Relationship between geographical origin and contents of Pb,Cd, and Cr in honey samples from the state of Paraná (Brazil) with chemometric approach

The aim of this study was to determine the trace elements, Pb, Cd, and Cr in honey samples from eight different regions from the state of Paraná (Brazil), using slurry sampling graphite furnace atomic absorption spectrometry. Chemometric analysis (principal component analysis (PCA)) was applied to classify honey samples according to their levels of the trace elements Pb, Cd, and Cr, which is also related to the geographical origin of honey samples. The mean concentration for the elements followed the order Pb?>?Cr >?>?Cd. The mean values were 200?±?76, 88?±?14, and 4.1?±?4 ng g^?1 for Pb, Cr, and Cd, respectively. It could be verified that honey samples are geographically separated, especially with regard to Pb and Cd contents. Thus, honey can be considered a bioindicator of environmental contamination, suggesting possible contamination in soil, water, and air. This contamination can be related to natural or anthropogenic sources present in the study regions.     

EPA SITE Demonstration of the BioTrol Soil Washing Process

A pilot-scale soil washing process, patented by BioTrol, Inc., was demonstrated on soil contaminated by wood treating waste, primarily pentachlorophenol (PCP) and creosote-derived polynuclear aromatic hydrocarbons (PAHs). Although soil washing was the main object of this demonstration, the treatment train that was evaluated included two other BioTrol technologies for treatment of waste streams from the soil washer. The three technologies were: ? The BioTrol Soil Washer (BSW)—a volume reduction process, which uses water to separate contaminated soil fractions from the bulk of the soil.

? The BioTrol Aqueous Treatment System (BATS)—a biological water treatment process.

? The Slurry Bioreactor (SBR)—a BioTrol biological slurry treatment process conducted in an EIMCO BIOLIFT^tm reactor.

The sandy soil at the site, consisting of less than 10 percent of fines, was well suited for treatment by soil washing. The soil washer was evaluated in two tests on soil samples containing 130 ppm and 680 ppm of PCP, respectively.

The BSW successfully separated the feed soil (dry weight basis) into 83 percent of washed soil, 10 percent of woody residues, and 7 percent of fines. The washed soil retained about 10 percent of the feed soil contamination while 90 percent of the feed soil contamination was contained within the woody residues, fines, and process water.

The soil washer achieved up to 89 percent removal of PCP and 88 percent of total PAHs, based on the difference between their levels in the as-is (wet) feed soil and the washed soil. PCP concentrations of 14 ppm and 87ppm in the washed soil were achieved from PCP concentrations of 130 ppm and 680ppm in the feed soil. Concentrations of total PAHs were reduced from 247 ppm to 42 ppm and 404 ppm to 48 ppm, respectively, in the two tests.

The BATS degraded up to 94 percent of PCP in the process water from soil washing. PAH removal could not be determined due to low influent concentrations.

The SBR achieved over 90 percent removals of PCP and 70 to 90 percent removals of PAHs from the slurry of contaminated fines from soil washing. However, steady state operation was not achieved during the single test and the results were variable.

Cost of a commercial-scale soil washing, assuming use of all three technologies, was estimated to be $168 per ton of soil treated. Incineration of woody material accounts for 76 percent of the cost.     

Source apportionment of polycyclic aromatic hydrocarbons in surface sediments of the Bohai Sea, China

A total of 112 surface sediment samples covering virtually the entire Bohai Sea were analyzed for polycyclic aromatic hydrocarbons (PAHs), in order to provide the extensive information of recent occurrence levels, distribution, possible sources, and potential biological risk of these compounds in this area. Surface sediment samples were collected from the Bohai Sea using a stainless steel grab sampler. Sixteen PAHs were determined by a Finnigan TRACE DSQ gas chromatography/mass spectrometry. Diagnostic ratios, cluster analysis, and principal component analysis (PCA) with multivariate linear regression (MLR) were performed to identify and quantitatively apportion the major sources of sedimentary PAHs in the Bohai Sea. Concentrations of total PAHs in the Bohai Sea ranged widely from 97.2 to 300.7 ng/g (mean, 175.7?±?37.3 ng/g). High concentrations of PAHs were found in the vicinity of Luan River Estuary-Qinhuangdao Harbor, Cao River Estuary-Bohai Sea Center, and north of the Yellow River Estuary. The three-ring PAHs were most abundant, accounting for about 37?±?5 % of total PAHs. The four-ring and five-ring PAHs were the next dominant ones comprising approximately 29?±?7and 23?±?3 % of total PAHs, respectively. Concentrations of acenaphthylene, acenaphthene, and dibenz[a,h]anthracene are higher than Canadian interim marine sediment quality guideline values at most of the sites in the study area. Contamination levels of PAHs in the Bohai Sea were low in comparison with other coastal sediments in China and developed countries. The distribution pattern of PAHs and source identification implied that PAH contamination in the Bohai Sea mainly originates from petrogenic and pyrogenic sources. Further PCA/MLR analysis suggested that the contributions of spilled oil products (petrogenic), coal combustion, and traffic-related pollution were 39, 38, and 23 %, respectively. Pyrogenic sources (coal combustion and traffic-related pollution) contributed 61 % of anthropogenic PAHs to sediments, which indicates that energy consumption could be a dominant factor in PAH pollution in this area. Acenaphthylene, acenaphthene, and dibenz[a,h]anthracene are the three main species of PAHs with more ecotoxicological concern in the Bohai Sea.     

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.     

Polycyclic aromatic hydrocarbon contamination in an urban area assessed by Quercus ilex leaves and soil

We investigated the PAH contamination of Naples urban area, densely populated and with high traffic flow, by analyses of environmental matrices: soil and Quercus ilex leaves. Being some PAHs demonstrated to have hazardous effects on human health, the accumulation of carcinogenic and toxic PAHs (expressed as B(a)Peq) was evaluated in the leaves and soil. The main sources of the PAHs were discriminated by the diagnostic ratios in the two matrices. The urban area appeared heavily contaminated by PAHs, showing in soil and leaves total PAH concentrations also fivefold higher than those from the remote area. The soil mainly accumulated heavy PAHs, whereas leaves the lightest ones. Median values of carcinogenic PAH concentrations were higher in soil (440 ng g^?1 d.w.) and leaves (340 ng g^?1 d.w.) from the urban than the remote area (60 and 70 ng g^?1 d.w., respectively, for soil and leaves). Also, median B(a)Peq concentrations were higher both in soil and leaves from the urban (137 and 63 ng g^?1 d.w., respectively) than those from the remote area (19 and 49 ng g^?1 d.w., respectively). Different from the soils, the diagnostic ratios found for the leaves discerned PAH sources in the remote and urban areas, highlighting a great contribution of vehicular traffic emission as main PAH source in the urban area.     

Implications for long-range atmospheric transport of polycyclic aromatic hydrocarbons in Lhasa, China

The Tibetan Plateau is suggested to be an important indicator region to study the global long-range atmospheric transport of persistent organic pollutants. In this study, atmospheric polycyclic aromatic hydrocarbons (PAHs) were studied in Lhasa City in the Tibetan Plateau, China. Air samples in gas and particle phases were concurrently collected by a modified high-volume air sampler from 5 August 2008 to 13 July 2009. The concentration of ∑₁₆PAHs ranged from 18 to 160 ng?m^?3 (with a geometric mean of 68 ng?m^?3). The most abundant PAHs were phenanthrene and benzo(b)fluoranthene in gas and particle phases, respectively. Compared with other two similar studies in Beijing and Harbin, different temporal trends were found between gas and particle phases PAHs in Lhasa. The influences of meteorological parameters (ambient temperature and relative humidity) and air masses from China, India, Southeast Asia, and West Asia were the two important reasons for explaining the difference, which was confirmed by the 5-day backward trajectories. This is the first comprehensive study to provide the evidence for the different influences of long-range atmospheric transport on gas and particle phases PAHs pollution in the Tibetan Plateau.     

Pesticide residues in Indian raw honeys,an indicator of environmental pollution

Honey has multifaceted beneficial properties, but polluted environment and unapproved apicultural practices have led to its contamination. In this study, QuEChERS method followed by chromatographic analysis by GC-μECD/FTD and GC-MS was validated and used for determination of 24 pesticides in 100 raw honey samples from various floral origins of Northern India. Matrix-matched calibrations showed that the method was selective and linear (r²?>?0.99) with detection limit <?9.1 ng g^?1 for all the studied pesticides except for monocrotophos (21.3 ng g^?1). The average recoveries at different fortification levels ranged from 86.0 to 107.7% with relative standard deviation <?20%. Pesticide residues were detected in 19.0% samples, and most prevalent compounds detected were dichlorvos in 6.0% samples followed by monocrotophos (5.0%), profenofos (5.0%), permethrin (4.0%), ethion (3.0%), and lindane (3.0%) with concentrations ranging from 58.8 to 225.5, from 96.0 to 430.1, from 14.6 to 43.2, from 27.8 to 39.6, from 25.6 to 28.0, and from 19.6 to 99.2 ng g^?1, respectively. Honey samples originating from cotton, sunflower, and mustard crops (33.3%) that tested positive for pesticide residues were found to be significantly higher (p?<?0.05) than the honey originating from natural and fruity vegetation (13.5%). Therefore, considering the contamination of environmental compartments due to extensive application of pesticides in the study area and their potential for subsequent transfer to honey by the expeditious bees, the results of present study proclaim that honey may be used as an indicator of environmental pollution. Further, estimated daily intakes of all contaminants were found to be at levels well below their acceptable daily intakes suggesting that consumption of honeys at current levels does not pose deleterious effects on human health. However, precautionary measures should always be taken considering the customary honey feeding in infants and cumulative effect of these chemicals in the foreseeable future.     

Remediation of polycyclic aromatic hydrocarbon and metal-contaminated soil by successive methyl-β-cyclodextrin-enhanced soil washing–microbial augmentation: a laboratory evaluation

Polycyclic aromatic hydrocarbon (PAH) and metal-polluted sites caused by abandoned coking plants are receiving wide attention. To address the associated environmental concerns, innovative remediation technologies are urgently needed. This study was initiated to investigate the feasibility of a cleanup strategy that employed an initial phase, using methyl-β-cyclodextrin (MCD) solution to enhance ex situ soil washing for extracting PAHs and metals simultaneously, followed by the addition of PAH-degrading bacteria (Paracoccus sp. strain HPD-2) and supplemental nutrients to treat the residual soil-bound PAHs. Elevated temperature (50 °C) in combination with ultrasonication (35 kHz, 30 min) at 100 g MCD L^?1 was effective in extracting PAHs and metals to assist soil washing; 93 % of total PAHs, 72 % of Cd, 78 % of Ni, 93 % of Zn, 84 % of Cr, and 68 % of Pb were removed from soil after three successive washing cycles. Treating the residual soil-bound PAHs for 20 weeks led to maximum biodegradation rates of 34, 45, 36, and 32 % of the remaining total PAHs, 3-ring PAHs, 4-ring PAHs, and 5(+6)-ring PAHs after washing procedure, respectively. Based on BIOLOG Ecoplate assay, the combined treatment at least partially restored microbiological functions in the contaminated soil. The ex situ cleanup strategy through MCD-enhanced soil washing followed by microbial augmentation can be effective in remediating PAH and metal-contaminated soil.     

Dietary risk evaluation for 28 polycyclic aromatic hydrocarbons (PAHs) in tea preparations made of teas available on the Polish retail market

The aim of this work was to assess dietary risk resulting from consumption of polycyclic aromatic hydrocarbons (PAHs) with tea infusions. To this end, levels of 28 PAHs in black, green, red and white teas available on the Polish retail market have been assessed. Profiles and correlation between concentrations of individual PAHs have been identified. A model study on transfer of PAHs from tea leaves into tea preparations has been conducted. Relatively high concentrations of 28 evaluated PAHs have been found in 58 tested samples of black, green, red and white teas sampled on the Polish retail market. Total concentration ∑28PAH ranged from 57 to 696 µg kg^?1 with mean 258 µg kg^?1 (dry tea leaves). The most mature tea leaves fermented to a small degree contained relatively the highest PAH levels among all four tested tea types. Relatively low PAH transfer rates into tea infusions and limited volumes of the consumed tea keep the risks associated with PAH dietary intake at a safely low level.

The worst-case scenario dietary intake values were 7.62/0.82/0.097 ng kg^?1 b.w. day^?1 (estimated on the basis of the maximum found concentrations 696/113/23 µg kg^?1 and maximum observed transfer rates 24/16/9%) for ∑28PAH/∑PAH4/B[a]P, respectively. MOE values calculated using the above worst case estimates exceeded 700,000 and 400,000 (BMDL₁₀ 0.07 and 0.34 mg kg^?1 b.w. day^?1) for B[a]P and PAH4, respectively. Both B[a]P and PAH4 concentrations may be used as indicators of total PAH concentration in tea leaves; PAH4 slightly better fits low molecular weight PAHs. Several correlations between various PAHs/groups of PAHs have been identified, the strongest one (R² = 0.92) between PAH4 and EU PAH 15+1.     

Polycyclic aromatic hydrocarbon (PAH) dispersion and deposition to vegetation and soil following a large scale chemical fire

Polycyclic aromatic hydrocarbons (PAHs) were determined in soil and vegetation following a large scale chemical fire involving 10,000 ton of polypropylene. In comparison with sites outside the plume from the fire, PAH concentrations were elevated in grass shoots (by up to 70-fold) and in soil (by up to 370-fold). The pattern of PAH dispersion under the plume was dependent on the physical-chemical properties of individual PAHs. The lighter, least hydrophobic PAHs were dispersed into the environment at greater distances than heavier, more hydrophobic PAHs. At the most distant sampling point (4.5 km) under the plume, the low molecular weight PAHs were still considerably elevated in vegetation samples compared to control sites. Dispersion appeared to be regulated by the compounds partitioning between the vapour and particulate phase, with dry particulate deposition occurring closer to the fire source than gaseous deposition. For all PAHs, the fire resulted in greater contamination of soils compared to grasses, with the relative ratio of plant/soil contamination decreasing as hydrophobicity increased.     

Continental bottled water assessment by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry (SBSE-GC-MS/MS)

This study was aimed to determine the presence of 69 organic contaminants in 77 representative bottled waters collected from 27 countries all over the world. All water samples were contained in polyethylene terephthalate bottles. Target compounds were (1) environmental contaminants (including 13 polycyclic aromatic hydrocarbons (PAHs), 31 pesticides including organochlorine (OCPs), organophosphorus, and pyrethroids; 7 polychlorinated biphenyls (PCBs); and 7 triazines) and (2) plasticizers (including 6 phthalates and 5 other compounds). Samples were analyzed by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry. PAHs, OCPs, PCBs, and triazines, which are indicators of groundwater pollution, were not detected in most of the samples, except for naphthalene (0.005–0.202 μg/L, n?=?16). On the other hand, plastic components were detected in 77 % of the samples. Most frequently detected compounds were dimethyl phthalate and benzophenone at concentrations of 0.005–0.125 (n?=?41) and 0.014–0.921 (n?=?32), respectively. Levels detected are discussed in terms of contamination origin and geographical distribution. Target compounds were detected at low concentrations. Results obtained showed the high quality of bottled water in the different countries around the world.     

Characterization of dioxin-like contamination in soil and sediments from the ��hot spot�� area of petrochemical plant in Pancevo (Serbia)

Purpose

Combinatorial bio/chemical approach was applied to investigate dioxin-like contamination of soil and sediment at the petrochemical and organochlorine plant in Pancevo, Serbia, after the destruction of manufacturing facilities that occurred in the spring of 1999 and subsequent remediation actions.

Materials and methods

Soil samples were analyzed for indicator polychlorinated biphenyls (PCBs) by gas chromatography/electron capture detection (GC/ECD). Prioritized soil sample and sediment samples from the waste water channel were analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). Microethoxyresorufin o-deethylase (Micro-EROD) and H4IIE?Cluciferase bioassays were used for monitoring of dioxin-like compounds (DLC) and for better characterization of dioxin-like activity of soil samples.

Results

Bioanalytical results indicated high dioxin-like activity in one localized soil sample, while the chemical analysis confirmed the presence of large quantities of DLC: 3.0?×?10⁵ ng/g d.w. of seven-key PCBs, 8.2 ng/g d.w. of PCDD/Fs, and 3.0?×?10⁵ ng/g d.w. of planar and mono-ortho PCBs. In the sediment, contaminant concentrations were in the range 2?C8 ng/g d.w. of PCDD/Fs and 9?C20 ng/g d.w. of PCBs.

Conclusions

This study demonstrates the utility of combined application of bioassays and instrumental analysis, especially for developing and transition country which do not have capacity of the expensive instrumental analysis. The results indicate the high contamination of soil in the area of petrochemical plant, and PCDD/Fs contamination of the sediment from the waste water channel originating from the ethylene dichloride production.     

Monitoring of pyrrolizidine alkaloids in beehive products and derivatives on the Belgian market

Pyrrolizidine alkaloids (PAs) and related N-oxides (PANOs) are secondary plant metabolites thought to be found in approximately 3% of the flowering plants worldwide and exhibiting hepatotoxic properties to humans. As a consequence, beehive products are prone to be contaminated with those compounds by bees foraging PA-producing plants. Downstream contamination can also occur through food items containing honey. Analytical methods based on UHPLC separation and MS/MS detection were developed with a focus on very low LOQs and validated for the analysis of 16 PAs and 14 PANOs in honey, honey-based candies and snacks, as well as beehive product–based food supplements. A maximum level of 182 ng/g of PAs was detected in a Mediterranean honey, and high levels of heliotrine-type compounds were reported for the first time. An extensive sampling of honeys harvested in Belgium was performed (N = 374), the concentration levels were more limited with a maximum of 60 ng/g, and the contamination pattern was dominated by senecionine-type PAs. The PA levels in honey-based candies and snacks were very low, with respective maxima of 7.61 ng/g and 0.36 ng/g. Seventy-five percent among the pre-dosed food supplements based on beehive products were contaminated, with a maximum of 43 ng/g. The highest level was detected in a bee-collected pollen sample (1672 ng/g). The analytical results were consistent with the previously reported data for beehive products and confirmed that PA/PANO contamination in these food commodities is recurrent.     

Comparison of solid-phase bioassays and ecoscores to evaluate the toxicity of contaminated soils

Five bioassays (inhibition of lettuce germination and growth, earthworm mortality, inhibition of springtail population growth, avoidance by springtails) were compared, using four coke factory soils contaminated by PAHs and trace elements, before and after biotreatment. For each bioassay, several endpoints were combined in an ‘ecoscore’, a measure of test sensitivity. Ecoscores pooled over all tested bioassays revealed that most organisms were highly sensitive to the concentration of 3-ring PAHs. When four soils were combined, behavioural tests using the springtail Folsomia candida showed higher ecoscores, i.e. they were most sensitive to soil contamination. However, despite overall higher sensitivity of behavioural tests, which could be used for cheap and rapid assessment of soil toxicity, especially at low levels of contamination, some test endpoints were more sensitive than others, and this may differ from a soil to another, pointing to the need for a battery of bioassays when more itemized results are expected.     

Identification and removal of polycyclic aromatic hydrocarbons in wastewater treatment processes from coke production plants

Identification and removal of polycyclic aromatic hydrocarbons (PAHs) were investigated at two coke plants located in Shaoguan, Guangdong Province of China. Samples of raw coking wastewaters and wastewaters from subunits of a coke production plant were analyzed using gas chromatography–mass spectrometry (GC/MS) to provide a detailed chemical characterization of PAHs. The identification and characterization of PAH isomers was based on a positive match of mass spectral data of sample peaks with those for PAH isomers in mass spectra databases with electron impact ionization mass spectra and retention times of internal reference compounds. In total, 270 PAH compounds including numerous nitrogen, oxygen, and sulfur heteroatomic derivatives were positively identified for the first time. Quantitative analysis of target PAHs revealed that total PAH concentrations in coking wastewaters were in the range of 98.5?±?8.9 to 216?±?20.2 μg/L, with 3-4-ring PAHs as dominant compounds. Calculation of daily PAH output from four plant subunits indicated that PAHs in the coking wastewater came mainly from ammonia stripping wastewater. Coking wastewater treatment processes played an important role in removing PAHs in coking wastewater, successfully removing 92 % of the target compounds. However, 69 weakly polar compounds, including PAH isomers, were still discharged in the final effluent, producing 8.8?±?2.7 to 31.9?±?6.8 g/day of PAHs with potential toxicity to environmental waters. The study of coking wastewater herein proposed can be used to better predict improvement of coke production facilities and treatment conditions according to the identification and removal of PAHs in the coke plant as well as to assess risks associated with continuous discharge of these contaminants to receiving waters.     

Degradation of PAHs in soil by Lasiodiplodia theobromae and enhanced benzo[a]pyrene degradation by the addition of Tween-80

Benzo[a]pyrene (BaP), a five-ring polycyclic aromatic hydrocarbon (PAH), which has carcinogenic potency, is highly recalcitrant and resistant to microbial degradation. A novel fungus, Lasiodiplodia theobromae (L. theobromae), which can degrade BaP as a sole carbon source in liquid, was isolated in our laboratory. To prompt the further application of L. theobromae in remediation of sites polluted by BaP and other PAHs, the present study was targeted toward the removal of BaP and PAHs from soil by L. theobromae. The degradation of BaP by L. theobromae was studied using a soil spiked with 50 mg/kg BaP. L. theobromae could remove 32.1 % of the BaP after 35 days of cultivation. Phenanthrene (PHE) inhibited BaP degradation as a competitive substrate. The tested surfactants enhanced BaP degradation in soil by different extents, and a removal rate of 92.1 % was achieved at a Tween-80 (TW-80) concentration of 5 g/kg. It was revealed that TW-80 could not only enhance BaP bioavailability by increasing its aqueous solubility and decreasing the size of its colloid particles but also increase enzyme secretion from L. theobromae and the population of L. theobromae. Moreover, ergosterol content together with the biomass C indicated the increase in L. theobromae biomass during the BaP biodegradation process in soils. Finally, a soil from a historically PAH-contaminated field at Beijing Coking Plant in China was tested to assess the feasibility of applying L. theobromae in the remediation of polluted sites. The total removal rate of PAHs by L. theobromae was 53.3 %, which is 13.1 % higher than that by Phanerochaete chrysosporium (P. chrysosporium), an effective PAH degrader. The addition of TW-80 to the field soil further enhanced PAH degradation to 73.2 %. Hence, L. theobromae is a promising novel strain to be implemented in the remediation of soil polluted by PAHs.     

Enhancement of PAH biodegradation in soil by physicochemical pretreatment

The effects were studied of short-term heating of contaminated soil and its soaking in an organic solvent on the subsequent biodegradation of PAHs. In a clayey dredged sludge with a high organic-matter content (12%), heating at 120°C for one hour increased the degree of degradation after 21 days of an aged PAH contamination from 9.5 ± 0.7% to 27 ± 5%. Lower temperatures resulted in smaller increases. The observed increase in biodegradation is caused by either transfer of PAHs from sorption sites with low desorption rates to those with high ones or transformation of slow-sorption sites into fast-sorption ones. Soaking of the above sludge in a 4:1 (v/vj acetone-water mixture increased the degree of degradation from 9.5 ± 0.7% to 20.4 ± 1.4%, probably as a result of dissolution of the PAHs in the pore liquid during soaking. Thermal pretreatment of a contaminated sandy soil with a low organic-matter content showed no significant effect on the degradation of aged PAHs. Soaking of the sandy soil increased the degradation of only PAHs of high molecular weight, namely from 24 ± 5% to 48 ± 7%.     

Soil mobility of surface applied polyaromatic hydrocarbons in response to simulated rainfall

Polyaromatic hydrocarbons (PAHs) are emitted from a variety of sources and can accumulate on and within surface soil layers. To investigate the level of potential risk posed by surface contaminated soils, vertical soil column experiments were conducted to assess the mobility, when leached with simulated rainwater, of six selected PAHs (naphthalene, phenanthrene, fluoranthene, pyrene, benzo(e)pyrene and benzo(ghi)perylene) with contrasting hydrophobic characteristics and molecular weights/sizes. The only PAH found in the leachate within the experimental period of 26 days was naphthalene. The lack of migration of the other applied PAHs was consistent with their low mobilities within the soil columns which generally paralleled their log K _oc values. Thus, only 2.3 % of fluoranthene, 1.8 % of pyrene, 0.2 % of benzo(e)pyrene and 0.4 % of benzo(ghi)perylene were translocated below the surface layer. The PAH distributions in the soil columns followed decreasing power relationships with 90 % reductions in the starting levels being shown to occur within a maximum average depth of 0.94 cm compared to an average starting depth of 0.5 cm. A simple predictive model identifies the extensive time periods, in excess of 10 years, required to mobilise 50 % of the benzo(e)pyrene and benzo(ghi)perylene from the surface soil layer. Although this reduces to between 2 and 7 years for fluoranthene and pyrene, it is concluded that the possibility of surface-applied PAHs reaching and contaminating a groundwater aquifer is unlikely.     

Effect of cropping and tillage on the dissipation of PAH contamination in soil

This study examined the effect of regular tillage and cropping on the dissipation rate of PAHs in contaminated soil. Lysimeters were placed under natural climatic conditions for 2 years and designed to measure the concentration of PAHs in soil and leachates and their toxicity. The soil initially contained 2077 microg PAHs g(-1). The largest decrease in PAHs concentration occurred during the first 6 months. No further significant decrease was observed after this time. The surface soil layer always contained significantly less PAHs than the deeper layer, regardless of the treatments. Less than 8.4 x 10(-8)% of the PAH initially present in the soil (e.g. less or equal to 33 microg PAHs per lysimeter) were leached from the soils during the experiment and the leachates presented no toxicity (as measured by the Microtox test). The toxicity of the soils decreased with time and was significantly lower on the cropped soil compared to the other treatments, despite the residual concentration of PAHs being the highest in this soil. This study demonstrated that the dissipation rates of PAHs were slow after using natural attenuation even when tillage and cropping were performed at the soil surface.     

Distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in Sediment Cores of Selected Creeks in Delta State,Nigeria

The spatial and seasonal distribution and concentrations of polycyclic aromatic hydrocarbons (PAHs) were investigated in core sediments of Ubeji, Ifie, and Egbokodo creeks in the Niger Delta, Nigeria. A total of 222 core sediment samples were collected during the wet season (August 2010) and the dry season (January 2011). The samples were dried, Soxhlet extracted, fractionated, and injected into a gas chromatograph with flame ionization detector (GC-FID). The concentrations of PAHs ranged from not detected to 2,654 μg/kg (wet season) and not detected to 3,513 μg/kg (dry season). In general, the concentrations of PAHs for a number of stations in this study are comparable to sites with high anthropogenic activities in the Niger Delta. The toxicity risk assessment based on the total BaP equivalent quotient of the seven carcinogenic PAHs (BaA, Chry, BbF, BkF, BaP, DBA, and Iper) was 97.416 μg/kg and did not exceed the method B cleanup level for benzo(a)pyrene (137 μg/kg), according to toxic equivalency factors, which implied that PAHs in sediments of the present study currently have minimal adverse effects. This study provided information on the concentrations and profiles of PAHs sediment cores, which is useful for source diagnosis, environmental quality management, contamination history, and environmental forensic studies.