ENVIRONMENTAL AUDITING: An Approach for Characterizing Tropospheric Ozone Risk to Forests

/ The risk tropospheric ozone poses to forests in the United States is dependent on the variation in ozone exposure across the distribution of the forests in question and the various environmental and climate factors predominant in the region. All these factors have a spatial nature, and consequently an approach to characterization of ozone risk is presented that places ozone exposure-response functions for species as seedlings and model-simulated tree and stand responses in a spatial context using a geographical information systems (GIS). The GIS is used to aggregate factors considered important in a risk characterization, including: (1) estimated ozone exposures over forested regions, (2) measures of ozone effects on species' and stand growth, and (3) spatially distributed environmental, genetic, and exposure influences on species' response to ozone. The GIS-based risk characterization provides an estimation of the extent and magnitude of the potential ozone impact on forests. A preliminary risk characterization demonstrating this approach considered only the eastern United States and only the limited empirical data quantifying the effect of ozone exposures on forest tree species as seedlings. The area-weighted response of the annual seedling biomass loss formed the basis for a sensitivity ranking: sensitive-aspen and black cherry (14%-33% biomass loss over 50% of their distribution); moderately sensitive-tulip popular, loblolly pine, eastern white pine, and sugar maple (5%-13% biomass loss); insensitive-Virginia pine and red maple (0%-1% loss). In the future, the GIS-based risk characterization will include process-based model simulations of the three- to 5-year growth response of individual species as large trees with relevant environmental interactions and model simulated response of mixed stands. The interactive nature of GIS provides a tool to explore consequences of the range of climate conditions across a species' distribution, forest management practices, changing ozone precursors, regulatory control strategies, and other factors influencing the spatial distribution of ozone over time as more information becomes available.KEY WORDS: Ecological risk assessment; GIS; Ozone; Risk characterization; Forests; Trees     

Removal of Alachlor from Water by Catalyzed Ozonation in the Presence of Fe2+, Mn2+, and Humic Substances

Abstract

The effects of Fe(II), Mn(II) and humic substances on the catalyzed ozonation of alachlor, an endocrine disruptor were investigated. Results revealed that small amounts of Fe(II), Mn(II), and humic substances could enhance the ozonation of alachlor, but larger amounts of them would retard the oxidation. These results were successfully identified by an electron paramagnetic resonance (EPR) spectroscopy/spin-trapping method that could quantify hydroxyl radicals. The production of hydroxyl radicals was obviously increased with the increasing of Fe(II) concentration, which contributed to enhance ozonation at low concentrations. But the excess Fe(II) consumed some of the radicals when it was added at a higher concentration (1.5 mg/L). However, no obvious radicals were observed when a different amount of Mn(II) was used, and the catalytic ozonation of alachlor by Mn(II) mainly followed the mechanism of “active sites created on the surface of MnO₂.” The radical pathway was followed when alachlor was ozonated with different concentrations of humic substances because of its radical initiating, promoting, and inhibiting effects.     

An Approach for Evaluating the Effectiveness of Various Ozone Air Quality Standards for Protecting Trees

We demonstrate an approach for evaluating the level of protection attained using a variety of forms and levels of past, current, and proposed Air Quality Standards (AQSs). The U.S. Clean Air Act requires the establishment of ambient air quality standards to protect health and public welfare. However, determination of attainment of these standards is based on ambient pollutant concentrations rather than prevention of adverse effects. To determine if a given AQS protected against adverse effects on vegetation, hourly ozone concentrations were adjusted to create exposure levels that “just attain” a given standard. These exposures were used in combination with a physiologically-based tree growth model to account for the interactions of climate and ozone. In the evaluation, we used ozone concentrations from two 6-year time periods from the San Bernardino Mountains in California. There were clear differences in the level of vegetation protection achieved with the various AQSs. Based on modeled plant growth, the most effective standards were the California 8-hr average maximum of 70 ppb and a seasonal, cumulative, concentration-weighted index (SUM06), which if attained, resulted in annual growth reductions of 1% or less. Least effective was the 1-hr maximum of 120 ppb which resulted in a 7% annual reduction. We conclude that combining climate, exposure scenarios, and a process-based plant growth simulator was a useful approach for evaluating effectiveness of current or proposed air quality standards, or evaluating the form and/or level of a standard based on preventing adverse growth effects.     

Modification of the biochemical pathways of plants induced by ozone: what are the varied routes to change?

When plants are observed under a low dose of ozone, some physiological and metabolic shifts occur. Barring extreme injury such as tissue damage or stomata closure, most of these disruptive changes are likely to have been initiated at the level of gene expression. The belief is oxidative products formed in ozone exposed leaves, e.g. hydrogen peroxide, are responsible for much of the biochemical adjustments. The first line of defense is a range of antioxidants, such as ascorbate and glutathione, but if this defense is overwhelmed, subsequent actions occur, similar to systemic acquired resistance or general wounding. Yet there are seemingly unrelated metabolic responses which are also triggered, such as early senescence. We discuss here the current understanding of gene control and signal transduction/control in order to increase our comprehension of how ozone alters the basic metabolism of plants and how plants counteract or cope with ozone.     

Interactions of forests with secondary air pollutants: some challenges for future research

The effects of ozone and other photochemical oxidants on individual trees have been studied for several decades, but there has been much less research on the potential effects on entire forest ecosystems. Given that ozone and other oxidants affect the production and subsequent fate of biogenic volatile organic compounds that act as signalling molecules, there is a need for more detailed study of the role of oxidants in modifying trophic interactions in forests. Deposition of fine particulates to forests may act as a source of nutrients, but also changes leaf surface properties, increasing the duration of surface wetness and modifying the habitat for epiphytic organisms, leading to increased risks from pathogens. Even where this pathway contributes a relatively small input of nutrients to forests, the indirect effects on canopy processes and subsequent deposition to the forest floor in throughfall and litter may play a more important role that has yet to be fully investigated.     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.     

Visible leaf injury in young trees of Fagus sylvatica L. and Quercus robur L. in relation to ozone uptake and ozone exposure. An Open-Top Chambers experiment in South Alpine environmental conditions

An Open-Top Chambers experiment on Fagus sylvatica and Quercus robur seedlings was conducted in order to compare the performance of an exposure-based (AOT40) and a flux-based approaches in predicting the appearance of ozone visible injuries on leaves. Three different ozone treatments (charcoal-filtered; non-filtered; and open plots) and two soil moisture treatments (watered and non-watered plots) were performed. A Jarvisian stomatal conductance model was drawn up and parameterised for both species and typical South Alpine environmental conditions, thus allowing the calculation of ozone stomatal fluxes for every treatment. A critical ozone flux level for the onset of leaf visible injury in beech was clearly identified between 32.6 and 33.6 mmolO3 m(-2). In contrast, it was not possible to identify an exposure critical level using the AOT40 index. Water stress delayed the onset of the leaf visible injuries, but the flux-based approach was able to take it into account accurately.     

Exposure to moderate concentrations of tropospheric ozone impairs tree stomatal response to carbon dioxide

With rising concentrations of both atmospheric carbon dioxide (CO₂) and tropospheric ozone (O₃), it is important to better understand the interacting effects of these two trace gases on plant physiology affecting land-atmosphere gas exchange. We investigated the effect of growth under elevated CO₂ and O₃, singly and in combination, on the primary short-term stomatal response to CO₂ concentration in paper birch at the Aspen FACE experiment. Leaves from trees grown in elevated CO₂ and/or O₃ exhibited weaker short-term responses of stomatal conductance to both an increase and a decrease in CO₂ concentration from current ambient level. The impairement of the stomatal CO₂ response by O₃ most likely developed progressively over the growing season as assessed by sap flux measurements. Our results suggest that expectations of plant water-savings and reduced stomatal air pollution uptake under rising atmospheric CO₂ may not hold for northern hardwood forests under concurrently rising tropospheric O₃.     

Within season and carry-over effects following exposure of grassland species mixtures to increasing background ozone

Few studies have investigated effects of increased background ozone in the absence of episodic peaks, despite a predicted increase throughout the northern hemisphere over the coming decades. In this study Leontodon hispidus was grown with Anthoxanthum odoratum or Dactylis glomerata and exposed in the UK to one of eight background ozone concentrations for 20 weeks in solardomes. Seasonal mean ozone concentrations ranged from 21.4 to 102.5 ppb. Ozone-induced senescence of L. hispidus was enhanced when grown with the more open canopy of A. odoratum compared to the denser growing D. glomerata. There was increased cover with increasing ozone exposure for both A. odoratum and D. glomerata, which resulted in an increase in the grass:Leontodon cover ratio in both community types. Carry-over effects of the ozone exposure were observed, including delayed winter die-back of L. hispidus and acceleration in the progression from flowers to seed-heads in the year following ozone exposure.