Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Humans and Ecosystems Over the Coming Millennia: Overview of a Biosphere Assessment of Radioactive Waste Disposal in Sweden

This is an overview of the strategy used to describe the effects of a potential release from a radioactive waste repository on human exposure and future environments. It introduces a special issue of AMBIO, in which 13 articles show ways of understanding and characterizing the future. The study relies mainly on research performed in the context of a recent safety report concerning a repository for spent nuclear fuel in Sweden (the so-called SR-Site project). The development of a good understanding of on-site processes and acquisition of site-specific data facilitated the development of new approaches for assessment of surface ecosystems. A systematic and scientifically coherent methodology utilizes the understanding of the current spatial and temporal dynamics as an analog for future conditions. We conclude that future ecosystem can be inferred from a few variables and that this multidisciplinary approach is relevant in a much wider context than radioactive waste.     

Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment

The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na⁺ and Ca²⁺ on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH = 7. Isotherms for the beta-blocker metoprolol were obtained by sediment–water batch tests over a wide concentration range (1–100 000 μg L^?1). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n = 0.9), indicating slightly non-linear behavior. Results show that the influence of Ca²⁺ compared to Na⁺ is more pronounced. A logarithmic correlation between the Freundlich coefficient K_Fr and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface.     

Impacts of Surface Gold Mining on Land Use Systems in Western Ghana

Land use conflicts are becoming increasingly apparent from local to global scales. Surface gold mining is an extreme source of such a conflict, but mining impacts on local livelihoods often remain unclear. Our goal here was to assess land cover change due to gold surface mining in Western Ghana, one of the world’s leading gold mining regions, and to study how these changes affected land use systems. We used Landsat satellite images from 1986–2002 to map land cover change and field interviews with farmers to understand the livelihood implications of mining-related land cover change. Our results showed that surface mining resulted in deforestation (58%), a substantial loss of farmland (45%) within mining concessions, and widespread spill-over effects as relocated farmers expand farmland into forests. This points to rapidly eroding livelihood foundations, suggesting that the environmental and social costs of Ghana’s gold boom may be much higher than previously thought.     

Composting projects under the Clean Development Mechanism: sustainable contribution to mitigate climate change

The Clean Development Mechanism (CDM) of the Kyoto Protocol aims to reduce greenhouse gas emissions in developing countries and at the same time to assist these countries in sustainable development. While composting as a suitable mitigation option in the waste sector can clearly contribute to the former goal there are indications that high rents can also be achieved regarding the latter. In this article composting is compared with other CDM project types inside and outside the waste sector with regards to both project numbers and contribution to sustainable development. It is found that, despite the high number of waste projects, composting is underrepresented and a major reason for this fact is identified. Based on a multi-criteria analysis it is shown that composting has a higher potential for contribution to sustainable development than most other best in class projects. As these contributions can only be assured if certain requirements are followed, eight key obligations are presented.     

Socio-cultural valuation of ecosystem services in a transhumance social-ecological network

The ecosystem services framework is receiving increasing attention in the fields of policy and research. The assessment of human attitudes and perceptions regarding ecosystem services has been proposed as a promising tool for addressing complex problems associated with environmental change, particularly in the context of cultural landscapes. Transhumance is not only a farming practice responsible for shaping cultural landscapes but also an adaptive strategy based on mobility that may represent a useful approach to overcoming the growing challenges posed by accelerated environmental change. A socio-cultural valuation of ecosystem services associated with the Conquense Drove Road, one of the major transhumant networks still in use in Mediterranean Spain, was conducted via the distribution of questionnaires to 416 local residents and visitors to capture their perceptions regarding the importance of 34 ecosystem services (10 provisioning, 12 regulating, and 12 cultural) for both social and personal well-being. Overall, the ecosystem services considered to be the most important for social well-being were fire prevention, air purification and livestock. Most of the ecosystem services in question were perceived as declining, with the exception of those associated with recreation, scientific knowledge and environmental education. This study revealed that perceptions regarding the value of ecosystem services differed among respondents, depending on their age, place of origin and gender. Several methodological issues, as well as the implications of socio-cultural valuation for policy making, are also discussed here.     

The farmer as a landscape steward: Comparing local understandings of landscape stewardship,landscape values,and land management actions

We develop a landscape stewardship classification which distinguishes between farmers’ understanding of landscape stewardship, their landscape values, and land management actions. Forty semi-structured interviews were conducted with small-holder (<5 acres), medium-holders (5–100 acres), and large-holders (>100 acres) in South-West Devon, UK. Thematic analysis revealed four types of stewardship understandings: (1) an environmental frame which emphasized the farmers’ role in conserving or restoring wildlife; (2) a primary production frame which emphasized the farmers’ role in taking care of primary production assets; (3) a holistic frame focusing on farmers’ role as a conservationist, primary producer, and manager of a range of landscape values, and; (4) an instrumental frame focusing on the financial benefits associated with compliance with agri-environmental schemes. We compare the landscape values and land management actions that emerged across stewardship types, and discuss the global implications of the landscape stewardship classification for the engagement of farmers in landscape management.     

Toxic masking and synergistic modulation of the estrogenic activity of chemical mixtures in a yeast estrogen screen (YES)

Background, aim and scope

Estrogenic and non-estrogenic chemicals typically co-occur in the environment. Interference by non-estrogenic chemicals may confound the assessment of the actual estrogenic activity of complex environmental samples. The aim of the present study was to investigate whether, in which way and how seriously the estrogenic activity of single estrogens and the observed and predicted joint action of estrogenic mixtures is influenced by toxic masking and synergistic modulation caused by non-estrogenic chemical confounders.

Materials and methods

The yeast estrogen screen (YES) was adapted so that toxicity and estrogenicity could be quantified simultaneously in one experimental run. Mercury, two organic solvents (dimethyl sulfoxide (DMSO) and 2,4-dinitroaniline), a surfactant (LAS-12) and the antibiotic cycloheximide were selected as toxic but non-estrogenic test chemicals. The confounding impact of selected concentrations of these toxicants on the estrogenic activity of the hormone 17ß-estradiol was determined by co-incubation experiments. In a second step, the impact of toxic masking and synergistic modulation on the predictability of the joint action of 17ß-estradiol, estrone and estriol mixtures by concentration addition was analysed.

Results

Each of the non-estrogenic chemicals reduced the apparent estrogenicity of both single estrogens and their mixtures if applied at high, toxic concentrations. Besides this common pattern, a highly substance- and concentration-dependent impact of the non-estrogenic toxicants was observable. The activity of 17ß-estradiol was still reduced in the presence of only low or non-toxic concentrations of 2,4-dinitroaniline and cycloheximide, which was not the case for mercury and DMSO. A clear synergistic modulation, i.e. an enhanced estrogenic activity, was induced by the presence of slightly toxic concentrations of LAS-12. The joint estrogenic activity of the mixture of estrogens was affected by toxic masking and synergistic modulation in direct proportion to the single estrogens, which allowed for an adequate adaptation of concentration addition and thus unaffected predictability of the joint estrogenicity in the presence of non-estrogenic confounders.

Discussion

The modified YES proved to be a reliable system for the simultaneous quantification of yeast toxicity and estrogen receptor activation. Experimental results substantiate the available evidence for toxic masking as a relevant phenomenon in estrogenicity assessment of complex environmental samples. Synergistic modulation of estrogenic activity by non-estrogenic confounders might be of lower importance. The concept of concentration addition is discussed as a valuable tool for estrogenicity assessment of complex mixtures, with deviations of the measured joint estrogenicity from predictions indicating the need for refined analyses.

Conclusions

Two major challenges are to be considered simultaneously for a reliable analysis of the estrogenic activity of complex mixtures: the identification of known and suspected estrogenic compounds in the sample as well as the substance- and effect-level-dependent confounding impact of non-estrogenic toxicants.

Recommendations and perspectives

The application of screening assays such as the YES to complex mixtures should be accompanied by measures that safeguard against false negative results which may be caused by non-estrogenic but toxic confounders. Simultaneous assessments of estrogenicity and toxicity are generally advisable.     

PUMP-CTD-System for trace metal sampling with a high vertical resolution. A test in the Gotland Basin, Baltic Sea

It is a great challenge to sample seawater across interfaces, for example the halocline or the redoxcline, to investigate trace metal distribution. With the use of 10l sampling bottles mounted to a wire or a CTD-Rosette it is possible to obtain a maximum vertical resolution of 5m. For the detection of small vertical structures in the vertical distribution of trace metals across the redoxcline, the CTD-Bottle-Rosette is not sufficient. Therefore, a PUMP-CTD-System was developed, which enables water sampling with high resolution (1m maximum) along a vertical profile. To investigate the suitability and possible contamination sources of this device two experiments were carried out in the Gotland Basin. The first experiment consisted of two separate profiles. The first profile was obtained with the CTD-Bottle-Rosette and the second with the PUMP-CTD-System. Both were taken from the bottom to the surface water layer. The second experiment was a combined profile obtained from the surface to the bottom with the PUMP-CTD-System attached to the CTD-Bottle-Rosette. Concentrations of dissolved Pb, Cd, Cu, Zn, Fe, Mn, Co and Ni from the "Niskin Bottles" and from the PUMP were measured and compared for each investigation. We demonstrate that it is useful to perform vertical sampling from lower to higher concentrations, e.g. surface to bottom in this environment, and that a longer flushing is required for sampling seawater in the anoxic bottom water. A comparison of the two systems for oxygen and hydrogen sulphide measurements showed an improvement of the precision and the quality of the sampling when using the PUMP. Thus, metal speciation at the oxic-anoxic gradient zone and on a high vertical resolution will be accessible. As concentrations of dissolved Pb, Cd, Cu, Zn, Co, Ni, Fe and Mn in seawater sampled with both devices were in the same range, we conclude that the PUMP-CTD-System is well suited to sample seawater for trace metal analyses.     

Erprobung und Erfolgskontrolle eines Phytoremediationsverfahrens zur Sanierung Sprengstoff-kontaminierter Böden

On the area of a former ordnance plant (‘Werk Tanne’, Clausthal-Zellerfeld, Germany), a field experiment for phytoremediation of TNT-contaminated soils has been carried out since May 1999. The concept is based on a stepwise degradation of TNT by white-rot fungi and mycorrhiza within the rhizosphere of site-specific seedlings. An appropiate site with contaminants in the surface-soil was prepared with a large-scale soil grader and subsequently divided into different experimental plots, including an uncontaminated control as well as a contaminated plot without treatment. Planting of the selected trees and shrubs (infected with mycorrhiza during nursery) and inoculation with wood chips (inoculated with white-rot fungi) is followed by a detailed monitoring of the experimental plots (chemical analyses, biotest-battery, ecological field indicators). For the evaluation of the results, multivariate methods are applied.