The Impact of Stratospheric Ozone on Tropospheric Air Quality

A background of ozone (O₃), principally of stratospheric origin, is present in the lower free troposphere. Typical mean O₃ levels of 50 ppb, 40 ppb, and 30 ppb are encountered here in spring, summer, and fall, respectively. Maximum hourly O₃ concentrations which are twice these mean values can be expected. Ozone from the free troposphere is routinely brought down to ground level under turbulent atmospheric conditions. Deep and rapid Intrusions of stratospheric air into the lower troposphere are associated with low-pressure troughs and occur regularly. In the mid troposphere, O₃ levels as high as 300 ppb are found within these intrusions. Observational data showing these intrusions, containing high O₃ concentrations, to directly reach ground level are currently lacking. Over the United States, an intrusion was present aloft on 8 9% of the days in 1978. The frequency, however, is somewhat reduced in summer and a northward movement is evident. During 1978, no intrusion occurred south of 30°N between June and August and none south of 40 °N in August.

The hypothesis that low levels of stratospheric O₃ produce disproportionately large amounts of O₃ in the polluted atmosphere cannot be supported from currently known chemistry but should be studied further. The experimental technique involving a ⁷Be/O₃ ratio to estimate the daily stratospheric component of ground level O₃ is unverified and considered to be inadequate for air quality applications. Estimates resulting from such a technique are considered uncertain by a factor of more than three. Specially designed aircraft studies provide the best means to determine quantitatively the impact of stratospheric O₃ on ground level air quality.     

Pilot-Scale Evaluation of an Incinerability Ranking System for Hazardous Organic Compounds

The U.S. Environmental Protection Agency’s (EPA) hazardous waste incinerator performance standards specify a minimum destruction and removal efficiency (DRE) for principal organic hazardous constituents (POHCs) designated in the incinerator waste feed. In the past, selection of appropriate POHCs for incinerator trial burns has been based largely on their heats of combustion. Attempting to improve upon this approach, the University of Dayton Research Institute (UDRI), under contract to the EPA Risk Reduction Engineering Laboratory, has developed a thermal stability-based ranking of compound "incinerability". The subject study was conducted to evaluate the laboratory-developed ranking system in a pilot-scale incinerator.

Mixtures of POHCs, spanning the ranking scale from most- to least-difficult to destroy (Class 1 to Class 7, respectively), were prepared and combined with a clay-based sorbent matrix. These mixtures were then fed into the rotary kiln incineration system at the U.S. EPA Incineration Research Facility (IRF). In a series of five tests, the following conditions were evaluated: baseline/ typical operation; thermal failure (quenching); mixing failure (overcharging); matrix failure (low feed H/CI ratio); and a worst-case combination of the three failure modes.

Under baseline conditions, mixing failure, and matrix failure, kiln-exit DREs for each compound were comparable from test to test. Operating conditions in these 3 modes appeared to be sufficient to effect considerable destruction (greater than 99.99 percent DRE) of all compounds. As a result, separation of the highest-ranked POHCs from the lowest-ranked POHCs according to observed DRE was not possible; a correlation between POHC ranking and DRE could not be confirmed.

A correlation between predicted and observed incinerability was more evident for the thermal failure and worst-case conditions. Kiln-exit DREs for the four POHCs predicted to be most stable (those in Classes 1 and 2) ranged from 99% to 99.99% under these conditions, and were generally lower than DREs for the POHCs predicted to be more easily destroyed. Statistically significant correlations above the 99 percent and 93 percent confidence intervals were identified for the thermal-failure and worst-case tests, respectively.     

Evaluation of Trickle Bed Air Biofilter Performance as a Function of Inlet VOC Concentration and Loading,and Biomass Control

ABSTRACT

The 1990 Amendments to the Clean Air Act have stimulated strong interest in the use of biofiltration for the economical, engineered control of volatile organic compounds (VOCs) in effluent air streams. Trickle bed air biofilters (TBABs) are especially applicable for treating VOCs at high loadings. For long-term, stable operation of highly loaded TBABs, removal of excess accumulated bio-mass is essential. Our previous research demonstrated that suitable biomass control for TBABs was achievable by periodic backwashing of the biofilter medium. Backwashing was performed by fluidizing the pelletized biological attachment medium with warm water to about a 40% bed expansion. This paper presents an evaluation of the impact of backwashing on the performance of four such TBABs highly loaded with toluene. The inlet VOC concentrations studied were 250 and 500 ppmv toluene, and the loadings were 4.1 and 6.2 kg COD/m³ day (55 and 83 g toluene/m³ hr). Loading is defined as kg of chemical oxygen demand per cubic meter of medium per day. Performance deterioration at the higher loading was apparently due to a reduction of the specific surface of the attached biofilm resulting from the accumulation of excess biomass. For a toluene loading of 4.1 kg COD/m³ day, it was demonstrated that the long-term performance of biofilters with either inlet concentration could be maintained at over 99.9% VOC removal by employing a backwashing strategy consisting of a frequency of every other day and a duration of 1 hr.     

Measuring Ammonia Concentrations and Emissions from Agricultural Land and Liquid Surfaces: A Review

Abstract

Aerial ammonia concentrations (C _g) are measured using acid scrubbers, filter packs, denuders, or optical methods. Using C _g and wind speed or airflow rate, ammonia emission rate or flux can be directly estimated using enclosures or micrometeorological methods. Using nitrogen (N) recovery is not recommended, mainly because the different gaseous N components cannot be separated. Although low cost and replicable, chambers modify environmental conditions and are suitable only for comparing treatments. Wind tunnels do not modify environmental conditions as much as chambers, but they may not be appropriate for determining ammonia fluxes; however, they can be used to compare emissions and test models. Larger wind tunnels that also simulate natural wind profiles may be more useful for comparing treatments than micrometeorological methods because the latter require larger plots and are, thus, difficult to replicate. For determining absolute ammonia flux, the micrometeorological methods are the most suitable because they are nonintrusive. For use with micrometeorological methods, both the passive denuders and optical methods give comparable accuracies, although the latter give real-time C _g but at a higher cost. The passive denuder is wind weighted and also costs less than forced-air C _g measurement methods, but it requires calibration. When ammonia contamination during sample preparation and handling is a concern and separating the gas-phase ammonia and aerosol ammonium is not required, the scrubber is preferred over the passive denuder. The photothermal interferometer, because of its low detection limit and robustness, may hold potential for use in agriculture, but it requires evaluation. With its simpler theoretical basis and fewer restrictions, the integrated horizontal flux (IHF) method is preferable over other micrometeorological methods, particularly for lagoons, where berms and land-lagoon boundaries modify wind flow and flux gradients. With uniform wind flow, the ZINST method requiring measurement at one predetermined height may perform comparably to the IHF method but at a lower cost.     

Trivalent chromium solubility and its influence on quantification of hexavalent chromium in ambient particulate matter using EPA method 6800

Measurement of carcinogenic Cr(VI) in ambient PM is challenging due to potential errors associated with conversion between Cr(VI) (a carcinogen) and Cr(III) (an essential nutrient). Cr(III) conversion is a particular concern due to its >80% atomic abundance in total Cr. U.S. Environmental Protection Agency (EPA) method 6800 that uses water-soluble isotope spikes can be used to correct the interconversion. However, whether the enriched Cr(III) isotope spikes can adequately mimic the Cr(III) species originally in ambient PM is unknown. This study examined the water solubility of Cr(III) in ambient PM and discussed its influence on Cr(VI) measurement. Ambient PM₁₀ samples were collected on Teflon filters at four sites in New Jersey that may have different Cr emission sources. The samples were ultrasonically extracted with 5 mL DI-H₂O (pH 5.7) at room temperature for 40 min, and then analyzed by ion chromatography–inductively coupled plasma mass spectrometry (IC-ICPMS). Cr(III) was below detection limit (0.06 ng/m³) for all samples, suggesting water-soluble Cr(III) species, such as CrCl₃, Cr(NO₃)₃, and amorphous Cr(OH)₃, in the ambient PM were negligible. Therefore, the enriched ⁵⁰Cr(III) isotope spike (in the form of Cr(NO₃)₃) could not mimic the original ambient Cr(III). Only the conversion of ⁵³Cr(VI) (in the form of K₂CrO₄) was taken into account when correcting the interconversion. We then used NaHCO₃-pretreated MCE filters (prespiked with enriched isotope species) to measure Cr(VI) in the ambient PM₁₀. The samples were ultrasonically extracted at 60 C pH 9 solutions for 40 min followed by IC-ICPMS analysis. Due to the correction of Cr(VI) reduction, the Cr(VI) concentrations determined by EPA method 6800, 0.26 ± 0.16 (summer) and 0.16 ± 0.11(winter) ng/m³ (n = 64), were significantly greater than those by the external standard curve, 0.21 ± 0.17 (summer) and 0.10 ± 0.07 (winter) ng/m³ (n = 56) (p < 0.01, Student’s t-test). Our study revealed that appropriate application of EPA method 6800 is important because it only applies to soluble fraction of Cr species in ambient PM.

ImplicationsAccurate measurement of carcinogenic Cr(VI) in ambient PM is challenging due to conversion between Cr(VI) (a human carcinogen) and Cr(III) (a human essential nutrient). The conversion of Cr(III) is of particular concern due to its dominant presence in total Cr (>80%). This study examined the water solubility of Cr(III) in ambient PM that was collected at four locations in New Jersey. Then we discussed the influence of Cr(III) solubility on the application of EPA method 6800, which utilizes enriched isotope spikes to correct the interconversion. Our results suggested that appropriate application of EPA method 6800 is important because it only applies to soluble fraction of Cr species.     

Moderate seawater acidification does not elicit long-term metabolic depression in the blue mussel Mytilus edulis

Marine organisms are exposed to increasingly acidic oceans, as a result of equilibration of surface ocean water with rising atmospheric CO₂ concentrations. In this study, we examined the physiological response of Mytilus edulis from the Baltic Sea, grown for 2 months at 4 seawater pCO₂ levels (39, 113, 243 and 405 Pa/385, 1,120, 2,400 and 4,000 μatm). Shell and somatic growth, calcification, oxygen consumption and \textNH₄ ⁺ {\text{NH}}_{4}^{ + } excretion rates were measured in order to test the hypothesis whether exposure to elevated seawater pCO₂ is causally related to metabolic depression. During the experimental period, mussel shell mass and shell-free dry mass (SFDM) increased at least by a factor of two and three, respectively. However, shell length and shell mass growth decreased linearly with increasing pCO₂ by 6–20 and 10–34%, while SFDM growth was not significantly affected by hypercapnia. We observed a parabolic change in routine metabolic rates with increasing pCO₂ and the highest rates (+60%) at 243 Pa. \textNH₄ ⁺ {\text{NH}}_{4}^{ + } excretion rose linearly with increasing pCO₂. Decreased O:N ratios at the highest seawater pCO₂ indicate enhanced protein metabolism which may contribute to intracellular pH regulation. We suggest that reduced shell growth under severe acidification is not caused by (global) metabolic depression but is potentially due to synergistic effects of increased cellular energy demand and nitrogen loss.     

Feeding ecology and niche segregation in oceanic top predators off eastern Australia

We examined the feeding ecology and niche segregation of the ten most abundant fish species caught by longline operations off eastern Australia between 1992 and 2006. Diets of 3,562 individuals were examined. Hook timer data were collected from a further 328 fish to examine feeding behaviour in relation to depth and time of day. Prey biomass was significantly related to predator species, predator length and year and latitude of capture. Although the fish examined fed on a mix of fish, squid and crustacea, fish dominated the diet of all species except small albacore (Thunnus alalunga) which fed mainly on crustacea and large swordfish (Xiphias gladius) and albacore which fed mainly on squid. Cannibalism was observed in lancetfish (Alepisaurus spp.). Multidimensional scaling identified three species groups based on their diet composition. One group consisted of yellowfin tuna (T. albacares), striped marlin (Tetrapturus audax) and dolphinfish (Coryphaena hippurus); a second group consisted of bigeye tuna (T. obesus), swordfish and albacore; and a third consisted of southern bluefin tuna (T. maccoyii) and blue shark (Prionace glauca). Of note was the separation of mako shark (Isurus oxyrhynchus) and lancetfish from all other predators. Prey length generally increased with increasing predator length although even large predators fed on a wide range of prey lengths including very small prey. Overall, differences in prey type and size, feeding times and depths were noted across the range of species examined to the extent that predators with overlapping prey, either in type or size, fed at different times of the diel period or at different depths. Taken together these data provide evidence for feeding niche segregation across the range of oceanic top predators examined.     

Learning from the rubble: the case of Christchurch,New Zealand,after the 2010 and 2011 earthquakes

Learning after a disaster is crucial in creating more resilient places. However, many societies are repeatedly overwhelmed by disasters. This can be because of missed opportunities to learn in post‐disaster settings or because of actions implemented that seem to be highly relevant to recovery in the short term, but potentially constrain aspirations in the longer term. This paper assesses learning processes among state and non‐state actors and the ways in which these are bridged and scaled up to wider improvements in governance. Aiming to enrich understanding of post‐disaster learning, it explores different actors’ response actions after the earthquakes in Christchurch, New Zealand, in 2010 and 2011. On the one hand, ‘learning by doing’ is occurring, yet, on the other hand, systemic learning is hindered by mismatches between top‐down steering and bottom‐up initiatives. The study concludes that better linking and synergising of learning processes among different levels is vital for enhancing resilience in post‐disaster societies.     

Coexistence of oceanic predators on wintering areas explained by population-scale foraging segregation in space or time

Ecological niche theory predicts segregation mechanisms that mitigate potential competition between closely related organisms. However, little is known outside the breeding season, when central-place foraging animals may move on larger scales. This study tested for segregation mechanisms within the same 2007 inter-breeding period on three neighboring populations of avian predators from the southern Indian Ocean: Eastern Rockhopper Penguins Eudyptes filholi from Crozet and Kerguelen and Northern Rockhopper Penguins E. moseleyi from Amsterdam. Using state-of-the-art geolocation tracking and stable isotope analysis techniques, we quantified and compared the ecological niches in time, space, and diet. The three populations showed large-scale movements over deep oceanic waters near the Subantarctic Front, with generally little individual variation. The two neighboring populations of Eastern Rockhopper Penguins showed strikingly distinct distribution in space, while foraging in similar habitats and at the same trophic level (crustacean-eaters). In contrast, Northern Rockhoppers showed marked spatial overlap with birds of the sibling Eastern species, but their temporal delay of two months enabled them to effectively avoid significant overlap. Our results highlight parsimonious mechanisms of resource partitioning operating at the population level that may explain how animals from neighboring localities can coexist during the nonbreeding period.     

Social competition masculinizes the communication signals of female electric fish

Male intrasexual competition and female choice explain the evolution of male ornaments. Except in sex-role-reversed taxa, female ornaments have been regarded as an epiphenomenon of genetic correlation, with no female-specific function or independently selected basis. Females from species with conventional sex roles may still experience some degree of female–female competition and male choice that could explain the persistence of female ornaments. We studied the effect of female competition on the expression of a sexually dimorphic communication signal. In the electric fish Brachyhypopomus gauderio, both sexes produce an electric signal pulse for communication and electrolocation. Male electric pulses are longer in duration and greater in amplitude than those of females. As competition increases, males further enhance their signals in response to elevated androgen levels. We explored whether females respond to social competition as males do, by enhancing their communication signals and increasing androgen levels. We measured amplitude and duration of the electric signal pulse, and testosterone levels in female B. gauderio in their natural habitat in Uruguay and estimated social competition by calculating population density and adult sex ratio (ASR). In the lab, we manipulated ASR and population density independently to separate these factors and eliminate seasonal confounds. Under both field and lab conditions, signal pulse amplitude increased with population density, while pulse duration increased with female bias in ASR. In the field, but not the lab, androgen levels increased when ASR was female biased. Our findings indicate that the socially mediated mechanism of signal regulation is shared by the sexes, although whether androgens regulate this signal plasticity in females remains unclear.