Substance-related environmental monitoring

Background  Due to the requirements of the EU Water Framework Directive and other legal regulations (e.g., national laws like the German Federal Soil Protection Act), but also due to the implementation of the new EU chemicals management system REACH, environmental monitoring will gain increasing importance for the surveillance of environmental quality as well as for the assessment of chemicals. Against this background, the Work Group on ‘Environmental Monitoring’ of the Division of ‘Environmental Chemistry and Ecotoxicology’ within the German Chemical Society has compiled a position paper on substance-related environmental monitoring. Scope  Core elements of this position paper are the definitions of important terms like monitoring, exposure monitoring, effect monitoring, and integrated monitoring. Moreover, temporal and spatial aspects (monitoring of spatial distributions, trend monitoring, and retrospective monitoring) and their applications are discussed. The main focus of this position paper is the coverage of aspects which have to be observed for the preparation and implementation of a monitoring program. Essential is the clear specification of the targets of the monitoring which determine the development of the monitoring concept and its realization, e.g., if environmental media (compartments) or organisms are most appropriate as samples for the aim of the study. Of course, also the properties of the target substances are important (e.g., lipophilicity/bioaccumulation as pre-requisite for an exposure monitoring with organisms). Finally, the monitoring phases of sample planning, sampling, storage and transport of samples, selection of analytical methods, quality assurance measures as well as reporting are discussed. Perspectives  An important issue for the future is to link the quantification of chemicals in environmental compartments (exposure and pollution monitoring) more closely to the study of biological effects (effect monitoring) than has been the case up to now. Furthermore, by inclusion of a spatial differentiation, a comprehensive evaluation of the state of an ecosystem can be obtained and the relevance of the results improved. Practical examples of monitoring studies which illustrate various aspects covered in this position paper will be presented in a series of publications by members of the Work Group in the following issues of this journal.

Assessing the long-term supply risks for mineral raw materials—a combined evaluation of past and future trends

This paper develops a method for identifying and assessing long-term supply risks for mineral raw materials. The method is based on a combined evaluation of past and future supply and demand trends. By analysing raw material boom and bust cycles over the past 50 years, we have quantified indicators and defined benchmarks for identifying critical market situations. By applying the method, risks for supply shortage may be identified at an early stage. In addition, a numerical evaluation model has been developed for better comparison between various mineral raw materials. Compared to other assessment methods this method uses specific benchmarks for each raw material to better assess supply risks. The method is embedded within a systematic and comprehensive analytical approach.     

Models at the interface between science and society: impacts and options

Within the CLEAR project a new approach to integrated assessment modelling has been developed for the participatory integrated assessment of regional climate change involving citizens' focus groups. The climate change decision problem was structured by focusing separately on climate impacts and mitigation options. The attempt was made to link the different scales of the problem from the individual to the global level. The abstract topic of climate change was related to options on the level of a citizen's individual lifestyle. The option of a low energy society was emphasised in order to embed the climate change decision problem in a wider range of societal concerns. Special emphasis was given to the characterisation and communication of uncertainties. The chosen approach allows different kinds of uncertainties in one framework to be addressed. The paper concludes with a summary of the experience made, and recommendations for the use of models in participatory integrated assessments. This revised version was published online in July 2006 with corrections to the Cover Date.     

Net methylmercury production as a basis for improved risk assessment of mercury-contaminated sediments

Sediments contaminated by various sources of mercury (Hg) were studied at 8 sites in Sweden covering wide ranges of climate, salinity, and sediment types. At all sites, biota (plankton, sediment living organisms, and fish) showed enhanced concentrations of Hg relative to corresponding organisms at nearby reference sites. The key process determining the risk at these sites is the net transformation of inorganic Hg to the highly toxic and bioavailable methylmercury (MeHg). Accordingly, Hg concentrations in Perca fluviatilis were more strongly correlated to MeHg (p < 0.05) than to inorganic Hg concentrations in the sediments. At all sites, except one, concentrations of inorganic Hg (2-55 microg g(-1)) in sediments were significantly, positively correlated to the concentration of MeHg (4-90 ng g(-1)). The MeHg/Hg ratio (which is assumed to reflect the net production of MeHg normalized to the Hg concentration) varied widely among sites. The highest MeHg/Hg ratios were encountered in loose-fiber sediments situated in southern freshwaters, and the lowest ratios were found in brackish-water sediments and firm, minerogenic sediments at the northernmost freshwater site. This pattern may be explained by an increased MeHg production by methylating bacteria with increasing temperature, availability of energy-rich organic matter (which is correlated with primary production), and availability of neutral Hg sulfides in the sediment pore waters. These factors therefore need to be considered when the risk associated with Hg-contaminated sediments is assessed.     

XAFS studies of cobalt(II) binding by solid peat and soil-derived humic acids and plant-derived humic acid-like substances

This work has examined cobalt(II) binding by a variety of solid humic acids (HAs) isolated from peat, plant and soil sources at temperatures down to 60K. The results confirm that X-ray absorption near-edge spectroscopy (XANES) measurements cannot distinguish between aquo and carboxylato ligands in the inner coordination sphere of Co(II). However, between 1 and 2 inner-sphere carboxylato ligands can be detected in all the peat, plant and soil-derived HA samples by extended X-ray absorption fine structure (EXAFS) measurements, indicating inner-sphere coordination of HA-bound Co(II). The precision of C(carboxylate) detection is limited by the extent and quality of the data and the contribution from inner-sphere O to the Fourier transformed peaks used to detect carbon. Putative chelate ring formation is consistent with a relatively negative entropy change in step A, the stronger Co(II) binding step by HA functional groups, and could relate to 'non-exchangeable' metal binding by HSs.     

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.     

The influence of EDDS and EDTA on the uptake of heavy metals of Cd and Cu from soil with tobacco Nicotiana tabacum

Phytoextraction, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. In order to enhance phytoextraction the use of chelating agents has been proposed. This study aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposed, as an alternative to ethylene diamine tetraacetate (EDTA). EDDS revealed a higher toxicity to tobacco (Nicotiana tabacum) in comparison to EDTA, but no toxicity to microorganisms. The uptake of Cu was increased by the addition of EDTA and EDDS, while no increase was observed in the uptake of Cd. Both chelating agents showed a very low root to shoot translocation capability and the translocation factor was lower than the one of the control. Heavy metals where significantly more phytoavailable than in the control, even after harvesting, resulting in a high heavy metal leaching possibility, probably owing to a low biodegradation rate of EDDS. New seedlings which were transplanted into the EDDS treated pots 7d after the phytoextraction experiment, showed signs of necrosis and chlorosis, which resulted in a significantly lower biomass in comparison to the control. The seedlings on the EDTA treated pots showed no toxicity signs. Contrary to previous opinions the results of this study revealed the chelating agents EDTA and EDDS as unsuitable for enhanced phytoextraction using tobacco.     

How Plants Cope with Foreign Compounds. Translocation of xenobiotic glutathione conjugates in roots of barley (Hordeum vulgare) (9 pp)

Background, Aim and Scope Numerous herbicides and xenobiotic organic pollutants are detoxified in plants to glutathione conjugates. Following this enzyme catalyzed reaction, xenobiotic GS-conjugates are thought to be compartmentalized in the vacuole of plant cells. In the present study, evidence is presented for long range transport of these conjugates in plants, rather than storage in the vacuole. To our knowledge this is the first report about the unidirectional long range transport of xenobiotic conjugates in plants and the exudation of a glutathione conjugate from the root tips. This could mean that plants possess an excretion system for unwanted compounds which give them similar advantages as animals. Materials and Methods: Barley plants (Hordeum vulgare L. cv. Cherie) were grown in Petri dishes soaked with tap water in the greenhouse. - Fluorescence Microscopy. Monobromo- and Monochlorobimane, two model xenobiotics that are conjugated rapidly in plant cells with glutathione, hereby forming fluorescent metabolites, were used as markers for our experiments. Their transport in the root could be followed sensitively with very good temporal and spatial resolution. Roots of barley seedlings were cut under water and the end at which xenobiotics were applied was fixed in an aperture with a thin latex foil and transferred into a drop of water on a cover slide. The cover slide was fixed in a measuring chamber on the stage of an inverse fluorescence microscope (Zeiss Axiovert 100). - Spectrometric enzyme assay. Glutathione S-transferase (GST) activity was determined in the protein extracts following established methods. Aliquots of the enzyme extract were incubated with 1-chloro-2,4-dinitrobenzene (CDNB), or monochlorobimane. Controls lacking enzyme or GSH were measured. - Pitman chamber experiments. Ten days old barley plants or detached roots were inserted into special incubation chambers, either complete with tips or decapitated, as well as 10 days old barley plants without root tips. Compartment A was filled with a transport medium and GSH conjugate or L-cysteine conjugate. Compartments B and C contained sugar free media. Samples were taken from the root tip containing compartment C and the amount of conjugate transported was determined spectro-photometrically. Results: The transport in roots is unidirectional towards the root tips and leads to exsudation of the conjugates at rates between 20 and 200 nmol min-1. The microscopic studies have been complemented by transport studies in small root chambers and spectroscopic quantification of dinitrobenzene-conjugates. The latter experiments confirm the microscopic studies. Furthermore it was shown that glutathione conjugates are transported at higher rates than cysteine conjugates, despite of their higher molecular weights. This observation points to the existence of glutathione specific carriers and a specific role of glutathione in the root. Discussion: It can be assumed that long distance transport of glutathione conjugates within the plant proceeds like GSH or amino acid transport in both, phloem and xylem. The high velocity of this translocation of the GS-X is indicative of an active transport. For free glutathione, a rapid transport-system is essential because an accumulation of GSH in the root tip inhibits further uptake of sulfur. Taking into account that all described MRP transporters and also the GSH plasmalemma ATPases have side activities for glutathione derivatives and conjugates, co-transport of these xenobiotic metabolites seems credible. - On the other hand, when GS-B was applied to the root tips from the outside, no significant uptake was observed. Thus it can be concluded that only those conjugates can be transported in the xylem which are formed inside the root apex. Having left the root once, there seems to be no return into the root vessels, probably because of a lack of inward directed transporters. Conclusions: Plants seem to possess the capability to store glutathione conjugates in the vacuole, but under certain conditions, these metabolites might also undergo long range transport, predominantly into the plant root. The transport seems dependent on specific carriers and is unidirectional, this means that xenobiotic conjugates from the rhizosphere are not taken up again. The exudation of xenobiotic metabolites offers an opportunity to avoid the accumulation of such compounds in the plant. Recommendations and Perspectives: The role of glutathione and glutathione related metabolites in the rhizosphere has not been studied in any detail, and only scattered data are available on interactions between the plant root and rhizosphere bacteria that encounter such conjugates. The final fate of these compounds in the root zone has also not been addressed so far. It will be interesting to study effects of the exuded metabolites on the biology of rhizosphere bacteria and fungi.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

Goals and remedial strategies for water quality and wildlife management in a coastal lagoon--a case-study of Ringkøbing Fjord, Denmark

The aim of this work is (1) to discuss approaches and tools to set management goals using operational indicators for coastal management (i.e., indicators that are easy to measure, understand and predict) and validated predictive models and (2) to discuss remedial strategies for sustainable coastal management regarding water quality and the abundance of fish, waterfowl and large aquatic plants. These approaches are exemplified using data from Ringkøbing Fjord, Denmark, which has undergone two major regime shifts during the last decades. This work discusses the changes taken place during the period from 1980 to 2004 (when there are good empirical data). For Ringkøbing Fjord, which is a very shallow, well-oxygenated lagoon dominated by resuspension processes, we have targeted on the following operational indicators, which are meant to reflect seasonal median values for the entire defined coastal area (the ecosystem scale) and not conditions at individual sites or data from shorter time periods: Secchi depth (as a standard measure of water clarity) and chlorophyll-a concentrations (as a key measure of algal biomass). The operational indicators are regulated by a set of standard abiotic factors, such as salinity, suspended particulate matter (SPM), nutrient concentrations (N and P), coastal morphometry and water exchange. Such relationships are quantified using well-tested, general quantitative models, which illustrate how these indicators are interrelated and how they reflect fundamental aspects of coastal ecosystems. We demonstrate that the regime shift in the lagoon can be modelled and quantitatively explained and is related to changes in salinity and nutrient inflow. A very important threshold is linked to increased salinities in the lagoon. For example, when the mean annual salinity is higher than about 9.5‰, large numbers of saltwater species of clams can survive and influence the structure and function of the ecosystem in profound ways. The model also illustrates the dynamic response to changes in nutrient loading. We have presented several management strategies with the goal of keeping the Secchi depth at 2 m, which would stimulate the growth of higher aquatic plants, which are fundamental for fish production and bird abundance in the lagoon. Given the fact that the Secchi depth depends on many variable factors (temperature, TP-inflow from land, salinity, changes in biomasses of macrophytes and clams, which are accounted for in these simulations), our results indicate that in practice it will likely be very difficult to reach that goal. However, it would be realistic to maintain a Secchi depth of 1.5 m if the variability in salinity is minimized and the mean salinity is kept at about 10.2‰.