Compounds In Aquatic Organisms Research Articles

Ibuprofen and diclofenac in the marine environment - a critical review of their occurrence and potential risk for invertebrate species

The presence of the two main non-steroidal anti-inflammatory drugs (NSAIDs), diclofenac (DCF) and ibuprofen (IBU), in marine and estuarine systems has been reported. Although the available information about the toxicity of these compounds in aquatic organisms has increased in recent years, the database about marine organisms, specifically invertebrates, is limited. Consequently, the assessment of potential risks posed by these compounds to aquatic species should be improved, given their relevance for aquatic life and the trophic chain. To fill this gap, we analyze the potential risk of IBU and DCF in marine invertebrates. To assess the risk, the database was built with available information from the scientific literature about the occurrence, bioaccumulation, and toxicity of both compounds in the estuaries and marine environments. Risk assessment of both compounds in these environments is scarce and based essentially on their acute toxicity. Data compiled in this review, including environmental concentrations and toxicity thresholds, were used to calculate risk quotients and classify the risk for invertebrate communities in coastal areas with different contamination levels. The results indicated a higher risk for DCF than IBU. Additionally, the simultaneous presence of the two NSAIDs in the aquatic environment increases the risk for exposed organisms. The use of classical methods (e.g., biochemical markers, gene expression), new approaches (e.g., adverse outcome pathway, AOP), and omic techniques has contributed to understanding the underlying toxicity mechanisms and improving the risk assessment. However, in a global change scenario involving multiple drivers and pressures such as ocean acidification, heat waves, climate change, etc., the risk assessment for these emerging pollutants needs improvement. This can be achieved by increasing our knowledge about the metabolic pathway and biotransformation routes of these compounds in marine species and understanding how these changes can affect the bioaccumulation, toxicity, fate, and behavior of both NSAIDs.

Heart rate and behavioral responses in three phylogenetically distant aquatic model organisms exposed to environmental concentrations of carbaryl and fenitrothion

Carbaryl and fenitrothion are two insecticides sharing a common mode of action, the inhibition of the acetylcholinesterase (AChE) activity. Their use is now regulated or banned in different countries, and the environmental levels of both compounds in aquatic ecosystems have decreased to the range of pg/L to ng/L. As these concentrations are below the non-observed-adverse-effect-concentrations (NOAEC) for AChE inhibition reported for both compounds in aquatic organisms, there is a general agreement that the current levels of these two chemicals are safe for aquatic organisms. In this study we have exposed zebrafish, Japanese medaka and Daphnia magna to concentrations of carbaryl and fenitrothion under their NOAECs for 24-h, and the effects on heart rate (HR), basal locomotor activity (BLA), visual motor response (VMR), startle response (SR) and its habituation have been evaluated. Both pesticides increased the HR in the three selected model organisms, although the intensity of this effect was chemical-, concentration- and organism-dependent. The exposure to both pesticides also led to a decrease in BLA and an increase in VMR in all three species, although this effect was only significant in zebrafish larvae. For SR and its habituation, the response profile was more species- and concentration-specific. The results presented in this manuscript demonstrate that concentrations of carbaryl and fenitrothion well below their respective NOAECs induce tachycardia and the impairment of ecologically relevant behaviors in phylogenetically distinct aquatic model organisms, both vertebrates and invertebrates, emphasizing the need to include this range of concentrations in the environmental risk assessment.

Tissue-specific accumulation, depuration, and effects of perfluorooctanoic acid on fish: Influences of aqueous pH and sex

Perfluorooctanoic acid (PFOA) is widely distributed in nature, particularly in aquatic environments. Its bioaccumulation and toxicity in aquatic organisms can be affected by both the chemical status of PFOA in water and the physiology of the organism. However, research on the patterns of these effects is scarce. In this study, we investigated the influence of aqueous pH (pH 6, acidic; pH 7.5, neutral; pH 9, basic) and fish sex on PFOA uptake, clearance, and biochemical effects in crucian carp (C. auratus) using flow-through exposure. In the 17-d kinetic experiment, PFOA bioaccumulation adhered to a uniform first-order model in which PFOA uptake rates from water to blood and liver in acidic conditions were faster than those in other conditions, indicating possible acidic pH influence on PFOA uptake. PFOA clearance rates in these compartments of males were slower than in females, which was attributed to the notably stronger expression of Oat2 (organic anion transporter 2, responsible for reabsorption) in the kidneys of males. Similar responses were observed for peroxisome proliferation-related biomarkers at different pH levels and in different sexes. These biochemical responses were driven by the internal concentrations of PFOA. The inhibition acetylcholinesterase activity in the fish brain was closely linked to changes in P-glycoprotein content, demonstrating a protective relationship. Collectively, an aqueous pH lower than 7.5 might affect the uptake of PFOA by fish. The clearance discrepancies between the sexes highlight the importance of anion carriers for ionizable organic compounds in aquatic organisms.

An Overview of Analytical Methods to Determine Pharmaceutical Active Compounds in Aquatic Organisms.

There is increasing scientific evidence that some pharmaceuticals are present in the marine ecosystems at concentrations that may cause adverse effects on the organisms that inhabit them. At present, there is still very little scientific literature on the (bio)accumulation of these compounds in different species, let alone on the relationship between the presence of these compounds and the adverse effects they produce. However, attempts have been made to optimize and validate analytical methods for the determination of residues of pharmaceuticals in marine biota by studying the stages of sample treatment, sample clean-up and subsequent analysis. The proposed bibliographic review includes a summary of the most commonly techniques, and its analytical features, proposed to determine pharmaceutical compounds in aquatic organisms at different levels of the trophic chain in the last 10 years.

Environmental Metabolomics Promises and Achievements in the Field of Aquatic Ecotoxicology: Viewed through the Pharmaceutical Lens.

Scientists often set ambitious targets using environmental metabolomics to address challenging ecotoxicological issues. This promising approach has a high potential to elucidate the mechanisms of action (MeOAs) of contaminants (in hazard assessments) and to develop biomarkers (in environmental biomonitoring). However, metabolomics fingerprints often involve a complex mixture of molecular effects that are hard to link to a specific MeOA (if detected in the analytical conditions used). Given these promises and limitations, here we propose an updated review on the achievements of this approach. Metabolomics-based studies conducted on the effects of pharmaceutical active compounds in aquatic organisms provide a relevant means to review the achievements of this approach, as prior knowledge about the MeOA of these molecules could help overcome some shortcomings. This review highlighted that current metabolomics advances have enabled more accurate MeOA assessment, especially when combined with other omics approaches. The combination of metabolomics with other measured biological endpoints has also turned out to be an efficient way to link molecular effects to (sub)-individual adverse outcomes, thereby paving the way to the construction of adverse outcome pathways (AOPs). Here, we also discuss the importance of determining MeOA as a key strategy in the identification of MeOA-specific biomarkers for biomonitoring. We have put forward some recommendations to take full advantage of environmental metabolomics and thus help fulfil these promises.

Toxicity mechanisms of arsenic compounds in aquatic organisms.

Arsenic is a toxic metalloid that is widely distributed in the environment due to its persistence and accumulative properties. The occurrence, distribution, and biological effects of arsenic in aquatic environments have been extensively studied. Acute and chronic toxicities to arsenic are associated with fatal effects at the individual and molecular levels. The toxicity of arsenic in aquatic organisms depends on its speciation and concentration. In aquatic environments, inorganic arsenic is the dominant form. While trivalent arsenicals have greater toxicity compared with pentavalent arsenicals, inorganic arsenic can assume a variety of forms through biotransformation in aquatic organisms. Biotransformation mechanisms and speciation of arsenic have been studied, but few reports have addressed the relationships among speciation, toxicity, and bioavailability in biological systems. This paper reviews the modes of action of arsenic along with its toxic effects and distribution in an attempt to improve our understanding of the mechanisms of arsenic toxicity in aquatic organisms.

Bioaccumulation, Biodistribution, Toxicology and Biomonitoring of Organofluorine Compounds in Aquatic Organisms.

This review is a survey of recent advances in studies concerning the impact of poly- and perfluorinated organic compounds in aquatic organisms. After a brief introduction on poly- and perfluorinated compounds (PFCs) features, an overview of recent monitoring studies is reported illustrating ranges of recorded concentrations in water, sediments, and species. Besides presenting general concepts defining bioaccumulative potential and its indicators, the biodistribution of PFCs is described taking in consideration different tissues/organs of the investigated species as well as differences between studies in the wild or under controlled laboratory conditions. The potential use of species as bioindicators for biomonitoring studies are discussed and data are summarized in a table reporting the number of monitored PFCs and their total concentration as a function of investigated species. Moreover, biomolecular effects on taxonomically different species are illustrated. In the final paragraph, main findings have been summarized and possible solutions to environmental threats posed by PFCs in the aquatic environment are discussed.

Molecular and biochemical evaluation of effects of malathion, phenanthrene and cadmium on Chironomus sancticaroli (Diptera: Chironomidae) larvae

In-vitro effects of sub-lethal concentrations of malathion, phenanthrene (Phe) and cadmium (Cd) were tested on Chironomus sancticaroli larvae in acute bioassays by measuring biochemical and molecular parameters. Malathion was evaluated at 0.001, 0.0564 and 0.1006 mg L-1; Phe at 0.0025, 1.25 and 2.44 mg L-1; and Cd at 0.001, 3.2 and 7.4 mg L-1. The recovery test carried out at the highest concentration of each compound showed that survival of larvae exposed to Phe ranged from 4% to 5%, while the effects of malathion and Cd were irreversible, not allowing the emergence of adults. Results showed that malathion and Cd inhibited AChE, EST-α and ES-β activities at the two highest concentrations. Phe at 0.0025, 1.25 and 2.44 mg L-1; and Cd at 3.2 and 7.4 mg L-1 inhibited glutathione S-transferase activity. Oxidative stress was exclusively induced by the lowest concentration of malathion considering SOD activity once CAT was unaffected by the stressors. Lipid peroxidation was registered exclusively by malathion at the two highest concentrations, and total hemoglobin content was only reduced by Cd at the two highest concentrations. The relationship among biochemical results, examined using the PCA, evidenced that malathion and Cd concentrations were clustered into two groups, while Phe only formed one group. Four hemoglobin genes of C. sancticaroli were tested for the first time in this species, with Hemoglobin-C being upregulated by malathion. The toxicity ranking was malathion > Phe > Cd, while biochemical and molecular results showed the order malathion > Cd > Phe. Our results highlight the importance of combining different markers to understand the effects of the diverse compounds in aquatic organisms.

Hazardous Effects of Endocrine Disrupting Compounds in Aquatic Organisms

Hazardous Effects of Endocrine Disrupting Compounds in Aquatic Organisms

Identifying degradation products responsible for increased toxicity of UV-Degraded insensitive munitions

Degradation of insensitive munitions (IMs) by ultraviolet (UV) light has become a topic of concern following observations that some UV-degradation products have increased toxicity relative to parent compounds in aquatic organisms. The present investigation focused on the Army's IM formulation, IMX-101, which is composed of three IM constituents: 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and nitroguanidine (NQ). The IM constituents and IMX-101 were irradiated in a UV photo-reactor and then administered to Daphnia pulex in acute (48 h) exposures comparing toxicities relative to the parent materials. UV-degradation of DNAN had little effect on mortality whereas mortality for UV-degraded NTO and NQ (and associated degradation products) increased by factors of 40.3 and 1240, respectively, making UV-degraded NQ the principle driver of toxicity when IMX-101 is UV-degraded. Toxicity investigations for specific products formed during UV-degradation of NQ, confirmed greater toxicity than the parent NQ for degradation products including guanidine, nitrite, ammonia, nitrosoguanidine, and cyanide. Summation of the individual toxic units for the complete set of individually measured UV-degradation products identified for NQ only accounted for 25% of the overall toxicity measured in the exposures to the UV-degraded NQ product mixture. From these toxic unit calculations, nitrite followed by CN− were the principal degradation products contributing to toxicity. Given the underestimation of toxicity using the sum toxic units for the individually measured UV-degradation products of NQ, we conclude that: (1) other unidentified NQ degradation products contributed principally to toxicity and/or (2) synergistic toxicological interactions occurred among the NQ degradation product mixture that exacerbated toxicity.

The use of immobilized artificial membrane chromatography to predict bioconcentration of pharmaceutical compounds

The potential of immobilized artificial membrane chromatography (IAM) to predict bioconcentration factors (BCF) of pharmaceutical compounds in aquatic organisms was studied. For this purpose, retention factors extrapolated to pure aqueous phase, logkw(IAM), of 27 drugs were measured on an IAM stationary phase, IAM.PC.MG type. The data were combined with retention factors on two IAM columns, IAM.PC.MG and IAM.PC.DD2 types, reported previously by our research group and correlated with logBCF values predicted by Estimation Program Interface (EPI Suite) Software. Linear models were established upon exclusion of ionic or highly hydrophilic nonionic drugs, for which a constant value of logBCF equal to 0.50 was arbitrarily assigned by EPI Suite Software. As additional physicochemical parameter BioWin5 proved to be statistically significant, expressing the decrease of bioaccumulation potential as a result of biodegradation in the aquatic environment. The constructed IAM model was successfully validated by application to a set of pharmaceuticals, whose experimental BCF values are available. Better predictions compared to EPI Suite Software were achieved for the dataset under study. Since bioconcentration process involves electrostatic interactions, IAM retention may be a better measure for BCF values, especially for ionic species, compared to octanol-water partition coefficients widely implemented in environmental sciences. The developed approach can be considered as a novel tool for the prediction of bioconcentration of pharmaceutical compounds in aquatic organisms in order to minimize further experimental assays in the future.

Monitoring Toxic Ionic Liquids in Zebrafish (Danio rerio) with Desorption Electrospray Ionization Mass Spectrometry Imaging (DESI-MSI).

Ambient mass spectrometry imaging has become an increasingly powerful technique for the direct analysis of biological tissues in the open environment with minimal sample preparation and fast analysis times. In this study, we introduce desorption electrospray ionization mass spectrometry imaging (DESI-MSI) as a novel, rapid, and sensitive approach to localize the accumulation of a mildly toxic ionic liquid (IL), AMMOENG 130 in zebrafish (Danio rerio). The work demonstrates that DESI-MSI has the potential to rapidly monitor the accumulation of IL pollutants in aquatic organisms. AMMOENG 130 is a quaternary ammonium-based IL reported to be broadly used as a surfactant in commercialized detergents. It is known to exhibit acute toxicity to zebrafish causing extensive damage to gill secondary lamellae and increasing membrane permeability. Zebrafish were exposed to the IL in a static 96-h exposure study in concentrations near the LC50 of 1.25, 2.5, and 5.0 mg/L. DESI-MS analysis of zebrafish gills demonstrated the appearance of a dealkylated AMMOENG 130 metabolite in the lowest concentration of exposure identified by a high resolution hybrid LTQ-Orbitrap mass spectrometer as the trimethylstearylammonium ion, [C21H46N]+. With DESI-MSI, the accumulation of AMMOENG 130 and its dealkylated metabolite in zebrafish tissue was found in the nervous and respiratory systems. AMMOENG 130 and the metabolite were capable of penetrating the blood brain barrier of the fish with significant accumulation in the brain. Hence, we report for the first time the simultaneous characterization, distribution, and metabolism of a toxic IL in whole body zebrafish analyzed by DESI-MSI. This ambient mass spectrometry imaging technique shows great promise for the direct analysis of biological tissues to qualitatively monitor foreign, toxic, and persistent compounds in aquatic organisms from the environment. Graphical Abstract ᅟ.

Two novel multidrug resistance associated protein (MRP/ABCC) from the Mediterranean mussel (Mytilus galloprovincialis): characterization and expression patterns in detoxifying tissues

Multidrug resistance associated proteins (MRP) belong to the ABCC branch of the ABC transporters. The MRP together with P-gp (P-glycoprotein; MDR1; ABCB1) and BCRP (breast cancer resistance protein; ABCG2) confer multixenobiotic resistance (MXR) in marine vertebrates. In aquatic invertebrates, little is known about the presence and role of these ABC transporters. The ABC transporters play an important role in the absorption, distribution, and excretion of drugs, xenobiotics, and endogenous compounds and are predominantly expressed in excretory organs. In the present study, we identified and characterized two MRP/ABCC transporters (mrp1 and mrp2) from the Mediterranean mussel (Mytilus galloprovincialis Lamarck, 1819). The two cDNAs finally obtained were 4648 bp for mrp1 and 5065 bp for mrp2 with open reading frames of 1500 and 1524 residues, respectively. Analysis of the amino acid sequences revealed the structural organization of ABC transporters with the typical and highly conserved motifs. The expression levels of these genes revealed that the highest expression of mrp1 and mrp2 genes was found in the digestive gland followed by gills, and the lowest expression of the three tissues was detected in the mantle. The expression of these genes was also studied in mussels naturally contaminated with okadaic acid (from a bloom of Dinophysis acuminata Claparède and Lachmann, 1859). The overexpression of mrp2 in the digestive gland suggests that this gene is involved in the process of detoxification of okadaic acid in M. galloprovincilais. These expression patterns agree with the suggested role of these genes in the protection against endogenous or exogenous compounds in aquatic organisms.

How does predation affect the bioaccumulation of hydrophobic organic compounds in aquatic organisms?

It is well-known that the body burden of hydrophobic organic compounds (HOCs) increases with the trophic level of aquatic organisms. However, the mechanism of HOC biomagnification is not fully understood. To fill this gap, this study investigated the effect of predation on the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs), one type of HOC, in low-to-high aquatic trophic levels under constant freely dissolved PAH concentrations (1, 5, or 10 μg L(-1)) maintained by passive dosing systems. The tested PAHs included phenanthrene, anthracene, fluoranthene, and pyrene. The test organisms included zebrafish, which prey on Daphnia magna, and cichlids, which prey on zebrafish. The results revealed that for both zebrafish and cichlids, predation elevated the uptake and elimination rates of PAHs. The increase of uptake rate constant ranged from 20.8% to 39.4% in zebrafish with the amount of predation of 5 daphnids per fish per day, and the PAH uptake rate constant increased with the amount of predation. However, predation did not change the final bioaccumulation equilibrium; the equilibrium concentrations of PAHs in fish only depended on the freely dissolved concentration in water. Furthermore, the lipid-normalized water-based bioaccumulation factor of each PAH was constant for fish at different trophic levels. These findings infer that the final bioaccumulation equilibrium of PAHs is related to a partition between water and lipids in aquatic organisms, and predation between trophic levels does not change bioaccumulation equilibrium but bioaccumulation kinetics at stable freely dissolved PAH concentrations. This study suggests that if HOCs have not reached bioaccumulation equilibrium, biomagnification occurs due to enhanced uptake rates caused by predation in addition to higher lipid contents in higher trophic organisms. Otherwise, it is only due to the higher lipid contents in higher trophic organisms.

Characterization of retinoic acid–induced neurobehavioral effects in developing zebrafish

Retinoic signaling plays an important role in cell proliferation and differentiation. Disruption of retinoic signaling via excessive or deficient retinoic acid can cause teratogenic effects on developing embryos. Similar to retinoic acid, many xenobiotic environmental pollutants have been found to disrupt retinoic signaling through binding and eliciting agonistic activity on retinoic acid receptors. Currently, studies of retinoic acid or retinoic acid-like compounds in aquatic organisms have mainly focused on teratogenicity and few studies have explored their neurobehavioral toxicity. In the present study, the authors used retinoic acid as an example to explore the neurobehavioral toxicity associated with developmental exposure of retinoic acid-like compounds in zebrafish. The findings confirmed retinoic acid's teratogenic effects such as bent spine, malformed tail, and pericardial edema in developing zebrafish with a median effective concentration of 2.47 nM. Retinoic acid-induced cell apoptosis at 24 h postfertilization was consistently found in the eye and tail regions of embryos. Spontaneous movement as characterized by tail bend frequency was significantly increased in zebrafish embryos following exposure to 2 nM and 8 nM retinoic acid. Relatively low-dose retinoic acid exposure of 2 nM led to fast locomotion behavior in the dark period and hyperactivity during light-dark photoperiod stimulation. The 2-nM retinoic acid exposure also led to alterations of neurobehavior- and optic nerve-related genes, with the transforming growth factor-β signal transduction inhibitor noggin (nog) and the spinal cord marker homeobox c3a (hox) being underexpressed and the retinal G protein-coupled receptor a (rgr), the photoreceptor cell marker rhodopsin (rho), and the short wave-sensitive cone pigment opsin 1 (opn1sw1) being overexpressed. Increased expression of opn1sw1 and rho was confirmed by whole-mount in situ hybridization. Whether the misexpression of these genes leads to the neurobehavioral changes merits further study. The findings demonstrated that low-dose retinoic acid exposure perturbed the visual system and optic nerve development and caused hyperactivity in developing zebrafish.

Method validation and reconnaissance of pharmaceuticals, personal care products, and alkylphenols in surface waters, sediments, and mussels in an urban estuary

Novel methods utilizing liquid chromatography–tandem mass spectrometry and gas chromatography–mass spectrometry were validated for low-level detection of 104 pharmaceuticals and personal care products ingredients (PPCPs) and four alkylphenols (APs) in environmental samples. The methods were applied to surface water, sediment, and mussel tissue samples collected from San Francisco Bay, CA, USA, an urban estuary that receives direct discharge from over forty municipal and industrial wastewater outfalls. Among the target PPCPs, 35% were detected in at least one sample, with 31, 10, and 17 compounds detected in water, sediment, and mussels, respectively. Maximum concentrations were 92ng/L in water (valsartan), 33ng/g dry weight (dw) in sediments (triclocarban), and 14ng/g wet weight (ww) in mussels (N,N-diethyl-m-toluamide). Nonylphenol was detected in water (<2–73ng/L), sediments (22–86ng/g dw), and mussels (<0.04–95ng/g ww), and nonylphenol mono- and diethoxylates were detected in sediments (<1–40ng/g dw) and mussels (<5–192ng/g ww). The concentrations of PPCPs and APs detected in the San Francisco Bay samples were generally at least an order of magnitude below concentrations expected to elicit toxic effects in aquatic organisms. This study represents the first reconnaissance of PPCPs in mussels living in an urban estuary and provides the first field-derived bioaccumulation factors (BAFs) for select compounds in aquatic organisms.

Determination of perfluorinated compounds in aquatic organisms: a review

Bioaccumulation of PFAS in aquatic organisms is an environmental problem of growing concern around the world. This problem has been tackled by regulatory bodies by proposing EQS for biota in EU water bodies and tolerable daily intake for food. The introduction of regulatory limits requires the availability of harmonised and validated analytical methods of sufficient sensitivity. This paper reviews recent advances in analytical methods for analysis of PFAS in aquatic organisms. The methods available for biota analysis are mostly based on three extraction procedures: ion-pair extraction, solvent liquid extraction, and alkaline digestion. The resulting extracts are then subjected to different clean-up or enrichment steps on solid adsorbents, for example graphitized carbon black, C(18), and WAX phases. All methods reviewed in this work give reliable results but are partially validated only, because of the lack of certified reference materials and regular interlaboratory exercises. The few interlaboratory exercises performed on real unspiked samples did not afford satisfactory results for PFAS other than PFOS, especially for matrices with high lipid content, for example mussels. The reasons for those partially negative results have been identified, and can mainly be attributed to calibration procedures and availability and purity of standards. The urgent need for certified reference materials for this type of analysis is emphasized.

The relative contributions of diet and associated microbiota to the accumulation of UV‐absorbing mycosporine‐like amino acids in the freshwater copepod Boeckella antiqua

Summary1. Mycosporine‐like amino acids (MAAs) are ubiquitous compounds in aquatic organisms that are usually considered sunscreens that protect them from harmful ultraviolet radiation. Given that virtually all animals lack the metabolic pathways to synthesise MAAs de novo, they must acquire them either from their diet or from microorganisms living in close association. In freshwater copepods, accumulation of MAAs is stimulated by exposure to ultraviolet and/or visible radiation.2. A 2 × 2 factorial experiment was performed to assess the contributions of dietary and microbial sources of MAAs in the freshwater copepod Boeckella antiqua. The treatments consisted of two different diets: an MAA‐free diet, including only Chlamydomonas reinhardtii, and an MAA‐rich diet, including both C. reinhardtii and Peridinium inconspicuum, crossed with two antibiotic treatments, with and without chloramphenicol. Treatment with chloramphenicol was intended to inhibit the development of bacteria associated with the copepods.3. MAA concentration in B. antiqua was affected by the experimental conditions: (i) exposure to artificial PAR + UVR stimulated the accumulation of several MAAs (up to 62% increase in total MAA concentration with respect to the initial concentration); (ii) the presence of chloramphenicol in the culture media reduced the MAA concentration in copepods fed an MAA‐free diet; (iii) in the absence of chloramphenicol, copepods fed the MAA‐rich diet had significantly higher total MAA concentration than those fed the MAA‐deficient diet; but (iv) dietary supplementation with an MAA‐rich algae in the presence of chloramphenicol failed to significantly increase total MAA concentration.4. Analysis of profiles from denaturing gradient gel electrophoresis (DGGE) showed that the prokaryotic community associated with the copepods was affected by chloramphenicol. Dendograms constructed from digitalised DGGE images consistently grouped the antibiotics treatments separately from the initial samples and the treatments without antibiotics. Two band positions were exclusive to treatments without antibiotics.5. We conclude that when offered an MAA‐rich diet, B. antiqua may accumulate a proportion of MAAs from diet. However, we suspect that in the absence of an MAA‐rich dietary source (as in its natural habitat), virtually all MAAs present in B. antiqua are produced by copepod‐associated prokaryotes.

Survey of patterns, levels, and trends of perfluorinated compounds in aquatic organisms and bird eggs from representative German ecosystems

Samples from the German Environmental Specimen Bank (ESB) covering particularly the years 1994-1996, 2000-2002, and 2006-2009 were analyzed for perfluorinated compounds (PFC; mainly C4-C13 carboxylic and sulfonic acids) to gain an overview on current PFC levels and patterns in marine, limnetic, and terrestrial biota; to assess their concentrations in different trophic levels; and to investigate whether risk management measures for PFC are successful. Specimens, either standardized annual pooled samples (blue mussels, eelpout liver, bream liver, pigeon eggs) or individual single samples (cormorant eggs, rook eggs), were collected for the German ESB program from representative sampling sites according to documented guidelines. After appropriate extraction, PFC were quantified under ISO/IEC 17025 accreditation by HPLC/MS-MS with isotopically labeled internal standards. Limits of quantification (LOQs) were 0.2-0.5 ng/g. Data are reported on a wet weight basis. In most samples the predominant PFC was perfluorooctane sulfonic acid (PFOS). However, in marine mussels from North and Baltic Seas, PFOS levels were mostly below the LOQ, but low residues of PFOS amide were found which declined in recent years. Livers of eelpout showed maximum concentrations of 15-25 ng/g PFOS in the period 2000-2002 and low amounts of perfluoropentanoate in all years. Beside PFOS (median 48 ng/g) several PFC could be determined in cormorant eggs sampled in 2009 from a Baltic Sea site. For a freshwater ecosystem, current PFC burdens for cormorant eggs were even higher (median 400 ng/g PFOS). Livers of bream from rivers showed concentrations of 130-260 ng/g PFOS, but for bream from a reference lake levels were only about 6 ng/g. In contrast to cormorants, eggs of rook and feral pigeon from terrestrial ecosystems displayed only low PFC burdens (up to 6 ng/g PFOS). Generally, PFC levels were lower in marine than in freshwater biota. PFC burdens were higher in biota from the ESB-North Sea sites than in Baltic Sea organisms. Levels of PFC were quite high especially in top predators of both limnetic and marine ecosystems. Only low PFC levels were detected in eggs of terrestrial birds. A decrease of PFOS levels from maximum values around the year 2000 observed at least in North Sea biota may be a result of a production cease and shifts in marketing pattern.

A review of the tissue residue approach for organic and organometallic compounds in aquatic organisms

This paper reviews the tissue residue approach (TRA) for toxicity assessment as it applies to organic chemicals and some organometallic compounds (Sn, Hg, and Pb) in aquatic organisms. Specific emphasis was placed on evaluating key factors that influence interpretation of critical body residue (CBR) toxicity metrics including data quality issues, lipid dynamics, choice of endpoints, processes that alter toxicokinetics and toxicodynamics, phototoxicity, species- and life stage-specific sensitivities, and biotransformation. The vast majority of data available on TRA is derived from laboratory studies of acute lethal responses to organic toxicants exhibiting baseline toxicity. Application of the TRA to various baseline toxicants as well as substances with specific modes of action via receptor-mediated processes, such as chlorinated aromatic hydrocarbons, pesticides, and organometallics is discussed, as is application of TRA concepts in field assessments of tissue residues. In contrast to media-based toxicity relationships, CBR values tend to be less variable and less influenced by factors that control bioavailability and bioaccumulation, and TRA can be used to infer mechanisms of toxic action, evaluate the toxicity of mixtures, and interpret field data on bioaccumulated toxicants. If residue-effects data are not available, body residues can be estimated, as has been done using the target lipid model for baseline toxicants, to derive critical values for risk assessment. One of the primary unresolved issues complicating TRA for organic chemicals is biotransformation. Further work on the influence of biotransformation, a better understanding of contaminant lipid interactions, and an explicit understanding of the time dependency of CBRs and receptor-mediated toxicity are all required to advance this field. Additional residue-effects data on sublethal endpoints, early life stages, and a wider range of legacy and emergent contaminants will be needed to improve the ability to use TRA for organic and organometallic compounds.