Reducing plant uptake of PAHs by cationic surfactant-enhanced soil retention

Reducing the transfer of contaminants from soils to plants is a promising approach to produce safe agricultural products grown on contaminated soils. In this study, 0-400 mg/kg cetyltrimethylammonium bromide (CTMAB) and dodecylpyridinium bromide (DDPB) were separately utilized to enhance the sorption of PAHs onto soils, thereby reducing the transfer of PAHs from soil to soil solution and subsequently to plants. Concentrations of phenanthrene and pyrene in vegetables grown in contaminated soils treated with the cationic surfactants were lower than those grown in the surfactant-free control. The maximum reductions of phenanthrene and pyrene were 66% and 51% for chrysanthemum (Chrysanthemum coronarium L.), 62% and 71% for cabbage (Brassica campestris L.), and 34% and 53% for lettuce (Lactuca sativa L.), respectively. Considering the impacts of cationic surfactants on plant growth and soil microbial activity, CTMAB was more appropriate to employ, and the most effective dose was 100-200 mg/kg.     

Estimation of the volatilization of organic compounds from soil surfaces

Several simple models for the estimation of the half-life (t(1/2)) for the depletion of an organic chemical from a soil surface to air were examined. For moist surfaces, two models are proposed: the first requires knowledge of the soil/organic carbon partition coefficient (K(oc)) and the Henry's law constant (H) and the second the vapor pressure (P(s)) of the chemical involved. Due to uncertainties in the experimental K(oc) values those ones predicted by the group-contribution model of Meylan et al. [Environ. Sci. Technol. 26 (1992) 1560]-and proposed by the U.S. Environmental Protection Agency (EPA)-should be used. If reliable experimental P(s) values are not available, the first model is proposed, where in cases when H values are not available, predicted ones by the Bond-Contribution method of Meylan and Howard [Environ. Toxicol. Chem. 10 (1991) 1283]-and also proposed by EPA-can be used. In general, the agreement of the predicted t(1/2) values with the measured ones is within a factor of 3-5. Similar expressions, but with somewhat poorer results, are presented for dry field soils. In all cases, the obtained results represent a substantial improvement over those obtained with the currently used Dow method: t(1/2) = 1.58 x 10(-8)((K(oc) x S)/P(S)), where S is the solubility of the compound in water.     

Roles of oxidant,activator, and surfactant on enhanced electrokinetic remediation of PAHs historically contaminated soil

Electrokinetic (EK) remediation technology can enhance the migration of reagents to soil and is especially suitable for in situ remediation of low permeability contaminated soil. Due to the long aging time and strong hydrophobicity of polycyclic aromatic hydrocarbons (PAHs) from historically polluted soil, some enhanced reagents (oxidant, activator, and surfactant) were used to increase the mobility of PAHs, and remove and degrade PAHs in soil. However, under the electrical field, there are few reports on the roles and combined effect of oxidant, activator, and surfactant for remediation of PAHs historically contaminated soil. In the present study, sodium persulfate (PS, oxidant, 100 g L^?1) or/and Tween 80 (TW80, surfactant, 50 g L^?1) were added to the anolyte, and citric acid chelated iron(II) (CA-Fe(II), activator, 0.10 mol L^?1) was added to catholyte to explore the roles and contribution of enhanced reagents and combined effect on PAHs removal in soil. A constant voltage of 20 V was applied and the total experiment duration was 10 days. The results showed that the removal rate of PAHs in each treatment was PS + CA-Fe(II) (21.3%) > PS + TW80 + CA-Fe(II) (19.9%) > PS (17.4%) > PS + TW80 (11.4%) > TW80 (8.1%) > CK (7.5%). The combination of PS and CA-Fe(II) had the highest removal efficiency of PAHs, and CA-Fe(II) in the catholyte could be transported toward anode via electromigration. The addition of TW80 reduced the electroosmotic flow and inhibited the transport of PS from anolyte to the soil, which decreased the removal of PAHs (from 17.4 to 11.4% with PS, from 21.3 to 19.9% with PS+CA-Fe(II)). The calculation of contribution rates showed that PS was the strongest enhancer (3.3~9.9%), followed by CA-Fe(II) (3.9~8.5%) (with PS), and the contribution of TW80 was small and even negative (?1.4~0.6%). The above results indicated that the combined application of oxidant and activator was conducive to the removal of PAHs, while the addition of surfactant reduced the EOF and the migration of oxidant and further reduced the PAHs removal efficiency. The present study will help to further understand the role of enhanced reagents (especially surfactant) during enhanced EK remediation of PAHs historically contaminated soil.

     

Outdoor experiments on enhanced volatilization by venting of kerosene component from soil

The effect of soil properties on the retention of kerosene in soils, at equilibrium and under venting, was studied. Eleven soils were studied, which represent a wide range of chemical properties and mechanical composition. The retention of kerosene in dry soils ranges from 3.5 to 18.1 mL/(100 g), and was related linearly to clay, silt and organic matter (OM) contents. A coarsely-aggregated dry vertisol (2–5 mm aggregates) retained half as much kerosene as its finely-aggregated (<2 mm) counterpart. Moisture content had a strong inverse effect on kerosene retention. The soil factors that inversely affected kerosene retention also enhanced kerosene stripping by venting. Of these, soil aggregation and porosity were the most important. In addition, kerosene volatilized faster and more completely from an initially moist soil, as compared with an initially dry soil. Differential volatilization of lighter components of kerosene changed the chemical composition of the residue in the soil substantially, as compared with the initial composition.     

Effect of surfactant alkyl chain length on soil cadmium desorption using surfactant/ligand systems

The effect of surfactant alkyl chain length on soil Cd desorption was studied using nonionic surfactants of polyethylene oxide (PEO) of PEO chain lengths of 7.5 (Triton X-114), 9.5 (Triton X-100), 30 (Triton X-305), or 40 units (Triton X-405) in combination with the I- ligand. Triplicate 1 g soil samples were equilibrated with 15 ml of surfactant-ligand mixture, at concentrations of 0.025, 0.50 or 0.10, and 0.0, 0.168 or 0.336 mol/l, respectively. After shaking the samples for 24 h, the supernatant fraction was analyzed for Cd content to determine the percent of Cd desorbed from the soil. After five successive washings, 53%, 40% and 25% of Cd had been desorbed by 0.025, 0.050 or 0.10 mol/l of Triton X-114, respectively, in the presence of 0.336 mol/l of I-, whereas with the same conditions, Triton X-100 desorbed 61%, 57% and 56% Cd and either Triton X-305 or Triton X-405 desorbed 51, 40 and 14 to 16% Cd. The most efficient Cd desorption was obtained using 0.025 mol/l Triton X-100 in admixture with 0.336 mol/l I-. Increased surfactant concentration was detrimental to Cd desorption consistent with a process that blocked ligand access to the soil particle surface. After 5 washings,the cumulative cadmium desorption decreased with increasing surfactant alkyl chain length, indicating that the metal-ligand complexes are preferably stabilized by the micelles' hydrophobic octyl phenyl (OP) group rather than by the hydrophilic PEO group. In the absence of ligand, the surfactants alone desorbed less than 1% Cd from the contaminated soil, suggesting that the ligand, rather than the surfactant, extracts the metal, to be subsequently stabilized within the surfactant micelles.     

页岩对污泥氨气挥发的抑制作用

氨气是城市污水污泥产生的恶臭气体之一,控制或抑制其产生是资源化利用甚至处置过程中至关重要的.通过改进氨气测量方法定量分析外掺页岩对污泥氨气挥发的抑制作用和机理,实验研究了页岩掺量、陈放形式以及环境温度对污泥氨气挥发浓度的影响.结果表明,外掺页岩对污泥氨气挥发具有明显的抑制作用,随温度升高、陈放时间延长抑制效果有所减弱但仍具有明显作用;页岩对污泥氨气挥发的抑制作用主要为对氨气的吸附作用.     

Dissolution and removal of PAHs from a contaminated soil using sunflower oil

This study reports on the feasibility of remediation of polycyclic aromatic hydrocarbon (PAH) contaminated soils using sunflower oil, an environmentally-friendly solvent. Batch experiments were performed to test the influence of oil/soil ratio on the remediation of PAH contaminated soil, and to test the mass transfer behaviors of PAHs from soil to oil. An empirical model was employed to describe the kinetics of PAH dissolution and to predict equilibrium concentrations of PAHs in oil. PAH containing oil was regenerated using active carbon. Results show that dissolution of PAHs from a Manufactured Gas Plant (MGP) soil at oil/soil ratios of one or two were almost the same. Nearly all PAHs (81-100%) could be removed by sunflower oil dissolution. Mass transfer coefficients for low molecular PAHs namely fluoranthene, phenanthrene and anthracene were one or two orders of magnitude higher than those for high molecular PAHs with 4-6 rings. Ninety milliliters of PAH containing oil could be regenerated by 10 g active carbon in a batch reactor. Such a remediation procedure indicates that sunflower oil is a promising agent for the removal of PAHs from MGP soils. However, further research is required before the method can be used for in situ remediation of contaminated sites.     

Benzene removal from waste water using aqueous surfactant two-phase extraction with cationic and anionic surfactant mixtures

A novel separation technique known as an aqueous surfactant two-phase (ASTP) extraction is a promising method to remove organic contaminants from wastewater. When cationic and anionic surfactants are mixed at certain surfactant concentrations and compositions, the solution separates into two immiscible aqueous phases. One is the surfactant-rich and the other is the surfactant-dilute phase. The organic contaminants will solubilize into the surfactant aggregates and concentrate in the small volume surfactant-rich phase. The other phase contains only small amount of surfactants and contaminants as the treated water. Most ASTP studies have used nonionic surfactants above the cloud point. Mixtures of anionic and cationic surfactants can also exhibit aqueous-aqueous phase separation and can be used in the ASTP extraction process. The phase behavior and performance of ASTP extraction using cationic surfactant dodecyltrimethylammonium bromide (DTAB) and anionic surfactant alkyldiphenyloxide di-sulfonate (DPDS) to extract benzene from wastewater was investigated in batch experiments. It was found that phase separation only occurs over a narrow range of molar ratios of DTAB:DPDS from 1.6:1 to 2.4:1. In this study, a 2:1 molar ratio of DTAB:DPDS at which there is no net charge in the surfactant aggregates show the highest extraction efficiency and lowest critical micelle concentration value with greatest synergism (highest negative values of the micellar interaction parameter). At a total surfactant concentration of 50mM, the benzene partition ratio is 48 and 72% of the benzene is extracted into the surfactant-rich phase solution in a single stage extraction, which is superior performance compared to ASTP extraction using nonionic surfactants.     

Ammonia volatilization from sows on grassland

According to regulations, sows with piglets on organic farms must graze on pastures. Volatilization of ammonia (NH₃) from urine patches may represent a significant source of nitrogen (N) loss from these farms. Inputs of N are low on organic farms and losses may reduce crop production. This study examined spatial variations in NH₃ volatilization using a movable dynamic chamber, and the pH and total ammoniacal nitrogen (TAN) content in the topsoil of pastures with grazing sows was measured during five periods between June 1998 and May 1999. Gross NH₃ volatilization from the pastures was also measured with an atmospheric mass balance technique during seven periods from September 1997 until June 1999. The dynamic chamber study showed a high variation in NH₃ volatilization because of the distribution of urine; losses were between 0 and 2.8 g NH₃–N m⁻² day⁻¹. Volatilization was highest near the feeding area and the huts, where the sows tended to urinate. Ammonia volatilization rate was linearly related to the product of NH₃ concentration in the boundary layer and wind speed. The NH₃ in the boundary layer was in equilibrium with NH₃ in soil solution. Gross NH₃ volatilization was in the range 0.07–2.1 kg NH₃–N ha⁻¹ day⁻¹ from a pasture with 24 sows ha⁻¹. Ammonia volatilization was related to the amount of feed given to the sows, incident solar radiation and air temperature during measuring periods, and also to temperature, incident solar radiation and rain 1–2 days before measurements. Annual ammonia loss was 4.8 kg NH₃–N sow⁻¹.     

Improving the extraction of tetrachloroethylene from soil columns using surfactant gradient systems

In this work, we extend the recently developed gradient approach for surfactant-enhanced remediation of dense non-aqueous phase liquid (DNAPL)-impacted sites. The goal of the gradient approach is to maximize the DNAPL solubilization capacity in swollen micelles (Type I aqueous microemulsions) while at the same time minimizing the potential for DNAPL mobilization. In this work, we introduce a modified version of the capillary/trapping curve that we refer to as the gradient curve to help interpret and/or design the gradient approach. The gradient curve presents the residual DNAPL saturation as a function of interfacial tension and microemulsion viscosity. This approach demonstrates that keeping a low viscosity of the microemulsion phase is not only important for keeping a low head loss during surfactant flooding but also to prevent oil mobilization. Eight microemulsion systems were evaluated in this research; these systems were evaluated based on their tetrachloroethylene (PCE) solubilization capacity, interfacial tension (IFT), viscosity, density, and coalescence kinetics. Two of these systems were chosen for evaluation in site-specific column tests using an increasing electrolyte gradient to produce a decreasing IFT/increasing solubilization gradient system. The column studies were conducted with media from Dover Air Force Base in Dover, DE. Both solubilized and mobilized DNAPL were quantified. During the column studies, we observed that substantial PCE was mobilized when the residual level of PCE in the column was significantly higher than the steady-state residual saturation level being approach (as predicted from the gradient curve). Four column studies were performed, three of which were used to asses the validity of the gradient curve in predicting the residual saturation after each gradient step. From these tests we observed that starting IFTs of less than 1 mN/m all produced the same mobilization potential. In the last column, we used an additional gradient step with an initial IFT above 1 mN/m to dramatically reduce the amount of PCE mobilize. Based on the good agreement between column results and projections based on the gradient curve, we propose this as a preferred method for designing gradient surfactant flushing systems.     

阳离子表面活性剂改性油茶果壳对水溶液中甲基橙的吸附

以阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)对油茶果壳进行改性,制备CTAB-油茶果壳(CTAB-COS)吸附材料,并采用批实验法对其对水溶液中甲基橙的吸附去除进行了研究。考察了溶液pH、吸附剂用量和离子强度等对水溶液中甲基橙的吸附影响,并研究了体系的吸附动力学和吸附热力学特征。结果表明,向100 mL浓度为50 mg/L的甲基橙溶液中加入0.40 g CTAB-COS,在最佳实验条件下,CTAB-COS对甲基橙的去除率可达96.66%。溶液离子强度增大,甲基橙去除率降低。CTAB-COS对甲基橙的吸附行为符合拟二级动力学模型,吸附等温线可用Langmuir模型进行较好拟合,在20 ℃时最大吸附量为18.31 mg/g。吸附热力学结果表明,吸附过程为可自发进行的放热过程。再生性实验结果表明,再生6次后,CTAB-COS对甲基橙的吸附去除率仍可达到80%。该改性油茶果壳可应用于阴离子型染料废水的吸附法处理。     

Rate of pesticide volatilization from soil: an experimental approach with a wind tunnel system applied to trifluralin

Pesticide volatilization to the atmosphere may be a major pathway of dissipation closely linked with environmental, physico-chemical and technical factors. Understanding the volatilization process requires systems that make it possible to control some of these factors. Wind tunnels meet to these criteria. The volatilization flux is determined from a mass balance, using the difference in atmospheric pesticide concentration between the entrance and the exit of the tunnel and the airflow rate. An experiment was carried out in June 2000 to study the repeatability of this technique. Volatilization of trifluralin was measured in three wind tunnels for 8 days with a sampling period varying between 3 h and 2 days. Pesticide concentration was determined by trapping by XAD-2 resin in a two-stage cartridge, solvent extraction and analysis by gas chromatography. Cumulated losses through volatilization reached 30% of the measured application dose after 8 days, with a variability of less than 20% between the three tunnels. Approximately 20% remained in the topsoil (0–2 cm), with a variability of 14% between the three tunnels. The decrease in the volatilization flux over time is coherent with the expected theoretical evolution for a volatile pesticide such as trifluralin and with previous experimental works.     

Modelling pesticide volatilization after soil application using the mechanistic model Volt'Air

Volatilization of pesticides participates in atmospheric contamination and affects environmental ecosystems including human welfare. Modelling at relevant time and spatial scales is needed to better understand the complex processes involved in pesticide volatilization. Volt'Air-Pesticides has been developed following a two-step procedure to study pesticide volatilization at the field scale and at a quarter time step. Firstly, Volt'Air-NH₃ was adapted by extending the initial transfer of solutes to pesticides and by adding specific calculations for physico-chemical equilibriums as well as for the degradation of pesticides in soil. Secondly, the model was evaluated in terms of 3 pesticides applied on bare soil (atrazine, alachlor, and trifluralin) which display a wide range of volatilization rates. A sensitivity analysis confirmed the relevance of tuning to K_h. Then, using Volt'Air-Pesticides, environmental conditions and emission fluxes of the pesticides were compared to fluxes measured under 2 environmental conditions. The model fairly well described water temporal dynamics, soil surface temperature, and energy budget. Overall, Volt'Air-Pesticides estimates of the order of magnitude of the volatilization flux of all three compounds were in good agreement with the field measurements. The model also satisfactorily simulated the decrease in the volatilization rate of the three pesticides during night-time as well as the decrease in the soil surface residue of trifluralin before and after incorporation. However, the timing of the maximum flux rate during the day was not correctly described, thought to be linked to an increased adsorption under dry soil conditions. Thanks to Volt'Air's capacity to deal with pedo-climatic conditions, several existing parameterizations describing adsorption as a function of soil water content could be tested. However, this point requires further investigation. Practically speaking, Volt'Air-Pesticides can be a useful tool to make decision about agricultural practices such as incorporation or for the estimation of overall pesticide volatilization rates, and it holds promise for time specific dynamics.     

Levels of PAHs in soil and vegetation samples from Tarragona County, Spain

The levels of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in 24 soil and 12 wild chard samples collected in Tarragona County (Catalonia, Spain), an area with an important number of chemical and petrochemical industries. Samples were also collected in urban/residential zones and in presumably unpolluted sites (control samples). In soils, the sum of the 16 PAHs ranged between 1002 and 112 ng/g (dry weight) for samples collected near chemical industries and unpolluted sites, respectively. With the exception of acenaphthylene, acenaphthene, anthracene and benzo[k]fluoranthene, no significant differences in the levels of the remaining PAHs were found among the different zones of sample collection. In chard samples, the highest value (sum of 16 PAHs) was observed in the residential area, followed by the industrial and the unpolluted zones, with concentrations of 179, 58 and 28 ng/g (dry weight), respectively. In general terms, the current PAH concentrations in soil and vegetation are lower than the levels reported in a number of investigations from different regions and countries. They are also below the maximum PAH concentrations allowed by the Catalan legislation for different uses of soil.     

Measurement of trifluralin volatilization in the field: Relation to soil residue and effect of soil incorporation

Volatilization may represent a major dissipation pathway for pesticides applied to soils or crops. A field experiment (September, 2002), consisted in volatilization fluxes measurements during 6 days, covering the periods before and after soil incorporation carried out 24 h after trifluralin spraying on bare soil. Evolution of concentration in soil was measured during 101 days, together with soil physical and meteorological variables. Volatilization fluxes were very high immediately after application (1900 ng m(-2) s(-1)), decreased down to 100 ng m(-2) s(-1) in the following 24 h. Soil incorporation strongly abated trifluralin concentration in the air. 99% of the total volatilization losses recorded over the 6 days following application occurred before incorporation. Volatilization fluxes evidenced a diurnal cycle driven by environmental conditions. Soil trifluralin residues could still be quantified 101 days after application. Our results highlight the caution required when using soil degradation half-life values in the field for volatile compounds.     

Combined effect of nonionic surfactant Tween 80 and DOM on the behaviors of PAHs in soil--water system

Batch experiments were performed to examine the desorption behavior of phenanthrene and pyrene in soil–water system in the presence of nonionic surfactant Tween 80 and dissolved organic matter (DOM) derived from pig manure or pig manure compost. Addition of 150 mg l⁻¹ Tween 80 desorbed 5.8% and 2.1% of phenanthrene and pyrene from soil into aqueous phase, respectively, while the addition of both Tween 80 and DOM derived from pig manure compost and pig manure could further enhance the desorption of phenanthrene to 15.8% and 16.2%, respectively, and 6.4% and 10.9%, respectively, for pyrene. In addition, our finding also suggested that subsequent addition of Tween 80 into the soil–water system could further enhance PAHs desorption. The enhancement effect of the co-existence of Tween 80 and DOM was more than the additive effect of the Tween 80 and DOM individually. It is likely that the formation of DOM–surfactant complex in the soil–water system may be a possible reason to explain such desorption enhancement phenomenon. Therefore, it is anticipated that the coexistence of both Tween 80 and DOM derived from pig manure or pig manure compost in soil environment will enhance the bioavailability of PAHs as well as other hydrophobic organic contaminants (HOCs) by enhancing the desorption during remediation process.     

Remediation of contaminated soil by a solvent/surfactant system

This study investigates a new approach using a solvent/surfactant-aided soil-washing process to improve the performance of conventional surfactant-aided soil remediation. Three surfactants (Brij 35, Tween 80, and SDS) and three organic solvents (acetone, triethylamine, and squalane) were used to evaluate the desorption performances of 4,4'-dichlorobiphenyl (DCB) out of three soils with different sorption characteristics. The performance improvement is likely due to better dissolution of the hydrophobic contaminants from the soil assisted by the solvent, and the formation of solvent-incorporated surfactant micelles, which increases both the size (i.e. capacity) and affinity of micelles for more effective contaminant extraction. The foc of soils were found to be important in determining the performance of a solvent/surfactant-aided soil-washing process. Judging from the experimental data and as verified by the two constants in the proposed soil-washing model, as the organic solvent is coexisting with the surfactant micelles, both the marginal soil-washing performance (right after the use of a very small amount of solvent compared to that of none) and the final soil-washing capacity are increased compared to those of a pure surfactant-aided washing process.     

Effects of heterocyclic PAHs (N, S, O) on the biodegradation of typical tar oil PAHs in a soil/compost mixture

The interaction phenomena during the biodegradation of typical coal tar polycyclic aromatic hydrocarbons and their heterocyclic analogues (N, S, O) were investigated in an artificially contaminated AhA1-horizon/compost mixture. All compounds were partly or completely biodegraded. Degradation of two- to five-ring PAHs was inhibited by the presence of hetero-PAHs, whereas degradation of just some hetero-PAHs was inhibited by the presence of PAHs. Among the hetero-PAHs the sulphur-containing compounds were less susceptible to degradation than the corresponding oxygen- or nitrogen-containing analogues. The basic azaarene acridine showed an extreme persistence and strong sorption to the soil matrix proved by an increase of recovery after saponification of the soil matrix.     

环境胁迫因子对固定菌修复污染土壤效果的研究

通过对环境胁迫因子参数的不同设定,对固定菌修复污染土壤效果进行了研究.结果显示,当环境胁迫因子温度(高温40 ℃和低温15 ℃)、酸碱度(pH＝4和pH＝9)及重金属(Cd和Pb)存在时,对固定菌降解污染物的影响并不大,而游离菌降解率却有一定的下降趋势.进一步观察了固定化载体内部微观结构,为固定菌用于有机污染土壤的异位修复提供了一定的理论基础.