Analysis of polycyclic aromatic hydrocarbons (PAHs) in airborne particles by direct sample introduction thermal desorption GC/MS

The technique of thermal desorption (TD)–GC/MS was evaluated for measuring airborne, 4–6 ring polycyclic aromatic hydrocarbons (PAHs) collected onto quartz filters. TD provides a more readily automated and sensitive alternative to traditional solvent extraction, decreasing the time/cost of analysis and reducing the risk of analyte loss or sample contamination. The developed method was successfully applied to the analysis of PAH standard solutions loaded on sorbent tubes packed with quartz wool and the graphitized carbon black sorbent Carbograph2. The optimized method showed high desorption efficiency over the whole range of target PAHs with good precision, linearity and sensitivity. The proposed method was verified on an urban dust Standard Reference Material (SRM 1649a); the experimentally determined concentrations agreed with the certified ranges (95% confidence limit) for all target compounds except benzo[a]anthracene, which fell just outside the narrow certified range. The desorption efficiency and the reproducibility of the method was evaluated by analysing pieces of real sample filters sampled from urban air for a period of 24 h. The results confirmed the homogeneity of the filter and showed high recovery efficiencies for all target PAHs.     

HPLC-MSn and GC-MS methods to study sunlight and UV-lamp degradations of 1-amino-5-naphthalene sulfonate

HPLC-DAD, HPLC-MS/MS, GC-MS and spectrophotometric methods are employed to investigate the degradation process of sodium 1-amino-5-naphthalene sulfonate (1A5NS) aqueous solutions, when exposed to sunlight and UV-lamp (254 nm) irradiations. Experimental results show that both sunlight and 254 nm UV-lamp irradiations destroy the chemical and give rise to major degradation products, characterised by the same m/z ratios. Degradation times are lower for sunlight irradiation, for which a t(1/2) value of 137.4 min has been evaluated, in comparison with the value of t(1/2) of 26.8 min, observed for UV-lamp irradiation. The degradation pathway and the structures of the degradation products are proposed.     

The impact of infield biomass burning on PM levels and its chemical composition

In the South of Italy, it is common for farmers to burn pruning waste from olive trees in spring. In order to evaluate the impact of the biomass burning source on the physical and chemical characteristics of the particulate matter (PM) emitted by these fires, a PM monitoring campaign was carried out in an olive grove. Daily PM10 samples were collected for 1 week, when there were no open fires, and when biomass was being burned, and at two different distances from the fires. Moreover, an optical particle counter and a polycyclic aromatic hydrocarbon (PAH) analyzer were used to measure the high time-resolved dimensional distribution of particles emitted and total PAHs concentrations, respectively. Chemical analysis of PM10 samples identified organic and inorganic components such as PAHs, ions, elements, and carbonaceous fractions (OC, EC). Analysis of the collected data showed the usefulness of organic and inorganic tracer species and of PAH diagnostic ratios for interpreting the impact of biomass fires on PM levels and on its chemical composition. Finally, high time-resolved monitoring of particle numbers and PAH concentrations was performed before, during, and after biomass burning, and these concentrations were seen to be very dependent on factors such as weather conditions, combustion efficiency, and temperature (smoldering versus flaming conditions), and moisture content of the wood burned.     

Indoor air quality (IAQ) assessment in a multistorey shopping mall by high-spatial-resolution monitoring of volatile organic compounds (VOC)

In order to assess indoor air quality (IAQ), two 1-week monitoring campaigns of volatile organic compounds (VOC) were performed in different areas of a multistorey shopping mall. High-spatial-resolution monitoring was conducted at 32 indoor sites located in two storehouses and in different departments of a supermarket. At the same time, VOC concentrations were monitored in the mall and parking lot area as well as outdoors. VOC were sampled at 48-h periods using diffusive samplers suitable for thermal desorption. The samples were then analyzed with gas chromatography–mass spectrometry (GC–MS). The data analysis and chromatic maps indicated that the two storehouses had the highest VOC concentrations consisting principally of terpenes. These higher TVOC concentrations could be a result of the low efficiency of the air exchange and intake systems, as well as the large quantity of articles stored in these small spaces. Instead, inside the supermarket, the food department was the most critical area for VOC concentrations. To identify potential emission sources in this department, a continuous VOC analyzer was used. The findings indicated that the highest total VOC concentrations were present during cleaning activities and that these activities were carried out frequently in the food department. The study highlights the importance of conducting both high-spatial-resolution monitoring and high-temporal-resolution monitoring. The former was able to identify critical issues in environments with a complex emission scenario while the latter was useful in interpreting the dynamics of each emission source.     

Growth responses of crop and weed species to heavy metals in pot and field experiments

Greenhouse and field studies were performed to examine the growth responses and possible phytoremediation capacity towards heavy metals of several Brassicaceae (Brassica alba, Brassica carinata, Brassica napus and Brassica nigra) and Poaceae (durum wheat and barley). Soils used featured total concentrations of Cr, Cu, Pb and Zn largely exceeding the maximum levels permitted by the Italian laws. Different organic amendments were tested such as a compost and the plant growth-promoting rhizobacterium Bacillus licheniformis. In the greenhouse experiment, plant length, leaf area index and shoots dry matter were evaluated periodically for the Brassicaceae examined. Whereas plant length, grains production, weight of 1,000 seeds, ear fertility and tiller density were determined under field conditions at the end of the crop cycle for wheat and barley. In general, the species tested appeared to be tolerant to high heavy metal concentrations in soil, and slightly significant differences were found for all parameters considered. A marked growth increase was shown to occur for Brassicaceae cultivated on compost- and bacillus-amended contaminated soils, with respect to non-amended contaminated soils. With some exception, higher growth parameters were measured for wheat and barley plants cropped from contaminated soils in comparison to non-contaminated soils. Further, bacillus amendment enhanced the length of wheat and barley plants in both non-contaminated and contaminated soils, while different effects were observed for the other parameters evaluated.     

Sorption and desorption behavior of chloroanilines and chlorophenols on montmorillonite and kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

An unconventional method for the recovery of caustic soda from spent Al-rich pickling solutions

This work presents an unconventional procedure for the recovery of spent Al-rich caustic soda solutions from the pickling of dies for the production of aluminium extrusions. Caustic soda was regenerated at roughly 70%, by precipitating aluminate, after addition of a silica source, in the form of zeolite A, a microporous material that is widely used in many technological sectors. It was shown that the process is reliable and can be repeated for several cycles, provided the concentration of the caustic soda solution is suitably restored. The by-product obtained, zeolite A, proved to be a high-grade material with performance as a cation exchanger and physical sorbent that is certainly comparable to that reported in literature (e.g., cation exchange capacity equal to 5.14 meq g(-1) vs. 5.48 meq g(-1) and water vapour adsorption capacity of 26.5% vs. 27.6% at 16 torr and 298 K). The economics of the process, although not examined yet, would appear generally favourable, considering that zeolite A is a valuable by-product which widely covers the costs for the recovery of the spent solutions. There are, therefore, significant prospects for the use of zeolite A, particularly as a builder in detergent formulation.     

The influence of successional processes and disturbance on the structure of Tsuga canadensis forests

Old-growth forests are valuable sources of ecological, conservation, and management information, yet these ecosystems have received little study in New England, due in large part to their regional scarcity. To increase our understanding of the structures and processes common in these rare forests, we studied the abundance of downed coarse woody debris (CWD) and snags and live-tree size-class distributions in 16 old-growth hemlock forests in western Massachusetts. Old-growth stands were compared with eight adjacent second-growth hemlock forests to gain a better understanding of the structural differences between these two classes of forests resulting from contrasting histories. In addition, we used stand-level dendroecological reconstructions to investigate the linkages between disturbance history and old-growth forest structure using an information-theoretic model selection framework. Old-growth stands exhibit a much higher degree of structural complexity than second-growth forests. In particular, old-growth stands had larger overstory trees and greater volumes of downed coarse woody debris (135.2 vs. 33.2 m3/ha) and snags (21.2 vs. 10.7 m3/ha). Second-growth stands were characterized by either skewed unimodal or reverse-J shaped diameter distributions, while old-growth forests contained bell-shaped, skewed unimodal, rotated sigmoid, and reverse J-shaped distributions. The variation in structural attributes among old-growth stands, particularly the abundance of downed CWD, was closely related to disturbance history. In particular, old-growth stands experiencing moderate levels of canopy disturbance during the last century (1930s and 1980s) had greater accumulations of CWD, highlighting the importance of gap-scale disturbances in shaping the long-term development and structural characteristics of old-growth forests. These findings are important for the development of natural disturbance-based silvicultural systems that may be used to restore important forest characteristics lacking in New England second-growth stands by integrating structural legacies of disturbance (e.g., downed CWD) and resultant tree-size distribution patterns. This silvicultural approach would emulate the often episodic nature of CWD recruitment within old-growth forests.     

Environmental features of two commercial surfactants widely used in soil remediation

One of the main limitations for a wider application of surfactants in soil remediation is the lack of knowledge about environmental fate and toxicity of surfactant itself especially for in situ application. Sorption behaviour, biodegradability, toxicity of parent compound and its metabolites are important processes that affect environmental fate of surfactants in site remediation applications. Tween 80 (poly(oxyethylene)(20)-sorbitane monooleate) and Aerosol MA+80 (dihexyl sodium sulfosuccinate) are surfactants that have been tested in laboratory and field scale remediation of soil and groundwater. In this work, the sorption and biodegradability of these surfactants were assessed to provide conditions and limitations for their use. The soil used in this experimentation was analysed for organic carbon content, soil bacteria, and size fraction and resulted to be a good model because is characterised by mean values for almost all considered parameters. Tween 80 showed high degree of biodegradability but a high affinity for soil matrix. Results suggest that Tween 80 could find its best application in ex situ solid phase remediation like ex situ bioremediation; its high affinity to soil could limit in situ applications. Biodegradation tests for Aerosol MA+80 show low degree of biodegradability and mineralisation. Biodegradation experiments, coupled with analysis of toxicity, could support the hypothesis that degradation of Aerosol MA+80 is not complete and leads to an accumulation of intermediates with at least the same toxicity of the parental compound. Therefore, aquifer remediation application with Aerosol MA+80 has to be conducted with necessary precautions to avoid product loss and excess surfactant should be flushed from the soil.     

Sorption of pesticides on kaolinite and montmorillonite as a function of hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.