Performance Characteristics of Instrumental Methods for Monitoring Sulfur Dioxide

The performance characteristics of commercially available sulfur dioxide monitors were determined. Con-ductimetric, colorimetric, and coulometric analyzers were investigated. During this phase of the study, characteristics that were more closely related to field operation were studied. These included comparability of data among the instruments over a period of time, weekly calibration drift, maintenance requirements (including operating cost), unattended operation performance, and the effect of rotameter changes on calibration. The methodology and apparatus used to determine each operational parameter are described. The results of this study should be useful in the selection of instruments for monitoring sulfur dioxide.     

Performance Characteristics of Instrumental Methods for Monitoring Sulfur Dioxide

The performance characteristics of commercially available continuous sulfur dioxide monitors were determined. Conductimetric, colorimetric, and coulometric analyzers were investigated. The study was conducted to develop information on such instrument characteristics as stability, sensitivity, response time, collection efficiency, and response to interfering substances. The methodology and apparatus used to determine each operational parameter are described. The instrument performance data developed in this study should be useful to those involved in selection of instrumental methods for monitoring atmospheric sulfur dioxide.     

Polar organic chemical integrative sampler (POCIS) uptake rates for 17 polar pesticides and degradation products: laboratory calibration

Polar organic chemical integrative samplers (POCIS) are useful for monitoring a wide range of chemicals, including polar pesticides, in water bodies. However, few calibration data are available, which limits the use of these samplers for time-weighted average concentration measurements in an aquatic medium. This work deals with the laboratory calibration of the pharmaceutical configuration of a polar organic chemical integrative sampler (pharm-POCIS) for calculating the sampling rates of 17 polar pesticides (1.15?≤?logK _ow?≤?3.71) commonly found in water. The experiment, conducted for 21 days in a continuous water flow-through exposure system, showed an integrative accumulation of all studied pesticides for 15 days. Three compounds (metalaxyl, azoxystrobine, and terbuthylazine) remained integrative for the 21-day experiment. The sampling rates measured ranged from 67.9 to 279 mL?day^?1 and increased with the hydrophobicity of the pesticides until reaching a plateau where no significant variation in sampling rate is observed when increasing the hydrophobicity.     

A Comparison Study of Various Types of Ozone and Oxidant Detectors Which Are Used for Atmospheric Air Sampling

Four continuous automatic analyzers for measurement of atmospheric levels of ozone were used in a calibration and field study. These were (1) a colorimetric instrument based upon detection of iodine released from neutral potassium iodide reagent, {2) a coulometric instrument utilizing the polarization current as a measurement of iodine released by ozone in a cell contacted by potassium iodide reagent, (8) a galvanic cell measuring bromine release by ozone, and (4) an ultraviolet photometer. Some ozone determinations by the manual rubber cracking procedure were included. After calibration with ozone the average relative response to atmospheric ozone levels for each instrument was determined using the colorimetric oxidant analyzer as an arbitrary standard. These responses ranged from 77 percent for the galvanic cell 90 percent for the photometer. The instrument of choice for any given application would seem to be governed by requirements for precision specificity, portability, reliability, and ease of operation.     

Ten-Year Ozone Trends in California and Texas

Ozone trends have been developed for 50 California sites located in six basins and for 15 Texas sites in two regions. All data were obtained directly from state or local monitoring agencies and have been standardized to the current ultraviolet calibration basis. Rigorous standards of data representativeness and statistical validity have been adhered to throughout. The effect of monitoring variance upon apparent trends is reviewed as well as implications of this work for the ozone control strategy. Trends for 1973-82 for three key robust ozone statistics were developed in detail and analyzed. These are: annual average, annual hours >120 ppb and average daily maximum hour (May through October). Summaries for three other statistics including annual maximum hour are also included as well as composite trends for California basins and Texas regions. The statistical significance of all trends is discussed.     

Characterizing sources of nitrate leaching from an irrigated dairy farm in Merced County, California

Dairy farms comprise a complex landscape of groundwater pollution sources. The objective of our work is to develop a method to quantify nitrate leaching to shallow groundwater from different management units at dairy farms. Total nitrate loads are determined by the sequential calibration of a sub-regional scale and a farm-scale three-dimensional groundwater flow and transport model using observations at different spatial scales. These observations include local measurements of groundwater heads and nitrate concentrations in an extensive monitoring well network, providing data at a scale of a few meters and measurements of discharge rates and nitrate concentrations in a tile-drain network, providing data integrated across multiple farms. The various measurement scales are different from the spatial scales of the calibration parameters, which are the recharge and nitrogen leaching rates from individual management units. The calibration procedure offers a conceptual framework for using field measurements at different spatial scales to estimate recharge N concentrations at the management unit scale. It provides a map of spatially varying dairy farming impact on groundwater nitrogen. The method is applied to a dairy farm located in a relatively vulnerable hydrogeologic region in California. Potential sources within the dairy farm are divided into three categories, representing different manure management units: animal exercise yards and feeding areas (corrals), liquid manure holding ponds, and manure irrigated forage fields. Estimated average nitrogen leaching is 872 kg/ha/year, 807 kg/ha/year and 486 kg/ha/year for corrals, ponds and fields respectively. Results are applied to evaluate the accuracy of nitrogen mass balances often used by regulatory agencies to assess groundwater impacts. Calibrated leaching rates compare favorably to field and farm scale nitrogen mass balances. These data and interpretations provide a basis for developing improved management strategies.     

Calibration and field performance of membrane-enclosed sorptive coating for integrative passive sampling of persistent organic pollutants in water

Membrane-enclosed sorptive coating (MESCO) is a miniaturised monitoring device that enables integrative passive sampling of persistent, hydrophobic organic pollutants in water. The system combines the passive sampling with solventless preconcentration of organic pollutants from water and subsequent desorption of analytes on-line into a chromatographic system. Exchange kinetics of chemicals between water and MESCO was studied at different flow rates of water, in order to characterize the effect of variable environmental conditions on the sampler performance, and to identify a method for in situ correction of the laboratory-derived calibration data. It was found that the desorption of chemicals from MESCO into water is isotropic to the absorption of the analytes onto the sampler under the same exposure conditions. This allows for the in situ calibration of the uptake of pollutants using elimination kinetics of performance reference compounds and more accurate estimates of target analyte concentrations. A field study was conducted to test the sampler performance alongside spot sampling. A good agreement of contaminant patterns and water concentrations was obtained by the two sampling techniques.     

Instrumenting Light Aircraft for Air Pollution Research

Light aircraft and helicopters have been occasionally used to conduct aerial traverses for a single pollutant or atmospheric tracer. The continuous analyzer or sample collector is temporarily tied down with a seat belt or hand held. Flight variables are visually observed and written on the recorder chart, a notebook or possibly voice-recorded on a portable tape recorder. The versatile airborne instrumentation package described can measure and record up to 27 pollutant and flight variables from a Cessna Skymaster center-line thrust, light twin. Real-time analysis instrumentation include non-dispersive infrared analyzers for CO₂, CO, and hydrocarbons, conductivity and coulometric analyzers for sulfur dioxide and sulfur-containing gases, and Charlson-Ahlquist visual range nephelometer. A Battelle “bulk sampler” is used to collect particulates for weighing and microscopic examination. Indicated air speed, altitude, rate of climb, magnetic heading, temperature, and relative humidity are continuously measured. All variables are sequentially recorded on a 7-track, 200 bit per second, 27-channel, magnetic tape data logging system. Measured variables are recorded once each 0.3 to 0.8 sec—equivalent to 33-100 ft of traversedepending upon the number of variables recorded (i.e., between 9 and 27) when flying at 90 mph. Tape data are reduced directly by IBM 360 computer to a digital print-out or from tape to an X-Y analog plot.     

水环境监测实验室的质量控制和质量保证

质量控制和质量保证是水环境监测工作的重要组成部分,质量体系是实验室内部实施质量管理的法规,覆盖了监测样品、监测过程、仪器设备、人员素质、设施与环境、量值溯源与校准、检验方法和化学试剂等全部质量控制要求。能够准确地反应水环境质量现状和预测污染的发展趋势。     

Uptake rates of alkylphenols, PAHs and carbazoles in semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS)

Passive sampling devices provide a useful contribution to the monitoring of contaminants in the aquatic environment. However, calibration data needed for the calculation of water concentrations from sampler accumulations are restricted to a limited number of compound classes. Thus uptake of a range of alkylated phenols (AP), polycyclic aromatic hydrocarbons (PAH) and carbazoles was determined for semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS) using a flow through exposure system. Sampling rates ranged from 0.02 to 0.26 l d(-1) for POCIS and 0.02 to 13.83 l d(-1) for SPMDs. Observed SPMD uptake was also compared to that predicted by an empirical model including the use of performance reference compounds (PRCs). Predicted sampling rates did not differ by more than a factor of 1.3 from experimental values for PAH, providing further evidence that the PRC approach can be successfully used to determine in situ sampling rates for these compounds. Experimental sampling rates for AP in SPMDs were, however, much lower than predicted. This discrepancy was too large to be explained by small uncertainties in the calibration system or in the calculations. Based on these data we conclude that while hydrophobic AP are accumulated by SPMDs their partitioning cannot be predicted from their logK(ow) using current methods. Due to this lower than expected uptake, sampling rates were only higher in SPMDs than POCIS in the range of logK(ow)>5.0. Simultaneous deployment of both sampler types allows the study of compounds with a broad range of physicochemical properties.     

The nonlinearity and related band strength of carbon monoxide when applied in ambient air measurement using open long-path Fourier transform infrared spectrometry

The accuracy of CO concentration determination by open-path Fourier transform infrared (FTIR) spectrometry has been re-evaluated in detail. The evaluation focuses on the correction of the calibration curve--the integrated intensity of a standard spectrum--that is used as a comparison spectrum when doing quantitative analysis of CO. Results show that the calibration curve (with 0.5 cm(-1) or 1 cm(-1) resolution) is apparently inclined to be nonlinear under standard conditions, and that the threshold point of nonlinearity is approximately 0.1 atm-cm. Two commercial FTIR field monitoring systems have been used to investigate the nonlinearity trend. The experimental method consists of using open-path FTIR systems in combination with nondispersive infrared (NDIR) monitors to establish the calibration curve in a semi-closed corridor The results have been double-checked using closed-cell dynamic equilibrium systems. When the optical density is larger than a certain value, the curves begin to bend, and when the optical density approaches zero, the band strength is around 178 +/- 3 atm(-1) cm(-2) and 173 +/- 2 atm(-1) cm(-2), respectively, for 0.5 and 1 cm(-1) resolution at standard temperature and pressure (STP). These values are quite different from other published data that have been acquired by the pressurized method or by high-resolution (<0.006 cm(-1)) spectrometers. It is thought that a higher accuracy is achieved when these new calibration results are used to quantify the CO concentration. The error in concentration determination within 0.1 optical density is less than 2%, and that in the higher optical density region is less than 5%.     

The Nonlinearity and Related Band Strength of Carbon Monoxide When Applied in Ambient Air Measurement Using Open Long-Path Fourier Transform Infrared Spectrometry

ABSTRACT

The accuracy of CO concentration determination by open-path Fourier transform infrared (FTIR) spectrometry has been re-evaluated in detail. The evaluation focuses on the correction of the calibration curve—the integrated intensity of a standard spectrum—that is used as a comparison spectrum when doing quantitative analysis of CO. Results show that the calibration curve (with 0.5 cm^-1 or 1 cm^-1 resolution) is apparently inclined to be nonlinear under standard conditions, and that the threshold point of nonlinearity is ~0.1 atm-cm. Two commercial FTIR field monitoring systems have been used to investigate the nonlinearity trend. The experimental method consists of using open-path FTIR systems in combination with nondispersive infrared (NDIR) monitors to establish the calibration curve in a semi-closed corridor. The results have been double-checked using closed-cell dynamic equilibrium systems.

When the optical density is larger than a certain value, the curves begin to bend, and when the optical density approaches zero, the band strength is around 178 ± 3 atm^-1 cm^-2 and 173 ± 2 atm^-1 cm^-2, respectively, for 0.5 and 1 cm^-1 resolution at standard temperature and pressure (STP). These values are quite different from other published data that have been acquired by the pressurized method or by high-resolution     

Fine PM measurements: personal and indoor air monitoring

This review compiles personal and indoor microenvironment particulate matter (PM) monitoring needs from recently set research objectives, most importantly the NRC published "Research Priorities for Airborne Particulate Matter (1998)". Techniques and equipment used to monitor PM personal exposures and microenvironment concentrations and the constituents of the sampled PM during the last 20 years are then reviewed. Development objectives are set and discussed for personal and microenvironment PM samplers and monitors, for filter materials, and analytical laboratory techniques for equipment calibration, filter weighing and laboratory climate control. The progress is leading towards smaller sample flows, lighter, silent, independent (battery powered) monitors with data logging capacity to store microenvironment or activity relevant sensor data, advanced flow controls and continuous recording of the concentration. The best filters are non-hygroscopic, chemically pure and inert, and physically robust against mechanical wear. Semiautomatic and primary standard equivalent positive displacement flow meters are replacing the less accurate methods in flow calibration, and also personal sampling flow rates should become mass flow controlled (with or without volumetric compensation for pressure and temperature changes). In the weighing laboratory the alternatives are climatic control (set temperature and relative humidity), and mechanically simpler thermostatic heating, air conditioning and dehumidification systems combined with numerical control of temperature, humidity and pressure effects on flow calibration and filter weighing.     

The continuous analysis of nitrate and ammonium in aerosols by the steam jet aerosol collector (SJAC): extension and validation of the methodology

Classical methodology based on the application of filters for sampling, followed by extraction and analysis, introduces severe artifacts for semi-volatile compounds like ammonium nitrate. These filter methods do not meet the requirements for the assessment of the impact of aerosols on acidification, air quality and especially on the radiative balance, in terms of required speed, detection limits and selectivity. These artifacts are avoided by using a steam jet aerosol collector sampler, based on scavenging of aerosols by droplet formation, in combination with on-line analytical techniques such as ion-chromatography for nitrate and membrane separation followed by conductivity detection for ammonium. The SJAC sampler combines very low blanks with high efficiency of collection of particles. The ammonium detector and the IC system, based on 1-point internal standard calibration in combination with correction for curved calibration graphs, enables detection of ammonium and nitrate at background conditions, the detection limit is about 0.02 μg m⁻³ of ammonium and nitrate. Accuracy is, depending on ambient concentration, in the order of 5–10% relative, at a range of 0.05–50 μg m⁻³. The time resolution is 15–120 min, depending on required detection limit, and is short enough for continuously monitoring the chemical composition of aerosols. Quality assurance and quality control experiments and intercomparison experiments with classical filter methods, thermo-denuder systems, denuder difference methods and other continuous monitoring techniques have shown that the results are reliable. The instrument has successfully been employed in field campaigns in Europe and the US.     

Monitoring of Atmospheric Aerosol Parameters with the Integrating Nephelometer

The integrating nephelometer of Beuttel and Brewer has been adapted successfully for continuous, objective monitoring of atmospheric aerosols. The paper includes a summary of work done to date with this improved device. In particular, the following points are discussed: (1) the design and operation of the instrument; (2) calibration of the instrument; (3) correlation of nephelometer output to the mass concentration of atmospheric aerosol; (4) correlation of nephelometer output with visual range; (5) the wavelength dependent nephelometer and the regularity of the wavelength dependence of haze; and (6) application of integrating nephelometer to mobile reconnaissance of aerosols. The utility of the integrating nephelometer for monitoring visibility and aerosol mass concentration is also emphasized.     

Development of Criteria for Siting Air Monitoring Stations

A critical problem arises if one attempts to compare data from air monitoring stations in different cities, because there are so many differences in monitoring site locations. Some air monitoring stations are on the 6 th and 8 th floors of tall buildings in downtown areas; some are at ground level beside streets with heavy traffic; some are in residential areas with little traffic or industry; and some are in suburban or nonurban areas. Unfortunately, there is ample evidence that the location of a monitoring station relative to nearby sources (such as highways) affects the values observed at the station, particularly for carbon monoxide and other vehicular pollutants. Thus, a standardized system of site selection, such as the one proposed here, appears essential to improve the comparability and meaningfulness of data obtained from different air monitoring stations throughout the Nation.     

Data fusion modeling for groundwater systems

Engineering projects involving hydrogeology are faced with uncertainties because the earth is heterogeneous, and typical data sets are fragmented and disparate. In theory, predictions provided by computer simulations using calibrated models constrained by geological boundaries provide answers to support management decisions, and geostatistical methods quantify safety margins. In practice, current methods are limited by the data types and models that can be included, computational demands, or simplifying assumptions. Data Fusion Modeling (DFM) removes many of the limitations and is capable of providing data integration and model calibration with quantified uncertainty for a variety of hydrological, geological, and geophysical data types and models. The benefits of DFM for waste management, water supply, and geotechnical applications are savings in time and cost through the ability to produce visual models that fill in missing data and predictive numerical models to aid management optimization. DFM has the ability to update field-scale models in real time using PC or workstation systems and is ideally suited for parallel processing implementation. DFM is a spatial state estimation and system identification methodology that uses three sources of information: measured data, physical laws, and statistical models for uncertainty in spatial heterogeneities. What is new in DFM is the solution of the causality problem in the data assimilation Kalman filter methods to achieve computational practicality. The Kalman filter is generalized by introducing information filter methods due to Bierman coupled with a Markov random field representation for spatial variation. A Bayesian penalty function is implemented with Gauss–Newton methods. This leads to a computational problem similar to numerical simulation of the partial differential equations (PDEs) of groundwater. In fact, extensions of PDE solver ideas to break down computations over space form the computational heart of DFM. State estimates and uncertainties can be computed for heterogeneous hydraulic conductivity fields in multiple geological layers from the usually sparse hydraulic conductivity data and the often more plentiful head data. Further, a system identification theory has been derived based on statistical likelihood principles. A maximum likelihood theory is provided to estimate statistical parameters such as Markov model parameters that determine the geostatistical variogram. Field-scale application of DFM at the DOE Savannah River Site is presented and compared with manual calibration. DFM calibration runs converge in less than 1 h on a Pentium Pro PC for a 3D model with more than 15,000 nodes. Run time is approximately linear with the number of nodes. Furthermore, conditional simulation is used to quantify the statistical variability in model predictions such as contaminant breakthrough curves.     

Carbon Monoxide Levels in Athletes during Exercise in an Urban Environment

ABSTRACT

Gas phase concentrations of individual polycyclic aromatic hydrocarbons (PAHs) were measured in real time in combustion products from a co-flow diffusion flame using laser photoionization (LP) time-of-flight mass spectrometry (TOF/MS). In particular, a naphthalene detection sensitivity of 4 parts per billion (ppb) was demonstrated. The use of calibration mixtures with argon indicated the feasibility of naphthalene detection at about 45 parts per trillion (ppt) at a signal-to-noise (S/N) ratio of 20. This suggests the possibility of low-ppt level detection at a S/N of 1. The novelty of the system is the use of a heated sampling probe and a continuously purged, heated-pulse valve that was positioned close to the ionization zone, thereby allowing the generation of photoions in the high-density region of the sample jet, where concentrations of PAH are high. Because the system developed allows for the real time detection of select species, it represents a useful tool in continuous emissions monitoring (CEM) for environmental compliance as well as direct process control.     

A study on the characteristics of silt loading on paved roads in the Seoul metropolitan area using a mobile monitoring system

This study is considered the first attempt to apply a mobile monitoring system to estimating silt loading on paved roads in a mega-city such as the Seoul metropolitan area. Using a mobile monitoring system developed in 2005, we estimated silt loadings on representative paved roads in the Seoul metropolitan area, including the city of Incheon, over a period of 3 yr. The temporal and spatial characteristics of silt loading were investigated for the carefully selected roads that may reflect the characteristics of the cities of Seoul and Incheon. In this study, changes in the average silt loading values were investigated in terms of land use, the temporal resolution of data acquisition (i.e., seasonal, daily, three-hour scale), the road width or number of lanes, and rainfall, which may affect the characteristics of the average silt loading significantly. It was found that the advantages of using the mobile monitoring system are its ability to obtain a large quantity of silt loading data in a short period of time and over a wide area and its ability to create a silt loading map showing the relative magnitude of silt loading in relation to a specific location, which makes it possible to easily locate hot spots.

Implications: This study may be considered the first practical application of a mobile monitoring system to obtain the silt loading data on paved roads in a mega-city such as Seoul. It was found that the advantages of using the mobile monitoring system are its ability to obtain a large quantity of silt loading data in a short period of time and over a wide area and its ability to create a silt loading map showing the relative magnitude of silt loading in relation to a specific location, which makes it possible to easily locate hot spots to be cleaned cost-effectively by city officials.     

Evaluation of a Coulometric Procedure For the Detection of Strong and Weak Acid Components in Rainwater

A rapid coulometric procedure is described for the determination of non-volatile strong and non-volatile and volatile weak acids in rain samples. A constant current with known amperage is passed into a measured volume of the sample, with and without volatiles, and the changes in the electromotive force monitored with a potentiometer. Molarities of the different acids are calculated by plotting the function of the electromotive force against time in seconds according to Gran’s theory. The method is useful at acid concentrations of 10^-6 to 10^-4 M.