Kimmo Mäenpää

Equilibrium Sampling of Persistent and Bioaccumulative Compounds in Soil and Sediment: Comparison of Two Approaches To Determine Equilibrium Partitioning Concentrations in Lipids

The equilibrium sampling in silicone is increasingly applied to measure freely dissolved concentrations and chemical activities within bioaccumulation research of hydrophobic organic chemicals. Two equilibrium methods were applied to PCB-contaminated soil and sediment, and directly calibrated with respect to equilibrium partitioning concentrations in lipids (C(lipid,partitioning)): (i) Solid phase microextraction in the headspace above the sample (HS-SPME) required optimization for its application to PCBs, and it was calibrated above external partitioning standards in olive oil. (ii) Equilibrium sampling with internally coated glass jars with varying thicknesses of silicone (PDMS) resulted in proportionality between coating and analyte mass, which confirmed several validity criteria. C(lipid,partitioning) was here determined as product of PDMS concentration and PDMS to lipid partition ratio. The results of the two methods were in good agreement and thus validated each other. Finally, the coated glass jar method was applied to field sediment containing invertebrates, which lead to C(lipid,partitioning) that were about two times higher than measured lipid-normalized concentrations in the organisms. Temperature differences and animal lipid structure were discussed as possible reasons for this discrepancy. Both methods combine high analytical performance, reduced equilibration times and new calibration possibilities, which makes them suited for bioaccumulation research and environmental monitoring.

Bioaccumulation and toxicity of sediment associated herbicides (ioxynil, pendimethalin, and bentazone) in Lumbriculus variegatus (Oligochaeta) and Chironomus riparius (Insecta).

The benthic macroinvertebrates Lumbriculus variegatus and Chironomus riparius were used in toxicity and bioaccumulation tests to determine the toxic concentrations and accumulation potential of sediment associated herbicides. The tested chemicals were ioxynil, bentazone, and pendimethalin. The bioaccumulation tests with L. variegatus were performed in four different sediments, each having different characteristics. Water-only LC(50) tests were performed with both L. variegatus and C. riparius. A sublethal effect of model compounds in sediments was assessed by a C. riparius larvae growth-inhibition test. Of the model compounds, ioxynil appeared to be the most toxic, with LC(50) values 1.79 and 2.79 mgL(-1) for L. variegatus and C. riparius, respectively. The LC(50) water concentrations for bentazone were 79.11 and 62.31 mgL(-1) for L. variegatus and C. riparius, respectively. Similarly, ioxynil revealed the highest bioaccumulation potential in bioaccumulation tests. The most important characters affecting chemical fate in the sediment seemed to be the organic matter content and the particle size fraction. The sediments with low organic material and coarse particle size consistently showed high bioaccumulation potential and vice versa. In C. riparius growth tests bentazone had a statistically significant effect on larval growth at sediment concentrations of 1160 and 4650 mgkg(-1) (P<0.05). It is noteworthy that standard deviations tend to be greater at high chemical concentrations, which addresses the fact that part of the individuals started to suffer. Ioxynil had an effect on the larval growth in other test sediment at the highest concentration (15.46 mgkg(-1)dw), in which head capsule length correlated with larval weight, decreasing toward higher exposure concentrations. The current results show the importance of sediment organic matter as a binding site of xenobiotics.

Sublethal toxicity and biotransformation of pyrene in Lumbriculus variegatus (Oligochaeta)

The aim of this work was to study the toxicity and biotransformation of polyaromatic hydrocarbon (PAH) pyrene in the oligochaete aquatic worm, Lumbriculus variegatus. PAHs are ubiquitous environmental pollutants that pose a hazard to aquatic organisms, and metabolizing capability is poorly known in the case of many invertebrate species. To study the toxicity and biotransformation of pyrene, the worm was exposed for 15 days to various concentrations of water-borne pyrene. The dorsal blood vessel pulse rate was used as a sublethal endpoint. Pyrene biotransformation by L. variegatus was studied and the critical body residues (CBR) were estimated for pyrene toxicity. The toxicokinetics of pyrene uptake was evaluated. A combination of radiolabeled (14C) and nonlabeled pyrene was used in the exposures, and liquid scintillation counting (LSC) and high-pressure liquid chromatography were employed in both water and tissue residue analyses. The results showed that L. variegatus was moderately able to metabolize pyrene to 1-hydroxypyrene (1-HP), thus demonstrating that the phase-I-like oxidizing enzyme system metabolizes pyrene in L. variegatus. The amount of the 1-HP was 1-2% of the amount of pyrene in the worm tissues. The exposure to pyrene reduced the blood vessel pulse rate significantly (p<0.05), showing that pyrene had a narcotic effect. The estimated CBRs remained constant during the exposure time, varying from 0.120 to 0.174 mmol pyrene/kg worm wet weight. The bioconcentration factors (BCF) decreased as exposure concentration increased. It was suggested that the increased toxicity of pyrene accounted for the decrease in BCFs by lowering the activity of the organism.

Trophic transfer of polychlorinated biphenyls (PCB) in a boreal lake ecosystem: Testing of bioaccumulation models

Understanding the fate of persistent organic chemicals in the environment is fundamental information for the successful protection of ecosystems and humans. A common dilemma in risk assessment is that monitoring data reveals contaminant concentrations in wildlife, while the source concentrations, route of uptake and acceptable source concentrations remain unsolved. To overcome this problem, different models have been developed in order to obtain more precise risk estimates for the food webs. However, there is still an urgent need for studies combining modelled and measured data in order to verify the functionality of the models. Studies utilising field-collected data covering entire food webs are particularly scarce. This study aims to contribute to tackling this problem by determining the validity of two bioaccumulation models, BIOv1.22 and AQUAWEBv1.2, for application to a multispecies aquatic food web. A small boreal lake, Lake Kernaalanjärvi, in Finland was investigated for its food web structure and concentrations of PCBs in all trophic levels. Trophic magnification factors (TMFs) were used to measure the bioaccumulation potential of PCBs, and the site-specific environmental parameters were used to compare predicted and observed concentrations. Site-specific concentrations in sediment pore water did not affect the modelling endpoints, but accurate site-specific measurements of freely dissolved concentrations in water turned out to be crucial for obtaining realistic model-predicted concentrations in biota. Numerous parameters and snapshot values affected the model performances, bringing uncertainty into the process and results, but overall, the models worked well for a small boreal lake ecosystem. We suggest that these models can be optimised for different ecosystems and can be useful tools for estimating the bioaccumulation and environmental fate of PCBs.

Sorptive Capacity of Membrane Lipids, Storage Lipids, and Proteins: A Preliminary Study of Partitioning of Organochlorines in Lean Fish from A PCB-Contaminated Freshwater Lake

Knowledge on the internal distribution of halogenated organic chemicals (HOCs) would improve our understanding of dose–effect relationships and subsequently improve risk assessment of contaminated sites. Herein, we determine the concentrations of HOCs based on equilibrium partitioning in storage lipids, membrane lipids, and proteins in field-contaminated fish using equilibrium sampling devices. The study shows the importance of protein as a sorptive phase in lean fish. Our results provide a basis for using species-specific equilibrium partitioning coefficients between sorptive tissues and fish internal water as a substitute for Kow in, for example, upgrading models that simulate food-chain accumulation of the chemical.

Bioavailability of Organic Contaminants in Freshwater Environments

It has been well established that in many cases total concentration of a chemical in the environment is not the best indicator for the potential threats that the chemical may cause. The term bioavailability describes the fact that only a fraction of a chemical in the environment is available for uptake by organisms, which then determines possible biological effects. Uptake of contaminants is a complex interplay among biological, chemical, and physical factors and processes. Properties of chemicals, environmental conditions, and characteristics of the organisms and the interaction among these ultimately dictate the exposure. This chapter represents the important factors determining bioavailability of organic contaminants in both the water phase and sediment in freshwater systems. In addition, we introduce techniques to measure bioavailability by passive sampling and present modeling tools for estimations. In the end, we offer a short insight about bioavailability in risk management.

Effects of activated carbon ageing in three PCB contaminated sediments: Sorption efficiency and secondary effects on Lumbriculus variegatus

The sorption efficiency and possible secondary effects of activated carbon (AC) (ø 63-200 μm) was studied with Lumbriculus variegatus in three PCB contaminated sediments applying long AC-sediment contact time (3 years). AC amendment efficiently reduced PCB bioavailability as determined with both, L. variegatus bioaccumulation test and passive samplers. However, dose related secondary effects of AC on egestion rate and biomass were observed (applied doses 0.25% and 2.5% sediment dry weight). The sorption capacity and secondary effects remained similar when the experiments were repeated after three years of AC-sediment contact time. Further, transmission electron microscopy (TEM) samples revealed morphological changes in the L. variegatus gut wall microvilli layer. Sediment properties affected both sorption efficiency and secondary effects, but 2.5% AC addition had significant effects regardless of the sediment. In, conclusion, AC is an efficient and stable sorbent to decrease the bioavailability of PCBs. However, sediment dwelling organisms, such as Oligochaete worms in this study, may be sensitive to the carbon amendments. The secondary effects and possible morphological changes in benthic organisms should not be overlooked as in many cases they form the basis of the aquatic food webs.

Effects of Activated Carbon on PCB Bioaccumulation and Biological Responses of Chironomus riparius in Full Life Cycle Test

The nonbiting midge Chironomus riparius was used to study the remediation potential and secondary effects of activated carbon (AC, ø 63-200 μm) in PCB contaminated sediments. AC amendments efficiently reduced PCB bioavailability determined by Chironomus riparius bioaccumulation tests and passive samplers. PCBs were shown to transfer from larvae to adults. Lower PCB concentrations were observed in adult midges emerging from AC amended compared to unamended sediments. Increased reproduction, survival, larval growth and gut wall microvilli length were observed with low AC dose (0.5% sediment dw) compared to unamended sediment, indicating an improved success of larvae in the sediment with low organic carbon content. On the other hand, higher AC doses (2.5% sediment dw) caused adverse effects on emergence and larval development. In addition, morphological changes in the gut wall microvilli layer were observed. This study showed that the secondary effects of AC amendments are dependent on the dose and the sediment characteristics. Metamorphic species, such as C. riparius, may act as a vector for organic pollutants from aquatic to terrestrial ecosystems and according to this study the AC amendments may reduce this transport.

Assessing the influence of confounding biological factors when estimating bioaccumulation of PCBs with passive samplers in aquatic ecosystems

Passive samplers are promising surrogates for organisms, mimicking bioaccumulation. However, several biological characteristics disturb the passive partitioning process in organisms by accelerating or restraining bioaccumulation, resulting in species-specific body residues of hydrophobic organic contaminants (HOCs). In addition to site-specific characteristics and HOC concentrations, age, sex, diet, biotransformation capability and habitat-specific characteristics may affect body residues. Two passive sampler types, polyethylene (PE) and polydimethylsiloxane (PDMS) were deployed in a PCB-contaminated freshwater lake water and sediment, respectively, to assess their bioaccumulation prediction capacity. In order to understand the importance of biological characteristics in the bioaccumulation process, we explored bioaccumulation in biota from plants and plankton to mussels and fish. The PCB concentrations in the PE sheet reflected the bioavailable concentration of PCBs slightly better than those in the PDMS samplers. Passive samplers were good predictors of PCB concentrations in fish, whereas concentrations in algae and invertebrates were overestimated. When comparing the measured concentrations in biota to the estimated concentrations using the PE samplers, the average regression slope was 0.87 for all biota and 1.22 for fish, and average modeling efficiency (EF) was 3.02 for all biota and 0.6 for fish. The best model performance was achieved for fish in trophic levels 3-4. Bioaccumulation was species-specific and dependent on the trophic level and diet. Closer examination revealed that metabolic capability changes during the life span, and source of nutrition determined the biomagnification of HOCs, which differed between the fish species. Thus, species composition and available prey selection compose a unique bioaccumulation scenario and the resulting body residues. Due to the existing variation in body residues derived from passive samplers, extrapolating the results from one to another ecosystem must be done with caution. Passive samplers, however, offer a very powerful tool for risk assessment on the ecosystem level.

Effects of activated carbon amended sediment on biological responses in Chironomus riparius multi-generation testing

The biological effects of activated carbon (AC) amendments in sediments were studied with the midge Chironomus riparius. The effects on larvae growth were studied using three different AC particles sizes (PAC: 90% <63μm, MAC: ø 63-200μm and GAC: ø 420-1700μm). The long- term effects of MAC were studied in an emergence experiment over two generations (P, F1), together with larvae growth experiment over three generations (P, F1, F2). Retarded growth and development of the larvae were observed in the two smallest particle sizes (PAC and MAC), as well as morphological changes in the gut wall microvilli layer studied from transmission electron micrographs. In addition, at high AC treatments the larvae reaching fourth instar stage were of a smaller size compared to the controls. With PAC treatment AC amendment dosages higher than 1% of sediment dry weight induced mortality. In the emergence experiment there was an indication of a delay in F1 generation emergence. Male dry weight (dw) in P generation was significantly reduced in the 2.5% MAC treatment. The effects of AC amendments were more obvious in the C. riparius larvae compared to the effects seen in emerging adults exposed to AC-amended sediment during the larval stage.