Carl E. Orazio

Considerations involved with the use of semipermeable membrane devices for monitoring environmental contaminants.

Semipermeable membrane devices (SPMDs) are used with increasing frequency, and throughout the world as samplers of organic contaminants. The devices can be used to detect a variety of lipophilic chemicals in water, sediment/soil, and air. SPMDs are designed to sample nonpolar, hydrophobic chemicals. The maximum concentration factor achievable for a particular chemical is proportional to its octanol-water partition coefficient. Techniques used for cleanup of SPMD extracts for targeted analytes and for general screening by full-scan mass spectrometry do not differ greatly from techniques used for extracts of other matrices. However, SPMD extracts contain potential interferences that are specific to the membrane-lipid matrix. Procedures have been developed or modified to alleviate these potential interferences. The SPMD approach has been demonstrated to be applicable to sequestering and analyzing a wide array of environmental contaminants including organochlorine pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polychlorinated dioxins and dibenzofurans, selected organophosphate pesticides and pyrethroid insecticides, and other nonpolar organic chemicals. We present herein an overview of effective procedural steps for analyzing exposed SPMDs for trace to ultra-trace levels of contaminants sequestered from environmental matrices.

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-g SPMD samples from each site were analyzed by GC/MS, 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.

Determination of waterborne bioavailable organochlorine pesticide residues in the Lower Missouri River

The semipermeable membrane device (SPMD) technology, was used to determine the presence of bioavailable organochlorine (OC) pesticides in the water of the main stem Missouri River. SPMDs were deployed for 28 days at five main stem sites - Sioux City, IA; Nebraska City,NE; Kansas City, MO; Glasgow, MO; and Hermann, MO. In general, OCs were present at all sites. Of all targeted analytes, the chlordane components, heptachlor expoxide, toaxaphene, and dieldrin were generally present at the highest concentrations. Replicate (n = 4) SPMD samplers sequestered similar quantities (typical CV = 10-35% ) of each OC pesticide. The sequestered residues represent an estimation of bioavailable (by respiration process) or dissolved OCs present in the main stem of the Missouri River.

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in harbor sediments from Sea Lots, Port-of-Spain, Trinidad and Tobago

Concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were determined in nearshore marine surficial sediments from three locations in Trinidad. Sediments were sampled at Sea Lots on the west coast, in south Port-of-Spain Harbor, south of Sea Lots at Caroni Lagoon National Park, and on Trinidads east coast at Manzanilla. Total PCB concentrations in Sea Lots sediments ranged from 62 to 601ng/g (dry weight {dw}), which was higher than at Caroni and Manzanilla, 13 and 8ng/g dw, respectively. Total OCP concentrations at Sea Lots were ranged from 44.5 to 145ng/g dw, compared with 13.1 and 23.8n/g (dw), for Caroni and Manzanilla respectively. The concentrations of PCBs and of some OCPs in sediments from Sea Lots were above the Canadian interim sediment quality guidelines. To date, this data is the first report on the levels of PCBs and other organochlorine compounds from Trinidad and Tobago.

Dietary exposure of mink (Mustela vison) to fish from the Housatonic River, Berkshire County, Massachusetts, USA: Effects on reproduction, kit growth, and survival

We evaluated the effects of feeding farm-raised mink (Mustela vison) diets containing polychlorinated biphenyl (PCB)-contaminated fish from the Housatonic River (HR; Berkshire County, MA, USA) on adult reproductive performance and kit growth and survival. Diets contained 0.22-3.54% HR fish, providing 0.34-3.7 microg total PCBs (TPCB)/g feed wet wt (3.5-68.5 pg toxic equivalence [TEQ]/g). Female mink were fed diets before breeding through weaning of kits. Twelve kits from each treatment were maintained on their respective diets for an additional 180 d. Dietary PCBs had no effect on the number of offspring produced, gestation period, or other measures of adult reproductive performance. Mink kits exposed to 3.7 microg TPCB/g feed (68.5 pg TEQ/ g) in utero and during lactation had reduced survivability between three and six weeks of age. The lethal concentrations to 10 and 20% of the population (LC10 and LC20, respectively) were estimated to be 0.231 and 0.984 microg TPCB/g feed, respectively. Because inclusion of PCB-contaminated fish that composed approximately 1% of the diet would reduce mink kit survival by 20% or more, it is likely that consumption of up to 30-fold that quantity of HR fish, as could be expected for wild mink, would have an adverse effect on wild mink populations.

Toxicological and chemical screening of Antarctica sediments: Use of whole sediment toxicity tests, microtox, mutatox and semipermeable membrane devices (SPMDs)

Abstract Eight whole sediment samples from Antarctica (four from Winter Quarters Bay and four from McMurdo Sound) were toxicologically and chemically evaluated. Also, the influence of ultraviolet radiation on the toxicity and bioavailability of contaminants associated with the sediment samples was assessed. The evaluations were accomplished by use of a 10-day whole sediment test with Leptocheirus plumulosus, Microtox®, Mutatox® and semipermeable membrane devices (SPMDs). Winter Quarters Bay sediments contained about 250 ng g−1 (dry weight) total PCBs and 20 μg g−1 total PAHs. These sediments elicited toxicity in the Microtox test and avoidance and inhibited burrowing in the L. plumulosus test. The McMurdo Sound sediment samples contained only trace amounts of PCBs and no PAHs, and were less toxic in both the L. plumulosus and Microtox tests compared to the Winter Quarters Bay sediments. The sediments from McMurdo Sound apparently contained some unidentified substance which was photolytically modified to a more toxic form. The photolytic modification of sediment-associated contaminants, coupled with the polar ozone hole and increased incidence of ultraviolet radiation could significantly increase hazards to Antarctic marine life.

Dietary exposure of mink (Mustela vison) to fish from the Housatonic River, Berkshire County, Massachusetts, USA: Effects on organ weights and histology and hepatic concentrations of polychlorinated biphenyls and 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalence

The effects of feeding ranch mink (Mustela vison) diets containing polychlorinated biphenyl (PCB)-contaminated fish (88 gold fish [Carassius auratus] weighing a total of 70.3 kg and 16 carp [Cyprinus carpio] weighing a total of 77.3 kg) collected from the Housatonic River (HR; Berkshire County, MA, USA) in October 1999 on organ weights and histology and hepatic concentrations of total PCBs (sigmaPCBs) and 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalence (TEQ) were evaluated. Diets contained 0.22 to 3.54% HR fish, which provided 0.34 to 3.7 microg sigmaPCBs/g feed (3.5-69 pg TEQ/g feed). Female mink were fed the diets eight weeks before breeding through weaning of kits at six weeks of age. Offspring were maintained on their respective diets for an additional 180 d. The dietary concentration of PCBs that caused a decrease in kit survival (3.7 microg EPCBs/g feed [69 pg TEQ/g]) resulted in a maternal hepatic concentration of 3.1 microg sigmaPCBs/g wet weight (218 pg TEQ/g). Organ weights were not consistently affected. Mandibular and maxillary squamous cell proliferation was apparent in 31-week-old juveniles exposed to as low as 0.96 microg sigmaPCBs/g feed (9.2 pg TEQ/g). Juveniles in this treatment group had a liver concentration of 1.7 microg sigmaPCBs/g wet weight (40 pg TEQ/g). Because inclusion of PCB-contaminated fish, which comprised approximately 1% of the diet, resulted in mandibular and maxillary squamous cell proliferation, it is possible that consumption of up to 30-fold that quantity of HR fish, as could be expected for wild mink, would result in more severe lesions characterized by loss of teeth, thus impacting survivability.

Polybrominated diphenyl ether metabolism in field collected fish from the Gila River, Arizona, USA-Levels, possible sources, and patterns

Polybrominated diphenyl ethers (PBDEs) were determined in fish collected from the Gila River, Arizona, a tributary of the Colorado River in the lower part of the Colorado River Basin. Fish samples were collected at sites on the Gila River downstream from Hayden, Phoenix, and Arlington, Arizona in late summer 2003. The Gila River is ephemeral upstream of the Phoenix urban area due to dams and irrigation projects and has limited perennial flow downstream of Phoenix due to wastewater and irrigation return flows. Fifty PBDE congeners were analyzed by high resolution gas chromatography/high resolution mass spectrometry using labeled surrogate standards in composite samples of male and female common carp (Cyrpinus carpio), largemouth bass (Micropterus salmoides) and channel catfish (Ictalurus punctatus). The predominant PBDE congeners detected and quantified were 47, 100, 153, 49, 28, and 17. Concentrations of total PBDEs in these fish ranged from 1.4 to 12700 ng g(-1) wet weight, which are some of the highest concentrations reported in fish from the United States. Differences in metabolism of several PBDE congeners by carp is clear at the Phoenix site; congeners with at least one ring of 2,4,5-substitution are preferentially metabolized as are congeners with 2,3,4-substitution.

Metals in sediments and fish from Sea Lots and Point Lisas Harbors, Trinidad and Tobago.

Concentrations of heavy metals were determined in nearshore marine sediments and fish tissue from Sea Lots area on the west coast, at Caroni Lagoon National Park, and in the Point Lisas harbor, Trinidad. The most dominant metals found in sediments were Al, Fe and Zn with mean concentrations highest at Sea Lots (Al-39420 μg/g; Fe-45640 μg/g; Zn-245 μg/g), when compared to sediments from Point Lisas (Al-11936 μg/g; Fe-30171 μg/g; Zn-69 μg/g) and Caroni (Al-0400 μg/g; Fe-19000 μg/g; Zn-32 μg/g), High concentration of Cu, Al, Fe and Zn were also detected in fish tissue from Point Lisas and Caroni. Metal concentrations in fish tissue showed significant correlation with sediment metals concentration, which suggests that tissue levels are influenced by sediment concentration. Of the metals, only Zn, Hg and Cu had a bioaccumulation factor (BAF) greater than one, which suggests a high bioaccumulation potential for these metals.

Pollution of Aquatic Ecosystems II: Hydrocarbons, Synthetic Organics, Radionuclides, Heavy Metals, Acids, and Thermal Pollution

Inland waters can be negatively impacted by pollution from industry, transportation, agriculture, mining, power generation, nuclear energy, weapons production, and other activities. Aquatic pollution can result of human use, misuse, and improper disposal of chemical products and by-products. Fossil fuel-related industries are potential sources of pollutant aliphatic and aromatic hydrocarbons, inorganic compounds, and metals. Inland waters can become polluted with synthetic organic chemicals, including plastics and plasticizers, flame retardants, pesticides, surfactants, and pharmaceuticals from waste water effluent, spills, and runoff from landfills. Some pollutants are both persistent and toxic and can bioaccumulate in biota in aquatic systems. Heavy metals and other toxic elements emitted by industrial and agricultural activity can negatively impact fish and wildlife populations. Metal mining operations can produce toxic acidic conditions in streams, rivers, and lakes. Accidental releases of radionuclides from nuclear activities have polluted inland waters. Warm industrial effluents negatively alter the habitat of aquatic organisms.