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.     

Accumulation and elimination kinetics of di-, tri- and tetra chlorobiphenyls by goldfish after dietary and aqueous exposure

Bioaccumulation kinetics of five di-, tri- and tetrachlorobiphenyls from water and food were studied in laboratory experiments with goldfish (Carassius auratus). First order rate constants for uptake from water and clearance were determined after simultaneous administration of the five compounds in constant concentration, and were related to bioconcentration factors obtained in a static fish-water equilibration system. Biomagnification by retention of the PCB's from food was studied in a separate experiment.The difference in clearance rates for the chlorobiphenyls is the main reason for the different bioconcentration and biomagnification factors.Absorption efficiencies from water and food are higher than 40%. Clearance half lives vary from 10 days for 2,5-dichlorobiphenyl to 60 days for 2,3′,4′5-tetrachlorobiphenyl, which is correlalated with the decreasing aqueous solubilities of the compounds. Bioconcentration factors are between 0.4 × 10⁶ and 1.5 × 10⁶, biomagnification factors between 0.2 and 1.7, based on extractable lipids. Substitution of chlorine in the position para to the phenyl-phenyl bond influences hydrophobicity and bioaccumulation of the PCB's more strongly than substitution in ortho position.A kinetic model is developed which accounts for the influence of the lipid content of the fish on the clearance rate of a chemical. Reproducible determination of the bioconcentration potential of environmental chemicals is possible by use of an “internal bioaccumulation standard” in a kinetic test system. Food chain accumulation in fish is likely to be an important process only for persistent chemicals with extremely low water solubility.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

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.

     

Comparative acute toxicities of selected pesticides to Anguilla anguilla.

The acute toxicities (24, 48, 72 and 96 hr) of eight pesticides to Anguilla anguilla were determined. The organochlorine pesticide, endosulfan was the most toxic, with LC50 values in the range of 0.042 to 0.041 mg/L. Endosulfan was followed in order of decreasing toxicity by diazinon, fenitrothion, chlorpyrifos, lindane, methidathion, trichlorfon and methylparathion. When fishes were exposed to the pesticides tested they exhibited signs of restlessness, erratic swimming, convulsions and difficulty in respiration. This response was more persistent in fishes exposed to organophosphorus pesticides.     

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.     

Accumulation of trinitrotoluene (TNT) in aquatic organisms: part 1--Bioconcentration and distribution in channel catfish (Ictalurus punctatus)

Little is currently known regarding the toxicokinetics of TNT in fish. In the present study, the bioconcentration and distribution of trinitrotoluene (TNT) and TNT biotransformation products was investigated in juvenile channel catfish by exposing catfish to 14C-labeled TNT in water. Uptake experiments showed relatively fast rates (k(u)=10.1 ml g(-1) h(-1)) for TNT from the water; however, bioconcentration factors for TNT were low (0.79 ml g(-1)) due to rapid biotransformation and potential elimination of TNT. Accumulation of extractable radioactivity (TNT and all extractable biotransformation products) was much greater (BCF=10.5 ml g(-1)) than that for parent compound. TNT (parent compound) bioconcentrated to the greatest extent in the gills of the fish, while total radioactivity bioconcentrated to the greatest extent in the viscera. Residual portions of the fish that contained muscle and skin had lower concentrations of TNT than the whole fish, indicating that ingestion of fish fillets would result in decreased exposure to human consumers. Although the bioconcentration potential of TNT is very low, future research needs to be conducted to identify the biotransformation products that make up most of the radioactivity in exposed fish and evaluate their potential to promote toxicity.     

Comparative acute toxicities of selected pesticides to Anguilla anguilla

Abstract

The acute toxicities (24, 48, 72 and 96 hr) of eight pesticides to Anguilla anguilla were determined. The organochlorine pesticide, endosulfan was the most toxic, with LC50 values in the range of 0.042 to 0.041 mg/L Endosulfan was followed in order of decreasing toxicity by diazinon, fenitrothion, chlorpyrifos, lmdane, methidathion, trichlorfon and methylparathion. When fishes were exposed to the pesticides tested they exhibited signs of restlessness, erratic swimming, convulsions and difficulty in respiration. This response was more persistent in fishes exposed to organophosphorus pesticides.     

Predicting bioconcentration factors (BCFs) of polychlorinated bornane (Toxaphene) congeners in fish and comparison with bioaccumulation factors (BAFs) in biota from the aquatic environment.

Polychlorinated bornanes, the main components of Toxaphene, are bioconcentrated in aquatic organisms to a high extent. However, up to this time no bioconcentration tests with individual chlorinated bornanes in aquatic organisms have been performed. Therefore, the bioconcentration factors (BCFs) of seven selected persistent chlorinated bornane congeners which are regularly found in aquatic organisms, were predicted from their n-octanol/water partition coefficients (log Kow). Furthermore, these BCF values were compared with the measured bioaccumulation factors (BAFs) in zooplankton and different fish species from the aquatic environment.     

Influence of alum on cyanobacterial blooms and water quality of earthen fish ponds

Eruption of blue-green algal blooms occurs frequently in eutrophic lakes and fish ponds, with associated unpleasant odor and horrid scums. In the present study, we conducted a pre-test experiment in 3 m³ outdoor concrete ponds to determine the optimum concentration of aluminum sulfate (alum) required for reduction of the cyanobacterial blooms without negative effect on fish growth. As a consequence, 10 mg L^?1 alum was named as the optimum concentration that was applied in 1000 m³ earthen fish ponds. Obtained results showed that Secchi disc values significantly increased from 10 to 24 cm after 14 days of alum application. Alum-treated ponds showed a reduction in total phytoplankton counts by 94 and 96 % compared to the corresponding controls after 10 and 14 days, respectively. Abundance of blue-green algae in the treated ponds was decreased by 98 % compared to the corresponding control after 14 days of alum application. Consequently, dissolved oxygen, pH, total phosphorus, orthophosphate, and chlorophyll “a” content declined significantly. Our study revealed that using 10 mg L^?1 of alum is an effective way to control cyanobacterial blooms in eutrophic waters, especially in fish ponds, without negative effect in water quality.     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.     

Multibiomarker approach in fish to assess the impact of pollution in a large Brazilian river, Paraiba do Sul

This article examines the advantages of the use of biomarkers as environmental indicators by applying it to Paraiba do Sul watershed, one of the most important Brazilian water bodies, which is in a critical environmental situation. We use a multibiomarker approach in fish as an integrated strategy to assess the impact of pollution. It comprehends a general biomarker of fish health, the condition factor (CF), and specific biomarkers of contaminant exposure such as metallothionein (MT), acetylcholinesterase (AChE) activity and biliary polycyclic aromatic hydrocarbons (PAH) metabolites. Our results revealed different effects in the fish from diverse locations with varying degrees of pollution. Furthermore, fish located just upstream of the water-treatment plant of the metropolitan area of Rio de Janeiro has shown to be affected by metals. This study indicates the usefulness of integrating a set of biomarkers to define the effects of anthropogenic inputs in aquatic bodies under complex polluted situations.     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.     

Potential risk to wood storks (Mycteria americana) from mercury in Carolina Bay fish

Carolina bays are freshwater wetlands that serve as important feeding habitats for the endangered wood stork (Mycteria americana). Water levels in these bays fluctuate greatly and tend to be acidic and rich in dissolved organic carbon (DOC), factors that favor mercury (Hg) methylation and bioaccumulation in fish. To assess potential risks to wood storks consuming mercury contaminated fish in bays, we sampled fish from 10 bays on the Savannah River Site (SRS), South Carolina, an area with documented use by wood storks. Whole body mercury concentrations in 258 fishes of three species (Erimyzon sucetta, Acantharchuspomotis and Esox americanus) commonly consumed by wood storks were determined. Risk factors for nestlings and free-ranging adults were calculated using published no and lowest observable adverse effect concentration (NOAEC and LOAEC) values for birds. Fish from higher trophic levels and those from wetlands with relatively shallow maximum depths and fluctuating water levels were more likely to exceed NOAEC and LOAEC values. Calculation of exposure rates of nestling wood storks indicated they are at highest risk during the first 10 days of the nestling period. These calculations suggest that there is potential concern for wood storks foraging in relatively shallow bays with fluctuating water levels, even though there is no obvious local source of mercury to these wetlands.     

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.     

Aquatic fate assessment of the polycyclic musk fragrance HHCB. Scenario and variability analysis in accordance with the EU risk assessment guidelines

By means of the environmental fate and distribution models laid down in the Technical Guidance Documents (TGD) and implemented in the European Union System for the Evaluation of Substances (EUSES) environmental concentrations of the polycyclic musk fragrance HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-[g]-2- benzopyrane; trade name: e.g. Galaxolide) were calculated for the aquatic environment under consideration of various scenarios. The results were then compared to monitoring data from the region of North Rhine-Westphalia (River Ruhr). An uncertainty analysis was carried out to determine sensitive parameters, to integrate environmental variability and to confirm the model's calculations. The standard scenario of EUSES overestimates the measured concentrations, which confirms the conservative nature of the calculations. The regional-specific scenarios lead to lower deviations from the measured values than the standard scenario. Deviations range from one to two orders of magnitude in the effluent of sewage treatment plants; they amount to one order of magnitude for surface water concentrations on a local scale and conform to monitoring data on a regional scale. The use of measured bioconcentration factors for fish instead of estimated ones reduces deviations remarkably. The investigation reveals that unrealistic worst-case calculations of HHCB can at best be ameliorated by the application of more realistic emission rates and measured bioconcentration factors. The use of regional-specific parameters also diminishes the deviations of the calculations from the measured concentrations.     

Improved Gas Chromatographic method for analysis of trichlorfon insecticide in soil and turfgrass thatch

Abstract

An improved Gas Chromatographic method utilizing simple extraction and one‐step purification on solid phase extraction tubes was developed for analysis of trichlorfon as an intact insecticide compound in turfgrass thatch and soil. A Gas Chromatograph/Mass Spectrum (GC/MS) was used for confirmation of trichlorfon structure. The method readily determines trichlorfon in the presence of dichlorvos. Using an electron capture (EC) detector, the detection limits were 0.02 ppm in soil, 0.04 ppm in turfgrass thatch, and 0.09 ppm in soil, and 0.2 ppm in turfgrass thatch using an nitrogen phosphorus (NP) detector.     

An examination of the physical properties,fate, ecotoxicity and potential environmental risks for a series of propylene glycol ethers

Propylene glycol ethers (PGEs) are comprised of mono-, di- and tri-PGEs and several of their acetate esters. The nature of the range of applications that use PGEs suggests that there is a potential for both intentional and unintentional entry of the materials into the environment. Selected physical/chemical properties, fate characteristics, aquatic toxicity data and calculated environmental concentrations were used to assess potential risks from the manufacture, handling, use, and disposal of PGEs. In general, the PGEs are low to moderately volatile, have high aqueous solubilities, low octanol-water partition coefficients (Kow), and bioconcentration factor values of <10, which indicate they are unlikely to accumulate in aquatic food chains. Both abiotic and biological degradation processes reduce environmental concentrations of PGEs. In air, vapor-phase PGEs react with photo-chemically produced hydroxyl radicals and have half-lives ranging from 5.5 to 34.4 h. A variety of ready and inherent biodegradation test methods, as well as tests that simulate biodegradation in wastewater treatment plants, surface water and soil have been conducted on PGEs. Significant aerobic biodegradation was generally observed, with a range of biodegradation half-lives on the order of 5-25 d. Acute aquatic toxicity studies with PGEs resulted in LC50 values ranging from approximately >100 to >20,000 mg/l for freshwater fish, the pelagic invertebrate Daphnia magna, green algae Selenastrum capricornutum (now called Pseudokirchneriella capricornutum) and bacteria. Level 3 multi-media modeling (EQC model of Mackay) was used to simulate regional-scale concentrations of PGEs in air, soil, water, and sediment. Toxicity thresholds were then compared with regional-scale water, soil and sediment concentrations to determine hazard quotients. Based upon this analysis, concentrations of PGEs are unlikely to pose adverse risks to the environment.     

Bioaccumulation kinetics and bioconcentration factor of chlorinated pesticides in tissues of Puntius ticto (Ham.)

Bioaccumulation kinetics and bioconcentration factor (BCF) of chlorinated pesticides like Aldrin, Dieldrin, Benzene hexachloride (BHC), and Dichlorodiphenyl-dichloro-ethane (DDT) in fish tissues of Puntius ticto was studied in detail in a continuous fed system. The bioconcentration process is summarized by using a first order uptake model and the steady-state BCF is calculated based on the 30 days exposure. Rate of bioaccumulation of DDT was maximum of 4.6432 microg g(-1) wet weight per day in liver tissue whereas it was minimum of 0.0002 microg g(-1) wet weight per day in case of Dieldrin in the muscle tissue among the pesticides. It was observed that DDT showed maximum BCF of 89.010 in case of liver tissue of the fish exposed to 30 days. The regression coefficient (r2) between pesticide concentration and exposure time varied between 0.6212 and 0.9817 indicating high correlation. Based on actual calculated BCF values, the octanol water partition coefficient (Kow) values were predicted. In order to prove the hydrophobic property of chlorinated compounds and its affinity towards lipid, the Kow is predicted. Results showed that pesticide burden differ from tissue to tissue and can be correlated to the lipid content, size, exposure time, and species.