Field Detector Evaluation of Organic Clay Soils Contaminated with Diesel Fuel

Due to numerous types of uncontrolled petroleum releases into the environment such as leaking storage tanks, spills, and improper disposal of petroleum wastes, there is a need for quicker, more efficient methods to determine the levels of soil contamination for site remediation. The portable field detectors used most often in preliminary site evaluations are the flame ionization detector (FID) and the photoionization detector (PID). This research explored the relationship between these two instruments in analysis of two clay soil sites contaminated with diesel fuel. As in previous research, a log-log linear correlation was found between the PID and FID instruments for diesel fuel-contaminated soil at each site (R 2 > 0.91). Also, the correlation factors (0.64 and 0.60) between the field instruments at each site were found to be similar. It was asserted that either field instrument can be used to delineate the diesel fuel contamination at that site based upon a previously calculated correlation between the two instruments, and an overall numerical correlation between the field instruments can be used at various sites of similar soil and contamination characteristics. The implementation of the relationships between these two instruments could facilitate and accelerate site characterization in the future.     

Evaluation of the efficacy of a portable LIBS system for detection of CWA on surfaces

Laser-induced breakdown spectroscopy (LIBS) is a laser-based optical technique particularly suited for in situ surface analysis. A portable LIBS instrument was tested to detect surface chemical contamination by chemical warfare agents (CWAs). Test of detection of surface contamination was carried out in a toxlab facility with four CWAs, sarin (GB), lewisite (L1), mustard gas (HD), and VX, which were deposited on different substrates, wood, concrete, military green paint, gloves, and ceramic. The CWAs were detected by means of the detection of atomic markers (As, P, F, Cl, and S). The LIBS instrument can give a direct response in terms of detection thanks to an integrated interface for non-expert users or so called end-users. We have evaluated the capability of automatic detection of the selected CWAs. The sensitivity of our portable LIBS instrument was confirmed for the detection of a CWA at surface concentrations above 15 μg/cm². The simultaneous detection of two markers may lead to a decrease of the number of false positive.     

Development of a field test method to evaluate gaseous air cleaner performance in a multizone building

The performance of gaseous air cleaners for commercial and residential buildings has typically been evaluated using test protocols developed for a controlled laboratory chamber or a test duct. It is currently unknown how laboratory measurements relate to the actual performance of an air cleaner installed in a real building. However, to date, there are no air cleaner field test protocols available, thereby limiting the existing field data. The National Institute of Standards and Technology (NIST) has conducted a series of experiments to support test procedure development for evaluating the installed performance of gaseous air cleaning equipment, as well as metrics for characterizing field performance. To date, over 100 experiments have been completed, of which 23 portable air cleaner experiments and 6 in-duct air cleaner experiments are described in this paper. Tests were conducted in a finished three-bedroom/two-bathroom manufactured house equipped with several gas chromatographs to semi-continuously measure air change rates and volatile organic compound concentrations. Experimental variables included air cleaner location, isolation of zones by closing doors, and contaminant source location. For each experiment, air cleaner removal of decane was directly measured using the air cleaner inlet and outlet concentrations, as well as with mass balance analyses using measured room concentrations. With a verified mass balance model, a field performance metric was developed to compare installed whole-building performance to the performance predicted by a laboratory result. The results provide insight into the protocols and metrics that might prove useful for characterizing the field performance of air cleaners as well as the impact of air cleaner removal on zonal concentration levels in a variety of situations.     

Analysis of munitions constituents in groundwater using a field-portable GC-MS

The use of munitions constituents (MCs) at military installations can produce soil and groundwater contamination that requires periodic monitoring even after training or manufacturing activities have ceased. Traditional groundwater monitoring methods require large volumes of aqueous samples (e.g., 2-4 L) to be shipped under chain of custody, to fixed laboratories for analysis. The samples must also be packed on ice and shielded from light to minimize degradation that may occur during transport and storage. The laboratory’s turn-around time for sample analysis and reporting can be as long as 45 d. This process hinders the reporting of data to customers in a timely manner; yields data that are not necessarily representative of current site conditions owing to the lag time between sample collection and reporting; and incurs significant shipping costs for samples.The current work compares a field portable Gas Chromatograph-Mass Spectrometer (GC-MS) for analysis of MCs on-site with traditional laboratory-based analysis using High Performance Liquid Chromatography with UV absorption detection. The field method provides near real-time (within ∼1 h of sampling) concentrations of MCs in groundwater samples. Mass spectrometry provides reliable confirmation of MCs and a means to identify unknown compounds that are potential false positives for methods with UV and other non-selective detectors.     

Estimation of road traffic emission factors from a long term tracer study

Road traffic emissions, one of the largest source categories in megacity inventories, are highly uncertain. It is essential to develop methodologies to reduce these uncertainties to manage air quality more effectively. In this paper, we propose a methodology to estimate road traffic emission factors (EFs) from a tracer experiment and from roadside pollutants measurements. We emitted continuously during about 300 non-consecutive hours a passive tracer from a finite line source placed on one site of an urban street. At the same time, we measured continuously the resulting tracer concentrations at the other side of the street with a portable on-line gas chromatograph. We used n-propane contained in commercial liquid petroleum gas (LPG) as a passive tracer. Propane offers several advantages to traditional tracers (SF6, N2O, CFCs): low price, easily available, non-reactive, negligible global warming potential, and easy to detect with commercial on-line gas chromatographs.The tracer experiment was carried out from January to March 2007 in a busy street of Ho Chi Minh City (Vietnam). Traffic volume, weather information and pollutant concentrations were also measured at the measurement site. We used the results of the tracer experiment to calculate the dilution factors and afterwards we used these dilution factors, the traffic counts and the pollutant concentrations to estimate the EFs. The proposed method assumes that the finite emission line represents the emission produced by traffic in the full area of the street and therefore there is an error associated to this assumption. We use the Computational Fluids Dynamics (CFD) model MISKAM to calculate this error and to correct the HCMC EFs. EFs for 15 volatile organic compounds (VOCs) and NO are reported here. A comparison with available studies reveals that most of the EFs estimated here are within the range of EFs reported in other studies.     

A comparison of Cu, Pb, As, Cd, Zn, Fe, Ni and Mn determined by acid extraction/ICP-OES and ex situ field portable X-ray fluorescence analyses

Total concentrations of Cu, Pb, As, Cd, Zn, Fe, Ni and Mn were determined for 81 soil samples using two types of field portable X-ray fluorescence (FPXRF) system; dual isotope and X-ray tube. FPXRF metal concentrations were statistically compared with analytical results from aqua regia extractions followed by Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES) analysis. The ability of each FPXRF instrument to produce analytical results comparable to the reference method was assessed by linear regression. A high degree of linearity was found for Fe and Pb with the X-ray tube instrument and for Fe, Cu, Pb, Zn, Cd and Mn with the dual source instrument. FPXRF analyser performance improved with increased analysis time for Cu, Mn and Pb, whilst Fe, Zn, Cd, Ni and As showed no significant improvement. Particle size did not influence FPXRF analyser performance. Both the dual isotope and the X-ray tube FPXRF instruments are effective tools for rapid, quantitative assessment of soil metal contamination and for monitoring the efficacy of remediation strategies.     

Quality assured measurements of animal building emissions: gas concentrations

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), methane (CH4), nonmethane hydrocarbons (NMHC), particulate matter <10 microm in diameter, and total suspended particulate from swine and poultry production buildings in the United States. This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with > or =10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH3, H2S, CO2, CH4, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

一台气相色谱仪同时测定陆地生态系统CO2、CH4和N2O排放

通过对气相色谱仪进样、分析气路和阀驱动系统的改造 ,同一台色谱仪可以同时检测空气样品中的CO2 、CH4和N2 O。测试结果表明 ,仪器的灵敏度、分辨率和精密度均很高 ,线性范围符合要求 ;仪器系统能够在野外实验室长期稳定运转 ,可方便用于测定陆地生态系统CO2 、CH4和N2 O排放 ,能快速、准确、可靠地获取观测数据。     

Evaluation of a diode laser based photoacoustic instrument combined with preconcentration sampling for measuring surface–atmosphere exchange of ammonia with the aerodynamic gradient method

We present here a novel instrument for measuring surface–atmosphere exchange fluxes of ammonia. The instrument is the upgraded version of a recently developed near-infrared diode laser based photoacoustic ammonia concentration monitoring instrument, i.e. the original instrument is supplemented with two additional sampling lines, an appropriate gas handling system and an advanced software controlling gradient measurements. As a result of these developments, ammonia concentration can be measured simultaneously at three different heights above the ground and ammonia fluxes can be calculated from these data using the aerodynamic gradient method. The instrument operates fully automatically, requires minimal maintenance and has a temperature controlled, waterproof housing which makes it suitable for measurements even under harsh field conditions. Preliminary tests on stability and accuracy were carried out during two two-week field measurement campaigns, with the three sampling inlets being placed at the same height together with the inlet of a reference instrument. The readings of the three channels agreed well (with correlation coefficients above 0.96). Comparison to reference instruments showed good stability of the photoacoustic instrument, there was no measurable zero-drift or change in sensitivity during the tests. Flux measurements were carried out during a three-week field campaign in southern Scotland over fertilized grassland with reference to a wet-chemical AMANDA instrument in gradient configuration. Ammonia fluxes calculated from the data of the two instruments agreed well. Fluxes up to 2500 ng m^?2 s^?1 were observed after fertilization. The minimum detectable ammonia flux was calculated on the basis of “virtual ammonia fluxes”, from measurements carried out with all inlets at the same height and was found to be ±60 ng m^?2 s^?1 which ensures reliable measurements above intensively managed grasslands or agricultural fields.     

Biological sweetening of energy gases mimics in biotrickling filters

Removal of hydrogen sulfide from waste and energy-rich gases is required, not only because of environmental health and safety reasons, but also because of operational reasons if such gases have to be used for energy generation. A biotrickling filter for the removal of ultra-high concentrations of H2S from oxygen-poor gases is proposed and studied in this work. Two laboratory-scale biotrickling filters were used to study the startup period and to determine the long-term performance of the gas sweetening process. The inlet H2S concentration ranged from 900 to 12000ppmv and two different packing materials were investigated. There was no toxicity effect observed even at a the highest H2S concentration, and maximum elimination capacities of 280 and 250g H2Sm(-3)h(-1) were obtained at gas contact times of 167 and 180s, respectively. Elemental sulfur and sulfate were found to be the most abundant end-products of the biological oxidation of sulfide when operated under microaerophilic conditions. The biotrickling filter was able to quickly recover its nominal performance after different load increases and system shutdowns simulating field operation. The results reported here show that biotreatment can be an interesting alternative to conventional gas sweetening systems normally used for such applications.     

Sensor transition failure in the high flow sampler: Implications for methane emission inventories of natural gas infrastructure

Quantification of leaks from natural gas (NG) infrastructure is a key step in reducing emissions of the greenhouse gas methane (CH₄), particularly as NG becomes a larger component of domestic energy supply. The U.S. Environmental Protection Agency (EPA) requires measurement and reporting of emissions of CH₄ from NG transmission, storage, and processing facilities, and the high-flow sampler (or high-volume sampler) is one of the tools approved for this by the EPA. The Bacharach Hi-Flow Sampler (BHFS) is the only commercially available high-flow instrument, and it is also used throughout the NG supply chain for directed inspection and maintenance, emission factor development, and greenhouse gas reduction programs. Here we document failure of the BHFS to transition from a catalytic oxidation sensor used to measure low NG (~5% or less) concentrations to a thermal conductivity sensor for higher concentrations (from ~5% to 100%), resulting in underestimation of NG emission rates. Our analysis includes both our own field testing and analysis of data from two other studies (Modrak et al., 2012; City of Fort Worth, 2011). Although this failure is not completely understood, and although we do not know if all BHFS models are similarly affected, sensor transition failure has been observed under one or more of these conditions: (1) Calibration is more than ~2 weeks old; (2) firmware is out of date; or (3) the composition of the NG source is less than ~91% CH₄. The extent to which this issue has affected recent emission studies is uncertain, but the analysis presented here suggests that the problem could be widespread. Furthermore, it is critical that this problem be resolved before the onset of regulations on CH₄ emissions from the oil and gas industry, as the BHFS is a popular instrument for these measurements.

Implications: An instrument commonly used to measure leaks in natural gas infrastructure has a critical sensor transition failure issue that results in underestimation of leaks, with implications for greenhouse gas emissions estimates as well as safety.     

Quality Assured Measurements of Animal Building Emissions: Gas Concentrations

Abstract

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH₃), hydrogen sulfide (H₂S), carbon dioxide (CO₂), methane (CH₄), nonmethane hydrocarbons (NMHC), particulate matter <10 µm in diameter, and total suspended particulate from swine and poultry production buildings in the United States.

This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with ≥10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH₃, H₂S, CO₂, CH₄, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

Emission of specific pollutants from a compression ignition engine. Influence of fuel hydrotreatment and fuel/air equivalence ratio

A compression ignition engine is used for the study of the fuel (one reference and one hydrotreated) and the fuel/air equivalence ratio influence on the exhaust emissions of specific pollutants. Under the experimental conditions used, seven hydrocarbons, nine aldehydes and three organic acids are detected in the exhaust gas. No alcohols are detected under these conditions, indicating that these compounds are emitted only if they (or probably other oxygenated compounds) are introduced in the fuel. Fuel hydrotreatment decreases most of the exhaust pollutants, the four toxics and also the quantity of the ozone that could be formed from the exhaust gas. It also changes the composition of exhaust gas: it increases the proportion of methane, benzene, formaldehyde, acetaldehyde, acroleine, and propionic acid, while it decreases the proportion of all other pollutants detected. Fuel/air equivalence ratio also decreases most of the exhaust emissions, the emission of the total toxics and the quantity of the ozone that could be formed. It also changes the proportion of each pollutant in exhaust gas: the percentages of methane, benzene, acetone and acetic acid increase, while those of the other pollutants detected decrease. The majority of the specific pollutants detected corresponds to organic acids, followed by hydrocarbons and aldehydes.     

Detection limits of optical gas imagers as a function of temperature differential and distance

Optical gas imaging (OGI) is an effective tool for detecting gas leaks from process equipment. Despite the fact that OGI has been used for leak detection for over a decade, its detection limit is an elusive performance metric and has not been systematically characterized and quantified like other detection instruments. A substantial body of research has been performed that has shed some light on the OGI detection limits and the factors that dictate the detection limits. The OGI detection limit expressed as ppm-m and ppm now can be quantified as a function of ΔT (differential temperature between the gas plume and the background), the OGI camera type, and the specific gas in question. Furthermore, the OGI detection limit expressed as grams per hour can be calculated based on the ΔT and the distance from the OGI camera to the leak location under common leak survey conditions. For the same OGI camera, the detection limit can vary by several orders of magnitude due to ΔT and distance. The present work has demonstrated how different OGI detection limits can be. More importantly, this work has, for the first time, formulated equations that can be used to determine OGI detection limits with a given set of leak detection conditions. Being able to quantify OGI detection limit and understand the variables that dictate the detection limit is a significant advancement. It will help OGI to become accepted as a mature field instrument. The variables characterized in this work should have an impact on the development of OGI leak survey protocols, such as Appendix K to Code of Federal Regulations 40 CFR Part 60 in the United States. Established detection limits will also help emission inventory for fugitive emissions when OGI is used as the sole leak detection method.

Implications: Optical gas imaging (OGI) has been used for leak detection and control of fugitive volatile organic compound (VOC) emissions and methane emissions due to equipment leaks. However, detection limits of OGI have not been characterized and quantified like other detection instruments. The lack of well-understood detection limits has hindered broader applications of OGI. The work presented in this paper represents important steps that will enable OGI users and policymakers to establish (1) OGI detection limits under various conditions, (2) OGI leak survey criteria for a desired minimum detectable leak size, and (3) maximum potential emissions from the nondetect sources in emission inventory studies.     

Evaluating the capabilities of Aerosol-to-Liquid Particle Extraction System (ALPXS)/ICP-MS for monitoring trace metals in indoor air

This study investigates the application of the Aerosol-to-Liquid Particle Extraction System (ALPXS), which uses wet electrostatic precipitation to collect airborne particles, for multi-element indoor stationary monitoring. Optimum conditions are determined for capturing airborne particles for metal determination by inductively coupled plasma–mass spectrometry (ICP-MS), for measuring field blanks, and for calculating limits of detection (LOD) and quantification (LOQ). Due to the relatively high flow rate (300 L min^?1), a sampling duration of 1 hr to 2 hr was adequate to capture airborne particle-bound metals under the investigated experimental conditions. The performance of the ALPXS during a building renovation demonstrated signal-to-noise ratios appropriate for sampling airborne particles in environments with elevated metal concentrations, such as workplace settings. The ALPXS shows promise as a research tool for providing useful information on short-term variations (transient signals) and for trapping particles into aqueous solutions where needed for subsequent characterization. As the ALPXS does not provide size-specific samples, and its efficiency at different flow rates has yet to be quantified, the ALPXS would not replace standard filter-based protocols accepted for regulatory applications (e.g., exposure measurements), but rather would provide additional information if used in conjunction with filter based methods.

ImplicationsThis study investigates the capability of the Aerosol-to-Liquid Particle Extraction System (ALPXS) for stationary sampling of airborne metals in indoor workplace environments, with subsequent analysis by ICP-MS. The high flow rate (300 L/min) permits a short sampling duration (< 2 hr). Results indicated that the ALPXS was capable of monitoring short-term changes in metal emissions during a renovation activity. This portable instrument may prove to be advantageous in occupational settings as a qualitative indicator of elevated concentrations of airborne metals at short time scales.     

Monitoring personal,indoor, and outdoor exposures to metals in airborne particulate matter: Risk of contamination during sampling,handling and analysis

Rigorous sampling and quality assurance protocols are required for the reliable measurement of personal, indoor and outdoor exposures to metals in fine particulate matter (PM_2.5). Testing of five co-located replicate air samplers assisted in identifying and quantifying sources of contamination of filters in the laboratory and in the field. A field pilot study was conducted in Windsor, Ont., Canada to ascertain the actual range of metal content that may be obtained on filter samples using low-flow (4 L min⁻¹) 24-h monitoring of personal, indoor and outdoor air. Laboratory filter blanks and NIST certified reference materials were used to assess contamination, instrument performance, accuracy and precision of the metals determination. The results show that there is a high risk of introducing metal contamination during all stages of sampling, handling and analysis, and that sources and magnitude of contamination vary widely from element to element. Due to the very small particle masses collected on low-flow 24-h filter samples (median 0.107 mg for a sample volume of approximately 6 m³) the contribution of metals from contamination commonly exceeds the content of the airborne particles being sampled. Thus, the use of field blanks to ascertain the magnitude and variability of contamination is critical to determine whether or not a given element should be reported. The results of this study were incorporated into standard operating procedures for a large multiyear personal, indoor and outdoor air monitoring campaign in Windsor.     

Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.     

Influence of several fungicides on the antioxidant activity of red wines (var. Monastrell)

The antioxidant activity of wines obtained from grapes treated with six fungicides (famoxadone, fenhexamid, fluquinconazole, kresoxim-methyl, quinoxyfen and trifloxystrobin) was investigated. Two field trials in triplicate were carried out for each formulation of the fungicide at the recommended dose of the manufacturer. The first trial was carried out under good agricultural practices (GAP), following the recommended pre-harvest interval, and the second one under critical agricultural practices (CAP) that involves treating the same field just before the harvest. The residue levels were determined by gas and liquid chromatography coupled to mass detectors (GC-MS and LC-MS). The antioxidant activity was determined in the wines obtained from the thirteen trials including one control, six from treated grapes obeying the pre-harvest interval, and six from grapes treated at the day of harvest or at most unfavorable conditions. Elimination of 40–100% of the initial fungicide residues present in grapes was observed during the wine-making process. It can be inferred from the results that the use of these fungicides did not produce any decrease of the antioxidant activity in the wines (7.19 ± 0.22 mmol Trolox/L for the blank wine versus a range of 6.45 ± 0.82 mmol Trolox/L to 10.06 ± 0.59 mmol Trolox/L for the treated wines) at the pre-harvest interval and most unfavorable conditions. Nevertheless, the presence of famoxadone, kresoxim-methyl and quinoxyfen increased the antioxidant activity and this was directly related to their residue levels in the grapes. Also, the wine phenolic composition was altered in variable intensity by the presence of the fungicide residues.