality of treated water led to slightly energy intensive. Third, the higher level of energy consumption was most likely to be attributed to the relatively high temperature of wastewater and total nitrogen (TN)-rich wastewater, and both of the factors were preferably to be avoided to alleviate the burden of energy consumption. The study provided an efficient approach to controlling the energy consumption of wastewater treatment in the perspective of statistical regression modeling, and offered valuable suggestions for the future energy saving.     

卤代苯化合物水溶解度及正辛醇/水分配系数的三维构效关系研究

对卤代苯化合物的水溶解度(-lg Sw)和正辛醇/水分配系数(lg Kow)分别进行了基于三维结构的比较分子场(Co MFA)和比较分子相似性指数(Co MSIA)分析,建立了三维定量结构-性质相关(3D-QSPR)模型,并将所获结果与密度泛函理论(DFT)方法得到的2D-QSPR模型进行了比较.结果表明:-lg Sw的Co MFA和Co MSIA模型交叉验证相关系数Q2分别为0.902和0.940,决定系数R2分别为0.982和0.986,模型稳定性和估算能力较好;lg Kow的Co MFA和Co MSIA模型Q2分别为0.926和0.988,R2分别为0.983和0.997;本研究所建的3D-QSPR模型的估算能力优于2D-QSPR模型;Co MFA和Co MSIA模型三维等势图表明,取代基的疏水效应对该类化合物的水溶解性能及正辛醇/水分配系数的影响更为显著,立体效应次之,静电场效应影响较小.     

Acidibility established as a characteristic of high strength organic wastewater quality

Acidification processes of the alcohol wastewater on molasses and the sugar-peptone manual make-up water were studied to determine their acidification capability. The two types of wastewater were both diluted into serial gradient dilutions and acidified separately. The volatile fatty acids (VFAs) and were detected daily until acidification reached a maximum state. The degraded COD in each dilution, which were considered as degraded VFAs and analyzed. The ratio of the sum of produced VFAs and degraded VFAs to the initial COD of dilutions was defined as acidibility (V/C). It showed that within a large concentration extent, the V/C values were consistent for different dilutions of each wastewater. Thus acidibility becomes a characteristic of high strength organic wastewater quality. The acidibility of the alcohol wastewater on molasses was analyzed to be 0.71, and the acidibility of sugar-peptone manual make-up water was 0.76. In a practicable view, it is meaningful to set up acidibility as a new water quality index, which can be used to guide the design of acidification technique in various high concentration organic wastewater treatment practices.     

Cleaner production option in a food (Kimchi) industry

In the Kimchi (a salt-pickled and fermented food) manufacturing industry, the process of brining and rinsing the raw vegetable produces a vast amount of wastewater of high salinity. Instead of the expensive and low-efficient conventional treatment system, a brining wastewater reuse system was developed using hybrid chemical precipitation/microfiltration. In the microfiltration of chemically treated brining wastewater, a comparison of flux, backwashing frequency and energy consumption was made between dead-end and crossflow filtration modes. The optimum location of the neutralization step in this system was also discussed in connection with the microfiltration performance. The quality test of Kimchi prepared by the reuse system confirmed the new approach to the cleaner production option was successful in terms of water/raw material (salt) savings and wastewater reduction.     

Advanced process systems design technology for pollution prevention and waste treatment

The paper presents a generic process synthesis and optimisation tool suitable to take up applications in the design of waste treatment systems and in pollution prevention. The main component of the technology is a generalized process synthesis representation for simultaneous consideration of reaction and separation in multiphase systems that is amenable for stochastic optimisation. The flexibility of the representation allows applications to overall process synthesis problems as well as to decomposed reactor, reactive separation and mass exchange network design problems. Applications of the synthesis framework to waste water treatments processes using activated sludge and to natural gas sweetening in hybrid membrane-adsorption processes are presented. The paper highlights the use of the systematic technology in environmental systems design and shows how novel designs of improved performance as well as optimal design knowledge can be revealed using the systematic design framework. Context abstract: Environmental process systems for waste treatment and pollution prevention become increasingly complicated to design. There is a strong need for technology that provides systematic decision support to the process synthesis team in order to enable the timely selection of processes that operate close to the performance limits of the system under consideration. Conventional, optimisation-based process design technology is severely limited by the number of design decisions they can support simultaneously as well as by the increasingly complex process models required for the meaningful mathematical representation of environmental process systems. We have devised an optimisation-based process design methodology for integrated reaction and separation systems that overcomes major limitations of existing tools. This paper illustrates the use of this technology to provide systematic decision-support to the environmental process systems designer.     

Rapid aerobic granulation in an SBR treating piggery wastewater by seeding sludge from a municipal WWTP

Aerobic sludge granulation was rapidly obtained in the erlenmeyer bottle and sequencing batch reactor (SBR) using piggery wastewater. Aerobic granulation occurred on day 3 and granules with mean diameter of 0.2 mm and SVI₃₀ of 20.3 mL/g formed in SBR on day 18. High concentrations of Ca and Fe in the raw piggery wastewater and operating mode accelerated aerobic granulation, even though the seed sludge was from a municipal wastewater treatment plant (WWTP). Alpha diversity analysis revealed Operational Taxonomic Units, Shannon, ACE and Chao 1 indexes in aerobic granules were 2013, 5.51, 4665.5 and 3734.5, which were obviously lower compared to seed sludge. The percentages of major microbial communities, such as Proteobacteria, Bacteroidetes and Firmicutes were obviously higher in aerobic granules than seed sludge. Chloroflexi, Planctomycetes, Actinobacteria, TM7 and Acidobacteria showed much higher abundances in the inoculum. The main reasons might be the characteristics of raw piggery wastewater and granule structure.     

The potential application of red mud and soil mixture as additive to the surface layer of a landfill cover system

Red mud, the by-product of aluminum production, has been regarded as a problematic residue all over the world. Its storage involves risks as evidenced by the Ajka red mud spill,an accident in Hungary where the slurry broke free, flooding the surrounding areas. As an immediate remediation measure more than 5 cm thick red mud layer was removed from the flooded soil surface. The removed red mud and soil mixture(RMSM) was transferred into the reservoirs for storage. In this paper the application of RMSM is evaluated in a field study aiming at re-utilizing waste, decreasing cost of waste disposal and providing a value-added product. The purpose was to investigate the applicability of RMSM as surface layer component of landfill cover systems. The field study was carried out in two steps: in lysimeters and in field plots. The RMSM was mixed at ratios ranging between 0 and 50% w/w with low quality subsoil(LQS) originally used as surface layer of an interim landfill cover. The characteristics of the LQS + RMSM mixtures compared to the subsoil(LQS) and the RMSM were determined by physical–chemical, biological and ecotoxicological methods. The addition of RMSM to the subsoil(LQS) at up to 20% did not result any ecotoxic effect, but it increased the water holding capacity. In addition, the microbial substrate utilization became about triple of subsoil(LQS) after 10 months. According to our results the RMSM mixed into subsoil(LQS) at20% w/w dose may be applied as surface layer of landfill cover systems.     

Performance and microbial community analysis of bioaugmented activated sludge for nitrogen-containing organic pollutants removal

Nitrogen-containing organic pollutants (quinoline, pyridine and indole) are widely distributed in coking wastewater, and bioaugmentation with specific microorganisms may enhance the removal of these recalcitrant pollutants. The bioaugmented system (group B) was constructed through inoculation of two aromatics-degrading bacteria, Comamonas sp. Z1 (quinoline degrader) and Acinetobacter sp. JW (indole degrader), into the activated sludge for treatment of quinoline, indole and pyridine, and the non-bioaugmented activated sludge was used as the control (group C). Both groups maintained high efficiencies (> 94%) for removal of nitrogen-containing organic pollutants and chemical oxygen demand (COD) during the long-term operation, and group B was highly effective at the starting period and the operation stage fed with raw wastewater. High-throughput sequencing analysis indicated that nitrogen-containing organic pollutants could shape the microbial community structure, and communities of bioaugmented group B were clearly separated from those of non-bioaugmented group C as observed in non-metric multidimensional scaling (NMDS) plot. Although the inoculants did not remain their dominance in group B, bioaugmentation could induce the formation of effective microbial community, and the indigenous microbes might play the key role in removal of nitrogen-containing organic pollutants, including Dokdonella, Comamonas and Pseudoxanthomonas. Phylogenetic Investigation of Communities by Reconstruction of Unobserved States (PICRUSt) analysis suggested that bioaugmentation could facilitate the enrichment of functional genes related to xenobiotics biodegradation and metabolism, probably leading to the improved performance in group B. This study indicated that bioaugmentation could promote the removal of nitrogen-containing organic pollutants, which should be an effective strategy for wastewater treatment.     

化学沉淀法去除稀土湿法冶炼废水中钙与高浓度氨氮研究

离子型稀土湿法冶炼过程中会产生大量氨氮废水,由于废水中含有大量Ca2+,而Ca2+是影响磷酸铵镁沉淀法脱氮效率的重要因素.向废水中投入Na2CO3固体生成CaCO3沉淀物,去除废水中的Ca2+,再利用磷酸铵镁(MAP)沉淀法去除废水中的氨氮.实验采用响应面实验设计方法中的中心复合设计法,利用响应面分析法对磷酸铵镁沉淀法反应参数进行优化,得到最优反应条件及最优反应条件下沉淀产物.利用扫描电子显微镜(SEM)及X射线衍射(XRD)对最优反应条件下两种沉淀物进行分析.结果表明,当n(Ca2+)∶n(CO23-)=1∶1.05,搅拌速率为1 500 r.min-1,反应时间为30 min时,Ca2+去除率接近100%;对除钙后废水进行磷酸铵镁法脱氮处理的最优反应条件为:pH=9.03,n(Mg)∶n(N)=1.20,n(P)∶n(N)=1.1,反应时间为30 min,搅拌速率为1 000 r.min-1,氨氮去除率达到95.40%,剩余总磷浓度为5.65 mg.L-1;沉淀物分别为纯净的CaCO3及MgNH4PO4.6H2O.     

Practical experiences with the implementation of the concept of zero emissions in the surface treatment industry in Austria

The authors have developed the approach of the “Zero emission retrofitting method for existing galvanizing plants” (ZERMEG). The goal of this approach is to take existing galvanizing plants as far as possible towards zero emissions. The development was supported by the Austrian ministry for science and technology within the programme “Factory of the Future”. The method consists first of an analytical step to describe the existing performance of the plant in terms of production, water input and input of chemicals, a second step is designed to characterize the theoretically possible minimum consumption using the present equipment and the third step is the comparison of the present to the ideal situation to identify optimisation options (improved draining, dosage of chemicals, control of rinsing water, mixing in the tanks, etc.).To facilitate the calculations, a Microsoft-Excel-programme was developed (Zero Emission Program Analysis, ZEPRA), which allows to calculate the ideal water consumption of different configurations of rin ses, drag out for different shapes and surface conditions of parts, and changes in concentrations of active baths. A technology data bank was developed that includes information on different technologies to enlarge the useful time of galvanizing baths or to recycle spent solutions and rinsing water.This paper describes case studies in five galvanizing plants. The measures which were implemented include changing the rinsing cascades in three plants at the wire producer Pengg (reduction of the water consumption in the batch pickling plant by 50%), the use of spent caustics to preneutralise spent process baths and the implementation of an electrolysis plant to recover copper at the printed circuit board manufacturer AT&S (recovery of 20 kg/day of copper), optimising the pickling baths of the hot dip galvanizer Mosdorfer (50% reduction of consumption of acids) and the optimisation of the spray rinses in the automatic copper plating plants of the producer of printing cyclinders Rotoform (reduction of water consumption by 50%, reduction of acid consumption by 40%).The work showed, that in three of the five plants it was possible to fully avoid the discharge of spent process baths. One plant now operates at zero emissions. In one plant it would be technically feasible to do so, however, it is not economically feasible, at this time.     

Bioaugmentation with a pyridine-degrading bacterium in a membrane bioreactor treating pharmaceutical wastewater

The bacterial strain Paracoccus denitrificans W12, which could utilize pyridine as its sole source of carbon and nitrogen, was added into a membrane bioreactor （MBR） to enhance the treatment of a pharmaceutical wastewater. The treatment efliciencies investigated showed that the removal of chemical oxygen demand, total nitrogen, and total phosphorus were similar between bioaugmented and non-bioaugmented MBRs, however, significant removal of pyridine was obtained in the bioaugmented reactor. When the hydraulic retention time was 60 hr and the influent concentration of pyridine was 250-500 mg/L, the mean effluent concentration of pyridine without adding W12 was 57.2 mg/L, while the pyridine was degraded to an average of 10.2 mg/L with addition of W12. The bacterial community structure of activated sludge during the bioaugmented treatment was analyzed using polymerase chain reaction-denaturing gradient gel electrophoresis （PCR-DGGE）. The results showed that the W12 inoculum reversed the decline of microbial community diversity, however, the similarity between bacterial community structure of the original sludge and that of the sludge after bioaugmentation decreased steadily during the wastewater treatment. Sequencing of the DNA recovered from DGGE gel indicated that sp., Sphingobium sp., Comamonas sp., and Hyphomicrobium sp. were the dominant organisms in time sequence in the bacterial community in the bioaugmented MBR. This implied that the bioaugmentation was affected by the adjustment of whole bacterial community structure in the inhospitable environment, rather than being due solely to the degradation performance of the bacterium added.     

高效水解酸化UASB活性污泥的菌群结构分析

采用454高通量测序技术对低能耗、低污泥产量且具有脱氮效能的印染废水处理工艺中UASB污泥的微生物菌群结构进行了分析.结果表明,UASB内污泥的微生物菌种呈多样性分布且优势菌群突出,通过菌群鉴定发现,脱硫橄榄样菌属(Desulfobacula)、Levilinea、长绳菌属(Longilinea)、Candidatus Tammella、Paludibacter、索氏菌属(Thauera)、Tepidimicrobium、杆状脱硫菌属(Desulforhabdus)、类芽孢杆菌属(Paenibacillus)、梭菌属(Clostridium)是主要的优势菌属.其中,梭菌属是起到产酸和污泥减量作用的主要菌种.另外,具有脱氮效能的原因可能是由于发生了硫酸盐型厌氧氨氧化作用.通过Shannon、Chao、Simpson、Shannon指数的计算,发现该UASB中微生物较其他废水处理系统,群落结构拥有较高的多样性和丰度,有利于稳定产酸.     

四环素抗性基因在人工湿地中的去除及累积

以垂直潜流人工湿地系统为试验装置,考察了猪场养殖废水中四环素类抗生素抗性基因(tetW、tetM和tetO)在人工湿地中的去除及累积情况.结果表明,养猪废水中的3种抗性基因均有检出且含量较高,tetW、tetM和tetO的平均绝对含量分别为1.07×1010、4.03×1010和4.92×1010copies.L-1.通过湿地系统处理后,水体中抗生素抗性基因绝对拷贝数和相对表达量均明显降低,tetW、tetM和tetO的平均去除率分别为95.73%、92.21%和95.05%.在系统运行末期,湿地表层土壤和底层土壤中tetW、tetM和tetO的绝对拷贝数和相对表达量均有明显的升高,并且抗性基因在表层土壤中的累积水平高于底层土壤.因此,人工湿地系统可有效降低养猪废水中抗生素抗性基因的绝对及相对含量水平,系统的运行条件可对抗生素抗性基因在湿地系统中的积累产生影响.     

焦化废水活性污泥法处理中微型动物群落及其与处理性能之间的关系

为了分析难降解焦化废水活性污泥法处理中的微型动物群落特征,本研究考察了活性污泥法焦化废水处理厂中的微型动物群落,分析了其与处理性能之间的相互关系.结果发现,本研究共采集的64个水样中,鉴别出28个种属微型动物,其中,原生动物27种(22种纤毛虫、4种鞭毛虫、1种有壳变形虫),1个类群微型后生动物.固着型和匍匐型纤毛虫为共优势群,固着型小口钟虫(Vorticella microstoma)为绝对优势种.除小口钟虫(V.microstoma)(出现频率100%)外,出现频率较高的种类还有轮虫(rotifers)(97%)、沟钟虫(Vorticella convallaria)(69%)等.与常规废水活性污泥法处理系统相比,焦化废水处理系统中的微型动物种类和数量相对偏低.相关性分析结果表明,生物学参数与出水水质、运行参数间存在着不同的相关性.其中,累枝虫属(Epistylis spp.)与出水氨氮(r=-0.740,p0.01)、氰化物(r=0.509,p0.05)和DO(r=0.514,p0.05)存在着显著的相关性;吸管虫属(Podophrya spp.)与硝化效率呈显著负相关(p0.05),它们可作为系统处理性能参数的指示微生物;其他种属与出水水质和运行参数间的相关性不显著(p0.05).因子分析揭示了与系统相关联的潜在的重要影响因素,以及某些微型动物种属间存在的相互关系.     

丹江口库区新生消落带不同土地利用酶活性比较

随着南水北调中线工程的建成,丹江口水库水位上涨形成了大量新生消落带,消落带生态环境变化对水库水质具有较大影响,土壤酶活性和土壤养分的改变在一定程度上能反映土壤生态环境的变化.基于此,以丹江口水库新生消落带为研究区域,选取库周从未经历淹没的区域作为对照,采用裂区试验设计方法,以样地类型（新生消落带和对照区）为主处理,以3种不同土地利用类型（林地、农田和草地）为副处理,研究了土壤酶（脲酶、转化酶、过氧化氢酶和碱性磷酸酶）活性与土壤养分之间的关系.结果表明:①新生消落带土壤中w（TN）、w（NO₃--N）和w（OM）均显著低于对照区（P < 0.05）,而农田、草地的w（NH₄+-N）与林地的w（TP）显著高于对照区（P < 0.05）.②与对照区相比,新生消落带农田和草地的脲酶、转化酶、碱性磷酸酶和过氧化氢酶活性均降低,其中,农田和草地脲酶活性分别降低了79%和54%,而林地脲酶与过氧化氢酶显著增加,林地脲酶活性升高了133%,林地碱性磷酸酶与转化酶活性变化不显著.③不同土地利用类型的土壤理化性质对酶活性的影响不同,新生消落带农田土壤含水量、w（NH₄+-N）的升高及w（TN）、w（TP）、w（OM）的降低是导致酶活性降低的主要影响因素,新生消落带林地土壤pH、w（TP）、w（TN）对酶活性的增加有主要影响,新生消落带草地土壤含水量、w（NH₄+-N）、w（TN）、w（TP）、w（OM）对酶活性的降低有主要影响.研究显示,消落带林地在淹没期间能够吸附固定土壤及水体中的氮磷,水落后土壤酶活性的升高有利于土壤中养分的分解,减少氮磷对库区水体的污染.      

Quantification of hookworm ova from wastewater matrices using quantitative PCR

A quantitative PCR(q PCR) assay was used to quantify Ancylostoma caninum ova in wastewater and sludge samples.We estimated the average gene copy numbers for a single ovum using a mixed population of ova.The average gene copy numbers derived from the mixed population were used to estimate numbers of hookworm ova in A.caninum seeded and unseeded wastewater and sludge samples.The newly developed qP CR assay estimated an average of3.7 × 10~3 gene copies per ovum,which was then validated by seeding known numbers of hookworm ova into treated wastewater.The qP CR estimated an average of(1.1 ± 0.1),(8.6 ± 2.9)and(67.3 ± 10.4) ova for treated wastewater that was seeded with(1 ± 0),(10 ± 2) and(100 ± 21)ova,respectively.The further application of the q PCR assay for the quantification of A.caninum ova was determined by seeding a known numbers of ova into the wastewater matrices.The qP CR results indicated that 50%,90% and 67% of treated wastewater(1 L),raw wastewater(1 L)and sludge(~4 g) samples had variable numbers of A.caninum gene copies.After conversion of the q PCR estimated gene copy numbers to ova for treated wastewater,raw wastewater,and sludge samples,had an average of 0.02,1.24 and 67 ova,respectively.The result of this study indicated that qP CR can be used for the quantification of hookworm ova from wastewater and sludge samples;however,caution is advised in interpreting qP CR generated data for health risk assessment.     

Effects of residual organics in municipal wastewater on hydrogenotrophic denitrifying microbial communities

Hydrogenotrophic denitrification is promising for tertiary nitrogen removal from municipal wastewater. To reveal the influence of residual organics in municipal wastewater on hydrogenotrophic denitrifiers, we adopted high-throughput 16S rRNA gene amplicon sequencing to examine microbial communities in hydrogenotrophic denitrification enrichments. Using effluent from a municipal wastewater treatment plant as water source, COD, nitrate and pH were controlled the same except for a gradient of biodegradable carbon (i.e., primary effluent (PE), secondary effluent (SE), or combined primary and secondary effluent (CE)). Inorganic synthetic water (IW) was used as a control. Hydrogenophaga, a major facultative autotroph, accounted for 17.1%, 5.3%, 32.7% and 12.9% of the sequences in PE, CE, SE and IW, respectively, implicating that Hydrogenophaga grew well with or without organics. Thauera, which contains likely obligate autotrophic denitrifiers, appeared to be the most dominant genera (23.6%) in IW and accounted for 2.5%, 4.6% and 8.9% in PE, CE and SE, respectively. Thermomonas, which is related to heterotrophic denitrification, accounted for 4.2% and 7.9% in PE and CE fed with a higher content of labile organics, respectively. In contrast, Thermomonas was not detected in IW and accounted for only 0.6% in SE. Our results suggest that Thermomonas are more competitive than Thauera in hydrogenotrophic denitrification with biodegradable organics. Moreover, facultative autotrophic denitrifiers, Hydrogenophaga, are accommodating to residual organic in effluent wastewater, thus we propose that hydrogenotrophic denitrification is amenable for tertiary nitrogen removal.     

Role of sorbent surface functionalities and microporosity in 2,2’,4,4’-tetrabromodiphenyl ether sorption onto biochars

The study provides insight into the combined effect of sorbent surface functionalities and microporosity on2,2 ′,4,4 ′-tetrabromodiphenyl ether (BDE-47) sorption onto biochars. A series of biochars prepared underdifferent conditionswere used to test their sorption behaviorswith BDE-47. The extents of sorption behaviorswere parameterized in terms of the single-point adsorption equilibrium constant (Koc ) at three equilibrium concentration (C e ) levels (0.001Sw (solubility), 0.005Sw , and 0.05Sw )whichwasdetermined using the Freundlich model. To elucidate the concentration-dependentdominant mechanisms for BDE-47 sorption onto biochars, K ocwas correlatedwith four major parameters using multiple parameter linear analysis accompaniedwith significance testing. The results indicated that at low concentration (Ce = 0.001Sw ), the surface microporosity term,which represented a pore-filling mechanism, contributed significantly to this relationship,while as concentrationwas increased to higher levels, surface functionality related to surface adsorption began to take thedominant role,whichwas further confirmed by the results of Polanyi-based modeling. Given the above results, adual mode model based on Dubinin-Radushkevich andde Boer-Zwikker equationswas adopted to quantitatively assess the changes of significance of surface adsorption aswell as that of pore fillingwith sorption processdevelopment. In addition, UV spectra of four typical aromatic compoundswhich represented the key structural fragments of biochars before and after interactionswith BDE-47were analyzed todetermine the active functional groups and supply complementary evidence for thedominant interaction force for surface adsorption, based onwhich π-π electron-donor-acceptor interactionwas proposed to contribute greatly to surface adsorption.