Flux measurements of volatile organic compounds by the relaxed eddy accumulation method combined with a GC-FID system in urban Houston,Texas

A tall tower flux measurement setup was established in metropolitan Houston, Texas, to measure trace gas fluxes from emission sources in the urban surface layer. We describe a new relaxed eddy accumulation (REA) system combined with a dual-channel GC-FID used for VOC flux measurements, focusing on benzene, toluene, ethylbenzene and xylenes (BTEX) results. Ambient air sampled from 60 m above the ground next to a sonic anemometer was subsampled by a membrane pump and pushed into an REA valve system with two Teflon bag reservoirs, then transferred to two preconcentration units for thermal desorption. We discuss the performance of our system and the selected BTEX measurement results using approximately 8 weeks of data (May 22–July 22, 2008), presenting diurnal variations of concentrations and fluxes of these traffic tracers. The measured values exhibited diurnal cycles with dominant morning and midday peaks during weekdays related to rush hour traffic and additional weekday daytime toluene and xylenes emissions. Local evaporative emissions, likely from solvent usage, significantly contributed to the measured fluxes. We upscaled measured emissions to the county level using a high resolution land cover data set and compared the results with EPA’s National Emission Inventory (NEI).     

Three-dimensional characterization of the ammonia plume from a beef cattle feedlot

In Canada approximately 45% of ammonia (NH₃) emissions are attributed to dairy and beef cattle industries. The present study focused on NH₃ emissions from a beef feedlot with a one-time capacity of 17,220 head. The aim was to improve the Canadian NH₃ emission inventories and air quality forecasting capabilities. A Cessna 207, equipped with a fast-response NH₃/NO_y detector and a quadrupole aerosol mass spectrometer, was flown in a grid pattern covering an area of 8 × 8 km centered on a feedlot (800 × 800 m) at altitudes ranging from 30 to 300 m above ground. Stationary ground measurements of NH₃ concentration and turbulence parameters were made downwind of the feedlot. Three flights were conducted under varying meteorological conditions, ranging from very calm to windy with near-neutral stratification. NH₃ mixing ratios up to 100 ppbv were recorded on the calm day, up to 300 m above ground. An average feedlot NH₃ emission rate of 76 ± 4 μg m^?2 s^?1 (equivalent to 10.2 g head^?1 h^?1) was estimated. Characteristics of the measured NH₃ plume were compared to those predicted by a Lagrangian dispersion model. The spatially integrated pattern of NH₃ concentrations predicted and measured agreed but the measured was often more complex than the predicted spatial distribution. The study suggests that the export of NH₃ through advection accounted for about 90% of the emissions from the feedlot, chemical transformation was insignificant, and dry deposition accounted for the remaining 10%.     

Field validation of an active sampling cartridge as a passive sampler for long-term carbonyl monitoring

A carbonyl sampler originally designed for the active sampling method (Sep-Pak XPoSure) was used for long-term passive sampling, and its applicability as a passive sampler was examined through field experiments. The uptake rates of passive sampling were determined experimentally from collocated passive and active samplings for various sampling periods. The obtained uptake rates of formaldehyde, acetaldehyde, and acetone were 1.48, 1.23, and 1.08 mL/min, respectively. These uptake rates were consistent for a wide range of the sampling term (12 hr-2 weeks). Uptake rates of each carbonyl were proportional to the diffusion coefficients of each. Therefore, the ratios of diffusion coefficients were used to calculate the uptake rates of carbonyls for which the rates were not determined experimentally. Lower limits of determination were 2.16-17.5 microg/m3 for 2-week sampling. It was confirmed that 2-week monitoring of carbonyl concentrations up to 118-229 microg/m3 was possible. Relative standard deviations of the passive method generated from the repeatability test were 2-12.3% error for five samplings, and the recovery efficiencies were larger than 90%. Thus, the passive sampler was found to be highly suitable for long-term monitoring of carbonyl compounds.     

A passive flux denuder for evaluating emissions of ammonia at a dairy farm

Passive samplers have been shown to be an inexpensive alternative to direct sampling. Diffusion denuders have been developed to measure the concentration of species such as ammonia (NH3), which is in equilibrium with particulate ammonium nitrate. Conventional denuder sampling has required active sampling that inherently requires air pumps and, therefore, electrical power. To estimate emissions of NH3 from a fugitive source would require an array of active samplers and meteorological measurements to estimate the flux. A recently developed fabric denuder was configured in an open tube to passively sample NH3 flux. Passive and active samplers were collocated at a dairy farm at the California State University, Fresno, Agricultural Research Facility. During this comparison study, NH3 flux measurements were made at the dairy farm lagoon before and after the lagoon underwent acidification. Comparisons were made of the flux measurements obtained directly from the passive flux denuder and those calculated from an active filter pack sampler and wind velocity. The results show significant correlation between the two methods, although a correction factor needed to be applied to directly compare the two techniques. This passive sampling approach significantly reduces the cost and complexity of sampling and has the potential to economically develop a larger inventory base for ambient NH3 emissions.     

The recovery of ammonia and hydrogen sulfide from ground-level area sources using dynamic isolation flux chambers: bench-scale studies

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH3) and hydrogen sulfide (H2S) from dynamic isolation flux chambers. H2S (80-4000 ppb) and NH3 (5000-40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H2S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H2S could be recovered during the given sampling period. NH3 emissions exhibited similar behavior between concentrations of 5000-40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH3 sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH3 or H2S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH3 and H2S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH3 and H2S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the fullscale sensitivity of the gas sensing equipment. The use of 46-90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Abatement of ammonia and hydrogen sulfide emissions from a swine lagoon using a polymer biocover

The purpose of this research was to determine the efficiency of a polymer biocover for the abatement of H2S and NH3 emissions from an east-central Missouri swine lagoon with a total surface area of 7800 m2. The flux rate of NH3, H2S, and CH4 was monitored continuously from two adjacent, circular (d = 66 m) control and treatment plots using a nonintrusive, micrometeorological method during three independent sampling periods that ranged between 52 and 149 hr. Abatement rates were observed to undergo a temporal acclimation event in which NH3 abatement efficiency improved from 17 to 54% (p = < 0.0001 to 0.0005) and H2S abatement efficiency improved from 23 to 58% (p < 0.0001) over a 3-month period. The increase in abatement efficiency for NH3 and H2S over the sampling period was correlated with the development of a stable anaerobic floc layer on the bottom surface of the biocover that reduced mass transfer of NH3 and H2S across the surface. Analysis of methanogenesis activity showed that the biocover enhanced the rate of anaerobic digestion by 25% when compared with the control. The biocover-enhanced anaerobic digestion process was shown to represent an effective mechanism to counteract the accumulation of methanogenic substrates in the biocovered lagoon.     

A study on emission of phthalate esters from plastic materials using a passive flux sampler

Phthalate esters are used as plasticizer in many plastics, and several studies have shown their toxicity. Phthalate esters are gradually emitted over time, and so it is conceivable that they pose a significant health risk. This study aims to investigate the temperature dependence of the emissions of various phthalate esters and to estimate the health risks of these emissions at various temperatures. A passive-type sampler was developed to measure the flux of phthalate esters from the surface of plastic materials. With this sampler, we examined three widely used plastic materials: synthetic leather, wallpaper and vinyl flooring. The observed maximum emissions of diethyl phthalate, dibutyl phthalate, and diethylhexyl phthalate (DEHP) from these materials at 20°C were 0.89, 0.77, and 14 μg m⁻² h⁻¹, respectively. Emissions at 80°C were 2.8, 4.5×10², and 1.5×10³ μg m⁻² h⁻¹, respectively. The results showed this temperature dependence is determined primarily by the type of phthalate ester and less so by the type of material. The estimation from the results of temperature dependence indicated the concentration of DEHP in a vehicle left out in the sunshine during the day can exceed the recommended levels of Japan Ministry of Health, Labour and Welfare.     

Assessment of polychlorinated dibenzo-p-dioxin and dibenzofuran emissions from a hazardous waste incineration plant using long-term sampling equipment

The aim of this work is to evaluate the performance of a continuous monitoring system for the analysis of the mass concentration of PCDD/Fs from stationary sources. Data was acquired from a modern, state of the art, hazardous waste thermal treatment plant for a period of more than 2 years using a commercial available continuous monitoring system. The study consisted of a total of 16 samples, collected in periods from 1 week to 2 months resulting in an average of 360 m³ sampled flue gas per sample. The study showed the system was able to confirm that for a period of more than 2 years the plant was complying with the limit of 0.1 ng I-TEQ/Nm³. In addition, the data showed the typical fingerprint of such installations which is useful for example in impact studies. Long-term samples were compared to five short-term samples (6 h) collected every 6 months during the study period. Principal component analysis was applied to PCDD/Fs obtained data as useful statistical tool to find out trends and similarities between different samples. Improvement in terms of representativeness of data was achieved through continuous assessment since the starts of the project. The obtained data was further used to determine the emission factor for this activity and the total annual PCDD/Fs release to the atmosphere.     

Extraction and cleanup methods of dioxins in house dust from two cities in Japan using accelerated solvent extraction and a disposable multi-layer silica-gel cartridge

A simple and rapid method for the extraction and cleanup of dioxins from house dust was developed using an accelerated solvent extraction (ASE) method and a multi-layer silica-gel cartridge. It was found that the WHO-TEQ levels of dioxins extracted from the house dust obtained by both a conventional soxhlet extraction and the ASE were almost equal, when the data obtained by both methods were compared. As for the cleanup method, a multi-layer silica-gel cartridge yielded higher dioxin recoveries than the alkaline digestion method. The average values of the dioxins in house dust from Kumagaya city and Sendai city in Japan (Sendai city is bigger than Kumagaya city with respect to the population and industry), were 15.6 pg TEQ/g (8.6-26.0 pg TEQ/g, n=5, Kumagaya city) and 16.0 pg TEQ/g (5.9-30.5 pg TEQ/g, n=5, Sendai city), respectively.     

A comparison of two stomatal conductance models for ozone flux modelling using data from two Brassica species

In this study we tested and compared a multiplicative stomatal model and a coupled semi-empirical stomatal-photosynthesis model in their ability to predict stomatal conductance to ozone (g_st) using leaf-level data from oilseed rape (Brassica napus L.) and broccoli (Brassica oleracea L. var. italica Plenck). For oilseed rape, the multiplicative model and the coupled model were able to explain 72% and 73% of the observed g_st variance, respectively. For broccoli, the models were able to explain 53% and 51% of the observed g_st variance, respectively. These results support the coupled semi-empirical stomatal-photosynthesis model as a valid alternative to the multiplicative stomatal model for O₃ flux modelling, in terms of predictive performance.     

Global sensitivity analysis of a process-based model for ammonia emissions from manure storage and treatment structures

The development of process-based models to estimate ammonia emissions from animal feeding operations (AFOSs) is sought to replace costly and time-consuming direct measurements. Critical to process-based model development is conducting sensitivity analysis to determine the input parameters and their interactions that contribute most to the variance of the model output. Global and relative sensitivity analyses were applied to a process-based model for predicting ammonia emissions from the surface of anaerobic lagoons for treating and storing manure. The objectives were to compare global sensitivity analysis (GSA) to relative (local) sensitivity analysis (RSA) on a process-based model for ammonia emissions. Based on the first-order coefficient, both GSA and RSA showed the model input parameters in order of importance in process model for ammonia emissions from lagoon surfaces were: (i) pH, (ii) lagoon liquid temperature, (iii) wind speed above the lagoon surface, and (iv) the concentration of ammoniacal nitrogen in the lagoon. The GSA revealed that interactions between model parameters accounted for over two-thirds of the model variance, a result that cannot be achieved using traditional RSA. Also, the GSA showed that parameter interactions involving liquid pH had more impact on the model output variance than the single parameters: (i) temperature, (ii) wind speed, or (iii) total ammoniacal nitrogen. This study demonstrates that GSA provides a more complete analysis of model input parameters and their interactions on the model output compared to RSA. A comprehensive tutorial regarding the application of GSA to a process model is presented.     

Certification of a long-term sampling system for PCDFs and PCDDs in the flue gas from industrial facilities

AMESA (adsorption method for sampling of dioxins) is a fully automatic system for long term monitoring of dioxin emissions from industrial processes based on the adsorption method. The system has been tested and undergoing a certification procedure according to the German guidelines for certification of systems for continuous monitoring of special substances. The certification covered parameters such as disposability of the system, reproducibility of the results and comparability of the sampling method with German and European standard methods. Furthermore break through, blanks and sample storability were investigated. The results prove that AMESA is a state of the art sampling system for continuous monitoring of dioxin/furan emissions.     

Assessment of the emission of PCDD/Fs and dioxin-like PCBs from an industrial area over a nearby town using a selective wind direction sampling device

The development of new sampling devices or strategies to assess the concentration of persistent organic pollutants (POPs) in the environment has increased in the last two decades. In this study, a selective sampling device was used to evaluate the impact of potential local sources of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) and dioxin-like polychlorinated biphenyl (dl-PCBs) emissions on the ambient air levels of such compounds in a town near an important industrial estate. Average concentrations of target compounds of up to 2.5 times for PCDD/Fs and 2 times for dl-PCBs were found to come from the industrial state confirming this area as the main responsible for the majority of such compounds reaching the town.This finding was supported by a PCDD/F and dl-PCB sample profile analysis and a principal component analysis (PCA), which established a direct link between the dioxin-like compounds found in the samples collected in the town and their source.     

Assessment of Ni accumulation capability by fungi for a possible approach to remove metals from soils and waters

ABSTRACT

Abandoned industrial sites and mines may constitute possible hazards for surrounding environment due to the presence of toxic compounds that may contaminate soils and waters. The possibility to remove metal contaminants, specifically nickel (Ni), by means of fungi was presented exploiting a set of fungal strains isolated from a Ligurian dismissed mine. The achieved results demonstrate the high Ni(II) tolerance, up to 500 mg Ni l^?1, and removal capability of a Trichoderma harzianum strain. This latter hyperaccumulates up to 11,000 mg Ni kg^?1, suggesting its possible use in a bioremediation protocol able to provide a sustainable reclamation of broad contaminated areas.     

Determination of ammonia and hydrogen sulfide emissions from a commercial dairy farm with an exercise yard and the health-related impact for residents

Environmental Science and Pollution Research - Airborne emissions from concentrated animal feeding operations (CAFOs) have the potential to pose a risk to human health and the environment. Here, we...     

Dynamic flux chamber measurement of gaseous mercury emission fluxes over soils. Part 1: simulation of gaseous mercury emissions from soils using a two-resistance exchange interface model

A two-resistance exchange interface model (TREIM) was developed to simulate gaseous mercury (Hg) emissions from soils measured by dynamic flux chamber (DFC) operations. The model is based on mass balance principles and a Hg air/soil exchange theory that considers the influence of flushing flow rate on Hg air/soil exchange. We used this model to examine the effect of the flushing flow rate and understand the optimum conditions for DFC measurements of Hg emission fluxes over soils. Our model simulations indicate that the flushing flow rate is a most critical operation condition. We recommend adoption of high flushing flow rates (e.g., ∼15–40 l min⁻¹ for DFCs of common design) based on our simulation findings that underestimation of actual emission fluxes can occur at low flushing flow rates. The biased low fluxes are caused by suppression of emission potential resulting from internal accumulation of emitted Hg and by higher exchange resistance both at low flushing flow rates. This model provides a useful means for estimating maximum steady-state fluxes and soil air Hg concentrations and for adjustment of the fluxes measured under different operating conditions. The model also finds its value in understanding mechanical processes of Hg emissions from soils.     

Identification of volatiles from Pinus silvestris attractive for Monochamus galloprovincialis using a SPME-GC/MS platform

Introduction

A myriad of volatile organic compounds (VOCs) released by terrestrial vegetation plays an important role in environmental sciences. A thorough chemical identification of these species at the molecular level is essential in various fields, ranging from atmospheric chemistry to ecology of forest ecosystems. In particular, the recognition of VOCs profiles in a context of plant?Cinsect communication is a key issue for the development of forest protection tools.

Purpose

This work was aimed at the development of a simple, robust and reliable method for the identification of volatiles emitted from plant materials, which can attract or deter pest insects. Specifically, volatiles emitted from the bark of Pinus sylvestris were studied, which might attract the black pine sawyer beetle Monochamus galloprovincialis??a serious pest of the tree and a vector of a parasitic nematode Bursaphelenchus xylophius.

Method

The volatiles from bark samples were collected using a solid-phase micro-extraction technique, and subsequently analysed by gas-chromatography/mass-spectrometry (GC/MS). The characterisation of the volatile fraction was based on the comparison with data in mass spectral libraries, and in most cases, with the available authentic standards. The identified compounds were screened against the available entomological data to select insect attractors.

Results

The identified components included terpenes (??-pinene, ?-3-carene, and para-cymenene), oxygenated terpenes (??-terpineol and verbenone), sesquiterpenes (??-longipinene, longifolene, E-??-farnesene, ??-cadinene and pentadecane), and diterpenes (manoyl oxide and (+)-pimaral). Of these, longifolene and (+)-pimaral are of particular interest as plausible attractors for the M. galloprovincialis beetle that might find application in the construction of insect bait traps.     

Adsorptive removal of pollutants from water using magnesium ferrite nanoadsorbent: a promising future material for water purification

Environmental Science and Pollution Research - Nanoadsorbents having large specific surface area, high pore volume with tunable pore size, affordability and easy magnetic separation gained much...     

Kinetic studies on the extraction of oil from a new feedstock (Chukrasia tabularis L. seed) for biodiesel production using a heterogeneous catalyst

Environmental Science and Pollution Research - This study has identified a new feedstock Chukrasia tabularis L. (C. tabularis) seed for the production of biodiesel. Oil was extracted from the seeds...     

Synergy optimization for the removal of dye and pesticides from drinking water using granular activated carbon particles in a 3D electrochemical reactor

Environmental Science and Pollution Research - The combination of adsorption on particulate materials and electrochemical oxidation in 3D electrochemical systems is potentially a very efficient...