Sonja Zimmermann

First report on the uptake of automobile catalyst emitted palladium by European eels (Anguilla anguilla) following experimental exposure to road dust

Following the introduction of automobile catalysts in the middle of the 1980s in Germany there is an increasing emission of the platinum-group-metals platinum, palladium (Pd) and rhodium. Still, it remains unclear if these metals are bioavailable for aquatic animals and to which extent they become accumulated by the aquatic biosphere. Because of analytical problems in detecting Pd in small biological samples the present investigation concentrates on the bioavailability of this metal. To answer the question of a Pd uptake by aquatic organisms experimental studies were conducted with European eels maintained in water containing road dust at a concentration of 10 kg/100 l. Following an exposure period of four weeks, samples of liver and kidney were analysed by total-reflection X-ray fluorescence analysis after co-precipitation of Pd with mercury. These experiments revealed an uptake of traffic related Pd by European eels which showed a mean liver Pd concentration of 0.18 +/- 0.05 ng/g (wet wt.), whereas the Pd concentration in the kidney ranged below the detection limit. Thus, in this study we can demonstrate for the first time that automobile catalyst emitted Pd is bioavailable for aquatic animals.

Relevance and analysis of traffic related platinum group metals (Pt, Pd, Rh) in the aquatic biosphere, with emphasis on palladium.

Following the introduction of automobile catalysts in the middle of the Eighties in Germany there is an increasing emission of the platinum-group-metals (PGM) platinum (Pt), palladium (Pd) and rhodium (Rh). Still, it remains unclear if these metals are bioavailable for aquatic animals and to which extent they accumulate in the aquatic biosphere. Zebra mussels (Dreissena polymorpha ) were maintained in water containing road dust at a concentration of 1 kg/10 l. Following an exposure period of 26 weeks, soft tissues of the mussels were analysed applying adsorptive cathodic stripping voltammetry (ACSV) for the determination of Pt and Rh and total-reflection X-ray fluorescence analysis after co-precipitation of Pd with mercury. This experiment revealed for the first time that all the three catalyst emitted metals were accumulated by mussels. The bioaccumulation increased in the following manner: Rh<Pt<Pd. Thus, the application of sentinel organisms in combination with modern trace analytical procedures in environmental impact studies does allow an assessment of the distribution and the degree of bioaccumulation of PGM in the environment, which is highly appreciated.

Significance of platinum group metals emitted from automobile exhaust gas converters for the biosphere

Intention, Goal, Scope, BackgroundFollowing the introduction of automobile catalytic converters the platinum group metals (PGM) platinum (Pt), palladium (Pd) and rhodium (Rh) gain on increasing interest in environmental research as these metals are emitted with exhaust fumes into the environment. Consequently, elevated PGM levels were found in different environmental matrices uch as road dusts, soils along heavily frequented roads, sediments of urban rivers etc. Accordingly, the effects of increasing PGM emissions on the biosphere are controversially discussed.ObjectiveThis paper summarizes the present knowledge on the biological availability of PGM to plants and animals. As biological availability is one of the most decisive factors determining the toxicologi-cal potential of xenobiotics, this information is very important to evaluate the possible threat of the noble metals to ecosystems.Results and DiscussionThe availability of soluble as well as particle bound PGM to terrestrial plants was demonstrated in several studies. Experimental investigations revealed uptake of Pt, Pd and Rh also by aquatic plants. Additionally, the biological availability of the noble metals for animals has been verified in experimental studies using soluble metal salts, catalytic converter model substances, sediments of urban rivers, road dust or tunnel dust as metal sources. These studies refer mainly to aquatic animals. Beside of free living organisms, in particular worms parasitizing fish demonstrated a high potential to accumulate PGM. This could be of great interest in respect of biomonitoring purposes. Generally, for plants as well as for animals Pd turns out to be the best available metal among the PGM. Compared to other heavy metals, the biological availability of PGM from road dust to zebra mussels(Dreissena polymorpha) ranged between that of Cd and Pb.ConclusionEspecially chronic effects of PGM on the biosphere can not be excluded due to (1) their cumulative increase in the environment, (2) their unexpected high biological availability and bioaccumulation and (3) their unknown toxicological and ecotoxicological potential. However, it appears that acute effects on ecosystems due to anthropogenic PGM emission are not likely.Recommendation and OutlookResearch on environmental PGM contamination of the biosphere, especially the fauna, and on long-term toxiciry of low PGM concentrations is highly appreciated. These studies require very sensitive analytical techniques to determine PGM even in low sample amounts. Research has to be done in particular on reliable determination of (ultra) trace levels of Pd and Rh as the lack of data on these two metals is mainly due to analytical problems.

The acanthocephalan Paratenuisentis ambiguus as a sensitive indicator of the precious metals Pt and Rh from automobile catalytic converters.

Recent studies revealed that intestinal acanthocephalans of fish can accumulate heavy metals to concentrations orders of magnitude higher than those in the host tissues or the aquatic environment. This significant heavy metal accumulation by acanthocephalans, even surpassing that of established free living accumulation bioindicators, encouraged us to study the bioavailability of the platinum-group-metals (PGM) Pt and Rh for parasites. These precious metals are used in catalytic converters of cars for exhaust gas purification in Europe since the early 1980s. In addition to the beneficial effect in reducing the emission of CHx, CO and NOx of cars there is an increasing emission of these metals. However, it still remains unclear if these elements become accumulated in the biosphere and whether they affect the health of organisms. The present study reveals that in European eels (Anguilla anguilla) naturally infected with the eoacanthocephalan parasite Paratenuisentis ambiguus and experimentally exposed to ground catalytic converter material, the parasites take up and accumulate the catalytic active metals Pt and Rh whereas in the examined host tissues we found no metal uptake. Compared with the PGM concentrations in the water the worms contained 1600 times higher Rh and 50 times higher Pt concentrations. Thus, the parasites can be used as sentinel organisms reflecting even very low levels of precious metals.

Lipid solubility of the platinum group metals Pt, Pd and Rh in dependence on the presence of complexing agents.

Investigations on the bioaccumulation of the platinum group metals (PGM) Pt, Pd and Rh in aquatic organisms are of growing interest in environmental research due to the increasing emission of these metals by motor vehicles with catalytic converters. Until now, nothing is known about the possible influence of complexing agents on the bioaccumulation capacity of these precious metals. According to the partition coefficient between 1-octanol and water (POW) as a measure of bioaccumulation, in this study a simple shaking method was performed in order to investigate the effects of different complexing agents (-methionine, thio urea, EDTA, humic substances, bile compounds) on the octanol solubility of the PGM. The results demonstrated a significant influence of all agents used. -Methionine and thio urea decreased the lipid solubility. In contrast, the presence of EDTA, humic substances and especially bile caused a higher transfer of metals in the octanol phase. For most complexing agents tested, the transfer of Pd to the lipid phase was significantly higher compared with Rh and Pt, except for bile acid where the highest octanol solubility was found for Pt. Recent experimental results on PGM accumulation in zebra mussels confirm a high bioaccumulation of Pd which could be predicted from the lipid solubility.

Effects of Silver Nitrate and Silver Nanoparticles on a Planktonic Community: General Trends after Short-Term Exposure

Among metal pollutants silver ions are one of the most toxic forms, and have thus been assigned to the highest toxicity class. Its toxicity to a wide range of microorganisms combined with its low toxicity to humans lead to the development of a wealth of silver-based products in many bactericidal applications accounting to more than 1000 nano-technology-based consumer products. Accordingly, silver is a widely distributed metal in the environment originating from its different forms of application as metal, salt and nanoparticle. A realistic assessment of silver nanoparticle toxicity in natural waters is, however, problematic and needs to be linked to experimental approaches. Here we apply metatranscriptome sequencing allowing for elucidating reactions of whole communities present in a water sample to stressors. We compared the toxicity of ionic silver and ligand-free silver nanoparticles by short term exposure on a natural community of aquatic microorganisms. We analyzed the effects of the treatments on metabolic pathways and species composition on the eukaryote metatranscriptome level in order to describe immediate molecular responses of organisms using a community approach. We found significant differences between the samples treated with 5 µg/L AgNO3 compared to the controls, but no significant differences in the samples treated with AgNP compared to the control samples. Statistical analysis yielded 126 genes (KO-IDs) with significant differential expression with a false discovery rate (FDR) <0.05 between the control (KO) and AgNO3 (NO3) groups. A KEGG pathway enrichment analysis showed significant results with a FDR below 0.05 for pathways related to photosynthesis. Our study therefore supports the view that ionic silver rather than silver nanoparticles are responsible for silver toxicity. Nevertheless, our results highlight the strength of metatranscriptome approaches for assessing metal toxicity on aquatic communities.

COST action TD1407: network on technology-critical elements (NOTICE)—from environmental processes to human health threats

The current socio-economic, environmental and public health challenges that countries are facing clearly need common-defined strategies to inform and support our transition to a sustainable economy. Here, the technology-critical elements (which includes Ga, Ge, In, Te, Nb, Ta, Tl, the Platinum Group Elements and most of the rare-earth elements) are of great relevance in the development of emerging key technologies—including renewable energy, energy efficiency, electronics or the aerospace industry. In this context, the increasing use of technology-critical elements (TCEs) and associated environmental impacts (from mining to end-of-life waste products) is not restricted to a national level but covers most likely a global scale. Accordingly, the European COST Action TD1407: Network on Technology-Critical Elements (NOTICE)—from environmental processes to human health threats, has an overall objective for creating a network of scientists and practitioners interested in TCEs, from the evaluation of their environmental processes to understanding potential human health threats, with the aim of defining the current state of knowledge and gaps, proposing priority research lines/activities and acting as a platform for new collaborations and joint research projects. The Action is focused on three major scientific areas: (i) analytical chemistry, (ii) environmental biogeochemistry and (iii) human exposure and (eco)-toxicology.

Accumulation of the precious metals platinum, palladium and rhodium from automobile catalytic converters in Paratenuisentis ambiguus as compared with its fish host, Anguilla anguilla

The platinum group metals (PGM) Pt, Pd and Rh are emitted into the environment mainly by catalytic exhaust gas converters of cars. As PGM accumulate in sediments of aquatic ecosystems, the study was focused on the uptake of the noble metals by European eels, Anguilla anguilla infected with the acanthocephalan Paratenuisentis ambiguus. Eels were exposed to ground catalytic converter material for six weeks. After exposure Pt and Pd were detected in the liver and kidney of the eels and in the parasites. Palladium was also found in fish muscle and intestine. No Rh uptake by the eel tissues and the parasites occurred. Paratenuisentis ambiguus contained the highest levels of both metals with 40 times higher Pt concentrations and four times higher Pd concentrations than the liver of its host. Due to its accumulation capacity for PGM, P. ambiguus can be applied as a sensitive accumulation indicator in field studies to assess the degree of environmental PGM contamination in aquatic ecosystems.

How does the metallothionein induction in bivalves meet the criteria for biomarkers of metal exposure

Metallothionein (MT) concentrations in the whole soft tissue or in a particular tissue of bivalves have widely been used in ecotoxicological studies and biomonitoring programmes. This approach is based on the reported results on the enhancement of MT induction in bivalves in response to metal exposure. The validity of using MT induction as a biomarker is briefly assessed in the present study. The sensitivity of MT induction in these organisms is questionable due to the high basal MT level as well as the high natural variability related to the effects of a number of biotic and abiotic factors, which are not well described yet. Moreover, the relationship between exposure to metals, the toxic effects of that exposure, and the appearance of MT in soft tissue, is not well characterized. A variety of factors may influence the appearance and distribution of MT: 1) the uneven distribution of metals in particular portions of the soft tissue and in particular subcellular compartments; 2) pre-exposure to metals, perhaps at non-toxic levels; 3) metal-metal competition and metal-protein interactions; and 4) tissue-specific induction, functions, and isoforms of MT. Therefore, attention is required when using MT induction in bivalves for assessment of metal exposure or consequent toxic effects. The MT concentration can be a reliable indicator only when it is considered in relation with metal uptake kinetics and subcellular partitioning while specifying the isoform of MT synthesised and considering various confounding factors. The kinetic turnover of MT may provide useful information on metal exposure and biological effects since it covers both the synthesis and breakdown of MT as well as the chemical species of metals accumulated and MT.

Is metal accumulation in Pomphorhynchus laevis dependent on parasite sex or infrapopulation size

Concentrations of the elements As, Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Sn, V, Zn were analysed by inductively coupled plasma mass spectrometry (ICP-MS) in the acanthocephalan Pomphorhynchus laevis and its fish host Barbus barbus. A total of 27 barbels were collected from the Danube River in autumn 2006 close to the town Kozloduy (685 river kilometer) on the Bulgarian river bank. Fish were divided into 3 groups. According to their P. laevis infrapopulation size hosts were considered as heavily infected (>100 worms per fish) and lightly infected (<20 worms per fish). The third group was used to compare heavy metal concentrations between male and female P. laevis. The 5 elements As, Cd, Cu, Pb and Zn were detected in significantly higher concentrations in parasites compared to host tissues (muscle, intestine, liver). According to the calculated mean bioconcentration factors, 3 more elements (Co, Mn, V) showed usually higher concentrations in P. laevis. Comparisons between heavily and lightly infected fish revealed significant differences only for V with higher concentrations for the heavily infected group. Concerning sex-specific metal accumulation V and Zn showed significant differences (V, at P<0.05; Zn, at P=0.05), with higher levels of both metals in females of P. laevis. Our results suggest that - for the metals analysed - the size of the parasite infrapopulation plays no role in the degree of metal accumulation. Similarly, parasite sex seems not to be a crucial factor for metal accumulation in the parasites. Thus, for metal monitoring purposes there is no need to take these aspects into account, which makes the use of parasites as bioindicators more applicable.