Comparison of Outdoor and Classroom Ozone Exposures for School Children in Mexico City

Abstract

To evaluate methods of reducing exposure of school children in southwest Mexico City to ambient ozone, outdoor ozone levels were compared to indoor levels under three distinct classroom conditions: windows/doors open, air cleaner off; windows/doors closed, air cleaner off; windows/ doors closed, air cleaner on. Repeated two-minute average measurements of ozone were made within five minutes of each other inside and outside of six different school classrooms while children were in the room. Outdoor ozone two-minute average levels varied between 64 and 361 ppb; mean outdoor levels were above 160 ppb for each of the three conditions. Adjusting for outdoor relative humidity, for a mean outdoor ozone concentration of 170 ppb, the mean predicted indoor ozone concentrations were 125.3 (±5.7) ppb with windows/doors open; 35.4 (±4.6) ppb with windows/ doors closed, air cleaner off; and 28.9 (±4.3) ppb with windows/ doors closed, air cleaner on. The mean predicted ratios of indoor to outdoor ozone concentrations were 0.71 (±0.03) with windows/doors open; 0.18 (±0.02) ppb with windows/doors closed, air cleaner off; and 0.15 (±0.02) ppb with windows/doors closed, air cleaner on. As outdoor ozone concentrations increased, indoor ozone concentrations increased more rapidly with windows and doors open than with windows and doors closed. Ozone exposure in Mexican schools may be significantly reduced, and can usually be kept below the World Health Organization (WHO) guideline of 80 ppb, by closing windows and doors even when ambient ozone levels reach 30Q ppb or more.     

A Methodological Approach for Exposure Assessment Studies in Residences Using Volatile Organic-Compound-Contaminated Water

Abstract

This paper presents a methodological approach for assessing total exposures to volatile organic compounds (VOCs) in residences using contaminated water supplies. This approach is founded on assessment of ingestion, inhalation, and dermal exposures; both long-term (i.e., 12 to 24 hr) lowlevel exposures and short-term (i.e., =10 min) high-level exposures are considered.

The methodology is based on the collection of water samples to establish the identity of the contaminants, maximum source terms, and possible dermal and ingestion exposures; integrated whole-air samples are collected to assess long- and short-term inhalation exposures; whole-air grab samples are used to confirm peak and typical inhalation exposures; and alveolar breath samples are used to confirm exposures and to estimate contaminant concentrations in the blood of the test subjects. While we do not suggest that this methodology should supersede any current investigative approach, this material is primarily offered as a consolidated reference to the many people or organizations who might contemplate a study of this type. Application of this investigative protocol should provide detailed exposure assessment information, while it supplies critical real world data for risk assessment specialists, toxicologists, and modeling experts. Data from a recent field study assessing exposures to trichloroethylene are presented to illustrate the utility and some of the limitations of this strategy.     

Evaluation of Tire-Derived Fuel for Use in Nitrogen Oxide Reduction by Reburning

ABSTRACT

Tire-derived fuel (TDF) was tested in a small-scale (44 kW or 150,000 Btu/hr) combustor to determine its feasibility as a fuel for use in reburning for control of nitrogen oxide (NO). TDF was gravity-fed into upward flowing combustion gases from a primary natural gas flame doped with ammonia to simulate a high NO combustion process. Emissions of NO, oxygen, carbon dioxide, carbon monoxide, and particulate matter were measured. The tests varied the nominal primary NO level from 600 to 1,200 ppm and the primary stoichiometry from 1.1 to 1.2, and used both natural gas and TDF as reburn fuels. The reburn injection rate was varied to achieve 8–20% of the total heat input from the reburn fuel. NO emissions reductions ranged between 20 and 63% when using TDF, depending upon the rate of TDF injection, primary NO, and primary stoichiometry. NO emission reductions when using natural gas as the reburn fuel were consistently higher than those when using TDF. While additional work remains to optimize the process and evaluate costs, TDF has been shown to have the potential to be a technically viable reburning fuel.     

Characterization of Fine Particulate Matter Produced by Combustion of Residual Fuel Oil

ABSTRACT

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 |j.m in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM_2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 |j.m in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM_2.5 samples than in the PM₂₅₊ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO₄, while most of the V spectra closely resembled that of vanadyl sulfate (VO?SO₄?xH₂O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsen-ate (As⁺⁵). X-ray diffraction patterns of the PM_2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM_2.5 fraction and from 88 to 97% for the PM_2.5+ fraction. Based on ¹³C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.     

Pilot-Scale Demonstration of an Innovative Treatment for Vapor Emissions

ABSTRACT

Researchers from the National Renewable Energy Laboratory recently conducted a pilot-scale study at McClellan Air Force Base (AFB) in Sacramento, CA. The objective of the test was to determine the effectiveness of an ambient-temperature, solar-powered photocatalytic oxidation treatment unit for destroying emissions of chlorinated organic compounds from an air stripper. This paper reports test results and discusses applications and limitations of the technology.

A 10-standard-cubic-foot-per-minute (SCFM) (28.3 L/min) slip stream of air from an air stripper at Operative Unit 29-31 at McClellan AFB was passed through a reactor that contained a lightweight, perforated, inert support coated with photoactive titanium dioxide. The reactor faced south and was tilted at a 45° angle from vertical so that the light-activated catalyst received most of the available sunlight. An online portable gas chro-matograph with two identical columns simultaneously analyzed the volatile organic compounds contained in the reactor inlet and outlet air streams. Summa canister grab samples of the inlet and outlet were also collected and sent to a certified laboratory for U.S. Environmental

Protection Agency Method TO-14 analysis and verification of our field analyses. Three weeks of testing demonstrated that the treatment system's destruction and removal efficiencies (DREs) are greater than 95% at 10 SCFM with UV intensities at or greater than 1.5 milliwatts/square centimeter (mW/cm²). DREs greater than 95% at 20 SCFM were obtained under conditions where UV irradiation measured at or greater than 2 mW/cm². In Sacramento, this provided 6 hours of operation per clear or nearly clear day in April. A solar tracking system could extend operating time. The air stream also contained trace amounts of benzene. We observed no loss of system performance during testing.     

Speciation and transport of arsenic in an acid sulfate soil-dominated catchment, eastern Australia

Factors controlling the transport of geogenically-derived arsenic from a coastal acid sulfate soil into downstream sediments are identified in this study with both solid-phase associations and aqueous speciation clearly critical to the mobility and toxicity of arsenic. The data from both sequential extractions and X-ray adsorption spectroscopy indicate that arsenic in the unoxidised Holocene acid sulfate soils is essentially non-labile in the absence of prolonged oxidation, existing primarily as arsenopyrite or as an arsenopyrite-like species, likely arsenian pyrite. Anthropogenically-accelerated pedogenic processes, which have oxidised this material over time, have greatly enhanced the potential bioavailability of arsenic, with solid-phase arsenic almost solely present as As(V) associated with secondary Fe(III) minerals present. Analyses of downstream sediments reveal that a portion of the arsenic is retained as a mixed As(III)/As(V) solid-phase, though not at levels considered to be environmentally deleterious. Determination of arsenic speciation in pore waters using high performance liquid chromatography/Inductively Coupled Plasma-Mass Spectrometry shows a dominance of As(III) in upstream pore waters whilst an unidentified As species reaches comparative levels within the downstream, estuarine locations. Pore water As(V) was detected at trace concentrations only. The results demonstrate the importance of landscape processes to arsenic transport and availability within acid sulfate soil environments.     

Growth of soybean at future tropospheric ozone concentrations decreases canopy evapotranspiration and soil water depletion

Tropospheric ozone is increasing in many agricultural regions resulting in decreased stomatal conductance and overall biomass of sensitive crop species. These physiological effects of ozone forecast changes in evapotranspiration and thus in the terrestrial hydrological cycle, particularly in intercontinental interiors. Soybean plots were fumigated with ozone to achieve concentrations above ambient levels over five growing seasons in open-air field conditions. Mean season increases in ozone concentrations ([O₃]) varied between growing seasons from 22 to 37% above background concentrations. The objective of this experiment was to examine the effects of future [O₃] on crop ecosystem energy fluxes and water use. Elevated [O₃] caused decreases in canopy evapotranspiration resulting in decreased water use by as much as 15% in high ozone years and decreased soil water removal. In addition, ozone treatment resulted in increased sensible heat flux in all years indicative of day-time increase in canopy temperature of up to 0.7 °C.     

Impact of soil quality on elemental uptake by, and distribution in, Colocasia esculenta (Amadumbe), an edible root

In this study the elemental distribution of selected essential (Ca, Mg, Al, Mn, Cu, Fe, Co, Cr, Zn, Ni and Se) and the non-essential (Pb, Hg and As) elements were determined in the bulb and peel of Amadumbe (Colocasia esculenta) samples from eight different sites in KwaZulu-Natal, South Africa. The concentration of Se and As in the soil and in the Amadumbe bulbs were below the detection limit of 0.09 μg g?1. The total and bioavailable concentrations of the elements in conjunction with pH, soil organic matter (SOM) and cation exchange capacity (CEC) were determined in the soil samples from the eight sites. Statistical analysis was done to evaluate the impact of soil quality parameters on the chemical composition of the Amadumbe root. The results show accumulation or exclusion of certain elements by the bulb as evidenced by the noticeable increase or decrease of the concentrations of elements, respectively. Ca and Mg were found to be major elements in the range (2000-12000 μg g?1), whilst Mn, Zn, Fe and Al were found to be minor elements in the range (20-400 μg g?1). A general trend observed was that the plant favours the absorption of Zn over Cu. A positive correlation between Mg & Ca, Cu & Fe and Co & Ni was also observed. Statistical analysis revealed that the plant tended to accumulate Mg, Ca, Co, Cr and Pb whilst it excluded Hg and Fe, to a lesser extent.     

Probability of intellectual disability is associated with soil concentrations of arsenic and lead

Background

The association between metals in water and soil and adverse child neurologic outcomes has focused on the singular effect of lead (Pb), mercury (Hg), and arsenic (As). This study describes the complex association between soil concentrations of As combined with Pb and the probability of intellectual disability (ID) in children.

Methods

We used a retrospective cohort design with 3988 mother child pairs who were insured by Medicaid and lived during pregnancy and early childhood in South Carolina between 1/1/97 and 12/31/02. The children were followed until 6/1/08, using computerized service files, to identify the diagnosis of ID in medical records and verified by either school placement or disability service records. The soil was sampled using a uniform grid and analyzed for eight metals. The metal concentrations were interpolated using Bayesian Kriging to estimate concentration at individual residences.

Results

The probability of ID increased for increasing concentrations of As and Pb in the soil. The Odds Ratio for ID, for one unit change in As was 1.130 (95% confidence interval 1.048-1.218) for Pb was 1.002 (95% confidence interval 1.000-1.004). We identified effect modification for the infants based on their birth weight for gestational age status and only infants who were normal size for their gestational age had increased probability of ID based on the As and Pb soil concentrations (OR for As at normal weight for gestational age = 1.151 (95% CI: 1.061-1.249) and OR for Pb at normal for gestational age = 1.002 (95% CI: 1.002-1.004)). For normal weight for gestational age children when As = 22 mg kg⁻¹ and Pb = 200 mg kg⁻¹ the risk for ID was 11% and when As = 22 mg kg⁻¹and Pb = 400 mg kg⁻¹ the probability of ID was 65%.

Conclusion

The probability of ID is significantly associated with the interaction between Pb and As for normal weight for gestational age infants.     

Innovative applications of subgrade biogeochemical reactors: Three case studies

Subgrade biogeochemical reactors (SBGRs) are an in situ remediation technology shown to be effective in treating contaminant source areas and groundwater hot spots, while being sustainable and economical. This technology has been applied for over a decade to treat chlorinated volatile organic compound source areas where groundwater is shallow (e.g., less than approximately 30 feet below ground surface [ft bgs]). However, this article provides three case studies describing innovative SBGR configurations recently developed and tested that are outside of this norm, which enable use of this technology under more challenging site conditions or for treatment of alternative contaminant classes. The first SBGR case study addresses a site with groundwater deeper than 30 ft bgs and limited space for construction, where an SBGR column configuration reduced the maximum trichloroethene (TCE) groundwater concentration from 9,900 micrograms per liter (μg/L) to <1 μg/L (nondetect) within approximately 15 months. The second SBGR is a recirculating trench configuration that is supporting remediation of a 5.7‐acre TCE plume, which has significant surface footprint constraints due to the presence of endangered species habitat. The third SBGR was constructed with a new amendment mixture and reduced groundwater contaminant concentrations in a petroleum hydrocarbon source area by over 97% within approximately 1 year. Additionally, a summary is provided for new SBGR configurations that are planned for treatment of additional classes of contaminants (e.g., hexavalent chromium, 1,4‐dioxane, dissolved explosives constituents, etc.). A discussion is also provided describing research being conducted to further understand and optimize treatment mechanisms within SBGRs, including a recently developed sampling approach called the aquifer matrix probe.