Effects of sterile storage,cation saturation and substrate additions on the degradability and extractability of nonylphenol and phenanthrene in soil

The main objective of this study was to determine the effects of long-term abiotic processes during aging of organic pollutants in soil on their microbial degradability and formation of non-extractable residues. The specific aims of our study were to investigate how the fate of p353-nonylphenol (NP) and phenanthrene (Phe) in soils might be affected by: (i) saturation of soil by cations with different valency (Na⁺, Ca²⁺ or Al³⁺), (ii) addition of organic substrate (wood flour) during incubation period and (iii) different soil moisture levels.     

Handling the phosphorus paradox in agriculture and natural ecosystems: Scarcity,necessity, and burden of P

This special issue of Ambio compiles a series of contributions made at the 8th International Phosphorus Workshop (IPW8), held in September 2016 in Rostock, Germany. The introducing overview article summarizes major published scientific findings in the time period from IPW7 (2015) until recently, including presentations from IPW8. The P issue was subdivided into four themes along the logical sequence of P utilization in production, environmental, and societal systems: (1) Sufficiency and efficiency of P utilization, especially in animal husbandry and crop production; (2) P recycling: technologies and product applications; (3) P fluxes and cycling in the environment; and (4) P governance. The latter two themes had separate sessions for the first time in the International Phosphorus Workshops series; thus, this overview presents a scene-setting rather than an overview of the latest research for these themes. In summary, this paper details new findings in agricultural and environmental P research, which indicate reduced P inputs, improved management options, and provide translations into governance options for a more sustainable P use.     

Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy

C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).     

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.     

From traditional to modern fee systems

This paper deals with the environmentally important issue regarding how best to motivate citizens to reduce their individual waste production. The paper discusses the pros and cons of the various financial incentives incorporated into the waste charging mechanism, pay-as-you-throw (PAYT). Pay-as-you-throw breaks with the tradition of paying for waste services through general blanket taxes or levies in the form of flat rates in that households are required to pay individually adjusted fees in the same way as water and electricity bills are calculated on an individual consumption basis. This difference is achieved through the interplay of three principal components which mark the technical implementation of PAYT: identification as a vehicle to attain accountability, measurement of the generated waste and/or corresponding services, and unit pricing as the basis for individual charges proportional to the extent of the obtained services. However, any motivating factor for inducing citizens to dispose of their recyclable discards and residual waste must be supported by a well developed collection infrastructure, good media information and an appropriate, transparent charging policy. Of particular importance is the use of a multi-tiered charge model, i.e., the charging of a fixed minimum fee plus certain variable components payable in respect of the service structure. The introduction of a basic charge, albeit reducing the intensity of the incentives created by the PAYT system, ensures that certain fixed costs for the provision of waste services will be covered independently from the actual waste developments and, at the same time, minimises the temptation to attempt to bypass the system. Such an arrangement for the waste charges neither contradicts the principle of pay-as-you-throw nor does it impair the waste diversion for which it is implemented. Waste statistics and figures representing the waste charging situation in Germany indicate that there is a relatively good correlation between the level of recycling and the amount of perceived financial motivation provided by PAYT. Waste stream developments in areas using such charging schemes generally suggest that the reduction goals are being achieved. Single figures on decreasing quantities of collected residual waste, however, say little about the actual efficiency of differentiated waste charging models and deliver little in the way of reasoned explanation as to why the diffusion of variable rate pricing is progressing painstakingly slowly. To evaluate the success, feasibility and problems of PAYT schemes, one needs to consider the various ways for technically implementing this approach in practice, and must take a broader look into the wide spectrum of available waste services and into more factors that influence their efficiency and acceptance. Urban structure settings assume a particular importance here as do the specific goals of social policy which, among others, are reflected in the charging mechanisms applied. Practical experience, however, shows that solutions can be found which allow most of the concerns and area specifics to be accommodated and waste streams to be influenced in the desired way. Aside from this, positive effects as to waste collection efficiency can also be achieved, which contribute towards long-term environmental improvements and countervail the incremental costs of implementing PAYT.     

Initial Changes in Refilled Lysimeters Built with Metal Polluted Topsoil and Acidic or Calcareous Subsoils as Indicated by Changes in Drainage Water Composition

Soil translocation for recultivation of soil removed from construction sites and for the preparation of refilled lysimeters inevitably involves disturbance of soil structure, and, if intermediate storage is included, also drying and rewetting of the soil. We report on an experiment with model forest ecosystems, where uncontaminated forest subsoils were covered with non-contaminated or freshly heavy metal (mainly Zn and Cu) contaminated topsoil in large lysimeters. Monitoring of the chemical composition of the drainage water revealed two distinct soil conditioning phases. During an initial phase of about a year strongly elevated nitrate and sulfate concentrations occurred that were attributed to a mineralisation flush caused by the increased accessability of mineralisable nitrogen and sulfur in destroyed aggregates. These effects were significantly larger in lysimeters with calcareous subsoil than in those with acidic subsoil. The second phase was characterised by a gradual decrease in dissolved organic carbon and sulfate concentrations, in particular in the acidic subsoil. This decrease may be attributed to the depletion of pools made accessible during aggregate destruction or the formation of new aggregates. These chemical changes had only little effects on the concentrations of copper and zinc in the drainage water. Based on our results, it can be concluded that large refilled lysimeters can be used for many purposes without risk of compromised results, if a conditioning phase of about 1 year with sufficiently moist soil conditions is respected. Nevertheless, gradual changes in soil chemical characteristics still occur after this initial phase. Implications for the recultivation of sites using relocated soils are discussed.     

Biomonitoring zur wirkungsbezogenen Ermittlung der Schadstoffbelastung in terrestrischen Ökosystemen

Biomonitoring programmes provide relevant information, which may supplement ambient air pollution monitoring or modelling around emission sources. As a prerequisite, assessment scales for biomonitoring data have to be derived based on an objective evaluation of available data, as well as on a scheme of presentation, which is suggestive and easily understandable even for laymen. Based on an evaluation of numerous monitoring programmes, assessment scales for biomonitoring results are derived for plant biomonitoring, which also serve as a basis for the graphical presentation of monitoring results. This study is focussed on bioindicator plants like mosses (passive biomonitoring) and exposed lichens (active biomonitoring), in which 14 metal elements are investigated. As an example, data from a local biomonitoring network around a cement plant were used to demonstrate the use of the assessment scales derived and the presentation scheme developed. Data sets from about 15 moss and 24 lichen biomonitoring programmes, comprising more than 1000 specimens, were sorted by their pollutant characteristics in order to form the database. Data on the metal contents of species demonstrating similar values with respect to growth characteristics and habit, and representing background or low pollution levels, are aggregated and their statistical distributions are evaluated. Spacing of the assessment scales and their colour designations are derived from the 50-, 75-, 90- and 95-percentile values. Graphical presentation allows a comparison of the absolute values of metal contents and a relative association of measured values. Exemplary results from moss and lichen monitoring around a cement plant are generally below or slightly above the median values at background and low-pollution sites. Metal contents are higher in lichens compared to mosses for 7 elements (Cd, Cu, Hg, Pb, Sb, Sn, Zn), and are lower in lichens only for thallium. The assessment scheme presented is mainly aimed at the practitioner in the field of biomonitoring in order to provide a reliable and sound scale of assessment by comparison on an absolute scale rather than presenting the basis of ecological risk assessment. Differences in metal content of co-located samples of various moss species and possible correction procedures are briefly discussed- as well as the consequences of pooling monitoring data across various moss species for the quality of assessment scales. Further evaluations shall focus on species-specific rather than on pooled databases and will investigate the consequences of the use of correction factors when extrapolating metal data from one monitoring species to another.     

Identification of heavy metal pollutants using multivariate analysis and effects of land uses on their accumulation in urban soils in Beijing, China

In order to evaluate the current state of the environmental quality of soils in Beijing, we investigated contents of 14 metals in Beijing urban soils inside the 5th ring road by even grids sampling. Statistic analyses were conducted to identify possible heavy metal pollutants, as well as the effects of land uses on their accumulation. Our results revealed that the urban soils in Beijing were contaminated by Cd, Pb, Cu, and Zn. Land uses and urbanization ages affected the accumulation of the four heavy metals in soils significantly. Soils in industrial areas have the highest average Cu and Zn contents, while Pb contents in park areas and Cd in agricultural areas are the highest. The accumulations of Pb and Zn in urban soils increase significantly with sampling plots approaching the city center. And Pb, Cd, and Zn contents in soils in traffic areas also tend to increase in the city center. However, residential areas have the lowest contents of all the four heavy metals.     

Physical Modeling of Emissions from Naturally Ventilated Underground Parking Garages

The dispersion of pollutants from naturally ventilated underground parking garages has been studied in a boundary layer wind tunnel. Two idealized model setups have been analysed, one was simulating pollutant dispersion around an isolated rectangular building and one was representing dispersion in a finite array of idealized building blocks. Flow and dispersion close to modelled ground level emission sources was measured. The results illustrate the complexity of the flow around buildings and provide insight in pollutant transport from ground level sources located directly on building surfaces. As a result, areas critical with respect to high pollutant concentrations could be visualized. Particularly, the results show high concentration gradients on the surface of the buildings equipped with modelled emission sources. Inside the boundary layers on the building walls, a significant amount of pollutants is transported to upwind locations on the surface of the building. The paper documents the potential of physical modelling to be used for the simulation and measurement of dispersion close to emission sources and within complex building arrangements.     

Nitrogen and metals in two regions in Central Europe: Significant differences in accumulation in mosses due to land use?

The study was conducted to test the hypothesis that the regional variability of nitrogen (N) and metal accumulations in terrestrial ecosystems are due to historical and recent ways of landuse. To this end, two regions of Central Europe were selected for investigation: the Weser-Ems Region (WER) and the Euro Region Nissa (ERN). They were assumed to have land use-specific accumulation profiles. Thus, the metal and N accumulations in both regions were examined by means of geostatistically based comparative moss analysis. The sampling and chemical analysis of mosses were conducted in accordance with the convenient guidelines and methods, respectively. The spatial representativity of the sampling sites was computed by means of a land classification which was calculated for Europe by means of classification trees and GIS-techniques. The differences of deposition loads were tested for statistical significance with regard to time and space. The measurement values corroborated the decline of metal accumulation observed since the beginning of the European Metals in Mosses Surveys in 1990. The metal loads of the mosses in the ERN exceeded those in the WER significantly. The opposite holds true for the N concentrations: those in the WER were significantly higher than those in the ERN. The reduction of emissions from power plants, factories and houses was strongly correlated with the decline of deposition and bioaccumulation of metals. As proved by the European Metals in Mosses Surveys, this tendency is due to successful environmental policies. But no such success could be verified by monitoring the accumulation of N in mosses.