The seasonal cycles and photochemistry of C2–C5 alkanes at Mace Head

Continuous in-situ measurements of NMHCs at Mace Head, Ireland during two full annual cycles from January 2005 to January 2007 were used to investigate NMHC emission sources and transport including dilution and photochemical oxidation. The Mace Head research station is ideally located to sample a wide range of air masses including polluted European transport, clean North Atlantic and Arctic air masses and the ultra-clean, Southern Atlantic air masses. The variety in air mass sampling is used to investigate interaction of emissions, transport, dilution and photochemistry. Variability of long-lived hydrocarbon ratios is used to assess and estimate typical transport times from emission source to the Mace Head receptor. Seasonality in the ratios of isomeric alkane pairs (for butane and pentanes) are used to assess the effects of atmospheric transport and photochemical ageing. Finally, the natural logarithms of NMHC ratios are used to assess photochemical oxidation.     

Carbon/nitrogen ratio as a major factor for predicting the effects of organic wastes on soil bacterial communities assessed by DNA-based molecular techniques

Background, aim, and scope  

Current Australian legislation permits the beneficial application of grease trap waste (GTW) to agricultural soil, viewing it as a beneficial source of organic matter and soil conditioner containing no/low amounts of metals or pathogenic organisms. However, little is known about the influence of GTW on soil bacterial community. A field experiment was established at Menangle in south western Sydney in Australia to quantitatively assess the impacts of different types (GTW CO and GTW CL) and amounts of GTW application on the soil bacterial community and diversity. Furthermore, a municipal solid waste (MSW) compost was simultaneously examined to compare against the other organic wastes. Knowledge about the shifts in microbial community structure and diversity following the applications of organic wastes could help to evaluate the ecological consequences on the soil and thus to develop sound regulatory guidelines for the beneficial reuse of organic wastes in agricultural lands.     

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

High and low value fish chains in the Mekong Delta: challenges for livelihoods and governance

This paper investigates the structure, function and wealth distribution within the Pangasius hypophthalmus and Henicorhynchus spp./Labiobarbus spp. value chains in the Mekong Delta of Vietnam. The analysis is driven by key questions relating to the form and function of value chains, their contribution to the livelihoods of farmers and fishers, the effectiveness of government policy and the potential for value chain governance mechanisms, such as contracts and certification, to steer towards sustainable production. The results indicate that actors in the high value Pangasius hypopthalmus export chain have a higher potential income, but face considerably higher economic vulnerability from global markets. Alternatively, Henichorhychus/Labiobarbus spp. fishers are severely constrained in their ability to negotiate higher prices for their fish but appear to be less vulnerable to economic and environmental change. The paper concludes that for value chain governance to improve the livelihoods of fishers and farmers in both high and low value chains, new arrangements are needed that better accommodate customary institutions and informal market relations.     

Acid Particles and the Tracheobronchial Region of the Respiratory System—An “Irritation-Signaling” Model for Possible Health Effects

This paper explores some detailed mechanistic hypotheses for the possible action of acid particles on the tracheobronchial region of the human respiratory system. Because of the buffering capacity and volume of mucus produced per day it appears doubtful that ordinary ambient exposures to acid particles could markedly change the overall pH of tracheobronchial mucus considered as a whole. However it is possible that individual acidic particles could contain enough acid to deliver localized “irritant signals” that could be the triggers for enhanced mucus secretion and cell division in sensitive portions of the bronchial tree, and thereby contribute to the processes involved in chronic bronchitis.

Depending on the exact pH depression required for a “signal” to be perceived by the tracheobronchial epithelium, the acid content of the incoming particles per unit weight, and the effect of neutralization by ammonia in the upper respiratory tract, the minimum size of an acidic particle required to deliver a perceptible signal might range from about 0.4 to 0.7 microns for portions of the epithelium that are frequently swept by 4-micron mucus droplets. (For unprotected epithelium, however, it is conceivable that the minimum effective size for acid particles could be less.) Since particle number per unit weight declines dramatically with increasing particle size, the most potent fraction of particles in terms of signals delivered per μg/m³is likely to be just above the minimum size that is needed to produce an effective signal. The model developed here makes predictions of the relative potency of particles of different size and acid delivery capacity that could be tested in both experimental animal systems and human epidemiological studies.     

Benzo[b]fluoranthene,a Potential Alternative to Benzo[a]pyrene as an Indicator of Exposure to Airborne PAHs in the Vicinity of Söderberg Aluminum Smelters

ABSTRACT

Benzo[b]fluoranthene (B[b]F) was used in relative abundance ratios (RARs), a parameter obtained by dividing the concentration of individual polycyclic aromatic hydrocarbons (PAHs) found in a given sample by the concentration of B[b]F in the same sample. The B[b]F RARs were derived for PAH concentrations measured at stacks and sampling stations in the vicinity of two Söderberg aluminum horizontal stud smelters (HSSs). The samples collected were analyzed by high-performance liquid chromatography using UV and fluorescence detection. A total of 15 PAHs were analyzed, but, due to the inefficiency of the sampling method used in collecting gaseous PAHs, only particulate PAHs were considered. Comparisons between the B[b]F RARs obtained simultaneously at the source (stack) and those obtained at sampling stations at the two smelters showed that B[b]F degrades more slowly than or at the same rate as most other particulate PAHs monitored. Twenty-three months of urban sampling in the vicinity of one of the aluminum HSSs are also presented, and the results indicate that B[b]F is more stable than all other particulate PAHs investigated. Sampling conducted during a smelter shutdown period confirmed that B[b]F was a much better marker of this source than was benzo[a]pyrene (B[a]P), the usual indicator. The remarkable stability of the benzo[k]fluoranthene (B[k]F)/B[b]F ratio is also discussed.     

Combustion Characteristics of Spent Catalyst and Paper Sludge in an Internally Circulating Fluidized-Bed Combustor

Abstract

Combustion of spent vacuum residue hydrodesulfurization catalyst and incineration of paper sludge were carried out in thermo-gravimetric analyzer and an internally circulating fluidized-bed (ICFB) reactor. From the thermogravimetric analyzer-differential thermo-gravimetric curves, the pre-exponential factors and activation energies are determined at the divided temperature regions, and the thermo-gravimetric analysis patterns can be predicted by the kinetic equations. The effects of bed temperature, gas velocity in the draft tube and annulus, solid circulation rate, and waste feed rate on combustion efficiency of the wastes have been determined in an ICFB from the experiments and the model studies. The ICFB combustor exhibits uniform temperature distribution along the bed height with high combustion efficiency (>90%). The combustion efficiency increases with increasing reaction temperature, gas velocity in the annulus region, and solid circulation rate and decreases with increasing waste feed rate and gas velocity in the draft tube. The simulated data from the kinetic equation and the hydrodynamic models predict the experimental data reasonably well.     

Second generation anticoagulant rodenticides in predatory birds: Probabilistic characterisation of toxic liver concentrations and implications for predatory bird populations in Canada

Second-generation anticoagulant rodenticides (SGARs) are widely used to control rodent pests but exposure and poisonings occur in non-target species, such as birds of prey. Liver residues are often analysed to detect exposure in birds found dead but their use to assess toxicity of SGARs is problematic. We analysed published data on hepatic rodenticide residues and associated symptoms of anticoagulant poisoning from 270 birds of prey using logistic regression to estimate the probability of toxicosis associated with different liver SGAR residues. We also evaluated exposure to SGARs on a national level in Canada by analysing 196 livers from great horned owls (Bubo virginianus) and red-tailed hawks (Buteo jamaicensis) found dead at locations across the country. Analysis of a broader sample of raptor species from Quebec also helped define the taxonomic breadth of contamination. Calculated probability curves suggest significant species differences in sensitivity to SGARs and significant likelihood of toxicosis below previously suggested concentrations of concern (<0.1mg/kg). Analysis of birds from Quebec showed that a broad range of raptor species are exposed to SGARs, indicating that generalised terrestrial food chains could be contaminated in the vicinity of the sampled areas. Of the two species for which we had samples from across Canada, great horned owls are exposed to SGARs to a greater extent than red-tailed hawks and the liver residue levels were also higher. Using our probability estimates of effect, we estimate that a minimum of 11% of the sampled great horned owl population is at risk of being directly killed by SGARs. This is the first time the potential mortality impact of SGARs on a raptor population has been estimated.     

Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength

The influence of pH (6.0-9.0), natural organic matter (NOM) (0-10 mg C/L) and ionic strength (IS) (1.7-40 mM) on 14 nm CeO₂ NP aggregation and ecotoxicity towards the alga Pseudokirchneriella subcapitata was assessed following a central composite design. Mean NP aggregate sizes ranged between 200 and 10000 nm. Increasing pH and IS enhanced aggregation, while increasing NOM decreased mean aggregate sizes. The 48 h-E_rC20s ranged between 4.7 and 395.8 mg CeO₂/L. An equation for predicting the 48 h-E_rC20 (48 h-E_rC20 = −1626.4 × (pH) + 109.45 × (pH)² + 116.49 × ([NOM]) − 14.317 × (pH) × ([NOM]) + 6007.2) was developed. In a validation study with natural waters the predicted 48 h-E_rC20 was a factor 1.08-2.57 lower compared to the experimental values.