Texas Regulation Requires Control of Opacity Using Instrumental Measurements

For over four years, a Texas air pollution control regulation has been in force which permits use of a stack mounted transmissometer instrument to measure visible emissions, thus avoiding the necessity for visual observations. Many types of industrial plants have installed instruments, and extensive experience has been obtained with this method of measurement and control. Plant operators and enforcement officials have expressed a strong preference for this method, both to demonstrate compliance and to provide data to aid in operating control equipment. Some operational problems have been encountered, but these usually can be overcome with proper care. Because of the advantages obtained with this regulation a new regulation has been adopted which makes the instrumental method mandatory for large sources of visible emissions.     

Elemental carbon (EC) and black carbon (BC) measurements with a thermal method and an aethalometer at the high-alpine research station Jungfraujoch

A thermal method for the determination of ambient organic carbon (OC) and elemental carbon (EC) concentrations in carbonaceous samples was further developed. Possible artifacts were investigated and were shown to be low. Good agreement of EC data with the German VDI reference method was found and detection limits were 1.3 μg for EC and 1.8 μg for OC. The method was applied to samples obtained with an aethalometer from an ongoing campaign at the high-alpine research station Jungfraujoch from July 1995 to June 1997. Measurements of EC concentration were used to derive a new site-specific calibration factor (instrumental absorption efficiency α_API) for the determination of the black carbon (BC) concentration. Despite a distinct seasonal cycle in BC, of around one order in magnitude with a maximum in summer and minimum in winter, α_API exhibited no significant seasonality. The derived calibration factor for the Jungfraujoch, α_API=9.3±0.4 m² g^-1, is lower than the manufacturer calibration by a factor ∼2. The results confirm the observation that the aethalometer determined BC concentration, underestimates the true value at remote sites, when the manufacturer calibration is used.     

Determination of S02 Emission from Oil Combustion Sources by Fuel Analyses and S02/C02 Relations

The current S0₂ emission test methods, based on wet chemistry, are time consuming and costly. Final results depend on at least 10 separate measurements of quantities which may introduce significant errors due to human factors especially under unfavorable field environment. Performance evaluation of several promising S0₂ instrumental methods indicated that results were reliable and reproducible, but instrumental problems still exist. The problems were found to be calibration, mechanical and electronic components, and sample conditioning system. An alternative method proposed requires only two separate analyses: ultimate fuel analysis and stack gas analysis for C0₂. This method can be further simplified with reasonable accuracy by a single measurement of sulfur in the fuel if results are corrected to 12% C0₂. The method can be a useful addition to the current methods, especially if cost and manpower preclude actual stack tests. A test program was conducted at four industrial and utility power plants. Results are presented with discussion to show the application and validity of the simplified method.     

Development,Calibration and Use of a Plume Evaluation Training Unit

The Bay Area Air Pollution Control District adopted a regulation limiting plume visibility in terms of the Ringelmann Chart and also in terms of obscuration of the observer’s view. Since both limitations were adopted in terms requiring the judgment of an observer, preparation for enforcement required development and calibration of a training unit, so that inspectors could be qualified to testify as expert witnesses under this regulation.

This paper summarizes the design, calibration and use of the training unit developed for this purpose.     

Screening of bean cultivars for their response to ozone as evaluated by visible symptoms and leaf chlorophyll fluorescence

Fourteen Italian cultivars of Phaseolus vulgaris were exposed to a single pulse of ozone (O(3), 150 nl l(-1)) or to filtered air (<3 nl l(-1)) for 3.5 h. O(3) sensitivity was assessed by recording the extent of visible symptoms, effects on chlorophyll (Chl) content and changes in Chl a fluorescence parameters. This paper reports the results of an initial screening of 14 bean cultivars that was used to select a small number of cultivars for further work. Seven cultivars showed visible symptoms of injury in the range of 2-60 h after the end of the O(3) fumigation. O(3) significantly depressed total Chl content in most cultivars and a significant correlation was found between Chl content and visible symptoms. Most cultivars showed a significant change in the F(v)/F(m) ratio, even when there were no visual symptoms. There was no relationship between the extent of visual symptoms and quenching coefficients, indicating that these parameters were of no use in the determination of sensitivity to O(3) stress.     

Validation of a multiclass multiresidue method and monitoring results for 210 pesticides in fruits and vegetables by gas chromatography-triple quadrupole mass spectrometry

A rapid, sensitive, accurate and reliable multiresidue method for the identification and quantification of 210 relevant pesticides in four representative fruit and vegetable commodities (tomato, potato, spring onion and orange) has been developed and validated by gas chromatography in tandem with triple quadrupole mass spectrometry. The method has been fully validated and applied to 292 samples from different countries. Prior to instrumental analysis, an extraction procedure based on a sample extraction of multiclass analytes, using the ethyl acetate method was employed. Mass spectrometric conditions were individually optimized for each compound in the selected reaction monitoring (SRM) mode to achieve maximum sensitivity. The pesticides were separated in less than 25 min. This was followed by an exhaustive control of the retention times. The Retention Time Locking Method was applied, working at a constant pressure throughout the analysis. System maintenance was reduced by using a purged capillary flow device that provided backflush capabilities by reversing column flow immediately after elution of the last compound of interest. Istotopically labelled internal standards were employed to improve the quality of the analytical results.     

Estimate of the uncertainty in measurement for the determination of mercury in seafood by TDA AAS

An approach for the estimate of the uncertainty in measurement considering the individual sources related to the different steps of the method under evaluation as well as the uncertainties estimated from the validation data for the determination of mercury in seafood by using thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) is proposed. The considered method has been fully optimized and validated in an official laboratory of the Ministry of Agriculture, Livestock and Food Supply of Brazil, in order to comply with national and international food regulations and quality assurance. The referred method has been accredited under the ISO/IEC 17025 norm since 2010. The approach of the present work in order to reach the aim of estimating of the uncertainty in measurement was based on six sources of uncertainty for mercury determination in seafood by TDA AAS, following the validation process, which were: Linear least square regression, Repeatability, Intermediate precision, Correction factor of the analytical curve, Sample mass, and Standard reference solution. Those that most influenced the uncertainty in measurement were sample weight, repeatability, intermediate precision and calibration curve. The obtained result for the estimate of uncertainty in measurement in the present work reached a value of 13.39%, which complies with the European Regulation EC 836/2011. This figure represents a very realistic estimate of the routine conditions, since it fairly encompasses the dispersion obtained from the value attributed to the sample and the value measured by the laboratory analysts. From this outcome, it is possible to infer that the validation data (based on calibration curve, recovery and precision), together with the variation on sample mass, can offer a proper estimate of uncertainty in measurement.     

Quantification of ecotoxicological tests based on bioluminescence using Polaroid film

Assays based on the measurement of bacterial luminescence are widely used in ecotoxicology. Bacterial strains responding either to general toxicity or specific pollutants are rapid, cost-effective and easy to use. However, quantification of the signal requires relatively expensive instrumentation. We show here that the detection of luminescence of BioTox, a Vibrio fischeri-based toxicity test, and of a specific recombinant bacterial strain for arsenic determination, is possible using common Polaroid film. The exposed films can be used for visual or computer-assisted quantification of the signal. Qualitative visual comparison to standards can be used in the rapid and relatively accurate estimation of toxicity or pollutant concentration. The computer-assisted method significantly improves the accuracy and quantification of the results. The results obtained by computer-assisted quantification were in good agreement with the values obtained with a luminometer.     

Importance of considering intraborehole flow in solute transport modeling under highly dynamic flow conditions

Correct interpretation of tracer test data is critical for understanding transport processes in the subsurface. This task can be greatly complicated by the presence of intraborehole flows in a highly dynamic flow environment. At a new tracer test site (Hanford IFRC) a dynamic flow field created by changes in the stage of the adjacent Columbia River, coupled with a heterogeneous hydraulic conductivity distribution, leads to considerable variations in vertical hydraulic gradients. These variations, in turn, create intraborehole flows in fully-screened (6.5m) observation wells with frequently alternating upward and downward movement. This phenomenon, in conjunction with a highly permeable aquifer formation and small horizontal hydraulic gradients, makes modeling analysis and model calibration a formidable challenge. Groundwater head data alone were insufficient to define the flow model boundary conditions, and the movement of the tracer was highly sensitive to the dynamics of the flow field. This study shows that model calibration can be significantly improved by explicitly considering (a) dynamic flow model boundary conditions and (b) intraborehole flow. The findings from this study underscore the difficulties in interpreting tracer tests and understanding solute transport under highly dynamic flow conditions.     

Spiking of performance reference compounds in low density polyethylene and silicone passive water samplers

A method for spiking performance reference compounds (PRCs) into low density polyethylene (LDPE) and silicone polymers is described. This method is based on equilibration of the polymers in aqueous/methanolic solutions of PRCs. Equilibration times range from minutes to hours for perdeuterated polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) with a hydrophobicity in the range 3.9 < logKow < 7.7. Best results were obtained for methanol-water ratios of 80/20 (v/v). The method allows for the use of PRCs for in situ calibration of the uptake kinetics of these solvent-free sampling phases in a similar way as for semipermeable membrane devices (SPMDs).     

Dioxin screening in fish product by pattern recognition of biomarkers

Two alternative, cost- and time-effective dioxin screening methods relying on two categories of potential lipid biomarkers were investigated. A dioxin range varying from 1.1 to 47.1 pg PCDD/F TEQ-WHO/g lipid using 64 fish meal samples was used for model calibration. The methods were based on multivariate models using either (1) fatty acid composition monitored by GC-FID or (2) fluorescence landscape signals analysed using the PARAFAC model and in both cases predicting dioxin content as pgPCDD/F TEQ-WHO/g lipid. In both cases, Partial Least Squares (PLS) regression was performed for predicting the dioxin content of a sample. The GC-FID data analyses was based on automatic peak alignment and integration, enabling extraction of the area of 140 peaks from the gas chromatograms, as opposed to the 31 fatty acids usually considered for fish oil characterisation. In addition to classic PLS employing the whole dataset for calibration, a two-step local PLS modeling approach was performed based upon an initial selection of k number of calibration samples providing the best match to the prediction sample using a so-called k Nearest Neighbors (kNN) approach, then followed by PLS calibration on these kNN selected samples for dioxin prediction. Fluorescence spectroscopy offers a promising non-invasive and ultra-rapid technique, with less than two minutes analysis time. However, fluorescence spectroscopy using the pattern recognition "kNN-PLS" yielded a correlation of 0.76 (r2) and a high root mean square error of prediction of 11.4 pg PCDD/F TEQ-WHO/g lipid. The predictions were improved when the PLS calibration was performed on all the sample with a root mean square error of prediction of 7.0 pg PCDD/F TEQ-WHO/g lipid. Unfortunately, these results failed to demonstrate the potential of fluorophore monitoring as a screening method. In contrast, the overall best screening performance was obtained with the fatty acid profile, when the kNN-PLS combination employed for pattern recognition (kNN) all the areas of the 140 detected peaks and the PLS regression used the areas of 46 selected peaks. This "kNN-PLS" prediction with three latent variables and based upon the 12 nearest neighbors selected out of the 64 x 2 fatty acid profiles (duplicate analyses), yielded a correlation of 0.85 (r2) and a root mean square error of prediction of 2.1 pg PCDD/F TEQ-WHO/g lipid and resulted in a total analysis time of one and half hour per sample.     

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%.     

A rapid spectrophotometric determination of persulfate anion in ISCO

Due to a gradual increase in the use of persulfate as an in situ chemical oxidation (ISCO) oxidant, a simple measurement of persulfate concentration is desirable to analyze persulfate distribution at designated time intervals on/off a site. Such a distribution helps evaluate efficacy of ISCO treatment at a site. This work proposes a spectrophotometric determination of persulfate based on modification of the iodometric titration method. The analysis of absorption spectra of a yellow color solution resulting from the reaction of persulfate and iodide in the presence of sodium bicarbonate reveals an absorbance at 352 nm, without significant interferences from the reagent matrix. The calibration graph was linear in the range of persulfate solution concentration of 0-70 mM at 352 nm. The proposed method is validated by the iodometric titration method. The solution pH was at near neutral and the presence of iron activator does not interfere with the absorption measurement. Also, analysis of persulfate in a groundwater sample using the proposed method indicates a good agreement with measurements by the titration method. This proposed spectrophotometric quantification of persulfate provides a simple and rapid method for evaluation of ISCO effectiveness at a remediation site.     

Evaluation of the impact of matrix effects in LC/MS measurement on the accurate quantification of neonicotinoid pesticides in food by isotope-dilution mass spectrometry

The use of isotope-labeled internal standards is the most widely accepted approach to overcome the matrix effects on quantification of pesticides in food by LC/MS. We evaluated the impact of the matrix effects on quantification of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam, in food by using deuterated internal standards. The calibration curves for each pesticide were obtained by using matrix-free and matrix-matched calibration solutions with blank brown rice, carrot, and green onion extracts. For brown rice and carrot, the matrix effects were not observed. In contrast, the slopes of calibration curves for each pesticide were influenced by presence of green onion extracts in calibration solutions (variability of the slopes was 4–9%), because the ratios of peak area for native pesticide to those for internal standards were influenced by matrix. The spike-and-recovery test with green onion was also performed. The analytical values obtained by using matrix-free calibration solution were biased from the spiked concentration, whereas those obtained by using matrix-matched calibration solution were comparable to the spiked concentration. These results indicate that matrix-matched calibration solution should be used for accurate quantification of neonicotinoid pesticides in food by LC/MS using deuterated internal standards.     

Assessment of opacimeter calibration according to International Standard Organization 10155

This paper compares the calibration method for opacimeters issued by the International Standard Organization (ISO) 10155 with the manual reference method for determination of dust content in stack gases. ISO 10155 requires at least nine operational measurements, corresponding to three operational measurements per each dust emission range within the stack. The procedure is assessed by comparison with previous calibration methods for opacimeters using only two operational measurements from a set of measurements made at stacks from pulp mills. The results show that even if the international standard for opacimeter calibration requires that the calibration curve is to be obtained using 3 x 3 points, a calibration curve derived using 3 points could be, at times, acceptable in statistical terms, provided that the amplitude of individual measurements is low.     

Fractional factorial experiments using a test atmosphere to assess the accuracy and precision of a new passive sampler for the determination of formaldehyde in the atmosphere

A new analytical method was developed for the determination of formaldehyde in ambient air based on the use of a modified configuration of the Analyst^® passive sampler. It consists of a polyethylene cylinder filled with appropriate reactive adsorbent and a special anti-turbulence net which works as an ozone scrubber.The performance of a diffusive sampler depends critically on the selection and use of a suitable adsorbent and on environmental factors, such as temperature, humidity and the interference of oxidant species. In this study two adsorbent types were investigated: 2,4-dinitrophenylhydrazine (2,4-DNPH) coated silica gel and Florisil^® particles. Interference of ozone was removed by using a silver net upstream as an anti-turbulence device. The performance of this net was then compared with that of stainless steel. Furthermore, the aim of the work was the optimization of the adsorbent type and the study of the interference of ozone with particular attention placed on the effect of relative humidity and temperature.A dynamic system for generating a known concentration of the test gas (formaldehyde) in an appropriate exposure chamber was used to evaluate the performance of the passive sampler and to allow the calibration of the methodology. Inter-comparisons with a reference method, active sampling using 2,4-DNPH-silica gel coated cartridges, were also carried out. Results were in accordance with each other.Tests were planned using a statistical method based on Design of Experiment methodology. The operating conditions were chosen in order to obtain the best configuration of the passive device by evaluating the statistical significance of the different factors and their interactions by analysis of variance.Results showed that the best configuration was achieved using 2,4-DNPH Florisil^® coated particles as an adsorbent and a silver anti-turbulence net as an ozone scrubber.With the aim of achieving further results in realistic conditions, some field experiments were also carried out.     

Aerosol Aerodynamic Size Conventions For Inertia! Sampler Calibration

The body of information presented in this paper is directed to investigators using inertial samplers for precise and accurate studies of respirable aerosols. The conventions commonly used for aerodynamic size for aerosol particles are discussed including the definition popularized by the "Task Group on Lung Dynamics" of the ICRP, and the "Lovelace" definition. To emphasize the distinction, the Task Group definition (unit density sphere equivalent) is called the aerodynamic equivalent diameter, D_ae, and the Lovelace definition (characteristic expression based upon viscous resistance) is called the aerodynamic resistance diameter, D_ar. The implications and efficacy of these conventions are related to procedures for calibration of cascade impactors, cyclones, and spiral centrifuges. The calibration of a spiral centrifuge at different altitudes is used as an example of the potential problems associated with the use of the different conventions for describing aerodynamic size. The aerodynamic resistance diameter is recommended for calibration of inertial samplers to be used to collect aerosols in the respirable size range.     

Evaluation of GC-ion trap-MS/MS methodology for monitoring PCDD/Fs in infant formulas

The application of high resolution gas chromatography in combination with low resolution mass spectrometry with electron ionization and MS/MS detection (HRGC-MS/MS) is tested for its use in the analysis of PCDD/Fs in infant formulas. Development of the analytical method was based upon EPA directrices and international recommendations. Calibration linearity was tested and average relative response for any native and labelled compound over the five-point calibration range below 14% was found. The precision and accuracy of the proposed analytical procedure are also presented. Results obtained are in agreement with EPA criteria. The method is applied to the analysis of a number of initial and follow-on milk based infant formulas. In general, HRGC-MS/MS constitutes an interesting method for the analysis of dioxins in such matrices.     

Detection and quantification of chlordecone in contaminated soils from the French West Indies by GC-MS using the 13C10-chlordecone stable isotope as a tracer

Chlordecone is an organochlorine insecticide that has been widely used to control banana weevil in the French West Indies. As a result of this intense use, up to 20,000 ha are contaminated by this insecticide in the French West Indies, and this causes environmental damage and health problems. A scenario of exposure was drawn by French authorities, based on land usage records. Many efforts have been made to monitor the occurrence of chlordecone and its main metabolites using different analytical methods, including GC, GC/MS, LC/MS, and NIRS. Although these different methods allow for the detection and quantification of chlordecone from soils, none of them estimate the bottleneck caused by extraction of this organochlorine from soils with high adsorption ability. In this study, we used ¹³C₁₀-chlordecone as a tracer to estimate chlordecone extraction yield and to quantify chlordecone in soil extracts based on the ¹³C/¹²C isotope dilution. We report the optimization of ¹³C₁₀-chlordecone extraction from an Andosol. The method was found to be linear from 0.118 to 43 mg kg^?1 in the Andosol, with an instrumental detection limit estimated at 8.84 μg kg^?1. This method showed that chlordecone ranged from 35.4 down to 0.18 mg kg^?1 in Andosol, Nitisol, Ferralsol, and Fluvisol soil types. Traces of the metabolite β-monohydrochlordecone were detected in the Andosol, Nitisol, and Ferralsol soil samples. This last result indicates that this method could be useful to monitor the fate of chlordecone in soils of the French West Indies.