Bruce A. Tomkins

Analysis of methylphosphonic acid, ethyl methylphosphonic acid and isopropyl methylphosphonic acid at low microgram per liter levels in groundwater

A method is described for determining methylphosphonic acid, ethyl methylphosphonic acid and isopropyl methylphosphonic acid, which are hydrolysis products of the nerve agents VX (S-2-diisopropylaminoethyl O-ethyl methylphosphonothiolate) and GB (sarin, isopropylmethyl phosphonofluoridate). The analytes are extracted from 50 ml groundwater using a solid-phase extraction column packed with 500 mg of silica with a bonded quaternary amine phase, and are eluted and derivatized with methanolic trimethylphenylammonium hydroxide. Separation and quantitation are achieved using a capillary column gas chromatograph equipped with a flame photometric detector operated in its phosphorus-selective mode. Two independent statistically-unbiased procedures were employed to determine the detection limits, which ranged between 3 and 9 micrograms/l, for the three analytes.

Development and application of protocols for the determination of response of real-time particle monitors to common indoor aerosols.

Abstract Protocols have been developed and applied for the generation of aerosols that are likely to be comparable to those encountered in field settings for the calibration of easily transportable/portable real-time particle monitors. Aerosols generated were simulated environmental tobacco smoke, cedar wood smoke, cooking oil fumes, and propane stove particles. The time-integrated responses of three nephelometers and a monitor for particle-bound polynuclear aromatic hydrocarbons (PAH) were compared with gravimetric respirable suspended particulate matter (RSP) in a controlled-atmosphere chamber. In general, the monitor responses increased linearly with increasing mass concentration. However, the two monitors that reported mass per volume concentrations tended to overreport the actual RSP concentrations by factors up to 4.4. The real-time PAH monitor did not respond to cooking oil fumes, indicative of little PAH being present in the aerosol. One of the monitors that has been used in a variety of studies reported in the literature (DustTrak) was collocated with gravimetric RSP samplers in several hospitality venues in the Louisville, KY, area. Field studies indicated that the units overreported actual RSP concentrations by factors of 2.6–3.1, depending on whether the sampling was conducted in the nonsmoking or smoking sections of the facilities.

Influence of carbonaceous particles on the interaction of coal combustion stack ash with organic matter

Stack ash samples were fractionated by aerodynamic size, and the largest particle size fraction was separated into constituent particle type subfractions. Comparison of the mineral, magnetic, and carbonaceous particles showed that coked coal is responsible for the sorptivity of the large particle size fraction for carbon-14 labeled benzo(a)pyrene ((/sup 14/C)BaP) and for low solvent extraction recoveries. Elevated levels of organic matter and surface area also are contributed by the carbonaceous particles. In contrast, solvent extraction recoveries of polar degradation products of (/sup 14/C)BaP are attributable more to the mineral and magnetic particles and to exposure of the ash to light and oxygen. Analysis of bulk ash samples may not fully reflect the true organic composition of stack ash. 27 references, 1 figure, 4 tables.

Determination of munitions components in water by resin adsorption and high-performance liquid chromatography—electrochemical detection☆

Abstract A method has been developed for the determination of several munitons components (nitro-organic compounds) in environmental waters. The method is based on Porapak resin adsorption of the munitions components from aqueous samples. Following desorption with acetone, the nitro compounds are measured by high-performance liquid chromatography with electrochemical detection at a gold—mercury electrode, which is maintained at −1.0 V vs. a silver—silver chloride references electrode. This technique provides a high degree of selectivity and sensitivity for these compounds in actual samples. Detection limits approach 1 μg/1 for many components.

Synthesis and Properties of Calix[4]arene‐bis[4‐(2‐ethylhexyl)benzo‐crown‐6], A Cesium Extractant with Improved Solubility

Abstract The new cesium‐selective macrocycle calix[4]arene‐bis[4‐(2‐ethylhexyl) benzo‐crown‐6] (“BEHBCalixC6”) has been found to have improved solubility in a modified alkane diluent over calix[4]arene‐bis(4‐tert‐octylbenzo‐crown‐6) (“BOBCalixC6”). The synthesis of this new calixcrown extractant, together with its solubility and extraction properties, is described in this report. The solubility, cesium extraction, and potassium loading behavior are compared with those of BOBCalixC6, the macrocycle currently employed in the caustic‐side solvent extraction (CSSX) process for extracting cesium from alkaline nitrate solutions such as high‐level nuclear waste. Replacement of the tert‐octyl alkyl chains on the benzo‐crown portion of the calixcrown by 2‐ethylhexyl chains improves the equilibrium solubility of the free calixcrown in aliphatic diluents while not affecting the cesium extraction strength. Equilibrium concentrations of BEHBCalixC6 in Isopar L diluent modified with 0.5 M 1‐(2,2,3,3‐tetrafluoropropoxy)‐3‐(4‐sec‐butylphenoxy)‐2‐propanol (Cs‐7SB) over the course of 41 weeks of gentle agitation at 25°C maintained the initial concentration of 57 ± 2 mM, with no evidence of precipitation or third‐phase formation. In contrast, 57 ± 2 mM solutions of BOBCalixC6 prepared using sonication were not stable, with precipitation occurring to afford an equilibrium concentration of only 6.7 ± 0.2 mM after 41 weeks. Third‐phase tests showed that BEHBCalixC6 resists third‐phase formation as well as, or better than, BOBCalixC6. With increasing potassium loading from an alkaline sodium nitrate solution, both calixcrowns at 20 mM in modified Isopar L exhibited comparable onset of third‐phase formation, gauging by the decreasing mass balance in cesium extraction from the same solutions. However, the BEHBCalixC6 solvent exhibited no visible indications of third‐phase formation until the aqueous potassium concentration reached 0.75 M, whereas the BOBCalixC6 suffered visible third‐phase formation when the aqueous potassium nitrate concentration reached 0.25 M. Calixcrowns with higher solubility in alkane diluents may find application in cesium extraction from waste matrices containing moderate (≥0.2 M) quantities of potassium, such as that stored at the US Department of Energys Hanford Site, where higher concentrations of the calixcrown extractant may be required to obtain practical cesium distribution coefficients for process flowsheets.

Carbonaceous particles in coal combustion stack ash and their interaction with polycyclic aromatic hydrocarbons

Carbonaceous particles consisting of uncombusted coal, coal coke, and intermediates are concentrated in the large particle size fractions (>14 μm) of stack ash. Although they do not constitute a major portion of the ash, they appear to contribute significantly to the interaction of fly ash with organic matter. The carbonaceous particle-enriched fractions are more sorptive, have higher levels of organic matter, and exhibit higher specific surface areas than mineral or magnetic particle-enriched subfractions. Extraction recoveries of organics from fly ash appear to be limited mainly by the carbonaceous particles.

The Quantitation of Sulfur Mustard By-Products, Sulfur-Containing Herbicides, and Organophosphonates in Soil and Concrete

Over the past fifty years, the facilities at Rocky Mountain Arsenal have been used for the manufacturing, bottling, and shipping sulfur- containing herbicides, sulfur mustard, and Sarin. There is a need for analytical methods capable of determining these constituents quickly to determine exactly how specific waste structural materials should be handled, treated, and landfilled.These species are extracted rapidly from heated samples of soil or crushed concrete using acetonitrile at elevated pressure, then analyzed using a gas chromatograph equipped with a flame photometric detector. Thiodiglycol, the major hydrolysis product of sulfur mustard, must be converted to a silylated derivative prior to quantitation. Detection limits, calculated using two statistically-unbiased protocols, ranged between 2-13 micrograms analyte/g soil or concrete.

Environmental tobacco smoke in an unrestricted smoking workplace: area and personal exposure monitoring

The objective of this investigation was to determine the extent of areal and day-to-day variability of stationary environmental tobacco smoke (ETS) concentrations in a single large facility where smoking was both prevalent and unrestricted, and to determine the degree of daily variation in the personal exposure levels of ETS constituents in the same facility. The subject facility was a relatively new four-story office building with an approximate volume of 1.3 million ft3. The exchange of outside air in the building was determined to be between 0.6 and 0.7 air changes per hour. Eighty-seven area samples (excluding background) were collected at 29 locations over the course of 6 days of sampling. Locations included offices and cubicles occupied by smokers and nonsmokers, common areas, and the computer and mail rooms. Twenty-four nonsmoking subjects wore personal sampling systems to collect breathing zone air samples on each of 3 days in succession. This generated a total of seventy-two 8-h time-weighted average (TWA) personal exposure samples. In all samples, respirable suspended particulate matter, ultraviolet light-absorbing and fluorescing particulate matter, solanesol, nicotine, and 3-ethenyl pyridine were determined. With the exception of a few locations, tobacco-specific airborne constituents were determined in all samples. Not surprisingly, areas with the highest ETS constituent concentrations were offices and cubicles of smokers. Median and 95th percentile concentrations for all area samples, excluding background, were determined to be 1.5 and 8.7 μg/m3 for nicotine, and 8.2 and 59 μg/m3 for ETS-specific particles (as solanesol-related particulate matter, Sol-PM), respectively. Personal exposure concentrations of ETS components were similar to those levels found in the area samples (median nicotine and Sol-PM concentrations were 1.24 and 7.1 μg/m3, respectively), but the range of concentrations was somewhat smaller. For example, the 95th percentile 8-h TWA nicotine and ETS-specific particle (as Sol-PM) concentrations were 3.58 and 21.9 μg/m3, respectively. Intrasubject variation of daily concentrations ranged from 20% to 60%, depending on the component. Self-reported proximity to smokers was supported by higher ETS concentrations determined from the personal monitors, but only to a modest extent. Although smoking was completely unrestricted inside the main office areas of the facility, ETS levels, either areal or from personal exposure measurements, were lower than those estimated by Occupational Safety and Health Administration to be present in such facilities.

Derivatizat Ion of Primary Aromatic Amines with Fluorescamine

Abstract Fluorescamine forms stable, fluorescent derivatives with sterically-unhindered primary aromatic amines in both aqueous (borate buffer, pH 9/acetonitrile) and nonaqueous (pyridine/-acetonitrile) media. Aromatic amines with a substituent such as a methyl group or an aromatic ring ortho to the amine functionality either derivatized poorly or not at all because of steric hindrance.

Detection of primary and secondary amines in energy-related materials using an element-selective glow-discharge detector

Abstract Mutagenic primary polycyclic aromatic amines present in shale oil and synthetic crudes may be readily detected by a simple derivatization and Chromatographic procedure. Nitrogenous bases and amines are extracted from the sample with dilute mineral acid and derivatized with trifluoroacetic anhydride. The derivatized amines are separated by gas chromatography and specifically detected using a glow-discharge detector tuned to an emission wavelength of fluorine. Under these conditions, the aromatic nitrogenous bases, such as acridine, are not detected even though they are present in the sample. As little as 14 ng of fluorine, arising from the derivative of 33 ng of 2,4,6-trimethylaniline, can be detected. The selectivity of the glow-discharge detector for derivatized amines vs. nonderivatized aromatic nitrogenous bases was estimated to be a minimum of 200:1.