Validation of an evacuated canister method for measuring part-per-billion levels of chemical warfare agent simulants

The National Institute for Occupational Safety and Health (NIOSH) research on direct-reading instruments (DRIs) needed an instantaneous sampling method to provide independent confirmation of the concentrations of chemical warfare agent (CWA) simulants. It was determined that evacuated canisters would be the method of choice. There is no method specifically validated for volatile organic compounds (VOCs) in the NIOSH Manual of Analytical Methods. The purpose of this study was to validate an evacuated canister method for sampling seven specific VOCs that can be used as a simulant for CWA agents (cyclohexane) or influence the DRI measurement of CWA agents (acetone, chloroform, methylene chloride, methyl ethyl ketone, hexane, and carbon tetrachloride [CCl4]). The method used 6-L evacuated stainless-steel fused silica-lined canisters to sample the atmosphere containing VOCs. The contents of the canisters were then introduced into an autosampler/preconcentrator using a microscale purge and trap (MPT) method. The MPT method trapped and concentrated the VOCs in the air sample and removed most of the carbon dioxide and water vapor. After preconcentration, the samples were analyzed using a gas chromatograph with a mass selective detector. The method was tested, evaluated, and validated using the NIOSH recommended guidelines. The evaluation consisted of determining the optimum concentration range for the method; the sample stability over 30 days; and the accuracy, precision, and bias of the method. This method meets the NIOSH guidelines for six of the seven compounds (excluding acetone) tested in the range of 2.3-50 parts per billion (ppb), making it suitable for sampling of these VOCs at the ppb level.     

A new method for monitoring long-term transport variability in the Baltic

Direct measurements of the potential induced by motion of electrically conducting seawater through the earth's magnetic field may be used to estimate ocean transports. For the purpose of evaluating the feasibility of monitoring the Baltic climate, a number of temporary observational systems based on this principle have been established around the Swedish coast. Some results from these investigations are presented, and the study is concluded by an outlook towards the prospects for future work along these lines.     

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.     

Designing of sampling programmes for industrial effluent monitoring

Introduction  

Monitoring of effluent discharges from industrial establishments discharging directly into municipality sewers is one of the major water pollution control activities conducted by municipalities. For largely industrialised municipalities, the task can be quite expensive and not effective if sampling programmes are not properly designed. In most cases, samples are randomly collected without proper knowledge of the discharge patterns of various industries. As a result, the information obtained does not give a good reflection of the quality of effluent being discharged.     

工业聚合铝的形态分析方法研究

主要探讨了工业聚合铝 (PACl)的形态分析方法 ,即Al Ferron逐时络合比色法。重点研究了 2类Ferron比色液的稳定性及其对工业PACl形态分析的影响特征。     

A new method for the determination of collection efficiency of an aerosol sampler by electron microscopy

A method was developed to determine the particle collection efficiency of an aerosol sampler by electron microscopy. The determination method measures the absolute concentration of particles and the particle size distribution at the sampler inlet by two aerosol samplers connected in series. Particle samples collected in each sampler were microscopically observed and analyzed by electron microscopy. By this “double-sampler method”, the particle collection efficiencies of the thermal and electrostatic precipitators were determined as a function of particle size. The average particle size ranged from 0.02 to 0.4 μm and mean collection efficiencies were found to be 72 and 79% for the thermal and electrostatic precipitators, respectively.     

A mass transfer based method for measuring the reaction coefficients of a photocatalyst

We have developed a new method, the mass transfer based (MTB) method, for measuring the Langmuir–Hinshelwood (L–H) rate form reaction coefficients of photocatalysts. The conventional method for determining the reaction coefficients disregards the effect of mass transfer on the reaction surface by designing and controlling a reaction process to be reaction-limited. In contrast, the new MTB method takes the mass transfer effect into account by using a computational fluid dynamics (CFD) method. The reaction coefficients can be regressed by the measured reaction rates and the calculated VOC concentrations in the air adjacent to the reaction surface. Thus, by using the new method, the reaction coefficient of a reaction process can be accurately determined even if it is not reaction-limited. This is very important in cases where it is difficult to realize reaction-limited processes, such as photocatalytic oxidation of VOCs with strong UV radiation intensity. The relative error of the regressed reaction coefficients obtained by the new method is analyzed. To illustrate, we apply this method to measuring the reaction coefficients of TiO₂ photocatalytic decomposing formaldehyde. This method is very useful in determining the reaction coefficients of the photocatalytic oxidation of various VOCs simultaneously.     

Validation of a test method for the measurement of methanol emissions from stationary sources

Title III of the 1990 Clean Air Act Amendments designated methanol as a pollutant to be regulated. The U.S. Environmental Protection Agency (EPA), through a contract with Research Triangle Institute, has developed a method for measuring methanol emissions from stationary sources. The methanol sampling train (MST) consists of a glass-lined heated probe, two condensate knockout traps, and three sorbent cartridges packed with Anasorb 747. Samples are desorbed with a 1:1 mixture of carbon disulfide (CS2) and N,N-dimethylformamide (DMF). Condensate water and CS2/ DMF samples are analyzed by gas chromatography with flame ionization detection. The MST has a practical quantitation limit of approximately 3 ppm for a 20-L sample. Samples were shown to be stable for at least two weeks after collection. Field tests of the MST and the National Council of the Paper Industry for Air and Stream Improvement (NCASI) methanol sampling method were conducted at two pulp and paper mills. Sampling and analysis procedures followed EPA Method 301 requirements. The sampling location for the first field test was the inlet vent to a softwood bleach plant scrubber, where the methanol concentration was approximately 30 ppm. The mean recovery of spike was 108.3% for the MST method and 81.6% for the NCASI method. Although neither method showed significant bias at the 95% confidence level, the between-methods bias was significantly different. A second field test was conducted at a vent from a black liquor oxidation tank where the methanol concentration was approximately 350 ppm. Mean spike recoveries were 96.6 and 94.2% for the MST and NCASI methods, respectively. The biases of the two methods and the between-methods bias were not significantly different for the second field test.     

A method for measuring the anoxic biodegradability under denitrifying conditions

A test for assessing the anoxic biodegradability of organic compounds under denitrifying conditions is proposed. The method is based on the recovery and quantification of the CO2 produced, which is evidence of complete biodegradation of the test compound (added as the sole carbon source). The tests were carried out in a mineral medium, with nitrate as electron acceptor. Whole lake sediments, sediment extracts and a commercial inoculum were assayed as a possible inoculum source by means of glucose biodegradability tests. It was found that the sediment extracts constitute a suitable and environmentally-relevant inoculum source, since they add non-significant amounts of carbon to the tests. Two xenobiotic compounds, namely, aniline and phenol, were tested in the aforementioned conditions as well as in a standard aerobic biodegradability test. Both aniline and phenol attained a biodegradation level higher than 60% in a short time period (<28 days) and thus can be considered as readily biodegradable in denitrifying environments. Nevertheless, the kinetics obtained in the anoxic test were slower than in aerobic conditions, and even suggested the accumulation of intermediate metabolites in the case of phenol. The results of this study indicate that the fate of xenobiotic compounds under anoxic conditions differs from that observed in an oxic environment, and therefore it should be considered by standard biodegradability testing procedures.     

Mutatox test: a new test for monitoring environmental genotoxic agents

In this study, Yamaska River water and Milli-Q water and organically extracted sediment extracts were used to evaluate the sensitivity of a new genotoxicity screening test, the Mutatox test. Also in this study, the samples were tested for acute and chronic toxicity using the following screening test procedures: Microtox, Daphnia magna, Ceriodaphnia reticulata and ATP-TOX Systems. The Mutatox test is based on the use of a dark mutant strain of Photobacterium phosphoreum and is sensitive to chemicals which are (1) DNA damaging agents (2) DNA intercalating agents, (3) DNA synthesis inhibitors and (4) direct mutagens. In this study, the Mutatox test was found to be a simple-to-perform sensitive procedure which added greater scope to the battery of tests approach. Preliminary indications are that this procedure may prove to be one of the more responsive and valuable tests in the 'battery of tests' approach to environmental screening.     

Autonomous mobile platform for monitoring air emissions from industrial and municipal wastewater ponds

Significant amounts of volatile organic compounds and greenhouse gases are generated from wastewater lagoons and tailings ponds in Alberta, Canada. Accurate measurements of these air pollutants and greenhouse gases are needed to support management and regulatory decisions. A mobile platform was developed to measure air emissions from tailings pond in the oil sands region of Alberta. The mobile platform was tested in 2015 in a municipal wastewater treatment lagoon. With a flux chamber and a CO₂/CH₄ sensor on board, the mobile platform was able to measure CO₂ and CH₄ emissions over two days at two different locations in the pond. Flux emission rates of CO₂ and CH₄ that were measured over the study period suggest the presence of aerobic and anaerobic zones in the wastewater treatment lagoon. The study demonstrated the capabilities of the mobile platform in measuring fugitive air emissions and identified the potential for the applications in air and water quality monitoring programs.

Implications: The Mobile Platform demonstrated in this study has the ability to measure greenhouse gas (GHG) emissions from fugitive sources such as municipal wastewater lagoons. This technology can be used to measure emission fluxes from tailings ponds with better detection of spatial and temporal variations of fugitive emissions. Additional air and water sampling equipment could be added to the mobile platform for a broad range of air and water quality studies in the oil sands region of Alberta.     

Investigations into a novel method for atmospheric polycyclic aromatic hydrocarbon monitoring

A novel analytical method for atmospheric polycyclic aromatic hydrocarbons (PAHs) was developed based on laser induced fluorescence (LIF) of samples on quartz multi-channel polydimethylsiloxane traps. A tunable dye laser with a frequency doubling crystal provided the excitation radiation, and a double monochromator with a photomultiplier tube detected emitted fluorescence. The method allowed for the rapid (<5 min), cost effective analysis of samples. Those yielding interesting results could be further analysed by direct thermal desorption-gas chromatography–mass spectrometry (TD–GC–MS, with limits of detection of ～0.3 ng m^?3), as photodegradation was minimal (<10% over 5 min irradiation). Small amounts of naphthalene photodegradation products identified by TD–GC–MS after >15 min irradiation, included phenol, benzyl alcohol and phthalic anhydride. Without any signal optimization, a LIF detection limit of ～1 μg m^?3 was established for naphthalene using a diffusion tube (diffusion rate of 2 ng s^?1) and 292 nm excitation.     

A novel method for measuring the evaporation of contaminant liquids from sands

A novel experimental system, electrodynamic levitation, is used to measure the evaporation of liquids from microparticles of sand. The levitator is used to measure the evaporation rate of diethylphthalate (DEP) from microparticles of Saudi Arabian sand at 1 atm pressure and 25 degrees C. Evaporation experiments were conducted for both inland- and coastal-sand microparticles, the diameter of which is 50 microm. The DEP-evaporation rate is determined from gravimetric changes in the DEP-sand-mixture particle, the weight of which is directly proportional to the levitating electric-field intensity. From telemicroscopical observations, it is found that, when the sand particle is enclosed in DEP liquid, the sand-DEP-mixture particle evaporates like a pure DEP droplet. However, when sufficient DEP liquid has evaporated and the DEP is adsorbed into the sand microparticle, the DEP evaporation rate is reduced by a factor of 3-5 as compared with a pure DP droplet.     

A GC-TCD method for measuring the liquid water mass of collected aerosols

This work presents a gas chromatographic method that uses a thermal conductivity detector (GC-TCD) to measure the liquid water mass (LWM) of collected aerosols. The method is a modification of the previously developed EA-TCD method (Journal of Aerosol Science 29, 827). A microcomputer was incorporated into the system to control the analytical procedures, improve the measurement precision, and make possible a continuous operation. To validate the method, the aerosol LWMs of NaCl, Na₂SO₄, NH₄NO₃, (NH₄)₂SO₄, NH₄Cl, and Na₂CO₃ were measured at room temperature under relative humidities (RHs) varying between 20% and 90%, in both humidifying and dehumidifying conditions. Estimates of aerosol LWMs for varying aerosol chemical compositions and RHs by various measurement methods and predictive models are comprehensively compared. The comparison shows that the GC-TCD measurements agree closely with those of the other methods. The GC-TCD measurements are closer to the ISORROPIA model predictions than those of the AIM2 model. Most notably, our method determines, for the first time, the hygroscopic behavior of Na₂CO₃ aerosol yielding the deliquescence relative humidity and crystallization relative humidity at 78% and 39% RH, respectively. The hygroscopic characteristics of various NaCl mole fractions in mixed NaCl–Na₂SO₄ aerosols, determined by GC-TCD, are used to show the discrepancy between the measurements and the model's prediction.     

Evaluation of municipal sewage treatment systems for pollutant removal efficiency by measuring levels of micropollutants

In order to evaluate the municipal sewage treatment systems used at Harbin municipal sewage treatment plant for their pollutant removal efficiency, raw sewage and effluent samples at different treatment stages from the sewage treatment systems were taken, priority pollutants (PPs) were identified and quantified using gas chromatography-mass spectrometry (GC-MS) and inductively coupled plasma-atomic emission spectrograph (ICP-AES). The test results indicated that there were one hundred and fifty species of organic pollutants identified in the raw sewage sample, and only ten species of PPs in all the sewage samples. The levels of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), di-n-octyl phthalate (DnOP) in the sewage samples were 0.779-0.111 microg l(-1), 1.977-0.022 microg l(-1), 6.411-2.194 microg l(-1) and 7.152-2.953microg l(-1), respectively, and most of these phthalate esters (PAEs) were removed through anaerobic/aerobic (A/O) process; The levels of alachlor, acetochlor, atrazine were 0.074-0.021 microg l(-1), 0.160-0.096 microg l(-1) and 0.238-0.184 microg l(-1), respectively, and the total removal efficiency of atrazine was poorest through the sewage treatment systems. The levels of Cu, Cr, Se, Hg, Ni and Zn were 0.0030-0.2327 mg l(-1). It is therefore concluded from these results that the sewage treatment systems were efficient in removing most of the organic and inorganic compounds in this study, and so, the discharged effluent could cause little of the secondary pollution of the aquatic environment.     

Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 +/- 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.     

Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 ± 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.