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James N. Huckins

Publications and source records attributed to James N. Huckins.

15 recordsLinked to original sources

Application of enzyme-linked immunosorbent assay for measurement of polychlorinated biphenyls from hydrophobic solutions: Extracts of fish and dialysates of semipermeable membrane devices: Chapter 26

Determination of PCBs in biological tissue extracts by enzyme-linked immunosorbent assays (ELISAs) can be problematic, since the hydrophobic solvents used for their extraction and isolation from interfering biochemicals have limited compatibility with the polar solvents (e.g. methanol/water) and the immunochemical reagents used in ELISA. Our studies of these solvent effects indicate that significant errors can occur when microliter volumes of PCB containing extracts, in hydrophobic solvents, are diluted directly into methanol/water diluents. Errors include low recovery and excess variability among sub-samples taken from the same sample dilution. These errors are associated with inhomogeneity of the dilution, which is readily visualized by the use of a hydrophobic dye, Solvent Blue 35. Solvent Blue 35 is also used to visualize the evaporative removal of hydrophobic solvent and the dissolution of the resulting PCB/dye residue by pure methanol and 50% (v/v) methanol/water, typical ELISA diluents. Evaporative removal of isooctane by an ambient temperature nitrogen purge with subsequent dissolution in 100% methanol gives near quantitative recovery of model PCB congeners. We also compare concentrations of total PCBs from ELISA (ePCB) to their corresponding concentrations determined from capillary gas chromatography (GC) in selected fish sample extracts and dialysates of semipermeable membrane device (SPMD) passive samplers using an optimized solvent exchange procedure. Based on Aroclor 1254 calibrations, ePCBs (ng/mL) determined in fish extracts are positively correlated with total PCB concentrations (ng/mL) determined by GC: ePCB = 1.16 * total-cPCB - 5.92. Measured ePCBs (ng/3 SPMDs) were also positively correlated (r 2 = 0.999) with PCB totals (ng/3 SPMDs) measured by GC for dialysates of SPMDs: ePCB = 1.52 * total PCB - 212. Therefore, this ELISA system for PCBs can be a rapid alternative to traditional GC analyses for determination of PCBs in extracts of biota or in SPMD dialysates.

Book chapter

Feasibility of a simple laboratory approach for determining temperature influence on SPMD–air partition coefficients of selected compounds

Semipermeable membrane devices (SPMDs) are a widely used passive sampling methodology for both waterborne and airborne hydrophobic organic contaminants. The exchange kinetics and partition coefficients of an analyte in a SPMD are mediated by its physicochemical properties and certain environmental conditions. Controlled laboratory experiments are used for determining the SPMD–air ( K sa 's) partition coefficients and the exchange kinetics of organic vapors. This study focused on determining a simple approach for measuring equilibrium K sa 's for naphthalene (Naph), o -chlorophenol ( o -CPh) and p -dichlorobenzene ( p -DCB) over a wide range of temperatures. SPMDs were exposed to test chemical vapors in small, gas-tight chambers at four different temperatures (−16, −4, 22 and 40 °C). The exposure times ranged from 6 h to 28 d depending on test temperature. K sa 's or non-equilibrium concentrations in SPMDs were determined for all compounds, temperatures and exposure periods with the exception of Naph, which could not be quantified in SPMDs until 4 weeks at the −16 °C temperature. To perform this study the assumption of constant and saturated atmospheric concentrations in test chambers was made. It could influence the results, which suggest that flow through experimental system and performance reference compounds should be used for SPMD calibration.

Atmospheric Environment

Chapter 8 Tool for monitoring hydrophilic contaminants in water: polar organic chemical integrative sampler (POCIS)

The development of the polar organic chemical integrative sampler (POCIS) provides environmental scientists and policy makers a tool for assessing the presence and potential impacts of the hydrophilic component of these organic contaminants. The POCIS provides a means for determining the time-weighted average (TWA) concentrations of targeted chemicals that can be used in risk assessments to determine the biological impact of hydrophilic organic compounds (HpOCs) on the health of the impacted ecosystem. Field studies have shown that the POCIS has advantages over traditional sampling methods in sequestering and concentrating ultra-trace to trace levels of chemicals over time resulting in increased method sensitivity, ability to detect chemicals with a relatively short residence time or variable concentrations in the water, and simplicity in use. POCIS extracts can be tested using bioassays and can be used in organism dosing experiments for determining toxicological significance of the complex mixture of chemicals sampled. The POCIS has been successfully used worldwide under various field conditions ranging from stagnant ponds to shallow creeks to major river systems in both fresh and brackish water.

Comprehensive Analytical Chemistry

Theory, modelling and calibration of passive samplers used in water monitoring: Chapter 7

This chapter discusses contaminant uptake by a passive sampling device (PSD) that consists of a central sorption phase, surrounded by a membrane. A variety of models has been used over the past few years to better understand the kinetics of contaminant transfer to passive samplers. These models are essential for understanding how the amounts of absorbed contaminants relate to ambient concentrations, as well as for the design and evaluation of calibration experiments. Models differ in the number of phases and simplifying assumptions that are taken into consideration, such as the existence of (pseudo-) steady-state conditions, the presence or absence of linear concentration gradients within the membrane phase, the way in which transport within the WBL is modeled and whether or not the aqueous concentration is constant during the sampler exposure. The chapter introduces the basic concepts and models used in the literature on passive samplers for the special case of triolein-containing semipermeable membrane devices (SPMDs). These can easily be extended to samplers with more or with less sorption phases. It also discusses the transport of chemicals through the various phases constituting PSDs. the implications of these models for designing and evaluating calibration studies have been discussed.

Book chapter

Towards quantitative monitoring of semivolatile organic compounds using passive air samplers: Chapter 6

Passive air samplers can be used to measure the air concentration of various semivolatile organic compounds (SOCs) with reasonable reliability. To use passive air samplers to measure atmospheric concentrations of pollutants, calibration data are required. Calibration data include parameters such as sampling rates, sampler/air partition coefficients and loss rate constants. These parameters are usually determined in the laboratory, at a reference site or in situ . When using passive sampler data to estimate the air concentration of SOCs, investigators commonly assume that sampling follows first-order exchange kinetics. Thus, during the first stage of sampler uptake, chemicals are accumulated linearly relative to time. The accumulation of many pollutants in passive air samplers is influenced by factors such as changes in wind speed and temperature. The use of performance reference compounds (PRCs) holds considerable promise for assessing the effects of wind speed and temperature on passive sampler performance. The use of PRCs in semipermeable membrane devices (SPMDs) has also shown that photolysis of accumulated polyaromatic hydrocarbons (PAHs) occurs without adequate shading.

Book chapter

Use of the semipermeable membrane device as an in situ sampler of waterborne bioavailable PCDD and PCDF residues at sub-parts-per-quadrillion concentrations

Semipermeable membrane devices (SPMDs) were used to passively sample aqueous polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in Bayou Meto, AR. The two sites were upstream and downstream from the confluence with a tributary that delivers PCDDs and PCDFs to the Bayou. Following dialysis, cleanup, and fractionation, four replicate 17-9 SPMD samples from each site were analyzed by GUMS, and four were evaluated by H411E bioassay. Traces of only OCDD and HpCDDs were detected in samples from the upstream site. The four samples from below the tributary contained averages of 1550 ± 80 pg of 2,3,7,8-TCDD, 1640 ± 80 pg of 2,3,7,8-TCDF, and lesser quantities of other congeners. The TCDD equivalents obtained by bioassay of replicate SPMD samples agreed well with results obtained by GC/MS. The quantities of 2,3,7,8- TCDD and 2,3,7,8-TCDF sequestered by SPMDs at the downstream site were used to estimate the aqueous concentrations for both compounds as 2 pg/L.

Environmental Science & Technology

The role of water ventilation and sediment ingestion in the uptake of benzo[A]pyrene in gizzard shad ( Dorosoma cepedianum )

The objective of this study was to determine whether sediment ingestion or water ventilation was the primary route of uptake for benzo[ a ]pyrene (B a P) in the gizzard shad ( Dorosoma cepedianum ), a detritivorous fish. Two experiments were conducted in which fish were exposed to sediments spiked with 1 μg/g B a P. In the first experiment, fish were prevented from feeding by esophagus ligation. In the second experiment, 20 nonligated fish and 30 ligated fish were added to the aquarium. The nonligated fish roiled the water as they fed. Fish were collected 4, 8, 15, and 22 d after the experiments began. Gizzard shad metabolize B a P; therefore, the concentrations of B a P equivalents (parent B a P plus metabolite) were determined. Concentrations of B a P equivalents were significantly greater in the ligated fish in experiment 2 relative to those in experiment 1. In contrast, the concentration of B a P equivalents in the ligated fish in experiment 2 was not significantly different than that in the nonligated fish. Our results suggest that ventilation of turbid water may be a significant source of B a P for gizzard shad. Sediment ingestion, however, does not appear to significantly influence the total body concentration of B a P equivalents in gizzard shad.

Environmental Toxicology and Chemistry

Evaluation of lipid-containing semipermeable membrane devices for monitoring organochlorine contaminants in the Upper Mississippi river

Organochlorine contaminants sequestered in lipid-containing semipermeable membrane devices (SPMDs) were compared to those found in tangential-flow ultrafilter permeates as part of a pilot study at 10 sites in the Upper Mississippi River system. Caged and feral fish from three primary sites were also analyzed for comparison. Concentrated organochlorine (OC) compounds were readily extracted from the SPMDs by dialysis into hexane, and samples were analyzed by gas chromatography-negative chemical ionization-mass spectrometry. Fish and water samples were processed by conventional methods. Reasonable agreement was found between analyte SPMD-derived water concentrations and measured values of ultrafilter permeates; however, concentrations of the same analytes in caged fish did not appear to be proportional to water concentrations derived from SPMDs and ultrafilter permeates. The greatest number of OC compounds was detected in SPMDs; fewer were detected in caged fish and feral fish.

Illinois, Iowa, Minnesota, Missouri, Wisconsin

A survey of recent results in passive sampling of water and air by semipermeable membrane devices

A survey is presented of some recent results for passive sampling of water and air for trace organic contaminants using lipid-filled semipermeable membrane devices (SPMDs). Results of water sampling for trace organochlorine compounds using simultaneously exposed SPMDs and the most universally applied biomonitor (bivalves) are discussed. In general, the total amounts of accumulated analytes available for analysis in bivalves and SPMDs were comparable. However, SPMD controls typically had negligible levels of contamination, which was not always the case for transplanted bivalves, even after prolonged depuration prior to exposure. In surveys of the spatial trends of organochlorines at a series of sites, data from bivalves and SPMDs provided the same picture of contaminant distribution and severity. An exception was ionizable contaminants such as the chlorinated phenolic compounds and their transformation products found in pulp mill effluents. In these cases the two monitoring approaches compliment each other, i.e. what is not found in bivalves appears in SPMDs and vice versa. SPMDs have also been applied in environments where biomonitoring is not feasible. SPMDs have shown their utility in studies of trace levels of polyaromatic hydrocarbons by locating and characterizing point sources. An example is given of their application to the calculation of contaminant half-lives from aqueous SPMD residues, a direct measurement of the persistence of contaminants in an environmental compartment. Similarly, results of air sampling with SPMDs in a relatively pristine coastal location are cited which reveal a tremendous enhancement in p,p′ -DDE relative to open ocean values.

Marine Pollution Bulletin

Use of semipermeable membrane devices (SPMDS) to determine bioavailable organochlorine pesticide residues in streams receiving irrigation drainwater

The semipermeable membrane device (SPMD), consisting of a neutral lipid (triolein) enclosed in polyethylene layflat tubing, is very effective in sequestering bioavailable organochlorine (OC) pesticides in the environment. We used SPMDs to sequester OC pesticide residues in streams receiving irrigation drainwater and found toxaphene, the DDT complex, dieldrin, and endrin. Ambient water concentrations of the OC pesticides were calculated using an algorithm developed previously. Toxaphene residues were estimated to range from 300 to 7,000 ng/L.

Chemosphere

Separation of selenium species released from Se-exposed algae

We have assessed a fractionation scheme for selenium species that separates Se-containing amino acids and other organoselenium compounds in aqueous samples. We investigated the retention of standard solutions of selenate (Se +6 ), selenite (Se +4 ), and selenomethionine (Se −2 ) by fractionation media (Sephadex A-25 ion-exchange resin, copper-treated Chelex-100 ligand-exchange resin, and activated charcoal) and by several types of membrane filters. The fractionation method successfully isolated Se from the standard solutions into appropriate fractions for radiometric quantitation of 75 Se. However, some filter media retained unacceptably large amounts of selenate and selenite. Mass balance microcosms were inoculated with green algae ( Chlamydomonas "> Chlamydomonas reinhardtii "> reinhardtii ) previously exposed to inorganic 75 Se, and the fractionation scheme was used to examine the release of 75 Se species into water and air. The results of the microcosm exposure indicate that seasonal blooms and crashes of phytoplankton populations may produce increased concentrations of organoselenium species.

Chemosphere

Application of semipermeable membrane devices (SPMDs) as passive air samplers

The semipermeable membrane device (SPMD), consisting of a neutral lipid (triolein) enclosed in polyethylene layflat tubing, is demonstrated to be a highly efficient passive air sampler. These devices readily sequester lipophilic organic contaminants from the vapor phase. Specifically, the SPMDs are shown to concentrate polychlorinated biphenyl (PCB) residues from a laboratory atmosphere in a linear manner through 28 days. Under the conditions of this study, a three device composite (1.4 g triolein) extracted PCB residues from ≈ 7 m 3 of air per day.

Chemosphere

Use of semipermeable membrane devices for in situ monitoring of polycyclic aromatic hydrocarbons in aquatic environments

A method is given for the recovery, cleanup, and analysis of polycyclic aromatic hydrocarbons (PAHs) that have been sequestered in SPMDs (semipermeable membrane devices). SPMDs are polymeric membranes enclosing lipids, and mimic the bioconcentration process of aquatic animals. SPMDs are used as passive, in situ monitors of contamination by organic pollutants of aquatic environments. The method reported here includes dialytic recovery of the PAHs, cleanup of the dialysates using size exclusion, adsorption, and argentation chromatographic modules in tandem, then analysis by gas chromatography with photoionization or mass spectrometric detection. The method is demonstrated to overcome the presence of a variety of environmental co-contaminants and other potential interferents in the dialysates. A field application is also demonstrated in which SPMDs are used to monitor PAH contamination in an urban creek. Approaches to the use of SPMD data to calculate aqueous concentrations of PAHs are discussed. The use of SPMDs in combination with the complementary, PAH-specific cleanup procedure provides a unique approach to the analysis of PAH residues in the aquatic environment.

Chemosphere

Role of exposure mode in the bioavailability of triphenyl phosphate to aquatic organisms

A laboratory study was conducted to investigate the role of the route of triphenyl phosphate (TPP) entry on its aquatic bioavailability and acute biological effects. Three TPP treatments were used for exposures of fish and invertebrates. These consisted of TPP dosed directly into water with and without clean sediment and TPP spiked onto sediment prior to aqueous exposures. Results of static acute toxicity tests (no sediment) were 0.78 mg/L (96-h LC50) for bluegill, 0.36 mg/L (48-h EC50) for midge, and 0.25 mg/L (96-h EC50) for scud. At 24 h, the sediment (1.1% organic carbon)/water partition coefficient (Kp) for TPP was 112. Use of this partition coefficient model to predict the sediment-mediated reduction of TPP concentration in water during toxicity tests resulted in a value that was only 10% less than the nominal value. However, the required nominal concentration of TPP to cause acute toxicity responses in test organisms was significantly higher than the predicted value by the model for both clay and soil-derived sediment. Direct spiking of TPP to soil minimized TPP bioavailability. Data from parallel experiments designed to track TPP residues in water through time suggest that sorption kinetics control residue bioavailability in the initial 24 h of exposure and may account for observed differences in LC50 and EC50 values from the sediment treatments.

Archives of Environmental Contamination and Toxico