Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany

Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well.     

Monitoring plastic ingestion by the northern fulmar Fulmarus glacialis in the North Sea

The abundance of plastics in stomachs of northern fulmars from the North Sea is used in the OSPAR Ecological Quality Objective (EcoQO) for marine litter. The preliminary EcoQO defines acceptable ecological quality as the situation where no more than 10% of fulmars exceed a critical level of 0.1 g of plastic in the stomach. During 2003-2007, 95% of 1295 fulmars sampled in the North Sea had plastic in the stomach (on average 35 pieces weighing 0.31 g) and the critical level of 0.1 g of plastic was exceeded by 58% of birds, with regional variations ranging from 48 to 78%. Long term data for the Netherlands since the 1980s show a decrease of industrial, but an increase of user plastics, with shipping and fisheries as the main sources. The EcoQO is now also used as an indicator for Good Environmental Status in the European Marine Strategy Framework Directive.     

The use of environmental metabolomics to determine glyphosate level of exposure in rapeseed (Brassica napus L.) seedlings

Metabolic profiling in plants can be used to differentiate between treatments and to search for biomarkers for exposure. A methodology for processing Ultra-High-Performance Liquid Chromatography-Diode-Array-Detection data is devised. This methodology includes a scheme for selecting informative wavelengths, baseline removal, retention time alignment, selection of relevant retention times, and principal component analysis (PCA). Plant crude extracts from rapeseed seedling exposed to sublethal concentrations of glyphosate are used as a study case. Through this approach, plants exposed to concentrations down to 5 μM could be distinguished from the controls. The compounds responsible for this differentiation were partially identified and were different from those specific for high exposure samples, which suggests that two different responses to glyphosate are elicited in rapeseed depending on the level of exposure. The PCA loadings indicate that a combination of other metabolites could be more sensitive than the response of shikimate to detect glyphosate exposure.     

Factors affecting the growth rates of ammonium and nitrite oxidizing bacteria

The maximum specific growth rates of both ammonium oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) were investigated under varying aerobic solids retention time (SRT_a) and in the presence/absence of anoxic (alternating) conditions. Two bench SBRs, reactor R1 and R2, were run in parallel for 150 d. Reactor R1 was operated in aerobic conditions while R2 operated in alternating anoxic/aerobic conditions. The feed (synthetic wastewater), temperature, hydraulic retention time and mixing were identical in both reactors. The SRT_a in both reactors was, sequentially, set at four values: 5, 4, 3 and 2 d.Kinetic tests with the biomasses from both reactors were carried out to estimate the maximum specific growth rates (μ_max) at each tested SRT_a and decay rates, in both aerobic and anoxic conditions. The kinetic parameters of nitrifier were estimated through the calibration of a two step nitrification-denitrification activated sludge model.The results point to a slightly higher μ_max,AOB and μ_max,NOB in alternating conditions, while both μ_max,AOB and μ_max,NOB were shown not to vary in the tested range of SRT_a (from 2 to 5 d) at 20 °C. They were relatively high when compared to literature data: 1.05 d⁻¹ < μ_max,AOB < 1.4 d⁻¹ and 0.91 d⁻¹ < μ_max,NOB < 1.31 d⁻¹. The decay coefficients of both AOB and NOB were much higher in aerobic (from 0.22 d⁻¹ to 0.28 d⁻¹) than in anoxic (0.04 d⁻¹ to 0.16 d⁻¹) conditions both in R1 and R2, which explained the higher nitrification rates observed in the alternating reactor.     

Polymeric cracking of waste polyethylene terephthalate to chemicals and energy

Polyethylene terephthalate (PET) is a widely used thermoplastic. PET residues represent on average 7.6 wt% of the different polymer wastes in Europe. Pyrolysis of these wastes is attracting increasing interest, and PET is a potential candidate for this thermal process. The paper measures and discusses the kinetics of the pyrolysis reaction in terms of the reaction rate constants as determined by dynamic thermogravimetric analysis, with special emphasis on the required heating rate to obtain relevant results. The product yields and compositions are also determined. Gaseous products represent 16-18 wt%. The amounts of condensables and carbonaceous residue are a function of the operating mode, with slow pyrolysis producing up to 24 wt% of carbonaceous residue. Major condensable components are benzoic acid, monovinyl terephthalate, divinyl terephthalate, vinyl benzoate, and benzene. The present paper complements previous literature findings by (1) the study of the influence of the heating rate on the reaction kinetics in dynamic pyrolysis tests, (2) the isothermal investigation in a fluidized bed reactor to pyrolyze PET, and (3) the assessment of upgrading and recovery of the products. The paper concludes with a proposed reactor recommendation for PET pyrolysis, in either the bubbling or circulating fluidized bed operating mode.     

Status and prospects of pay-as-you-throw in Europe - a review of pilot research and implementation studies

Over the past 20 years, significant advances have been made in developing efficient schemes to charge households for their actual waste generation. Viable fee models and technical solutions which are applicable to different environments and provide waste generators with individual incentives for waste diversion efforts have increased the recognition of pay-as-you-throw (PAYT) as an effective instrument for recycling-oriented waste management and financing. On this basis, PAYT has become a practical reality in an increasing number of countries in Europe. Even countries with traditional reservations for direct charging have started to make consideration of PAYT in the revision of their national policy programmes. A situational analysis performed at the European level showed that detailed insights regarding the concrete reactions, red flags and wider benefits inherent to such scheme may still have to be further dispersed in order to overcome the caveats on PAYT and eventually adopt the approach on a larger scale. Claims that the results of PAYT applications are only local in meaning can be disproved as many of the developments bear universal character and can be verified even for larger territories using such schemes in different ways. Including results from an international research co-operation and comparative studies conducted in Germany, this article examines the state-of-the-art of PAYT and shades light onto some of the generally observed implications of its implementation. In conclusion, an outlook on the further potentials and propagation of this scheme is given.     

Is colloid-facilitated phosphorus leaching triggered by phosphorus accumulation in sandy soils?

The leaching of colloidal phosphorus (P(coll)) contributes to P losses from agricultural soils. In an irrigation experiment with undisturbed soil columns, we investigated whether the accumulation of P in soils due to excess P additions enhances the leaching of colloids and P(coll) from sandy soils. Furthermore, we hypothesized that large concentrations of P(coll) occur at the onset of leaching events and that P(coll) mobilized from topsoils is retained in subsoils. Soil columns of different P saturation and depth (0-25 and 0-40 cm) were collected at a former disposal site for liquid manure and at the Thyrow fertilization experiment in northeastern Germany. Concentrations of total dissolved P, P(coll), Fe(coll), Al(coll), optical density, zeta potential, pH, and electrical conductivity of the leachates were determined. Colloidal P concentrations ranged from 0.46 to 10 micromol L(-1) and contributed between 1 and 37% to total P leaching. Large P(coll) concentrations leached from the P-rich soil of the manure disposal site were rather related to a large P-content of colloids than to the mobilization of additional colloids. Concentrations of colloids and P(coll) in leachates from P-poor and P-rich columns from Thyrow did not differ significantly. In contrast, accumulation of P in the Werbellin and the Thyrow soil consistently increased dissolved P concentrations to maximum values as high as 300 micromol L(-1). We observed no first-flush of colloids and P(coll) at the beginning of the leaching event. Concentrations of P(coll) leached from 40-cm soil columns were not smaller than those leached from 25-cm columns. Our results illustrate that an accumulation of P in sandy soils does not necessarily lead to an enhanced leaching of colloids and P(coll), because a multitude of factors independent from the P status of soils control the mobility of colloids. In contrast, P accumulation generally increases dissolved P concentrations in noncalcareous soils due to the saturation of the P sorption capacity. This indicates that leaching of dissolved P might be a more widespread environmental problem in areas with P-saturated sandy soils than leaching of P(coll).     

Seasonal density dependence, timing of mortality, and sustainable harvesting

Birth-pulse populations are often characterized with discrete-time models, that use a single function to relate the post-breeding population size to the post-breeding size of the previous year. Recently, models of seasonal density dependence have been constructed that emphasize interactions during shorter time periods also. Here, we study two very simple forms of density-dependent mortality, that lead to Ricker and Beverton-Holt type population dynamics when viewed over the whole year. We explore the consequences of harvest timing to equilibrium population sizes under such density dependence. Whether or not individual mortality compensates for the harvested quota, the timing of harvesting has a strong impact on the sustainability of a harvesting quota. Further, we show that careless discretization of a continuous mortality scheme may seriously underestimate the reduction in population size caused by hunting and overestimate the sustainable yield. We also introduce the concept of the demographic value of an individual, which reflects the expected contribution to population size over time in the presence of density dependence. Finally, we discuss the possibility of calculating demographic values as means of optimizing harvest strategies. Here, a Pareto optimal harvest strategy will minimize the loss of demographic value from the population for a given yield.     

Developmental dental defects in children exposed to PCBs in eastern Slovakia

The effects of long-term exposure to polychlorinated biphenyls (PCBs) on developmental dental defects of deciduous and permanent teeth in children in eastern Slovakia, where PCBs from a chemical plant manufacturing Delors contaminated the surrounding district were evaluated. Four hundred and thirtytwo children, lifelong residents, aged 8-9 years were examined. Children's caries susceptibility and gingival health was assessed by standard dental indices, and developmental enamel defects by the FDI index. Data from the PCBRISK project data set and questionnaires completed by the parents provided information on exposure and various confounding factors. The proportion of teeth with different types and extensions of developmental enamel defects correlated with serum PCB concentration. The proportion of deciduous teeth affected with enamel defects was significantly higher in higher exposed children (chi(2)=8.35; p=0.03) according to their serum PCB concentration (group 0: <200; group 1: 200-600; group 2: >600 ng PCBs g(-1) serum lipids). The proportion of permanent teeth affected with any enamel defect was significantly higher in higher exposed children (chi2=7.237; p=0.027). Furthermore, the extent of the enamel defects was also greater (chi2=10.714; p=0.005). In multivariate linear regression analysis PCB exposure was significantly related to developmental enamel defects of permanent teeth only. No associations between PCB exposure and caries susceptibility, gingival health or number of teeth were observed. This study demonstrated a dose-response relationship between PCB exposure and developmental enamel defects of permanent teeth in children, the evidence for deciduous teeth was not conclusive.     

Microbial degradation pathways of the herbicide dichlobenil in soils with different history of dichlobenil-exposure

This is the first detailed study of metabolite production during degradation of the herbicide 2,6-dichlorobenzonitrile (dichlobenil). Degradation of dichlobenil and three potential metabolites: 2,6-dichlorobenzamide (BAM), 2,6-dichlorobenzoic acid (2,6-DCBA) and ortho-chlorobenzamide (OBAM) was studied in soils either previously exposed or not exposed to dichlobenil using a newly developed HPLC method. Dichlobenil was degraded in all four soils; BAM and 2,6-DCBA were only degraded in soils previously exposed to dichlobenil (100% within 35-56 days and 85-100% in 56 days, respectively), and OBAM in all four soils (25-33% removal in 48 days). BAM produced from dichlobenil was either hydrolyzed to 2,6-DCBA or dechlorinated to OBAM, which was further hydrolyzed to ortho-chlorobenzoic acid. BAM was rapidly mineralized in previously exposed soils only. All potential metabolites and the finding that BAM was a dead-end metabolite of dichlobenil in soils not previously exposed to dichlobenil needs to be included in risk assessments of the use of dichlobenil.