'This is a three-year project which started on October 1, 1997. This report summarizes the progress achieved for the first eight months of the study (through May, 1998). Thermospray positive ion mass spectra of seven different organic complexants have been defined in a water:methanol (1:1 by volume) solvent system that was buffered with 0.1 M ammonium acetate (pH = 6.7). These complexants were imidodiacetic acid (IDA), ethylenediamine-N,N{prime}-diacetic acid (EDDA), N-(2-hydroxyethyl)iminodiacetic acid (HEIDA), nitrilotriacetic acid (NTA), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA). Mass spectra of all these complexants showed a peak at mass [M+1] + when vaporized from this solvent medium. Only NTA showed a significant peak at mass [M+18] + which was interpreted as the formation of an adduct with an ammonium ion from the buffered solvent medium. This observation for the vaporized NTA is consistent with the measured acidity in aqueous solution where the first acid dissociation for NTA has a lower pK value than those reported for EDTA, HEDTA, and IDA (1). This tendency to form an ammonium adduct in the gas phase would indicate that NTA has a lower proton affinity than the other complexants in the vaporized phase. This lower proton affinity in the vapor phase would be consistent with the greater observed acidity in the solution phase. Accordingly, this observation provides an indication that characteristics observed after thermospray vaporization may aid in defining behavior in solution. Such interpretations of thermospray mass spectra should be useful in the characterization of DOE mixed waste solutions. Progress has also been made in developing thermospray mass spectra at source temperatures of less than 170 C. Such lower source temperatures should reduce the amount to thermal degradation for labile species. Pressures in the analyzer chamber of the mass spectrometer tend to elevate as the thermospray source temperature is reduced; however, the instrument has been operated for up to 8 hours at a source temperature of 175 C and a solvent flow of 1 ml/min. This time interval is of sufficient duration to analyze multiple liquid chromatography separations.'

This method employs a ternary gradient generated from (1) a 90:10 water:methanol solution that is 0.015 M in potassium phosphate at pH 5.1; (2) methanol; and (3) acetonitrile to separate fifteen explosives, byproducts, and metabolites of 2,4,6-trinitrotoluene (TNT) on a C-18/anion exchange stationary phase. TNT, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), six reduction metabolites and three oxidation metabolites of TNT have been separated and quantitated in a single chromatographic run. Because of the anion exchange character of the stationary phase, the anionic TNT metabolite 2,4,6-trinitrobenzoic acid also may be separated and quantitated using this method. Quantitation limits generally lower than 1 ppm have been established by a systematic certification procedure. The performance of the mixed mode separation method combined with diode array ultraviolet absorbance detection has been demonstrated with samples derived from both biological (tissues and physiological fluids) and environmental (soil, composts, and leachates) sources.

Aerated and nonaerated windrow composts of explosives-contaminated sediments at the Umatilla Army Depot Activity (UMDA, Hermiston, OR) were characterized chemically and toxicologically as a function of composting time. The concentrations of explosives in organic solvent extracts of the composts and in the aqueous leachates of the composts, the bacterial mutagenicity of organic solvent extracts from the composts, and the toxicity of aqueous leachates from the composts to Ceriodaphnia dubia all declined rapidly (<15 d) with composting. The nonaerated windrow method of composting was slightly more efficient than was the aerated windrow method for reducing explosives concentrations in the composts (TNT, 99.9%; RDX, >99.7%; HMX, 98.5%) and in their leachates (>99.6%, >98.8%, and >97.5%, respectively). Extractable mutagenicity declined 99.7 and 97.9%, respectively, for strains TA-98 and TA-100 (without S-9 metabolic activation) in the nonaerated compost. The two types (aerated and nonaerated) of windrow composts had about the same level of efficiency in lowering leachable toxicity (by 92% and 87%, based on reductions in C. dubia survival and fecundity, respectively). Thus, windrow composting appeared to be at least as effective as static-pile and mechanically stirred composting evaluated previously. Windrow composting also appeared to be somewhat more effective for HMX transformation.

Soil contaminated with explosives was supplemented with carbon-14 labelled 2,4,6-trinitrotoluene (C-14-TNT) and was composted in a field static pile composting experiment. After 90 d of composting, the distribution of carbon-14 (C-14) activity in fractions from acetonitrile extraction (''free'' fraction, 1.2% of the initial C-14-activity) and filtration (''insoluble - particle'' fraction, 17.9%), alkaline hydrolysis (''insoluble hydrolyzable'' fraction, 56.8%), and combustion of the residue (''insoluble nonhydrolyzable'' fraction, 4.7%) showed that the bulk of the C-14-activity, and presumably transformed product(s) of the C-14-TNT, accumulated in a nonextractable, but hydrolyzable fraction. Repetitive aqueous leaching of the compost and also ultraviolet light irradiation followed by leaching suggest that the insoluble fraction of transformed TNT should not be released appreciably by the action of acid rain or sunlight.

The initial development is reported for a novel countercurrent filtration/dialysis and solid phase extractant system for the rapid isolation of low molecular weight target compounds from biological media. Except for piperazine (a highly water-soluble drug), recoveries of 50 - 85% were achieved for chemical warfare agent simulants and anthelmintic drugs extracted from meat, grain, or milk. The results suggest the potential for broad applications to complex samples such as environmental media and physiological specimens which traditionally require extensive fractionation prior to analysis.

Static-pile and mechanically stirred composts of explosives-contaminated soil at the Umatilla Army Depot Activity (UMDA, Umatilla, OR) in a field composting optimization study were characterized chemically and toxicologically. The concentrations of extractable explosives (e.g., 2,4,6-trinitrotoluene) in the composts and their aqueous leachates, the mutagenicity of organic solvent extracts from the composts, and the toxicity of compost aqueous leachates to Ceriodaphnia dubia all decreased considerably with 20 d of composting. After 44 d (mechanical composters) or 90 d (static piles) of composting, the toxicity, mutagenicity, and concentrations of extractable explosives decreased more than 90% in some cases. The composting efficiency was generally inversely proportional to the percentage (v/v) of contaminated soil. Composting in static piles was efficient up to about 20% (v/v) of contaminated soil; composting in the mechanically stirred composters was efficient up to about 25% soil. Mechanical composting was more efficient than composting in static piles. The main conclusion of this study is that composting can effectively remediate explosives-contaminated soil and sediment. However, low levels of explosives and metabolites, bacterial mutagenicity, and leachable toxicity to Ceriodaphnia may remain after composting. The sources of residual toxicity and mutagenicity and the ultimate fate of the explosives are unknown.

Static pile and mechanically stirred composts generated at the Umatilla Army Depot Activity in a field composting optimization study were chemically and toxicologically characterized to provide data for the evaluation of composting efficiency to decontaminate and detoxify explosives-contaminated soil. Characterization included determination of explosives and 2,4,6,-trinitrotoluene metabolites in composts and their EPA Synthetic Precipitation Leaching Procedure Leachates, leachate toxicity to Ceriodaphnia Dubia and mutagenicity of the leachates and organic solvent extracts of the composts to Ames bacterial strains TA-98 and TA-100. The main conclusion from this study is that composting can effectively reduce the concentrations of explosives and bacterial mutagenicity in explosives -- contaminated soil, and can reduce the aquatic toxicity of leachable compounds. Small levels of explosive and metabolites, bacterial mutagenicity, and leachable aquatic toxicity remain after composting. The ultimate fate of the biotransformed explosives, and the source(s) of residual toxicity and mutagenicity remain unknown.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDetermination of regulatory organic compounds in radioactive waste samples. Semivolatile organics in aqueous liquidsBruce A. Tomkins, John E. Caton, G. Scott. Fleming, Manuel E. Garcia, Sara H. Harmon, Robert L. Schenley, Cheryl A. Treese, and Wayne H. GriestCite this: Anal. Chem. 1990, 62, 3, 253–257Publication Date (Print):February 1, 1990Publication History Published online1 May 2002Published inissue 1 February 1990https://pubs.acs.org/doi/10.1021/ac00202a006https://doi.org/10.1021/ac00202a006research-articleACS PublicationsRequest reuse permissionsArticle Views84Altmetric-Citations10LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

Using a sequential h.p.l.c. technique, the levels of each of the eight benzoquinoline isomers were estimated for two petroleum crude oils, several coal liquids shale oils and a coal gasifier tar. Significant concentrations (5–420 ppm) of phenanthridine, acridine, benzo(h)quinoline and benzo(f)quinoline were found in all coal-derived materials with the former two isomers being most abundant. In contrast, benzo(g)quinoline, benz(g)isoquinoline, benz(h)isoquinoline and benz(f)isoquinoline were seldom present at levels above 1 ppm. None or trace quantities of the eight isomers were detected in two petroleum crude oil samples. Major benzoquinoline isomers from one coal liquid were individually isolated and the presence of phenanthridine, benzo(h)quinoline and benzo(f)quinoline was unequivocally confirmed by matching infrared spectra.

The extractive recovery of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-(2,4,5-trichloro)phenoxypropionic acid (Silvex) from environmental samples was evaluated using carbon-14 tracers of the acid form of both herbicides. Recoveries using methylene chloride or 1:1 methylene chloride:acetone for solids exceeded 75% when the material being extracted was maintained at an acid pH (pH less than or equal to2). Following extraction, the extract is taken to dryness and then dissolved in the solution being used for HPLC elution. Two slightly different isocratic elutions with reversed phase columns were studied. In the first system studied a heavily loaded (18% carbon by weight), completely endcapped C18 reversed phase column was eluted with an aqueous solution of 30% (v/v) acetonitrile that contained 0.001 M concentration of a pH 4.6 acetate buffer. The effluent from this column was monitored at 280 nm. The minimum amount detected, when monitoring at 280 nm, is 100 ng of either Silvex or 2,4-D in the injected sample. A second isocratic elution system avoided the use of a buffered eluent by utilizing a high performance reversed phase column and an aqueous methanol (20% v/v) eluent. This second column has been monitored at multiple wavelengths with a diode array detector. The sensitivity of detectionmore » can be greatly increased at wavelengths below 240 nm; however, any real sample must be very ''clean'' in order to avoid interferences when monitoring below 230 nm. Thus monitoring at 280 nm is probably optimal for real environmental samples. At this wavelength the detectable concentration of either herbicide in the solution being injected is 5 ppM for a 20 ..mu..l injection.« less

This project developed methodology for analyzing polycyclic aromatic hydrocarbons (PAH) and other organic compounds in airborne fly ash from coal-fired power plants. Stack ash samples were used as surrogates for fly ash in sorptivity studies and development of analytical methods. A major finding of this project was the identification of carbonaceous particles, ranging from uncombusted coal to coal coke, as the species principally responsible for the strong sorptivity of ash for PAH. The carbonaceous particles also influence the distribution of surface area and organic matter in the ash, and may provide a transport mechanism for the emitted organic matter from coal combustion. The total organic content of the carbonaceous particles ranged up to 1.6 mass %. Several procedures for the determination of organic matter on ash were developed and evaluated. These ranged from gas chromatographic (GC) screening procedures featuring derivatized solvent extracts and thermal desorptions to more complex sequential procedures involving semipreparative scale high-performance liquid chromatographic (HPLC) fractionation followed by GC or analytical scale HPLC analysis. A preliminary investigation was conducted on the nature of the 60 to 80% off the organic matter (estimated from gravimetric or total organic carbon measurements) which is unaccounted for using current chromatographic procedures. Size-exclusionmore » chromatography and spectroscopic characterization of solvent extracts indicated the presence of oxygenated species with apparent molecular masses 200 to 1000.« less

Di-n-butyl phthalate, di-n-butyl isophthalate, di-n-butyl terephthalate, di-n-octyl phthalate, di-n-octyl isophthalate, di-n-octyl terephthalate, and ..cap alpha..,..omega..-butylene di(o-(4-hydroxybutoxycarbonyl)benzoate) were either obtained from commercial sources or synthesized. After appropriate clean-up procedures, the chemical purity of each product was estimated from both gas chromatographic and liquid chromatographic profiles. Subsequently, some spectroscopic characteristics, including /sup 13/C nuclear magnetic resonance spectra, mid-infrared spectra, ultraviolet spectra, and mass spectra, were carefully documented for the purified compounds. The toxicity of di-n-butyl phthalate (DBP) and di-n-octyl phthalate (DOP) was assessed by measuring the effect of exposure to these compounds on the fecundity of Daphnia magna and on the hatching and survival of the early life stages of the fathead minnow, Pimephales promelas. For D. magna, exposure to 1.8 mg/L of DBP or 1.0 mg/L of DOP caused a significant reduction in reproduction. Doses of 0.56 mg/L of DBP or 0.32 mg/L of DOP had no significant effect in decreasing reproduction. Survival of fathead minnow larvae was decreased by exposure to 1.8 mg/L of DBP; none of the larvae exposed to this level hatched successfully. Hatching and larval survival were affected by exposure to 1.0 mg/L of DBP, but not to 0.56 mg/L. Exposure to DOP did not affect survivalmore » of either early embryos or larvae of the fathead minnow at doses up to 10 mg/L (the highest dose tested); hatching of the embryos was significantly decreased at 10 mg/L, but not at 3.2 mg/L. 27 references, 41 figures, 28 tables.« less

The nonfluorescent pyrimidodiazepine in Drosophila melanogaster 6-acetyldihydrohomopterin (H2Ahp) was studied using ultraviolet and infrared spectroscopy. The H2Ahp was unstable in 3% NH4Cl whereas a related pteridine sepiapterin was stable. Since Ni2+ stabilized H2Ahp completely, the structure of the H2Ahp · Ni complex was examined. Among 15 pterins, including sepiapterin, the spectral properties in the presence of Ni2+ reflect the pKa's and the reactive group on the side chain but for H2Ahp the spectral properties are rather different from the pteridines and they indicate that the seven-membered ring seemed to have the predominant influence. The Ni2+ comples of H2Ahp resulted in a shift in the absorption maximum from 383 to 436 nm. The corresponding spectral shift of the pteridines due to Ni2+ was much less. From the infrared spectra of H2Ahp and sepiapterin in the presence and absence of Ni2+, the sites of interaction of Ni2+ with H2Ahp were shown to be the phenolic oxygen and N5 in the ring. In the absence of Ni2+ an internal hydrogen bond in sepiapterin was indicated that may involve the carbonyl oxygen and the secondary alcoholic oxygen on the side chain. Other metal ions were tested (Cd2+, Zn2+) but were not as effective as Ni2+ in stabilizing H2Ahp.

Thermal desorption of coal fly ash in a flowing stream of helium liberates volatile compounds which are collected on Tenax resin. A chemical “fingerprint” of these components collected from the fly ash is obtained by using thermal desorption of the material collected on the Tenax resin and capillary-column gas chromatography. Compounds ranging in volatility from that of benzene (b.p. 80°C) through C1-phenanthrene (b.p. ca. 360°C) are detected, but recoveries of components only through naphthalene (b.p. 218°C) are suitable for quantitative work. The method provides chemical information on volatile organic compounds complementary to that achieved by procedures based on solvent extraction.

The mutagen, 2-aminonaphthalene, which is the dominant aromatic amine species in several fossil fuels, may be isolated readily by using a sequential high-performance liquid chromatographic procedure. An initial isolation is achieved on a semi-preparative scale aminosilane column and the final separation is completed with a nonpolar stationary phase column on an analytical scale with a pH-adjusted solvent. The use of fluorescence detection permits discrimination (at least 100-fold) against the nonmutagenic isomer, 1-aminonaphthalene. The overall recovery of 2-aminonaphthalene, as determined by scintillation counting of a radioactive 1-aminonaphthalene tracer, typically exceeds 50% and can reach 92% depending on both the sample matrix and the solubility of the isolate in acetonitrile. The minimum detectable quantity is 0.06 μg g-1 of crude sample.