John P. Knezovich

The bioavailability of sediment-sorbed organic chemicals: A review

Xenobiotic chemicals that are present in aquatic environments are typically concentrated on suspended particles and sedimentary materials where they represent a source of chronic contamination to benthic and pelagic organisms. Laboratory and field studies of bioaccumulation, toxicity, and food-chain transfer of chemicals bound to sediment have shown the potential ecological impacts that may result from the contamination of sediments. In this review, the chemical and physical processes that determine the environmental fate of sediment-sorbed organic chemicals are outlined, and their relationship to bioavailability is discussed. Methods currently used to predict the fate of pollutants in the aquatic environment are of limited use for the assessment of sediment-sorbed chemical bioavailability because they are based on the compounds behavior in the water column. Furthermore, an organisms morphology and ecological niche can profoundly affect its ability to accumulate xenobiotic chemicals from sediments and these must be considered before the populations at greatest risk can be identified.

The toxicity of copper to the adult and early life stages of the freshwater clam,Corbicula manilensis

The copper sensitivity of adult and larval stages of the freshwater clamCorbicula manilensis was evaluated. In addition, copper concentrations were determined in adult clams exposed for 4 to 10 weeks to copper in a high-volume, flow-through bioassay. All bioassay systems utilized water that was low in total hardness and alkalinity.The response of the clams to copper depended on life stage. Copper sensitivity of larvae decreased markedly in successive developmental stages. LC5024s of veliger and juvenile larvae were 28 and 600 μg Cu/L, respectively. The mortality of trochophore larvae exposed to 10 μg Cu/L for one hr was 91.5%. The sensitivity to copper decreased with increased amounts of larval shell deposition.Adult clams were resistant to copper; the LC5096 was greater than 2,600 μg Cu/L. By comparison, the incipient lethal concentration (ILC, was lowless than 10 μg Cu/L. Adult clams accumulated more copper as concentrations in the water increased. Evidence was obtained for copper loss near or at death.Labile and total copper, as well as the coppercomplexing capacity, in the bioassay water were determined; the majority of copper was present as labile species. Toxicity was related to the quantities of labile copper in the water.

The influence of organic chelators on the toxicity of copper to embryos of the pacific oyster,Crassostrea gigas

The effects of copper on the development ofCrassostrea gigas embryos were determined with a 48-hr static bioassay. In filtered, sterilized seawater from Bodega Bay, California, the LC100 was 20μg Cu/L, and the LC50 was 12μg Cu/L. Destruction of the naturally occurring dissolved organic material in the culture water by UV oxidation decreased embryo survival at 10μg Cu/L.The addition to seawater of five organic chelators (ethylenediaminetetraacetic acid (EDTA), sodium citrate, glycine, and oxalate at 1×10−6 M, and humic matter at 2 mg/L) increased embryo survival. EDTA and humic matter were the most effective chelators; EDTA significantly increased survival at 100μg Cu/L and humic matter did so at 40μg Cu/L. The ability of a chelator to increase survival was related to the stability constant of the copper-chelator complex.

The bioavailability of sediment-sorbed chlorobenzenes to larvae of the midge, Chironomus decorus

Larval stages of the midge, Chironomus decorus, were used to define the bioaccumulation of sediment-sorbed mono-, di-, tri-, and hexachlorobenzene. Larvae were exposed to high- and low-organic-content sediments that had been equilibrated with individual radiolabeled chlorobenzenes prior to testing. Equilibrium or nonequilibrium aqueous concentrations of the volatile test chemicals were flowed through sealed chambers in a sediment-water exposure system. The uptake of chlorobenzenes by midge larvae was rapid for all compounds tested, and apparent steady-state conditions were reached within 48 hr of exposure. Bioconcentration factors for the accumulation of chlorobenzenes from sediments and from interstitial and overlying waters were related to the octanol/water partition coefficients of the compounds. Because the diffusion of chlorobenzenes to overlying water during nonequilibrium flow through conditions was very slow, bioaccumulation was dependent on the concentration of the chemicals in interstitial water. These results show how benthic organisms may be able to accumulate significant levels of chlorinated aromatic compounds from ecosystems where their concentrations in the water column are relatively low.

The transfer of trichloroethylene (TCE) from a shower to indoor air: Experimental measurements and their implications

Experiments were performed to measure the transfer of trichloroethylene (TCE), a volatile organic compound (VOC), from tap water in showers to indoor air. In these experiments, the loss of TCE from tap water in the shower is based on the difference between influent and effluent concentrations. We have developed and previously published a three-compartment model, which we use to simulate the 24-h concentration history of VOCs in the shower, bathroom, and remaining household volumes resulting from the use of contaminated tap water. An important input to this model is the transfer efficiency of the VOC from water to air. The experiments reveal that the transfer efficiency of TCE from shower water to air has an arithmetic mean value of 61 percent and an arithmetic standard deviation of 9 percent. Analysis of the results shows that there is no statistically significant difference between the transfer efficiency measured with hot (37 degrees C) or cold (22 degrees C) shower water and that there is no statistically significant change in transfer efficiency with time during a 20-min shower. The implications for exposure assessment are considered.

Bioaccumulation and tissue distribution of a quaternary ammonium surfactant in three aquatic species.

Quaternary ammonium compounds (QACs) are commonly used as surfactants in drilling muds and fabric softeners and as biocides in antiseptics and disinfectants. QACs and cationic polyelectrolytes elicit acute toxic effects in aquatic organisms by disrupting the structure and function of gill tissues, which may result in the suffocation of the organism. Little information is available, however, on the relative availability and distribution of QACs in the tissues of aquatic organisms. Information of this nature is required to understand the potential consequences of releases of sublethal concentrations of QACs into the aquatic environment. In this study, hexadecylpyridinium bromide (HPB; CAS 140-72-7) was selected as a compound for initial study because it belongs to a chemical class (alkylpyridinium QACs) that includes the most toxic and environmentally persistent QACs. Clams, minnows, and tadpoles were chosen as test organisms to define the relative availability of HPB to organisms that occupy distinctly different ecological niches.

Behavior of phenol and aniline on selected sorbents and energy-related solid wastes

The sorption and desorption of phenol and aniline on selected soils and soil components and on some energy-related solid wastes were investigated. Isotherms were generally nonlinear and were described usually by the Freundlich equation. Most partition coefficients were low, and no significant correlation was shown with organic C content, pH, cation exchange capacity, or particle-size of the sorbent. It appears that sorption of small polar aromatic compounds, such as phenol and aniline, cannot be defined by a single sorbent characteristic, but is affected by both the organic and mineral components of the sorbents. Hysteresis was observed in most sorption-desorption experiments; a fraction of the sorbate was irreversibly held by the sorbent.

In vivo metabolism of aromatic amines by the bay mussel, Mytilus edulis

The hazard posed to aquatic organisms by exposure to aromatic amines will depend on their ability to activate or detoxify these potentially genotoxic compounds. We studied the metabolism of four aromatic amines (p-toluidine, aniline, 2-acetylaminofluorene (2-AAF) and 2-aminofluorene (2-AF)) in Bay mussels (Mytilus edulis) to gain an understanding of their metabolic capabilities in vivo. Mussels rapidly accumulated these compounds from the water column and depurated the majority of their steady-state body burdens as metabolites and unmetabolized parent compounds. The biotransformation pathways of [14C]-labeled parent compounds were determined by analyses of depurated metabolites and tissue residues. Biotransformation of p-toluidine and aniline resulted in the formation of their corresponding N-acetylated detoxification products. Mussels converted small amounts of 2-AAF into a deacetylated product (2-AF) and a mutagenically active metabolite (N-hydroxy-2-AF). 2-AF was extensively detoxified via N-acetylation, which limited the amount of primary amine available for activation.

Non-DNA Methods for Biological Signatures

Publisher Summary This chapter focuses on the methods that can determine chemical or structural features of biological agent particles that are signatures of particular methods of growth and post-growth processing (often referred to as “weaponization”). The detection of these signatures in a sample of a bio-weapon (BW) agent can aid the attribution by indicating: (1) the level of sophistication of the producer, (2) the access to particular types of agent weaponization information, (3) the likelihood that the material could be or has been produced at a significant scale, (4) and by providing essential sample matching data for ascertaining a putative relationship with other samples obtained in other venues. An example of the use of biologicals in forensic science is DNA, amplied by the Polymerase Chain Reaction (PCR) technique, legally admissible in courtas evidence. DNA evidence is successfully used in the court to convict or clear people of crimes because each persons DNA is unique. High-resolution techniques are being applied to investigations; such as Environmental scanning electron microscopy (ESEM) is used for taking high-resolution images under hydrated conditions; this avoids any artifacts associated with the critical point drying process that is required under normal Scanning Electron Microscopy (SEM) operations. ESEM is also equipped with Energy Dispersive X-ray (EDX) microanalysis and Backscatter capabilities. SEM is a standard “workhorse” technique for characterizing particulate samples, found in many laboratories worldwide. It provides excellent imaging of the surfaces of agent particles and other material in a sample, and is used for identifying likely agent particles for analysis by other instruments. When combined with EDX, the elemental composition of the material in the imaged region can be determined. These techniques continue to signature libraries of correlations between analyses and growth and processing conditions of growth, it will be necessary to develop an information system which combines types of data to determine unique signatures.

Radiation-induced DNA-strand breakage and repair in the marine polychaete, Neanthes arenaceodentata

Abstract We used an alkaline unwinding assay, which provides an index of DNA-strand breakage and repair, to study the genotoxic effects of gamma radiation in adult Neanthes arenaceodentata . To determine radiation-induced DNA-strand damage, we exposed the worms to radiation levels from 3·13 to 100 Gy. Significant DNA-strand damage was found at exposures ≥3·13 Gy. To determine the repair of radiation-induced DNA-strand damage, we irradiated worms at 100 Gy and then harvested and analyzed their DNA on days 0, 2, 5 and 14 post-irradiation. A significant increase in DNA-strand breaks was found to exist between control and radiation-exposed groups on days 0–5. By day 14 post-irradiation, however, no significant relationship was found between control and radiation-exposed groups.