Amorphous and condensed organic matter domains: the effect of persulfate oxidation on the composition of soil/sediment organic matter

The composition of amorphous and condensed soil/sediment organic matter (SOM) domains was investigated for one soil sample and four sediment samples. These samples were oxidized with persulfate to remove amorphous SOM, before and after which the composition of SOM was studied by thermogravimetric analysis, pyrolysis-GC/MS, and cross polarization magic angle spinning 13C-NMR. Comparison of the SOM composition before and after oxidation showed that condensed SOM was more thermostable and less polar than amorphous SOM. Condensed SOM was relatively low in O-alkyl C and carboxyl C and it was likely to contain only small amounts of labile organic components (carbohydrates, peptides, fatty acids). Apart from these general characteristics, the composition of the condensed and amorphous domains appeared to be highly dependent on the origin and nature of the SOM investigated. Condensed domains in relatively undecomposed SOM were enriched in aliphatic C, whereas condensed domains in relatively weathered SOM were enriched in aromatic C. Altogether, the compositional changes upon persulfate oxidation were similar to the compositional changes upon humification, which supports the idea that weathered SOM is more condensed than the original material.     

Impacts of microbial redox conditions on the phase distribution of pyrene in soil-water systems

Variations in the soil/sediment organic matter (SOM)-hydrophobic organic contaminant (HOC) bindings upon microbially mediated redox conditions were examined. While the extractability of pyrene associated with soil declined after its biodegradation began during aerobic incubation, its variations were almost constant (±3.0-4.4%) during anoxic/anaerobic incubations. The dissolved organic matter released from the soil incubated under highly reduced conditions became more humified and aromatic, had a higher average molecular weight, and was more polydispersed compared to that obtained from oxic incubation, similar to the SOM alterations in the early stage of diagenesis (humification). The concentrations of pyrene in the aqueous phase increased significantly during the soil incubations under highly reduced conditions due to its favorable interaction with the altered DOM. Our results suggest that the microbially mediated redox conditions have significant impacts on SOM and should be considered for the transport, fate, bioavailability, and exposure risk of HOCs in the geo-environments.     

The stability of butyltin compounds in a dredged heavily-contaminated sediment

A treatment process for marine sediment heavily contaminated with tributyltin (TBT) was designed that included dehydrating, sunlight drying and dumping processes. The time course in butyltin (BTs) compounds, TBT, dibutyltin (DBT) and monobutyltin concentrations were investigated in the sediment treated under various conditions (light (UV, sunlight and light exclusion), moisture (air-drying and water saturation) and wetting and drying cycles). Significant changes in all the BT compound concentrations with time were not found regardless of the sediment conditions for light and moisture. The results indicated the high stabilities of TBT and DBT in the sediments versus light and moisture condition changes, probably taking place in the treatment process. It is also estimated that the BTs in the sediment are resistant to photo-degradation and biochemical degradation and their half lives are relatively long. In contrast, the decreases in the TBT and DBT were observed during the wetting and drying cycle treatment for the water saturated sediment both during exposure to sunlight and under a dark condition. This result suggested the hypothesis that the TBT degradation could be accelerated by the high microbial activity induced by the moisture changing treatments.     

A laboratory study of sediment and contaminant release during gas ebullition

Significant quantities of gas are generated from labile organic matter in contaminated sediments. The implications for the gas generation and subsequent release of contaminants from sediments are unknown but may include enhanced direct transport such as pore water advection and diffusion. The behavior of gas in sediments and the resulting migration of a polyaromatic hydrocarbon, viz phenanthrene, were investigated in an experimental system with methane injection at the base of a sediment column. Hexane above the overlying water layer was used to trap any phenanthrene migrating out of the sediment layer. The rate of suspension of solid particulate matter from the sediment bed into the overlying water layer was also monitored. The experiments indicated that significant amounts of both solid particulate matter and contaminant can be released from a sediment bed by gas movement with the amount of release related to the volume of gas released. The effective mass transfer coefficient of gas bubble-facilitated contaminant release was estimated under field conditions, being around three orders of magnitude smaller than that of bioturbation. A thin sand-capping layer (2 cm) was found to dramatically reduce the amount of contaminant or particles released with the gas because it could prevent or at least reduce sediment suspension. Based on the experimental observations, gas bubble-facilitated contaminant transport pathways for both uncapped and capped systems were proposed. Sediment cores were sliced to obtain phenanthrene concentration. X-ray computed tomography (CT) was used to investigate the void space distribution in the sediment penetrated by gas bubbles. The results showed that gas bubble migration could redistribute the sediment void spaces and may facilitate pore water circulation in the sediment.     

Artificial and enhanced humification of soil organic matter using microwave irradiation

Microwave (MW) irradiation, a less energy-intensive irradiation technique, was employed to promote the changes in physicochemical properties of soil organic matter (SOM). MW was irradiated to forest soils for 10 min. Then, the physical and chemical properties of the SOM were analyzed with UV absorbance spectroscopy, Fourier transform infrared spectroscopy, elemental analysis, and size exclusion chromatography. Also, the SOM was fractionated into biopolymer, fulvic acid, and humic acid, and each fraction was analyzed quantitatively. These analyses revealed that the SOM became more aromatic and nonpolar, highly condensed, and macromolecular organic substances that possess a higher amount of functional groups found in highly humified substances than the original SOM as a result of the MW irradiation. The humification-like alteration of SOM property was attributable to the thermal cracking and to the radical reaction, particularly when the MW was irradiated along with activated carbon under the aerobic condition. The results of this study suggest that the artificial and enhanced property changes of SOM can be accomplished by MW irradiation on an engineering time scale, which can contribute to the successful soil and groundwater remediation practice.     

A review on the application of microbial toxicity tests for deriving sediment quality guidelines

The results of microbial toxicity tests are needed for the risk assessment of polluted sediments. In comparison with animals the anaerobic microorganisms are more tolerant to natural sediment conditions whereas they are more sensitive for a number of specific pollutants. Microbial toxicity tests from a literature search were classified in seven categories. Category A, B and C use polluted sediments and are applied for sediment monitoring. In category D, a pure chemical is added and the organisms and the test conditions were derived from sediment. Therefore this category can be used for setting sediment quality guidelines which protect sediment functions for the toxic effects of chemicals. In category E, organisms from a polluted site are separated from the sediment and are tested with pure chemicals. Organisms from a more polluted site can be more tolerant to a local pollutant. This is called pollution-induced community tolerance and can be used as evidence for the occurrence of toxic effects in a specific sediment. In category F pure chemicals are tested with a pure culture of microorganisms under sediment conditions. The results of category F tests can be combined with single species tests with animals and plants to obtain sediment quality guidelines sufficient for species protection. This can be compared with the sediment quality guidelines which protect sediment functions. When one of these quality guidelines is exceeded for a compound at a specific location a category E test can be used to determine whether the compound shows toxic effects in that sediment.     

Remediation of heavy metal polluted sediment by suspension and solid-bed leaching: estimate of metal removal efficiency

Remediation of heavy metal polluted sediment by extracting the metals with sulfuric acid can be performed as follows: abiotic suspension leaching, microbial suspension leaching, abiotic solid-bed leaching, and microbial solid-bed leaching. Abiotic leaching means that the acid is directly added, while microbial leaching means that the acid is generated from sulfur by microbes (bioleaching). These four principles were compared to each other with special emphasis on the effectiveness of metal solubilization and metal removal by subsequent washing. Abiotic suspension leaching was fastest, but suspending the solids exhibits some disadvantages (low solid content, costly reactors, permanent input of energy, high water consumption, special equipment required for solid separation, large amounts of waste water, sediment properties hinder reuse), which prevent suspension leaching in practice. Abiotic solid-bed leaching implies the supply of acid by percolating water which proceeds slowly due to a limited bed permeability. Microbial solid-bed leaching means the generation of acid within the bed and has been proven to be the only principle applicable to practice. Metal removal from leached sediment requires washing with water. Washing of solid beds was much more effective than washing of suspended sediment. The kinetics of metal removal from solid beds 0.3, 0.6 or 1.2m in height were similar; when using a percolation flow of 20lm(-2)h(-1), the removal of 98% of the mobile metals lasted 57-61h and required 8.5, 4.2 or 2.3lkg(-1) water. This means, the higher the solid bed, the lower the sediment-mass-specific demand for time and water.     

不同水温时底泥扰动对不同形态磷分布的影响

研究了江南地区典型水温条件下,底泥扰动对上覆水中不同形态磷迁移的影响.结果表明,不同水温条件下,底泥扰动均有利于上覆水中溶解态磷(即溶解性总磷酸盐(DTP),包括溶解性正磷酸盐(DIP)和溶解性有机磷(DOP))向底泥迁移.与对照试验相比,不同水温时的扰动均导致DIP/TP和DTP/TP明显降低.与初始状态(第0天时)相比,扰动导致DIP/TP分别降低了39.61百分点(冬季水温)和17.38百分点(夏季水温),而DTP/TP则分别降低了39.16百分点(冬季水温)和19.06百分点(夏季水温).相反,对照试验中,DTP/TP分别上升了24.90百分点(冬季水温)和23.37百分点(夏季水温).这说明底泥扰动促进了溶解态磷向颗粒态磷(PP)的转化.     

水体沉积物毒性鉴别与评价研究进展

综述了水体沉积物毒性鉴别与评价的主流方法以及研究进展,指出毒性测试和致毒因子鉴别方法是限制水体沉积物污染生态风险评价的关键因素,认为发展和应用以生物标记物和生物效应为导向,尤其是各种具有污染专一性指示作用的生物效应标志测试方法的建立和应用,并结合具有选择性的样品分级技术和先进的仪器进行定性定量分析,将是以生物效应为导向、以化学分析为基础的复杂水体沉积物毒性鉴别与评价的重要发展方向.     

A field study on phytoremediation of dredged sediment contaminated by heavy metals and nutrients: the impacts of sediment aeration

Compared to traditional chemical or physical treatments, phytoremediation has proved to be a cost-effective and environmentally sound alternative for remediation of contaminated dredged sediment. A field study was conducted in a sediment disposal site predominantly colonized by Typha angustifolia under different sediment moisture conditions to estimate the phytoremediation effects of dredged sediment. The moisture content was 37.30 % and 48.27 % in aerated and waterlogged sediment, respectively. Total nitrogen (TN) content was higher in the waterlogged sediment than in the aerated sediment. The total Cd contents were lower in aerated sediment, which was mainly resulted from the lower exchangeable fraction of Cd. The bioaccumulation of P, Cu and Pb in T. angustifolia was promoted by waterlogging, and the belowground tissue concentrations and accumulation factors (AFs) of Cu were higher than that of other metals, which can be explained by that Cu is an essential micronutrient for plants. Consistent with many previous studies, T. angustifolia showed higher metal levels in roots than in above-ground tissues at both the sediment conditions. Due to the improved biomass produced in the aerated sediment, the removals of nutrients and the metals by plant harvest were higher from aerated sediment than from waterlogged sediment. It was indicated that maintaining the dredged sediment aerated can avoid release risk and plant uptake of metals, while the opposite management option can promote phytoextraction of these contaminants.     

Seasonal variation of sediment toxicity in the Rivers Dommel and Elbe

Contaminated sediment in the river basin has become a source of pollution with increasing importance to the aquatic ecosystem downstream. To monitor the temporal changes of the sediment bound contaminants in the River Elbe and the River Dommel monthly toxicity tests were applied to layered sediment and river water samples over the course of 10 months. There is an indication that contaminated sediments upstream adversely affected sediments downstream, but this process did not cause a continuous increase of sediment toxicity. A clear decrease of toxic effects in water and upper layer sediment was observed at the River Elbe station in spring related to high water discharge and algal blooms. The less obvious variation of sediment toxicity in the River Dommel could be explained by stable hydrological conditions. Future monitoring programmes should promote a more frequent and intensive sampling regime during these particular events for ecotoxicological evaluation.     

Predicting organic contaminant concentrations in sediment porewater using solid-phase microextraction

Because of its cost and time saving features, solid-phase microextraction (SPME) is a leading candidate as a biomimic technique in assessing the bioavailable fraction of hydrophobic organic contaminants (HOCs) in sediment porewater. However, no predictive modeling framework in which to systematically address the effect of key parameters on SPME performance for this application exists. In this study, we derived two governing equations to predict (1) the minimum sediment volume (V(s)min) required to achieve non-depletive conditions, and (2) dissolved phase HOC porewater concentrations (C(pw)) as functions of HOC- and sediment specific characteristics in a conceptual three compartment system. The resulting model predicted that V(s)min was independent of HOC concentrations both in sediment and porewater, but did vary with hydrophobicity (characterized by logK(ow)), the fraction of sediment porewater (f(pw)), and the volume (V(f)) of the SPME sorbent phase. Moreover, the effects of these parameters were minimized (i.e., V(s)min reached plateaus) as logK(ow) approached 4-5. Model predictions of C(pw), a surrogate for SPME-based detection limits in porewater, decreased with increasing sediment volume (V(s)) at low V(s) values, but rapidly leveled off as V(s) increased. A third result suggested that the sediment HOC concentration required for SPME is completely independent of K(ow). These results suggest that relatively small sediment volumes participate in exchange equilibria among sediment, porewater and the SPME fiber, and that large sediment HOC reservoirs are not needed to improve the detection sensitivity of SPME-based porewater samplers. The ultimate utility of this modeling framework will be to assist future experimental designs and help predict in situ bioavailability of sediment-associated HOCs.     

Laboratory studies to characterize the efficacy of sand capping a coal tar-contaminated sediment

Placement of a microbial active sand cap on a coal tar-contaminated river sediment has been suggested as a cost effective remediation strategy. This approach assumes that the flux of contaminants from the sediment is sufficiently balanced by oxygen and nutrient fluxes into the sand layer such that microbial activity will reduce contaminant concentrations within the new benthic zone and reduce the contaminant flux to the water column. The dynamics of such a system were evaluated using batch and column studies with microbial communities from tar-contaminated sediment under different aeration and nutrient inputs. In a 30-d batch degradation study on aqueous extracts of coal tar sediment, oxygen and nutrient concentrations were found to be key parameters controlling the degradation rates of polycyclic aromatic hydrocarbons (PAHs). For the five PAHs monitored (naphthalene, fluorene, phenanthrene, anthracene, and pyrene), degradation rates were inversely proportional to molecular size. For the column studies, where three columns were packed with a 20-cm sand layer on the top of a 5 cm of sediment layer, flow was established to sand layers with (1) aerated water, (2) N(2) sparged water, or (3) HgCl(2)-sterilized N(2) sparged water. After steady-state conditions, PAH concentrations in effluents were the lowest in the aerated column, except for pyrene, whose concentration was invariant with all effluents. These laboratory scale studies support that if sufficient aeration can be achieved in the field through either active and passive means, the resulting microbially active sand layer can improve the water quality of the benthic zone and reduce the flux of many, but not all, PAHs to the water column.     

In situ bioassay chambers and procedures for assessment of sediment toxicity with Chironomus riparius

The purpose of this study was to develop an in situ sediment bioassay chamber and respective procedures, suitable for performing toxicity bioassays with benthic invertebrates, using the midge Chironomus riparius. It was also our objective to compare the responses obtained under controlled conditions (laboratory 10-day larval growth and survival test) with those obtained in situ. Clean sand and a formulated sediment were incorporated in the in situ bioassay, along with local sediments, as a way of minimizing natural variability due to physicochemical differences among sediments or due to interactions with indigenous organisms. Recovery of organisms was good (80-100% in the control and reference site), indicating that the developed chamber and protocol were suitable for exposing and retrieving C. riparius in situ. Results also showed differences between responses obtained with formulated and natural sediment in situ, as well as between laboratory and in situ.     

Role of extractable and residual organic matter fractions on sorption of phenanthrene in sediments

Two sediments were demineralized and sequentially fractionated into extracted fractions [free lipid (FL), bound lipid (BL) and lignin (LG)] and residual fractions [free lipid free (FLF), bound lipid free (BLF) and lignin free (LGF)]. The sorption isotherms of phenanthrene (Phen) were examined to evaluate the importance of various fractions on sorption. A lignin extraction procedure was for the first time applied to separate the lignin or degraded lignin fraction from sediment organic matter (SOM). The extracted LG was similar to model lignin in terms of elemental ratios and sorption behavior. FL and LG fractions were quite important, as their contents were much higher than reported values. Phen sorption for the extracted fractions was almost linear, whereas that for the residual fractions was nonlinear, especially for LGF with n 0.56–0.63. As the different organic fractions were removed sequentially, sorption energy distribution on the residual sediment organic matter (SOM) became more heterogeneous. In addition, increasing sorption capacity for the residual fractions, except for BLF with its high polarity, suggested that more sorption sites on the SOM matrix became accessible to Phen. The sorption capacity for LGF was comparable to that of condensed SOM. The residual fraction LGF generally controlled the overall sorption at low Phen concentration, but the extractable fraction FL surpassed the former fraction at high Phen concentration, demonstrating the importance of condensed SOM in the sorption of hydrophobic organic compounds (HOCs) in sediments.     

Assessing sediment hazard through a weight of evidence approach with bioindicator organisms: a practical model to elaborate data from sediment chemistry, bioavailability, biomarkers and ecotoxicological bioassays

Quality assessments are crucial to all activities related to removal and management of sediments. Following a multidisciplinary, weight of evidence approach, a new model is presented here for comprehensive assessment of hazards associated to polluted sediments. The lines of evidence considered were sediment chemistry, assessment of bioavailability, sub-lethal effects on biomarkers, and ecotoxicological bioassays. A conceptual and software-assisted model was developed with logical flow-charts elaborating results from each line of evidence on the basis of several chemical and biological parameters, normative guidelines or scientific evidence; the data are thus summarized into four specific synthetic indices, before their integration into an overall sediment hazard evaluation. This model was validated using European eels (Anguilla anguilla) as the bioindicator species, exposed under laboratory conditions to sediments from an industrial site, and caged under field conditions in two harbour areas. The concentrations of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons and trace metals were much higher in the industrial compared to harbour sediments, and accordingly the bioaccumulation in liver and gills of exposed eels showed marked differences between conditions seen. Among biomarkers, significant variations were observed for cytochrome P450-related responses, oxidative stress biomarkers, lysosomal stability and genotoxic effects; the overall elaboration of these data, as those of standard ecotoxicological bioassays with bacteria, algae and copepods, confirmed a higher level of biological hazard for industrial sediments. Based on comparisons with expert judgment, the model presented efficiently discriminates between the various conditions, both as individual modules and as an integrated final evaluation, and it appears to be a powerful tool to support more complex processes of environmental risk assessment.     

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.     

微生物絮凝剂用于河道疏浚底泥快速脱水的研究

河道疏浚底泥含水率高、体积庞大,不便于储存、运输和资源化利用。首先需要对其进行减量化,使其快速脱水。通过筛选获得一株高效的微生物絮凝剂产生菌F22,通过试验获得其最佳培养条件:葡萄糖为碳源,酵母膏和尿素为氮源,培养时间为60h,培养温度为32℃。将F22菌株所产絮凝剂应用于底泥脱水,试验结果表明,当底泥泥浆(含水率为93%)体积为100mL时,絮凝体系最佳pH为8～10,助凝剂CaCl2最佳投加量为4～5mL,F22菌株发酵液最佳投加量为3mL;絮体在1min左右大部分沉降至底部,F22菌株所产絮凝剂能够使底泥快速脱水。F22菌株所产絮凝剂在絮凝过程中起作用的是糖类物质,其通过氢键结合力产生絮凝作用。     

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.