纳米零价铁去除磷酸盐机理研究

纳米零价铁(nanoscale zero-valent iron,nZVI)颗粒具有独特核-壳结构,使其具有较强氧化还原特性,比表面积大和表面活性高等特点,因此被广泛用于不同环境介质中多种污染物的去除修复。本研究采用传统的液相化学还原法合成nZVI颗粒并用于去除水溶液中的磷酸盐。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射仪(XRD)表征nZVI颗粒的性质。实验研究了nZVI投加量、PO3-4初始浓度、溶液初始pH值对nZVI去除PO3-4效率的影响及微米零价铁(micro-ZVI)和nZVI去除PO3-4的对比。实验结果表明,当PO3-4初始浓度为20mg/L时,随着nZVI投加量从200mg/L增加到1000mg/L,PO3-4去除效率从32.94%上升到90.17%;当nZVI投加量为600mg/L时,随着PO3-4初始浓度从10mg/L增加到100mg/L,PO3-4去除效率从87.33%下降到45.77%;当nZVI投加量为600mg/L且PO3-4初始浓度为20mg/L,溶液pH分别为3和4时,PO3-4去除效率分别为83.63%和92.36%;nZVI和mZVI投加量均为600mg/L且PO3-4初始浓度为10mg/L,nZVI的PO3-4去除率(87.33%)是mZVI(8.86%)的9.86倍。研究结果表明,nZVI能够高效去除水体中的磷酸盐,主要去除机理是吸附和化学沉淀的双重作用。     

零价纳米铁在修复受污染地下水中的最新进展

本文针对零价纳米铁(nZVI)在修复受污染地下水中存在的易于团聚、迁移性低及易于老化等问题,详细介绍了近年在这些问题研究上的最新进展,包括材料的改性,改性材料对污染物降解的效果及研究中不同因素的影响等。并就nZVI对难降解复杂有机污染物的降解进行了总结,在此基础上展望了nZVI对一类新兴污染物,药品和个人护理用品(PPCPs)的降解。     

Removal of trichloroethylene from soil using the hydration of calcium oxide

Quicklime addition to soil at a remediation site was observed to sufficiently reduce TCE levels, but the cause of the removal could not be confirmed with the field data collected. Potential mechanisms for CaO treatment of trichloroethylene (TCE) in soil include degradation and volatilization. Since earlier studies found TCE degradation to occur during the hydration of CaO under conditions where volatilization was limited, research was conducted on mechanisms of TCE removal from soil by CaO application under conditions where volatilization was allowed to occur. TCE volatilization in soil treated with 0%, 5%, 10%, and 20% CaO doses was measured in experiments where the degree of volatilization could be tracked. The total TCE removal from soil spiked with TCE at CaO doses from 5% to 20% ranged from 97% to 99% of the initial TCE mass. Volatilization accounted for 64.4-92.5% of the TCE removal, with unrecovered TCE and TCE degradation accounting for the remaining fraction. The greater heat encountered with higher CaO doses helped minimize obstacles to TCE volatilization, such as high soil organic and clay content. Treatment with a 20% CaO dose, however, led to the formation of byproducts such as dichloroacetylene. TCE degradation to dichloroacetylene at the 20% CaO dose ranged from 2.7% to 6.4% of the initial TCE. Volatilization was concluded to be the dominant process for TCE removal from soil during CaO treatment.     

活性炭烟气脱硫技术研究新进展

研制了新型活性炭脱硫剂－脱硫活性碳纤维。研究表明，脱硫活性碳纤维由于含碳量高、比表面积大、微孔丰富、孔径分布窄、有较多适于吸附ＳＯ２的表面官能团，因而吸附能力及吸附、脱附速度显著大于普通活性炭。在相同工艺条件下，脱硫活性碳纤维吸附容量为粒状疾性炭的４－５倍，空速粒达活性炭的１０倍。采用活性碳纤维脱硫可比普通活性碳脱硫剂用量成倍减少。另外，由于活性碳纤维阻力小，系统能耗可显著降低。活性碳烟气脱硫采用     

苏州市某水厂深度处理工艺活性炭选型试验

为筛选出适合苏州地区深度处理工艺所需的活性炭,对活性炭的吸附性能、生物膜挂膜情况以及出水浑浊度、高锰酸盐指数、TOC、UV254、氨氮、亚硝酸盐氮等水质指标进行了考察。结果表明,GAC3和GAC4活性炭在各项性能方面均优于其他活性炭。从价格上考虑,选取GAC4活性炭作为苏州市该水厂深度处理活性炭。活性炭滤池运行3个月后,对其出水进行了106项全分析,所有水质指标均能达到GB 5749-2006的要求。     

臭氧在"臭氧-生物活性炭"饮用水处理工艺中的作用研究

本文通过分析饮用水深度处理中试工艺各处理单元出水水质指标的变化研究臭氧在臭氧生物活性炭工艺中的作用。试验结果表明：在中试工艺中，臭氧具有很好的氧化、杀藻和消毒的作用；并且两级臭氧氧化分别对常规处理单元和颗粒活性炭去除污染物具有一定的促进作用。     

What is soil organic matter worth?

The conservation and restoration of soil organic matter are often advocated because of the generally beneficial effects on soil attributes for plant growth and crop production. More recently, organic matter has become important as a terrestrial sink and store for C and N. We have attempted to derive a monetary value of soil organic matter for crop production and storage functions in three contrasting New Zealand soil orders (Gley, Melanic, and Granular Soils). Soil chemical and physical characteristics of real-life examples of three pairs of matched soils with low organic matter contents (after long-term continuous cropping for vegetables or maize) or high organic matter content (continuous pasture) were used as input data for a pasture (grass-clover) production model. The differences in pasture dry matter yields (non-irrigated) were calculated for three climate scenarios (wet, dry, and average years) and the yields converted to an equivalent weight and financial value of milk solids. We also estimated the hypothetical value of the C and N sequestered during the recovery phase of the low organic matter content soils assuming trading with C and N credits. For all three soil orders, and for the three climate scenarios, pasture dry matter yields were decreased in the soils with lower organic matter contents. The extra organic matter in the high C soils was estimated to be worth NZ$27 to NZ$150 ha(-1) yr(-1) in terms of increased milk solids production. The decreased yields from the previously cropped soils were predicted to persist for 36 to 125 yr, but with declining effect as organic matter gradually recovered, giving an accumulated loss in pastoral production worth around NZ$518 to NZ$1239 ha(-1). This was 42 to 73 times lower than the hypothetical value of the organic matter as a sequestering agent for C and N, which varied between NZ$22,963 to NZ$90,849 depending on the soil, region, discount rates, and values used for carbon and nitrogen credits.     

功率超声应用于有机污染物降解的研究概况

功率超声是一项降解有机污染物的新型技术。本文介绍了功率超声降解有机污染物的原理：声空化理论及功率超声降解过程中导致有机物分解的三个主要机理,即高温热解机理、OH自由基氧化机理以及超临界水氧化机理。并系统地介绍了挥发性及难挥发性有机物应用功率超声降解时,在不同降解机理影响下的处理效果。文章同时介绍了影响超声降解的一些重要的物理、化学因素。最后提到目前超声降解存在的问题和发展前景。     

Dynamic modeling of chemical fate and transport in multimedia environments at watershed scale-II: trichloroethylene test case

A multimedia environmental fate model was developed to study the temporal dynamics and spatial distribution of a chemical pollutant at watershed scale. The theoretical considerations and implementation of the model were described in the accompanying paper (Part I). This paper presents the result of a test simulation on the transport of trichloroethylene (TCE) in the Connecticut River Basin. The simulation results were reported as time series of concentrations and inter-media transport fluxes in the compartments of atmosphere, plant, soil, surface water, and sediment. Predicted concentrations from the test simulation were compared with published field data or predictions by validated models. The temporal trends in TCE predictions were evaluated by comparing the simulation results with monthly TCE concentrations in various environmental compartments and monthly fluxes of inter-media transport processes. Results indicated that the simulation results were in reasonable agreement with reported data in the literature. The results also revealed that the mass transport of TCE from the atmosphere compartment to soil and surface water was a major route of TCE dispersion in the environment.     

Nanosponges for water purification

We synthesized a new class of organic nanoporous polymers using cyclodextrins as basic building blocks. These processible nanoporous polymers were named 'nanosponges' because they have nanometer-size pores (distribution 0.7-1.2 nm) and exhibit superior ability to absorb organic molecules in water. Cyclodextrin cavities provide a hydrophobic environment and hence generate a strong affinity to organic molecules at water-solid interfaces. Indeed, the formation constant (K) of polymeric cyclodextrins and organic guest molecules is more than eight orders of magnitude larger than molecular cyclodextrin systems in water, and yet the process is completely reversible in organic solvents such as ethanol. The significant potential of these results is that hazardous organic contaminants may be reduced to parts-per-trillion levels in water by these polymers, as measured by ion-trap mass spectroscopy and UV-visible spectroscopy.     

Forest fertilization with wood ash: effect on the distribution and storage of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs)

Before wood ash can be safely used as a fertilizer in forests, possible negative effects such as input of organic contaminants or remobilization of contaminants already stored in the soil must be investigated. The objective of this study was to examine the effects of wood ash application on concentrations, storage, and distribution of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in a Swiss forest soil. In May 1998, we added 8 Mg wood ash ha(-1) to a forest soil. We determined 20 PAHs and 14 PCBs in the organic layer, in the bulk mineral soil, and in soil material taken from preferential flow paths and from the matrix before and after the wood ash application. In the control plots, the concentrations of PAHs in the organic layer indicated moderate pollution (sum of 20 PAHs: 0.8-1.6 mg kg(-1)), but sum of PCB concentrations was high (21-48 microLg kg(-1)). The wood ash had high concentrations of PAHs (sum of 20 PAHs: 16.8 mg kg(-1)), but low concentrations of PCBs (sum of 14 PCBs: 3.4 microg kg(-1)). The wood ash application increased the PAH concentrations in the organic horizons up to sixfold. In contrast, PCB concentrations did not change in the Oa horizon and decreased up to one third in the Oi and Oe horizons. The decrease was probably caused by the mobilization of stored PCBs because of the high pH of the wood ash. This probably results in a higher mobility of dissolved organic matter, acting as PCB carrier. In the mineral soil, the preferential flow paths of the A horizon contained more PAHs and PCBs (+20 +/- 15% and +43 +/- 60%, respectively) than the matrix. This was particularly true for higher molecular weight compounds (molecular weight > 200 g mol(-1)). Below 50 cm depth, concentrations of PAHs and PCBs were smaller in the preferential flow paths, suggesting that in deeper depths, processes acting as sinks dominated over inputs in the preferential flow paths.     

Changes in crested wheatgrass root exudation caused by flood, drought, and nutrient stress

Root exudates can chelate inorganic soil contaminants, change rhizosphere pH, and may increase degradation of organic contaminants by microbial cometabolism. Root-zone stress may increase exudation and enhance phytoremediation. We studied the effects of low K+, high NH4+/NO3- ratio, drought, and flooding on the quantity and composition of exudates. Crested wheatgrass (Agropyron cristatum) was grown in Ottawa sand in sealed, flow-through glass columns under axenic conditions for 70 d. Root exudates were collected and analyzed for total organic carbon (TOC) and organic acid content to compare treatment effects. Plants in the low K+ treatment exuded 60% more TOC per plant per day (p = 0.01) than the unstressed control. Drought stress increased cumulative TOC exuded per gram dry plant by 71% (p = 0.05). The flooded treatment increased TOC exuded per gram dry plant by 45%, although this was not statistically significant based on the two replicate plants in this treatment. Exudation from the high NH4+/NO3- ratio treatment was 10% less than the control. Exudation rates in this study ranged from 8 to 50% of rates in four other published studies. Gas chromatography-mass spectrometry (GC-MS) analysis indicated that malic acid was the predominant organic acid exuded. Fumaric, malonic, succinic, and oxalic acids were also detected in the exudates of all treatments. These results demonstrate that nutrient and water stress have significant effects on the quantity and composition of root exudates. Cultural manipulations to induce stress may change the quantity of root exudates and thus increase the effectiveness of phytoremediation.     

Use of mini-sprinklers to strip trichloroethylene and tetrachloroethylene from contaminated ground water

Three low-volume mini-sprinklers were tested for their efficacy to strip trichloroethylene (TCE) and tetrachloroethylene (PCE) from water. Deionized water spiked with TCE and PCE was pumped for approximately 1 h at 0.19 to 0.21 MPa (28 to 30 lb in(-2)) through a mini-sprinkler supported on top of a 1.8-m-tall riser. Water was collected in collection vessels at 0.61 and 1.22 m above the ground on support columns that were spaced at 0.61-m intervals from the riser base, and samples were composited per height and distance from the riser. Overall, air-stripping reduced dissolved concentrations of TCE and PCE by 99.1 to 100 and 96.9 to 100%, respectively, from mean influent dissolved concentrations of 466 to 1675 microg L(-1) TCE and 206 to 940 microg L(-1) PCE. In terms of mass removed, the mini-sprinklers removed TCE and PCE at a rate of approximately 1400 to 1700 and 700 to 900 microg L(-1), respectively, over a 1-h test period. Mini-sprinklers offer the advantages of (i) easy setup in series that can be used on practically any terrain; (ii) operation over a long period of time that does not threaten aquifer depletion; (iii) use in small or confined aquifers in which the capacity is too low to support large irrigation or purging systems; and (iv) use in forests in which the small, low-impact droplets of the mini-sprinklers do not damage bark and in which trees can help manage (via evapotranspiration) excess waste water.     

Polycyclic aromatic hydrocarbon release from a soil matrix in the in vitro gastrointestinal tract

Soil ingestion is an important exposure route by which immobile soil contaminants enter the human body. We assessed polycyclic aromatic hydrocarbon (PAH) release from a contaminated soil, containing 49 mg PAH kg(-1), using a SHIME (Simulator of the Human Intestinal Microbial Ecosystem) reactor comprising the stomach, duodenal, and colon compartments. Polycyclic aromatic hydrocarbon release was defined as that fraction remaining in the digest supernatant after centrifugation for 5 min at 1500 x g. The PAH release in the stomach digest was only 0.44% of the total PAH present in soil, resulting in PAH concentrations of 23 micrograms PAH L(-1) chyme. The lower PAH releases in duodenum (0.13%) and colon (0.30%) digests, compared with the stomach digest, were thought to be attributed to combined complexation and precipitation with bile salts, dissolved organic matter, or colon microbiota. We studied these complexation processes in an intestinal suspension more in depth by preparing mixtures of 9-anthracenepropionic acid, a Bacillus subtilis culture, and cholin as model compounds for PAHs, organic matter, and bile salts, respectively. Bile salts or organic matter in the aqueous phase initially enhance PAH desorption from soil. However, desorbed PAHs may form large aggregates with bile and organic matter, lowering the freely dissolved PAH fraction in the supernatant. Using the model compounds, mathematical equations were developed and validated to predict PAH complexation processes in the gastrointestinal tract. Contaminant release and subsequent complexation in the gut is an important prerequisite to intestinal absorption and thus bioavailability of that contaminant. The data from this research may help in understanding the processes to which PAHs are subjected in the gastrointestinal tract, before intestinal absorption.     

Trichloroethylene (TCE) removal in a single pulse suspension bioreactor

This work describes TCE biotic removal in a single-pulse bioreactor under aerobic conditions. Activated sludge from a wastewater-treatment plant was used for inoculation of the cultivator. The experiment focused on a more detailed verification of microbial composition of mixed heterotrophic culture during pulsed phenol dosage. Attention was given to suppressing eucaryotic organisms, particularly yeasts and fungi, by the addition of cycloheximide. The TCE-removal capacity of the heterotrophic culture, described by kinetic tests, was dependent on pulsed phenol injection and on cyclic addition of phenol and TCE. Maximum TCE degradation was determined in a batch test. It was found that the addition of cycloheximide (an antibiotic against propagation and growth of fungi and yeast) increased the TCE degradation activity of the mixed microbial suspension. A certain residual amount of TCE remained in some of the experiments.     

Removal of organic matter and nitrogen from river water in a model floodplain

A significant improvement in river water quality cannot be expected unless nonpoint-source contaminants are treated in addition to the further treatment of point-source contaminants. If river water is sprayed over a floodplain, the consequent water filtration through the sediment profile can simultaneously remove organic matter and nitrogen in the water through aerobic and denitrifying reactions. This hypothesis was tested using lysimeters constructed from polyvinyl chloride (PVC) pipe (150 cm long, 15 cm in diameter) packed with loamy sand floodplain sediment. Water was applied to the top of the lysimeters at three different flow rates (48, 54, and 68 mm d(-1)). Concentrations of NO3 and dissolved oxygen (DO), chemical oxygen demand (COD), and redox potential (Eh) in the water were measured as functions of depth after the system reached steady states for both water flow and reactions. At the rate of 68.0 mm d(-1), a reducing condition for denitrification developed below the 5-cm depth due to the depletion of O2 by organic matter degradation in the surface oxidizing layer; Eh and DO were below 205 mV and 0.4 mg L(-1), respectively. At a depth of 70 cm, COD and NO3-N concentration decreased to 5.2 and 3.8 mg L(-1) from the respective influent concentrations of 17.1 and 6.2 mg L(-1). Most biodegradable organic matter was removed during flow and further removal of NO3 was limited by the lack of an electron donor (i.e., organic matter). These results indicate that the floodplain filtration technique has great promise for treatment of contaminated river water.     

The application of potassium ferrate for sewage treatment

The comparative performance of potassium ferrate(VI), ferric sulphate and aluminium sulphate for the removal of turbidity, chemical oxygen demand (COD), colour (as Vis400-abs) and bacteria in sewage treatment was evaluated. For coagulation and disinfection of sewage, potassium ferrate(VI) can remove more organic contaminants, COD and bacteria in comparison with the other two coagulants for the same doses used. Also, potassium ferrate(VI) produces less sludge volume and removes more contaminants, which should make subsequent sludge treatment easier.     

Stability constants for the complexation of various metals with a rhamnolipid biosurfactant

The presence of toxic metals in natural environments presents a potential health hazard for humans. Metal contaminants in these environments are usually tightly bound to colloidal particles and organic matter. This represents a major constraint to their removal using currently available in situ remediation technologies. One technique that has shown potential for facilitated metal removal from soil is treatment with an anionic microbial surfactant, rhamnolipid. Successful application of rhamnolipid in metal removal requires knowledge of the rhamnolipid-metal complexation reaction. Therefore, our objective was to evaluate the biosurfactant complexation affinity for the most common natural soil and water cations and for various metal contaminants. The conditional stability constant (log K) for each of these metals was determined using an ion-exchange resin technique. Results show the measured stability constants follow the order (from strongest to weakest): Al3+ > Cu2+ > Pb2+ > Cd2+ > Zn2+ > Fe3+ > Hg2+ > Ca2+ > Co2+ > Ni2+ > Mn2+ > Mg2+ > K+. These data indicate that rhamnolipid will preferentially complex metal contaminants such as lead, cadmium, and mercury in the presence of common soil or water cations. The measured rhamnolipid-metal stability constants were found in most cases to be similar or higher than conditional stability constants reported in the literature for metal complexation with acetic acid, oxalic acid, citric acid, and fulvic acids. These results help delineate the conditions under which rhamnolipid may be successfully applied as a remediation agent in the removal of metal contaminants from soil, as well as surface waters, ground water, and wastestreams.     

Impact of ectomycorrhizal colonization of hybrid poplar on the remediation of diesel-contaminated soil

Infection by ectomycorrhizal (ECM) fungi may benefit hybrid poplar growing in contaminated soils by providing greater access to water and nutrients and possibly protecting the trees from direct contact with toxic contaminants. The objective of this research was to determine the effect of colonization of the ECM fungus Pisolithus tinctorius (Pers.) Coker & Couch on hybrid poplar fine root production, biomass and N and P uptake when grown in diesel-contaminated soil (5000 mg diesel fuel kg soil(-1)). Commercially available Mycogrow Tree Tabs were the source of inoculum. A minirhizotron camera was used to provide the data necessary for estimating fine root production. Colonization of hybrid poplar roots (P. deltoides x [P. laurifolia x P. nigra] cv. Walker) by P. tinctorius increased total fine root production in diesel-contaminated soil to 56.58 g m(-2) compared to 22.59 g m(-2) in the uncolonized, diesel-contaminated treatment. Hybrid poplar leaf N and P concentrations were significantly greater in the diesel-contaminated/ECM-colonized treatment compared to the diesel-contaminated/uncolonized treatment after 12 wk, while significantly less diesel fuel was recovered from the soil of the uncolonized treatment compared to the colonized treatment. Both planted treatments removed more contaminants from the soil than an unplanted control. Significantly greater concentrations of total petroleum hydrocarbons (TPH) were found sequestered in hybrid poplar root/fungal-sheath complexes from the colonized treatment compared to the roots of the uncolonized treatment. The results of this study indicate that over a 12-wk growth period, ECM colonization of hybrid poplar in diesel-contaminated soils increased fine root production and whole-plant biomass, but inhibited removal of TPH from the soil.     

A polymer-ceramic composite membrane for recovering volatile organic compounds from wastewaters by pervaporation

A composite membrane was constructed on a porous ceramic support from a block copolymer of styrene and butadiene (SBS). It was tested in a laboratory pervaporation apparatus for recovering volatile organic compounds (VOCs) such as 1,1,1-trichloroethane (TCA) and trichloroethylene (TCE) from dilute aqueous solutions. This polymer-ceramic composite membrane yielded significantly higher VOC selectivity than an SBS membrane without the ceramic support, for comparable fluxes. At VOC concentrations near 100 ppm, fluxes and selectivities of VOCs were essentially independent of the number of VOCs in solution. The liquid-side boundary layer resistance dominated mass transport. The experimental data fitted the resistance-in-series model and yielded reliable membrane permeability values. This method using this high-performing membrane offers potentially cleaner and cost-effective means of recovering VOCs from contaminated streams.