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W. E. Pereira

Publications and source records attributed to W. E. Pereira.

18 recordsLinked to original sources

Bonded-phase extraction column isolation of organic compounds in groundwater at a hazardous waste site

A procedure for isolation of hazardous organic compounds from water for gas chromatography/mass spectrometry analysis Is presented and applied to creosote- and pentachlorophenol-contaminated groundwater resulting from wood-treatment processes. This simple procedure involved passing a 50-100-mL sample through a bonded-phase extraction column, eluting the trapped organic compounds from the column with 2-4 mL of solvent, and evaporating the sample to 100 ??L with a stream of dry nitrogen, after which the sample was ready for gas chromatography/mass spectrometry analysis. Representative compounds indicative of creosote contamination were used for recovery and precision studies from the cyclohexyl-bonded phase. Recovery of these compounds from n-octyl-, n-octadecyl-, cyclohexyl-, and phenyl-bonded phases was compared. The bonded phase that exhibited the best recovery and least bias toward acidic or basic cmpounds was the n-octadecyl phase. Detailed compound Identification Is given for compounds Isolated from creosote- and pentachlorophenol-contaminated groundwater using the cyclohexyl-bonded phase.

Analytical Chemistry

Occurrence, distributions, and transport of herbicides and their degradation products in the lower Mississippi river and its tributaries

The Mississippi River and its tributaries drain extensive agricultural regions of the midcontinental United States, where large amounts of herbicides are applied as weed control agents on crops such as corn and soybeans. Studies being conducted by the U.S. Geological Survey along the lower Mississippi River and its major tributaries, representing a 1930-km river reach, have confirmed that several triazine and chloroacetanilide herbicides and their degradation products are present in this riverine system. These herbicides include atrazine, and its degradation products, desethyl- and desisopropylatrazine; cyanazine; simazine; metolachlor; and alachlor and its degradation products, 2-chloro-2',6'-diethylacetanilide, and 2-hydroxy-2',6'-diethylacetanilide. Loads of these compounds were determined at 17 different sampling stations under various seasonal and hydrologic conditions, during five sampling trips from July 1987 to June 1989. Stream loads of herbicides were relatively small during the drought of 1987 and 1988. Stream loads were much greater during the relatively wet year of 1989. Trace levels of atrazine, cyanazine, and metolachlor also were associated with suspended sediments. Distribution coefficients (Koc) of these compounds varied considerably between sites and were much larger than Koc values reported in the literature. The annual transport of atrazine into the Gulf of Mexico was estimated to be less than 2% of the amount of atrazine applied each year in the midwest.

Lower Mississippi River

Contamination of estuarine water, biota, and sediment by halogenated organic compounds: A field study

Studies conducted in the vicinity of an industrial outfall in the Calcasieu River estuary, Louisiana, have shown that water, bottom and suspended sediment, and four different species of biota are contaminated with halogenated organic compounds (HOC) including haloarenes. A "salting-out" effect in the estuary moderately enhanced the partitioning tendency of the contaminants into biota and sediments. Contaminant concentrations in water, suspended sediments, and biota were found to be far below the values predicted on the basis of the assumption of phase equilibria with respect to concentrations in bottom sediment. Relative concentration factors of HOC between biota (catfish) and bottom sediment increased with increasing octanol/estuarine water partition coefficients (Kow*), maximizing at log Kow* of about 5, although these ratios were considerably less than equilibrium values. In contrast, contaminant concentrations in water, biota, and suspended sediments were much closer to equilibrium values. Bioconcentration factors of HOC determined on the basis of lipid content for four different biotic species correlated reasonably well with equilibrium triolein/water partition coefficients (Ktw).

Louisiana

Accumulation of butyltins in sediments and lipid tissues of the Asian clam, Potamocorbula amurensis, near Mare Island Naval Shipyard, San Francisco Bay

Studies of butyltin compounds in soil, benthic sediments and the Asian clam Potamocorbula amurensis were conducted at the former Mare Island Naval Shipyard, and nearby Mare Island and Carquinez Straits in San Francisco Bay, California. Soils from a sandblast abrasives dump site at the shipyard contained low concentrations of mono-, di- and tributyltin (0.3-52 ng/g, total butyltin). Similarly, concentrations of total butyltin in benthic sediments from nearby Mare Island and Carquinez Straits ranged from 1.3 to 8.1 ng/g. In contrast, clams accumulated much greater concentrations (152-307 ng/g, total butyltin). Tributyltin (TBT) and dibutyltin (DBT) made up from 54-85% to 15-46%, respectively, of the total butyltin body burden of the clams. Biota Sediment Accumulation Factors (BSAFs) for butyltins in Potamocorbula were in reasonable agreement with literature values; they are greater than those of neutral hydrophobic compounds, suggesting that partitioning and binding processes may be involved in bioaccumulation. Tributyltin is a potent endocrine disrupting chemical. There is potential for long-term chronic effects of TBT in San Francisco Bay.

Marine Pollution Bulletin

A record of hydrocarbon input to San Francisco Bay as traced by biomarker profiles in surface sediment and sediment cores

San Francisco Bay is one of the world's largest urbanized estuarine systems. Its water and sediment receive organic input from a wide variety of sources; much of this organic material is anthropogenically derived. To document the spatial and historical record of the organic contaminant input, surficial sediment from 17 sites throughout San Francisco Bay and sediment cores from two locations Richardson Bay and San Pablo Bay were analyzed for biomarker constituents. Biomarkers, that is, 'molecular fossils', primarily hopanes, steranes, and n-alkanes, provide information on anthropogenic contamination, especially that related to petrogenic sources, as well as on recent input of biogenic material. The biomarker parameters from the surficial sediment and the upper horizons of the cores show a dominance of anthropogenic input, whereas the biomarker profiles at the lower horizons of the cores indicate primarily biogenic input. In the Richardson Bay core the gradual upcore transition from lower maturity background organics to a dominance of anthropogenic contamination occurred about 70-100 years ago and corresponds to the industrial development of the San Francisco Bay area. In San Pablo Bay, the transition was very abrupt, reflecting the complex depositional history of the area. This sharp transition, perhaps indicating a depositional hiatus or erosional period, dated at pre-1952, is clearly visible. Below, the hiatus the biomarker parameters are immature; above, they are mature and show an anthropogenic overlay. Higher concentrations of terrigenous n-alkanes in the upper horizons in this core are indicative of an increase in terrigenous organic matter input in San Pablo Bay, possibly a result of water diversion projects and changes in the fresh water flow into the Bay from the Delta. Alternatively, it could reflect a dilution of organic material in the lower core sections with hydraulic mining debris.

California

Distributions and fate of chlorinated pesticides, biomarkers and polycyclic aromatic hydrocarbons in sediments along a contamination gradient from a point-source in San Francisco Bay, California

The distribution and fate of chlorinated pesticides, biomarkers, and polycyclic aromatic hydrocarbons (PAHs) in surficial sediments along a contamination gradient in the Lauritzen Canal and Richmond Harbor in San Francisco Bay was investigated. Compounds were identified and quantified using gas chromatography-ion trap mass spectrometry. Biomarkers and PAHs were derived primarily from weathered petroleum. DDT was reductively dechlorinated under anoxic conditions to DDD and several minor degradation products, DDMU, DDMS, and DDNU. Under aerobic conditions, DDT was dehydrochlorinated to DDE and DBP. Aerobic degradation of DDT was diminished or inhibited in zones of high concentration, and increased significantly in zones of lower concentration: Other chlorinated pesticides identified in sediment included dieldrin and chlordane isomers. Multivariate analysis of the distributions of the DDTs suggested that there are probably two sources of DDD. In addition, DDE and DDMU are probably formed by similar mechanisms, i.e. dehydrochlorination. A steep concentration gradient existed from the Canal to the Outer Richmond Harbor, but higher levels of DDD than those found in the remainder of the Bay indicated that these contaminants are transported on particulates and colloidal organic matter from this source into San Francisco Bay. Chlorinated pesticides and PAHs may pose a potential problem to biota in San Francisco Bay.

Marine Environmental Research

Occurrence and accumulation of pesticides and organic contaminants in river sediment, water and clam tissues from the San Joaquin River and tributaries, California

A study was conducted in 1992 to assess the effects of anthropogenic activities and land use on the water quality of the San Joaquin River and its major tributaries. This study focused on pesticides and organic contaminants, looking at distributions of contaminants in water, bed and suspended sediment, and the bivalve Corbicula fluminea. Results indicated that this river system is affected by agricultural practices and urban runoff. Sediments from Dry Creek contained elevated concentrations of polycyclic aromatic hydrocarbons (PAHs), possibly derived from urban runoff from the city of Modesto; suspended sediments contained elevated amounts of chlordane. Trace levels of triazine herbicides atrazine and simazine were present in water at most sites. Sediments, water, and bivalves from Orestimba Creek, a westside tributary draining agricultural areas, contained the greatest levels of DDT (1,1,1-trichloro-2-2-bis[p-chlorophenyl]ethane), and its degradates DDD (1,1-dichloro-2,2-bis[p-chlorophenyl]ethane), and DDE (1,1-dichloro-2,2- bis[p-chlorophenyl]ethylene). Sediment adsorption co efficients (K(oc)), and bioconcentration factors (BCF) in Corbicula of DDT, DDD, and DDE at Orestimba Creek were greater than predicted values. Streams of the western San Joaquin Valley can potentially transport significant amounts of chlorinated pesticides to the San Joaquin River, the delta, and San Francisco Bay. Organochlorine compounds accumulate in bivalves and sediment and may pose a problem to other biotic species in this watershed.

California

A reconnaissance study of halogenated organic compounds in catfish from the lower Mississippi river and its major tributaries

Blue catfish, (Ictarurus furcatus), black bullhead catfish, (Ictalurus melas), channel catfish (Ictalurus punctatus), and flathead catfish (Pylodictus olivaris), were collected along a 1200 mile river reach of the Mississippi River and its major tributaries. Tissue samples were extracted and analyzed by fused silica capillary gas chromatography/mass spectrometry (GC/MS) to determine the concentrations of hydrophobic organic halogenated contaminants that have bioconcentrated within the tissues. The compounds identified in the tissue include chlordane, polychlorinated biphenyls (PCBs), DDT and its metabolites along with several other chlorinated pesticides. The data indicates that the southern reach of the river system appears to be more contaminated than the middle and upper reaches of the study area.

Chemosphere

Determination of trace levels of herbicides and their degradation products in surface and ground waters by gas chromatography/ion-trap mass spectrometry

A rapid, specific and highly sensitive method is described for the determination of several commonly used herbicides and their degradation products in surface and ground waters by using gas chromatography/ion-trap mass spectrometry. The compounds included atrazine, and its degradation products desethylatrazine and desisopropylatrazine; Simazine; Cyanazine; Metolachlor; and alachlor and its degradation products, 2-chloro-2', 6'-diethylacetanilide, 2-hydroxy-2', 6'-diethylacetanilide and 2,6-diethylaniline. The method was applied to surface-water samples collected from 16 different stations along the lower Mississippi River and its major tributaries, and ground-water samples beneath a cornfield in central Nebraska. Average recovery of a surrogate herbicide, terbuthylazine, was greater than 99%. Recoveries of the compounds of interest from river water spiked at environmental levels are also presented. Full-scan mass spectra of these compounds were obtained on 1 ng or less of analyte. Data were collected in the full-scan acquisition mode. Quantitation was based on a single characteristic ion for each compound. The detection limit was 60 pg with a signal-to-noise ratio of greater than 10:1.

Analytica Chimica Acta

Analysis of chlorinated organic compounds in estuarine biota and sediments by chemical ionization tandem mass spectrometry

Complex sample matrices of estuarine biota tissue and bed sediment extracts were analyzed for selected chlorinated compounds. By using gas chromatography/positive chemical ionization/tandem mass spectrometry, the coeluting interferences present in gas chromatography/electron ionization mass spectrometry were eliminated in the biota tissue and bed sediment extracts. The selected chlorinated compounds included chlorobenzene; 1,2‐, 1,3‐ and 1,4‐dichlorobenzene; 1,2,3‐, 1,2,4‐ and 1,3,5‐trichlorobenzene; 1,2,3,4‐, 1,2,3,5‐ and 1,2,4,5‐tetrachlorobenzene; pentachlorobenzene; hexachlorobenzene; hexachloro‐1,3‐butadiene; octachlorostyrene; and octachloronaphthalene. Daughter ion spectra for these compounds are included. The detection limit for most of the compounds was 20 pg, and the instrument response was linear over five orders of magnitude, by using 13 C‐labelled hexachlorobenzene as the internal standard.

Biological Mass Spectrometry

Microbial hydroxylation of quinoline in contaminated groundwater: evidence for incorporation of the oxygen atom of water.

Studies conducted in an aquifer contaminated by creosote suggest that quinoline is converted to 2(1H)quinolinone by an indigenous consortium of microorganisms. Laboratory microbial experiments using H 2 18 O indicate that water is the source of the oxygen atom for this hydroxylation reaction under aerobic and anaerobic conditions.

Applied and Environmental Microbiology

Microbial transformations of azaarenes in creosite-contaminated soil and ground water: Laboratory and field studies

Azaarenes or aromatic nitrogen heterocycles are a class of compounds found in wood-preservative wastes containing creosote. The fate and movement of these compounds in contaminated aquifers is not well understood. Water-quality studies in an aquifer contaminated with creosote near Pensacola, Florida, indicated that ground water was contaminated with several azaarenes and their oxygenated and alkylated derivatives, suggesting that these oxygenated compounds may be products of microbial transformation reactions. Accordingly, laboratory studies were designed to investigate the fate of these compounds. Under aerobic conditions, soil pseudomonads isolated from creosote-contaminated soil converted quinoline to 2(1H)quinoline that subsequently was degraded to unknown products. A methanogenic consortium isolated from an anaerobic sewage digestor, in presence of ground-water and creosote-contaminated soil, converted quinoline, isoquinoline, and 4-methylquinoline to their respective oxygenated analogs. In addition, N-, C-, and O-methylated analogs of oxygenated azaarenes were identified by gas chromatography-mass spectrometry (GC-MS) in aerobic cultures. Under the experimental conditions, 2-methylquinoline was biorefractory. Presence of similar biotransformation products in anaerobic cultures and contaminated ground water from the Pensacola site provided further evidence that these compounds indeed were mivrobial transformation products. Stable isotope labeling studies indicated that the source of the oxygen atom for this hydroxylation reaction under aerobic and anaerobic conditions was water. A mechanism was proposed for this hydroxylation reaction. Whereas parent azaarenes are biodegradable in both anaerobic and aerobic zones, oxygenated and alkylated analogs are more biorefractory and, hence, persistent in anaerobic zones of contaminated aquifers.

Water Science and Technology

Fate and movement of azaarenes and their anaerobic biotransformation products in an aquifer contaminated by wood-treatment chemicals

Infiltration of wastes containing creosote and pentachlorophenol from surface impoundments at an abandoned wood-treatment facility near Pensacola, Florida, resulted in contamination of the underlying sand and gravel aquifer. Pond sludges and sediments near the source were contaminated with 2- to 5-ring azaarenes having log Kow values of from 2.0 to 5.6. However, the ground water contained only azaarenes and their oxygenated and methylated derivatives having log Kow values of less than 3.5. These compounds also were present in coal tar-contaminated ground water at a site near St. Louis Park, Minnesota. Laboratory anaerobic degradation studies and on-site observations indicated that oxygenated azaarenes probably were biotransformation products of reactions mediated by indigenous microbial populations. Microbial N-methylation, C-methylation and O-methylation reactions are reported here for the first time. In the presence of nutrients and carbon sources such as acetate and propionate, all azaarenes studied were either partially or completely degraded. Evidence for the microbial degradation of azaarenes in ground water from anaerobic zones is presented. Oxygenated azaarenes were relatively more water-soluble, mobile and persistent in hydrogeologic environments.

Minnesota, Florida

Creosote compounds in snails obtained from Pensacola Bay, Florida, near an onshore hazardous-waste site

Snails, Thais haemostoma, were collected from two areas offshore in Pensacola Bay, Florida, near an onshore hazardous-waste site. Tissue from the snails was extracted to isolate the lipophilic compounds and analyzed by gas chromatography/mass spectrometry. Along with naturally occurring compounds, the snail tissue contained large concentrations of polycyclic aromatic compounds, such as phenanthrene, acridine, dibenzothiophene, dibenzofuran, and benzo[a]pyrene. Many of these compounds were characteristic of creosote contamination associated with the onshore hazardous-waste site.

Florida

Ground-water contamination by organic bases derived from coal-tar wastes

A fluid sample from a shallow aquifer contaminated by coal-tar wastes was analyzed for organic bases. The sample consisted of a mixture of aqueous and oily-tar phases. The phases were separated by centrifugation and filtration. Organic bases were isolated from each phase by pH adjustment and solvent extraction. Organic bases in the oily-tar phase were further purified by neutral-alumina, micro-column adsorption chromatography. Separation and identification of the organic bases in each phase were achieved by using capillary gas chromatography-mass spectrometry-computer (GC-MS-COM) and probe distillation-high resolution mass spectrometry (PD-HRMS) techniques. Organic bases present in the aqueous phase included primary aromatic amines (such as aniline, alkylated anilines, and naphthylamines) as well as azaarenes (such as alkylated pyridines, quinolines, acridine, and benzoquinolines). The oily-tar phase contained acridine, benzacridines, dibenzacridines, and numerous other azaarenes, the elemental compositions of which were determined by PD-HRMS. Azaarenes in the oily-tar phase, varying in size from 6 to 12 rings, are reported for the first time. The origin and environmental significance of these compounds are discussed.

Environmental Toxicology and Chemistry

Characterization of dissolved organic materials in surface waters within the blast zone of Mount St Helens, Washington

After the May 18, 1980, eruption of Mount St Helens, the concentration of dissolved organic material in surface waters near the volcano increased significantly as a result of the destruction of the surrounding conifer forest. Low molecular weight organic compounds identified in the blast zone surface waters were derived from pyrolysis of plant and soil organic materials incorporated into pyroclastic flow, mud flow and debris avalanche deposits. A major fraction of the dissolved organic material consisted of high molecular weight, colored, organic acids that are similar in their general properties to aquatic fulvic acids found in more typical surface waters except for greater sulfur contents. The other major fraction of the dissolved organic material consisted of hydrophilic acids, which may include compounds capable of supporting heterotrophic microorganisms, and precursors in the formation of aquatic fulvic acids. The organic chemistry of blast zone surface waters will probably be greatly influenced by the May 18, 1980, eruption for many years.

Washington