Fate of the 14C-labeled herbicide prosulfocarb in a soil and in a sediment-water system

The fate of ¹⁴C-labeled herbicide prosulfocarb was studied in an agricultural soil and in a sediment-water system, the sediment part of which was derived from Yangtze Three Gorges Reservoir, China. Time-course studies were performed for 28 d and 49 d, respectively. Main transformation routes of ¹⁴C-prosulfocarb were mineralization to ¹⁴CO₂ and formation of nonextractable residues amounting to 12.13% and 10.43%, respectively, after 28 days (soil), and 9.40% and 11.98%, respectively, after 49 d (sediment-water system). Traces of prosulfocarbsulfoxide were detected by means of TLC, HPLC, and LC-MS; other transformation products were not found. Initial extraction of soil assays using 0.01 M CaCl₂ solution showed that the bioavailability of the herbicide was considerably low; immediately after application (0.1 d of incubation), only 4.78% of applied radioactivity were detected in this aqueous fraction. DT₅₀ values of ¹⁴C-prosulfocarb estimated from radio-TLC and -HPLC analyses were above 28 d in soil and ranged between 29 d and 49 d in the sediment-water system. Partitioning of ¹⁴C from water to sediment phase occurred with DT₅₀ slightly above 2 d. With regard to the sediment-water system, adsorption occurred with log K_oc = 1.38 (calculated from 2 day assays) and 2.35 (49 d assays). As similarly estimated from portions of ¹⁴C found in CaCl₂ extracts of the 0.1 d assays, ¹⁴C-prosulfocarb's log K_oc in soil was 2.96. With both experiments, similar portions of nonextractable radioactivity were associated with all soil organic matter fractions, i.e. nonhumics, fulvic acids, humic acids, and humin/minerals. Throughout all sample preparation, the experiments were severely impaired by losses of radioactivity especially with concentration of samples containing water in vacuo. All findings pointed to volatility of parent prosulfocarb in presence of water rather than volatility of transformation products. According to literature data, this behavior of prosulfocarb was not expected, though volatility was demonstrated under field conditions.     

Characterization of non-extractable ¹⁴C- and ¹³C-sulfadiazine residues in soil including simultaneous amendment of pig manure

Recently, we reported on soil fate of SDZ residues amended with pig manure treated with 1?C-labeled sulfadiazine 1?C-SDZ). The first objective of the present study was to determine whether this strategy can be substituted by application of 1?C-SDZ to soil. The second objective was to characterize non-extractable SDZ residues by fractionation, size exclusion chromatography (SEC) and solid state 13C-NMR. The fate of 1?C-SDZ was examined for 28 d, using two soils with and without amendment of pig manure. Mineralization of 1?C-SDZ was low; extractable residues decreased to 7-30%. Compared to the previous study, results were similar. 1?C-SDZ derived bound radioactivity was found in HCl-washings, fulvic, humic acids and humin. According to SEC, one bound 1?C portion (70%) co-eluted with fulvic acids (above 910 g mol?1); the other consisted of adsorbed/entrapped 1?C-SDZ. The 13C-SDZ study was performed for 30 d; humic acids were examined by 13C-NMR. A signal (100-150 ppm) was referred to 13C-SDZ. SEC and 13C-NMR demonstrated rapid integration of SDZ into humics.     

Spatial and temporal trends of metals and arsenic in German freshwater compartments

Cadmium, lead, mercury, copper, nickel, zinc, and arsenic were analyzed in suspended particulate matter (SPM), zebra mussels, and bream sampled yearly under the program of the German Environmental Specimen Bank (ESB) in the rivers Rhine, Elbe, Danube, Saar, Mulde, and Saale and in Lake Belau. Temporal and spatial trends were analyzed, correlations between metal levels in different specimen types assessed, and sampling sites ranked according to their metal levels by calculating a Multi-Metal Index (MMI) for every specimen type and site. SPM: Highest metal loads were detected in Mulde, Saale, and Elbe right downstream of the Saale confluence. In the Elbe, metal loads in SPM were mostly highest in the upper and middle section of the river while in Rhine and Saar concentrations increased downstream. Temporal trends since 2005 were detected only at three sites. Zebra mussel: MMIs were highest in the tidal section of the Elbe and the lower Rhine and lowest in Lake Belau and the upper Danube. Different temporal trends were detected since the early 1990s depending on site and metal. Bream: As, Pb, Cu, and Hg were analyzed in muscle tissue and Pb, Cd, Cu, and Zn in liver. For both tissues, MMIs were highest in Mulde and Saale and the lower and middle Elbe. Since the early 1990s, Hg, Pb, and Cu decreased in bream muscle at many sites while As increased at 6 of the 17 sites. The findings indicate that Hg, Pb, and Cu have obviously decreased in many freshwater ecosystems in recent years, whereas As and Ni levels have increased at several sites. Metal levels and temporal trends mostly differed between the specimen types under investigation and only few correlations between specimen types were detected. This underlines the importance of including different components of an ecosystem when assessing its environmental quality.     

Biodegradability of a polyacrylate superabsorbent in agricultural soil

Superabsorbent polymers (SAP) are used, inter alia, as soil amendment to increase the water holding capacity of soils. Biodegradability of soil conditioners has become a desired key characteristic to protect soil and groundwater resources. The present study characterized the biodegradability of one acrylate based SAP in four agricultural soils and at three temperatures. Mineralisation was measured as the ¹³CO₂ efflux from ¹³C-labelled SAP in soil incubations. The SAP was either single-labelled in the carboxyl C-atom or triple-labelled including additionally the two C-atoms interlinked in the SAP backbone. The dual labelling allowed estimating the degradation of the polyacrylate main chain. The ¹³CO₂ efflux from samples was measured using an automated system including wavelength-scanned cavity ring-down spectroscopy. Based on single-labelled SAP, the mean degradation after 24 weeks varied between 0.45 % in loamy sand and 0.82 % in loam. However, the differences between degradation rates in different soils were not significant due to a large intra-replicate variability. Similarly, mean degradation did not differ significantly between effective temperature regimes of 20° and 30 °C after 12 weeks. Results from the triple-labelled SAP were lower as compared to their single-labelled variant. Detailed results suggest that the polyacrylate main chain degraded in the soils, if at all, at rates of 0.12–0.24 % per 6 months.     

Fate in soil of 14C-sulfadiazine residues contained in the manure of young pigs treated with a veterinary antibiotic

The fate of (14)C-labeled sulfadiazine ((14)C-SDZ) residues was studied in time-course experiments for 218 days of incubation using two soils (A(p) horizon of loamy sand, orthic luvisol; A(p) horizon of silt loam, cambisol) amended with fresh and aged (6 months) (14)C-manure [40 g kg(-1) of soil; 6.36 mg of sulfadiazine (SDZ) equivalents per kg of soil], which was derived from two shoats treated with (14)C-SDZ. Mineralization of (14)C-SDZ residues was below 2% after 218 days depending little on soil type. Portions of extractable (14)C (ethanol-water, 9:1, v/v) decreased with time to 4-13% after 218 days of incubation with fresh and aged (14)C-manure and both soils. Non-extractable residues were the main route of the fate of the (14)C-SDZ residues (above 90% of total recovered (14)C after 218 days). These residues were high immediately after amendment depending on soil type and aging of the (14)C-manure, and were stable and not remobilized throughout 218 days of incubation. Bioavailable portions (extraction using CaCl(2) solution) also decreased with increasing incubation period (5-7% after 218 days). Due to thin-layer chromatography (TLC), 500 microg of (14)C-SDZ per kg soil were found in the ethanol-water extracts immediately after amendment with fresh (14)C-manure, and about 50 microg kg(-1) after 218 days. Bioavailable (14)C-SDZ portions present in the CaCl(2) extracts were about 350 microg kg(-1) with amendment. Higher concentrations were initially detected with aged (14)C-manure (ethanol-water extracts: 1,920 microg kg(-1); CaCl(2) extracts: 1,020 microg kg(-1)), probably due to release of (14)C-SDZ from bound forms during storage. Consistent results were obtained by extraction of the (14)C-manure-soil samples with ethyl acetate; portions of N-acetylated SDZ were additionally determined. All soluble (14)C-SDZ residues contained in (14)C-manure contributed to the formation of non-extractable residues; a tendency for persistence or accumulation was not observed. SDZ's non-extractable soil residues were associated with the soluble HCl, fulvic acids and humic acids fractions, and the insoluble humin fraction. The majority of the non-extractable residues appeared to be due to stable covalent binding to soil organic matter.     

Adapting the adaptive cycle: Hypotheses on the development of ecosystem properties and services

Ecosystems are dynamic complexes. These dynamics can be described by different ecophysiological parameters and systems theoretical concepts like succession, thermodynamics, information/network theory, resilience, adaptability and the orientor concept. In this paper, different indicators and concepts are linked to Holling's adaptive cycle metaphor in order to derive hypotheses on potential system trajectories. The hypotheses focus on an exemplary temperate forest ecosystem experiencing the adaptive cycle's four phases of exploitation, conservation, collapse and reorganization after an initializing fire event. The different properties are correlated to the number of total system connections and show varying trajectories. Additionally, the provision of selected forest ecosystem services during the different phases is hypothesized and compared to three other land use types.     

Metabolic pathways of polychlorinated biphenyls degradation by Pseudomonas sp. 2

Polychlorinated biphenyls (PCBs) included with the commercial mixture Delor 103 were degraded by immobilized cells of aerobic bacterial strain Pseudomonas sp. 2. The ability of the strain to metabolise selected tri- and tetrachlorobiphenyls, and the site of primary attack of the biphenyl skeleton were investigated. It was observed that the amount of residual PCBs was 1-48% of the original PCBs after three weeks of incubation. Identified metabolites indicate that the used bacterial strain attacks the biphenyl skeleton at the 2,3- and 3,4-positions, and it is also able to dehalogenate PCBs. Metabolic pathways of degradation of individual congeners were proposed. Transformation of 2,4- and 2,5-dichlorobenzoic acids by Pseudomonas sp. 2 was also observed.