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.     

A Dynamic Crediting Regime for Joint Implementation to Foster Innovation in the Long Term

Joint Implementation is a theoretically efficient instrument of climate policy at least in the short run. This need not apply for the long run. Joint Implementation can reduce innovation in the industrialized countries because of reduced incentives for emission reduction. To realize short run efficiency gains and to avoid long run efficiency losses, we need a ‘strategic’ climate policy. This policy should start with full crediting of Joint Implementation allowing short-run efficiency gains which can foster technology transfer and thus lead to ‘leapfrogging’ by developing countries. Over time, the crediting ratio should be gradually reduced while domestic carbon taxes are raised. Experiences from the second oil shock have shown that energy-saving innovation is positively correlated to energy prices. Both, the reduced crediting and the raising domestic carbon tax, will therefore lead to long-run innovation.     

Mercury transfer from fish carcasses to scavengers in boreal lakes: the use of stable isotopes of mercury

Scavengers play an important role in the flow of energy, matter and pollutants through food webs. For methylmercury (MeHg), which biomagnifies along food chains, the movement of this metal from fish carcasses to aquatic scavengers has never been demonstrated. We measured the transfer of MeHg from fish carcasses to scavenging leeches in two lakes and in the laboratory. The results of a field experiment indicated that leeches were attracted to fish carcasses and that their Hg concentrations increased by as much as a factor of 5 during the time that Hg-rich fish were available for consumption. Under controlled conditions, we exposed leeches to (202)Hg-labelled fish that had been marked in situ following a whole lake (202)Hg addition. Leeches rapidly accumulated Hg from carcasses, and within two weeks assumed the isotopic signature of the carcasses. Necrophagous invertebrates could therefore return Hg from fish carcasses to other trophic levels in lakes.     

Climate change impact on water quality: model results from southern Sweden

Starting from six regional climate change scenarios, nitrogen leaching from arable-soil, water discharge, and nitrogen retention was modeled in the R?nne? catchment. Additionally, biological response was modeled in the eutrophic Lake Ringsj?n. The results are compared with similar studies on other catchments. All scenarios gave similar impact on water quality but varied in quantities. However, one scenario resulted in a different transport pattern due to less-pronounced seasonal variations in the hydrology. On average, the study shows that, in a future climate, we might expect: i) increased concentrations of nitrogen in the arable root zone (+50%) and in the river (+13%); ii) increased annual load of nitrogen from land to sea (+22%) due to more pronounced winter high flow; moreover, remote areas in the catchment may start to contribute to the outlet load; iii) radical changes in lake biochemistry with increased concentrations of total phosphorus (+50%), total nitrogen (+20%), and planktonic algae such as cyanobacteria (+80%).     

Investigation on the chemical structure of nonextractable residues of the fungicide cyprodinil in spring wheat using 13C-C1-phenyl-cyprodinil on 13C-depleted plants-an alternative approach to investigate nonextractable residues

13C-labelled cyprodinil was applied on 13C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of 14C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The 13C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.