Purpose As one component of the German ecological environment observation, the Environmental Specimen Bank program was initiated in the mid-1980s. Under the program, representative specimens of marine, fresh water, and terrestrial ecosystems are sampled regularly and archived under chemically stable conditions. An initial characterization of the samples provides data regarding the status quo of the respective ecosystems. The aim of the present publication is to give insight into these real-time monitoring data, which have been generated for the last 10 to 20 years. This is done exemplarily for the heavy metals cadmium (Cd), mercury (Hg), and lead (Pb) in marine specimens of the Baltic and the North Sea. Methods Bladder wrack (Fucus vesiculosus), blue mussel (Mytilus edulis), eelpout (Zoarces viviparus), and eggs of herring gulls (Larus argentatus) were sampled at one location in the Baltic Sea and at two sites in the North Sea (Schleswig-Holstein Wadden Sea and Lower Saxony Wadden Sea). Annual samples were pooled, homogenized, and analyzed for a set of elements. Cd and Pb were quantified after freeze-drying and microwave digestion using inductively coupled plasma-mass spectrometry. Total Hg in freeze-dried samples was determined by atomic absorption spectrometry using a direct mercury analyzer. Results Time series data covering up to two decades revealed comparable cadmium levels at all three locations. Concentrations in bladder wrack ranged between 0.10 and 0.37 µg/g on a wet weight basis (ww). Respective values for blue mussel and eelpout liver were 0.07-0.29 and 0.01-0.10 µg/g ww. Herring gull eggs were not included in cadmium analyses. Declining trends were observed in North Sea bladder wrack and mussels, eelpout from the Lower Saxony site, and mussels from the Baltic Sea. Upward trends were apparent in eelpout from the Schleswig-Holstein location. Mercury concentrations in Baltic Sea specimens ranged from 1.1-2.7 ng/g ww in bladder wrack to 2.6-5.1, 26-52, and 86-226 ng/g ww in blue mussel, eelpout muscle, and herring gull eggs, respectively. No temporal trends were observed. North Sea bladder wrack had accumulated 5.4-24 ng/g ww Hg. The respective Hg values for blue mussel and eelpout muscle were 19-64 and 73-187 ng/g ww. Highest Hg contents were detected in herring gull eggs (90-1,100 ng/g ww). Declining trends of Hg were observed in herring gull eggs at both North Sea locations and in blue mussels at the Lower Saxony site. Lead concentrations in Baltic Sea specimens were 48-222 ng/g ww in bladder wrack, 85-189 ng/g ww in blue mussel, 2.0-9.5 and 10-42 ng/g ww in eelpout muscle and liver, and 2.7-26 ng/g ww in herring gull eggs. In the North Sea, Pb concentrations were as follows: 68-397 ng/g ww in bladder wrack, 101-507 ng/g ww in blue mussels, 2.6-35 and 5.9-158 ng/g ww in eelpout muscle and liver, and 3.5-55 ng/g ww in herring gull eggs. Highest Pb-levels were found at the Lower Saxony site. Declining Pb-trends were observed in bladder wrack from the Baltic Sea; in bladder wrack and mussel at the Schleswig-Holstein location; and in bladder wrack, mussels, eelpout liver, and herring gull eggs at the Lower Saxony site. Conclusions During the 10 to 20 years of monitoring, reliable data were obtained which allow a good insight into metal contamination of marine biota. Assessment of the data according to OSPAR criteria (OSPAR 2005) revealed cadmium levels above the derived background concentrations in mussels of all three sites. Mercury levels above background concentrations were found at both North Sea locations, whereas only mussels at the Lower Saxony site had Pb concentrations above the reference value. Archived specimens are available for further analyses and questions which may arise in the future (speciation of elements, metallomics).

Background, aim, and scope Soil remediation with ethylenediamine tetraacetic acid (EDTA) leaching is capable of removing only part of the total metal concentration in the soil, mostly the labile, bioavailable metal species (metal bioavailability stripping). However, reintroduction of remediated soil in the environment exposes the soil to various environmental factors, which could potentially shift nonlabile residual metals back to labile bioavailable forms. We studied the effect of autochthonous earthworm species as model biotic environmental factor on the fractionation and bioavailability of Cu residual in soil after remediation. Materials and methods We used soil from a 50-year-old vineyard regularly managed and treated with CuSO₄•5H₂O (Bordeaux mixture) as fungicide. Soil containing 400 mg kg⁻¹ of Cu was leached with total 15 mmol kg⁻¹ EDTA. Remediated and nonremediated soil was processed by fully clitellated adult specimens of Lumbricus terrestris L., a prevailing autochthonous soil earthworm species. Cu fractionation, phytoavailability, and oral-bioavailability in processed and nonprocessed soil were determined using six-step sequential extraction, extraction with diethylenediamine pentaacetic acid, and in vitro physiologically based extraction test, respectively. Results EDTA leaching removed 41% of the pseudototal Cu, mostly from the soil Fe- and Mn-oxides, carbonates, and organic matter. A 2.7-fold decrease in Cu phytoavailability and a 4.4- and 2.8-fold decrease in Cu oral-bioavailability in the stomach and small intestine fractions, respectively, were achieved after remediation. In nonremediated soil, earthworms increased the share of nonlabile Cu in residual soil fraction, while in remediated soil they increased the share of Cu bound to carbonates. A statistically significant 1.1- and 1.7-fold increase in Cu phytoavailability and intestinal oral-bioavailability, respectively, was observed in earthworm processed remediated soil. Discussion Cu occurs in various soil “pools” of different solubilities with different chemical characteristics and consequently different functions. By removing the labile part of the metals from the soil during remediation, we disrupt the chemical equilibrium; the nonlabile residual metals left in soil after remediation might become more labile in time in tendency to re-establish that equilibrium. Earthworms alter the physical and chemical properties of soil affecting consequently the fractionation of metals. The increase in earthworm's gut pH due to the excretion of ammonia and/or calcium carbonate into the intestine could lead to the transbounding of metals into the carbonate fraction. However, their activity in remediated soil increased Cu phytoavailability and intestinal oral-bioavailability, and it would, therefore, be improper to generalize the influence of earthworms on metal availability in soil. Conclusions The results presented here show that residual Cu in remediated soil is affected by environmental factors such as earthworms, which should be considered in evaluating the effect of Cu polluted soil remediation. Recommendations and perspectives Information on the behavior of residual metals in soil after its remediation is surprisingly scarce. The development of new effective remediation techniques should imply also the evaluation of postremediation effects on remediated soil. The results presented in this work indicate a possible tool for assessing the effect of biotic environmental factors on residual metals left in soil after its remediation.

Background, aim, and scope The occurrence and fate of pharmaceuticals in the aquatic environment is recognized as one of the emerging issues in environmental chemistry and as a matter of public concern. Existing data tend to focus on the concentrations of pharmaceuticals in the aqueous phase, with limited studies on their concentrations in particulate phase such as sediments. Furthermore, current water quality monitoring does not differentiate between soluble and colloidal phases in water samples, hindering our understanding of the bioavailability and bioaccumulation of pharmaceuticals in aquatic organisms. In this study, an investigation was conducted into the concentrations and phase association (soluble, colloidal, suspended particulate matter or SPM) of selected pharmaceuticals (propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine, tamoxifen, indomethacine, diclofenac, and meclofenamic acid) in river water, effluents from sewage treatment works (STW), and groundwater in the UK. Materials and methods The occurrence and phase association of selected pharmaceuticals propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine, tamoxifen, indomethacine, diclofenac, and meclofenamic acid in contrasting aquatic environments (river, sewage effluent, and groundwater) were studied. Colloids were isolated by cross-flow ultrafiltration (CFUF). Water samples were extracted by solid-phase extraction (SPE), while SPM was extracted by microwave. All sample extracts were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring. Results and discussion Five compounds propranolol, sulfamethoxazole, carbamazepine, indomethacine, and diclofenac were detected in all samples, with carbamazepine showing the highest concentrations in all phases. The highest concentrations of these compounds were detected in STW effluents, confirming STW as a key source of these compounds in the aquatic environments. The calculation of partition coefficients of pharmaceuticals between SPM and filtrate (observed partition coefficients, [graphic removed] , [graphic removed] ), between SPM and soluble phase (intrinsic partition coefficients, [graphic removed] , [graphic removed] ), and between colloids and soluble phase (K coc) showed that intrinsic partition coefficients [graphic removed] are between 25% and 96%, and between 18% and 82% higher than relevant observed partition coefficients values, and are much less variable. Secondly, K coc values are 3-4 orders of magnitude greater than [graphic removed] values, indicating that aquatic colloids are substantially more powerful sorbents for accumulating pharmaceuticals than sediments. Furthermore, mass balance calculations of pharmaceutical concentrations demonstrate that between 23% and 70% of propranolol, 17-62% of sulfamethoxazole, 7-58% of carbamazepine, 19-84% of indomethacine, and 9-74% of diclofenac are present in the colloidal phase. Conclusions The results provide direct evidence that sorption to colloids provides an important sink for the pharmaceuticals in the aquatic environment. Such strong pharmaceutical/colloid interactions may provide a long-term storage of pharmaceuticals, hence, increasing their persistence while reducing their bioavailability in the environment. Recommendations and perspectives Pharmaceutical compounds have been detected not only in the aqueous phase but also in suspended particles; it is important, therefore, to have a holistic approach in future environmental fate investigation of pharmaceuticals. For example, more research is needed to assess the storage and long-term record of pharmaceutical residues in aquatic sediments by which benthic organisms will be most affected. Aquatic colloids have been shown to account for the accumulation of major fractions of total pharmaceutical concentrations in the aquatic environment, demonstrating unequivocally the importance of aquatic colloids as a sink for such residues in the aquatic systems. As aquatic colloids are abundant, ubiquitous, and highly powerful sorbents, they are expected to influence the bioavailability and bioaccumulation of such chemicals by aquatic organisms. It is therefore critical for colloids to be incorporated into water quality models for prediction and risk assessment purposes.

Introduction and background Primary producers play critical structural and functional roles in aquatic ecosystems; therefore, it is imperative that the potential risks of toxicants to aquatic plants are adequately assessed in the risk assessment of chemicals. The standard required macrophyte test species is the floating (non-sediment-rooted) duckweed Lemna spp. This macrophyte species might not be representative of all floating, rooted, emergent, and submerged macrophyte species because of differences in the duration and mode of exposure; sensitivity to the specific toxic mode of action of the chemical; and species-specific traits (e.g., duckweed's very short generation time). Discussion and perspectives These topics were addressed during the workshop entitled “Aquatic Macrophyte Risk Assessment for Pesticides” (AMRAP) where a risk assessment scheme for aquatic macrophytes was proposed. Four working groups evolved from this workshop and were charged with the task of developing Tier 1 and higher-tier aquatic macrophyte risk assessment procedures. Subsequently, a SETAC Advisory Group, the Macrophyte Ecotoxicology Group (AMEG) was formed as an umbrella organization for various macrophyte working groups. The purpose of AMEG is to provide scientifically based guidance in all aspects of aquatic macrophyte testing in the laboratory and field, including prospective as well as retrospective risk assessments for chemicals. As AMEG expands, it will begin to address new topics including bioremediation and sustainable management of aquatic macrophytes in the context of ecosystem services.

Purpose Dissolved humic acids abiotically reduced inorganic arsenic to varying degrees, depending on solution pH, ionic strength, and type of humate used. The functionalities of dissolved organic matter responsible for these redox reactions remained in question, but quinoid moieties undoubtedly played an important role. It is not fully understood whether the quinoids are solely responsible for arsenate reduction, and what the kinetics of the relevant processes are. Methods Electron spin resonance (ESR) spectroscopy was used to monitor the radical content of the humates, both as bulk material and as size fractions. Information on the redox status of the humates was obtained from fluorescence excitation-emission matrices and correlated with the observed spin count. Size data were obtained from fractionation and UV-Vis spectrometry. Arsenic speciation was carried out by ion chromatography. Results ESR spectroscopy showed a free radical content of 3.4 × 1,017-20 × 1,017 spins/g for bulk and fractionated aqueous humic acids. The number of electrons corresponding to these counts could not account for the entire charge transferred to arsenate during abiotic reduction. The rate constants of the reactions were found to be independent of the humic concentration. Leonardite humic acid separated on a XAD-8 resin yielded fractions that on the short time frame (0-5 h) had rate constants of 0.035 h⁻¹ for the hydrophobic fraction compared to 0.0052 h⁻¹ for the hydrophilic fraction. The rate constants for the hydrophobic and hydrophilic fractions over the longer time frame (100-200 h) were similar—7.3 × 10⁻⁴ and 7.2 × 10⁻⁴ h⁻¹, respectively. Fluorescence excitation-emission matrices of humates involved in arsenate reduction exhibited shifts typical of quinoid components undergoing redox transformations. These gradual shifts took place during the first 24 h of reduction process, after which the spectra no longer changed. The reduction of arsenate, however, continued after this period, indicating that species other than quinoids were involved. This was consistent with the fact that the rate constants for the later processes were smaller. Conclusions The existence of different redox pools within the humate was confirmed, with the quinoid-centered redox entities showing the fastest kinetics. The results pertained to all size and polarity fractions.

Background, aim, and scope Carbonyl compounds have been paid more and more attention because some carbonyl species have been proven to be carcinogenic or a risk for human health. Plant leaves are both an important emission source and an important sink of carbonyl compounds. But the research on carbonyl compounds from plant leaves is very scarce. In order to make an approach to the emission mechanism of plant leaves, a new method was established to extract carbonyl compounds from fresh plant leaves. Materials, methods, and results The procedure combining derivatization with ultrasonication was developed for the fast extraction of carbonyl compounds from tree leaves. Fresh leaves (< 0.01 g) were minced and ultrasonicated in acidic 2,4-dinitrophenylhydrazine (DNPH)-acetonitrile solution for 30 min and then holding 30 min to allow aldehydes and ketones in leaves to react completely with DNPH. Conclusions The extraction process was performed under room temperature and only took 60 min. The advantages of this method were very little sample preparation, requiring short treatment time and usual equipment. Four greening trees, i.e., camphor tree (Cinnamomum camphora), sweet olive (Osmanthus fragrans), cedar (Cedrus deodara), and dawn redwood (Metasequoia glyptostroboides), were selected and extracted by this method. Seven carbonyl compounds, including formaldehyde, acetaldehyde, acetone, acrolein, p-tolualdehyde, m/o-tolualdehyde, and hexaldehyde were determined and quantified. The most common carbonyl species of the four tree leaves were formaldehyde, acrolein, and m/o-tolualdehyde. They accounted for 67.3% in cedar, 50.8% in sweet olive, 45.8% in dawn redwood, and 44.6% in camphor tree, respectively. Camphor tree had the highest leaf level of m/o-tolualdehyde with 15.0 ± 3.4 µg g⁻¹(fresh leaf weight), which indicated that camphor tree may be a bioindicator of the level of tolualdehyde or xylene in the atmosphere. By analyzing carbonyl compounds from different tree leaves, it is not only helpful for further studying the relationship between sink and emission of carbonyls from plants, but also helpful for exploring optimum plant population in urban greening.

Background, aim and scope Ambient air concentrations of polycyclic aromatic hydrocarbons (PAH) were determined at five elevated mountain sites on the European continent and the Atlantic Ocean. All sites can be considered remote background areas since they are situated above the timberline and they lack local emission sources of these compounds. Results and discussion Average gas phase concentrations of ΣPAH were 165, 1,475, 1,553, 1,822 and 4,443 pg m⁻³ for Tenerife, Pyrenees, Central Norway, Tyrolean Alps and High Tatras, respectively. Particulate phase concentrations were 55, 70, 383, 196 and 708 pg m⁻³, respectively. The PAH profiles of samples from the different sites are very similar, being typical of PAH mixtures after long-range atmospheric transport. Part of the fluctuations in PAH concentrations are explained by the influence of temperature on the particulate/gas phase partitioning. Conclusion The differences in PAH levels between sites, with the lowest concentrations found in Tenerife and the highest in the High Tatras, suggest the geographical influence of regional emissions on the sites, especially in the cold periods and for the sites in the eastern sector of the European continent. This is supported by air mass back-trajectories analysis for the samples on the different sites. The influence of the continent is not detectable in the case of the elevated site of Tenerife where the free troposphere has been sampled. The results in this study are consistent with the PAH levels found in soils and/or high mountain lake sediments from these areas.

Background, aim, and scope High mountain soils constitute a long-term cumulative record of atmospherically deposited trace elements from both natural and anthropogenic sources. The main aims of this study were to determine the level of major and trace metals (Al, Ti, Mn, Fe, and Zr) of lithologic origin and airborne contaminating trace elements (Ni, Cu, Zn, As, Cd, and Pb) in soils in the Central Pyrenees as an indication of background contamination over SW Europe, to establish whether there is a spatial pattern of accumulation of trace elements in soils as a function of altitude, and to examine whether altitude-related physicochemical properties of soils affect the accumulation of major metals and trace elements. Methods Major metals and trace elements were measured in “top” (i.e., first 10 cm) and “bottom” (i.e., below 10 cm) soil samples along an altitudinal transect (1,520-2,880 m a.s.l.) in the Central Pyrenees. Total concentrations were determined by X-ray fluorescense spectrometry. Total major metal concentrations were analysed by conventional X-ray fluorescence spectrometry (XRF) with a Siemens SRS 303 instrument. Total trace element concentrations were determined with an energy-dispersive multielement miniprobe XRF analyser. Acid-extractable concentrations were measured by inductively coupled plasma after previous extraction with nitric acid and hydrogen peroxide in closed beakers. Acid-extractable major metal concentrations were measured by inductively coupled plasma (ICP)-Optic Emission Spectrometry with a Perkin Elmer 3200 RL Instrument. Acid-extractable trace element concentrations were determined by ICP-Mass Spectrometry with a Perkin Elmer ELAN 6000. Results Trace element concentration ranges were (in mg kg⁻¹, inventories in g m⁻² between parenthesis) <2-58 (0.5-6.6) for Ni, 6-30 (0.2-3.4) for Cu, 38-236 (1.6-32.4) for Zn, 6-209 (0.2-12.8) for As, 0.02-0.64 (<0.04) for Cd, and 28-94 (0.6-13.0) for Pb. These concentrations were, in general, comparable to those recorded in soils from other European mountainous areas and were in many cases above the threshold recommended for ecosystem protection by regional and European environmental authorities. The highest concentrations were found at lower altitudes, indicating an effect of local contamination up to ∼2,300 m a.s.l. Only above this altitude can trace elements in soils be considered representative of a background, long-range atmospheric contamination. Conclusions None of the storage capacity properties of soils examined were determinant of the differences in elemental concentrations along the altitudinal transect. At the upper altitude range, Ni, Cu, and Pb showed a approximately two- to fivefold increase over the average concentration of the local dominant lithology, reflecting the regional and global background of atmospheric contamination in the area.

Purpose The environmental issues caused by the municipal solid waste disposal are becoming a worldwide concern. Methods We studied the situations both domestically and abroad by the strategic environmental assessment (SEA) approach and also conducted comprehensive evaluations of garbage disposal in Changchun City. Results On the basis of this study, we found that SEA is of great importance in the municipal solid waste disposal. Moreover, with the rapid socioeconomic development of Changchun City, municipal solid waste production increases on an annual basis, and thus, good waste management planning is of great significance. Conclusions Considering the situation of the economic development of Changchun City, garbage disposal was handled mainly in the major sanitary landfills with appropriate use of incineration technology. This plan is environmentally friendly at a relatively high degree and has met the requirements of minimum investment. It also takes into account the requirements of the development of incineration technology. Regarding environmental pollution in terms of groundwater pollution and atmospheric pollution, this plan is a feasible one by meeting various requirements with low environmental impact among the three plans discussed in this study.

Background, aim and scope A new method using sedimentary metals and geographic information system as indicators for assessing temporal and spatial anthropogenic change in estuaries has been applied to a large coastal lake (Lake Macquarie) in New South Wales, Australia. Materials, methods and results Two vintages of data (1975 and 2003) on surficial sediment metal (Cd, Cu, Pb and Zn) concentrations combined with ²¹⁰Pb core profiles were used to determine past changes in sediment quality and to predict possible future relaxation rates for the entire lake area in response to change in anthropogenic pressure. Sediment cores showed distinct vertical profiles; sedimentation rates in the northern part of the lake were consistent (14 mm year⁻¹) over the 55-year period investigated. Discussion and conclusions Surficial metal concentrations were highest in the 1975 sediment than in the 2003 samples, with the northern part of Lake Macquarie having much greater metal concentrations than the rest of the lake. Past and future declining sedimentary metal concentrations in the northern part of the lake were expected due to the closure of a nearby Pb-Zn smelter; however, possible increases in Cu in the south of the lake to the year 2020 were surprising. The new method presented in this study can assist estuary managers by providing data on past, present and future conditions, which are essential in making informed decisions for the improvement of estuarine systems.