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.     

Optical Resilience of the Paraíba do Sul River (Brazil) during a Toxic Spill of a Wood-Pulping Factory: The Cataguazes Accident

This study investigates the inherent optical properties (IOP) of a Brazilian river during a non-natural, anthropogenically mediated, toxic spill of a wood-pulping factory (the ‘Cataguazes accident’). The results indicated an outstanding transformation in the river water chromophoric dissolved organic matter (CDOM) pools. For instance, increases in CDOM absorption coefficients, a _CDOM (λ), which were averaged at specific spectral intervals, , ranged from 58-fold at the UV-B and UV-A ranges to 95-fold at the PAR range. As a result, the water color expressed as CDOM absorption at 440 nm, a _CDOM (440), varied from 4.16 to 365.03 m^-1. For S-coefficient, the variations ranged from ∼1.1 to 5.6-fold, respectively, at the 300–650 nm and UV-B range. The variability of S as a proxy of dissolved chromophores was thus clearly influenced by the spectral range used. Optical proportions were also investigated through the use of and S ratios at the UV-B, UV-A, and PAR ranges and, in the case of , also at the NIR range. This approach also showed clear variations between the water samples, likely reflecting changes in the composition of optically active substances in the river system. As a whole, the findings obtained here indicated that both the quantity and quality of the chromophoric material dissolved in the river water were greatly altered by the toxic spill. The changes in the optical properties of the river water, although extreme and likely with no parallel in the literature, were quite rapid as indicated by the optical resilience of the system. Overall, this study indicates that IOP might be thought, and possibly used, as a metric tool for monitoring the state of waters and aquatic ecosystems.     

Ability of fungi to degrade synthetic polymer nylon-6

Fifty-eight fungi have been tested for their ability to degrade a recalcitrant synthetic polymer polyamide-6, generally known as nylon-6. Most of them were isolated from a factory producing nylon-6. After preliminary screening, 12 strains were selected for submerged culture in a medium with nylon fibres as the only N-source. No degradation was observed with the isolates from the factory. Wood degrading fungi from a culture collection, however, degraded nylon after incubation for several weeks. Bjerkandera adusta disintegrated the fibres most efficiently, starting with the small transverse grooves, which deepened into cracks. The superficial layers crumbled to leave a thin inner core of the fibre, which finally broke down into fragments. The remaining insoluble part of the nylon showed a decrease in number average molecular mass from 16900 to 5600 during a 60-day incubation. Its thermal properties, such as shifts in melting points and broadening of the melting endotherms, were altered. The reduction of the amount of nylon and the composition of the liquid phase indicated that part of the polymer was degraded into soluble products. After 50 days, the total nitrogen content of the soluble fraction was 10-fold higher than in the control sample. Manganese peroxidase, presumably responsible for the degradation, was detected in the liquid phase. The study shows that only white rot fungi are able to break down nylon-6. For the first time this polymer was shown to be disrupted by B. adusta. The extent of the biodegradation indicates its potential for application in nylon waste reduction.     

Uptake and accumulation of cadmium, lead and zinc by Siam weed [Chromolaena odorata (L.) King & Robinson

The Siam weed, Chromolaena odorata (L.) King & Robinson, Family Asteraceae, was found to be a new Pb hyperaccumulator by means of field surveys on Pb soil and hydroponic studies. Plants from field collection accumulated 1377 and 4236mgkg(-1) Pb in their shoots and roots, respectively, and could tolerate soil Pb concentrations up to 100000 mgkg(-1) with a translocation factor of 7.62. Very low concentrations of Cd and Zn were found in plants collected from the field. Under nutrient solution culture condition, C. odorata from the contaminated site (CS) and from non-contaminated site (NCS) grew normally with all three metals (Pb, Cd, Zn) supplied. However, the relative growth rates of all treated plants decreased with increased metal concentrations. The percentage uptakes of Pb, Cd, and Zn by C. odorata increased with increasing metal concentrations. Pb concentration in shoots and roots reached its highest values (1772.3 and 60655.7mgkg(-1), respectively) at a Pb supply level of 10mgl(-1). While the maximum concentrations of Cd (0.5mgl(-1)) in shoots and roots of C. odorata were 102.3 and 1440.9mgkg(-1), and the highest concentrations of Zn (20mgl(-1)) were 1876.0 and 7011.8mgkg(-1), respectively. The bioaccumulation coefficients of Pb and Cd were greater than 1000. These results confirm that C. odorata is a hyperaccumulator which grows rapidly, has substantial biomass, wide distribution and has a potential for the phytoremediation of metal contaminated soils.     

PCDD/Fs and PCBs in butter samples from new European Union member states and a candidate country: analytical quality control, results and certain PCB-specific aspects

Milk and milk products have shown to be good indicator samples for the contamination of persistent organic pollutants (POPs) along the food chain. To gather information on whether exposure to dioxins and PCBs might cause a problem in countries about to join the European Union in 2004 or later, a study for evaluation of dioxin and levels of PCBs in 16 butter samples from eight countries (Cyprus, Czech Republic, Estonia, Lithuania, Poland, Romania, Slovenia and Slovakia) was performed. Comprehensive quality assurance/quality control (QA/QC) was requested. For this, eight quality control samples were included (in comparison to long-term mean, mean recovery for WHO-PCDD/F-TEQ of 97.9% with a CV of 3.0%, mean recovery for WHO-PCB-TEQ of 100.4% with a CV of 3.3%). Additionally, all butter samples were run as duplicates resulting in a confidence region of 95% statistical certainty of 4.6% for WHO-PCDD/F-TEQ and of 3.5% for WHO-PCB-TEQ. All samples except one from Romania were in the range of 0.21-0.59 pg WHO-PCDD/F-TEQ/g fat (upper bound), all samples except one from Romania and one from Estonia in the range of 0.32-0.82 pg WHO-PCB-TEQ/g fat (upper bound) and all samples except one from Romania and one from Estonia in the range of 0.57-1.23 pg sum WHO-TEQ/g fat (upper bound). The maximum values were found in samples from Romania (0.98 pg WHO-PCDD/F-TEQ/g fat; 1.75 pg WHO-PCB-TEQ/g fat) and Estonia (0.26 pg WHO-PCDD/F-TEQ/g fat; 1.62 pg WHO-PCB-TEQ/g fat). As a conclusion, all samples except one from Romania and one from Estonia were in the range of the actual low background contamination for PCDD/F and dioxin-like PCBs. The samples with elevated concentrations were below the EU action and maximum levels which have been valid since 2002, or will be applied from November 2006. In all samples except in one from Estonia, the contribution of dioxin-like PCBs to sum WHO-TEQ was 47-68% which reflects the usual range in Europe. In one sample from Estonia this contribution was 86% which points to a particular yet unknown PCB source. Thirty eight PCB congeners were determined allowing a detailed discussion of the relative contribution of individual congeners to the total PCB concentration. Correlation between PCB 153 and WHO-PCB-TEQ varied considerably between samples from different countries. Major tetra- or pentachlorinated mono-ortho PCBs without assigned TEFs were PCBs 60, 66, 74, and 110.     

PAH removal from spiked municipal wastewater sewage sludge using biological, chemical and electrochemical treatments

Polycyclic aromatic hydrocarbons (PAHs) have been widely studied due to their presence in all the environmental media and toxicity to life. These molecules are strongly adsorbed on the particulate matters of soils, sludges or sediments because of their strong hydrophobicity which makes them less bioavailability, thus limiting their bioremediation. Different sludge treatment processes were tested to evaluate their performances for PAH removal from sludge prealably doped with 11 PAHs (5.5mg each PAH kg(-1) of dry matter (DM)): two biological processes (mesophilic aerobic digestion (MAD) and simultaneous sewage sludge digestion and metal leaching (METIX-BS)) were tested to evaluate PAH biodegradation in sewage sludge. In parallel, two chemical processes (quite similar Fenton processes: chemical metal leaching (METIX-AC) and chemical stabilization (STABIOX)) and one electrochemical process (electrochemical stabilization (ELECSTAB)) were tested to measure PAH removal by these oxidative processes. Moreover, PAH solubilisation from sludge by addition of a nonionic surfactant Tween 80 (Tw80) was also tested. The best yields of PAH removal were obtained by MAD and METIX-BS with more than 95% 3-ring PAH removal after a 21-day treatment period. Tw80 addition during MAD treatment increased 4-ring PAHs removal rate. In addition, more than 45% of 3-ring PAHs were removed from sludge by METIX-AC and during ELECSTAB process were quiet good with approximately 62% of 3-ring PAHs removal. However, little weaker removal of 3-ring PAHs (<35%) by STABIOX. None of the tested processes were efficient for the elimination of high molecular weight (> or = 5-ring) PAHs from sludge.     

Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

Seasonal Variation of Toxic Benzene Emissions in Petroleum Refinery

Petroleum refineries are largest chemical industries that are responsible for the emission of several pollutants into the atmosphere. Benzene is among the most important air pollutants that are emitted by petroleum refineries, since they are involved in almost every refinery process. Volatile organic compounds (VOCs) are a major group of air pollutants, which play a critical role in atmospheric chemistry. These contribute to toxic oxidants, which are harmful to ecosystem, human health and atmosphere. The variability of pollutants is an important factor in determining human exposure to these chemicals. The ambient air concentrations of benzene were measured in several sites around the Digboi petroleum refinery, near the city of Gowahati in northeast India, during winter and summer 2004. The seasonal and spatial variations of the ambient air concentrations of this benzene were investigated and analyzed. An estimation of the contribution of the refinery to the measured atmospheric levels of benzene was also performed. The ambient air mixing ratios of benzene in a large area outside the refinery was generally low, in ppbv range, much lower than the ambient air quality standards. This article presents the temporal and spatial variation of air pollution in and around petroleum refinery and showed that no health risk due to benzene is present in the areas adjacent to the refinery.     

Ambient Aerosol and its Carbon Content in Gainesville, a Mid-Scale City in Florida

Ambient aerosols were collected during 2000–2001 in Gainesville, Florida, using a micro-orifice uniform deposit impactor (MOUDI) to study mass size distribution and carbon composition. A bimodal mass distribution was found in every sample with major peaks for aerosols ranging from 0.32 to 0.56 μm, and 3.2 to 5.6 μm in diameter. The two distributions represent the fine mode (<2.5 μm) and the coarse mode (>2.5 μm) of particle size. Averaged over all sites and seasons, coarse particles consisted of 15% carbon while fine particles consisted of 22% carbon. Considerable variation was noted between winter and summer seasons. Smoke from fireplaces in winter appeared to be an important factor for the carbon, especially the elemental carbon contribution. In summer, organic carbon was more abundant. The maximum secondary organic carbon was also found in this season (7.0 μg m⁻³), and the concentration is between those observed in urban areas (15–20 μg m⁻³) and in rural areas (4–5 μg m⁻³). However, unlike in large cities where photochemical activity of anthropogenic emissions are determinants of carbon composition, biogenic sources were likely the key factor in Gainesville. Other critical factors that affect the distribution, shape and concentration were precipitation, brushfire and wind.     

Types of Ectomycorrhiza as Pollution Stress Indicators: Case Studies in Slovenia

Mycorrhiza is the main spatial and temporal linkage between different constituents in a forest ecosystem. The functional compatibility and stress tolerance of ectomycorrhizal types is species specific, and therefore the information on the ectomycorrhizal community structure can add to the understanding of processes in forest ecosystems and can also be applied as tools for bioindication of pollution stress in forest soils. We have studied the effects of pollution (N and S) on trees and forest soils by: (1) quantification of ECM types diversity as in situ indicators in forest stands, (2) determination and quantification of pollution-sensitive or -insensitive ECM types as passive monitors, (3) root growth and development of ECM on nonmycorrhizal spruce seedlings, planted at the studied sites (active monitors), and (4) ECM infection (a bioassay based on mycorrhizal inoculum potential) of seedlings in an experimental set-up as ex situ testers. ECM species richness for Norway spruce trees (Picea abies) showed higher values in unpolluted sites than in polluted ones, while the differences were not significant for European beech trees (Fagus sylvatica). As pollution-sensitive or -insensitive ECM species in spruce forests, we suggest Hydnum rufescens (sensitive) and Paxillus involutus (unsensitive). Mycorrhizal potential in Norway spruce seedlings as a bioassay for soil N and S pollution was effective, and is suggested as an additional, standardized and widely comparable system in bioindication of soil pollution.