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A detailed structural investigation of a promising bio-based polymer, polyglycerol citrate polyester, obtained by the bulk polycondensation of glycerol (Gly) against citric acid (Cit) under mild reaction was performed. The reaction in conditions with and without catalyst use (sulfuric acid, H 2 SO 4 ) was investigated, showing evidence that it is possible to modify the polymer solubility according to the ratio and catalyst utilization. 13 C and 1 H NMR indicated that synthesis catalyzed with Cit excess leads to higher esterification degrees of citrate groups. In contrast, the Gly moieties are more prominent in catalyzed polymers regardless of the excess monomers. Overall, a successful conversion of Gly and Cit into polyesters was attained even without catalysis, enabling a simple route for the large-scale production of this green material to be used as a coating material. This polymer has been shown to be well-suited for coating seeds and might be a promising material for similar agricultural applications. Tests on soybean seed coating with a PGCit solution of 75% indicated that the seed quality and germination rate were not affected by the PGCit coating, concluding that this polymer is suitable for this application.

Due to its ample production of lignocellulosic biomass, Sida hermaphrodita (Sida), a perennial forb, is considered a valuable raw material for biorefinery processes. The recalcitrant nature of Sida lignocellulosic biomass towards pretreatment and fractionation processes has previously been studied. However, Sida is a non-domesticated species and here we aimed at expanding the potential of such plants in terms of their processability for downstream processes by making use of the natural variety of Sida. To achieve this goal, we established a collection comprising 16 different Sida accessions obtained from North America and Europe. First, we asked whether their cell wall characteristics are reflected in genetic distance or geographical distribution, respectively. A genotyping-by-sequencing (GBS) analysis resulting in a phylogenic tree based on 751 Single Nucleotide Polymorphisms (SNPs), revealed a high genetic diversity and a clear separation between accessions collected in North America and Europe. Further, all three North American accessions were separated from each other. Of the eleven European accessions, five form individual groups and six others belong to a single group. Clonal plants of seven selected accessions of American and European origin were produced and cultivated under greenhouse conditions and the resulting plant material was used for in-depth wet-chemical and spectroscopic cell wall characterization. Two accessions with contrasting cell wall characteristics were then selected and processed using the OrganoCat technology. Results of the different product yields and chemical compositions are reported. Overall, cell wall analyses revealed contrasting clusters regarding these main components between the accessions that can be related to genetic and, partly, geographical distance. Phenotypically, the accessions clustered into two groups that are not entirely overlapping with geographical origin. These results can be the basis for a targeted selection or cultivation of Sida accessions for biorefinery approaches., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Schrey, Martinez Diaz, Becker, Mademann, Ohrem, Drobietz, Chaloupsky, Jablonowski, Wever, Grande, Pestsova and Klose.)

Sugarcane bagasse is commonly combusted to generate energy. Unfortunately, recycling strategies rarely consider the resulting ash as a potential fertilizer. To evaluate this recycling strategy for a sustainable circular economy, we characterized bagasse ash as a fertilizer and measured the effects of co-gasification and co-combustion of bagasse with either chicken manure or sewage sludge: on the phosphorus (P) mass fraction, P-extractability, and mineral P phases. Furthermore, we investigated the ashes as fertilizer for soybeans under greenhouse conditions. All methods in combination are reliable indicators helping to assess and predict P availability from ashes to soybeans. The fertilizer efficiency of pure bagasse ash increased with the ash amount supplied to the substrate. Nevertheless, it was not as effective as fertilization with triple-superphosphate and K 2 SO 4 , which we attributed to lower P availability. Co-gasification and co-combustion increased the P mass fraction in all bagasse-based ashes, but its extractability and availability to soybeans increased only when co-processed with chicken manure, because it enabled the formation of readily available Ca-alkali phosphates. Therefore, we recommend co-combusting biomass with alkali-rich residues to increase the availability of P from the ash to plants., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Dombinov, Herzel, Meiller, Müller, Willbold, Zang, da Fonseca-Zang, Adam, Klose, Poorter, Jablonowski and Schrey.)

The knowledge of the structural and chemical properties of biochars is decisive for their application as technical products. For this reason, methods for the characterization of biochars that are generally applicable and allow quality control are highly desired. Several methods that have shown potential in other studies were used to investigate two activated carbons and seven biochars from different processes and feedstock. The chars were chosen to cover a wide range of chemical composition and structural properties as a hardness test for the analytical methods used in this study. Specific problems connected with the pretreatment of samples and drawbacks of some methods for some types of chars could be identified in an integrated consideration of the results from different methods. None of the spectroscopic methods was found to be suitable for the quality control of all types of chars. The most valuable results were obtained by chemical analysis that, however, required the complete determination of the main elements, including that of oxygen, and of inorganic components for adequate results. The combination of X-ray photoelectron spectroscopy (XPS) and FT-IR spectroscopy allows a rough characterization of surface functional groups, but cannot discriminate aliphatic and aromatic OH groups. FT-IR might be a suitable method for the quality control of biochars made at lower temperature. The results of Raman spectroscopy did not well correlate with the amount of sp2 hybridized carbon determined by XPS. A better correlation of XPS data was found with the electrical polarization determined by the method of spectral induced polarization that was used for the first time in conjunction with extensive analytical characterization., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2022 Ilić et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Agricultural output needs significant increases to feed the growing population. Fertilizers are essential for plant production systems, with nitrogen (N) being the most limiting nutrient for plant growth. It is commonly supplied to crops as urea. Still, due to volatilization, up to 50 % of the total N application is lost. Slow or controlled release fertilizers are being developed to reduce these losses. The co-application of zinc (Zn) as a micronutrient can increase N absorption. Thus, we hypothesize that the controlled delivery of both nutrients (N and Zn) in an integrated system can improve uptake efficiency. Here we demonstrate an optimized fertilizer nanocomposite based on urea:urea-formaldehyde matrix loaded with ZnSO 4 or ZnO. This nanocomposite effectively stimulates maize development, with consequent adequate N uptake, in an extreme condition - a very nutrient-poor sand substrate. Our results indicate that the Zn co-application is beneficial for plant development. However, there were advantages for ZnO due to its high Zn content. We discuss that the dispersion favors the Zn delivery as the nanoparticulated oxide in the matrix. Concerning maize development, we found that root morphology is altered in the presence of the fertilizer nanocomposite. Increased root length and surface area may improve soil nutrient uptake, potentially accompanied by increased root exudation of essential compounds for N release from the composite structure., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Amanda Soares Giroto reports financial support was provided by State of Sao Paulo Research Foundation. Amanda Soares Giroto reports a relationship with State of Sao Paulo Research Foundation that includes: funding grants., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Struvite (St) recovered from wastewaters is a sustainable option for phosphorus (P) recovery and fertilization, whose solubility is low in water and high in environments characterized by a low pH, such as acidic soils. To broaden the use of struvite in the field, its application as granules is recommended, and thus the way of application should be optimized to control the solubility. In this study struvite slow-release fertilizers were designed by dispersing St particles (25, 50, and 75 wt%) in a biodegradable and hydrophilic matrix of thermoplastic starch (TPS). It was shown that, in citric acid solution (pH = 2), TPS promoted a steadier P-release from St compared to the pure St pattern. In a pH neutral sand, P-diffusion from St-TPS fertilizers was slower than from the positive control of triple superphosphate (TSP). Nevertheless, St-TPS featured comparable maize growth (i.e. plant height, leaf area, and biomass) and similar available P as TSP in sand after 42 days of cultivation. These results indicated that St-TPS slow P release could provide enough P for maize in sand, achieving a desirable agronomic efficiency while also reducing P runoff losses in highly permeable soils., (© 2022. The Author(s).)

In face of the alarming world population growth predictions and its threat to food security, the development of sustainable fertilizer alternatives is urgent. Moreover, fertilizer performance should be assessed not only in terms of yield but also in root system development, as it impacts soil fertility and crop productivity. Fertilizers containing a polysulfide matrix (PS) with dispersed struvite (St) were studied for S and P nutrition due to their controlled-release behavior. Soybean cultivation in a closed system with St/PS composites provided superior biomass compared to a reference of triple superphosphate (TSP) with ammonium sulfate (AS), with up to 3 and 10 times higher mass of shoots and roots, respectively. Root system architectural changes may explain these results, with a higher proliferation of second order lateral roots in response to struvite ongoing P delivery. The total root length was between 1,942 and 4,291 cm for plants under St/PS composites and only 982 cm with TSP/AS. While phosphorus uptake efficiency was similar in all fertilized treatments (11-14%), St/PS achieved a 22% sulfur uptake efficiency against only 8% from TSP/AS. Overall, the composites showed great potential as efficient slow-release fertilizers for enhanced soybean productivity., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Valle, Giroto, Guimarães, Nagel, Galinski, Cohnen, Jablonowski and Ribeiro.)

Biomass from perennial plants can be considered a carbon-neutral renewable resource. The tall wheatgrass hybrid Szarvasi-1 ( Agropyron elongatum , hereafter referred to as "Szarvasi") belongs to the perennial Poaceae representing a species, which can grow on marginal soils and produce large amounts of biomass. Several conventional and advanced pretreatment methods have been developed to enhance the saccharification efficiency of plant biomass. Advanced pretreatment methods, such as microwave-assisted pretreatment methods are faster and use less energy compared to conventional pretreatment methods. In this study, we investigated the potential of Szarvasi biomass as a biorefinery feedstock. For this purpose, the lignocellulosic structure of Szarvasi biomass was investigated in detail. In addition, microwave-assisted pretreatments were applied to Szarvasi biomass using different reagents including weak acids and alkali. The produced pulp, hydrolysates, and extracted lignin were quantitatively characterized. In particular, the alkali pretreatment significantly enhanced the saccharification efficiency of the pulp 16-fold compared to untreated biomass of Szarvasi. The acid pretreatment directly converted 25% of the cellulose into glucose without the need of enzymatic digestion. In addition, based on lignin compositional and lignin linkage analysis a lignin chemical model structure present in Szarvasi biomass could be established., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Jablonowski, Pauly and Dama.)

Nitrogen fertilization has been a critical factor for high crop productivity, where urea is currently the most used N source due to its high concentration and affordability. Nevertheless, urea fast solubilization leads to frequent losses and lower agronomic efficiency. The modification of urea structure by condensation with formaldehyde has been proposed to improve nutrient uptake by plants and to reduce environmental losses. Herein we show that the co-formulation with Zn strongly modifies the N release (in lab conditions) and, more important, the Zn source-ZnSO 4 or ZnO-has a critical role. Urea-formaldehyde (UF) served as a matrix for the zinc sources, and chemical characterizations revealed that Zn particles influenced the length of the polymeric chain formation. Release tests in an aqueous medium showed that the UF matrix favors ZnO release and, on the other hand, delays ZnSO 4 delivery. Soil incubation with the fertilizer composites proved the slow-release of N from UF, is ideal for optimizing nutritional efficiency. Our results indicated that the ZnO-UF system has beneficial effects for both nutrients, i.e., reduces N volatilization and increases Zn release.

Intensive agriculture and horticulture heavily rely on the input of fertilizers to sustain food (and feed) production. However, high carbon footprint and pollution are associated with the mining processes of P and K, and the artificial nitrogen fixation for the production of synthetic fertilizers. Organic fertilizers or recovered nutrients from different waste sources can be used to reduce the environmental impact of fertilizers. We tested two recovered nutrients with slow-release patterns as promising alternatives for synthetic fertilizers: struvite and a commercially available organic fertilizer. Using these fertilizers as a nitrogen source, we conducted a rhizotron experiment to test their effect on plant performance and nutrient recovery in lupine plants. Plant performance was not affected by the fertilizer applied; however, N recovery was higher from the organic fertilizer than from struvite. As root architecture is fundamental for plant productivity, variations in root structure and length as a result of soil nutrient availability driven by plant-bacteria interactions were compared showing also no differences between fertilizers. However, fertilized plants were considerably different in the root length and morphology compared with the no fertilized plants. Since the microbial community influences plant nitrogen availability, we characterized the root-associated microbial community structure and functionality. Analyses revealed that the fertilizer applied had a significant impact on the associations and functionality of the bacteria inhabiting the growing medium used. The type of fertilizer significantly influenced the interindividual dissimilarities in the most abundant genera between treatments. This means that different plant species have a distinct effect on modulating the associated microbial community, but in the case of lupine, the fertilizer had a bigger effect than the plant itself. These novel insights on interactions between recovered fertilizers, plant, and associated microbes can contribute to developing sustainable crop production systems., (Copyright © 2020 Robles-Aguilar, Grunert, Hernandez-Sanabria, Mysara, Meers, Boon and Jablonowski.)

Synthetic fertilizer production is associated with a high environmental footprint, as compounds typically dissolve rapidly leaching emissions to the atmosphere or surface waters. We tested two recovered nutrients with slower release patterns, as promising alternatives for synthetic fertilizers: struvite and a commercially available organic fertilizer. Using these fertilizers as nitrogen source, we conducted a rhizotron experiment to test their effect on plant performance and nutrient recovery in juvenile tomato plants. Plant performance was significantly improved when organic fertilizer was provided, promoting higher shoot biomass. Since the microbial community influences plant nitrogen availability, we characterized the root-associated microbial community structure and functionality. Analyses revealed distinct root microbial community structure when different fertilizers were supplied. However, plant presence significantly increased the similarity of the microbial community over time, regardless of fertilization. Additionally, the presence of the plant significantly reduced the potential ammonia oxidation rates, implying a possible role of the rhizosheath microbiome or nitrification inhibition by the plant. Our results indicate that nitrifying community members are impacted by the type of fertilizer used, while tomato plants influenced the potential ammonia-oxidizing activity of nitrogen-related rhizospheric microbial communities. These novel insights on interactions between recovered fertilizers, plant and associated microbes can contribute to develop sustainable crop production systems.

Improving fertility of marginal soils for the sustainable production of biomass is a strategy for reducing land use conflicts between food and energy crops. Digestates can be used as fertilizer and for soil amelioration. In order to promote plant growth and reduce potential adverse effects on roots because of broadcast digestate fertilization, we propose to apply local digestate depots placed into the rhizosphere. We grew Sida hermaphrodita in large mesocosms outdoors for three growing seasons and in rhizotrons in the greenhouse for 3 months both filled with marginal substrate, including multiple sampling dates. We compared digestate broadcast application with digestate depot fertilization and a mineral fertilizer control. We show that depot fertilization promotes a deep reaching root system of S. hermaphrodita seedlings followed by the formation of a dense root cluster around the depot-fertilized zone, resulting in a fivefold increased biomass yield. Temporal adverse effects on root growth were linked to high initial concentrations of ammonium and nitrite in the rhizosphere in either fertilizer application, followed by a high biomass increase after its microbial conversion to nitrate. We conclude that digestate depot fertilization can contribute to an improved cultivation of perennial energy-crops on marginal soils.

The cultivation of perennial biomass plants on marginal soils can serve as a sustainable alternative to conventional biomass production via annual cultures on fertile soils. Sida hermaphrodita is a promising species to be cultivated in an extensive cropping system on marginal soils in combination with organic fertilization using biogas digestates. In order to enrich this cropping system with nitrogen (N) and to increase overall soil fertility of the production system, we tested the potential of intercropping with leguminous species. In a 3-year outdoor mesocosm study, we intercropped established S. hermaphrodita plants with the perennial legume species Trifolium pratense, T. repens, Melilotus albus , and Medicago sativa individually to study their effects on plant biomass yields, soil N, and above ground biomass N. As a control for intercropping, we used a commercial grass mixture without N 2 -fixing species as well as a no-intercropping treatment. Results indicate that intercropping in all intercropping treatments increased the total biomass yield, however, grass species competed with S. hermaphrodita for N more strongly than legumes. Legumes enriched the cropping system with fixed atmospheric nitrogen (N 2 ) and legume facilitation effects varied between the legume species. T. pratense increased the biomass yield of S. hermaphrodita and increased the total biomass yield per mesocosm by 300%. Further, the total above ground biomass of S. hermaphrodita and T. pratense contained seven times more N compared to the mono-cropped S. hermaphrodita. T. repens also contributed highly to N facilitation. We conclude that intercropping of legumes, especially T. pratense and T. repens can stimulate the yield of S. hermaphrodita on marginal soils for sustainable plant biomass production.

Phosphorus (P) is a non-renewable resource, a major plant nutrient that is essential for modern agriculture. Currently, global food and feed production depends on P extracted from finite phosphate rock reserves mainly confined to a small number of countries. P limitation and its potential socio-economic impact may well exceed the potential effects of fossil fuel scarcity. The efficiency of P usage today barely reaches 20%, with the remaining 80% ending up in wastewater or in surface waters as runoff from fields. When recovered from wastewater, either chemically or biologically, P is often present in a form that does not meet specifications for agricultural use. As an alternative, the potential of microalgae to accumulate large quantities of P can be a way to direct this resource back to crop plants. Algae can acquire and store P through luxury uptake, and the P enriched algal biomass can be used as bio-fertilizer. Technology of large-scale algae cultivation has made tremendous progress in the last decades, stimulated by perspectives of obtaining third generation biofuels without requiring arable land or fresh water. These new cultivation technologies can be used for solar-driven recycling of P and other nutrients from wastewater into algae-based bio-fertilizers. In this paper, we review the specifics of P uptake from nutrient-rich waste streams, paying special attention to luxury uptake by microalgal cells and the potential application of P-enriched algal biomass to fertilize crop soils., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Priority effects occur when species that arrive first in a habitat significantly affect the establishment, growth, or reproduction of species arriving later and thus affect functioning of communities. However, we know little about how the timing of arrival of functionally different species may alter structure and function during assembly. Even less is known about how plant density might interact with initial assembly. In a greenhouse experiment legumes, grasses or forbs were sown a number of weeks before the other two plant functional types were sown (PFT) in combination with a sowing density treatment. Legumes, grasses or non-legume forbs were sown first at three different density levels followed by sowing of the remaining PFTs after three or six-weeks. We found that the order of arrival of different plant functional types had a much stronger influence on aboveground productivity than sowing density or interval between the sowing events. The sowing of legumes before the other PFTs produced the highest aboveground biomass. The larger sowing interval led to higher asymmetric competition, with highest dominance of the PFT sown first. It seems that legumes were better able to get a head-start and be productive before the later groups arrived, but that their traits allowed for better subsequent establishment of non-legume PFTs. Our study indicates that the manipulation of the order of arrival can create priority effects which favour functional groups of plants differently and thus induce different assembly routes and affect community composition and functioning.

The fate of the 14C-labeled herbicides ethidimuron (ETD), methabenzthiazuron (MBT), and the fungicide anilazine (ANI) in soils was evaluated after long-term aging (9-17 years) in field based lysimeters subject to crop rotation. Analysis of residual 14C activity in the soils revealed 19% (ETD soil; 0-10 cm depth), 35% (MBT soil; 0-30), and 43% (ANI soil; 0-30) of the total initially applied. Accelerated solvent extraction yielded 90% (ETD soil), 26% (MBT soil), and 41% (ANI soil) of residual pesticide 14C activity in the samples. LC-MS/MS analysis revealed the parent compounds ETD and MBT, accounting for 3% and 2% of applied active ingredient in the soil layer, as well as dihydroxy-anilazine as the primary ANI metabolite. The results for ETD and MBT were matching with values obtained from samples of a 12 year old field plot experiment. The data demonstrate the long-term persistence of these pesticides in soils based on outdoor trials., (Copyright © 2012. Published by Elsevier Ltd.)

To assess the potential occurrence of accelerated herbicide degradation in soils, the mineralization and persistence of (14)C-labeled and nonlabeled atrazine was evaluated over 3 months in two soils from Belgium (BS, atrazine-treated 1973-2008; BC, nontreated) and two soils from Germany (CK, atrazine-treated 1986-1989; CM, nontreated). Prior to the experiment, accelerated solvent extraction of bulk field soils revealed atrazine (8.3 and 15.2 μg kg(-1)) in BS and CK soils and a number of metabolites directly after field sampling, even in BC and CM soils without previous atrazine treatment, by means of LC-MS/MS analyses. For atrazine degradation studies, all soils were incubated under different moisture conditions (50% maximum soil water-holding capacity (WHC(max))/slurried conditions). At the end of the incubation, the (14)C-atrazine mineralization was high in BS soil (81 and 83%) and also unexpectedly high in BC soil (40 and 81%), at 50% WHC(max) and slurried conditions, respectively. In CK soil, the (14)C-atrazine mineralization was higher (10 and 6%) than in CM soil (4.7 and 2.7%), but was not stimulated by slurried conditions. The results revealed that atrazine application history dramatically influences its degradation and mineralization. For the incubation period, the amount of extractable atrazine, composed of residues from freshly applied atrazine and residues from former field applications, remained significantly greater (statistical significance = 99.5 and 99.95%) for BS and CK soils, respectively, than the amount of extractable atrazine in the bulk field soils. This suggests that (i) mostly freshly applied atrazine is accessible for a complex microbial community, (ii) the applied atrazine is not completely mineralized and remains extractable even in adapted soils, and (iii) the microbial atrazine-mineralizing capacity strongly depends on atrazine application history and appears to be conserved on long time scales after the last application.

The repeated use of a given pesticide may induce a selection of the soil microbial population, resulting in a rapid degradation of the respective xenobiotic. Patterns of atrazine degradation (mineralization, formation of metabolites and nonextractable residues (NER)) were evaluated in two Brazilian soils with a history of atrazine application. Results were compared with those obtained from soils that had no agricultural use or herbicide application history. (14)C-Atrazine mineralization in unsaturated treated soils was high. By the 85th day of incubation, 82% of the applied (14)C-atrazine was mineralized in the Rhodic Hapludox and 74% in the Xanthic Haplustox. Mineralization remained low in nontreated soils (

Twenty-two years after the last application of ring-14C-labeled atrazine at customary rate (1.7 kg ha(-1)) on an agriculturally used outdoor lysimeter, atrazine is still detectable by means of accelerated solvent extraction and LC-MS/MS analysis. Extractions of the 0-10 cm soil layer yielded 60% of the residual 14C-activity. The extracts contained atrazine (1.0 microg kg(-1)) and 2-hydroxy-atrazine (42.5 microg kg(-1)). Extractions of the material of the lowest layer 55-60 cm consisting of fine gravel yielded 93% of residual 14C-activity, of which 3.4 microg kg(-1) was detected as atrazine and 17.7 microg kg(-1) was 2-hydroxy-atrazine. The detection of atrazine in the lowest layer was of almost four times higher mass than in the upper soil layer. These findings highlight the fact that atrazine is unexpectedly persistent in soil. The overall persistence of atrazine in the environment might represent a potential risk for successive groundwater contamination by leaching even after 22 years of environmental exposure.

The long-term behavior of the herbicide atrazine and its metabolites in the environment is of continued interest in terms of risk assessment and soil quality monitoring. Aqueous desorption, detection, and quantification of atrazine and its metabolites from an agriculturally used soil were performed 22 years after the last atrazine application. A lysimeter soil containing long-term aged atrazine for >20 years was subdivided into 10 and 5 cm layers (at the lysimeter bottom: soil 0-50 and 50-55 cm; fine gravel 55-60 cm depth, implemented for drainage purposes) to identify the qualitative and quantitative differences of aged (14)C-labeled atrazine residues depending on the soil profile and chemico-physical conditions of the individual soil layers. Deionized water was used for nonexhaustive cold water shaking extraction of the soil. With increasing soil depth, the amount of previously applied (14)C activity decreased significantly from 8.8% to 0.7% at 55-60 cm depth whereas the percentage of desorbed (14)C residues in each soil layer increased from 2% to 6% of the total (14)C activity in the sample. The only metabolite detectable by means of LC-MS/MS was 2-hydroxyatrazine while most of the residual (14)C activity was bound to the soil and was not desorbed. The amount of desorbed 2-hydroxyatrazine decreased with increasing soil depth from 21% to 10% of the total desorbed (14)C residue fraction. The amount of (14)C residues in the soil layers correlated well with the carbon content in the soil and in the aqueous soil extracts ( p value = 0.99 and 0.97, respectively), which may provide evidence of the binding behavior of the aged atrazine residues on soil carbon. The lowest coarse layer (55-60 cm) showed increased residual (14)C activity leading to the assumption that most (14)C residues were leached from the soil column over time.

After 22 years of aging under natural conditions in an outdoor lysimeter the bioaccessibility of 14C-labeled atrazine soil residues to bacteria was tested. Entire soil samples as well as sand-sized, silt-sized, and clay-sized aggregates (>20, 20-2, and <2microm aggregate size, respectively) were investigated under slurried conditions. The mineralization of residual radioactivity in the outdoor lysimeter soil reached up to 4.5% of the total 14C-activity after 16 days, inoculated with Pseudomonas sp. strain ADP. The control samples without inoculated bacteria showed a mineralization maximum of only about 1% after 44 days of incubation. Mineralization increased in the clay-sized aggregates up to 6.2% of the total residual 14C-activity within 23 days. With decreasing soil aggregate sizes, residual 14C-activity increased per unit of weight, but only minor differences of the mineralization in the soil and soil size aggregates using mineral-media for incubation was observed. Using additional Na-citrate in the incubation, the extent of mineralization increased to 6.7% in soil after 23 days following incubation with Pseudomonas sp. strain ADP. These results show that long-term aged 14C-atrazine residues are still partly accessible to the atrazine degrading microorganism Pseudomonas sp. strain ADP.