Simultaneous determination of volatile and semivolatile organic compounds in soil

A microscale solvent extraction (MSE) method was developed for the simultaneous determination of volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) in soil. Tests of precision, recovery, and comparability to other Environmental Protection Agency (EPA) methods have been completed, and the MSE method compares well to Soxhlet and sonication extraction. Based on these validation data, EPA has assigned number 3570 to this method. Method 3570 has several advantages, including reduced use of solvent and soil sample, generating much less laboratory waste. Laboratory space and labor requirements are reduced as compared to many other sample preparation methods. Consequently, Method 3570 can provide comparable chemical data at less cost or environmental impact.     

Electrochemical oxidation of benzene on boron-doped diamond electrodes

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H₂SO₄ 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1 × 10⁻² M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10⁻⁵ M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.     

Chemical analyses of spring waters and factor analysis to monitor the functioning of a karstic system. The role of precipitations regimen and anthropic pressures

An approach is presented to study the functioning of a karstic massif and assess the adverse effects of the anthropogenic pressure by monitoring some water chemical and physical parameters of its main springs. The approach has been applied to the Sette Comuni Plateau (Veneto Region, Italy) hosting a well developed karstic system, whose aquifer presents high vulnerability and undergoes a relevant anthropogenic pressure. The Oliero springs, amongst the largest karstic springs in Europe, are the main water output of the plateau. Electrical conductivity, pH, dissolved O(2), hardness, alkalinity, chemical oxygen demand, total suspended solids, ionic species (NH(4)(+), NO(3)(-), NO(2)(-), PO(4)(3-), SO(4)(2-), Cl(-), F(-)), elements (Cr(III), Cr(VI), Mn, Fe, Ni, Cu, Zn, As, Cd, Hg, Pb), and some chlorinated solvents were monitored for one year. This study presents the application of a factor analysis on the water parameters enabling the identification of the dominant chemical and biological processes and pollution sources affecting the karstic system. Results show four factors which are interpreted as karstification, photosynthesis, storm flow pollution and anions. Finally, by associating metals, chemical oxygen demand and total suspended solids with the amount of rainfall in the 48 h before samplings, further detailed information to the fast response of the aquifer to precipitation events was detected and interpreted according to the factor analysis results. The proposed approach, by providing information on the functioning of the aquifer, may help the management of the karstic plateau and is easily adaptable to similar environments.     

Soils and sediments of the Thua Thien-Hue Province (central Vietnam): recognizing trace element sources and the likely influence of natural events

Trace element concentrations have been measured in soil and sediment samples taken from the Thua Thien Hue (TT-H) Province and the Tam Giang-Cau Hai (TG-CH) Lagoon in 2002 and 2004. Results show that the lagoon is only slightly contaminated by elements such as Ag, Cd, Cr, Cu, Ni, Pb and Zn, whereas As, probably naturally enriched in this Asian region, reaches values above the lowest internationally accepted sediment quality guidelines. Concentrations in soils are ascribable to natural sources and distributions in the TG-CH Lagoon are mainly influenced by river inputs, with Ag and Cd undergoing estuarine desorption processes. However, concentration-depth profiles of most trace elements in sediments show a recent increasing trend that might be linked to the economic development of the area. The comparison of porosity and (210)Pb depth profiles (confirmed also by Cd and As) from repeated samplings of the same core locations in the TG-CH Lagoon seems to account for a loss of 5-10 cm of surficial sediment that took place during the time interval between the two samplings. It is hypothesized that extreme meteorological events (e.g. a major typhoon that hit the area in November 2003) could be responsible for such sediment displacement.     

Simultaneous radioassays of bacterial production and mercury methylation in the periphyton of a tropical and a temperate wetland

Laboratory radioassays were made to study mercury (Hg) methylation together with bacterial production in the periphyton of two aquatic macrophytes, the submerged Myriophyllum spicatum, from a constructed wetland in Sweden and the floating Eichhornia crassipes, from a eutrophied tropical lake in Brazil. Time course incubations were made by addition of (203)HgCl(2) and the methylmercury formed was extracted at pre-defined time intervals. Bacterial production ((14)C-leucine incorporation) was measured at the same time intervals, with plants removed from parallel incubations made with and without addition of cold HgCl(2). For E. crassipes, higher methylmercury production was observed at elevated bacterial production, whereas for M. spicatum, the bacterial production was significantly lower, and Hg methylation was below the detection limit. The combined results confirm the importance of microbial processes for Hg methylation, although other factors are known to influence this process in complex ways. The addition of Hg did not significantly influence bacterial production, while the incubation temperatures used (25 and 35 degrees C) resulted in different methylation rates. Radiotracer techniques for measurements of bacterial production such as (14)C-leucine uptake can provide useful insights into the Hg cycle in aquatic environments, and our data suggest that they may be used as a proxy of mercury methylation potentials.     

Habitat Mosaic, Wildlife Availability, and Hunting in the Tropical Forest of Calakmul, Mexico

Abstract: Habitat loss and subsistence hunting are two of the main activities that affect wildlife in frontier areas. We compared subsistence hunting patterns in four villages with different ethnic composition and degree of habitat disturbance in the vicinity of Calakmul Biosphere Reserve, Campeche, Mexico. We also compared differences between some of these villages in harvest composition and prey availability to determine hunting preferences. We used a Landsat TM satellite image to analyze the degree of disturbance around the villages. We conducted periodic surveys of subsistence hunting and prey availability. Wildlife availability was assessed monthly on nine transects (3000 m) established in the vicinity of three villages. The relative amount of disturbed habitat was smaller in an indigenous Maya village ( IV ) and larger in a mestizo village ( MV ). The two mixed-composition villages ( MCVs) had intermediate levels of disturbance. Ten species, four large and six small, of birds and mammals accounted for 97% of the hunting records. Hunting was more intense in IV and less intense in MCV1. The three village types had different hunting preferences. The habitat-mosaic composition in the vicinity of the villages influenced prey availability and subsistence-hunting preferences. Changes in the habitat mosaic were caused by the size of the holding and by ethnic composition. In spite of longer settlement time, the habitat mosaic in the vicinity of IV was less transformed than that of the other sites. Their larger holding size and greater diversity of economic activities may explain why the Mayas at IV have transformed the landscape less than the other groups and can hunt more and larger prey.     

Relationships between dissolved and particulate carbohydrate temporal patterns and mucilaginous aggregates formation: evidences from time series analysis and biochemical composition of aggregates

A 3-year monitoring of dissolved and particulate carbohydrate concentrations in four transects located in the Adriatic and Tyrrhenian Seas was performed in order to get information on the role played by carbohydrates in the mucilage formation in these areas. The application of time series analysis pointed out that the concentration of dissolved carbohydrates does not vary significantly in coincidence of the mucilage appearance showing an almost constant state with respect to time. In contrast, wider temporal variations of carbohydrate amounts, either increase or decrease, were observed when mucilages were lacking or reduced. This almost constant state of carbohydrate amounts observed in presence of mucilages that we define 'steady state' could be associated to an alteration of the complex chemical equilibrium between synthesis and degradation (either hydrolysis or oxidation) reactions of the organic polymers which are typical of the humification processes in the marine environment. The results of this study suggest that the monitoring of carbohydrates can represent an useful tool for the comprehension of the most relevant phenomena of mucilage appearance in the Northern Adriatic Sea.     

Possible Use of Rna:Dna Ratio for Detecting Oil Induced Disturbance: A Field Report

The effects of oil contamination on the metabolic state of suspended participate and sedimented organic matter were investigated through the analysis of the RNA:DNA ratio on samples collected from January 1991 to January 1992 in the Ligurian Sea (northwestern Mediterranean). the ratio of RNA to DNA appeared to be highly sensitive to hydrocarbon stress since the oil disturbance resulted in an evident decline in the RNA:DNA ratio relative to the pre-pollution conditions. Such a pattern was unusual since it occurred in a period when we would expect a seasonal increase in bacterial activity. Differences are seen when comparing the temporal trend of DNA in suspended particulates and in sediments. However, the effects of oil on the RNA:DNA ratio were similar. Oiled samples showed a RNA:DNA ratio lower than 1 whereas RNA concentrations exceeded DNA content in undisturbed samples. Bacterial DNA accounted for a significant fraction (average 26%) of total DNA in sediments. It is likely that changes in RNA:DNA ratio in oiled sediments are due to the disturbance of bacterial communities. Consistent with the meiofaunal response to oil contamination, the hydrocarbons had only temporary and limited effects and RNA:DNA values recovered to pre-pollution conditions after a few weeks. the possible use of the RNA:DNA ratio in pollution monitoring is discussed.     

GC-MS analyses and chemometric processing to discriminate the local and long-distance sources of PAHs associated to atmospheric PM2.5

Purpose

This study presents a procedure to differentiate the local and remote sources of particulate-bound polycyclic aromatic hydrocarbons (PAHs).

Methods

Data were collected during an extended PM_2.5 sampling campaign (2009?C2010) carried out for 1?year in Venice-Mestre, Italy, at three stations with different emissive scenarios: urban, industrial, and semirural background. Diagnostic ratios and factor analysis were initially applied to point out the most probable sources. In a second step, the areal distribution of the identified sources was studied by applying the discriminant analysis on factor scores. Third, samples collected in days with similar atmospheric circulation patterns were grouped using a cluster analysis on wind data. Local contributions to PM_2.5 and PAHs were then assessed by interpreting cluster results with chemical data.

Results

Results evidenced that significantly lower levels of PM_2.5 and PAHs were found when faster winds changed air masses, whereas in presence of scarce ventilation, locally emitted pollutants were trapped and concentrations increased. This way, an estimation of pollutant loads due to local sources can be derived from data collected in days with similar wind patterns. Long-range contributions were detected by a cluster analysis on the air mass back-trajectories. Results revealed that PM_2.5 concentrations were relatively high when air masses had passed over the Po Valley. However, external sources do not significantly contribute to the PAHs load.

Conclusions

The proposed procedure can be applied to other environments with minor modifications, and the obtained information can be useful to design local and national air pollution control strategies.     

Characterisation of sulphide-bearing waste-rock dumps using electrical resistivity imaging: the case study of the Rio Marina mining district (Elba Island, Italy)

Sulphide-bearing mine dumps are potential sources of pollution when acid mine drainage (AMD) occurs. Because the generation of AMD depends on the volume and composition of waste materials, their characterisation is crucial for the evaluation of geochemical hazards and for the design of remediation strategies to minimise their environmental impact. In this paper, a cost-effective strategy for the characterisation of an inactive mine dump in the Rio Marina mining district (Elba Island, Italy) using earth resistivity imaging (ERI) is presented. As no information regarding the nature of waste rocks is found in reports for the mine, five ERI profiles were acquired at the top of the waste pile. The results show that waste rocks are heterogeneous with a maximum thickness of 30 m. Due to the large amounts of dispersed sulphide minerals, the waste rocks are characterised by an electrically conductive geophysical signature in comparison to the surrounding resistive metamorphic bedrock. A geostatistical approach was adopted to estimate the elevation of the edges of the mine dump, and the net volume of the waste rocks was computed through a raster analysis of the elevations of the upper and lower boundaries of the mine dump. High-conductivity anomalies were detected within the core of the mine dump. The integration of the hydrogeological, geochemical and geological framework of the Rio Marina mining district suggests that these anomalies could be a geophysical signature of subsurface regions where AMD is currently generated or stored, thus representing sources of environmental pollution.