An experimental ecotoxicological study and its application to the behavioural study of organic mercury (CH3HgCl) in the environment: influence of temperature and pH

Laboratory experiments were carried out to study the influence of temperature (24, 28 and 30 °C) and pH (1–10) on organic mercury (CH₃HgCl) transfer and accumulation in an experimental ecotoxicological model. We followed the evolution of CH₃HgCl in a basic model (water+air) by varying temperature and pH. In a second step, we completed the model by adding sediment and fish. We added CH₃HgCl to water at the beginning of each experiment which was repeated at least three times. Results demonstrated that mercury was released from methylmercury into the air regardless of water pH and its concentration in the air increased with increasing pH. By contrast, in presence of sediment, almost all the mercury was fixed onto the sediment and no mercury was traced in air or in water. Interestingly, in the presence of sediment, the life span of fish under methylmercury exposure lasted longer despite their higher mercury body level content at their death. These results indicate that water is a bad exposure indicator for aquatic pollution. In case of chronic pollution, sediments, fish and aquatic plants are more appropriate indicators.     

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.     

Effect of a heavy metal model mixture on biological parameters of rainbow trout <Emphasis Type="Italic">oncorhynchus mykiss</Emphasis>

The effects of a model mixture (HMMM) of seven heavy metals (Cu, Zn, Ni, Cr, Pb, Cd, Mn) on the rainbow trout Oncorhynchus mykiss at all stages of development (embryos, larvae, adults) were investigated based on the annual average concentrations of these metals in cooling waste waters discharging from Ignalina Nuclear Power Plant (Lithuania) into the Drūk?iai lake. According to mortality parameters, the most sensitive to HMMM were larvae, although no significant differences between the sensitivity of embryos and adult fish to HMMM were found. Maximal toxic effect of HMMM was observed during the hatching period. Long-term exposure to sublethal concentrations of HMMM affected embryo development, growth of larvae, their cardio-respiratory and behavioural responses, induced significant changes in morphological, morpho-physiological, physiological and haematological parameters of adult fish. Respiratory responses and growth parameters of fish were found to be the most sensitive to low concentrations of HMMM. Adult fish were capable of detecting and avoiding low, sublethal concentrations of HMMM. Heavy metals in a mixture at low concentrations were more toxic than single ones. According to the background of the damages induced by HMMM, after-effects in a fish organism, as well as in a whole population, can be predicted.     

Acute toxicity of cadmium to fish Labeo rohita and copepod Diaptomus forbesi pre-exposed to CaO and KMnO4

96-h LC₅₀ values of cadmium (Cd) to fish Labeo rohita and the copepod Diaptomus forbesi, determined by static bioassays, were, respectively, 89.5 and 10.2 mg/l. LC₅₀ values increased significantly when fish pre-exposed to 100–350 mg/l CaO or 0.5–1.5 mg/l KMnO₄ for 4 d and the copepod to 20–70 mg/l CaO or 0.25–1.0 mg/l KMnO₄ for same period. The LC₅₀ values also increased when the pre-exposure period of CaO was increased to 12 d at concentration 100 mg/l for fish and 20 mg/l for copepod. All fish died when pre-exposed to 1.5 mg/l KMnO₄ for 8 d. But LC₅₀ values of Cd to copepod increased when pre-exposure period of 0.5 mg/l KMnO₄ was increased from 4 to 8 d.     

Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium

Levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and polychlorinated biphenyls (PCBs) were measured in several fish species originating from the river Scheldt (Belgium). Five sampling locations were chosen in a highly industrialized area along the river, while two ponds in the vicinity of the river served as reference sites. The present study is a follow-up of a survey performed in 2000 which reported extremely high levels of PBDEs and HBCDs in eel (Anguilla anguilla) collected from the same region (Oudenaarde, Flanders). The sum of tri- to hepta-BDE congeners (2270+/-2260 ng/g lipid weight (lw), range 660-11500 ng/g lw) and total HBCDs (4500+/-3000 ng/g lw, range 390-12100 ng/g lw) were one order of magnitude higher than levels usually reported from freshwater systems, indicating the presence of point sources. In most samples, levels of total HBCDs were higher than those of PBDEs, probably due to the high density of factories using HBCD as an additive brominated flame retardant (BFR). The high values of HBCDs were confirmed by both gas- and liquid-chromatography-mass spectrometry. Although BFR levels were between the highest ever reported in freshwater ecosystems, PCBs could be detected at even higher concentrations (16000+/-14300 ng/g lw, range 3900-66600 ng/g lw), being among the highest levels recorded in Belgium. The inter-sampling site variation of PBDEs, HBCDs and PCBs was comparable. All locations presented similar PBDE congener profiles, with BDE 47 being the dominant congener, followed by BDE 100, BDE 99 and BDE 49, probably originating from the former use of the penta-BDE technical mixture. In order to estimate the impact of these point sources on human exposure, we further focussed on eels which showed a considerable decrease in the PBDE and HBCD levels between 2000 and 2006. Due to the wide span in concentrations between the different sampling locations, a variable contribution to the total human exposure through local eel consumption was estimated. The calculated daily intake ranged from 3 ng to 330 ng PBDEs/day for normal eel consumers, but was as high as 9800 ng PBDEs/day for anglers, which may be considered at risk.     

Dynamic emergy evaluation of a fish farm rearing process

The environmental sustainability of a fish farm rearing process was examined by means of emergy analysis. Many emergy analyses integrate data for a whole year smoothing short term variations and sometimes losing meaningful information (aliasing). For this reason we developed a model for an instantaneous emergy evaluation in an aquacultural system so that transformities, efficiency and effort spent at each moment during the fish rearing activity could be calculated. By means of the model and dynamic emergy calculations it is possible to recognize step by step the importance of the various emergy contributions and verify where and when to modify the system to move toward optimum production of a sustainable product. By the application of the model we confirmed that the emergy trends in a fish farm installation follow wide oscillations during a year due to variations in both internal and external emergy contributions. Among the fluxes considered, those due to the introduction of fingerlings represented the highest contributions to the total emergy budget. Thus, to improve the sustainability of the analyzed system the amount, frequency and timing of these fluxes must be carefully considered. For this purpose, a comparison between two different fry introduction schedules was performed to evaluate differences in the efficiency of the rearing process.     

Risk assessment of PCDD/Fs levels in human tissues related to major food items based on chemical analyses and micro-EROD assay

Nine groups of food items (freshwater fish, marine fish, pork, chicken, chicken eggs, leafy, non-leafy vegetables, rice and flour) and three types of human samples (human milk, maternal serum and cord serum) were collected for the analysis of PCDD/Fs. Results of chemical analysis revealed PCDD/Fs concentrations (pg g^− 1 fat) in the following ascending order: pork (0.289 pg g^− 1 fat), grass carp (Ctenopharyngodon idellus) (freshwater fish) (0.407), golden thread (Nemipterus virgatus) (marine fish) (0.511), chicken (0.529), mandarin fish (Siniperca kneri) (marine fish) (0.535), chicken egg (0.552), and snubnose pompano (Trachinotus blochii) (marine fish) (1.219). The results of micro-EROD assay showed relatively higher PCDD/Fs levels in fish (2.65 pg g^− 1 fat) when compared with pork (0.47), eggs (0.33), chicken (0.13), flour (0.07), vegetables (0.05 pg g^− 1 wet wt) and rice (0.05). The estimated average daily intake of PCDD/Fs of 3.51 pg EROD-TEQ/kg bw/day was within the range of WHO Tolerable Daily Intake (1–4 pg WHO-TEQ/kg bw/day) and was higher than the Provisional Tolerable Daily Intake (PMTL) (70 pg for dioxins and dioxin-like PCBs) recommended by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) [Joint FAO/WHO Expert Committee on Food Additives (JECFA), Summary and conclusions of the fifty-seventh meeting, JECFA, 2001.]. Nevertheless, the current findings were significantly lower than the TDI (14 pg WHO-TEQ/kg/bw/day) recommended by the Scientific Committee on Food of the Europe Commission [European Scientific Committee on Food (EU SCF), Opinions on the SCF on the risk assessment of dioxins and dioxin-like PCBs in food, 2000.]. However, it should be noted that micro-EROD assay overestimates the PCDD/Fs levels by 2 to 7 folds which may also amplify the PCDD/Fs levels accordingly. Although the levels of PCDD/Fs obtained from micro-EROD assay were much higher than those obtained by chemical analysis by 2 to 7 folds, it provides a cost-effective and rapid screening of dioxin levels in food and human samples.     

Quantitative Identification of Disturbance Thresholds in Support of Aquatic Resource Management

The identification of disturbance thresholds is important for many aspects of aquatic resource management, including the establishment of regulatory criteria and the identification of stream reference conditions. A number of quantitative or model-based approaches can be used to identify disturbance thresholds, including nonparametric deviance reduction (NDR), piecewise regression (PR), Bayesian changepoint (BCP), quantile piecewise constant (QPC), and quantile piecewise linear (QPL) approaches. These methods differ in their assumptions regarding the nature of the disturbance-response variable relationship, which can make selecting among the approaches difficult for those unfamiliar with the methods. We first provide an overview of each of the aforementioned approaches for identifying disturbance thresholds, including the types of data for which the approaches are intended. We then compare threshold estimates from each of these approaches to evaluate their robustness using both simulated and empirical datasets. We found that most of the approaches were accurate in estimating thresholds for datasets with drastic changes in responses variable at the disturbance threshold. Conversely, only the PR and QPL approaches performed well for datasets with conditional mean or upper boundary changes in response variables at the disturbance threshold. The most robust threshold identification approach appeared to be the QPL approach; this method provided relatively accurate threshold estimates for most of the evaluated datasets. Because accuracy of disturbance threshold estimates can be affected by a number of factors, we recommend that several steps be followed when attempting to identify disturbance thresholds. These steps include plotting and visually inspecting the disturbance-response data, hypothesizing what mechanisms likely generate the observed pattern in the disturbance-response data, and plotting the estimated threshold in relation to the disturbance-response data to ensure the appropriateness of the threshold estimate.     

Assessment of risk to humans of bisphenol A in marine and freshwater fish from Pearl River Delta, China

Bisphenol A (BPA) is a high production-volume chemical used in the manufacture of a wide variety of consumer products. However it is also a ubiquitous contaminant that can interfere with endocrine systems of wildlife and humans. China is the “world factory” and the Pearl River Delta is the major manufacturing center and is consequently polluted. Concentrations of BPA in meats of marketable fish had not been previously reported for this region. In the study upon which we report here concentrations of BPA were determined in 20 common species of freshwater and marine fish, collected from markets in Hong Kong, SAR, China. A comprehensive analytical method based on SPE extraction and liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) was developed, validated and applied. The method limit of detection (LOD) and limit of quantification (LOQ) were 0.5 and 1.25 ng g⁻¹ dw, respectively. BPA was detected in 19 species of fish at concentrations, ranging from 0.5 to 2.0 ng g⁻¹ ww. Average daily BPA intake per person ranged from 1.1 × 10² ng d⁻¹ for marine fish and 2.2 × 10² ng d⁻¹ for freshwater fish. Concentrations of BPA in fish from Hong Kong markets unlikely would be causing adverse population-level effects in humans.     

Temporal trends in the bioaccumulation of trace metals in herring, sprat, and cod from the southern Baltic Sea in the 1994–2003 period

This study is based on raw data obtained from 1 225 samples of herring (Clupea harengus), sprat (Sprattus sprattus), and cod (Gadus morhua) collected in the 1994–2003 period from the Polish coastal zone of the Baltic Sea. This paper presents the results of investigations of the contents of Cu, Zn, Cd, Pb, Hg, and As in fish. The aim was to identify temporal trends in trace metal contamination and variations in the concentrations of Hg in the flesh of herring, sprat, and cod of different lengths. A positive correlation between fish length and Hg concentration was noted for cod, sprat, and herring. The temporal trend analyses of heavy metal concentrations in the fish in the 1994–2003 period indicated ten significant downward trends out of eighteen tests; these referred to concentrations of Cd, Hg, and Pb in all the species studied, and to As in sprat. Concentrations of Cu and Zn remained stable in all the species studied, as did As in herring and cod. No upward trends were detected in the concentration of trace metals in the fish studied. Smaller scale temporal variations in concentrations of some elements were also observed and were associated with natural events, such as increased river discharge resulting from floods. The most likely factors which contributed to the observed downward trends in heavy metals concentrations in fish could possibly stem from lesser quantities of Cd, Pb, and Hg being introduced to the Baltic Sea with the waters of rivers from Baltic countries, including Poland, and atmospheric depositions in the 1994–2003 period. Diminishing trends of concentrations of these elements in Baltic Sea waters are also evidence of this. These facts might indicate that advantageous changes are occurring in the concentrations of heavy metals in the southern Baltic environment.