Evaluation of an approach for the characterization of reactive and available pools of 20 potentially toxic elements in soils: part II--solid-solution partition relationships and ion activity in soil solutions

To assess environmental risks related to contaminants in soil it is essential to predict the available pool of inorganic contaminants at regional scales, accounting for differences between soils from variable geologic and climatic origins. An approach composed of a well-accepted soil extraction procedure (0.01 M CaCl(2)) and empirical Freundlich-type models in combination with mechanistically based models which to date have been used only in temperate regions was applied to 136 soils from a South European area and evaluated for its possible general use in risk assessment. Empirical models based on reactive element pools and soil properties (pH, organic carbon, clay, total Al, Fe and Mn) provided good estimations of available concentrations for a broad range of contaminants including As, Ba, Cd, Co, Cu, Hg, Mo, Ni, Pb, Sb, Se and Zn (r(2): 0.46-0.89). The variation of the pools of total Al in soils expressed the sorptive capacity of aluminosilicates and Al oxides at the surfaces and edges of clay minerals better than the actual variability of clay contents. The approach has led to recommendations for further research with particular emphasis on the impact of clay on the solubility of As and Sb, on the mechanisms controlling Cr and U availability and on differences in binding properties of soil organic matter from different climatic regions. This study showed that such approach may be included with a good degree of certainty for first step risk assessment procedures to identify potential risk areas for leaching and uptake of inorganic contaminants in different environmental settings.     

Inferring episodic atmospheric iron fluxes in the Western South Atlantic

Iron (Fe) and other trace elements such as Zn, Mn, Ni and Cu are known as key-factors in marine biogeochemical cycles. It is believed that ocean primary productivity blooms in iron deficient regions can be triggered by iron in aeolian dust. Up to now, scarce aerosol elemental composition, based on measurements over sea at the Western South Atlantic (WSA), exist. An association between the Patagonian semi-desert dust/Fe and chlorophyll-a variability at the Argentinean continental shelf is essentially inferred from models. We present here experimental data of Fe enriched aerosols over the WSA between latitudes 22°S–62°S, during 4 oceanographic campaigns between 2002 and 2005. These data allowed inferring the atmospheric Fe flux onto different latitudinal bands which varied from 30.4 to 1688 nmolFe m^?2 day^?1 (October 29th–November 15th, 2003); 5.83–1586 nmolFe m^?2 day^?1 (February 15th–March 6th, 2004) and 4.73–586 nmolFe m^?2 day^?1(October 21st–November 5th, 2005).     

Biomonitoring of oral epithelial cells in petrol station attendants: Comparison between buccal mucosa and lateral border of the tongue

Owing to the influence of geno- and cytotoxicity on chemical carcinogenesis, studies have demonstrated that petroleum derivatives are able to induce genetic damage and cellular death with conflicting results so far. The aim of the present study was to comparatively evaluate DNA damage (micronucleus) and cellular death (pyknosis, karyolysis and karyorrhexis) in exfoliated oral mucosa cells from gas petrol attendants using two different anatomic buccal sites: cheek mucosa and lateral border of the tongue. A total of 23 gas petrol attendants and 23 health controls (non-exposed individuals) were included in this setting. Individuals had epithelial cells from cheek and lateral border of the tongue mechanically exfoliated, placed in fixative and dropped in clean slides which were checked for the above nuclear phenotypes. The results pointed out significant statistical differences (p < 0.05) of micronucleated oral mucosa cells from gas petrol attendants for both oral sites evaluated. In the same way, petroleum derivate exposure was able to increase other nuclear alterations closely related to cytotoxicity such as karyorrhexis, pyknosis and karyolysis, being the most pronunciated effects as those found in the lateral border of the tongue. No interaction was observed between smoking and petroleum exposure. In summary, these data indicate that gas petrol attendants comprise a high risk group for DNA damage and cellular death. It seems that the lateral border of the tongue is a more sensitive site to geno- and cytotoxic insult induced by petroleum derivates.     

Comparison of emission of dioxins and furans from gasohol- and ethanol-powered vehicles

The exhaust emissions of 17 polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were investigated in two spark-ignition light-duty vehicles, one gasohol-fueled and a flexible-fuel one fueled with hydrated ethanol. Gasohol is a mixture of gasoline and 22% ethanol. The influence of fuel type and quality, lubricant oil type, and use of fuel additives on the formation of these compounds was tested using standardized U.S. Federal Test Procedure (FTP)-75 cycle tests. The sampling of the PCDD/Fs followed the recommendations of a modified U.S. Environmental Protection Agency (EPA) Method 23 (www.epa.gov/ttn/ emc/promgate/m-23.pdf) and the analysis basically followed the U.S. EPA Method 8290 (http://www.epa.gov/osw/ hazard/testmethods/sw846/pdfs/8290a.pdf). Results showed that emission factors of PCDD/Fs for the.gasohol vehicle varied from undetected to 0.068 pg international toxic equivalency (I-TEQ) km(-1) (average of 0.0294 pg I-TEQ km(-1)), whereas in the ethanol vehicle they varied from 0.004 to 0.157 pg (I-TEQ) km(-1) (average of 0.031 pg I-TEQ km(-1)). In the gasohol-powered vehicle, the use of fuel additive diminished the emission of Octachlorodibenzo-p-dioxin (OCDD) significantly, whereas in the ethanol vehicle no significant associations were observed between the investigated variables and the emissions.     

Heterogeneity of soil surface ammonium concentration and other characteristics, related to plant specific variability in a Mediterranean-type ecosystem

Heterogeneity and dynamics of eight soil surface characteristics essential for plants—ammonium and nitrate concentrations, water content, temperature, pH, organic matter, nitrification and ammonification rates—were studied in a Mediterranean-type ecosystem on four occasions over a year. Soil properties varied seasonally and were influenced by plant species. Nitrate and ammonium were present in the soil at similar concentrations throughout the year. The positive correlation between them at the time of greatest plant development indicates that ammonium is a readily available nitrogen source in Mediterranean-type ecosystems. The results presented here suggest that plant cover significantly affects soil surface characteristics.     

Phosphorus fractionation in volcanic lake sediments (Azores - Portugal)

The phosphorus distribution in volcanic sediments of three lakes that are under different anthropogenic pressures in S?o Miguel island (Azores - Portugal) was evaluated using a sequential extraction scheme. The P-fractionation scheme employs sequential extractions of sediment with NH4Cl, bicarbonate-dithionite (BD), NaOH (at room temperature), HCl and NaOH (at 85 degrees C) to obtain five P-fractions. The P-fractionation shows that in lakes with higher trophic status (Lake Furnas and Lake Sete Cidades), the NaOH extracted P is the dominant fraction, that contribute with more than 50% to total sedimentary phosphorus. The rank order of P-fractionation for these two lakes was NaOH>NaOH (85 degrees C)>HCl>BD>NH4Cl for Furnas lake and NaOH>HCl>NaOH (85 degrees C)>NH4Cl>BD for Sete Cidades lake. On the other hand, the trend of P contribution in the oligotrophic lake Fogo shows that the most inert P pools have the higher concentrations, with more than 50% of the P contribution from the last extraction step with NaOH at 85 degrees C. For this lake, the rank order of P-fractionation was NH4Cl>BD>NaOH>HCl>NaOH (85 degrees C). The Phosphorus Maximum Solubilization Potential (P-MSP) was also calculated and the results show that for the more bio-available P-fractions (first and second extraction step), the P-MSP values for Furnas and Sete Cidades lakes are sensibly higher than the results obtained in Fogo lake, an indication of the non-point diffuse load discharged in the first ones.     

Numerical simulation of non-breaking solitary wave run-up using exponential basis functions

A meshless method based on exponential basis functions (EBFs) is developed to simulate the propagation of solitary waves and run-up on the slope. The presented method is a boundary-type meshless method applying the exponential basis functions with complex exponents. The solution of governing equations is considered as a series of these basis functions. Boundary conditions are satisfied through a point-wise collocation approach. Based on the presented EBF meshless method, a new formula is introduced for the maximum run-up height on different slopes, valuable for engineering applications. The results obtained through the numerical method in the prediction of solitary wave propagation and estimation of run-up are verified through the comparison with experimental data. The comparison with 159 experimental data indicates that this new formula is more accurate than the preceding formulas in predicting the maximum run-up of non-breaking solitary waves. Minimum calculation time and convenient performances are the other advantages of this method.     

A new typology for Portuguese beaches: An exploratory study

Beaches are now the most popular tourist destination and increased demand in the past 40 years has led not only to beach congestion but also to a differentiation between urban (resorts, overcrowded and under huge pressure), to natural (less crowded beaches). This diversity needs to be further explored not only to characterize individual beaches in a precise way, but also to understand the distinctive characteristics responsible for options made by beach users. Some attempts have been made to create a universal beach typology but sparse research has been undertaken. The topic is of extreme importance for beach management, as most studies only take into consideration beach usage type and few consider the surrounding environment (landscape). This paper presents an exploratory work for Portuguese beaches which creates a new classification, according to usage and surrounding environment, based on several variables, measured and weighted. The results scale between zero and five and assess how a beach can be classified along an urban (0) to natural (5) spectrum. Variables studied include population density, number of hotels urban density, car park distance to the beach, etc. A pilot study applied to 100 beaches in the Lisbon Metropolitan Area, found that a densely populated region, can also contain beaches with natural characteristics.     

Health risk assessment through consumption of vegetables rich in heavy metals: the case study of the surrounding villages from Panasqueira mine,Central Portugal

Panasqueira mine is a tin–tungsten mineralization hosted by metasediments with quartz veins rich in ferberite. The mineralization also comprises wolframite, cassiterite, chalcopyrite, several sulfides, carbonates and silver sulfosalts. The mining and beneficiation processes produce arsenic-rich mine wastes laid up in huge tailings (Barroca Grande and Rio tailings). The contents of As, Cd, Cr, Cu, Pb and Zn were estimated in rhizosphere soils, irrigation waters, road dusts and in potatoes, cabbages, lettuces and beans, collected on local gardens of four neighborhood Panasqueira mine villages: S. Francisco de Assis (SFA) and Barroca suffering the influence of tailings; Unhais-o-Velho and Casegas considered as non-polluted areas. The mean concentrations of metals in rhizosphere soils and vegetables exceed the reference guidelines values and seem to be linked to the sulfides. The rhizosphere ecological risks were ranked in the order of Cd > As > Cu > Pb > Zn > Cr and SFA > Barroca > Casegas > Unhais-o-Velho. Metal concentrations, in vegetables, were found in the order of lettuce > cabbage > potatoes and SFA > Barroca > Casegas > Unhais-o-Velho. For cabbages and lettuces, the tendency of contamination is roots > leaves and for potatoes is roots > leaves > tubers. The risk for residents, due to ingesting of metals/metalloid, by consuming vegetables grown around the sampling area, was calculated and the result indicates that the inhabitants of these villages are probably exposed to some potential health risks through the intake of heavy metals and metalloids via consuming their vegetables.     

Arsenic speciation in rice consumed in south-western Nigeria,and estimation of dietary intake of arsenic species through rice consumption

This study determined concentrations and speciation of arsenic (As) in rice samples obtained from the cities of Akure, Ore, Ondo and Ikare in Ondo State, south-western Nigeria. The estimated dietary intake of As from rice consumption for total As and the identified As species were compared with the As benchmark dose lower confidence limit. Analyses of rice from the four cities identified three As species: inorganic As, monomethylarsonic, acid and dimethylarsinic acid. Concentrations of total As and the As species differed significantly across the sampling locations (by a factor of 2.5 for total As). Mean levels (±S.D.) were 58.8 ± 0.7 µg/kg total As, 47.0 ± 0.6 µg/kg inorganic As, 0.33 ± 0.03 µg/kg monomethylarsonic acid, and 11.5 ± 0.1 µg/kg dimethylarsinic acid. The estimated mean dietary intakes were 4.1 µg/d total As, 3.3 µg/d inorganic As, 0.02 µg/d monomethylarsonic acid, and 0.8 µg/d dimethylarsinic acid. These values are below the benchmark dose lower confidence limit and comparable to, or lower than, those reported for other countries. Thus, consumption of rice cultivated in south-western Nigeria does not appear to have inherent As-associated health risks.