Risk of polycyclic aromatic hydrocarbon (PAH) exposure from ingested food: the Azerbaijan case study

Risks due to polycyclic aromatic hydrocarbons (PAHs) exposure from food consumption for the population of Azerbaijan were determined using deterministic and probabilistic methods. The guidelines and methods described and presented in the United States Environmental Protection Agency (U.S. EPA) Risk Assessment Guidance for Superfund (RAGS) Part A was used in performing the risk assessments. The current study utilized concentration data from different sources representing international studies performed over the past decade to determine those food products that contribute the most exposure to PAHs through ingestion for the Azeri population. Due to lack of concentration data from middle-Eastern countries, only European countries were considered and used for this analysis. Using the benzo[a]pyrene (BaP) toxicity equivalency factors (TEFs) to adjust the concentrations of the individual PAH compounds to BaP equivalent concentrations, risk analyses were performed. Deterministic risk estimates fell within probabilistic risk estimates. Child risks were consistently four to seven times higher in magnitude than adult risks. Risk potentials determined for the food exposure pathway were also determined to be up to ten times higher in magnitude than risks determined from exposures due to other pathways such as soil contamination. It was observed that three major factors contributed to the variability in the assessment results, which were child and adult body weights, consumption rates of the different food groups, and the variances of the input data. The most prevalent pathways of PAH exposure from the dietary patterns of the Azerbaijani population were determined to be from bread and bakery products, milk and dairy products, and egg products.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 x 10(- 3) h(- 1) to 7.0 x 10(- 3) h(- 1). The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State-Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, alpha and beta endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino-Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6% leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (alpha-endosulfan), 1.47E-162 (beta-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Reduced nitrogen in ecology and the environment

Since the beginning of the 19th century humans have increasingly fixed atmospheric nitrogen as ammonia to be used as fertilizer. The fertilizers are necessary to create amino acids and carbohydrates in plants to feed animals and humans. The efficiency with which the fertilizers eventually reach humans is very small: 5-15%, with much of the remainder lost to the environment. The global industrial production of ammonia amounts to 117 Mton NH(3)-Nyear(-1) (for 2004). By comparison, we calculate that anthropogenic emissions of NH(3) to the atmosphere over the lifecycle of industrial NH(3) in agriculture are 45.3 Mton NH(3)-Nyear(-1), about half the industrial production. Once emitted ammonia has a central role in many environmental issues. We expect an increase in fertilizer use through increasing demands for food and biofuels as population increases. Therefore, management of ammonia or abatement is necessary.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Influence of Relative Humidity and Ozone on the Sampling of Volatile Organic Compounds on Carbotrap/Carbosieve Adsorbents

By using a dynamic dilution system, the atmospheric measurement of 11 selected toxics VOCs (ethylene, acetylene, propene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, benzene, toluene, ethylbenzene, m+p-xylene) from the list WHO of 1996 and TO-14 method of US EPA by preconcentration by thermal desorption (TD), analysis by gas chromatography (GC), identification and quantification with a flame ionisation detector (FID) was developed and validated in term of metrology, especially the techniques of sampling of these VOCs with adsorbents cartridges "Air Toxics" when used with an "UMEG sampler" equipped in the inlet with a nafion membrane. In particular the influence of climatic conditions (temperature and relative humidity) and the influence of chemical factors like ozone, on the representativity of sampling were studied. Experiments made with various humidities showed that the addition of a nafion membrane in the inlet of the sampling system was required. Without this membrane, losses of compounds were observed for RH >50%. With this membrane, storage for 2 weeks in a refrigerator, as for canisters, did not induce a loss of compounds. No significative decrease of concentrations of the studied VOCs after 14 days storage, which are known to react with ozone, were observed with an ozone concentrations of 55 ppb. One explanation is that nafion membrane, placed in the inlet of the sampler, will neutralize ozone before entering the sampling tubes. This observation is in accordance with literature which states that the sampling of VOCs on Carbotrap cartridges without ozone scrubber induce a loss of compounds.     

The Distribution and Sources of Polycyclic Aromatic Hydrocarbons in Surface Sediments Along the Egyptian Mediterranean Coast

Coastal marine sediment samples were collected from 31 sampling stations along the Egyptian Mediterranean Sea coast. All sediment samples were analyzed to determine aliphatic and polycyclic aromatic hydrocarbons (PAHs) as well as total organic carbon (TOC) contents and grain size analysis. Total concentrations of 16 EPA-PAHs in the sediments were varied from 88 to 6338 ng g⁻¹ with an average value of 154 ng g⁻¹ (dry weight). However, the concentrations of total aliphatic were varied from 1.3 to 69.9 ng g⁻¹ with an average value of 15.6 ng g⁻¹ (dry weight). The highest contents of PAHs were found in the Eastern harbor (6338 ng g⁻¹), Manzala (5206 ng g⁻¹) and El-Jamil East (4895 ng g⁻¹) locations. Good correlations observed between a certain numbers of PAH concentrations allowed to identify its origin. The average total organic carbon (TOC) percent was varied from 0.91 to 4.54%. Higher concentration of total pyrolytic hydrocarbons (∑COMB) than total fossil hydrocarbons (∑PHE) declared that atmospheric fall-out is the significant source of PAHs to marine sediments of the Egyptian Mediterranean coast. The selected marked compounds, a principal component analysis (PCA) and special PAHs compound ratios (phenanthrene/anthracene vs fluoranthene/pyrene; ∑COMB/∑EPA-PAHs) suggest the pyrogenic origins, especially traffic exhausts, are the dominant sources of PAHs in most locations. Interferences of rather petrogenic and pyrolytic PAH contaminations were noticed in the harbors due to petroleum products deliveries and fuel combustion emissions from the ships staying alongside the quays.     

Distribution of PAHs in Surface Soils from Petroleum Handling Facilities in Calabar

The level of concentrations of polycyclic aromatic hydrocarbons (PAHs) in surface soils from petroleum handling facilities (kerosene tank, generating plant, petrol stations, mechanic workshops, leaking pipeline and air port fuel dump) from Calabar metropolis southeastern Nigeria was determined by gas chromatography/ mass spectrometry. The results show that total polycyclic aromatic hydrocarbons (PAHs) varied from 1.80 to 334.43 mg/kg with a mean of 50.31 mg/kg. The lowest value of 1.80 mg/kg was obtained from petrol station while the highest value of 334.43 mg/kg was obtained from facility characterised by petrol stations and mechanic workshops. The ratio of phenanthrene/anthracene and fluoranthene/pyrene, varied from 0.43 to 27.72 and from 0.14 to 17.76 respectively. These ratios indicate various sources for the PAH. The two to three ring PAHs are the most abundant. Based on the PAH ratios and content alone it is not possible to distinguish between contribution from motor vehicle exhaust, gasoline spillage, used engine oil or petroleum production. However, considering the area of the study, it is very likely that the major source of soil contamination is originating from petroleum product.     

A Procedure for NEPA Assessment of Selenium Hazards Associated With Mining

This paper gives step-by-step instructions for assessing aquatic selenium hazards associated with mining. The procedure was developed to provide the U.S. Forest Service with a proactive capability for determining the risk of selenium pollution when it reviews mine permit applications in accordance with the National Environmental Policy Act (NEPA). The procedural framework is constructed in a decision-tree format in order to guide users through the various steps, provide a logical sequence for completing individual tasks, and identify key decision points. There are five major components designed to gather information on operational parameters of the proposed mine as well as key aspects of the physical, chemical, and biological environment surrounding it — geological assessment, mine operation assessment, hydrological assessment, biological assessment, and hazard assessment. Validation tests conducted at three mines where selenium pollution has occurred confirmed that the procedure will accurately predict ecological risks. In each case, it correctly identified and quantified selenium hazard, and indicated the steps needed to reduce this hazard to an acceptable level. By utilizing the procedure, NEPA workers can be confident in their ability to understand the risk of aquatic selenium pollution and take appropriate action. Although the procedure was developed for the Forest Service it should also be useful to other federal land management agencies that conduct NEPA assessments, as well as regulatory agencies responsible for issuing coal mining permits under the authority of the Surface Mining Control and Reclamation Act (SMCRA) and associated Section 401 water quality certification under the Clean Water Act. Mining companies will also benefit from the application of this procedure because priority selenium sources can be identified in relation to specific mine operating parameters. The procedure will reveal the point(s) at which there is a need to modify operating conditions to meet environmental quality goals. By recognizing concerns early in the NEPA process, it may be possible for a mining company to match operational parameters with environmental requirements, thereby increasing the likelihood that the permit application will be approved.     

Using Spatial Pattern to Quantify Relationship Between Samples, Surroundings, and Populations

The need for accurate carbon budgeting, climate change modelling, and sustainable resource management has lead to an increase in the number of large area forest monitoring programs. Large area forest monitoring programs often utilize field and remotely sensed data sources. Sampling, via field or photo plots, enables the collection of data with the desired level of categorical detail in a timely and efficient manner. When sampling, the aim is to collect representative detailed data enabling the statistical reporting upon the characteristics of larger areas. As a consequence, approaches for investigating how well sample data represent larger areas (i.e., the sample neighbourhood and the population) are desired. Presented in this communication is a quantitative approach for assessing the nature of sampled areas in relation to surrounding areas and the overall population of interest. Classified Landsat data is converted to forest/non-forest categories to provide a consistent and uniform data set over a 130,000 km² study region in central British Columbia, Canada. From this larger study area 322 2 × 2 km photo plots on a 20 × 20 km systematic grid are populated with composition and configuration information for comparison to non-sampled areas. Results indicate that typically, within the study area, the spatial pattern of forest within a photo plot is representative of the forest patterns found within primary and secondary neighbourhoods and over the entire population of the study. These methods have implications for understanding the nature of data used in monitoring programs worldwide. The ability to audit photo and field plot information promotes an increased understanding of the results developed from sampling and provides tools identifying locations of possible bias.