Jörg Schäfer

Uptake of traffic-related heavy metals and platinum group elements (PGE) by plants

Abstract The distribution of the platinum group elements (PGE) caused by traffic emissions from autoexhaust catalysts has been determined in soils and different types of plants. The plants (spinach, cress, phacelia, stinging nettle) were cultivated on different soils collected from areas adjacent to a German highway and on uncontaminated sandy and clayey soils. The main result of the experiments was a measurable transfer of PGE from contaminated soil to plants. Following the definition of Sauerbeck (1989) , Pt, Rh and Pd transfer coefficients are within the range of immobile to moderately mobile elements, such as Cu. The transfer coefficient decreases from Pd>Pt≥Rh, palladium therefore is the most biologically available of this element group.

Platinum-Group-Metals (PGM) emitted from automobile catalytic converters and their distribution in roadside soils

Abstract The use of catalytic converters yields emissions of Pt, Rh and Pd. Geochemical background values, recent environmental concentrations and distribution patterns of these noble metals are very poorly known. In this paper a typical distribution of Pt, Rh and Pd in roadside soil is compared to the distribution of Pb and Zn. The effect of a barrier on airborne transport of aerosols is demonstrated as well as the influence of prevailing wind direction. Urban road-dusts are more likely to be inhaled than soil particles, therefore PGM-concentrations and their dependency on traffic intensity in road-dusts and soil was investigated. The importance of traffic-related emission for PGM-contents in sewage sludge is estimated based on the characteristic Pt/Rh ratio.

The distribution of Mo, U, and Cd in relation to major redox species in muddy sediments of the Bay of Biscay

In order to understand the relationship between authigenic precipitation of U, Mo, Cd, and the redox properties of the marine environment, we have studied the vertical distribution of these metals and of the major redox species (oxygen, nitrate, manganese, reactive iron, sulfate, carbon, and sulfur) in modern sediment. We have sampled four sites at 150 to 2800 m depth in the Bay of Biscay. At the shallowest station, where sediment is highly bioturbated, organic carbon levels are above 2% and particulate sulfides are abundant. At the deepest stations, sediment is much less bioturbated, and organic carbon levels are lower. At all sites, early diagenesis follows a well-established depth sequence of redox reactions, based on the bacterially mediated oxidation of organic matter. Manganese-oxides and authigenic U and Mo were extracted by an ascorbate solution. Molybdenum is associated with these oxides in the oxic part of cores. In the anoxic layer of the sediment, Mo precipitates as a detectable authigenic phase only when sulfide minerals are present, i.e. when sulfate reduction becomes important. In anoxic sediments, Cd enrichment is a good indicator of sulfide production from sulfate reduction even if the production is weak. Uranium precipitates at the depth of reactive iron (III) reduction. No relationship was observed between U and S. The U concentration at the depth of precipitation agrees with values calculated using estimated accumulation rates and a downward diffusive flux of dissolved U from the bottom seawater into the sediment. However, authigenic U concentrations continue to increase in the anoxic part of the cores. Therefore, it is difficult to establish a direct relationship between the process of U accumulation and the flux of Corg to the sediment. D 2002 Elsevier Science B.V. All rights reserved.

Ten-year observation of the Gironde tributary fluvial system: fluxes of suspended matter, particulate organic carbon and cadmium

A program of long-term observation of suspended solids (TSS), particulate organic carbon (POC) and cadmium transported into the Gironde estuary (France) by its major tributaries has been carried out between 1990 and 1999. This decade included contrasting hydrologic cycles and appears representative of a much longer period (1959-1999). The Garonne and the Dordogne river systems are the main tributaries of the Gironde estuary and derive their waters from drainage basins with different geological, industrial and agricultural features. To better understand their respective contributions, they have been observed separately and compared. Water and TSS fluxes of the Garonne River show greater temporal variations and discharge is more related to the hydrology of the drainage basin (e.g. wet/dry years, local flood events etc.). As POC and particulate Cd concentrations in suspended matter are much less variable than turbidity, their fluxes are mainly controlled by the TSS transport. A major part of annual fluxes of TSS and associated pollutants may occur within few flood days (depending on various parameters, e.g. intensity, duration, season, etc.), and also the succession of dry and wet years has an important influence on annual fluxes. The presented data allow calculating fluvial inputs into the Gironde as the sum of fluxes transported by its major tributaries, the Garonne and the Dordogne river systems. Mean annual fluxes into the Gironde observed in 1990-1999 are about 34 x 10 9 m 3 year -1 for river water, 3.24 x 10 6 t year -1 for suspended solids (TSS) and 9.88 × 10 9 mol year -1 for particulate organic carbon (POC). Generally, these fluxes are dominated by the contributions of the Garonne River. However, in dry years, the mean contribution of the Dordogne river system (including Dronne and Isle rivers) to the POC input into the estuary exceeded that of the Garonne. This reflects significant differences in vegetation and soil due to natural properties and land management of the basins. Mean Cd fluxes into the estuary are about 110 x 10 3 mol year -1 of which 19.6 × 10 3 mol year -1 are transported in the dissolved and 90.8 x 10 3 mol year -1 in the particulate phases, respectively. In 1991 (dry year), the net (dissolved) Cd flux towards the ocean exceeded the gross fluvial input of total Cd, suggesting the release of Cd from an important stock in the maximum turbidity zone (MTZ) or the fluid mud of the Gironde estuary.

The behaviour of arsenic in muddy sediments of the Bay of Biscay (France)

Abstract We have studied particulate and dissolved arsenic species in sediment and porewaters at sites in the Bay of Biscay, France, ranging in depths from 150 to 2,800 m. At all stations, major redox species (oxygen, nitrate, ammonia, total and reactive iron and manganese, sulphate and sulphur) reflect early diagenetic depth sequences of redox reactions comparable to other marine environments. Vertical distributions of dissolved and particulate As species and major redox species are related to changes in redox conditions and their major carrier phases, such as Fe and Mn-oxides. Arsenic diagenesis appears strongly dependent on Fe cycling. A subsurface maximum of dissolved As and surface enrichment of particulate As correspond to dissolution and precipitation of Fe (III) phases. Except for the shallowest and most bioturbated site, flux calculations show three different vertical diffusive As fluxes: two upwards and one downwards. Phase changes of recycled As result in local accumulations of reactive As at different redox fronts. Mass-balance calculations indicate that the upward As flux toward the oxidized layer can explain the enrichment of HCl extractable particulate As in this layer. A portion of the upward diffusing As can escape the sediment and may be fixed onto settling Fe-oxides by adsorption or co-precipitation and contribute to reactive particulate As input (i.e., As is recycled across the water sediment interface).

Metal mobilization in the Gironde Estuary (France): the role of the soft mud layer in the maximum turbidity zone

Vertical profiles of heavy metals (Cd, Cu, Cr, Fe, Mn, Ni and Pb) in the particulate and dissolved phases and redox sensitive parameters (dissolved oxygen, nitrate, nitrite and ammonium) were analyzed for the first time in the continuum Maximum Turbidity Zone (MTZ)–Fluid Mud (FM; 50 g l 1 <suspended particulate matter (SPM)<500 g l 1 )-consolidated sediment of a macrotidal, highly turbid estuary: the Gironde. The results show that the fluid mud is a layer of intense metal mobilization due to redox induced dissolution, releasing trace metals into the water column. This newly identified phenomenon creates a transient situation characterized by the onset of diagenetic sequences in the FM, i.e. in the lower part of the water column. These sequences overlie permanent diagenetic sequences in the consolidated sediment, similar to those typically observed in marine and estuarine sediments. The discontinuity of dissolved Cd, Ni and Pb concentrations at the sediment surface indicates that Mn reduction is faster in the FM than in the upper sediment, isolated from the oxic water column by the suboxic FM. Two separate diagenetic signals are preserved, as the installation of the diagenetic sequence in the FM is faster than the molecular diffusion of dissolved compounds through the FM–sediment interface. The diagenetic signal of trace metals (e.g. dissolved Cr maximum) in the upper sediment layer near the FM–sediment interface is interpreted as a transient record of past hydrologic situations, during which the absence of the FM layer permitted the installation of an oxic/suboxic front in the upper sediment. The resuspension of the FM during the spring tide probably results in a new distribution of these elements in the estuary, where they may be stabilized in the dissolved phase (e.g. by chloride complexes or dissolved organic compounds) or be adsorbed onto reactive particles (e.g. freshly precipitated Mn oxyhydroxides). D 2004 Elsevier B.V. All rights reserved.

Representative measurement of two-dimensional reactive phosphate distributions and co-distributed iron(II) and sulfide in seagrass sediment porewaters

The high degree of heterogeneity within sediments can make interpreting one-dimensional measurements difficult. The recent development and use of in situ techniques that measure two-dimensional distributions of porewater solutes have facilitated investigation of the role of spatial heterogeneity in sediment biogeochemistry. A colourimetric diffusive equilibration in thin films method has been developed that allows two-dimensional, high-resolution measurement of reactive phosphate in sediment porewaters. A method detection limit of 0.22 μM, an effective upper limit of ~1000 μM and relative standard deviations typically below 5% were achieved. This method was evaluated by deployment in seagrass (Zostera capricorni) colonised sediments, as part of combined probes with similar colourimetric methods for sulfide and iron(II). The two-dimensional, high resolution distributions obtained provide a highly representative measurement of the co-distributions of porewater solutes, allowing heterogeneous features and biogeochemical processes to be observed and interpreted. Microniches of high phosphate concentration >100 μM were observed throughout the distributions and were interpreted to be due to localised zones of rapid organic matter mineralisation, possibly using electron acceptors other than iron(III) oxyhydroxides (e.g. aerobic respiration) as often they did not correspond with microniches of higher Fe(II) concentration.

Long-term records of cadmium and silver contamination in sediments and oysters from the Gironde fluvial-estuarine continuum - Evidence of changing silver sources

The Gironde fluvial estuarine system is impacted by historic metal pollution (e.g. Cd, Zn, Hg) and oysters (Crassostrea gigas) from the estuary mouth have shown extremely high Cd concentrations for decades. Based on recent work (Chiffoleau et al., 2005) revealing anomalously high Ag concentrations (up to 65 mg kg(-1); dry weight) in Gironde oysters, we compared long-term (~1955-2001) records of Ag and Cd concentrations in reservoir sediment with the respective concentrations in oysters collected between 1979 and 2010 to identify the origin and historical trend of the recently discovered Ag anomaly. Sediment cores from two reservoirs upstream and downstream from the main metal pollution source provided information on (i) geochemical background (upstream; Ag: ~0.3 mg kg(-1); Cd: ~0.8 mg kg(-1)) and (ii) historical trends in Ag and Cd pollution. The results showed parallel concentration-depth profiles of Ag and Cd supporting a common source and transport. Decreasing concentrations since 1986 (Cd: from 300 to 11 mg kg(-1); Ag: from 6.7 to 0.43 mg kg(-1)) reflected the termination of Zn ore treatment in the Decazeville basin followed by remediation actions. Accordingly, Cd concentrations in oysters decreased after 1988 (from 109 to 26 mg kg(-1), dry weight (dw)), while Ag bioaccumulation increased from 38 up to 116 mg kg(-1), dw after 1993. Based on the Cd/Ag ratio (Cd/Ag~2) in oysters sampled before the termination of zinc ore treatment (1981-1985) and assuming that nearly all Cd in oysters originated from the metal point source, we estimated the respective contribution of Ag from this source to Ag concentrations in oysters. The evolution over the past 30 years clearly suggested that the recent, unexplained Ag concentrations in oysters are due to increasing contributions (>70% after 1999) by other sources, such as photography, electronics and emerging Ag applications/materials.

Mercury methylation rates of biofilm and plankton microorganisms from a hydroelectric reservoir in French Guiana.

The Petit-Saut ecosystem is a hydroelectric reservoir covering 365km(2) of flooded tropical forest. This reservoir and the Sinnamary Estuary downstream of the dam are subject to significant mercury methylation. The mercury methylation potential of plankton and biofilm microorganisms/components from different depths in the anoxic reservoir water column and from two different sites along the estuary was assessed. For this, reservoir water and samples of epiphytic biofilms from the trunk of a submerged tree in the anoxic water column and from submerged branches in the estuary were batch-incubated from 1h to 3 months with a nominal 1000ng/L spike of Hg(II) chloride enriched in (199)Hg. Methylation rates were determined for different reservoir and estuarine communities under natural nutrient (reservoir water, estuary freshwater) and artificial nutrient (culture medium) conditions. Methylation rates in reservoir water incubations were the highest with plankton microorganisms sampled at -9.5m depth (0.5%/d) without addition of biofilm components. Mercury methylation rates of incubated biofilm components were strongly enhanced by nutrient addition. The results suggested that plankton microorganisms strongly contribute to the total Hg methylation in the Petit-Saut reservoir and in the Sinnamary Estuary. Moreover, specific methylation efficiencies (%Me(199)Hg(net)/cell) suggested that plankton microorganisms could be more efficient methylating actors than biofilm consortia and that their methylation efficiency may be reduced in the presence of biofilm components. Extrapolation to the reservoir scale of the experimentally determined preliminary methylation efficiencies suggested that plankton microorganisms in the anoxic water column could produce up to 27mol MeHg/year. Taking into account that (i) demethylation probably occurs in the reservoir and (ii) that the presence of biofilm components may limit the methylation efficiency of plankton microorganisms, this result is highly consistent with the annual net MeHg production estimated from mass balances (8.1mol MeHg/year, Muresan et al., 2008a).

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.