http://library.um.ac.id/free-contents/downloadpdf.php/buku/complexation-reactions-in-aquatic-systems-an-analytical-approach-j-buffle-translators-s-p-kounaves-a-kounaves-and-r-s-altman-12623.pdf

Complexation reactions in aquatic systems : an analytical approach / J. Buffle, translators S.P. Kounaves, A. Kounaves and R.S. Altman

The bioconcentration factor (BCF) and bioaccumulation factor (BAF) are used as the criteria for bioaccumulation in the context of identifying and classifying substances that are hazardous to the aquatic environment. The BCF/BAF criteria, while developed as surrogates for chronic toxicity and/or biomagnification of anthropogenic organic substances, are applied to all substances including metals. This work examines the theoretical and experimental basis for the use of BCF/BAF in the hazard assessment of Zn, Cd, Cu, Pb, Ni, and Ag. As well, BCF/BAFs for Hg (methyl and inorganic forms) and hexachlorobenzene (HCB) were evaluated. The BCF/BAF data for Zn, Cd, Cu, Pb, Ni, and Ag were characterized by extreme variability in mean BCF/BAF values and a clear inverse relationship between BCF/BAF and aqueous exposure. The high variability persisted when even when data were limited to an exposure range where chronic toxicity would be expected. Mean BCF/BAF values for Hg were also variable, but the inverse relationship was equivocal, in contrast with HCB, which conformed to the BCF model. This study illustrates that the BCF/BAF criteria, as currently applied, are inappropriate for the hazard identification and classification of metals. Furthermore, using BCF and BAF data leads to conclusions that are inconsistent with the toxicological data, as values are highest (indicating hazard) at low exposure concentrations and are lowest (indicating no hazard) at high exposure concentrations, where impacts are likely. Bioconcentration and bioaccumulation factors do not distinguish between essential mineral nutrient, normal background metal bioaccumulation, the adaptive capabilities of animals to vary uptake and elimination within the spectrum of exposure regimes, nor the specific ability to sequester, detoxify, and store internalized metal from metal uptake that results in adverse effect. An alternative to BCF, the accumulation factor (ACF), for metals was assessed and, while providing an improvement, it did not provide a complete solution. A bioaccumulation criterion for the hazard identification of metals is required, and work directed at linking chronic toxicity and bioaccumulation may provide some solutions.

Inverse relationship between bioconcentration factor and exposure concentration for metals: implications for hazard assessment of metals in the aquatic environment.

Assessing metal bioaccumulation in aquatic environments: the inverse relationship between bioaccumulation factors, trophic transfer factors and exposure concentration.

The uptake of metals from food and water sources by insects is thought to be additive. For a given metal, the proportions taken up from water and food will depend both on the bioavailable concentration of the metal associated with each source and the mechanism and rate by which the metal enters the insect. Attempts to correlate insect trace metal concentrations with the trophic level of insects should be made with a knowledge of the feeding relationships of the individual taxa concerned. Pathways for the uptake of essential metals, such as copper and zinc, exist at the cellular level, and other nonessential metals, such as cadmium, also appear to enter via these routes. Within cells, trace metals can be bound to proteins or stored in granules. The internal distribution of metals among body tissues is very heterogeneous, and distribution patterns tend to be both metal and taxon specific. Trace metals associated with insects can be both bound on the surface of their chitinous exoskeleton and incorporated into body tissues. The quantities of trace meals accumulated by an individual reflect the net balance between the rate of metal influx from both dissolved and particulate sources and the rate of metal efflux from the organism. The toxicity of metals has been demonstrated at all levels of biological organization: cell, tissue, individual, population, and community. Much of the literature pertaining to the toxic effects of metals on aquatic insects is based on laboratory observations and, as such, it is difficult to extrapolate the data to insects in nature. The few experimental studies in nature suggest that trace metal contaminants can affect both the distribution and the abundance of aquatic insects. Insects have a largely unexploited potential as biomonitors of metal contamination in nature. A better understanding of the physicochemical and biological mechanisms mediating trace metal bioavailability and exchange will facilitate the development of general predictive models relating trace metal concentrations in insects to those in their environment. Such models will facilitate the use of insects as contaminant biomonitors.

Aquatic insects and trace metals: bioavailability, bioaccumulation, and toxicity.

https://wwwrcamnl.wr.usgs.gov/tracel/references/pdf/SciTotEnviron_v219p117.pdf

Trace element trophic transfer in aquatic organisms: a critique of the kinetic model approach.

Cadmium, Zn, Pb and Cu uptake and effects in larvae ofChironomus riparius (Meigen) were studied in an integrated laboratory investigation, in which metal analyses in different instar stages, uptake kinetics and effects on development and growth were considered in three separate experiments. In short-term experiments with fourth instar larvae, it was demonstrated that only a minor portion of metals was adsorbed on the larval exoskeletons. No conclusive evidence on the uptake mechanism was found, but active uptake of trace metals seemed highly unlikely. In partial life cycle experiments, all four metals studied were readily accumulated in chironomid larvae. Uptake could be described satisfactorily utilizing a first-order one-compartment uptake model which incorporated growth. In all cases steady state conditions were approached and high uptake and elimination rate constants were estimated. Distinct differences between essential (Zn and Cu) and non-essential (Cd and Pb) metals were noted. Larval growth was significantly impaired upon exposure. Finally, long-term exposure experiments with low Cd concentrations (0.010 and 0.025 mg 1−1) resulted initially in growth impairment and high mortality in first instar stages, but surviving larvae restored growth and adults emerged even before control adults. In similar experiments with Zn (0.1 and 1.0 mg 1−1), development of larvae was significantly retarded. High Zn concentrations in larvae were noted and almost no adult midges emerged.

Cadmium, zinc, lead and copper inChironomus riparius (Meigen) larvae (Diptera, Chironomidae): uptake and effects

Trace metals in a littoral foodweb: concentrations in organisms, sediment and water.

We examined the potential of a multiple regression model, including both biotic and abiotic variables, to predict trace metal levels (Cd, Pb, Cu and Zn) in benthic invertebrate communities from various aquatic habitats in The Netherlands. Variables included in the regression model and their relative contribution to the predictive power appeared to be highly element-specific. Sediment- and water-related abiotic variables were especially important for the prediction of Cd, Pb and, to a lesser extent, Zn. For the essential trace metals, the biotic variables such as the presence of hemocyanin (in the case of Cu) and trophic level (Zn) appeared to have a dominant influence. Species-body weight showed a negative log-linear relationship with trace metal levels of Pb and, to a lesser extent, Cu and Cd. For all metals, significant coefficients of multiple correlation were observed. The variance in invertebrate trace metal levels explained by the model ranged from 25% for Zn to 37% for Cd and Cu. For all trace metals, the introduction of biotic variables resulted in a significant increase in predictive power (p < 0.02), compared to the use of only abiotic predictors. Marked differences in predictive power of the model were observed among various species or taxonomic categories. For several species remarkably significant relationships were revealed, indicating the potential usefulness of the organisms for biological monitoring and further modeling studies.

Abiotic and biotic factors influencing in situ trace metal levels in macroinvertebrates in freshwater ecosystems

The fate of trace metals during the metamorphosis of chironomids (diptera, chironomidae).

The concentrations of Cd, Pb, Cu and Zn inChironomus gr.thummi were determined for 4th instar larvae from the polluted Dyle River, tributary of the Scheldt River (Belgium). Comparison was made between larvae with deformed and normal menta. Deformed larvae showed higher overall metal concentrations than normal larvae. Especially Pb and Cu had higher concentrations in deformed larvae (16.22 mg kg−1 dry weight and 39.66 respectively) than in normal larvae (12.80 mg kg−1 dry weight and 35.70 respectively). No significant differences were found in the concentrations of Cd and Zn (mean [Cd] = 0.81 mg kg−1 dry weight and mean [Zn] = 313.12 mg kg−1 dry weight). There was no difference between the two larval groups as far as total length, dry weight and developmental stage of the imaginal discs are concerned.

Klaas R. Timmermans

Papers

Cadmium, zinc, lead and copper inChironomus riparius (Meigen) larvae (Diptera, Chironomidae): uptake and effects

Trace metals in a littoral foodweb: concentrations in organisms, sediment and water.

Abiotic and biotic factors influencing in situ trace metal levels in macroinvertebrates in freshwater ecosystems

The fate of trace metals during the metamorphosis of chironomids (diptera, chironomidae).

The concentration of cadmium, lead, copper and zinc in Chironomus gr. thummi larvae (Diptera, Chironomidae) with deformed versus normal menta