Effect of exposure to soil-bound polycyclic aromatic hydrocarbons on milk contaminations of parent compounds and their monohydroxylated metabolites

The aim of this study was to determine the transfer kinetics of soil-bound polycyclic aromatic hydrocarbons to milk in lactating cows. Soil (500 g/day) fortified with fluorene (104 microg/g dry soil), phenanthrene (82 microg/g), pyrene (78 microg/g), and benzo[a]pyrene (33 microg/g) was administered to three dairy cows via a rumen cannulas for 28 consecutive days. Parent compounds and their major metabolites in milk were measured using gas chromatography-mass spectrometry. Secretion of parent compounds in milk did not increase significantly (P > 0.05) over the control values measured before supply. Target monohydroxylated metabolites were not detected in control samples, but 2-hydroxy fluorene, 3-hydroxy phenanthrene, and 1-hydroxy pyrene were present in milk by the second day of dosing. The highest concentrations of metabolites in milk (31-39 ng/mL) were for 1-hydroxy pyrene at days 7 and 14 of dosing. The observed plateaus for 3-hydroxy phenanthrene and 2-hydroxy fluorene were lower (respectively, 0.69 and 2.79 ng/mL) but significantly increased in comparison to the control samples. Contrarily, 3-hydroxy benzo[a]pyrene was not detected in milk at any sampling time. These results suggested a notable metabolism of the parent compounds after their extraction from soil during the digestive transfer. Thus, the metabolization of fluorene and pyrene can lead to higher concentrations of metabolites than of parent compounds in milk. Despite the absence of a significant transfer of parent PAHs to milk, the appearance of metabolites raises the questions of their impact on human health.     

Polycyclic aromatic hydrocarbons: pollution and source analysis of a black tea

Investigations into the manufacturing process of one kind of black tea revealed that it included five steps: withering, rolling, fermentation, drying, and drying and sorting. A total of 16 polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in fresh leaves, withered leaves, rolled leaves, fermented leaves, crude black tea, and black tea sampled after each manufacturing stage and in the indoor and outdoor air of the drying house. It was observed that the total contents of the 16 PAHs (SigmaPAHs) in the crude black tea and the black tea were obviously higher than those in the tea leaves sampled after each manufacturing step before the drying stage; the air SigmaPAHs in the drying house were about 100 times higher than those outside the drying house. It can be concluded that quantities of PAHs were released into the drying house from the combustion of pine firewood during the drying stage, and then were absorbed by the tea leaves, thus resulting in the high PAH contents in the black tea.     

Detecting interaction(s) and assessing the impact of component subsets in a chemical mixture using fixed-ratio mixture ray designs

An important environmental and regulatory issue is the protection of human health from potential adverse effects of cumulative exposure to multiple chemicals. Earlier literature suggested restricting inference to specific fixed-ratio rays of interest. Based on appropriate definitions of additivity, single chemical data are used to predict the relationship among the chemicals under the zero-interaction case. Parametric comparisons between the additivity model and the model fit along the fixed-ratio ray(s) are used to detect departure from additivity. Collection of data along reduced fixed-ratio rays, where subsets of chemicals of interest are removed from the mixture and the remaining compounds are at the same relative ratios as considered in the full ray, allow researchers to make inference about the effect of the removed chemicals. Methods for fitting simultaneous confidence bands about the difference between the best fitting model and the model predicted under additivity are developed to identify regions along the rays where significant interactions occur. This general approach is termed the “single chemicals required” (SCR) method of analysis. A second approach, termed “single chemicals not required” (SCNR) method of analysis, is based on underlying assumptions about the parameterization of the response surface. Under general assumptions, polynomial terms for models fit along fixed-ratio rays are associated with interaction terms. Consideration is given to the case where only data along the mixture rays are available. Tests of hypotheses, which consider interactions due to subsets of chemicals, are also developed.     

Sorption of polycyclic aromatic hydrocarbons to soils enhanced by heavy metals: perspective of molecular interactions

Purpose

Combined pollution by polycyclic aromatic hydrocarbons (PAHs) and heavy metals are commonly found in industrial soils. This study aims to investigate the effect of the coexistence of heavy metals on the sorption of PAHs to soils. We focused specifically on the relationship of the sorption capacity with the estimation of the binding energy between PAHs and heavy metals.

Materials and methods

The sorption of typical PAHs (naphthalene, phenanthrene, and pyrene) to soils coexisting with heavy metals (Cu(II), Pb(II), and Cr(III)) was characterized in batch sorption experiments. The binding energy between PAHs and heavy metals in aqueous solution was estimated by quantum mechanical (QM) method using density functional theory (DFT) at the M06-2x/def2svp level of theory.

Results and discussion

Sorption capacity and nonlinearity of the PAHs to the soils were enhanced by the coexisting heavy metals. The extent of increment was positively associated with the hydrophobicity of the PAHs and the electronegativity and radius of the metal cations: Cr(III)?>?Pb(II)?>?Cu(II). The cation-π interaction was revealed as an important noncovalent binding force. There was a high correlation between the binding energies of the PAHs and K _f ′ (K _f adjusted after normalizing the equilibrium concentration (C _e) by the aqueous solubility (C _s)) (R ²?>?0.906), indicating the significant role of the cation-π interactions to the improved PAH sorption to soils.

Conclusions

In the presence of heavy metals, the sorption capacities of naphthalene, phenanthrene, and pyrene to soils were enhanced by 21.1–107 %. The improved sorption capacity was largely contributed from the potent interactions between PAHs and heavy metals.

     

Distribution of polycyclic aromatic hydrocarbons (PAHs) in the bottom sediments of a dam reservoir,their interaction with organic matter and risk to benthic fauna

Journal of Soils and Sediments - The aims of the study were to investigate the interaction between fractions of organic matter and polycyclic aromatic hydrocarbons (PAHs) in bottom sediments and to...     

The maps of soil tolerance toward pollution with oil products and polycyclic aromatic hydrocarbons: Methodological aspects

Natural factors ensuring soil tolerance toward pollution with technogenic hydrocarbons, particularly, oil products and polycyclic aromatic hydrocarbons, are considered. The maps of the self-purification capacity of the soils of Russia and its particular humid and arid regions with respect to their contamination with technogenic hydrocarbons are analyzed. The principles lying in the basis of these maps are discussed. It is argued that the cartographic assessment of soil tolerance toward pollution with technogenic hydrocarbons is necessary for setting the values of maximum permissible concentrations of hydrocarbons in soils, for the choice of adequate soil rehabilitation procedures, and for the organization of soil monitoring.     

The relationship of a coal fired power plant to the levels of polycyclic aromatic hydrocarbons (PAH) in the sediment of Cayuga Lake

Polychlorinated biphenyls (PCBs) are chlorinated hydrocarbons primarily used as dielectric fluids and coolants for electrical equipment. At present, it is estimated that 200 Gg of PCBs have been released into the environment. In 1976, the Toxic Substances Control Act was passed by Congress, requiring regulation of PCBs. EPA-approved methods for destruction/disposal of PCBs include high temperature combustion in incinerators and high efficiency boilers, landfilling, chemical dechlorination, and alternate disposal techniques which achieve a level of performance equivalent to an approved incinerator or boiler. A discussion of these methods is presented as well as various other disposal methods which are still in the research phases.     

Statistical analysis of interactive cytotoxicity in human epidermal keratinocytes following exposure to a mixture of four metals

Exposure to mixtures of chemicals is an important and relevant environmental issue. Of particular interest is the detection and characterization of departure of biological effects from additivity. Methodology based on the assumption of additivity is used in fitting single-chemicaldata. Interactionsare determined and characterized by making comparisons between the observed and predicted responses at mixtures along a fixed ratio ray of the component substances. Two simultaneous tests are developed for testing for any departure from additivity. Multiple comparisons procedures are used to compare observed responses to that predicted under additivity. A simultaneous confidence band on the predicted responses along the mixture ray is also developed. The methods are illustrated with cytotoxicity data that arise when human epidermal keratinocytes are exposed to a mixture of arsenic, chromium, cadmium, and lead. Synergistic, antagonistic, and additive cytotoxicities were observed at different dose levels of the four-metal mixture.     

Effect of a novel chemical mixture on senescence processes and plant--fungus interaction in Solanaceae plants

The effects of exogenous application of a chemical mixture consisting of adipic acid monoethyl ester, furfurylamine, and 1,2,3,4-tetra-O-acetyl-beta-D-glucopyranose (FGA) on various metabolic pathways and the plant-fungus interaction have been studied in Solanaceae plants. Tomato and pepper plants were sprayed with the FGA mixture, and different biochemical parameters such as gas exchange, chlorophyll concentration, protein, cell wall sugar and phenolics contents, and peroxidase and phenylalanine ammonia lyase (PAL) activities were measured. FGA-treated plants showed, in general, an increase in cell wall sugar content and decreases in the chlorophyll degrading rate and the peroxidase activity. These results suggest that FGA (a possible synthetic regulator) could act as a retardant--antisenescence agent in Solanaceae plants. The FGA mixture increased the PAL activity and promoted an overall rise in the concentration of flavonoids and phenolic compounds. Therefore, FGA induced the synthesis of compounds that could give protection to plants against pathogens or insects. To further verify this putative protection, several fungi were inoculated in intact plants. Exogenous FGA applications on intact plants delayed fungus-provoked lesion development. In addition, data also showed that applications of 1,2,3,4-tetra-O-acetyl-beta-D-glucopyranose inhibited fungal growth in vitro. These results confirm that FGA can activate protective mechanisms in plants upon contact with invaders such as fungi.     

In situ gradient distribution of polycyclic aromatic hydrocarbons (PAHs) in contaminated rhizosphere soil: a field study

Purpose

Little information is available heretofore on the gradient distribution of persistent organic pollutants in rhizosphere on a field scale. In this field study, we seek to explore the in situ distribution gradient of polycyclic aromatic hydrocarbons (PAHs) in rhizosphere soil proximal to the roots.

Materials and methods

Clover (Trifolium pratense L.) and hyssop (Hyssopus officinalis L.) grew in situ in the contaminated field soil near a petrochemical plant and were harvested when about 30 cm tall with mature roots. Rhizosphere soils of the plants were sampled including the rhizoplane, strongly adhering soil, and loosely adhering soil. Eleven EPA-priority PAHs were detected in each layer of rhizosphere soils in proximity to the root surface.

Results and discussion

The PAH concentrations followed the descending order of bulk soil, loosely adhering soil, strongly adhering soil, and rhizoplane soil in proximity to the root surface of clover and hyssop. The rhizosphere effect (R, in percent) on PAH distribution clearly decreased with increasing distance from the root, and a more significant decrease was observed for hyssop compared to clover. R values were generally lower for three- and four-ringed PAHs in the rhizosphere, which were more significant in loosely and strongly adhering rhizosphere layers.

Conclusions

Our field observations combined with previous potted studies demonstrated that PAH concentrations in rhizosphere soils increased with distance from the root. Results of this work provide new information on the fate of PAHs in rhizosphere.     

Biochar reduces uptake and accumulation of polycyclic aromatic hydrocarbons (PAHs) in winter wheat on a PAH-contaminated soil

For years, biochar has been successfully used for the remediation of polycyclic aromatic hydrocarbons(PAHs) in contaminated soils, not only for improving their removal from soil but also for reducing their uptake by crops. However, the underlying mechanism of biochar application reducing PAH uptake and accumulation in winter wheat remains unclear. Pot trials were conducted on a PAH-contaminated soil amended with bamboo biochar, coconut shell biochar,and maize straw biochar(MSB) for an entire gro...     

The question of whether gut microflora of the millipede Ommatoiulus sabulosus could function as a threshold to food infections

The specific composition of bacterial flora in the intestines of O. sabulosus cannot be explained simply by antibiotic inhibition of contaminating microflora since the predominant types of bacteria present are unable to produce any bacteriolytic activity of lysozyme-like enzymes, bacteriocins or other antimicrobial molecules. The lack of microbial contaminators could rather result from the unfavourable biochemical niche in the midgut enzymes and little or no competition for the enteric bacteria group predominant in the millipede alimentary tract. In other words, the rapid colonization and overgrowth of the Ommatoiulus intestines eliminate adventitious bacteria, yeasts and moulds ingested with food.     

The need for enemy-free space: The impact of an invasive gecko on island endemics

How introduced reptiles cause the loss of endemic reptiles is poorly understood and currently there are no available techniques for dealing with this major conservation issue. We addressed both these problems by investigating the role of the introduced house gecko Hemidactylus frenatus in causing the catastrophic decline and extinction of the endemic night gecko Nactus populations of the Mascarene Islands and how this introduced species can be excluded from habitats on the basis of morphology. Competition for enemy free space was tested in experimental enclosures and showed that H. frenatus displace the endemic Nactus coindemirensis and Nactus durrelli from favoured positions close to and from refugia, thus increasing the risk of predation and exposure to stochastic events. The ability of H. frenatus to grip substrates with their pad-bearing toes was examined, and we demonstrated that naturally occurring substrates with a greater amount of loose surface material of a higher particulate concentration and size excludes H. frenatus, but not Nactus. These findings support the hypothesis that H. frenatus led to the fragmentation and extinction of the endemic Nactus populations and demonstrate that artificial refugia made of a crumbly substrate may be used to limit future disturbances by this gecko and others like it in the Mascarene Islands and elsewhere.     

Erratum to: Evaluation of toxicity risk of polycyclic aromatic hydrocarbons (PAHs) in crops rhizosphere of contaminated field with sequential extraction

Journal of Soils and Sediments -     

The effect of volatilization on the mass flow of a non-aqueous pollutant liquid mixture in an inert porous medium: experiments with kerosene

Kerosene, an industrial petroleum product characterized by the presence of a large number of petroleum hydrocarbons (C₉-C₁₅), was selected as an example of a non-aqueous pollutant liquid (NAPL) mixture for our studies. Three inert materials (fine, medium and coarse sand) were used in the experiments and the initial amount of kerosene applied ranged from residual to saturated retention capacity. Volatilization in the air phase and saturated mass flow of kerosene in the three sands were studied in the laboratory under controlled conditions. The volatilization was the major physicochemical process affecting the fate of kerosene in the inert porous medium. During volatilization the liquid kerosene changed its composition by gradually losing its light components (C₉-C₁₃), and the viscosity of the remaining liquid kerosene increased. The increase in viscosity led to a decrease in the infiltration rate, for example, by about 20% when the viscosity increased from 1.3 × 10^?3 to 2.0 × 10^?3 Pa s. The relationship between the composition of the residual kerosene following volatilization and its mass flow in a sand illustrates the behaviour of non-aqueous pollutants in inert porous media.     

Compositional changes of a fuel oil from an oil spill due to natural exposure

The purpose of this work was to determine the degree of oil retention from an oil spill area in view of natural physical weathering, and to evaluate the compositional changes of the natural oil retained in the soil material. The percentage of oil retained over the 1 yr period of weathering was determined at various intervals, and the compositional changes were studied by G.L.C. and I.R. The results of G.L.C. indicated the loss of low molecular weight n-paraffins, and that of I.R. indicated the formation of sulfones and ether groups as a result of oxidation reaction due to natural exposure. It was established that up to 4% oil was retained in the soil material after 6 mo of exposure, and that about 3.5% remained after a year.     

The impact of sport-hunting on the population dynamics of an African lion population in a protected area

Between 1999 and 2004 we undertook an ecological study of African lions (Panthera leo) in Hwange National Park, western Zimbabwe to measure the impact of sport-hunting beyond the park on the lion population within the park, using radio-telemetry and direct observation. 34 of 62 tagged lions died during the study (of which 24 were shot by sport hunters: 13 adult males, 5 adult females, 6 sub-adult males). Sport hunters in the safari areas surrounding the park killed 72% of tagged adult males from the study area. Over 30% of all males shot were sub-adult (<4 years). Hunting off-take of male lions doubled during 2001-2003 compared to levels in the three preceding years, which caused a decline in numbers of adult males in the population (from an adult sex ratio of 1:3 to 1:6 in favour of adult females). Home ranges made vacant by removal of adult males were filled by immigration of males from the park core. Infanticide was observed when new males entered prides. The proportion of male cubs increased between 1999 and 2004, which may have occurred to compensate for high adult male mortality.     

Impacts of particulate organic carbon and dissolved organic carbon on removal of polycyclic aromatic hydrocarbons, organochlorine pesticides, and nonylphenols in a wetland

Background, aim, and scope  The potential of wetlands for controlling point- and nonpoint-source pollution in surface water has attracted increasing interest. The partitioning process of organic contaminants between water, particulate organic carbon (POC) and dissolved organic carbon (DOC), impacts their behaviors in the aquatic environments. Meantime, the partitioning process of organic contaminants is closely related to their physicochemical properties, such as hydrophobicity (or K _ow), and their fates in wetlands may vary greatly depending on physicochemical properties. The aim of this study was to examine fates and removals of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and nonylphenols (NPs) in a wetland in Beijing, China, and provide useful information for ecological remediation. Materials and methods  Water samples, collected at five sites from inlet to outlet of the wetland once a month in summer 2006, were immediately filtered within 2 days through 0.45-μm glass fiber prefilters and enriched by solid-phase extraction. The filtered particulates were collected as the total suspended particulates (TSPs), freeze-dried, and Soxhlet-extracted. After extraction, samples were purified following a clean-up procedure and analyzed by GC-MS. Results  TSPs could be removed efficiently with a removal rate of 97.4%, and DOC could be moderately removed with a removal rate of 44.7% from inlet to outlet. The total removals of target contaminants varied widely from null to 82.0%. A good correlation between logK _ow and logK _oc (organic-carbon-normalized suspended-particulate partition coefficient) was observed (r ² = 0.84 for PAHs and r ² = 0.86 for OCPs, p < 0.01). Ratios of the POC-bound fraction of target contaminants (or DOC-bound fraction) to the freely dissolved fraction increased with their K _ow values. The removal of the POC fraction contributed more than 50% to the total removal for the contaminants with logK _ow > 5.0. Only a small portion of the removal was attributed to the removal of the freely dissolved fraction. Discussion  Hydrophobic compounds such as PAHs and OCPs with higher K _ow values would show stronger POC or DOC preference. Their removal depended greatly on their K _ow values and the removal of total suspended particulates. On the other hand, concentrations of NPs decreased little in the wetland, probably due to their production through degradation of their precursors and relatively low hydrophobicity. Conclusions  POC and DOC play essential roles on the fates and removals of hydrophobic organic contaminants in the wetland. The removal of target contaminants with a high K _ow should be mainly through association with the suspended particulates which were precipitated and retained in the wetland. The fates of the organic contaminants in the wetland greatly depended on their hydrophobicities. Recommendations and perspectives  Further work should be done to study the influence of hydraulic retention time and some other environmental factors, e.g., temperature, on removals and fates of organic contaminants. Behavior of NPs and their precursors in the wetland should also be investigated more thoroughly.