Determination of gaseous polycyclic aromatic hydrocarbons by a simple direct method using thermal desorption–gas chromatography–mass spectrometry

In the last decade, the development of novel analytical methodologies enabled the identification of several environmental pollutants responsible for health problems associated with indoor exposure. Polycyclic aromatic hydrocarbons (PAHs) are among the potential hazardous chemicals present in ambient air. Due to their bioaccumulation potential and carcinogenic/mutagenic effects, 16 PAHs are currently listed as priority air pollutants. The main goal of this work was to implement a new and simple method for sampling and determination of PAHs in air by using a thermal desorption (TD) technique followed by gas chromatography coupled with mass spectrometry analysis. A detailed study was carried out to optimise the experimental method in each of its phases, including (active) sampling, TD and chromatographic analysis. The results demonstrate that this approach allowed the detection and quantification of the six more volatile PAHs, namely, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, and anthracene. Acceptable precision and good linearity over the explored range were obtained. No carry-over was observed during experimental tests and the method provided a reproducible answer. The applicability of the novel methodology was tested in real environment, namely, on the roof of a building in an urban area, in a domestic kitchen and in a collective car garage. The method enabled the identification of two PAHs in the field samples, specifically, naphthalene (two rings) and phenanthrene (three rings). With regard to PAHs sample composition, the most abundant PAH found, in the three different locations, was naphthalene, accounting for about 84–100 % of the total PAH mass detected.     

Characterization of particulate matter and its related metal toxicity in an urban location in South West India

This study reports the quantification of the toxicity of particulate matter (PM)-bound metals and their possible associated risks to human health. For assessment of PM, 24-h samples of PM₁₀ and PM_2.5 were collected by Mini Vol-TAS sampler at an urban site of Pune. Samples were sequentially extracted with ultrapure water and concentrated HNO₃ and analyzed for “soluble” and “total” metals. Factor analysis identified the resuspension of road dust due to traffic, biomass burning, construction activities, and wind-blown dust as possible sources that played an important role for overall pollution throughout the year. Water-soluble proportion was found to be ≤20 % for Cr, Co, Fe, and Al; ≥50 % for Sr, Cd, Ca, and Zn; and a substantial proportion (～25–45 %) for Mn, Ba, K, Na, Ni, Mg, Cu, and Pb metals in PM₁₀. For PM_2.5, the water-soluble proportion was ≤20 % for Fe, Co, Ni, Cr, and Al, while Sr, K, and Cd were mostly soluble (>50 %) and Cu, Ba, Mn, Ca, Zn, Pb, Na, and Mg were substantially soluble (～25–45 %). In the present study, among the toxic metals, Cd and Pb show higher concentration in the soluble fraction and thus represent the higher bioavailability index and especially are harmful to the environment and exposed person. Risk calculations with a simple exposure assessment method showed that the cancer risks of the bioavailable fractions of Cr, Cd and Ni were greater than the standard goal.     

Status and effect of pesticide residues in soils under different land uses of Andaman Islands, India

Pesticides are shown to have a great effect on soil organisms, but the effect varies with pesticide group and concentration, and is modified by soil organic carbon content and soil texture. In the humid tropical islands of Andaman, India, no systematic study was carried out on pesticide residues in soils of different land uses. The present study used the modified QuEChERS method for multiresidue extraction from soils and detection with a gas chromatograph. DDT and its various metabolites, α-endosulfan, β-endosulfan, endosulfan sulfate, aldrin, and fenvalerate, were detected from the study area. Among the different pesticide groups detected, endosulfan and DDT accounted for 41.7 % each followed by aldrin (16.7 %) and synthetic pyrethroid (8.3 %). A significantly higher concentration of pesticide residues was detected in rice–vegetable grown in the valley followed by rice–fallow and vegetable–fallow in the coastal plains. Soil microbial biomass carbon is negatively correlated with the total pesticide residues in soils, and it varied from 181.2 to 350.6 mg?kg^?1. Pesticide residues have adversely affected the soil microbial populations, more significantly the bacterial population. The Azotobacter population has decreased to the extent of 51.8 % while actinomycetes were the least affected though accounted for 32 % when compared to the soils with no residue.     

Mapping afforestation and deforestation from 1974 to 2012 using Landsat time-series stacks in Yulin District, a key region of the Three-North Shelter region, China

The Three-North Shelter Forest Program is the largest afforestation reconstruction project in the world. Remote sensing is a crucial tool to map land use and land cover change, but it is still challenging to accurately quantify the change in forest extent from time-series satellite images. In this paper, 30 Landsat MSS/TM/ETM+ epochs from 1974 to 2012 were collected, and the high-quality ground surface reflectance (GSR) time-series images were processed by integrating the 6S atmosphere transfer model and a relative reflectance normalization algorithm. Subsequently, we developed a vegetation change tracking method to reconstruct the forest change history (afforestation and deforestation) from the time-series Landsat GSR images based on the integrated forest z-score (IFZ) model by Huang et al. (2009a), which was improved by multi-phenological IFZ models and the smoothing processing of IFZ data for afforestation mapping. The mapping result showed a large increase in the extent of forest, from 380,394 ha (14.8 % of total district area) in 1974 to 1,128,380 ha (43.9 %) in 2010. Finally, the land cover and forest change map was validated with an overall accuracy of 89.1 % and a kappa coefficient of 0.858. The forest change time was also successfully retrieved, with 22.2 % and 86.5 % of the change pixels attributed to the correct epoch and within three epochs, respectively. The results confirmed a great achievement of the ecological revegetation projects in Yulin district over the last 40 years and also illustrated the potential of the time-series of Landsat images for detecting forest changes and estimating tree age for the artificial forest in a semi-arid zone strongly influenced by human activities.     

Prediction of the solubility of zinc, copper, nickel, cadmium, and lead in metal-contaminated soils

Risk assessment of metal-contaminated soil depends on how precisely one can predict the solubility of metals in soils. Responses of plants and soil organisms to metal toxicity are explained by the variation in free metal ion activity in soil pore water. This study was undertaken to predict the free ion activity of Zn, Cu, Ni, Cd, and Pb in metal-contaminated soil as a function of pH, soil organic carbon, and extractable metal content. For this purpose, 21 surface soil samples (0–15 cm) were collected from agricultural lands of various locations receiving sewage sludge and industrial effluents for a long period. One soil sample was also collected from agricultural land which has been under intensive cropping and receiving irrigation through tube well water. Soil samples were varied widely in respect of physicochemical properties including metal content. Total Zn, Cu, Ni, Cd, and Pb in experimental soils were 2,015?±?3,373, 236?±?286, 103?±?192, 29.8?±?6.04, and 141?±?270 mg kg^?1, respectively. Free metal ion activity, viz., pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺, as estimated by the Baker soil test was 9.37?±?1.89, 13.1?±?1.96, 12.8?±?1.89, 11.9?±?2.00, and 11.6?±?1.52, respectively. Free metal ion activity was predicted by pH-dependent Freundlich equation (solubility model) as a function of pH, organic carbon, and extractable metal. Results indicate that solubility model as a function of pH, Walkley–Black carbon (WBC), and ethylenediaminetetraacetic acid (EDTA)-extractable metals could explain the variation in pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺ to the extent of 59, 56, 46, 52, and 51 %, respectively. Predictability of the solubility model based on pH, KMnO₄-oxidizable carbon, and diethylenetriaminepentaacetic acid-extractable or CaCl₂-extractable metal was inferior compared to that based on EDTA-extractable metals and WBC.     

Biodegradation or simple adsorption to the support material? Development of a simple, fast and low-cost technique

Biofilms are present in several areas and are studied in microbiology, medical sciences, biology and, of course, sanitary engineering. Biofilms are used for the treatment of municipal wastewater, and their application was even before the invention of the activated sludge process. The main objective of this work was to develop a simple, fast and low-cost technique to evaluate the nature of the first decay in the concentration of an organic compound in the presence of a solid material. Though simple, the technique developed has allowed the clarification of whether the initial concentration decay is due to adsorption to the support material or a result of biodegradation. The results show that, with two different support materials, adsorption does not take place, and the biodegradation processes are responsible for the first decay in the organic concentration. The technique used offers a fast and low-cost way of studying the existence of adsorption. Two feed concentration solutions and two different support materials were used.     

Saturated uptake kinetics: transient response of the marine diatom Thalassiosira pseudonana to ammonium,nitrate, silicate or phosphate starvation

Changes in the saturated uptake kinetics of the limiting nutrient were followed as Thalassiosira pseudonana (Clone 3 H) batch cultures entered ammonium, nitrate, silicate and phosphate starvation. Cultures starved of ammonium or phosphate developed very high specific uptake capacities over a 24 to 48 h starvation period, due to both decreases in cell quota and increases in uptake rates per cell. In particular, the cell phosphorus quota decreased ca. 8-fold during phosphate starvation and specific uptake rates exceeded 100 d^-1. In contrast, cultures entering nitrate or silicate starvation underwent little or no further cell division, and the uptake capacity declined during starvation. After 24 to 48 h starvation, an induction requirement for uptake of nitrate or silicate was apparent. These responses are consistent with adaptation to the pattern of supply of these nutrients in the field.     

Regional investigations of soil and overburden analysis and plant uptake of metals

Regional studies on the bioavailability of metals at native and disturbed sites were conducted over the past seven years by the USGS. The work was concentrated in the Fort Union, Powder River, and Green River coal resource regions where measures of extractable metals in soils were found to have limited use in predicting metal levels in plants.Correlations between Cu, Fe, and Zn in plants and extractable (DTPA, EDTA, and oxalate) or total levels in native A- and C-horizons of soil were occasionally significant. A simple linear model is generally not adequate, however, in estimating element uptake by plants. Prediction capabilities were improved when a number of soil chemical and physical parameters were included as independent variables in a stepwise linear multiple regression analysis; however, never more than 54% of the total variability in the data was explained by the equations for these metals. Soil pH was the most important variable relating soil chemistry to plant chemistry. This relation was always positive and apparently a response to soil levels of metal carbonates and not Fe and Mn oxides. Studies that compared the metal uptake by rehabilitation species to extractable (DTPA) metal levels in mice soils produced similar results.     

Croissance et structure de l'opercule calcifié du gastéropode polynésien Turbo setosus (Prosobranchia: Turbinidae): détermination de l'âge individuel

Turbo setosus Gmelin were collected in 1979 and 1982 in French Polynesia (Tuamotu). Ground cross-sections of calcified opercula revealed 3 distinct types of growth lines (A, B and C), the appearance and periodicity of which are described. Two months after fluorescent labelling with alizarin and fluorescein, permanent marks were easily visible in the operculum, enabling the 3 types of growth lines to be interpreted and a growth pattern distinguished: Type A growth lines, which are very translucent under transmitted light, are irregularly deposited after individual traumatisms and are termed stress lines; Type B lines exhibit a regular periodicity and correspond to a daily growth rhythm; Type C lines reflect a subdaily growth pattern. Vital staining enabled calcification of the operculum to be followed, and the speed of deposition has been estimated. The textural organization of the organic and mineral phases varies according to operculum area and depends on local speed of growth. In those areas of rapid growth (more than 20 m d^-1), deposits are cone-shaped and interlocked, and in those areas where growth is slower (less than 20 m d^-1), this type of organization disappears and is replaced by a regular organization without cone-shaped deposits. The number of daily growth lines, counted on 66 opercula, allowed us to accurately assess individual age and longevity in this species, which did not exceed 3 yr in our sample.     

Kinetics of light-intensity adaptation in a marine planktonic diatom

The marine planktonic diatom Thalassiosira weisflogii was grown in turbidostat culture under both continuous and 12 hL: 12 hD illumination regimes in order to study the kinetics of adaptation to growth-irradiance levels. In both illumination regimes adaptation to a higher growth-irradiance level was accompanied by an increase in cell division rates and a decrease in chlorophyll a cell^-1. The rates of adaptation for both processes, derived from first order kinetic analysis, equaled each other in each experiment. The results suggest that during the transition from low-to-high growth-irradiance levels chlorophyll a is diluted by cell division and is not actively degraded. Introduction of a light/dark cycle lowered the rate of adaptation. In transitions from high-to-low growth-irradiance levels there was a sharp drop in growth rates and a slow increase in chlorophyll a cell^-1 under both continuous and intermittent illumination. In the 12 hL:12hD cycle there was a circadian rhythm in chlorophyll a cell^-1, where cellular chlorophyll contents increased during the light cycle and decreased during the dark cycle. This circadian rhythm was distinctly different from light intensity adaptation. For kinetic analysis of light intensity adaptation in a 12 hL: 12 hD cycle, the circadian periodicity was separated from the light intensity response by subjecting the data to a Kaiser window optimization digital filter. Kinetic parameters for light-intensity adaptation were resolved from the filtered data. The kinetics of lightintensity adaptation of marine phytoplankton are discussed in relation to their spatial variations and time scales of mixing.This research was performed at Brookhaven National Laboratory under the auspices of the United States Department of Energy under Contract No. DE-AC02-76 CH00016