表面活性剂修复重金属污染土壤的研究

本文探讨了3种常用表面活性剂,十二烷基苯磺酸钠(SDBS)、十二烷基硫酸钠(SDS)、聚山梨脂(Tween-80)对被重金属铬、镉污染了的土壤的修复洗脱作用,以及被污染土壤对3种表面活性剂的吸附作用。淋洗实验结果表明,3种表面活性剂对土壤中的铬、镉有明显去除效果,聚山梨脂(Tween-80)对污染土壤中铬和镉的去除率分别为61.2%和37.06%。实验表明,土壤对3种表面活性剂均有较强的吸附作用,这种吸附作用对土壤重金属的去除会产生不利的影响。     

Effect of soil texture on surfactant-based remediation of hydrophobic organic-contaminated soil

Surfactants may be used in remediation of subsoil and aquifer contaminated with hydrophobic compounds. The objectives of this study were to examine the effect of soil texture on hydrophobic organic contaminant (HOC; toluene, or 1,2,4-trichlorobenzene [TCB]) removal from six soils and to evaluate the optimal composition of soil texture for maximum HOC removal using aqueous surfactant solution. Selected surfactants were 4% (vol/vol) sodium diphenyl oxide disulfonate (DOSL) and 4% (wt/vol) sodium lauryl sulfate (LS). Toluene and TCB were selected as the lighter-than-water nonaqueous phase liquid (LNAPL) and denser-than-water nonaqueous phase liquid (DNAPL) model substances, respectively. Soil types used for this study were Ottawa sand and five Iowa soils (Fruitfield, Keomah, Crippin, Webster, and Galvar). The greatest recovery of toluene and TCB in batch tests was 73% and 84%, respectively, which was obtained with DOSL surfactant in Ottawa sand. The toluene removal of 95% in column tests has been achieved in the Ottawa sand and three Iowa soils (Fruitfield, Keomah, Crippin) with DOSL after effluent volume of 3750 ml (about 32 pore volume) passed. TCB removal of 98% in column tests has been achieved in Ottawa sand and three Iowa soils (Fruitfield, Keomah, Crippin) with DOSL after effluent volume of 2500 ml (about 21 pore volume) passed. These results were related with soil texture (clay content 30%), clay mineralogy (kaolinite and smectite), as a function of transported pore volume.     

Surfactant enhanced recovery of tetrachloroethylene from a porous medium containing low permeability lenses. 1. Experimental studies

A matrix of batch, column and two-dimensional (2-D) box experiments was conducted to investigate the coupled effects of rate-limited solubilization and layering on the entrapment and subsequent recovery of a representative dense NAPL, tetrachloroethylene (PCE), during surfactant flushing. Batch experiments were performed to determine the equilibrium solubilization capacity of the surfactant, polyoxyethylene (20) sorbitan monooleate (Tween 80), and to measure fluid viscosity, density and interfacial tension. Results of one-dimensional column studies indicated that micellar solubilization of residual PCE was rate-limited at Darcy velocities ranging from 0.8 to 8.2 cm/h and during periods of flow interruption. Effluent concentration data were used to develop effective mass transfer coefficient (Ke) expressions that were dependent upon the Darcy velocity and duration of flow interruption. To simulate subsurface heterogeneity, 2-D boxes were packed with layers of F-70 Ottawa sand and Wurtsmith aquifer material within 20-30 mesh Ottawa sand. A 4% Tween 80 solution was then flushed through PCE-contaminated boxes at several flow velocities, with periods of flow interruption. Effluent concentration data and visual observations indicated that both rate-limited solubilization and pooling of PCE above the fine layers reduced PCE recovery to levels below those anticipated from batch and column measurements. These experimental results demonstrate the potential impact of both mass transfer limitations and subsurface layering on the recovery of PCE during surfactant enhanced aquifer remediation.     

Hydrolysis of a model surfactant as measured using ACYL coenzyme a synthetase

Hydrolysis of a model nonionic surfactant, [1‐¹⁴C]methyl palmitate, was compared between porcine esterase and lipase using a new hydrolase assay. The assay incorporates acyl coenzyme A (CoA) synthetase to convert the hydrolytic product of methyl palmitate, palmitic acid, to its acyl CoA derivative; palmitoyl CoA is separated from unreacted substrate for quantitation by a highly efficient extraction. The assay achieves quantitative separation between product and substrate due to the high water solubility of the acyl CoA derivative, eliminating the need for time‐consuming chromatographic separations. After 60 min under optimal conditions, only 20 U/mL porcine hepatic esterase hydrolyzed 93.6+0.9% of 20μM methyl palmitate, while 100U/mL porcine pancreatic lipase was required to hydrolyze only 82.3 ±0.7% of the same substrate. While both enzymes detoxified the surfactant, esterase was more efficient, possibly indicating preferential specificity for simple monoesters; generally selective for endogenous triacylglycerols, lipase may be less specific for surfactants. However, together both enzymes may enable mammals to hydrolyze ingested nonionic surfactants from oil spill dispersants, reducing their toxicity.     

有机膨润土吸附苯酚的性能及其在水处理中的应用初探

分别用氯化十六烷基吡啶（CPC）和溴化十六烷基三甲铵（CTMAB）改性膨润土,试验了制备有机膨润土的适宜条件及其对吸附苯酚性能的影响。上述两种有机膨润土吸附水中苯酚很快能达到平衡。pH值为3─9时,有机膨润土处理苯酚的效果基本一致;pH>11时,有较高的去除率。CPC－膨润土或CTMAB－膨润土对苯酚的饱和吸附容量分别为103.5mg/g和75.0mg/g。有机膨润土处理苯酚的效果比原土提高8倍以上。     

Recent developments of safer formulations of agrochemicals

The primary objectives of formulation technology are to optimise the biological activity of the pesticide, and to give a product which is safe and convenient for use. However, because of the wide variety of pesticide active ingredients which are available, many different types of formulations have been developed depending mainly on the physico-chemical properties of the active ingredients. In the past most formulations were based on simple solutions in water (SL), emulsifiable concentrates in a petroleum-based solvent (EC), or dusts (DP) and wettable powders (WP). The presence of petroleum-based solvents in EC formulations and dusty powders in DP and WP formulations can lead to safety hazards in use and a negative impact on the envirnoment generally. Most government and regulatory authorities are now demanding formulations which are cleaner and safer for the user, have minimal impact on the environment, and can be applied at the lowest dose rate. Developments in formulation technology and novel formulation types, sometimes in special packaging such as water-soluble packs, can also give products a competitive advantage, add value or extend the lif-cycle of active ingredients. There is also a demand from government authorities and consumer groups to use safer formulation additives and adjuvants, and to minimise the residues of pesticides on food crops after spraying. All of these aspects are putting increasing pressure on the development of improved formulation and adjuvant technologies. Pesticide formulations for spray application and for seed treatment are discussed, along with developments in bioenchancement.     

Soil- and surfactant-enhanced reductive dechlorination of carbon tetrachloride in the presence of Shewanella putrefaciens 200

Sorption of organic contaminants to soils has been shown to limit bioavailability and biodegradation in some systems. Use of surfactants has been proposed to reverse this effect. In this study, the effects of a high organic carbon content soil and a nonionic surfactant (Triton X-100) on the reductive dechlorination of carbon tetrachloride (CCl₄) were examined in anaerobic systems containing Shewanella putrefaciens. Although more than 70% of the added CCl₄ was sorbed to the soil phase in these systems, the reductive dechlorination of CCl₄ was not diminished. Rather, rates of CCl₄ dechlorination in systems containing soil were enhanced relative to systems containing non-sorptive sand slurries. This enhancement was also observed in sterile soil slurries to which a chemical reductant, dithiothreitol was added. It appears that the organic soil used in these experiments contains some catalytic factor capable of transforming CCl₄ in the presence of an appropriate chemical or microbial reductant. The addition of Triton X-100 to sand and soil slurries containing S. putrefaciens resulted in increased CCl₄ degradation in both systems. The effect of Triton could not be explained by: (i) surfactant induced changes in the distribution of CCl₄, (i.e. decreased sorption) or the rate of CCl₄ desorption; (ii) a direct reaction between Triton and CCl₄; or (iii) increased cell numbers resulting from use of the surfactant as a substrate. Rather, it appears that Triton X-100 addition resulted in lysis of bacterial cells, a release of biochemical reductant, and enhanced reductive transformation of CCl₄. These results provide insights to guide the development of more effective direct or indirect bioremediation strategies.     

Sources, transport and reactivity of anionic and non-ionic surfactants in several aquatic ecosystems in SW Spain: a comparative study

Presence, distribution and transport mechanisms of the four major synthetic surfactants -linear alkylbenzene sulfonates (LAS), alkyl ethoxysulfates (AES), nonylphenol ethoxylates (NPEOs) and alcohol ethoxylates (AEOs)- have been simultaneously studied in different aquatic ecosystems. Urban wastewater discharges and industrial activities were identified as the main sources for these compounds and their metabolites. LAS, AES and carboxylic metabolites remained in the dissolved form (87–99%). However, NPEOs and AEOs were mostly associated with particulate matter (65–86%), so their degradation in the water column was limited due to their lower bioavailability. It was also observed that sorption to the particulate phase was more intense for longer homologs/ethoxymers for all surfactants. With respect to surface sediments, AES levels were considerably below (<0.25 mg/kg) the values detected for LAS and NPEOs. Concentrations of AEOs, however, were occasionally higher (several tens of ppm) than those found for the rest of the target compounds in several sampling stations.     

Effect of scale and dimensionality on the surfactant-enhanced solubilization of a residual DNAPL contamination

The mass transfer rate from residual dense non-aqueous phase liquids (DNAPLs) to the mobile aqueous phase is an important parameter for the efficiency of surfactant-enhanced remediation through solubilization of this type of contamination. The mass transfer kinetics are highly dependent on the dimensionality of the system. In this study, irregularly shaped residual TCE saturations in two-dimensional saturated flow fields were flushed with a 2% polyoxyethylene sorbitan (20) monooleate (POESMO) solution until complete removal had been achieved. A numerical model was developed and used for the simulation of the various surfactant-flushing experiments with different initial saturation patterns and flow rates. Through optimization against in situ concentration and saturation data, a phenomenological power-law model for the relationship between the mass transfer rate from the DNAPL to the mobile aqueous phase on the one hand and the residual DNAPL saturation and the flow velocity on the other hand was derived. The obtained mass transfer rate parameters provide a reasonable fit to the experimental data, predicting the cleanup time and the general saturation and concentration pattern quite well but failing to predict the concentration curves at every individual sampling port. The obtained mass transfer rate model gives smaller values for the predicted mass transfer rate but shows a comparable dependence on water flow and saturation as in earlier published one-dimensional column experiments with identical characteristics for porous medium, DNAPL and surfactant. Mass transfer rate predictions were about one order of magnitude lower in the 2-D flow cell experiment than in 1-D column experiments. These results give an indication for the importance of dimensionality during surfactant remediation.     

Identification of surfactants emerged in aerobic granulation

In this study, aerobic granules were cultivated in sequencing batch reactors with activated sludge as the seed. The reactors were operated for 12 h per cycle with the organic loading rate (OLR) increasing in double stepwise from 0.5 to 4.0 g COD L⁻¹ d⁻¹. Within the 40 d running, black granules with regular and smooth morphology were cultivated, which had high wet density and high settling velocity. During the granulation process, foams emerged and disappeared in the reactor, coinciding with the proliferation of filamentous microorganisms in the granules, implying that surfactants might exist and play an important role in the granulation. Using ultra performance liquid chromatography-tandem mass spectrometry, the surfactants were identified as homologous compounds of polyethylene glycol (PEG) with molecular weights ranging mainly from 100 to 500 Da. Their general formulas were proposed as HO-[CH₂-CH₂-O]_n-H. The source of PEG still needs further investigation.