The ecological effects of trichloroacetic acid in the environment

Trichloroacetic acid (TCAA) is a member of the family of compounds known as chloroacetic acids, which includes mono-, di- and trichloroacetic acid. The significant property these compounds share is that they are all phytotoxic. TCAA once was widely used as a potent herbicide. However, long after TCAA's use as a herbicide was discontinued, its presence is still detected in the environment in various compartments. Methods for quantifying TCAA in aqueous and solid samples are summarized. Concentrations in various environmental compartments are presented, with a discussion of the possible formation of TCAA through natural processes. Concentrations of TCAA found to be toxic to aquatic and terrestrial organisms in laboratory and field studies were compiled and used to estimate risk quotients for soil and surface waters. TCAA levels in most water bodies not directly affected by point sources appear to be well below toxicity levels for the most sensitive aquatic organisms. Given the phytotoxicity of TCAA, aquatic plants and phytoplankton would be the aquatic species to monitor for potential effects. Given the concentrations of TCAA measured in various soils, there appears to be a risk to terrestrial organisms. Soil uptake of TCAA by plants has been shown to be rapid. Also, combined uptake of TCAA from soil and directly from the atmosphere has been shown. Therefore, risk quotients derived from soil exposure may underestimate the risk TCAA poses to plants. Moreover, TCE and TCA have been shown to be taken up by plants and converted to TCAA, thus leading to an additional exposure route. Mono- and di-chloroacetic acids can co-occur with TCAA in the atmosphere and soil and are more phytotoxic than TCAA. The cumulative effects of TCAA and compounds with similar toxic effects found in air and soil must be considered in subsequent terrestrial ecosystem risk assessments.     

Using air pollution based community clusters to explore air pollution health effects in children

To study respiratory health effects of long-term exposure to ambient air pollutant mixture, we observed 7058 school children 5-16 years of age living in the four Chinese cities of Lanzhou, Chongqing, Wuhan, and Guangzhou. These children were enrolled from elementary schools located in eight districts, one urban district and one suburban district in each of the above cities. Ambient levels of PM(2.5), PM(10-2.5), total suspended particles (TSP), SO(2), and NO(x) were measured in these districts from 1993 to 1996. Based on a cluster analysis of arithmetic mean concentrations of PM(2.5), PM(10-2.5), (TSP-PM(10)), SO(2), and NO(x), we classified these children into four ordinal categories of exposure to ambient air pollutant mixtures. We tested for exposure-response relationships using logistic regression models, controlling for relevant covariates. We observed monotonic, positive relationships of exposure to the pollutant mixture with prevalence rates of cough with phlegm and wheeze. Other outcomes were not associated with the exposure in a monotonic exposure-response pattern. Even so, odds ratios for cough, phlegm, bronchitis, and asthma in the higher exposure district clusters were all higher than in the lowest exposure district cluster. We found evidence that exposure to the pollutant mixtures had adverse effects on children living in the four Chinese cities.     

Seasonal monoterpene and sesquiterpene emissions from Pinus taeda and Pinus virginiana

Seasonal volatile organic compound emission data from loblolly pine (Pinus taeda) and Virginia pine (Pinus virginiana) were collected using branch enclosure techniques in Central North Carolina, USA. P. taeda monoterpene emission rates were at least ten times higher than oxygenated monoterpene and sesquiterpene emissions in all seasons. α-pinene and β-pinene were the most abundant emissions, while β-caryophyllene had the highest sesquiterpene emission rate from this species. β-phellandrene was the dominant compound emitted from P. virginiana, followed by the sesquiterpene β-caryophyllene. Sesquiterpene emissions from P. virginiana have not been reported in the literature previously. Summer sesquiterpene emissions from P. virginiana were nearly as high as monoterpene emissions, but were 4–12 times lower than monoterpene emissions in the other seasons. Oxygenated monoterpenes and 2-methyl-3-buten-2-ol were emitted at higher rates from P. taeda than from P. virginiana. Temperature response of the pinenes from P. taeda is similar to previously reported values used in emission models, while that for other compounds falls at the lower end of the previously reported range. Temperature response of all compounds from P. virginiana is in reasonable agreement with previously reported values from other pine species. There is evidence of light dependence of sesquiterpene emission after accounting for temperature response from both species. This effect is somewhat stronger in P. taeda. Bud break, needle expansion, and needle fall (and therefore wind events) seemed to increase monoterpene emission during non-summer seasons. In some instances springtime monoterpene emissions were higher than summertime emissions despite cooler temperatures. Emissions of individual compounds within monoterpene, oxygenated monoterpene, and sesquiterpene classes were highly correlated with each other. Compounds from different classes were much less correlated within each species. This is due to a varying temporal emission patterns for each BVOC class and suggests different production, storage, and emission controls for each. Analysis of enclosure blanks and diurnal patterns indicates that, despite precautions, disturbance due to the enclosure technique may still impact monoterpene emission rate estimates. This did not appear to affect sesquiterpene emissions.     

Modelling the contribution of different sources of sulphur to atmospheric deposition in the United Kingdom

In order to understand relationships between sources and receptors of atmospheric deposition, computer models must be used. This paper describes a Lagrangian acid deposition model that represents emissions of trace species across Northern Europe. The chemistry of sulphur dioxide, dimethyl sulphide and hydrogen sulphide is represented and the model tested against estimates of UK wet and dry deposition. Mean UK wet and dry deposition for the period 1992–1994 was 206 and 145 ktonne S yr^-1, respectively. The model predicted wet and dry deposition of 222 and 166 ktonne S yr^-1, in good agreement with measurements. The model has been used to examine the sources of deposited S to the UK. For a base year of 1992, 86% of the UK's SO₂ emissions are exported. The S deposition attributable from mainland European sources was 36% of the UK total S deposition, in good agreement with other UK models but this differs substantially from the calculations of the EMEP model. Natural sources of S deposition from planktonic emissions of dimethyl sulphide, biological emissions of hydrogen sulphide and non-eruptive volcanic emissions of sulphur dioxide contributed approximately 1% of the modelled UK S deposition, of which 95% originated from dimethyl sulphide. The explicit chemical scheme for dimethyl sulphide incorporated into the model showed that 24% of the resultant deposited S was methane sulphonic acid. Boundary conditions of the model were tested and it was found that initialisation of sulphur dioxide and sulphate concentrations to representative ambient conditions had a very small effect. The modelled contribution of UK and European sources to UK S deposition was approximately 40 and 60%, respectively, showing the dramatic change arising from projected UK SO₂ emissions in 2010. This revised version was published online in July 2006 with corrections to the Cover Date.     

Modeling of dispersion near roadways based on the vehicle-induced turbulence concept

A mathematical model is developed for dispersion near roadways by incorporating vehicle-induced turbulence (VIT) into Gaussian dispersion modeling using computational fluid dynamics (CFD). The model is based on the Gaussian plume equation in which roadway is regarded as a series of point sources. The Gaussian dispersion parameters are modified by simulation of the roadway using CFD in order to evaluate turbulent kinetic energy (TKE) as a measure of VIT. The model was evaluated against experimental carbon monoxide concentrations downwind of two major freeways reported in the literature. Good agreements were achieved between model results and the literature data. A significant difference was observed between the model results with and without considering VIT. The difference is rather high for data very close to the freeways. This model, after evaluation with additional data, may be used as a framework for predicting dispersion and deposition from any roadway for different traffic (vehicle type and speed) conditions.     

Introduction

Abstract

Eight pairs of O‐methyl and O‐ethyl O‐(substituted‐phenyl) phenylphosphonothionates were evaluated with respect to their delayed neurotoxic activity in hens. O‐methyl compounds were in all cases more active than their O‐ethyl analogs. The neurotoxic potential of the O‐methyl phenylphosphonothionates was 2,5‐diCl >4‐NO₂ >2,4,5‐triCl and 2,4,6‐triCl >2,4‐diCl >2,5‐diCl‐4‐Br >4‐CN, when single oral doses were given. Both EPN‐ethyl and leptophos‐raethyl were more neurotoxic in multiple dermal than multiple oral dosing regimens. LD₅₀s for mice and flies were established.     

Adjoint inverse modeling of NOx emissions over eastern China using satellite observations of NO2 vertical column densities

A four-dimensional variational data assimilation system for optimization of NO_x emissions (RC4-NO_x) was developed. A parameterized NO_x chemistry scheme was introduced into the RC4-NO_x system, and key parameters such as chemical production and loss terms of NO_x were calculated in advance using the Community Multiscale Air Quality (CMAQ) modeling system. RC4-NO_x was applied to optimize NO_x emissions over eastern China (EC) in July 1996, 1999, and 2002 using Global Ozone Monitoring Experiment (GOME) satellite observations of NO₂ vertical column densities (VCDs) and a priori emissions from the Regional Emission Inventory in Asia (REAS). After assimilation, RC4-NO_x generally reproduced the spatial distribution, regional averaged values, and time evolution of GOME NO₂ VCDs. Over EC, a priori emissions were reduced by 20% in 1996 and by 8% in 1999, whereas a posteriori emissions were almost the same as a priori emissions in 2002. A priori emissions in the Beijing region were reduced by optimization over the whole simulation period. A posteriori emissions over the Yangtze Delta were larger than a priori emissions in 2002, although they were smaller in both 1996 and 1999. As in other areas, a priori emissions over the North China Plain were reduced in 1996; but those over the eastern part of the plain were increased in 1999, and the area of increased emissions moved slightly westward in 2002. In each region, the growth rates of a posteriori emissions during both 1996–1999 and 1999–2002 became generally larger than those of a priori emissions, and the trends of a posteriori emissions became similar to those of GOME NO₂ VCDs. Our inverse modeling analysis indicates that the rate of increase of NO_x emissions over EC from 1996 to 2002 was much larger for a posteriori emissions (49%) than for a priori emissions (19%).     

Ultrafine particles near a major roadway in Raleigh,North Carolina: Downwind attenuation and correlation with traffic-related pollutants

Ultrafine particles (UFPs, diameter < 100 nm) and co-emitted pollutants from traffic are a potential health threat to nearby populations. During summertime in Raleigh, North Carolina, UFPs were simultaneously measured upwind and downwind of a major roadway using a spatial matrix of five portable industrial hygiene samplers (measuring total counts of 20–1000 nm particles). While the upper sampling range of the portable samplers extends past the defined “ultrafine” upper limit (100 nm), the 20–1000 nm number counts had high correlation (Pearson R = 0.7–0.9) with UFPs (10–70 nm) measured by a co-located research-grade analyzer and thus appear to be driven by the ultrafine range. Highest UFP concentrations were observed during weekday morning work commutes, with levels at 20 m downwind from the road nearly fivefold higher than at an upwind station. A strong downwind spatial gradient was observed, linearly approximated over the first 100 m as an 8% drop in UFP counts per 10 m distance. This result agreed well with UFP spatial gradients estimated from past studies (ranging 5–12% drop per 10 m). Linear regression of other vehicle-related air pollutants measured in near real-time (10-min averages) against UFPs yielded moderate to high correlation with benzene (R² = 0.76), toluene (R² = 0.49), carbon monoxide (R² = 0.74), nitric oxide (R² = 0.80), and black carbon (R² = 0.65). Overall, these results support the notion that near-road levels of UFPs are heavily influenced by traffic emissions and correlate with other vehicle-produced pollutants, including certain air toxics.     

Surface ozone background in the United States: Canadian and Mexican pollution influences

We use a global chemical transport model (GEOS-Chem) with 1° × 1° horizontal resolution to quantify the effects of anthropogenic emissions from Canada, Mexico, and outside North America on daily maximum 8-hour average ozone concentrations in US surface air. Simulations for summer 2001 indicate mean North American and US background concentrations of 26 ± 8 ppb and 30 ± 8 ppb, as obtained by eliminating anthropogenic emissions in North America vs. in the US only. The US background never exceeds 60 ppb in the model. The Canadian and Mexican pollution enhancement averages 3 ± 4 ppb in the US in summer but can be occasionally much higher in downwind regions of the northeast and southwest, peaking at 33 ppb in upstate New York (on a day with 75 ppb total ozone) and 18 ppb in southern California (on a day with 68 ppb total ozone). The model is successful in reproducing the observed variability of ozone in these regions, including the occurrence and magnitude of high-ozone episodes influenced by transboundary pollution. We find that exceedances of the 75 ppb US air quality standard in eastern Michigan, western New York, New Jersey, and southern California are often associated with Canadian and Mexican pollution enhancements in excess of 10 ppb. Sensitivity simulations with 2020 emission projections suggest that Canadian pollution influence in the Northeast US will become comparable in magnitude to that from domestic power plants.     

Aerosol formation yields from the reaction of catechol with ozone

The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (M_o) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm^?3. Analysis of the data clearly shows that Y is a strong function of M_o and that secondary organic aerosol formation can be expressed by a one-product gas–particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.