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At least 289 records · Page 16

A minor respiratory process with major global implications: is atmospheric methane oxidation in tree stems driven by stem respiration rather than microbial methanotrophy?

Tree stem surfaces are widely recognized as sites of carbon dioxide (CO₂) efflux and oxygen (O₂) influx, reflecting the dynamics of aerobic respiration of photosynthate substrates, such as sugars, delivered via the phloem. Stems are also largely considered passive conduits for methane (CH₄) produced in anoxic soils via microbial methanogenesis, where CH₄ is thought to be transported upward through the transpiration stream and/or diffusion and emitted through stem surfaces and the canopy. However, recent observations from dynamic stem chambers suggest that stems may also act as active sinks for atmospheric CH₄. Despite these findings, the extent and drivers of stem CH₄ consumption remain poorly characterized across biomes, species, and environmental gradients, and its quantitative relationship to stem respiration has not been established. Moreover, previous studies captured only snapshot fluxes, leaving diurnal patterns of CH₄ exchange uncharacterized. Here, we address these limitations by combining real-time measurements of stem CH₄ and O₂ uptake under ambient conditions in a California cherry tree, using a dynamic stem gas exchange system with three chambers receiving a continuous flow of ambient air and automated chamber and reference air sampling every 10 min. Our results confirm that stems of upland trees can actively consume both atmospheric CH₄ and O₂, but with decreasing temperature sensitivity as daily temperatures increase. Early mornings were marked by rapid influxes of both gases, followed by declining uptake as temperatures rose further. Methane uptake was tightly coupled with O₂ influx and represented a minor (0.012% ± 0.002%) fraction of stem respiratory activity, as determined by concurrent O₂ uptake. These findings suggest that while atmospheric CH₄ oxidation is a minor respiratory process in stems, it is strongly linked with stem physiological activity. This challenges the current assumption that terrestrial CH₄ uptake is driven solely by microbial methanotrophy and raises the possibility that living stem tissues may contribute to CH₄ oxidation through an as-yet-unidentified plant-based mechanism.

Atmospheric greenhouse gases↗

Merging flux-variance with surface renewal methods in the roughness sublayer and the atmospheric surface layer

In this article, Two micrometeorological methods utilizing high-frequency sampled air temperature were tested against eddy covariance (EC) sensible heat flux (𝐻) measurements at three sites representing agricultural, agro-forestry, and forestry systems. The two methods cover conventional and newly proposed forms of the flux-variance (FV) and surface renewal (SR) schemes of differing complexities. The sites represent measurements in surface, roughness, and roughness to surface transitional layers. Regression analyzes against EC show that the most reliable FV and SR forms estimate 𝐻 with slopes within ±10% from unity and coefficient of determination 𝑅2 > 0.9 across all the three sites. The best performance of both FV and SR was found at the agricultural site with measurements well within the surface layer, while the worst was found for the tall forest with measurements within the roughness sublayer where its thickness needed to be additionally estimated. The main variable driving 𝐻 in FV is the temperature variance, whereas in SR, it is the geometry of ramp-like structures. Since these structures are also responsible for most of the temperature variance, a novel FV-SR approach emerging from combining the methods is proposed and evaluated against EC measurements and conventional FV and SR schemes. The proposed FV-SR approach requiring only a single fast response thermocouple is potentially independent of calibration and ameliorates some of the theoretical objections that arise when combining ramp statistics with similarity arguments. The combination of methods also provides new insights into the contribution of coherent structures to the temperature variance and its dependence on atmospheric stratification. Other potential utility of the new method is to include it in multi-tool assessments of surface energy fluxes, since a convergence or divergence of the results has a high diagnostic value.

54 ENVIRONMENTAL SCIENCES↗

Polycyclic aromatic hydrocarbons and cannabinoids in secondhand cannabis smoke

The legalization of cannabis is exposing more people to secondhand smoke (SHS) generated during cannabis use. Given the serious health effects caused by tobacco SHS, there is a need to assess the potential health effects of exposure to cannabis SHS. As a step toward this, we measured the concentrations of cannabinoids, nicotine and polycyclic aromatic hydrocarbons (PAHs) in air samples collected in public places where cannabis was being consumed. These were compared with concentrations in exhaled aerosols from cannabis smoking and vaping, and in tobacco SHS. Tetrahydrocannabinol concentrations were 22 to 255 µg/m 3 in field samples, below the threshold for psychoactive effects. Nicotine concentrations in field samples did not exceed 1 µg/m 3 . The total PAH concentrations in field samples were from 3.2 to 80.5 ng/m 3 , depending on location type. By contrast, PAH levels averaged 72 ng/m 3 in tobacco SHS and 220 ng/m 3 in the more concentrated, exhaled cannabis aerosols. A total of 22 different PAHs were identified in field samples of cannabis aerosols, from which benz[a]anthracene (B[a]A) was present in the highest concentrations. The PAH profile of cannabis aerosols was different from that of tobacco SHS. A preliminary cancer risk evaluation showed that the dose associated with inhalation of cannabis SHS during an 8-h work shift exceeded the California No Significant Risk Level for B[a]A at all venues where cannabis was consumed primarily via smoking. In summary, the consumption of cannabis, by smoking and by vaporizing, can create aerosols that contain carcinogenic PAHs. Thus breathing secondhand cannabis aerosols increases exposure to carcinogens.

Aerosol↗

Source term estimation using noble gas and aerosol samples

Algorithms that estimate the location, time, and magnitude of a point-source atmospheric release using remotely sampled air concentrations typically use data for a single chemical or radioactive isotope. Here, a Bayesian algorithm is presented that uses data from multiple radioactive isotopes that are all released in the same short-duration event. Data from noble gas and aerosol samplers can be used simultaneously in the model. Application to a large synthetic data set using four isotopes shows the new algorithm generally gives more accurate location and time estimates than a comparable model using a single isotope.

54 ENVIRONMENTAL SCIENCES↗

Fibrosis biomarkers in workers exposed to MWCNTs

Multi-walled carbon nanotubes (MWCNT) with their unique physico-chemical properties offer numerous technological advantages and are projected to drive the next generation of manufacturing growth. As MWCNT have already found utility in different industries including construction, engineering, energy production, space exploration and biomedicine, large quantities of MWCNT may reach the environment and inadvertently lead to human exposure. This necessitates the urgent assessment of their potential health effects in humans. The current study was carried out at NanotechCenter Ltd. Enterprise (Tambov, Russia) where large-scale manufacturing of MWCNT along with relatively high occupational exposure levels was reported. The goal of this small cross-sectional study was to evaluate potential biomarkers during occupational exposure to MWCNT. All air samples were collected at the workplaces from both specific areas and personal breathing zones using filter-based devices to quantitate elemental carbon and perform particle analysis by TEM. Biological fluids of nasal lavage, induced sputum and blood serum were obtained from MWCNT-exposed and non-exposed workers for assessment of inflammatory and fibrotic markers. It was found that exposure to MWCNTs caused significant increase in IL-1β, IL6, TNF-α, inflammatory cytokines and KL-6, a serological biomarker for interstitial lung disease in collected sputum samples. Moreover, the level of TGF-β1 was increased in serum obtained from young exposed workers. Overall, the results from this study revealed accumulation of inflammatory and fibrotic biomarkers in biofluids of workers manufacturing MWCNTs. Therefore, the biomarkers analyzed should be considered for the assessment of health effects of occupational exposure to MWCNT in cross-sectional epidemiological studies. - Highlights: • The effects of MWCNT exposure in humans remain unclear. • We found increased KL-6/TGF-β levels in the biofluids of MWCNT-exposed workers. • Inflammatory cytokines content was also increased in these workers. • The identified markers could be useful for potential health surveillance in exposed populations.

60 APPLIED LIFE SCIENCES↗

Emissions from Heated Terpenoids Present in Vaporizable Cannabis Concentrates

Vaporizable cannabis concentrates (VCCs) consumed as a liquid (vaping) or a waxy solid (dabbing) are becoming increasingly popular. However, their associated emissions and impacts have not been fully described. Mixtures containing different proportions of 12 VCC terpenoids and high MW compounds were heated at 100-500 °C inside a room-sized chamber to simulate emissions. Terpenoids, thermal degradation byproducts, and ultrafine particles (UFPs) were quantified in the chamber air. Air samples contained over 50% of emitted monoterpenes and less than 40% of released sesquiterpenes and terpene alcohols. Eleven degradation byproducts were quantified, including acrolein (1.3-3.9 μg m -3 ) and methacrolein (2.0 μg m -3 ). A large amount of UFPs were released upon heating and remained airborne for at least 3 h. The mode diameter increased from 80 nm at 100 °C to 140 nm at 500 °C, and particles smaller than 250 nm contributed to 90% of PM 1.0 . Here, the presence of 0.5% of lignin, flavonoid, and triterpene additives in the heated mixtures resulted in a threefold increase in the particle formation rate and PM 1.0 concentration, suggesting that these high-molecular-weight compounds enhanced aerosol inception and growth. Predicted UFP emission rates in typical consumption scenarios (6 × 10 11 -2 × 10 13 # min -1 ) were higher than, or comparable with, other common indoor sources such as smoking and cooking.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trans-Himalayan transport of organochlorine compounds: Three- year observations and model-based flux estimation

Due to their low temperature and high precipitation, high mountains can trap semi-volatile chemicals, such as persistent organic pollutants (POPs), and hinder their dispersion. However, deep convection occurring at high elevation facilitates the upward transport of POPs, and mountain valleys provide channels for regional transport of POPs. The concerted impact of these processes on the transport of contaminants across a mountain range has not been investigated before. In this study, we conducted a three-year passive air sampling campaign along a south-north altitudinal transect (100-5200m) across the central Himalayas, the highest mountain range on Earth. A multi-compartment contaminant fate model was developed to simulate the fate and transport of POPs along this transect and an adjacent mountain valley. The results show that driven by the strong Indian monsoon, POPs emitted in the lowlands at the foot of the Himalayas can be transported northward to high altitudes and further to the inner part of the Tibetan Plateau. Modeling suggests that more than 90% of POPs are trapped along the way due to gaseous deposition to soil and foliage and rainfall scavenging; we estimate that in spite of this removal, 2×10-3 to 1×10-1 Giga-grams of POPs are transported across the Himalayas every year. This indicates that despite their height the Himalayas are not a perfect barrier to the North-bound transport of POPs. We further compared the contributions that valleys and high altitudes make to the transport of POPs. The transport flux along valleys is 2-3 times higher than that across the mountain ridge. However, due to the limited spatial coverage of mountain valleys, the amount of POPs transported through valleys only accounts for a small part of the total transport, demonstrating that high altitude transport across the mountain ridge is the dominant transport pathway. This study shows that POPs can overcome the blocking effect of the Himalayas and the transport does not depend on the ability to pass through lower-lying mountain passes.

Gong, Ping↗

The Modeled Seasonal Cycles of Surface N 2 O Fluxes and Atmospheric N 2 O

Nitrous oxide (N 2 O) is a greenhouse gas and stratospheric ozone-depleting substance with large and growing anthropogenic emissions. Previous studies identified the influx of N 2 O-depleted air from the stratosphere to partly cause the seasonality in tropospheric N 2 O (aN 2 O), but other contributions remain unclear. Here, we combine surface fluxes from eight land and four ocean models from phase 2 of the Nitrogen/N 2 O Model Intercomparison Project with tropospheric transport modeling to simulate aN 2 O at eight remote air sampling sites for modern and pre-industrial periods. Models show general agreement on the seasonal phasing of zonal-average N 2 O fluxes for most sites, but seasonal peak-to-peak amplitudes differ several-fold across models. The modeled seasonal amplitude of surface aN 2 O ranges from 0.25 to 0.80 ppb (interquartile ranges 21%–52% of median) for land, 0.14–0.25 ppb (17%–68%) for ocean, and 0.28–0.77 ppb (23%–52%) for combined flux contributions. The observed seasonal amplitude ranges from 0.34 to 1.08 ppb for these sites. The stratospheric contributions to aN 2 O, inferred by the difference between the surface-troposphere model and observations, show 16%–126% larger amplitudes and minima delayed by ~1 month compared to Northern Hemisphere site observations. Land fluxes and their seasonal amplitude have increased since the pre-industrial era and are projected to grow further under anthropogenic activities. Our results demonstrate the increasing importance of land fluxes for aN 2 O seasonality. Considering the large model spread, in situ aN 2 O observations and atmospheric transport-chemistry models will provide opportunities for constraining terrestrial and oceanic biosphere models, critical for projecting carbon-nitrogen cycles under ongoing global warming.

54 ENVIRONMENTAL SCIENCES↗

Optimizing detection of RDX vapors using designed experiments for remote sensing

Abstract: This paper presents results of experiments performed to study the effect of four factors on the detection of RDX vapors from desorption into an atmospheric flow tube mass spectrometer (AFT-MS). The experiments initially included four independent factors: gas flow rate, desorption current, solvent evaporation time and RDX mass. The values of three detection responses, peak height, peak width, and peak area were recorded but only the peak height response was analyzed. Results from the first block of experiments indicated that solvent evaporation time was not statistically significant. A second round of experiments was performed using flow rate, current, and RDX mass as factors and the results were used to create a model to predict conditions resulting in maximum peak height. Those conditions were confirmed experimentally and used to obtain data for a calibration model. The calibration model represented RDX amounts ranging from 1 to 25 pg desorbed into an air flow of 7 L/min. Air samples from a shipping container that held 2 closed explosive storage magazines were collected on metal filaments for varying amounts for time ranging from 5 to 90 minutes. RDX was detected from all of the filaments sampled by desorption into the AFT-MS. From the calibration model, RDX vapor concentrations within the shipping container were calculated to be in the range of 1 to 50 parts-per-quadrillion from data collected on 2 separate days.

Experimental Design↗

In situ Al 2 O 3 incorporation enhances the efficiency of CuIn(S,Se) 2 solar cells prepared from molecular-ink solutions

Here, we report an efficiency enhancement of solution-processed CuIn(S,Se) 2 (CISSe) thin film solar cells via in situ incorporation of Al 2 O 3 . These films were produced using inks containing CuCl, InCl 3 , AlNO 3 (Al/Al + In: 0.1) and thiourea dissolved in methanol. After spin coating of these solutions in air, samples were subjected to a selenization process. Auger electron spectroscopy depth-profiling analysis showed that Al is evenly distributed throughout the bulk of the film. Transmission electron microscopy revealed that AlNO 3 precursor reacted with oxygen to form nanosized amorphous Al 2 O 3 grains located within the bulk and grain boundaries of CISSe, as well as at both the top and bottom interfaces. Power conversion efficiency (PCE) as high as 11.6% (JS C : 35.8 mA cm –2 , V OC : 518 mV, FF: 62.2%, no anti-reflection coating) was achieved with Al–CISSe solar cell devices integrated with CdS (chemical bath deposition, thickness: 80 nm) and ZnO/ITO bilayers (sputtered, thickness: 300 nm). The average PCE (10.1%, $\langle$J SC $\rangle$: 34.5 mA cm –2 , $\langle$V OC $\rangle$: 491 mV, $\langle$FF$\rangle$: 59.8%) was nearly 4% (absolute) higher than that measured on CISSe baseline cells fabricated from solutions without Al ($\langle$PCE$\rangle$ = 6.4%, $\langle$J SC $\rangle$: 32.8 mA cm –2 , $\langle$V OC $\rangle$: 410 mV, $\langle$FF$\rangle$: 47.3%). This in situ Al 2 O 3 incorporation is speculated to play a role in the enhancement of the VOC and FF of the devices through passivation of defects in CISSe reducing interface and bulk recombination, as evidenced by a reduced defect density and an increased activation energy of the dominant recombination mechanism from capacitance and temperature-dependent VOC measurements, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Continued emissions of carbon tetrachloride from the United States nearly two decades after its phaseout for dispersive uses

National-scale emissions of carbon tetrachloride (CCl 4 ) are derived based on inverse modeling of atmospheric observations at multiple sites across the United States from the National Oceanic and Atmospheric Administration's flask air sampling network. We estimate an annual average US emission of 4.0 (2.0-6.5) Gg CCl 4 y -1 during 2008- 2012, which is almost two orders of magnitude larger than reported to the US Environmental Protection Agency (EPA) Toxics Release Inventory (TRI) (mean of 0.06 Gg y -1 ) but only 8% (3-22%) of global CCl 4 emissions during these years. Emissive regions identified by the observations and consistently shown in all inversion results include the Gulf Coast states, the San Francisco Bay Area in California, and the Denver area in Colorado. Both the observation-derived emissions and the US EPA TRI identified Texas and Louisiana as the largest contributors, accounting for one- to two-thirds of the US national total CCl 4 emission during 2008-2012. These results are qualitatively consistent with multiple aircraft and ship surveys conducted in earlier years, which suggested significant enhancements in atmospheric mole fractions measured near Houston and surrounding areas. Furthermore, the emission distribution derived for CCl 4 throughout the United States is more consistent with the distribution of industrial activities included in the TRI than with the distribution of other potential CCl 4 sources such as uncapped landfills or activities related to population density (e.g., use of chlorine-containing bleach).

54 ENVIRONMENTAL SCIENCES↗

Effect of Environmental Factors on Sulfur Gas Emissions from Drywall

Problem drywall installed in U.S. homes is suspected of being a source of odorous and potentially corrosive indoor pollutants. The U.S. Consumer Product Safety Commission's (CPSC) investigation of problem drywall incorporates three parallel tracks: (1) evaluating the relationship between the drywall and reported health symptoms; (2) evaluating the relationship between the drywall and electrical and fire safety issues in affected homes; and (3) tracing the origin and the distribution of the drywall. To assess the potential impact on human health and to support testing for electrical and fire safety, the CPSC has initiated a series of laboratory tests that provide elemental characterization of drywall, characterization of chemical emissions, and in-home air sampling.

54 ENVIRONMENTAL SCIENCES↗

Detecting Bioterrorism: Is Chemistry Enough?

This slide shows how most bioaerosol detection systems work. There is a lot of concern in the biothreat community, and in the federal government, about a large-scale aerosolized attack. Because of that, we’ve implemented environmental monitoring programs that use aerosol collectors to continuously monitor for the presence of threat agents in the air. Air samples are usually analyzed using PCR, which is one of the most effective analytical techniques we have for identifying DNA. Experiments and modeling have shown these systems are effective, and can warn public health of an impending crisis in time to mount an effective response.

54 ENVIRONMENTAL SCIENCES↗

Summary Report for the Environmental Protection Agency MERL/FRMAC/RAP Mission Alignment Exercise held at the Savannah River Site on June 9-13 2014

From June 9th thru June 13th 2014, members of the Federal Radiological Monitoring and Assessment Center (FRMAC), the Environmental Protection Agency (EPA) and the Department of Energy Radiological Assistance Program (DOE RAP) Region-3 participated in a joint nuclear incident emergency response exercise at the Savannah River Site (SRS) near Aiken, South Carolina. The purpose of this exercise was to strengthen the interoperability relationship between the FRMAC, RAP, and the EPA Mobile Environmental Radiation Laboratory (MERL) stationed in Montgomery, Alabama. The exercise was designed to allowed members of the DOE RAP Region-3 team to collect soil, water, vegetation and air samples from SRS and submit them through an established FRMAC hotline. Once received and processed through the hotline, FRMAC delivered the samples to the EPA MERL for sample preparation and laboratory radiological analysis. Upon completion of laboratory analysis, data was reviewed and submitted back to FRMAC via an electronic data deliverable (EDD). As part of the exercise, an evaluation was conducted to identify gaps and potential improvements in each step of the processes. Additionally, noteworthy practices and potential future areas of interoperability between FRMAC and EPA were acknowledged. The exercise also provided a unique opportunity for FRMAC personnel to observe EPA sample receipt and sample preparation processes and to gain familiarity with the MERL laboratory instrumentation and radiation detection capabilities. The observations and lessons-learned from this exercise will be critical for developing a more efficient, integrated response for future interactions between the FRMAC and EPA assets.

54 ENVIRONMENTAL SCIENCES↗

Atmospheric Tracer Depletion Testing for Unfiltered Air In-Leakage Determination at the Wolf Creek Nuclear Power Plant

Atmospheric Tracer Depletion tests were conducted at the Wolf Creek Nuclear Power Plant to quantify the unfiltered in-leakage (UI) into the Control Room (CR), Control Building (CB), and Equipment Rooms (ER) at the Wolf Creek Nuclear Power Plant. Wolf Creek has two independent charcoal filter Emergency Ventilation Systems (EVS) that can be used to purify air entering the control building and control room. The Bravo System contains a filtration system in Room 1501 in the Auxiliary Building for the Control Room and another filtration system (FGK02B) on Elevation 2016 for the Control Building. The Alpha system contains a filtration system in Room 1512 in the Auxiliary Building for the Control Room and another filtration system (FGK02A) on Elevation 2016 for the Control Building.The Atmospheric Tracer Depletion (ATD) test is a technique to measure in-leakage using the concentration of perfluorocarbon compounds that have a constant atmospheric background. These levels are present in the Control Room and Control Building under normal operating conditions. When air is supplied by either of the EVS, most of the PFTS are removed by the charcoal filters. If the concentrations of the PFTs measured in protected areas are the same as the levels at the output of the EVS, the in-leakage of outside air into the protected area would be zero. If the concentration is higher in the protected area than at the output of the filter system, there is in-leakage and the in-leakage can be quantified by the difference.Sampling was performed using state-of-the-art Brookhaven Atmospheric Tracer Samplers (BATS) air sampling equipment and analysis performed on Brookhaven National Laboratory (BNL) dedicated PFT analytical systems. In the Alpha test two tracers PMCH and mcPDCH were used to determine in-leakage into the control building. The analytical system was tuned to maximize sensitivity after initial analysis of the Alpha test. The increased sensitivity permitted accurate quantification of five isomers of the PFT PDCH (mtPDCH, pcPDCH, otPDCH, mcPDCH, and ptPDCH). These isomers were quantified in the low concentration samples in the Alpha test and in all samples in the Bravo test.The best estimates of UI (Rui) for the four zones are provided in Table ES-1. For the CB, this estimate averages the four tracers at the four elevations. For the CR, this estimate uses the four sampling units located in the Control Room.

54 ENVIRONMENTAL SCIENCES↗

Industrial Hygiene Asbestos Negative Exposure Assessment Class III Wallboard penetration and removal up to 10 square feet of wallboard with asbestos containing joint compound

This negative exposure assessment (NEA) for asbestos is a certification stating that a specific type of work involving one or more hazardous materials has been evaluated and found not to result in exposure in excess of applicable standards. This assessment included the collection of personal exposure air samples and a review of the operation by an Industrial Hygienist. Work which deviates from the provisions below falls outside of the scope of this NEA and may result in exposure of personnel to hazardous materials in excess of applicable standards. Such operations must be independently evaluated.

54 ENVIRONMENTAL SCIENCES↗

Applicability of Public Dose Limits to Individuals on the Nevada National Security Site

Historically all persons working on the Nevada National Security Site (NNSS) were considered subject to worker dose limits when calculations of potential dose from the air pathway were conducted to demonstrate compliance with Title 42 United States Code (USC) Chapter 85, “The Clean Air Act,” and Title 40 Code of Federal Regulations (CFR) Part 61, Subpart H, “National Emission Standards for Hazardous Air Pollutants (NESHAP).” Calculations were also conducted for the all-pathways potential dose to demonstrate compliance with U.S. Department of Energy (DOE) Order DOE O 458.1 Chg. 3, “Radiation Protection of the Public and the Environment.” The need to evaluate environmental air sampling locations and past regulator questions about the existence of persons potentially subject to public dose limits being on the NNSS drove this assessment (letter from EPA [U.S. Environmental Protection Agency] Region 9 to DOE/Nevada Operations Office, dated September 3, 1999). This assessment also supports determining those persons subject to public dose limits from the all pathways perspective. A person that is a member of the public is subject to public dose limits.

61 RADIATION PROTECTION AND DOSIMETRY↗