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T.J. Leiker

Publications and source records attributed to T.J. Leiker.

16 recordsLinked to original sources

Identification of methyl triclosan and halogenated analogues in male common carp (Cyprinus carpio) from Las Vegas Bay and semipermeable membrane devices from Las Vegas Wash, Nevada

Methyl triclosan and four halogenated analogues have been identified in extracts of individual whole-body male carp (Cyprinus carpio) tissue that were collected from Las Vegas Bay, Nevada, and Semipermeable Membrane Devices (SPMD) that were deployed in Las Vegas Wash, Nevada. Methyl triclosan is believed to be the microbially methylated product of the antibacterial agent triclosan (2, 4, 4'-trichloro-4-hydroxydiphenyl ether, Chemical Abstract Service Registry Number 3380-34-5, Irgasan DP300). The presence of methyl triclosan and four halogenated analogues was confirmed in SPMD extracts by comparing low- and high-resolution mass spectral data and Kovats retention indices of methyl triclosan with commercially obtained triclosan that was derivatized to the methyl ether with ethereal diazomethane. The four halogenated analogues of methyl triclosan detected in both whole-body tissue and SPMD extracts were tentatively identified by high resolution mass spectrometry. Methyl triclosan was detected in all 29 male common carp from Las Vegas Bay with a mean concentration of 596????g kg- 1 wet weight (ww) which is more than an order of magnitude higher than previously reported concentrations in the literature. The halogenated analogs were detected less frequently (21%-76%) and at much lower concentrations (< 51????g kg- 1 ww). None of these compounds were detected in common carp from a Lake Mead reference site in Overton Arm, Nevada.

Science of the Total Environment↗

A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants

As an integral part of our continuing research in environmental quality assessment approaches, we have developed a variety of passive integrative sampling devices widely applicable for use in defining the presence and potential impacts of a broad array of contaminants. The semipermeable membrane device has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler is applicable for sampling vapor phase or dissolved neutral mercury species. This suite of integrative samplers forms the basis for a new passive sampling approach for assessing the presence and potential toxicological significance of a broad spectrum of environmental contaminants. In a proof-of-concept study, three of our four passive integrative samplers were used to assess the presence of a wide variety of contaminants in the waters of a constructed wetland, and to determine the effectiveness of the constructed wetland in removing contaminants. The wetland is used for final polishing of secondary-treatment municipal wastewater and the effluent is used as a source of water for a state wildlife area. Numerous contaminants, including organochlorine pesticides, polycyclic aromatic hydrocarbons, organophosphate pesticides, and pharmaceutical chemicals (e.g., ibuprofen, oxindole, etc.) were detected in the wastewater. Herein we summarize the results of the analysis of the field-deployed samplers and demonstrate the utility of this holistic approach.

Chemosphere↗

Analytical interferences of mercuric chloride preservative in environmental water samples: Determination of organic compounds isolated by continuous liquid-liquid extraction or closed-loop stripping

Analytical interferences were observed during the determination of organic compounds in groundwater samples preserved with mercuric chloride. The nature of the interference was different depending on the analytical isolation technique employed. (1) Water samples extracted with dichloromethane by continuous liquid-liquid extraction (CLLE) and analyzed by gas chromatography/mass spectrometry revealed a broad HgCl2 'peak' eluting over a 3-5-min span which interfered with the determination of coeluting organic analytes. Substitution of CLLE for separatory funnel extraction in EPA method 508 also resulted in analytical interferences from the use of HgCl2 preservative. (2) Mercuric chloride was purged, along with organic contaminants, during closed-loop stripping (CLS) of groundwater samples and absorbed onto the activated charcoal trap. Competitive sorption of the HgCl2 by the trap appeared to contribute to the observed poor recoveries for spiked organic contaminants. The HgCl2 was not displaced from the charcoal with the dichloromethane elution solvent and required strong nitric acid to achieve rapid, complete displacement. Similar competitive sorption mechanisms might also occur in other purge and trap methods when this preservative is used.

Environmental Science & Technology↗

Contaminants in arctic snow collected over northwest Alaskan sea ice

Snow cores were collected over sea ice from four northwest Alaskan Arctic estuaries that represented the annual snowfall from the 1995-1996 season. Dissolved trace metals, major cations and anions, total mercury, and organochlorine compounds were determined and compared to concentrations in previous arctic studies. Traces (<4 nanograms per liter, ng L-1) of cis- and trans-chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, dieldrin, endosulfan II, and PCBs were detected in some samples, with endosulfan I consistently present. High chlorpyrifos concentrations (70-80 ng L-1) also were estimated at three sites. The snow was highly enriched in sulfates (69- 394 mg L-1), with high proportions of nonsea salt sulfates at three of five sites (9 of 15 samples), thus indicating possible contamination through long-distance transport and deposition of sulfate-rich atmospheric aerosols. Mercury, cadmium, chromium, molybdenum, and uranium were typically higher in the marine snow (n = 15) in relation to snow from arctic terrestrial studies, whereas cations associated with terrigenous sources, such as aluminum, frequently were lower over the sea ice. One Kasegaluk Lagoon site (Chukchi Sea) had especially high concentrations of total mercury (mean = 214 ng L-1, standard deviation = 5 ng L-1), but no methyl mercury was detected above the method detection limit (0.036 ng L-1) at any of the sites. Elevated concentrations of sulfate, mercury, and certain heavy metals might indicate mechanisms of contaminant loss from the arctic atmosphere over marine water not previously reported over land areas. Scavenging by snow, fog, or riming processes and the high content of deposited halides might facilitate the loss of such contaminants from the atmosphere. Both the mercury and chlorpyrifos concentrations merit further investigation in view of their toxicity to aquatic organisms at low concentrations.

Water, Air, & Soil Pollution↗

Diagenetic fate of organic contaminants on the Palos Verdes Shelf, California

Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6–8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT+metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p , p ′-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60–70% of ΣDDT. The p , p -DDE/ p , p ′-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p , p ′-DDE is occurring. Approximately 9–23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p , p ′-DDE inventory that has been observed at the study site for the period 1981–1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 10 2 –10 3 times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., Mueller, S.A., Jain, M.K., Tiedje, J.M., 1998. Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280, 722–724.). This explains why the DDT composition (i.e. o , p ′-, p , p ′-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB compositions in shelf sediments are highly uniform and show no evidence of diagenetic transformation. Apparently, the agents/factors responsible for reductive dechlorination of DDE are not also effecting alteration of the PCBs. Two types of long-chain alkylbenzenes were found in the contaminated sediments. Comparison of chain length and isomer distributions of the linear alkylbenzenes in wastewater effluent and surficial sediment samples indicate that these compounds undergo biodegradation during sedimentation. Further degradation of the linear alkylbenzenes occurs after burial despite relatively invariant isomer compositions. The branched alkylbenzenes are much more persistent than the linear alkylbenzenes, presumably due to extensive branching of the alkyl side chain. Based on these results, p , p ′-DDE, PCBs, and selected branched alkylbenzenes are sufficiently persistent for use in molecular stratigraphy. The linear alkylbenzenes may also provide information on depositional processes. However, their application as quantitative molecular tracers should be approached with caution.

California↗

Distribution and transport of selected anthropogenic lipophilic organic compounds associated with Mississippi River suspended sediment, 1989-1990

In the first study on this scale, distribution and transport of selected hydrophobic halogenated organic compounds associated with suspended sediment from the lower Mississippi River and its principal tributaries were determined during two spring and two summer cruises. Lipophilic organic compounds identified on the suspended sediment included hexachlorobenzene, pentachlorobenzene, pentachloroanisole, dacthal, chlordane (cis- and trans- ), nonachlor (trans-), chlorthalonil, and penta-, hexa-, hepta-, and octachlorobiphenyls. Most of these compounds come from nonpoint sources. Mass loadings of most of the compounds increased from upstream to downstream on the main stem of the Mississippi River. Of the tributaries studied, the Ohio River had the most significant effect on contaminant loads. Suspended sediment transport to the Gulf of Mexico of the most abundant, widely distributed compound class, PCBs, was estimated at 6,750 kg per year.

Mississippi River↗

Distribution and transport of selected anthropogenic organic compounds on Mississippi River suspended sediment (U.S.A.), May/June 1988

The distribution and transport of selected hydrophobic halogenated organic compounds on suspended sediment from the lower Mississippi River were determined using discharge-weighted sampling with concurrent discharge measurements. Trends in compound concentration from upstream to downstream and the effects of selected tributaries were determined. The compounds identified on the suspended sediment include pentachlorobenzene, hexachlorobenzene, pentachloroanisole, dacthal, chlordane (trans-), nonachlor (trans-), chlorthalonil, and penta-, hexa-, hepta- and octachlorobiphenyls. Loads of most of the compounds increased from upstream to downstream on the main stem of the Mississippi River. Of the tributaries studied, the Ohio River had the most significant effect on the loads.The distribution and transport of selected hydrophobic halogenated organic compounds on suspended sediment from the lower Mississippi River were determined using discharge-weighted sampling with concurrent discharge measurements. Trends in compound concentration from upstream to downstream and the effects of selected tributaries were determined. The compounds identified on the suspended sediment include pentachlorobenzene, hexachlorobenzene, pentachloroanisole, dacthal, chlordane (trans-), nonachlor (trans-), chlorthalonil, and penta-, hexa-, hepta- and octachlorobiphenyls. Loads of most of the compounds increased from upstream to downstream on the main stem of the Mississippi River. Of the tributaries studied, the Ohio River had the most significant effect on the loads.

Journal of Contaminant Hydrology↗

Synthetic organic agrochemicals in the lower Mississippi River and its major tributaries--Distribution, transport and fate

The Mississippi River and its major tributaries transport herbicides and their degradation products from agricultural areas in the mid-western U.S.A. These compounds include atrazine and its degradation products (desethyl- 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). These compounds were identified and confirmed by gas chromatography-ion trap mass spectrometry. Loads of these compounds were determined during five sampling trips in 1987–1989. Stream loads of these compounds indicated that atrazine and metolachlor were relatively conservative in downstream transport. Alachlor and its degradation products were generated from point and non-point sources. Seasonal variations and hydrologic conditions controlled the loads of these compounds in the Mississippi River. Cross-channel mixing was slow downstream from major river confluences, possibly requiring several hundred kilometers of downriver transit for completion. The annual transport of these compounds into the Gulf of Mexico was estimated to be < 2% of the annual application of each herbicide in the Midwest.

Journal of Contaminant Hydrology↗

Synthetic organic agrochemicals in the lower Mississippi River and its major tributaries: Distribution, transport and fate

The Mississippi River and its major tributaries transport herbicides and their degradation products from agricultural areas in the mid-western U.S.A. These compounds include atrazine and its degradation products (desethyl- 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). These compounds were identified and confirmed by gas chromatography-ion trap mass spectrometry. Loads of these compounds were determined during five sampling trips in 1987-1989. Stream loads of these compounds indicated that atrazine and metolachlor were relatively conservative in downstream transport. Alachlor and its degradation products were generated from point and non-point sources. Seasonal variations and hydrologic conditions controlled the loads of these compounds in the Mississippi River. Cross-channel mixing was slow downstream from major river confluences, possibly requiring several hundred kilometers of downriver transit for completion. The annual transport of these compounds into the Gulf of Mexico was estimated to be < 2% of the annual application of each herbicide in the Midwest.The Mississippi River and its major tributaries transport herbicides and their degradation products from agricultural areas in the mid-western U.S.A. These compounds include atrazine and its degradation products (desethyl- 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). These compounds were identified and confirmed by gas chromatography-ion trap mass spectrometry. Loads of these compounds were determined during five sampling trips in 1987-1989. Stream loads of these compounds indicated that atrazine and metolachlor were relatively conservative in downstream transport. Alachlor and its degradation products were generated from point and non-point sources. Seasonal variations and hydrologic conditions controlled the loads of these compounds in the Mississippi River. Cross-channel mixing was slow downstream from major river confluences, possibly requiring several hundred kilometers of downriver transit for completion. The annual transport of these compounds into the Gulf of Mexico was estimated to be <2% of the annual application of each herbicide in the Midwest.

Conference Paper↗

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↗

Distribution of agrochemicals in the lower Mississippi River and its tributaries

The Mississippi River and its tributaries drain extensive agricultural regions of the Mid-Continental United States. Millions of pounds of herbicides are applied annually in these areas to improve crop yields. Many of these compounds are transported into the river from point and nonpoint sources, and eventually are discharged into the Gulf of Mexico. Studies being conducted by the U.S. Geological Survey along the lower Mississippi River and its major tributaries, representing a 2000 km river reach, have confirmed that several triazine and acetanilide herbicides and their degradation products are ubiquitous in this riverine system. These compounds include atrazine and its degradation products desethyl and desisopropylatrazine, cyanazine, simazine, metolachlor, and alachlor and its degradation products 2-chloro-2',6'-diethylacetanilide, 2-hydroxy-2',6-diethylacetanilide and 2,6-diethylaniline. Loads of these compounds were determined at 16 different sampling stations. Stream-load calculations provided information concerning (a) conservative or nonconservative behavior of herbicides; (b) point sources or nonpoint sources; (c) validation of sampling techniques; and (d) transport past each sampling station.

Lower Mississippi River↗

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↗

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↗