Beschreibung: Culturing experiments exposed the scleractinian corals Porites lobata and Porites lichen to a mixture of dissolved chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), cadmium (Cd), tin (Sn), mercury (Hg) and lead (Pb) in a wide concentration range for a period of more than a year. The aim was to examine whether the incorporation of heavy metals into the aragonitic skeleton of the corals is a direct function of their concentration in seawater. Therefore, the trace-element-to-calcium ratio (TE/Ca) in the coral aragonite precipitated during culturing was measured by Laser ablation ICP-MS in 2020. The measurement showed that all metals used here were measureable in the coral skeleton and only minor, non-systematic intra- and interspecies differences in the trace metal concentrations was found. A positive correlation between the TE/Ca values and the coral skeleton was found for Cr, Mn, Ni, Zn, Ag, Cd and Pb. Cu, Sn and Hg did not show any clear trend. This dataset shows time resolved trace element-to-calcium values of coral colonies A to D cultured in the metal system along the measured Laser ablation ICP-MS scanning lines (Line XY stands for different Laser ablation lines measured at different positions at one respective coral colony) and values derived from the composite lines. Measurements were carried out from the top of the coral to the bottom and the distance starting from the top is indicated as “Elapse Time”. The energy density of the laser was set to 10 J/cm3, the laser spot size was 120 µm diameter and the stage moved 50 µm/s. Prior to every scan, a preablation pass with a spot size of 160 µm diameter was carried out to clean the cut surface of the coral skeleton. Culturing experiments were configured with two identically experimental aquaria. Four different coral colonies and two different species were used (Porites lobate Coral A-C, Porites lichen Coral D). All colonies were divided into subcolonies and growth control was performed with Alizarin Red S prior and during the experiment. One subcolony was placed in each experimental tank. The control aquarium remained unmodified while the trace metal concentration in the metal aquarium was elevated stepwise (Phase 1-4, Phase 1 = lowest metal concentration). The trace metal concentration in both tanks was monitored during the culturing period. After the experiment and more than 15 months later, specimens were cut again and the trace metal concentration in the coral skeleton was determined. It should be noted that coral D died 2.5 weeks after the exposure to the highest metal concentration in phase 4. TE/Ca values are processes as followed: (1) Time resolves raw intensities (in counts per seconds) for all isotopes measured were processed with the software Iolite (Version 4). The determination of element/Ca ratios was performed after the method of Rosenthal et al. (1999). High values of 25Mg, 27Al or 55Mn at the beginning of an ablation profile were related to contamination on the surface of the coral or remains of organic matter and these parts of the profiles were excluded from further data processing. (2) The NIST SRM 612 glass (Jochum et al., 2011) was used for monitoring and correction of the instrument drift. (3) The detection limit was defined by 3.3*SD of the gas blank in counts per seconds for every element in the raw data. Only values above this limit were used for further analyses and no data below the LOQ (limit of quantification = 10*SD) were interpreted. After processing the data with Iolite, an outlier detection of the TE/Ca ratios of the samples was performed. If trace metal values from deviated more than ±2SD from the average of the samples from the corresponding culturing phase, values were defined as outliers and discarded. (4) A composite line was calculated individually for all colonies consisting of the laser ablation measurements along the main growth axis of the coral (coral A line 1-3, coral B line 1-3, coral C line 2 + 3, coral D line 1). Laser ablation measurements along lines that were deviating from the main growth axis of the coral were not taken into account. Calculations were performed with QAnalyseries (Kotov and Paelike, 2018).

Beschreibung: Heavy metal uptake of benthic foraminifera in shelf regions influenced by anthropogenic impacts in terms of removing these potentially harmful metals from the seawater

Beschreibung: Heavy metal pollution from anthropogenic sources increasingly influence marine environments and biota because of their toxicity, persistence and bioaccumulation. Especially coastal environments act as natural catchments for anthropogenic pollutants because these areas are highly affected by industry, agriculture and urban sewage runoff. In nearly all natural environments that are harmed by heavy metal pollution, a combination of several pollutants occurs at the same time. In marginal seas and coastal areas, benthic foraminifera are common in meiofaunal associations, and they can be used as biomonitoring tool for changes in environmental parameters like temperature, salinity, or redox conditions. Furthermore, foraminifera take up heavy metals from the seawater and incorporate those into their carbonate shells during calcification. Moreover, foraminifera have a short life cycle and can therefore react immediately to contaminations of the environment. Here, we will present results from culturing studies with Ammonia aomoriensis, Elphidium excavatum and Ammonia batava addressing the relationship of heavy metal concentration in the seawater and in the foraminiferal tests. The partitioning factor between the ambient seawater and the calcium carbonate of the foraminifera is constrained by continuous water monitoring and laser ablation ICP – MS measurements on single chambers grown during the experiment in a manipulated culturing medium. The foraminifera were exposed to a combination of ten different heavy metals over a range of concentrations comparable to current conditions in medium to high pollutedhigh-polluted areas. A correlation between the heavy metal concentration in the culture medium and in the foraminiferal calcite was recognised for several heavy metals (e.g. Cd, Cr, Pb). Once the carbonate/seawater metal partitioning coefficients are constrained with certainty, investigations of the chemistry of benthic foraminiferal shells offer an advanced and reliable method to monitor short-term changes in the concentrations and bioavailability of toxic elements in seawater.

Beschreibung: Particular heavy metals e.g. zinc serve as micronutrients for eukaryotic life and play an important role for cellular metabolism, growth of organisms, reproduction and enzymatic activity. They occur naturally in the environment as trace ingredient in soils, water, rocks, plants and animals. However, in higher concentrations, most heavy metals become toxic and have serious hazard effects on marine biota. Furthermore, they are highly persistent in the marine environment and can be hardly degraded by organisms. Especially coastal environments act as natural catchment basins for anthropogenic pollutants because these areas are highly affected by industry, agriculture and urban runoff. Therefore, it is vitally important to assess past spatial and temporal distribution patterns and to compare those with recent pollution in order to evaluate contemporary emission reduction measures. An emerging paleo-tool is the heavy metal incorporation into foraminiferal shells calcite, which offers monitoring of anthropogenic footprints on the environmental system. Heavy metal records in foraminiferal tests along a sediment core from the North Sea track pollution events of local (e.g. shipyard, ironworks and metallurgy) and global (e.g. market cycles) origin. We analysed the heavy metal concentrations in tests of Ammonia batava (Mn, Zn, Cd Cu etc.) by laser ablation ICP – MS measurements. These metals reveal the pollution history of the North Sea during the last 500 years with focus on the Early Modern Period.

Beschreibung: Shallow marginal seas have been highly influenced by human activities since several hundred years. Especially near – shore environments were affected by the input of anthropogenic pollutants like heavy metals. Coastal cities rapidly expanded and greater shipyards were established during late 19th and early 20th century. This in turn, led to an elevated input of heavy metals into the coastal systems and to significant pollution of the environment. Heavy metals cause deleterious effects on biota because of their toxicity, persistence and bioaccumulation. Therefore, it is vitally important to assess past spatial and temporal distribution patterns and to compare those with recent pollution in order to evaluate contemporary emission reduction measures. An emerging paleo-tool is the heavy metal incorporation into foraminiferal shells calcite, which offers monitoring of anthropogenic footprints on the environmental system. Heavy metal records in foraminiferal tests along two sediment cores from the Baltic and the North Sea track pollution events of local (e.g. shipyard, ironworks and metallurgy) and global (e.g. market cycles) origin. We analysed the heavy metal concentrations in tests of Ammonia aomoriensis or Elphidium excavatum (Mn, Zn, Cd Cu etc.) by laser ablation ICP – MS measurements. These metals reveal the pollution history of Baltic and North Sea during the last 500 years.

Beschreibung: Heavy metal pollution originating from anthropogenic sources, e.g. mining, industry and extensive land use, increasingly influence tropical marine environments. The elevated input of heavy metals into the marine system potentially affects the biota because of their toxicity, persistence and bioaccumulation. Corals are increasingly used as an indicator for reconstructions of past dynamics of environmental factors like temperature or carbonate system parameters. Especially the massive scleractinian coral Porites provides an excellent tool for reconstructions because of their wide distribution (e.g. Great Barrier Reef, Caribbean, Australia or the tropical region of the Indo – Pacific) and because of their high growth rates allowing measurements at sub - annual resolution as well as building environmental archives covering hundreds of years. Furthermore, recent studies demonstrated that the trace metal concentration in the coral skeleton is most likely linked to local (or global) seawater chemistry including contaminations at various scales. Therefore, the metal concentration in the coral skeleton offers the opportunity of monitoring the spatial and temporal distribution patterns of heavy metals in the environment so contemporary emission reduction measures can be evaluated. Here we will present the final results of culturing studies addressing the relationship of heavy metal concentrations in the seawater and those in the coral skeleton. The partitioning factor between the ambient seawater and the aragonite of the corals is constrained by continuous water monitoring with weekly to biweekly sampling intervals and laser ablation measurements of grown skeleton. Culturing experiments with Porites lobata, Porites lichen, Montipora sp., Seriatopora sp. and Stylophora sp. are performed. The concentrations of heavy metals in the culturing medium are increased in four phases by a factor between 5 and 10 over a time period of more than a year. The results will facilitate a new way to monitor anthropogenic footprints in presumably pristine tropical environments as well as areas of high human impact.

Beschreibung: Marine carbon and nitrogen processing through microorganisms’ metabolism is an important aspect of the global element cycles. For that purpose, we used foraminifera to analyze the element turnover with different algae food sources. In the Baltic Sea, benthic foraminifera are quite common and therefore it is important to understand their metabolism. Especially, Cribroelphidium selseyense, also occurring in the Baltic Sea, has often been used for laboratory feeding experiments to test their effect on carbon or nitrogen turnover. Therefore, foraminifera were collected from the Kiel Fjord and fed with six different algal species in two qualities (freeze-dried algae vs. fresh algae, all 13C- and 15N-labeled). Also, labeled dissolved inorganic C and N compounds and glucose were offered to the foraminifera to test direct assimilation of dissolved compounds (carbon and nitrogen) from the water column. Our experiments showed that after 15 days of incubation, there were highly significant differences in isotope labeling in foraminifera fed with fresh algae and dry algae, depending on algal species. Further, different algal species led to different 13C and 15N enrichment in the studied foraminifera, highlighting a feeding preference for one diatom species and an Eustigmatophyte. A significant carbon assimilation from HCO3– was observed after 7 days of incubation. The N assimilation from NH4+ was significantly higher than for NO3– as an inorganic N source. The uptake of glucose showed a lag phase, which was often observed during past experiments, where foraminifera were in a steady state and showed no food uptake at regular intervals. These results highlight the importance of food quality on the feeding behavior and metabolic pathways for further studies of foraminiferal nutrition and nutrient cycling.

Beschreibung: Heavy metal pollution originating from anthropogenic sources like mining, industry and ship traffic is becoming an increasing threat for marine life. First evidences for human impacts on the heavy metal concentration in seawater were recorded in medieval times already. An emerging tool for palaeo-environmental applications is the heavy metal concentration in the tests of benthic foraminifera, which enable monitoring of the anthropogenic footprint on recent systems and the fossil record. The Helgoland mud area (HMA) in the German Bight is an important depositional area for fine sediments. Average sedimentation rates of up to 13 mm/yr offer high-resolution archives, which renders the site suitable for studying long-term variations of anthropogenic pollution on the marine system. The HMA also accumulates discharge from the Elbe and Weser rivers, which are affected by mining activities in their catchment areas since the Bronze Age. The concentration of chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), tin (Sn) and lead (Pb) in tests of Ammonia batava was analysed along a sediment core from the HMA by laser ablation inductively coupled mass spectrometry (LA-ICP-MS). Radiocarbon datings and stable oxygen and carbon isotope stratigraphy revealed that the core is covering the Early Modern Period (~1550–1700 AD) and the post-World War II period (~1958–2009 AD). The basal unconformity of a tempestite depicts a hiatus and non-sequence between both periods ranging from 1700 to 1958 AD. The concentration of Cu, Zn, Ag and Pb was clearly elevated in the post-1950 AD part of the core indicating a markedly higher anthropogenic influence induced by industrialisation and rapid growth of cities since the 1950s. Variations in Cu, Zn, Ni, Ag and Pb concentrations were linked to mining activities and the production rates of Pb and Ag in the Harz Mountains. Redox-sensitive elements like Mn were correlated to storm surges resulting in the extensive reworking of sediment material. Therefore, the chemistry of the tests of A. batava reflects human activities and natural impacts at the same time, which allows its application for unravelling the environmental history of the North Sea and beyond.

Beschreibung: Some heavy metals e.g., zinc, copper or manganese serve as micronutrients for eukaryotic life and play an important role for the cellular metabolism, growth of organisms, reproduction and enzymatic activity. However, other metals like mercury or lead are not known to have any beneficial effects for organisms and are believed to have a higher toxic potential. Heavy metals occur naturally in the environment. However, in higher concentrations, they become toxic and have hazardous effects on marine biota. Furthermore, they are highly persistent in the marine environment as they are not readily degraded by organisms. Pollution originating from anthropogenic sources, e.g., mining, industry and extensive land use, increased the heavy metal concentration in certain areas above a critical level. Especially temperate and tropical coastal environments act as natural catchment for anthropogenic pollutants because these areas are densely populated and highly affected by industry, agriculture and urban runoff. Therefore, it is vitally important to assess past heavy metal distributions, spatially and temporally and to compare those with recent pollution in order to evaluate contemporary emission reduction measures. The chemistry of the tests of benthic foraminifera and the skeletons of scleractinian corals are widely used for the reconstruction of changes in past environmental conditions including temperature, salinity and carbonate system parameters. Recent studies further demonstrated that the trace metal concentration in the aragonite of corals and the calcite of foraminifera is linked to that in seawater. Therefore, the geochemical analysis of coral skeletons and foraminiferal tests offers the opportunity to gain insights into past heavy metal concentrations in seawater, which can in turn help to improve coastal management. However, it is important to understand distribution patterns, ecological and environmental factors influencing the organism itself and associated species in order to evaluate which species is suitable and representative for a certain area. Therefore, the living and dead foraminiferal assemblage along a transect in the German North Sea was investigated. The results of this study indicate that transport via tidal currents is the dominant environmental factor shaping the foraminiferal assemblages. Haynesina germanica, Ammonia batava and different Elphidium species from the living foraminiferal fauna depict a close linkage between open North Sea areas like Helgoland and the mainland. These species share an opportunistic behaviour and are able to occupy a variety of environments rendering them as possible proxy-carriers for heavy metal contamination in seawater. Nevertheless, an application of the heavy metal concentration in the calcium carbonate of both of the organism groups will only be possible after a calibration of this proxy. Therefore, benthic foraminifera from temperate environments (Ammonia aomoriensis, Ammonia batava and Elphidium excavatum) and tropical corals (Porites lichen and Porites lobata) were exposed to a mixture of dissolved chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), cadmium (Cd), tin (Sn), mercury (Hg) and lead (Pb) over a wide concentration range. High frequency water monitoring in combination with laser ablation ICP-MS measurements of the calcium carbonate, which was precipitated during the culturing period, revealed the uptake of some of these metals mainly depends on its concentration in seawater, which is indicated by strong positive correlations between the metal concentration in seawater and in the calcium carbonate. All three foraminiferal species showed a strong positive correlation between Pb and Ag in the water and their calcite. Ammonia aomoriensis further revealed a correlation with Mn and Cu, Ammonia batava with Mn and Hg and Elphidium excavatum with Cr and Ni, and partially also with Hg. Zinc, Sn and Cd showed no clear trends in all three foraminiferal species studied, which in case of Cd may be due to the exposure to more than one metal at a time. The investigated coral species revealed a positive correlation between the trace metal concentration in seawater and in the coral skeleton for Cr, Mn, Ni, Zn, Ag, Cd and Pb. No correlation was found for Cu, Sn and Hg. The calculated partitioning coefficients (DTE) allow a determination of the heavy metal concentrations in seawater. Therefore, the trace element concentration in benthic foraminifera and in scleractinian corals provides a promising tool for ecosystem status assessments in the future, which can serve as a deciding support for governments and environmental agencies.