Measuring bioconcentration factors and rate constants of chemicals in aquatic organisms under conditions of variable water concentrations and short exposure time

A novel method, based on iterative numerical integration, is presented for deriving bioconcentration factors and rate constants of chemicals in aquatic organisms from experimental data of bioconcentration tests in which the chemical concentration in the water is variable over time and the test duration is too short to reach steady-state. The method is applied to reported data from fish and plant bioconcentration tests. The results demonstrate that this method can derive bioconcentration factors and rate constants with considerably less experimental error than other methods currently used, thus reducing uncertainty and variability in bioconcentration measurements.     

Prediction of bioconcentration factors under non-equilibrium conditions

With the bioconcentration of lipophilic compounds by aquatic organisms when equilibrium between water and biota is attained, the logarithm of the bioconcentration factor has a direct linear relationship with the logarithm of the octanol/water partition coefficient. In practice, however, equilibrium may not be reached, particularly for more lipophilic compounds. It is shown theoretically, and confirmed by use of published experimental results on fish, that a different direct linear relationship also exists between the logarithms of the bioconcentration factor and the partition coefficient for compounds not achieving equilibrium after a specific exposure time. Thus, non-equilibrium bioconcentration factors can be predicted from their partition coefficients. The constants in the non-equilibrium linear equation are related to those from the relationships between equilibrium bioconcentration factors and the partition coefficients, and between the first-order clearance rate constants and the partition coefficients.     

Accumulation of trinitrotoluene (TNT) in aquatic organisms: part 2--Bioconcentration in aquatic invertebrates and potential for trophic transfer to channel catfish (Ictalurus punctatus)

The potential of TNT to accumulate in aquatic organisms was assessed by determining bioconcentration factors for TNT and TNT biotransformation products using two benthic invertebrates (Chironomus tentans and Lumbriculus variegatus), and by determining the bioaccumulation factor of TNT and TNT biotransformation products due to TNT exposure via feeding for channel catfish (Ictalurus punctatus). In all three species, TNT was rapidly biotransformed resulting in minimal accumulation. The bioconcentration factors for parent TNT ranged from 3 to 4 ml g(-1) for the invertebrates studied, while the TNT bioaccumulation factor for catfish via oral exposure of food pellets was 2.4x10(-5) g g(-1) based on the concentration of TNT in the food pellet. As indicated by this small bioaccumulation factor, TNT accumulation in channel catfish through trophic transfer would be negligible compared to aqueous exposure (previously reported BCF of 0.79 ml g(-1)). TNT extractable biotransformation products accumulated to a greater degree than parent TNT for all three species. In addition, a large fraction of the radioactivity within all three species resisted solvent extraction. The highest bioconcentration factors occurred in L. variegatus with extractable radioactivity measuring 76 ml g(-1) and total radioactivity measuring 216 ml g(-1). Because the bioaccumulation of TNT is very low compared to the bioaccumulation of its biotransformation products, further research including identifying and determining the relative toxicities of these biotransformation products is necessary to fully evaluate the environmental risk posed by exposure to TNT.     

NMR and molecular modeling in environmental chemistry: prediction of 13C chemical shifts in selected C10-chloroterpenes employing DFT/GIAO theory

Accurate predictions of 13C NMR chemical shifts (standard error approximately 1.7 ppm) are achieved for a subset of chlorinated bornanes by empirical scaling of shifts from GIAO calculations with geometries obtained from HF/6-31G* calculations. The optimized molecular geometries were compared with X-ray structures for three of the toxaphene components most frequently detected in environmental samples (Parlar nos. 26, 50 and 62), and the concordance between the experimental and calculated values was found to be satisfactory. Taken overall, the results indicate that theoretical methods hold great promise for rationalizing 13C NMR chemical shifts in organohalogen compounds. However, it appeared that the DFT/GIAO shifts need to be empirically scaled to achieve good numerical agreement with experimental shifts in chlorinated bornanes. Obviously, there is a need to develop new computational methods to describe the large deshielding effects of chlorine atoms properly.     

Bioconcentration and depuration of endosulfan sulfate in mosquito fish (Gambusia affinis)

Endosulfan is an insecticide which has been widely used in agriculture. The technical grade material consists of two isomers (alpha and beta). Under natural environmental conditions, endosulfan is metabolized through oxidation and the main metabolite in the environment is endosulfan sulfate. Most ecotoxicology research has been conducted with technical grade endosulfan to determine effects on non-target aquatic organisms. Little data on the effects of endosulfan sulfate on aquatic organisms are available in the literature. This study characterizes endosulfan sulfate bioconcentration and depuration in mosquito fish (Gambusia affinis). During the study, G. affinis was exposed to an environmentally relevant endosulfan sulfate concentration of 0.25 μg L⁻¹ for 5 weeks (uptake phase) followed by a 3-week period (depuration phase) in clean water. This study found that G. affinis bioconcentrated endosulfan sulfate. During the exposure phase, fish tissue concentrations of endosulfan sulfate increased with time up to 730 μg kg⁻¹ dw or 215 μg kg⁻¹ ww. The bioconcentration data followed Michaelis-Menten kinetics better than the one-compartment first order kinetics (1-CFOK). Using these models, the bioconcentration factors for endosulfan sulfate-exposed G. affinis were from 687 to 888  L kg⁻¹ in wet weight or 2263 to 2936 L kg⁻¹ in dry weight. During the depuration phase, endosulfan sulfate concentrations in tissue significantly decreased and the data followed first order kinetics. The half-life of endosulfan sulfate in G. affinis was about 9 d. There was no significant difference in standard length or weight between control and exposed fish. The growth data followed the von Bertalanffy growth model. However, the condition factor of exposed fish increased with time during the exposure phase.     

Bioconcentration of ibuprofen in fathead minnow (Pimephales promelas) and channel catfish (Ictalurus punctatus)

Pharmaceutical products and their metabolites are being widely detected in aquatic environments and there is a growing interest in assessing potential risks of these substances to fish and other non-target species. Ibuprofen is one of the most commonly used analgesic drugs and no peer-reviewed laboratory studies have evaluated the tissue specific bioconcentration of ibuprofen in fish. In the current study, fathead minnow (Pimephales promelas) were exposed to 250 μg L⁻¹ ibuprofen for 28 d followed by a 14 d depuration phase. In a minimized bioconcentration test design, channel catfish (Ictalurus punctatus) were exposed to 250 μg L⁻¹ for a week and allowed to depurate for 7 d. Tissues were collected during uptake and depuration phases of each test and the corresponding proportional and kinetic bioconcentration factors (BCFs) were estimated. The results indicated that the BCF levels were very low (0.08-1.4) implying the lack of bioconcentration potential for ibuprofen in the two species. The highest accumulation of ibuprofen was observed in the catfish plasma as opposed to individual tissues. The minimized test design yielded similar bioconcentration results as those of the standard test and has potential for its use in screening approaches for pharmaceuticals and other classes of chemicals.     

Studies on the ability of water hyacinth (Eichhornia crassipes) to bioconcentrate and biomonitor aquatic mercury

Water hyacinth (Eichhornia crassipes, Mart solms) plants were employed to assess bioconcentration and genotoxicity of aquatic mercury. Plants were exposed to water contaminated with mercuric chloride (MC) or phenyl mercuric acetate (PMA) at 0.001 to 1.0 mg litre(-1), or mercury contaminated effluent from a chloralkali plant for various periods of 4 t0 96 h. Root samples taken after 4, 8, 12, 24, 48, 72 and 96 h of exposure were analysed for bioconcentration of mercury spectrophotometrically, and the root meristems were fixed in aceto-ethanol for cytological analysis to determine the frequencies of cells with micronuclei (MNC). Ethyl methane sulfonate and tap water served as positive and negative controls, respectively. The results indicated that bioconcentration of mercury in root tissue was both time- and concentration-dependent, providing evidence that water hyacinth is a good absorbant of aquatic mercury. The frequency of root meristematic cells with MNC followed a concentration-response. The findings indicate the potential of water hyacinth plants for in situ monitoring and for mitigation of aquatic mercury pollution.     

Correlation between the bioconcentration potential of organic environmental chemicals in humans and their n-octanol/water partition coefficients

A quantitative relationship was found to exist between the lipophilicity (n-octanol/water partition coefficient) of pentachlorophenol, dieldrin, hexachlorobenzene, 2,3,7,8-tetrachlorodibenzo-p-dioxin, Σ DDT, polychlorinated biphenyls, α-, β-, γ- and δ -hexachlorocyclohexane and their bioconcentration factor (BCF) in human adipose tissue. The equations were used to predict the bioconcentration factors of some chlorinated aromatic chemicals.     

Organochlorine pollution in tropical rivers (Guadeloupe): role of ecological factors in food web bioaccumulation

Concentrations of organochlorine pesticides and stable isotope ratios of nitrogen and carbon were measured in a tropical freshwater ecosystem to evaluate the contamination level of biota and examine the bioaccumulation patterns of pollutants through the food web. Chemical analyses showed a general and heavy contamination of the entire food web. They revealed the strong accumulation of pollutants by juveniles of diadromous fishes and shrimps, as they re-enter the river. The role of ecological factors in the bioaccumulation of pesticides was evaluated. Whereas the most persistent pollutants (chlordecone and monohydro-chlordecone) were related to the organisms diet and habitat, bioaccumulation of β-HCH was only influenced by animal lipid content. The biomagnification potential of chlordecone through the food chain has been demonstrated. It highlighted the importance of trophic transfer in this compound bioaccumulation process. In contrast, bioconcentration by passive diffusion from water seemed to be the main exposure route of biota to β-HCH.     

Kinetic models for predicting bioaccumulation of pollutants in ecosystems

Steady state kinetic models, which may be useful for the prediction from simple data, of the bioaccumulation of liophilic pollutants in ecosystems are discussed. For some aquatic species, such as Mytilus edulis, bioconcentration factors (BCFs) are closely related to water solubilities, and octanol: water partition coefficients (Kows). In other cases, more complex models are necessary to take account of metabolism and/or uptake from food. Somewhat different considerations apply in the estimation of bioaccumulation factors (BFs) for terrestrial organisms that cannot excrete lipophilic compounds by diffusion into ambient water. The relationship between half-lives and BFs is discussed. Metabolism is necessary for the effective elimination of lipophilic pollutants by terrestrial animals, and a model is proposed for the prediction of BFs from kinetic data obtained from in vitro metabolism studies. If such a model can be successfully developed it will make possible the prediction of bioaccumulation of pollutants by a wide range of species which cannot be studied by present methods.     

Relative retention times of chlorinated monoterpenes

GC retention times for 67 chlorinated monoterpenes, belonging to the technical pesticide Toxaphene have been measured under the same conditions and relative retention times have been determined. They consisted of 45 chlorinated bornanes, 13 chlorinated bornenes, 8 chlorinated dihydrocamphenes and 1 chlorinated camphene. Useful correlations between structure and retention time were found. Similar changes in structure for different compounds lead to similar changes in retention times. These correlations allow to predict retention times for yet unknown Toxaphene congeners.     

Bioconcentration of superlipophilic persistent chemicals

According to present understanding, persistent superlipophilic chemicals — such as octachlorodibenzo-p-dioxin, octachlorodibenzofuran, Mirex etc — with log K_ow > 6 and cross sections > 9.5 Å, bioconcentrate in aquatic organisms only little from ambient water. The most convincing argument against it is that in bioconcentration experiments with superlipophilic chemicals amounts applied exceeded water solubility by several orders of magnitude. This paper describes various methods for determining bioconcentration factors (BCF) of superlipophilic compounds. As exemplified with octachlorodibenzo-p-dioxin, BCF values evaluated by these methods match well with those calculated by QSARs for fish and mussels based on log K_ow and water solubility. As expected, these BCF values exceed previous values by several orders of magnitude. For BCF evaluation of superlipophilic chemicals in aquatic organisms we recommend:

1. flow-through systems, kinetic method (OECD guideline No. 305 E)
2. ambient concentrations < water solubility
3. during the uptake and especially during the elimination phase no toxic effects of the test organisms should occur.

     

Bioconcentration potential (BCP) of 2,3,7,8-Tetrachlorodibenzop-dioxin (2,3,7,8-TCDD) in terrestrial organisms including humans

The bioconcentration factors (BCFs) of 2,3,7,8-TCDD in adipose tissue of rats, beef cattle and monkeys have been calculated. The bioconcentration potential of TCDD in man was calculated by two indirect methods: 1) from daily intake of TCDD and its measured concentrations in adipose tissues and 2) from measured half-life and measured concentrations in body fat at steady state using a linear one compartment pharmacokinetic model. The BCFs in humans calculated by both methods are between 104 and 206, or 153, respectively.     

Validation of estuarine gammarid collectives (Amphipoda: Crustacea) as biomonitors for cadmium in semi-controlled toxicokinetic flow-through experiments

Concentrations of chemicals in organisms are regarded as being indicators of the bioavailable fraction of those substances in the environment. Three gammarid collectives (assemblages) from the Weser-estuary (NW Germany), showing different species compositions, were used as experimental units to evaluate their suitability as biomonitors. Uptake and clearance of cadmium was investigated in semi-controlled dynamic flow-through tests. Kinetic data obtained from two compartment models confirmed a net accumulation strategy of gammarids for Cd and resulted in similar bioconcentration factors (BCFs) within the same experimental treatments. Deviations in bioconcentration factors between two treatments (BCFs: 377-542 vs 947-1190, based on dry wt) obtained under similar exposures (17 +/- 2 and 23 +/- 2 microg Cd litre(-1)) could not be assigned to significant fluctuations of both Cd levels and particulate matter in the flow-through systems. The biological half-life of Cd in gammarids was 6 to 12 days. It is concluded that gammarid collectives of different species composition may be used as experimental units in biomonitoring studies. This conclusion was confirmed by homogeneous Cd concentrations in field samples of gammarids from the Weser-estuary (0.34 +/- 0.03 mg kg(-1) dry wt., mean +/- 95% confidence intervals, N = 58).     

Organo-tins in sediments and mussels from the Sado estuarine system (Portugal)

Analyses of methyl- and butyl-tin levels in freshwater, estuarine and marine sediments from the Sado estuarine system, and in mussels (Mytilus galloprovincialis) from its adjacent coast, have been performed in order to detect the contaminated areas. The main inputs of tributyl-tin (TBT), along with degradation products di- and monobutyl-tin (DBT and MBT), were detected in the estuarine zone, due to high discharge from shipyards located in this area. These levels are sometimes very high, ranging from 235 to 12,200 ng g(-1) total butyl-tins in sediments. Such inputs lead to higher bioconcentration values in mussels in the estuarine zone, as well as in a harbour located along the adjacent coast. The bioconcentration of organo-tins in mussel tissues could be enhanced in estuarine turbid waters, due to an ingestion of butyl-tins adsorbed onto fine particles, in comparison with non-turbid coastal waters. Debutylation processes occur in both sediments and mussel tissues; in organisms, these processes may lead to the formation of inorganic tin, which may be methylated differently according to the period of the year.     

Age to PCB concentration relationship with the striped bass (Morone saxatilis) in the Hudson River and Long Island Sound

An increase in PCB concentration with length has been observed with the striped bass in the Hudson River and Long Island Sound, New York. Physico-chemical characteristics and water concentrations were estimated for PCB's in the River and Sound waters. Using first order bioconcentration kinetics this data allowed possible fish concentrations at different lengths/ages to be calculated. This derived data was in reasonable agreement with the observed data. This indicated that the observed relationship between length and concentration is substantially due to the slow rate of bioconcentration of the PCB's, particularly the higher chlorinated congeners.     

Phytoextraction of cadmium by Ipomoea aquatica (water spinach) in hydroponic solution: effects of cadmium speciation

Phytoextraction is a promising technique to remediate heavy metals from contaminated wastewater. However, the interactions of multi-contaminants are not fully clear. This study employed cadmium, Triton X-100 (TX-100), and EDTA to investigate their interactions on phytotoxicity and Cd phytoextraction of Ipomoea aquatica (water spinach) in simulated wastewater. The Cd speciation was estimated by a chemical equilibrium model and MINEQL+. Statistic regression was applied to evaluate Cd speciation on Cd uptake in shoots and stems of I. aquatica. Results indicated that the root length was a more sensitive parameter than root weight and shoot weight. Root elongation was affected by Cd in the Cd-EDTA solution and TX-100 in the Cd-TX-100 solution. Both the root length and the root biomass were negatively correlated with the total soluble Cd ions. In contrast, Cd phytoextraction of I. aquatic was correlated with the aqueous Cd ions in the free and complex forms rather than in the chelating form. Additionally, the high Cd bioconcentration factors of I. aquatica (375-2227 l kg(-1) for roots, 45-144 l kg(-1) for shoots) imply that I. aquatica is a potential aquatic plant to remediate Cd-contaminated wastewater.     

Unique bioconcentration characteristics of new aryl fluoroalkyl ethers in common carp (Cyprinus carpio)

The bioconcentration factors (BCFs) of seven new aryl fluoroalkyl ethers--four bis-4-tetrafluoroethoxyphenyl-type (bis-type) compounds and three mono-4-tetrafluoroethoxyphenyl-type (mono-type) compounds--were obtained by bioconcentration tests using common carp. The BCFs of 4 of the 7 ethers were higher than 5000, indicating their high bioconcentration potential. The bioconcentration characteristics of the bis-type compounds were different from those of the mono-type compounds and non-fluoro diphenylmethanes with a similar skeleton structure to the bis-type compounds, in taking longer to reach a plateau and having a slower elimination rate and in their distribution patterns in the fish body. The BCF of 1 bis-type compound was much higher than the value predicted by an accepted correlation equation between BCF and P(ow). In addition, the logP(ow) of the bis-type compounds calculated by commercially available computer software was remarkably different from that measured.     

The effects of pH on fluoxetine in Japanese medaka (Oryzias latipes): acute toxicity in fish larvae and bioaccumulation in juvenile fish

Recent detection of fluoxetine in the aquatic environment and fish suggests a possibly high accumulation of fluoxetine; however, no report is available on the bioaccumulation of fluoxetine in aquatic organisms. Since bioaccumulation of fluoxetine was probably dependent on pH near the pK(a) value of 10.1, experiments were conducted approximately at pH 7, 8, and 9. Distribution coefficients between 1-octanol and water (D(ow)), and those between synthetic membrane vesicles (liposomes) and water (D(lip-wat)) were determined at pH 7, 8, and 9. The D(ow) and D(lip-wat) values increased significantly with increasing pH. Acute toxicity tests were performed using Japanese medaka (Oryzias latipes) prior to the bioaccumulation test, and 96-h LC(50) values were 5.5, 1.3, and 0.20mgl(-1) at pH 7, 8, and 9, respectively. In the bioaccumulation test, concentrations of fluoxetine and its major metabolite, norfluoxetine, in the fish body and liver were measured. The bioconcentration factors (BCF) of fluoxetine for Japanese medaka were 8.8, 3.0x10, and 2.6x10(2) in the body and 3.3x10(2), 5.8x10(2), and 3.1x10(3) in the liver at pH 7, 8, and 9, respectively. The BCF values were lower at pH 7 and higher at pH 9 mainly because of the increase in nonionized species with significantly higher hydrophobicity than the ionized species at pH values closer to pK(a). A similar trend was obtained for the concentration of norfluoxetine in the fish but the pseudo-BCF values (the ratio of the norfluoxetine concentration in the fish and the fluoxetine concentration in test water) were higher than the BCF value of fluoxetine at all pH conditions.