Concentrations and speciation of arsenic in groundwater polluted by warfare agents

Groundwater polluted with phenylarsenicals from former warfare agent deposits and their metabolites was investigated with respect to the behavior of relevant arsenic species. Depth profiles at the estimated source and at about 1 km downgradient from the source zone were sampled. The source zone is characterized by high total arsenic concentrations up to 16 mg L⁻¹ and is dominated by organic arsenic compounds. The concentrations in the downgradient region are much lower (up to 400 μg L⁻¹) and show a high proportion of inorganic arsenic species. Iron precipitation seems to be an effective mechanism to prevent dispersion of inorganic arsenic as well as phenylarsonic acid. Reductive conditions were observed in the deeper zone with predominant occurrence of trivalent arsenic species. The inorganic species are in redox equilibrium, whereas the phenylarsenic compounds have variable proportions. Methylphenylarsinic acid was identified in groundwater in traces which indicates microbial degradation activity.     

Sorption of thallium(I) onto geological materials: influence of pH and humic matter

The sorption behaviour of the severely toxic heavy metal thallium (Tl) as a monovalent cation onto three representative materials (goethite, pyrolusite and a natural sediment sampled from a field site) was examined as a function of pH in the absence and presence of two natural humic acids (HAs), using ²⁰⁴Tl(I) as a radiotracer. In order to obtain a basic understanding of trends in the pH dependence of Tl(I) sorption with and without HA, sorption of HAs and humate complexation of Tl(I) as a function of pH were investigated as well. In spite of the low complexation between Tl(I) and HAs, the presence of HAs results in obvious alterations of Tl(I) sorption onto pyrolusite and sediment. An influence on Tl(I) sorption onto goethite was not observed. Predictions of K_d (distribution coefficient) for Tl(I) on goethite in the presence of HAs, based on a linear additive model, agree well with the experimental data, while a notable disagreement occurs for the pyrolusite and sediment systems. Accordingly, it is suggested that HAs and goethite may act as a non-interacting sorbent mixture under the given conditions, but more complex interactions may take place between the HAs and the mineral phases of pyrolusite or sediment.     

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).     

Methylmercury speciation in the dissolved phase of a stratified lake using the diffusive gradient in thin film technique

The diffusive gradient in thin film (DGT) technique was successfully used to monitor methylmercury (MeHg) speciation in the dissolved phase of a stratified boreal lake, Lake 658 of the Experimental Lakes Area (ELA) in Ontario, Canada. Water samples were conventionally analysed for MeHg, sulfides, and dissolved organic matter (DOM). MeHg accumulated by DGT devices was compared to MeHg concentration measured conventionally in water samples to establish MeHg speciation. In the epilimnion, MeHg was almost entirely bound to DOM. In the top of the hypolimnion an additional labile fraction was identified, and at the bottom of the lake a significant fraction of MeHg was potentially associated to colloidal material. As part of the METAALICUS project, isotope enriched inorganic mercury was applied to Lake 658 and its watershed for several years to establish the relationship between atmospheric Hg deposition and Hg in fish. Little or no difference in MeHg speciation in the dissolved phase was detected between ambient and spike MeHg.     

Untersuchung von Abfällen mit biologischen Testverfahren zur Bewertung der Wassergefährdung

Wastes from three different types of waste treatment facilities (slag from a municipal waste incineration plant, slag granules from a pilot plant combining carbonization and incineration, mechanical and biological treated wastes) were examined to determine their hazard potential to different waters sites. The process temperature is seen to be the main difference between the three treatment processes. The wastes were extracted with water according to the German standard DIN 38414 S 4 and additionally at a constant pH value of 4. The leachates were investigated in a battery of aquatic bioassays and characterised physically and chemically. Every leachate revealed in a toxic effect at least in one test. The toxicity of the leachates prepared at a pH of 4 was significantly higher than the toxicity of the leachates prepared by extraction with water without pH adjustment. The leachates of the slag granules showed the lowest toxicity. On the basis of these experimental results, a scheme to derive Water Hazard Classes of wastes, which is presented in part II of this publication, was developed.     

Declines in migrant shorebird populations from a winter‐quarter perspective

Many long‐distance migrating shorebird (i.e., sandpipers, plovers, flamingos, oystercatchers) populations are declining. Although regular shorebird monitoring programs exist worldwide, most estimates of shorebird population trends and sizes are poor or nonexistent. We built a state‐space model to estimate shorebird population trends. Compared with more commonly used methods of trend estimation, state‐space models are more mechanistic, allow for the separation of observation and state process, and can easily accommodate multivariate time series and nonlinear trends. We fitted the model to count data collected from 1990 to 2013 on 18 common shorebirds at the 2 largest coastal wetlands in southern Africa, Sandwich Harbour (a relatively pristine bay) and Walvis Bay (an international harbor), Namibia. Four of the 12 long‐distance migrant species declined since 1990: Ruddy Turnstone (Arenaria interpres), Little Stint (Calidris minuta), Common Ringed Plover (Charadrius hiaticula), and Red Knot (Calidris canutus). Populations of resident species and short‐distance migrants increased or were stable. Similar patterns at a key South African wetland suggest that shorebird populations migrating to southern Africa are declining in line with the global decline, but local conditions in southern Africa's largest wetlands are not contributing to these declines. State‐space models provide estimates of population levels and trends and could be used widely to improve the current state of water bird estimates.     

Comparison of data-based methods for monitoring of air leakages into oxyfuel power plants

Air leakages compromise the CO₂ capture rate and auxiliary power consumption of oxyfuel power plants. Constructive measures can significantly improve the leakage rate in newly built plants. However, the mitigation of increasing leakage rates during the plant lifetime is crucial for high plant efficiency. In this paper, we apply three statistical methods on experimental process data gathered in an air leakage test in Vattenfall's Oxyfuel Pilot Plant in Schwarze Pumpe, Germany. The performance of the methods in identifying increasing leakage rates and localizing the leakage source is investigated. It was found that all three methods can identify and localize even small increases of the leakage rate. A combination of all three methods allows taking advantage of the individual features of each method. Additional installation of CO₂, O₂, H₂O, and SO₂ measurements in the oxidizer can considerably enhance localization performance. Finally, it is shown that the results can be transferred to commercial-scale oxyfuel pilot plants by generating training data with thermodynamic plant models.     

Constraints to implementation of sustainability indicator systems in five Asian cities

Contemporary studies on sustainability indicator systems (SISs) typically focus on the technical advancement of indicator construction, on qualitative impacts of indicator programmes and on impacts on governance, decision-making and sustainability as a social construct. Yet, their implementation so far has rarely been addressed, even though monitoring and the use of indicator results fall far behind the number of SISs developed. This study aims at the identification of requirements for the development of and constraints to the implementation of SISs in five Asian cities of developing countries. Interviews with local key actors are held, and a qualitative content analysis is carried out. Findings include evidence on the degree of indicator implementation in the case study cities, a hexagonal model for the classification of requirements and constraints, as well as general conclusions for barriers to the use of SISs.     

Historical development and future outlook of the flood damage potential of residential areas in the Alpine Lech Valley (Austria) between 1971 and 2030

In the recent past, the Alpine Lech valley (Austria) experienced three damaging flood events within 6 years despite the various structural flood protection measures in place. For an improved flood risk management, the analysis of flood damage potentials is a crucial component. Since the expansion of built-up areas and their associated values is seen as one of the main drivers of rising flood losses, the goal of this study is to analyze the spatial development of the assets at risk, particularly of residential areas, due to land use changes over a historic period (since 1971) and up to possible shifts in future (until 2030). The analysis revealed that the alpine study area was faced to remarkable land use changes like urbanization and the decline of agriculturally used grassland areas. Although the major agglomeration of residential areas inside the flood plains took place before 1971, a steady growth of values at risk can still be observed until now. Even for the future, the trend is ongoing, but depends very much on the assumed land use scenario and the underlying land use policy. Between 1971 and 2006, the annual growth rate of the damage potential of residential areas amounted to 1.1 % (‘constant values,’ i.e., asset values at constant prices of reference year 2006) or 3.0 % (‘adjusted values,’ i.e., asset values adjusted by GDP increase at constant prices of reference year 2006) for three flood scenarios. For the projected time span between 2006 and 2030, a further annual increase by 1.0 % (‘constant values’) or even 4.2 % (‘adjusted values’) may be possible when the most extreme urbanization scenario ‘Overall Growth’ is considered. Although socio-economic development is regarded as the main driver for increasing flood losses, our analysis shows that settlement development does not preferably take place within flood prone areas.     

Determination of naturally occurring MTBE biodegradation by analysing metabolites and biodegradation by-products

Methyl tert-butyl ether (MTBE) is one of the main additives in gasoline. Its degradation is known to be difficult in natural environments. In this study, significant MTBE degradation is demonstrated at a contaminated site in Leuna (eastern Germany). Since the extent of the plume appeared to be constant over the last 5 years, an extended study was performed to elucidate the degradation processes. Special attention was paid to the production, accumulation and degradation of metabolites and by-products. Groundwater samples from 105 monitoring wells were used to measure 20 different substances. During the degradation process, several intermediates such as tert-butyl alcohol (TBA), tert-butyl formate, formate and lactate were produced. However, the potentially carcinogenic by-product methacrylate was not detected in several hundred samples. At the Leuna site, MTBE degradation occurred under microaerobic conditions. In contrast to hydrocarbons and BTEX, there was no evidence for anaerobic MTBE degradation. Among the degradation products, TBA was found to be a useful intermediate to identify MTBE degradation, at least under microaerobic conditions. TBA accumulation was strongly correlated to MTBE degradation according to the kinetic properties of both degradation processes. Since maximum degradation rates (v(max)) and k(m) values were higher for MTBE (v(max)=2.3 mg/l/d and k(m)=3.2 mg/l) than for TBA (v(max)=1.35 mg/l/d and k(m)=0.05 mg/l), TBA significantly accumulated as an intermediate by-product. The field results were supported by bench scale model aquifer experiments.