Impact of water saturation level on arsenic and metal mobility in the Fe-amended soil

The impact of water saturation level (oxidizing-reducing environment) on As and metal solubility in chromium, copper, arsenic (CCA)-contaminated soil amended with Fe-containing materials was studied. The soil was mixed with 0.1 and 1 wt% of iron grit (Fe(0)) and 1, 7 and 15 wt% of oxygen scarfing granulate (OSG, a by-product of steel processing). Solubility of As and metals was evaluated by a batch leaching test and analysis of soil pore water. Soil saturation with water greatly increased As solubility in the untreated as well as in the Fe-amended soil. This was related to the reductive dissolution of Fe oxides and increased concentration of As(III) species. Fe amendments showed As reducing capacity under both oxic and anoxic conditions. The cytotoxicity of the soil pore water correlated with the concentration of As(III). The Fe-treatments as well as water saturation of soil were less significant for the solubility of Cu, Cr and Zn than for As. The batch leaching test used for waste characterization substantially underestimated As solubility that could occur under water-saturated (anaerobic) conditions. In the case of soil landfilling, other techniques than Fe-stabilization of As containing soil should be considered.     

Modeling potential herbicide loss to surface waters on the Swiss plateau

Lack of sufficiently detailed data often limits the applicability of complex transport-reaction models for estimating potential herbicide loss to surface waters. Therefore, there is also a need for simple models that are easy to apply but still capture the main features of the underlying processes.In this study, a simple regression model was developed to assess the vulnerability of catchments in the Swiss Plateau to diffuse herbicide loss to surface waters. The model is designed as a screening tool to rank the catchments in a relative sense and not to calculate Predicted Environmental Concentrations (PEC) of pesticides. The main goal is to capture two dominating factors controlling diffuse herbicide transport into streams and rivers. These factors are herbicide application and fast flow processes that are mainly responsible for herbicide transport. In a first step vulnerability of sites to herbicide loss is estimated based on site-specific conditions irrespective of actual herbicide application. In the second step, this vulnerability assessment is combined with actual herbicide application data to estimate the potential herbicide loss.The fast flow index (FFI), derived from discharge data using a base flow separation method, was applied as a proxy for the amount of fast flow occurring. The influence of catchment attributes (including topographic, climatic and soil data) on the FFI was analyzed using a multiple regression approach based on data from 57 catchments of the Swiss Plateau. By combining regression analysis with mechanistic knowledge, a two factor non-linear model based on river density and soil permeability as dominant input factors was selected as the best model for FFI prediction given the available data. Higher dimensional models had to be excluded because the strong correlation between the potential input factors led to unrealistic dependences while only minimally improving the quality of the fit.The spatial pattern of the predicted FFI as a measure for the vulnerability to diffuse herbicide losses shows a clearly increasing trend from the western to the eastern part of the Swiss Plateau and towards the pre-alpine/alpine regions in the south.In general the pattern of herbicide use corresponds to site conditions typical of a low FFI. However, the spatial analysis revealed exceptions, namely areas in which high actual herbicide use coincides with a high FFI.Despite the uncertainties in the model, this simple approach seems to be useful for supporting site-adapted agricultural practice whenever the higher accuracy of more detailed models is not required or too expensive to achieve. In addition, in combination with data on actual herbicide application, it can support the design of monitoring strategies by identifying critical areas of actual herbicide loss.     

A retrospective comparison of model-based forecasted PM2.5 concentrations with measurements

This study presents an assessment of the performance of the Community Multiscale Air Quality (CMAQ) photochemical model in forecasting daily PM2.5 (particulate matter < or = 2.5 microm in aerodynamic diameter) mass concentrations over most of the eastern United States for a 2-yr period from June 14, 2006 to June 13, 2008. Model predictions were compared with filter-based and continuous measurements of PM2.5 mass and species on a seasonal and regional basis. Results indicate an underprediction of PM2.5 mass in spring and summer, resulting from under-predictions in sulfate and total carbon concentrations. During winter, the model overpredicted mass concentrations, mostly at the urban sites in the northeastern United States because of overpredictions in unspeciated PM2.5 (suggesting possible overestimation of primary emissions) and sulfate. A comparison of observed and predicted diurnal profiles of PM2.5 mass at five sites in the domain showed significant discrepancies. Sulfate diurnal profiles agreed in shape across three sites in the southern portion of the domain but differed at two sites in the northern portion of the domain. Predicted organic carbon (OC) profiles were similar in shape to mass, suggesting that discrepancies in mass profiles probably resulted from the underprediction in OC. The diurnal profiles at a highly urbanized site in New York City suggested that the overpredictions at that site might be resulting from overpredictions during the morning and evening hours, displayed as sharp peaks in predicted profiles. An examination of the predicted planetary boundary layer (PBL) heights also showed possible issues in the modeling of PBL.     

Impact and cost of measures to reduce nutrient emissions from wastewater and storm water treatment in the German Elbe river basin

As a leading nutrient emitter, wastewater infrastructure harbors significant technical potentials to reduce the water-polluting emissions of phosphorus and nitrogen into the Elbe river basin. From the viewpoint of the central infrastructure, the effluent threshold value of urban wastewater treatment plants could be lowered further by advanced use of denitrification and membrane filtration, and storm water overflows of wastewater and contaminated rainwater from sewers could be treated in retention soil filters. In addition, small-scale wastewater treatment plants, infiltration and reducing or unsealing impervious surfaces could be used as decentralized elements of wastewater or storm water treatment. It can be shown that if the most advanced measures were applied in all wastewater-relevant areas, up to 60% of the phosphorus and 37% of the nitrogen emissions could be avoided. Alongside central wastewater treatment plants, small-scale treatment plants prove to be the most effective and cost-efficient option. To achieve an ecologically acceptable state of the Elbe, however, it may be necessary to employ more costly measures as well.     

The role of remote sensing in hydrological modelling of the Okavango Delta, Botswana

A coupled surface water-groundwater model of the Okavango Delta has been built based on the United States Geological Survey software MODFLOW 2000 including the SFR2 package for stream-flow routing. It will provide a new tool for evaluating water management and climate change scenarios. The delta's size and limited accessibility make direct, on the ground data acquisition difficult. Remote sensing methods are the most promising source of acquiring spatially distributed data for both model input parameters and calibration. Topography, aquifer thickness, channel positions, evapotranspiration and precipitation data are all based on remote sensing. Simulated flooding patterns are compared to patterns derived from visible to thermal NOAA-AVHRR data and microwave radar ENVISAT-ASAR data.     

Source to sink tracking of selected human pharmaceuticals from two Oslo city hospitals and a wastewater treatment works

The occurrence of twenty pharmaceutical compounds was quantitatively determined in effluents from two major Oslo city hospitals, Rikshospitalet and Ullev?l, along with influent, sludge and final effluent from the city's VEAS wastewater treatment works (WTW). Composite hospital effluents were collected over a twelve week period and were showed to contain paracetamol, metoprolol, diclofenac, ibuprofen, 17beta-Estradiol, estriol, estrone, oxytetracycline, tetracycline, doxycycline, chlorotetracycline, demeclocycline, trimethoprim, ciprofloxacin, sulfamethoxazole, cyclophosphamide and ifosfamide. Three pharmaceuticals were not detected above the limit of detection; cefuroxime, 17alpha-ethinylestradiol and meclocycline. Composite influent, sludge and effluent samples were collected from VEAS WTW over a seven week period. The influent into VEAS WTW contained all of the same selected substances detected in the hospital effluents, except for oxytetracycline, chlorotetracycline, demeclocycline, cyclophosphamide and ifosfamide. The percentage of pharmaceuticals entering the works from the hospitals was <10% for all of the selected compounds. VEAS sludge samples contained a different profile of substances reflecting their physico-chemical properties. Hydrophobic antibiotics, such as oxytetracycline, tetracycline and ciprofloxacin, were detected in all of the collected sludge samples. Their absence in the collected influent samples suggests that they enter the works bound to effluent particles, with the dissolved fraction observed in the hospital effluents partitioning onto particulate matter within the sewerage network. The final effluent from VEAS WTW contained reduced concentrations of many pharmaceuticals, including paracetamol, ibuprofen and sulfamethoxazole. For other compounds, such as metoprolol, diclofenac and trimethoprim, there were often higher concentrations in the effluent than the influent. These effluent concentrations represent median inputs varying from low g day(-1) (e.g. paracetamol and ibuprofen) to nearly 200 g day(-1) (e.g. metoprolol and trimethoprim) into Oslofjord. A simple risk assessment showed that the antibiotic ciprofloxacin may at times pose an acute risk to the Oslofjord aquatic environment.     

Extractability of elements in sugar maple xylem along a gradient of soil acidity

Dendrochemistry has been used for the historical dating of pollution. Its reliability is questionable due primarily to the radial mobility of elements in sapwood. In the present study, the extractability of seven elements was characterized to assess their suitability for the monitoring of environmental conditions. Nine mature sugar maple trees (Acer saccharum Marsh.), a wide-ranging species in eastern North America that has suffered decline in past decades, were sampled in three Quebec watersheds along a soil acidity gradient. Five-year groups of annual tree rings were treated by sequential chemical extractions using extractants of varying strength (deionized H2O, 0.05 M HCl, and concentrated HNO(3)) to selectively solubilize the elements into three fractions (water-soluble, acid-soluble, and residual). Monovalent K; divalent Ba, Ca, Cd, Mg, Mn; and trivalent Al cations were found mostly in the water-soluble, acid-soluble, and residual fractions, respectively. Forms more likely to be mobile within the tree (water-soluble and acid-soluble) do not seem to be suitable for temporal monitoring because of potential lateral redistribution in sapwood rings. However, certain elements (Cd, Mn) were responsive to current soil acidity and could be used in spatial variation monitoring. Extractability of Al varied according to soil acidity; at less acidic sites, up to 90% of Al was contained in the residual form, whereas on very acidic soils, as much as 45% was found in the water-soluble and acid-soluble fractions. Sequential extractions can be useful for determining specific forms of metals as key indicators of soil acidification.     

Sexual selection favours small and symmetric males in the polygynous greater sac-winged bat Saccopteryx bilineata (Emballonuridae, Chiroptera)

We investigated how morphological traits of territorial males in the polygynous bat Saccopteryx bilineata were related to their reproductive success. Because of the frequency of aerial courtship displays and defence manoeuvres, and the high energetic costs of flight, we expected small and symmetric males to be better able to court females on the wing and to monopolize copulations with females in their harems. We predicted that small and symmetric males would sire more offspring within the colony and a larger portion of the young born within their harem than large or asymmetric males. We measured size and fluctuating asymmetry of 21 territorial males and analysed their reproductive success in 6 offspring cohorts (n=209 juveniles) using 11 microsatellite loci. As predicted, small and symmetric males had, on average, a higher reproductive success in the colony than large and asymmetric males. The percentage of young sired by males within their harem increased as males decreased in size, but was not influenced by fluctuating asymmetry. As fluctuating asymmetry of males correlated with their reproductive success within the colony but not within their harems, we infer that fluctuating asymmetry is probably related to female choice, whereas male size is probably important for harem defence on the wing.Communicated by G. Wilkinson     

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.