Approach for detecting mutagenicity of biodegraded and ozonated pharmaceuticals, metabolites and transformation products from a drinking water perspective

Many pharmaceuticals and related metabolites are not efficiently removed in sewage treatment plants and enter into surface water. There, they might be subject of drinking water abstraction and treatment by ozonation. In this study, a systematic approach for producing and effect-based testing of transformation products (TPs) during the drinking water ozonation process is proposed. For this, two pharmaceutical parent substances, three metabolites and one environmental degradation product were investigated with respect to their biodegradability and fate during drinking water ozonation. The Ames test (TA98, TA100) was used for the identification of mutagenic activity present in the solutions after testing inherent biodegradability and/or after ozonation of the samples. Suspicious results were complemented with the umu test. Due to the low substrate concentration required for ozonation, all ozonated samples were concentrated via solid phase extraction (SPE) before performing the Ames test. With the exception of piracetam, all substances were only incompletely biodegradable, suggesting the formation of stable TPs. Metformin, piracetam and guanylurea could not be removed completely by the ozonation process. We received some evidence that technical TPs are formed by ozonation of metformin and piracetam, whereas all tested metabolites were not detectable by analytical means after ozonation. In the case of guanylurea, one ozonation TP was identified by LC/MS. None of the experiments showed an increase of mutagenic effects in the Ames test. However, the SPE concentration procedure might lead to false-positive results due to the generation of mutagenic artefacts or might lead to false-negative results by missing adequate recovery efficiency. Thus, these investigations should always be accompanied by process blank controls that are carried out along the whole ozonation and SPE procedure. The study presented here is a first attempt to investigate the significance of transformation products by a systematic approach. However, the adequacy and sensitivity of the methodology need to be further investigated. The approach of combining biodegradation and ozonation with effect-based assays is a promising tool for the early detection of potential hazards from TPs as drinking water contaminants. It can support the strategy for the evaluation of substances and metabolites in drinking water. A multitude of possible factors which influence the results have to be carefully considered, among them the selectivity and sensibility of the mutagenicity test applied, the extraction method for concentrating the relevant compounds and the biocompatibility of the solvent. Therefore, the results have to be carefully interpreted, and possible false-negative and false-positive results should be considered.     

Implementing landscape fragmentation as an indicator in the Swiss Monitoring System Of Sustainable Development (Monet)

There is an increasing need and interest in including indicators of landscape fragmentation in monitoring systems of sustainable landscape management. Landscape fragmentation due to transportation infrastructure and urban development threatens human and environmental well-being by noise and pollution from traffic, reducing the size and viability of wildlife populations, facilitating the spread of invasive species, and impairing the scenic and recreational qualities of the landscape. This paper provides the rationale, method, and data for including landscape fragmentation in monitoring systems, using as an example the Swiss Monitoring System of Sustainable Development (Monet). We defined and compared four levels of fragmentation analysis, or fragmentation geometries (FGs), each based on different fragmenting elements, e.g., only anthropogenic, or combinations of anthropogenic and natural elements. As each FG has specific strengths and weaknesses, the most appropriate choice of FG depends on the context and objectives of a study. We present data on the current degree of landscape fragmentation for the five ecoregions and 26 cantons in Switzerland for all four FGs. Our results show that the degree of landscape fragmentation as quantified by the effective mesh size method is strongly supported by the postulates and indicator selection criteria of Monet, and we identify the most suitable FG focusing on the land area below 2100 m (e.g., excluding lakes) and allowing for an equitable comparison of fragmentation degrees among regions that differ in area covered by lakes and high mountains. For a more detailed analysis of landscape fragmentation in the context of environmental impact assessments and strategic environmental assessments, a combination of all four FGs may provide a more informative tool than any single FG.     

Extent of pyrolysis impacts on fast pyrolysis biochar properties

A potential concern about the use of fast pyrolysis rather than slow pyrolysis biochars as soil amendments is that they may contain high levels of bioavailable C due to short particle residence times in the reactors, which could reduce the stability of biochar C and cause nutrient immobilization in soils. To investigate this concern, three corn ( L.) stover fast pyrolysis biochars prepared using different reactor conditions were chemically and physically characterized to determine their extent of pyrolysis. These biochars were also incubated in soil to assess their impact on soil CO emissions, nutrient availability, microorganism population growth, and water retention capacity. Elemental analysis and quantitative solid-state C nuclear magnetic resonance spectroscopy showed variation in O functional groups (associated primarily with carbohydrates) and aromatic C, which could be used to define extent of pyrolysis. A 24-wk incubation performed using a sandy soil amended with 0.5 wt% of corn stover biochar showed a small but significant decrease in soil CO emissions and a decrease in the bacteria:fungi ratios with extent of pyrolysis. Relative to the control soil, biochar-amended soils had small increases in CO emissions and extractable nutrients, but similar microorganism populations, extractable NO levels, and water retention capacities. Corn stover amendments, by contrast, significantly increased soil CO emissions and microbial populations, and reduced extractable NO. These results indicate that C in fast pyrolysis biochar is stable in soil environments and will not appreciably contribute to nutrient immobilization.     

Upscaling of Environmental Information: Support of Land-Use Management Decisions by Spatio-Temporal Regionalization Approaches

This article presents several case studies in southwest Germany, which aimed to support land use management decisions by a process-oriented statistical upscaling of point-related environmental monitoring data to the landscape scale. When techniques of data subsetting were used in a sensible way and corresponding to the appropriate scale for the evaluation envisaged, multiple linear regression offered a data mining technique which was able to spatially predict relatively complex environmental patterns with parsimonious, interpretable and accurate models, whereby different evaluation scales were best represented by different DTM resolutions. Scenario models based upon the regression formulas were a valuable tool for visualizing management options and evaluating management impacts (tree species selection) on soil functions (carbon storage), which qualifies the presented methodology as a useful aid in decision making. Such upscaling techniques may be used for forecasting long-term effects of ecosystem management, but they provided no information on temporal dynamics. Therefore, time trends of point information on soil solution data were scaled by linking them to soil chemical data which was available in higher spatial resolution, using both statistical and process-oriented methods.     

Application of a hierarchical framework for assessing environmental impacts of dam operation: changes in streamflow, bed mobility and recruitment of riparian trees in a western North American river

River systems have been altered worldwide by dams and diversions, resulting in a broad array of environmental impacts. The use of a process-based, hierarchical framework for assessing environmental impacts of dams is explored here in terms of a case study of the Kootenai River, western North America. The goal of the case study is to isolate and quantify the relative effects of multiple dams and other river management activities within the study area and to inform potential restoration strategies. In our analysis, first-order impacts describe broad changes in hydrology (determined from local stream gages), second-order impacts quantify resultant changes in channel hydraulics and bed mobility (predicted from a 1D flow model), and third-order impacts describe consequences for recruitment of riparian trees (recruitment box analysis). The study area is a 233km reach bounded by two dams (Libby and Corra Linn). Different times of dam emplacement (1974 and 1938, respectively) allow separation of their relative impacts. Results show significant changes in 1) the timing, magnitude, frequency, duration and rate of change of flows, 2) the spatial and temporal patterns of daily stage fluctuation, unit stream power, shear stress, and bed mobility, and 3) the potential for cottonwood recruitment (Populus spp.). We find that Libby Dam is responsible for the majority of first and second-order impacts, but that both dams diminish cottonwood recruitment; operation of Corra Linn adversely affects recruitment in the lower portion of the study reach by increasing stage recession rates during the seedling establishment period, while operation of Libby Dam affects recruitment in the middle and upper portions of the study reach by changing the timing, magnitude, and duration of flow. We also find that recent experimental flow releases initiated in the 1990s to stimulate recovery of endangered native fish may have fortuitous positive effects on cottonwood recruitment potential in the lower portion of the river. This case study demonstrates how a process-based, hierarchical framework can be used for quantifying environmental impacts of dam operation over space and time, and provides an approach for evaluating alternative management strategies.     

Organochlorine and mercury contamination in fish tissues from the River Nestos, Greece

Polychlorinated biphenyls (PCBs), hexachlorocyclohexane (HCH) isomers, dichlorodiphenyltrichloroethane (DDT) and its metabolites, other organochlorine pesticides such as hexachlorobenzene (HCB), chlordane compounds (CHLs, including trans-chlordane and cis- and trans-nonachlor) and the heavy metal mercury were quantified in muscle and liver of the European chub (Leuciscus cephalus, Linnaeus, 1758) and in the muscle of the barbel (Barbus cyclolepis, Heckel, 1837) at two sampling sites of the River Nestos, Greece. PCBs in muscle and DDTs in the liver tissues were the predominant organochlorinated contaminants. Among the PCBs, congeners 47 (up to 9.60 ng g(-1) wet wt.), 180 (up to 1.15 ng g(-1) wet wt.) and 190 (up to 1.50 ng g(-1) wet wt.) were the most frequent and abundant. The contamination degree by the sum of PCBs on the fish tissue samples from the River Nestos is lower or similar to PCB levels found in other ecosystems. Among the organochlorine pesticides, essentially only p,p'-DDD, p,p'-DDE and alpha-, beta- and gamma-HCH were found, with the former appearing at mean levels up to 30.71 ng g(-1) wet wt. From a public health standpoint, residue organochlorine pesticide levels from our work are considerably lower than the recommended tolerance limits. Finally, mean values of Hg in chub were significant lower (up to 31.04 ng g(-1) wet wt.) compared to those detected on barbel (up to 169.27 ng g(-1) wet wt.). The concentrations of Hg in fresh water fish from the River Nestos did not exceed WHO and US EPA health guidelines, and were suitable for human consumption.     

Elimination des Zytostatikums Ifosfamid während der simulierten Zersetzung von Hausmüll im Labormaßstab

Drugs are emitted into the environment by hospitals, private households, veterinary and human practices. Remnants of these products are primarily disposed of in landfill sites. At the present, there is no information available about the behaviour of pharmaceutical drugs, like their anaerobic biodegradation or adsorption, in sanitary landfills. Some of these drugs, e.g. antineoplastic substances such as ifosfamide, are supposed to be cancerogenic, mutagenic, fetotoxic or embryotoxic. Therefore, we investigated the behaviour of ifosfamide during waste decomposition in a laboratory-scale lysimeter. Up to 50% of the ifosfamide was eliminated under methanogenic conditions; but the mechanism applying for the elimination remains unclear. As far as present day knowledge is concerned, the risk for the environment through the emission of emitting ifosfamide from sanitary landfills should be negligible.     

Ultimate biodegradation and elimination of antibiotics in inherent tests

The biodegradation and elimination of antibiotics in municipal wastewater treatment plants is of particular concern because sewage is the main exposure route for antibiotics used in human medicine. The inherent biodegradability of 17 antibiotics was determined in a combined test design based on the Zahn-Wellens test (OECD 302 B, 1992) and the CO2-evolution test (OECD 301 B, 1992). CO2 Evolution test (Modified Sturm test). OECD Guideline for the Testing of Chemicals, Paris). Only benzylpenicillin sodium salt (Penicillin G) proved to be ultimately biodegradable, reaching ThCO2 degradation extents of 78-87%. Among the others, only amoxicillin, imipenem and nystatin showed certain ultimate biodegradation in few of the parallel flasks and can be regarded as partially biodegradable with formation of stable metabolites. The DOC-elimination of tetracycline-HCl showed a typical degradation curve starting with 18% and reaching the plateau phase at 80% after 21 days. Nevertheless, the CO2-evolution measured in parallel did not support the data, indicating that the time needed for reaching the adsorption equilibrium was underestimated. Several other antibiotics showed considerable DOC-elimination in the inherent test while only minor incidences of ultimate biodegradation were observed. The combination of CO2-evolution and DOC-elimination is a suitable instrument for assessing the behaviour of chemicals within one test. It enables one to assess both inherent ultimate biodegradability and DOC-elimination by sorption. The applicability of the test is limited to substances with a moderate toxicity.