Chemical composition of burnt smell caused by accidental fires: environmental contaminants

The chemical composition of the odors typical of fires has recently been deciphered. Basically the constituents are mixtures of acetophenone, benzyl alcohol, hydroxylated derivatives of benzaldehyde, methoxylated and/or alkylated phenols and naphthalene. This finding makes it possible to develop objective, practical analytic measurement methods for the burnt smell as a contribution to improving fire damage assessment and remediation monitoring. With the aid of an artificially produced burnt smell and a panel of testers the odor detection threshold of a test mixture was determined olfactometrically to 2 μg m⁻³. Using a defined burnt-smell atmosphere in a test chamber, analytical methods with active sampling, the adsorbents XAD 7 and TENAX TA, and GC/MS measurement were then optimized and tested with a view to being able to carry out sensitive quantitative measurement of burnt smells. A further practical method with particular application to the qualitative characterization of this odor is based on the use of a new SPME (solid-phase microextraction) field sampler with DVB/CAR/PDMS (divinylbenzene/Carboxen™/polydimethylsiloxane) fibers.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

Development of a combined isotopic and mass-balance approach to determine dissolved organic carbon sources in eutrophic reservoirs

A combined mass-balance and stable isotope approach was set up to identify and quantify dissolved organic carbon (DOC) sources in a DOC-rich (9 mg L⁻¹) eutrophic reservoir located in Western France and used for drinking water supply (so-called Rophemel reservoir). The mass-balance approach consisted in measuring the flux of allochthonous DOC on a daily basis, and in comparing it with the effective (measured) DOC concentration of the reservoir. The isotopic approach consisted, for its part, in measuring the carbon isotope ratios (δ¹³C values) of both allochthonous and autochthonous DOC sources, and comparing these values with the δ¹³C values of the reservoir DOC. Results from both approaches were consistent pointing out for a DOC of 100% allochthonous origin. In particular, the δ¹³C values of the DOC recovered in the reservoir (−28.5 ± 0.2‰; n = 22) during the algal bloom season (May-September) showed no trace of an autochthonous contribution (δ¹³C in algae = −30.1 ± 0.3‰; n = 2) being indistinguishable from the δ¹³C values of allochthonous DOC from inflowing rivers (−28.6 ± 0.1‰; n = 8). These results demonstrate that eutrophication is not responsible for the high DOC concentrations observed in the Rophemel reservoir and that limiting eutrophication of this reservoir will not reduce the potential formation of disinfection by-products during water treatment. The methodology developed in this study based on a complementary isotopic and mass-balance approach provides a powerful tool, suitable to identify and quantify DOC sources in eutrophic, DOC-contaminated reservoirs.     

Partitioning of metals in a degraded acid sulfate soil landscape: influence of tidal re-inundation

The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the “labile”, “acid-soluble”, “organic”, “crystalline oxide”, “pyritic” and “residual” fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The “acid-soluble”, “organic” and “pyritic” fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite.     

Determination of 2,4- and 2,6-dinitrotoluene biodegradation limits

This study was carried out to explore the lowest achievable dinitrotoluene (DNT) isomer concentrations that would support sustained growth of DNT degrading microorganisms under an aerobic condition. Studies were conducted using suspended (chemostat) and attached growth (column) systems. The biodegradation limits for 2,4-dinitrotoluene chemostat and column system were 0.054 ± 0.005 and 0.057 ± 0.008 μM, respectively, and for 2,6-dinitrotoluene, the limits for chemostat and column system were 0.039 ± 0.005 and 0.026 ± 0.013 μM, respectively. The biodegradation limits determined in this study are much lower than the regulatory requirements, inferring that bacterial ability to metabolize DNT does not preclude applications of bioremediation (including natural attenuation) for DNT contaminated media.     

Biomarker responsiveness in different tissues of caged Ruditapes philippinarum and its use within an integrated sediment quality assessment

Biomarkers comprising activities of biotransformation enzymes (ethoxyresorufin-O-deethylase -EROD-, dibenzylfluorescein dealkylase -DBF-, glutathione S-transferase -GST), antioxidant enzymes (glutathione reductase -GR- and glutathione peroxidase -GPX), lipid peroxidation -LPO- and DNA strand breaks were analyzed in the clam Ruditapes philippinarum caged at Cádiz Bay, Santander Bay and Las Palmas de Gran Canaria (LPGC) Port (Spain). Sediments were characterized. Digestive gland was the most sensitive tissue to sediment contamination. In Cádiz Bay, changes in LPO regarding day 0 were related with metals. In LPGC Port, DBF, EROD, and GST activity responses suggested the presence of undetermined contaminants which might have led to DNA damage. In Santander Bay, PAHs were related with EROD activity, organic and metal contamination was found to be associated with GR and GST activities and DNA damage presented significant (p < 0.05) induction. R. philippinarum was sensitive to sediment contamination at biochemical level. Biomarkers allowed chemical exposure and sediment quality assessment.     

TiO₂-based nanoparticles released in water from commercialized sunscreens in a life-cycle perspective: structures and quantities

This work investigates the physical-chemical evolution during artificial aging in water of four commercialized sunscreens containing TiO₂-based nanocomposites. Sunscreens were analyzed in terms of mineralogy and TiO₂ concentration. The residues formed after aging were characterized in size, shape, chemistry and surface properties. The results showed that a significant fraction of nano-TiO₂ residues was released from all sunscreens, despite their heterogeneous behaviors. A stable dispersion of submicronic aggregates of nanoparticles was generated, representing up to 38 w/w% of the amount of sunscreen, and containing up to 30% of the total nano-TiO₂ initially present in the creams. The stability of the dispersion was tested as a function of salt concentration, revealing that in seawater conditions, a major part of these nano-TiO₂ residues will aggregate and sediment. These results were put in perspective with consumption and life cycle of sunscreens to estimate the amount of nano-TiO₂ potentially released into AQUATIC environment.     

Petroleum refinery stripped sour water treatment using the activated sludge process

A pilot study was performed over 91 days to determine if the activated sludge process could treat a segregated stripped sour water (SSW) stream from a petroleum refinery. The study was performed in two periods. The first period was terminated after 19 days, as a result of excessive sludge bulking. The elimination of sludge bulking during the 70-day second period is attributed to operational changes, which included aerating the influent to oxidize reduced sulfur, adjusting the influent pH, and adding micronutrients to satisfy biological requirements. The pilot plant provided a chemical oxygen demand (COD) removal of up to 93%. Nitrification was achieved, with effluent ammonia values < 1 mg-N/L. These results indicate that direct treatment of SSW with the activated sludge process is possible and has direct application to full-scale petroleum refinery wastewater plant upgrades.     

A mathematical model for the interactive behavior of sulfate-reducing bacteria and methanogens during anaerobic digestion

Anaerobic degradation of waste involves different classes of microorganisms, and there are different types of interactions among them for substrates, terminal electron acceptors, and so on. A mathematical model is developed based on the mass balance of different substrates, products, and microbes present in the system to study the interaction between methanogens and sulfate-reducing bacteria (SRB). The performance of major microbial consortia present in the system, such as propionate-utilizing acetogens, butyrate-utilizing acetogens, acetoclastic methanogens, hydrogen-utilizing methanogens, and SRB were considered and analyzed in the model. Different substrates consumed and products formed during the process also were considered in the model. The experimental observations and model predictions showed very good prediction capabilities of the model. Model prediction was validated statistically. It was observed that the model-predicted values matched the experimental data very closely, with an average error of 3.9%.     

Evaluation of particulate matter abatement strategies for almond harvest

Almond harvest accounts for substantial PM10 (particulate matter [PM] < or =10 microm in nominal aerodynamic diameter) emissions in California each harvest season. This paper evaluates the effects of using reduced-pass sweepers and lower harvester separation fan speeds (930 rpm) on lowering PM emissions from almond harvesting operations. In-canopy measurements of PM concentrations were collected along with PM concentration measurements at the orchard boundary; these were used in conjunction with on-site meteorological data and inverse dispersion modeling to back-calculate emission rates from the measured concentrations. The harvester discharge plume was measured as a function of visible plume opacity during conditioning operations. Reduced-pass sweeping showed the potential for reducing PM emissions, but results were confounded because of differences in orchard maturity and irrigation methods. Fuel consumption and sweeping time per unit area were reduced when comparing a reduced-pass sweeper to a conventional sweeper. Reducing the separation fan speed from 1080 to 930 rpm led to reductions in PM emissions. In general, foreign matter levels within harvested product were nominally affected by separation fan speed in the south (less mature) orchard; however, in samples conditioned using the lower fan speed from the north (more mature) orchard, these levels were unacceptable.