重金属-多氯联苯复合污染土壤同步洗脱

电子垃圾拆解区土壤具有重金属与有机物复合污染的特性,尤其以Cu、Pb、Cd和多氯联苯(PCBs)的复合污染较为突出。为了同步脱除土壤中重金属与PCBs,选用增溶物质:Tween 80、TX-100、SDBS、β-环糊精与螯合剂柠檬酸依次组合进行复合污染土壤淋洗实验,应用批量平衡震荡法研究它们对重金属(Cu、Pb、Cd)与PCBs(Aroclor 1254)的洗脱效果。通过比较洗脱效果、环境友好性等方面,得出非离子表面活性剂Tween 80与天然螯合剂柠檬酸2种淋洗剂复合最佳;进一步研究两者的淋洗先后顺序、浓度配比、洗脱时间及淋洗剂pH对污染土壤洗脱效果的影响,结果表明,在Tween 80和柠檬酸均为10 g/L、pH=6、淋洗时间12 h时淋洗效果达到最佳,对Cu、Pb、Cd及PCBs的洗脱率分别达到98.77%、55.92%、66.82%和58.01%。因此,利用Tween80和柠檬酸组合可同时有效去除土壤重金属和PCBs,是复合污染土壤淋洗修复的有效淋洗剂。     

Mechanism of PCBs formation from the pyrolysis of chlorobenzenes

Polychlorinated biphenyls (PCBs) were formed by pyrolysis of chlorobenzenes in a HCl atmosphere. Varieties of substituted chlorobenzenes were used as model compounds to optimize the condensation reaction. Lower chlorinated benzenes produce more PCBs than that of higher ones. Up to 0.7 microg PCBs/mg 1,2,3-trichlorobenzene was produced through the condensation reaction.     

生物与化学表面活性剂协同洗脱土壤中PCBs的研究

通过序批实验和土柱淋洗实验研究了由生物表面活性剂鼠李糖脂(RL)与非离子化学表面活性剂十二烷基醇聚氧乙烯(6)醚(POE(6))混合得到的复配试剂洗脱污染土壤中多氯联苯(PCBs)的作用效果及其作用机理。结果表明,同一土样中,从批实验得到的PCBs洗脱率略高于土柱淋洗实验。RL与POE(6)两种单一试剂对人工污染土样中的PCBs洗脱率均大于60%,而对陈化土样中的洗脱率均不到20%,且土壤中的TOC含量越高,PCBs的洗脱率越低。在质量浓度为301 mg/L(10 CMC)及1 505 mg/L(50 CMC)的RL-POE(6)复配试剂中,RL与POE(6)对人工污染土壤中PCBs的洗脱具有一定的协同作用。当复配试剂的浓度为301 mg/L时,RL与POE(6)对陈化土样中PCBs的洗脱没有协同作用;但当RL-POE(6)的浓度增加到1 505 mg/L时,RL与POE(6)对陈化土样中PCBs的洗脱具有明显的协同作用。     

Emission characteristics of PCDD/Fs, PCBs, chlorobenzenes, chlorophenols, and PAHs from polyvinylchloride combustion at various temperatures

The effect of temperature on polyvinylchloride (PVC) combustion using a downstream tubular furnace was investigated for the formation of polycylcic aromatic hydrocarbons (PAHs) and chlorinated compounds. As the temperature increased, higher levels of PAHs were generated. Chlorinated compounds reached a peak at 600 degrees C, with low emissions recorded at 300 and 900 degrees C. There was a close correlation (R2 = 0.97) among polychlorinated biphenyls (PCBs), hexachlorobenzene, pentachlorobenzene, and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). PAHs at all temperatures were analyzed in the gas phase. PCDD/Fs and PCBs were emitted as a solid phase at 300 and 600 degrees C and as a gas phase at 900 degrees C. For some PAHs, chlorobenzenes, and PCDD/Fs, a mathematical equation between the gas and solid phase and the reciprocal temperature in semilog proportion was derived. The proposed equation, which is log (amount in gas phase/amount in solid phase) = -A/T + B, where T is the temperature of the furnace and A and B are constants, for these species relating their gas/solid distributions showed a good relationship.     

PBDEs and PCBs in sediments of the Thi Nai Lagoon (Central Vietnam) and soils from its mainland

Concentration and distribution of PCBs, PCB 11, and PBDEs in both surficial sediment and soil samples, taken from a zone subject to recent accelerated development, were investigated to assess the environmental quality and understand both natural and anthropogenic processes that influence contaminant behaviors. Values of PCB and PBDE are in the lower range of those reported in literature, typical of low impacted coastal zones. This could be due to efficient processes of resuspension and removal. Contaminants in the lagoon showed higher concentrations in sediments from sites close to the city and the outfalls of the industrial area, while soils showed maximum values in the northern samples. In addition, congener patterns and statistical analyses suggest the presence of effective degradation processes, especially for PBDEs, with the exception of the most concentrated samples that may indicate a direct input. PCB 11 is a significant component (up to 18%) in most lagoon sediments. Its presence is strongly associated with fine particles, thus the distribution seems to be driven mainly by the system hydrodynamic and does not trace the sources. Due to evaporation, only flooded agricultural soils show a similar relative abundance of this congener.     

Formation pathways of polychlorinated dibenzofurans (PCDFs) in sediments contaminated with PCBs during the thermal desorption process

Thermal desorption has attracted considerable interest as a remediation technology for the removal of dioxins and polychlorinated biphenyls (PCBs) from contaminated soils and sediments. Although several research groups have confirmed that polychlorinated dibenzofurans (PCDFs) are formed from PCBs during the thermal desorption of sediments contaminated with PCB, the formation pathways remain poorly understood. Herein, thermal desorption has been used to develop a greater understanding of the formation pathways of PCDFs from sediments contaminated with PCBs. PCB decomposition experiments of sediments contaminated with PCBs were performed over 5 min at 450 °C with a gas composition of 10% O(2)/90% N(2), either in the absence (Run 1) or presence (Run 2-4) of one of three different (13)C(12)-labeled PCB individual standards. The results of Run 1 showed that 99.96% of PCBs and 98.40% of polychlorinated dibenzo-p-dioxins (PCDDs) in the treated sediments had decomposed, whereas the concentration levels of PCDFs had increased by a factor of 31. The addition of different (13)C(12)-labeled PCBs to the sediment sample yielded different (13)C(12)-PCDFs isomer patterns, with formation pathways including loss of ortho-Cl(2), loss of HCl involving a 2,3-chlorine shift, loss of ortho-H(2) and dechlorination.     

Bioavailability of PCBs from field-collected sediments: application of Tenax extraction and matrix-SPME techniques

Two chemical approaches, Tenax extraction and matrix solid phase microextraction (matrix-SPME), were evaluated for their potential to improve the prediction of bioavailability by equilibrium partitioning theory (EPT) across sediments with various characteristics. Biota-sediment accumulation factors (BSAFs) and body residues were quantified by exposing Lumbriculus variegatus to three PCB-contaminated field sediments. The concentration of PCBs in biota was positively correlated to the total PCB sediment concentration, the PCB concentration in the rapidly desorbing fraction estimated using Tenax extraction, and the PCB concentration on the SPME fibers. Results showed EPT was acceptable for estimating bioavailability from the tested sediments with sum PCB BSAFs of 1.18-2.47; however, it overestimated PCB bioavailability from sandy sediment. Both Tenax extraction and matrix-SPME, which take sequestration into account, reduced variability in prediction of PCB bioavailability across sediments, including the sandy sediment, and could be used as cost- and time-efficient alternatives for bioassay. Matrix-SPME was considered the better technique due to its ability to directly predict PCB body residues in the exposed biota and its potential use with in situ applications in the field.     

Adsorption and desorption characteristics of hydrophobic pesticide endosulfan in four Indian soils

Adsorption and desorption characteristics of endosulfan in four Indian soils were studied extensively. The soils used were clayey soil (CL--lean clay with sand), red soil (GM--silty gravel with sand), sandy soil (SM--silty sand with gravel) and composted soil (PT--peat) as per ASTM (American Society for Testing and Materials) standards. Adsorption and desorption rates were calculated from kinetic studies. These values varied for alpha and beta endosulfan depending on the soil type. Maximum specific adsorption capacities (qmax) for different soils were calculated by Langmuir model. The values varied from 0.1 to 0.45 mg g(-1) for alpha endosulfan and 0.0942-0.2722 mg g(-1) for beta endosulfan. Maximum adsorption took place in clay soil followed by composted soil and red soil. Adsorptions of alpha and beta endosulfan were negligible in sand. The binding characteristics of various functional groups were calculated using Scatchard plot. Effect of functional groups was more predominant in clayey soil. Organic matter also played a significant role in adsorption and desorption of endosulfan. Endosulfan adsorption decreased drastically in clay soil when the pH was reduced. Desorption was higher at both acidic and alkaline pH ranges compared to neutral pH. Results indicated that alpha endosulfan is more mobile compared to beta endosulfan and mobility of endosulfan is maximum in sandy soil followed by red soil. It can be inferred that crystal lattice of the clay soil plays a significant role in endosulfan adsorption and desorption. Immobilization of endosulfan is more advisable in clay soil whereas biological and or chemical process can be applied effectively for the remediation of other soil types.     

Measured and predicted volatilisation fluxes of PCBs from contaminated sludge-amended soils

A laboratory experiment was carried out to measure volatilisation fluxes of polychlorinated biphenyls (PCBs) from sewage sludge-amended soils. The most commonly practised methods of applying sludge to agricultural land in the UK, namely, surface application, ploughing in to soil and subsurface injection, were simulated inside glass experimental chambers using an anaerobically digested sludge and a sandy loam soil. Humidified air was blown over the surface of the soil/sludge in the chambers for a period of 32 days, in order to sample a sufficient air volume to detect the volatilising PCBs. The resulting PCB volatilisation fluxes from the different sludge application methods were quantified and compared. Volatilisation fluxes of individual congeners were generally highest for the surface sludge (1-cm depth) application and slightly lower for the plough layer (5-cm depth) application. Fluxes from the subsurface layer of sludge (5-cm depth) were only quantified for the lightest congeners near to the end of the experimental run-time. Results from a multiple regression analysis showed that volatilisation fluxes of PCBs from the surface application are highly dependent on both the sludge concentration and the log of the octanol-air partition coefficient (K(OA)). A well-known soil volatilisation model, developed by Jury et al., was adapted and used to predict fluxes for the different sludge application methods during the experiment. The model predicted volatilisation fluxes that were reasonably comparable to measured fluxes for some congeners, but for others predicted fluxes that were more than an order of magnitude lower than measured fluxes. The model predicted similar loss kinetics to those observed in the experiment. Possible reasons for the dissimilarity between measured and predicted fluxes include inaccuracies in model input parameters and the fact that the models were not developed for predicting fluxes from sludge-amended soils.     

PAH desorption from sediments with different contents of organic carbon from wastewater receiving rivers

Background and aim  

Many rivers have to receive treated or untreated wastewater as the main water sources in the world, especially in the countries facing with water shortage. For instance, the Haihe and Huaihe River Basin, which are among areas facing crises for water resources in China, receive 33,400 million tons of wastewater per year. As the sediment has large capacity for sorbing hydrophobic organic pollutants such as polycyclic aromatic hydrocarbons (PAHs), it can act as a natural repository for the contaminants. This means pollutants can release into water phase again under some conditions, such as resuspension, sediment dredging, etc. The objective of this research was to study the trends of PAH release from sediments in rivers receiving much wastewater, such as Yongding New River (YD), Northsewer (NS), and Southsewer (SS) from Haihe River Basin. These rivers received most of the wastewater from Tianjin, China and merge into Bohai Bay finally.     

Development of a simple selective SFE method for the determination of desorption behaviour of PCBs in two Swedish sediments

A simple selective supercritical fluid extraction (SFE) method was developed for the determination of desorption behaviour of PCBs in sediments. This method was applied to determine the distribution of individual PCB congeners among sites of differing bonding strengths in two Swedish sediments (Lake J?rnsj?n and Baltic bay Orserumsviken). Four different PCB fractions were distinguished in each sediment by applying consecutively harsher supercritical fluid extraction conditions on the same sample. Even though the two sediments had completely different textures, they showed very similar extraction behaviour. It was shown that, in both sediments, a major part of the PCBs (58% and 65%, respectively) were located at "fast sites", from which they were extractable already with the mildest extraction conditions (60 min, 40 degrees C and 120 bar). Only a small fraction of the PCBs were so tightly bound to the sediments (located at "slow sites"), that they could be extracted only under the harshest conditions (60 min, 150 degrees C and 400 bar). Information of this kind should be of great value for the determination of bioavailability of pollutants in sediments and soils, and it is the author's belief that this technique has the potential to develop into a powerful tool in environmental risk assessment.     

Distribution characteristics of PCBs in the sediments of the lower Nakdong River, Korea

The objective of this study is to investigate the distribution characteristics of polychlorinated biphenyl (PCB) congeners in sediments of the lower Nakdong River of Korea. The sediments were collected using a grab sampler in May 1999. PCBs were extracted in the Soxhlet extractor and cleaned by using adsorption chromatographic techniques and concentrated sulfuric acid. A HP6890 gas chromatograph equipped with an electron capture detector was used for quantification. The results of congener specific analysis showed that the total concentration is ranged over 1.1-141 ng/g dry weight. The levels of PCB congeners are significantly correlated with the total organic carbons (TOC) in the sediments. The major fractions of PCBs in these sediments are congeners containing 4, 5 or 6 chlorine atoms per biphenyl molecule.     

Enhanced desorption of phenanthrene from soils using hydroxypropyl-beta-cyclodextrin: experimental results and model predictions

Objective of this study was to evaluate the effects of hydroxypropyl-beta-cyclodextrin (HPCD) on the removal of phenanthrene from solid phase. Batch tests for the phenanthrene distribution between aqueous and solid phase were conducted in the presence of HPCD. Column tests and numerical simulations were conducted to evaluate the roles of HPCD cavities and interaction rates between water, HPCD, and solid phase in the enhanced removal of phenanthrene. Experimental results showed that HPCD was effective in removing sorbed phenanthrene from subsurface environment, primarily due to its negligible sorption to the solid phase and the partitioning of phenanthrene into HPCD cavities. From the numerical simulations, it was found that rate-limited partitioning of phenanthrene into HPCD cavities was most influential factor in the enhanced elution of phenanthrene. Sorption and desorption rate of phenanthrene between aqueous and solid phase was very fast or near equilibrium state. Interaction rates of contaminant between water, HPCD, and solid phase could be affected by other factors such as soil types and organic matter contents. Results from this study implied that HPCD flushing could be effectively applied for the removal of hydrophobic organic pollutants existing in the soils as sorbed or NAPL state.     

Extraction of arsenate and arsenite species from soils and sediments

The primary objective of this study was to develop a simple method that can be used to extract the more readily mobilizable and bioavailable arsenic species from soil and sediment while at the same time minimizing the transformation between (AsIII) and (AsV), the two most commonly found arsenic species in the environment. Several extraction strategies were evaluated using phosphate as extractant in combination with either ethylenediaminetetraacetic acid (EDTA), hydroxylamine hydrochloride (NH2OH.HCl), or sodium diethyldithiocarbamate trihydrate (NaDDC). The addition of EDTA in the phosphate solution did not prevent AsIII from oxidation. While promising results were shown when 1% NH2OH.HCl was added, conversion of AsIII began to occur with extended extraction time (> 12 h). Good results were achieved using 10 mM phosphate and 0.5% NaDDC where AsIII oxidation was clearly minimized. The combined phosphate and NaDDC solution was applied to several soil and sediment samples. AsIII spiked was quantitatively recovered in all soil types tested.     

Effect of temperature and particle size on the thermal desorption of PCBs from contaminated soil

Thermal desorption is widely used for remediation of soil contaminated with volatiles, such as solvents and distillates. In this study, a soil contaminated with semivolatile polychlorinated biphenyls (PCBs) was sampled at an interim storage point for waste PCB transformers and heated to temperatures from 300 to 600 °C in a flow of nitrogen to investigate the effect of temperature and particle size on thermal desorption. Two size fractions were tested: coarse soil of 420–841 μm and fine soil with particles <250 μm. A PCB removal efficiency of 98.0 % was attained after 1 h of thermal treatment at 600 °C. The residual amount of PCBs in this soil decreased with rising thermal treatment temperature while the amount transferred to the gas phase increased up to 550 °C; at 600 °C, destruction of PCBs became more obvious. At low temperature, the thermally treated soil still had a similar PCB homologue distribution as raw soil, indicating thermal desorption as a main mechanism in removal. Dechlorination and decomposition increasingly occurred at high temperature, since shifts in average chlorination level were observed, from 3.34 in the raw soil to 2.75 in soil treated at 600 °C. Fine soil particles showed higher removal efficiency and destruction efficiency than coarse particles, suggesting that desorption from coarse particles is influenced by mass transfer.     

鼠李糖脂洗脱土壤中多氯联苯影响因素的研究

研究了由铜绿假单胞菌发酵产生的代表性生物表面活性剂鼠李糖脂（RL）对土壤中PCBs解吸的影响。结果表明,RL的种类与浓度、土壤污染类型、解吸时间、洗脱次数、pH以及离子强度对土壤中PCBs的洗脱有一定的影响,而温度对PCBs的洗脱影响很小。当RL浓度低于CMC时,对PCBs的洗脱没有明显的促进作用;当RL浓度高于CMC后,对PCBs的洗脱有显著的促进作用。具有较低HLB的单鼠李糖脂R2对PCBs的洗脱效果要优于二鼠李糖脂R1。人工污染土壤中PCBs的洗脱效果要高于陈化土壤。污染土壤中TOC的含量越高,PCBs的洗脱率越低。延长解吸时间和增加洗脱次数可增加土壤中PCBs的洗脱率。碱性环境（pH＞7）或增加RL溶液中的离子强度均有利于土壤中PCBs的洗脱。     

Effects of black carbon and montmorillonite clay on multiphasic hexachlorobenzene desorption from sediments

The desorption kinetics of hexachlorobenzene (HCB) in four freshly spiked artificial sediments were determined using a polymeric adsorbent Tenax-mediated desorption. The sediments included a standard sediment (SS) prepared as per Organisation for Economic Cooperation and Development 218 guidelines and three derived artificial sediments prepared by supplementing the SS sediment with various levels of black carbon (lamp black soot) and/or montmorillonite clay. The desorption kinetics exhibited biphasic behavior, i.e., a fast desorbing fraction followed by a slow desorbing fraction. The addition of either lamp black soot or montmorillonite clay resulted in the reduction of the fast desorbing fraction (Ffast) of HCB in three derived sediments compared with SS sediment. Both black carbon and montmorillonite clay treatment effects on the fast desorbing fraction were statistically significant for the four artificial sediments. The black carbon treatment (i.e., addition of 0.5% wt/wt lamp black soot) effect was an average reduction of Ffast by approximately 11%, whereas the montmorillonite treatment (i.e., addition of 15% wt/wt montmorillonite clay) effect was an average reduction of Ffast by approximately 17%. The presence of soot black carbon particles reduced the desorption rate of HCB in sediments since black carbon exhibits very high sorption capacity and extremely slow diffusion rate compared with those of the natural organic matter in sediment.     

Effect of drying on the desorption of diuron and terbuthylazine from natural soils

This work was initiated to study the effects of climate induced soil water status variations which can reach extreme values under natural conditions on the sorption process of hydrophobic organic compounds. Based on the classical slurry batch methodology an approach is developed that allows the fast and careful complete drying of soil suspensions (microwave technique). Classical adsorption experiments were followed by three desorption steps with and without drying cycles. Drying and re-wetting enhanced the sorption-desorption hysteresis and Freundlich adsorption coefficients increased from 5.9 to 16 and 5.2 to 21 over three drying cycles for diuron and terbuthylazine respectively. Assuming the validity of a dual stage adsorption process, model evaluation suggests that drying is as a shrinking-like process leading to conformational changes of the dominant sorbent (soil organic matter) which restrict the intra-micro-particle diffusion. Rewetting only leads to a partial recovery of the diffusional pore space.     

Chlorinated pesticides and PCBs in sediments and molluscs from freshwater canals in the Hanoi region

The concentrations of organochlorine pesticides and PCBs were determined in surface sediments and freshwater molluscs (Angulyagra sp.) from water canals in the region of Hanoi city. Results obtained show that the concentration of sigma DDT compounds in sediments range from 7 to 80 ng/g (dry weight) and from 6 to 864 ng/g (dry weight) in the soft tissues of molluscs. The concentrations of sigma DDTs were higher in populated sites and much lower in rural sites, indicating that the DDT has been used for mosquito control and not as a crop protection chemical. Hexachlocyclohexanes (HCHs) have also been widely used in the region but the current environmental concentrations are much lower than those of DDT's, which is due to the less persistence of those compounds. Polychlorinated biphenyls (PCBs) were measured, for example as aroclor 1254, in concentrations up to 40 ng/g (dry weight) and up to 76 ng/g (dry weight) in sediments and molluscs, respectively. Molluscs from water canals are a very popular food in the region. Taking into consideration the high DDT levels measured in these molluscs their consumption is worrisome and may expose the population to high levels of endocrine disrupting substances. Current PCB levels in sediments are lower than usually measured in industrialized countries. Therefore, PCB concentrations in aquatic molluscs are still also relatively low. These snails do not have enzyme ability to metabolize most of the CB congeners and, thus, are passive accumulators and a significant transfer pathway of CBs to consumers. Therefore, measures to phase out the use of these persistent and bioaccumulable chemicals should be adopted in order to prevent further environmental contamination.