Transformation of PAHs during ethanol-Fenton treatment of an aged gasworks' soil

PAH-contaminated soil from a former gasworks site was treated with Fenton's reagent in a number of lab-scale slurry reactors. The degradation result obtained by traditional Fenton oxidation and Fenton oxidation preceded by ethanol treatment were compared. The ethanol pre-treatment enhanced the depletion of all PAHs in the soil by facilitating their desorption from the soil matrix. However, some PAHs, especially anthracene, benzo[a]pyrene and perylene, were more extensively depleted than other PAHs with fewer or equal numbers of fused rings, indicating that the hydroxyl radicals react faster with these PAHs than with other kinds. The ethanol present in the slurry also appeared to influence the relative reactivity of the PAHs. Furthermore, the enhanced oxidation that occurred in the ethanol pre-treated soil resulted in the accumulation of oxidation products. For example, 1-indanone, anthracene-9,10-dione, 1-methylanthracenedione, 2-methylanthracenedione, 1,8-naphthalic anhydride, benz[a]anthracene-7,12-dione and two compounds tentatively identified as hydroxy-9-fluorenones were found at higher concentrations after the treatment than before it. The accumulation was most evident for the quinones, and in many cases it could be attributed to extensive oxidation of their parent PAHs, although the total oxidation efficiency in this study was relatively poor.     

LAS对土壤中多环芳烃吸附行为的影响

研究了阴离子表面活性剂十二烷基苯磺酸钠(LAS)对PAHs在土壤中吸附行为的影响.结果表明,LAS改变了PAHs在土水体系中的吸附/解吸平衡,吸附态LAS可提高土壤对PAHs的吸附,而溶解态LAS则增加了PAHs的表观溶解度,这2种作用的综合结果改变了PAHs在土水体系中的吸附系数.因此,文中用表观吸附系数来描述PAHs在土壤-水-LAS体系中的综合吸附行为.     

The influence of defoamer on removal of PAHs in soil washing

The use of surfactants during soil washing process can create massive foam, which has a negative impact on the effective use of equipment. A series of tests was conducted to evaluate the defoaming performance of three defoamers and to investigate the influence on removal of polycyclic aromatic hydrocarbons (PAHs) during enhanced soil washing by the addition of the defoamer. Results showed that polydimethylsiloxane oil, which is the most common biomaterial used in commercial antifoaming and defoaming agents, has the best defoaming performance. With the addition of 0.1% polydimethylsiloxane oil, the removal ratios of total 16 PAHs (ΣPAHs) increased up to 53.48% and 75.92% when washing time was 5 min and 30 min, respectively, compared with the removal ratios of 44.12% and 67.28% with Triton X-100 solution only. This indicated that the proper selection of defoamer not only solves massive foaming problem but also brings out a positive influence on PAH removal during the soil washing process.

Implications: Three kinds of defoamers (kieselguhr, dodecanol, and polydimethylsiloxane oil) were collected to destroy the foam produced by Triton X-100. Among those defoamers, the polydimethylsiloxane (PDMS) oil has the best defoaming performances. The surface tension of the Triton X-100 solution with the addition of PDMS was lower. The addition of PDMS could improve the removal ratio of ΣPAHs during soil washing. That may be attributed to the addition of the nonionic surfactant Tergitol NP-10 as the emulsifier in the defoamer. After all, the results do not provide any indication of the influence on the solubilization micelles. It is thus questionable whether other components of PDMS oil could improve the PAH solubilization.     

Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: laboratory column experiments

Laboratory column experiments were performed to remove PAHs (polycyclic aromatic hydrocarbons) from two contaminated soils using sunflower oil. Two liters of sunflower oil was added to the top of the columns (33 cm x 21 cm) packed with 1 kg of PAH-contaminated soil. The sunflower oil was applied sequentially in two different ways, i.e. five additions of 400 ml or two additions of 1l. The influence of PAH concentration and the volume of sunflower oil on PAH removal were examined. A soil respiration experiment was carried out and organic carbon contents of the soils were measured to determine degradability of remaining sunflower oil in the soils. Results showed that the sunflower oil was effective in removing PAHs from the two soils, more PAHs were removed by adding sunflower oil in two steps than in five steps, probably because of the slower flow rate in the former method. More than 90% of total PAHs was removed from a heavily contaminated soil (with a total 13 PAH concentration of 4721 mg kg(-1)) using 4 l of sunflower oil. A similar removal efficiency was obtained for another contaminated soil (with a total 13 PAH concentration of 724 mg kg(-1)), while only 2l was needed to give a similar efficiency. Approximately 4-5% of the sunflower oil remained in the soils. Soil respiration curves showed that remaining sunflower oil was degraded by allowing air exchange and supplying with nutrients. Organic carbon content of the soil was restored to original level after 180 d incubation. These results indicated that the sunflower oil had a great capacity to remove PAHs from contaminated soils, and sunflower oil solubilization can be an alternative technique for remediation of PAH contaminated soils.     

Screening of compost for PAHs and pesticides using static subcritical water extraction.

Static subcritical water extraction (SubWE) along with solid phase extraction (SPE) was used for the analysis of PAHs and pesticides in municipal solid waste compost. Yields obtained for PAHs in certified reference sediment (CRM 104) were acceptable. The extraction method was simple, rapid, used small sample sizes, and no sample drying was required. Analysis of samples was performed by GC/MS and HPLC. Recovery of spiked pesticides was greatest at 110 degrees C for 20 min extraction time. The optimum extraction for PAH analysis was achieved at 150 degrees C for 20 min. Addition of C-18 resin as an "alternate sorbent" upon cooling increased recovery of PAHs but not of pesticides, however, it increased the stability of atrazine and propazine at higher temperatures. Analysis of three municipal compost samples from the Dayton, OH (USA) area showed no pesticides above the detection limit, however, PAH totals for 11 PAHs were 15.97, 14.42, and 20.79 microg g(-1). The totals of six of the seven carcinogenic PAHs, for which remediation goals in the United States is 4.6 microg g(-1), were determined to be 9.89, 6.77, and 13.06 microg g(-1) dry weight. The highest PAH totals were obtained from compost containing sewage sludge.     

Separation of PCBs and PAHs in sediment samples using silica gel fractionation chromatography

The aim of this research is to develop a silica gel fractionation procedure for sediment sample extracts, which separates polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) into two groups, while simultaneously eliminating most interfering substances for subsequent instrumental analysis. This is achieved by optimizing the fraction cut-off volume of eluting solvent and the deactivation level of the silica gel. Using fully activated silica gel and cutting off PCB collection after passing 60-65 ml eluting solvent (pentane or hexane) through the column resulted in satisfactory separation of PCBs and PAHs. This procedure tends to have a higher reliability for PCBs and PAHs with higher molecular mass. This approach deviates only slightly from the standard methods of the USEPA, and it is less expensive due to reduced sample pre-treatment time and solvent consumption.     

Effect of a cationic surfactant on the volatilization of PAHs from soil

Purpose

Cationic surfactants are common in soils because of their use in daily cosmetic and cleaning products, and their use as a soil amendment for the mitigation and remediation of organic contaminated soils has been proposed. Such surfactant may affect the transfer and fate of organic contaminants in the environment. This study investigated the effect of a cationic surfactant, dodecylpyridinium bromide (DDPB), on the volatilization of polycyclic aromatic hydrocarbons (PAHs) from a paddy soil.

Materials and methods

The volatilization of PAHs from moist soil amended with different concentrations of DDPB was tested in an open system. The specific effects of DDPB on the liquid?Cvapor and solid?Cvapor equilibriums of PAHs were separately investigated in closed systems by headspace analysis.

Results and discussion

DDPB affects both liquid?Cvapor and solid?Cvapor processes of PAHs in soil. At DDPB concentrations below the critical micelle concentration (CMC), movement of PAHs from the bulk solution to the gas?Cliquid interface appeared to be facilitated by interaction between PAHs and the surfactant monomers adsorbed at the gas?Cliquid interface, promoting the volatilization of PAHs from solution. However, when DDPB was greater than the CMC, volatilization was inhibited due to the solubilization of PAHs by micelles. On the other hand, the formation of sorbed surfactant significantly inhibited the solid?Cvapor volatilization of PAHs.

Conclusions

The overall effect of the two simultaneous effects of DDPB on liquid?Cvapor and solid?Cvapor processes was a decreased volatilization loss of PAHs from soil. Inhibition of PAH volatilization was more significant for the soil with a lower moisture content.     

Assessment of the bioaccessibility of polycyclic aromatic hydrocarbons in soils from Beijing using an in vitro test

As an important human exposure pathway of contaminants, soil ingestion is of increasing concern for assessing health risk from polycyclic aromatic hydrocarbons (PAHs) in soils. A wide range of total PAH concentrations ranging from 0.112 microg g(-1) to 27.8 microg g(-1) in soils collected from different public sites, including gas stations, roadsides, bus stops, a kindergarten, primary and middle schools, a university and residential area, was detected. In general, total PAHs concentrations in soils from traffic areas were significantly higher than that from the other sites, indicating a dominant contribution from motor vehicles. Physiologically based in vitro tests were used to evaluate the oral bioaccessibility of PAHs in surface soil under different land uses in Beijing regarding both gastric and small intestinal conditions. It was found that the oral bioaccessibility of total PAHs in small intestinal condition, ranging from 9.2% to 60.5% of total PAHs in soil, was significantly higher than gastric condition, ranging from 3.9% to 54.9%. The bioaccessibility of individual PAHs in soils generally decreased with the increasing ring number of PAHs in both gastric and small intestinal conditions. However, the ratio of bioaccessibility of individual PAHs in gastric condition to that in small intestinal condition, generally increased with increasing ring number, indicating the relatively pronounced effect of bile extract on improving bioaccessibility of PAHs with relatively high ring numbers characterized by their high K(ow) values. The observation that bile extract at a level higher than critical micelle concentration could reduce the surface tension of digestive juice substantially, which may cause PAHs to be available for intestinal absorption, calls for more careful establishment of reliable soil criteria for PAHs, especially concerning the health of children who may ingest a considerable amount of PAH-contaminated soil via outdoor hand-mouth activities.     

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.     

Aqueous accelerated solvent extraction of native polycyclic aromatic hydrocarbons (PAHs) from carbonaceous river floodplain soils

In this study, three river floodplain soils with different compositions of carbonaceous materials and a reference coal sample were extracted with water using the accelerated solvent extraction (ASE) method. The desorption enthalpy values for 2-ring PAHs were highest in the coal sample, with values in the soil samples decreasing with decrease in coal content. The values for the higher condensed PAHs showed that the highest desorption enthalpies were from the samples with the largest amount of coal-derived particles. Elevated desorption enthalpies indicated a strong bonding between PAHs and geosorbents. Moreover, with the application of ASE this study was able to conclude that the PAHs in the samples were preferentially adsorbed to carbonaceous materials with high surface areas.     

Supercritical fluid extraction of polycyclic aromatic hydrocarbons from marine sediments and soil samples

Supercritical fluid extraction (SFE) was used to extract polycyclic aromatic hydrocarbons (PAH) from a certified sample of marine sediment. This sample contains a great number of organic pollutants that are present in low concentrations. The extractions were carried out at 50 and 80 degrees C, at a pressure varying from 230 to 600 bar and using CO2 in the supercritical phase and the effect of three organic modifiers (methanol, n-hexane and toluene), added at 5%/vol, at the same temperature and pressure conditions, were then considered. PAHs were characterized by GC-MS and the recover yield was estimated for 6 PAHs that were representative of those present in the sample, according to their molecular weight and to the number of condensed rings. The analytical conditions giving the best recovery efficiency were used on an unpolluted soil sample spiked with 11 PAHs of environmental importance at a concentration similar to that certified for the sediment sample. An increase in the yield of recovered PAHs, using methanol as co-solvent, was observed while higher temperatures caused a negative effect on the quantity of recovered pollutants. The recovery yield for PAHs from the spiked soil sample was measured and found to be greater than 90%. Better recoveries were obtained for those compounds with higher molecular weight.     

Study of factors affecting on the extraction efficiency of polycyclic aromatic hydrocarbons from soils using open-vessel focused microwave-assisted extraction

As part of an evaluation of focused microwave-assisted extraction (FMAE) using an open-vessel system, the effects of matrix, moisture content, ageing, and solvent have been studied on the extraction efficiency of polycyclic aromatic hydrocarbons (PAHs) from spiked soils. PAHs were spiked onto three different uncontaminated air dried and originally wet soil matrices with 1- and 20-day ageing periods. Solvents used were hexane–acetone (1:1), cyclohexane–acetone (1:1) and dichloromethane. FMAE only required a small amount of solvent (20 ml) and short extraction time (10 min) in the open cell under 90 W of microwave power. The results revealed that the extraction efficiency strongly depends on the nature of soil matrix; moisture content may enhance the recoveries of PAHs for many cases; and, the influence of the type of solvent is not significant. A comparison between microwave extraction and 16-h Soxhlet extraction has been made on spiked soils. It evidenced that the microwave method under ambient pressure is a suitable alternative to Soxhlet method for the analysis of PAHs in soils. For the evaluation of the developed FMAE method, three reference materials were used. The PAHs recovered from three reference materials were in a good agreement with reference values.     

Ozone pre-treatment as improver of PAH removal during anaerobic digestion of urban sludge

Polycyclic aromatic hydrocarbons are ubiquitous persistent pollutants. They may accumulate in sludge during wastewater treatment because of their low biodegradability and their hydrophobic characteristics. Combination of ozonation and anaerobic digestion may be efficient to remove PAHs naturally present in sludge. The objective of this study was to investigate the impact of ozone pre-treatment, with and without surfactant addition, on the anaerobic degradation of 12 PAHs (from low to high molecular weight). Under anaerobic digestion without ozonation pre-treatment, the highest removals were obtained for the lightest PAHs (3-aromatic rings). Ozonation pre-treatment of sludge allowed to increase biodegradability or bioavailability of each PAH, and the PAH removals were well correlated to the PAH solubility. Finally, addition of tyloxapol before sludge ozone pre-treatment had antagonist effects on PAH removal during anaerobic digestion: negative impact on anaerobic ecosystem activity and improvement of PAH bioaccessibility (particularly the PAHs with the highest octanol water partition coefficients).     

Concentrations and bioaccessibility of polycyclic aromatic hydrocarbons in wastewater-irrigated soil using in vitro gastrointestinal test

BACKGROUND, AIM, AND SCOPE: Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants and contribute to the pollution of soil environment. Soil ingestion is of increasing concern for assessing health risk from PAH-contaminated soils because soil ingestion is one of the potentially important pathways of exposure to environmental pollutants, particularly relevant for children playing at contaminated sites due to their hand-to-mouth activities. In vitro gastro-intestinal tests imitate the human digestive tract, based on the physiology of humans, generally more simple, less time-consuming, and especially more reproducible than animal tests. This study was conducted to investigate the level of PAH contamination and oral bioaccessibility in surface soils, using physiologically based in vitro gastro-intestinal tests regarding both gastric and small intestinal conditions. MATERIALS AND METHODS: Wastewater-irrigated soils were sampled from the metropolitan areas of Beijing and Tianjin, China, which were highly contaminated with PAHs. Reference soil samples were also collected for comparisons. At each site, four soils were sampled in the upper horizon at the depth of 0-20 cm randomly and were bulked together to form one composite sample. PAH concentrations and origin were investigated and a physiologically based in vitro test was conducted using all analytical grade reagents. Linear regression model was used to assess the relationship between total PAH concentrations in soils and soil organic carbon (SOC). RESULTS: A wide range of total PAH concentrations ranging from 1,304 to 3,369 mug kg(-1) in soils collected from different wastewater-irrigated sites in Tianjin, while ranging from 2,687 to 4,916 mug kg(-1) in soils collected from different wastewater-irrigated sites in Beijing, was detected. In general, total PAH concentrations in soils from Beijing sites were significantly higher than those from Tianjin sites, indicating a dominant contribution from both pyrogenic and petrogenic sources. Results indicated that the oral bioaccessibility of PAHs in small intestinal was significantly higher (from P < 0.05 to P < 0.001) than gastric condition. Similarly, the oral bioaccessibility of PAHs in contaminated sites was significantly higher (from P < or = 0.05 to P < 0.001) than in reference sites. Individual PAH ratios (three to six rings), a more accurate and reliable estimation about the emission sources, were used to distinguish the natural and anthropogenic PAH inputs in the soils. Results indicated that PAHs were both pyrogenic and petrogenic in nature. DISCUSSION: The identification of PAH sources and importance of in vitro test for PAH bioaccessibility were emphasized in this study. The oral bioaccessibility of individual PAHs in soils generally decreased with increasing ring numbers of PAHs in both the gastric and small intestinal conditions. However, the ratio of bioaccessibility of individual PAHs in gastric conditions to that in the small intestinal condition generally increased with increasing ring numbers, indicating the relatively pronounced effect of bile extract on improving the bioaccessibility of PAHs with relatively high ring numbers characterized by their high K ( ow ) values. Similarly, total PAH concentrations in soils were strongly correlated with SOC, indicating that SOC was the key factor determining the retention of PAHs in soils. CONCLUSIONS: Soils were contaminated with PAHs due to long-term wastewater irrigation. PAHs with two to six rings showed high concentrations with a significant increase over reference soils. Based on the molecular indices, it was suggested that PAHs in soils had both pyrogenic and petrogenic sources. It was also concluded that the oral bioaccessibility of total PAHs in the small intestinal condition was significantly higher than that in the gastric condition. Furthermore, the bioaccessibility of individual PAHs in soils generally decreased with the increasing ring numbers in both the gastric and small intestinal conditions. RECOMMENDATIONS AND PERSPECTIVES: It is suggested that more care should be given while establishing reliable soil criteria for PAHs, especially concerning the health of children who may ingest a considerable amount of PAH-contaminated soil via outdoor hand-to-mouth activities.     

Identification of carbonaceous geosorbents for PAHs by organic petrography in river floodplain soils

Organic petrographic analysis was applied to provide direct information on carbonaceous geosorbents for PAHs in river floodplain soils. The anthropogenic OM group (primarily coal and coal-derived particles) displayed large volume amounts for all the soil samples. Distinct PAH concentrations with similar PAH distribution patterns were determined in grain size and density fractions for each sample. Two-ring PAHs had stronger correlation to organic carbon (OC) than black carbon (BC) contents, while heavier PAHs showed correlation to BC, rather than OC. In this study, we combined grain size and density separation, PAH determinations, TOC and BC measurements, and organic petrographic identification, and concluded that two-ring PAHs in soils were associated to coal particles. Other heavier PAHs could be more controlled by black carbon (BC), which were mostly coal-derived particles from former coal mining and coal industrial activity.     

Validated sampling strategy for assessing contaminants in soil stockpiles

Dutch legislation on the reuse of soil requires a sampling strategy to determine the degree of contamination. This sampling strategy was developed in three stages. Its main aim is to obtain a single analytical result, representative of the true mean concentration of the soil stockpile. The development process started with an investigation into how sample pre-treatment could be used to obtain representative results from composite samples of heterogeneous soil stockpiles. Combining a large number of random increments allows stockpile heterogeneity to be fully represented in the sample. The resulting pre-treatment method was then combined with a theoretical approach to determine the necessary number of increments per composite sample. At the second stage, the sampling strategy was evaluated using computerised models of contaminant heterogeneity in soil stockpiles. The now theoretically based sampling strategy was implemented by the Netherlands Centre for Soil Treatment in 1995. It was applied to all types of soil stockpiles, ranging from clean to heavily contaminated, over a period of four years. This resulted in a database containing the analytical results of 2570 soil stockpiles. At the final stage these results were used for a thorough validation of the sampling strategy. It was concluded that the model approach has indeed resulted in a sampling strategy that achieves analytical results representative of the mean concentration of soil stockpiles.     

Distribution of polycyclic aromatic hydrocarbons in soil-water system containing a nonionic surfactant

The effect of a nonionic surfactant, Triton X-100 (TX100), on the distribution of four representative polycyclic aromatic hydrocarbons (PAHs), phenanthrene, fluorene, acenaphthene and naphthalene, in soil-water system was studied on a natural soil. The apparent soil-water distribution coefficient with surfactant (Kd*) for these compounds increased when TX100 equilibrium concentration from zero to around the critical micelle concentration (CMC), followed by a decrease in Kd* at TX100 equilibrium concentration greater than CMC. This is a direct result of surfactant sorption onto soil followed by PAHs partitioning to the sorbed surfactant. The values of carbon-normalized solute distribution coefficient (Kss) with the sorbed TX100 are greater than the corresponding partition coefficients with soil organic matter (Koc), which indicates the soil-sorbed nonionic surfactant is more effective per unit mass as a partitioning medium than the native soil organic matter for PAHs. When Kd* = Kd the corresponding initial concentration of surfactant was defined as critical washing concentration (CWC). Depending on the surfactant initial concentration below or above the CWC, the addition of nonionic surfactant can enhance the retardation of soil for PAHs or promote the removal of PAHs from soil, respectively. The values of Kd* and CWC can be predicted by a model, which correlates them with the compounds' octanol-water partition coefficients (Kow), soil property and the amount of soil-sorbed surfactant.     

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.     

The lack of microbial degradation of polycyclic aromatic hydrocarbons from coal-rich soils

Analytical techniques used to assess the environmental risk of contamination from polycyclic aromatic hydrocarbons (PAHs) typically consider only abiotic sample parameters. Supercritical fluid extraction and sorption enthalpy experiments previously suggested slow desorption rates for PAH compounds in two coal-contaminated floodplain soils. In this study, the actual PAH availability for aerobic soil microorganisms was tested in two series of soil-slurry experiments. The experimental conditions supported microbial degradation of phenanthrene if it was weakly sorbed onto silica gel. Native coals and coal-derived particles in two soils effectively acted as very strong sorbents and prevented microbial PAH degradation. The long history of PAH exposure and degree of coal contamination apparently had no influence on the capability of the microbial soil community to overcome constraints of PAH availability. Within the context of the experimental conditions and the compounds chosen, our results confirm that coal-bound PAHs are not bioavailable and hence of low environmental concern.