Benedikt Wimmer's research while affiliated with University of Tuebingen and other places

Glyphosate is the world's most widely applied herbicide. Despite its extensive and heavy use in agriculture and forestry, the microbial key players involved in glyphosate breakdown and the impact of this compound on the soil microbiota including fungi is not fully understood. Here, we used microcosm experiments to determine the impact of glyphosate application on the microbial community structure and abundance of four different agricultural soils from the Ammer valley, Germany, with a history of glyphosate application. We identified putative glyphosate degraders that could be active under in-situ conditions. Glyphosate was applied to the soils in a single dose of 15 mg⋅kg − 1 , which were incubated in the dark with 60 % water-filled pore space at 20 • C for 56 days. Soil samples were taken on the day of glyphosate addition (day 0) and after 7, 28 and 56 days. Capillary electrophoresis-mass spectrometry was used to quantify glyphosate and its major transformation product ami-nomethylphosphonic acid. Changes in the microbial community structure and abundance were evaluated using 16S rRNA gene or internal transcribed spacer region amplicon sequencing and qPCR. Our findings demonstrate that glyphosate was rapidly degraded in the four soils, with 60-85 % of the applied glyphosate disappearing within 7 days. However, the observed impact of glyphosate application on the microbial community composition was minimal and, notably, there was no significant time-dependent glyphosate effect at 7 days across all four soils. This suggests that glyphosate degradation in soil might be a concerted effort by a wide microbial network or it might be occurring co-metabolically. In addition, the sorption/desorption dynamics of glyphosate with the soil matrix can heavily influence its bioavailability, further reasoning the subtle effects observed on the microbial community structure.

The most widely used herbicide glyphosate contaminates surface waters around the globe. Being toxic to aquatic organisms and a possible carcinogenic, mitigation strategies attempt to reduce river contamination, but their impact is not evaluated. Investigating long-term time series, we discovered that – in contrast to the USA – glyphosate river water concentration patterns in Europe contradict a dominant input from herbicide application. Our large meta-analysis clearly shows that for decades, the main source of glyphosate has been municipal wastewater, visible in the close correlation to concentration patterns of, e.g. , pharmaceuticals, rather high and constant loads all over the year and failure of mitigation strategies. We suspect that glyphosate enters European rivers as a transformation product of aminopolyphosphonates, which are used in European but not U.S. detergents.

The most widely used herbicide glyphosate contaminates surface waters around the globe. Being toxic to aquatic organisms and a possible carcinogenic, mitigation strategies attempt to reduce river contamination, but their impact is not evaluated. Investigating long-term time series, we discovered that – in contrast to the USA – glyphosate river water concentration patterns in Europe contradict a dominant input from herbicide application. Our large meta-analysis clearly shows that for decades, the main source of glyphosate has been municipal wastewater, visible in the close correlation to concentration patterns of, e.g. , pharmaceuticals, rather high and constant loads all over the year and failure of mitigation strategies. We suspect that glyphosate enters European rivers as a transformation product of aminopolyphosphonates, which are used in European but not U.S. detergents.

The most widely used herbicide glyphosate contaminates surface waters around the globe. Both agriculture and urban applications are discussed as sources for glyphosate. To better delineate these sources, we investigated long-term time series of concentrations of glyphosate and its main transformation product aminomethylphosphonic acid (AMPA) in a large meta-analysis of about 100 sites in the USA and Europe. The U.S. data reveal pulses of glyphosate and AMPA when the discharge of the river is high, likely indicating mobilization by rain after herbicide application. In contrast, European concentration patterns of glyphosate and AMPA show a typical cyclic-seasonal component in their concentration patterns, correlating with patterns of wastewater markers such as pharmaceuticals, which is consistent with the frequent detection of these compounds in wastewater treatment plants. Our large meta-analysis clearly shows that for decades, municipal wastewater was a very important source of glyphosate has been municipal wastewater. In addition, European river water data show rather high and constant basic mass fluxes of glyphosate all over the year, not expected from herbicide application. From our meta-analysis, we define criteria for a source of glyphosate, which was hidden so far. Details from the meta-analysis and the knowledge that AMPA is a known transformation product of aminopolyphohsphonates let us hypothesize that also these antiscalants are an important source for glyphosate in Europe, where these compounds are used in detergents.

Residual concentrations of glyphosate and its main transformation product aminomethylphosphonic acid (AMPA) are often observed in soils. The factors controlling their biodegradation are currently not well understood. We analyzed sorption‐limited biodegradation of glyphosate and AMPA in soil with a set of microcosm experiments. A mechanistic model that accounts for equilibrium and kinetic sorption facilitated interpretation of the experimental results. Both compounds showed a biphasic dissipation with an initial fast (up to Days 7–10) and subsequent slower transformation rate, pointing to sorption‐limited degradation. Glyphosate transformation was well described by considering only equilibrium sorption. Model simulations suggested that only 0.02–0.13% of total glyphosate was present in the soil solution and thus bioavailable. Glyphosate transformation was rapid in solution (time required for 50 % dissipation of the total initially added chemical [DT50] = 3.9 min), and, despite strong equilibrium sorption, total glyphosate in soil dissipated quickly (DT50 = 2.4 d). Aminomethylphosphonic acid dissipation kinetics could only be described when considering both equilibrium and kinetic sorption. In comparison to glyphosate, the model simulations showed that a higher proportion of total AMPA was dissolved and directly bioavailable (0.27–3.32%), but biodegradation of dissolved AMPA was slower (DT50 = 1.9 h). The model‐based data interpretation suggests that kinetic sorption strongly reduces AMPA bioavailability, leading to increased AMPA persistence in soil (DT50 = 12 d). Thus, strong sorption combined with rapid degradation points to low risks of glyphosate leaching by vertical transport through soil in the absence of preferential flow. Ecotoxicological effects on soil microorganisms might be reduced. In contrast, AMPA persists, rendering these risks more likely.

Glyphosate (N-phosphonomethylglycine; GLP) and its main metabolite AMPA (aminomethylphosphonic acid), are frequently detected in relatively high concentrations in European agricultural topsoils. Glyphosate has a high sorption affinity, yet it can be detected occasionally in groundwater. We hypothesized that shrinkage cracks occurring after dry periods could facilitate GLP transport to greater depths where subsoil conditions slow further microbial degradation. To test this hypothesis, we simulated a heavy rainfall event (HRE) on a clay-rich arable soil. We applied 2.1 kg ha⁻¹ of 100% ¹³C3, ¹⁵N-labeled GLP one day before the simulated rainfall event. Microbial degradation of translocated GLP over a 21-day period was assessed by quantifying ¹³C incorporation into phospholipid fatty acids. Microbial degradation potential and activity were determined by quantifying the abundance and expression of functional genes involved in the two known degradation pathways of GLP; to AMPA (goxA) or sarcosine (sarc). We confirmed that goxA transcripts were elevated in the range of 4.23 x 10⁵ copy numbers g⁻¹ soil only one day after application. The increase in AMPA associated with a rise in goxA transcripts and goxA-harboring microorganisms indicated that the degradation pathway to AMPA dominated. Based on ¹³C-enrichment 3 h after the HRE, fungi appeared to initiate glyphosate degradation. At later time points, Gram⁺-bacteria proved to be the main degraders due to their higher ¹³C-incorporation. Once GLP reached the subsoil, degradation continued but more slowly. By comparing GLP distribution and its microbial degradation in macropores and in the bulk soil, we demonstrated different time- and depth-dependent GLP degradation dynamics in macropores. This indicates the need for field studies in which soil properties relevant to GLP degradation are related to limiting environmental conditions, providing a realistic assessment of GLP fate in soils.

We present field data on the effects of heavy rainfall after drought on the mobility of glyphosate and redox conditions in a clayey floodplain soil. By applying glyphosate together with deuterated water as conservative tracer in combination with time resolved in situ redox potential measurements, the spatial and temporal patterns of water infiltration and pesticide transport as well as the concomitant changes of the redox conditions were revealed. Our findings demonstrate that shrinkage cracks in dry soils can serve as effective transport paths for atmospheric oxygen, water and glyphosate. The rain intensity of a typical summer storm event (approx. 25 mm within one hour) was sufficient to translocate deuterated water and glyphosate to the subsoil (50 cm) within 2 hours. Soil wetting induced partial closure of the shrinkage cracks and stimulated microbial activity resulting in pronounced dynamics of in situ soil redox conditions. Redox potentials in 40 to 50 cm depth dropped permanently to strongly reducing conditions within hours to days but fluctuated between reducing and oxidizing conditions in 10 to 30 cm depth. Our findings highlight the close link between the presence of macropores (shrinkage cracks), heavy rainfall after drought, redox dynamics and pesticide translocation to the subsoil and thus call for further studies addressing the effects of dynamic redox conditions as a limiting factor for glyphosate degradation.

BACKGROUND Analytical constraints complicate environmental monitoring campaigns of the herbicide glyphosate and its major degradation product aminomethylphosphonic acid (AMPA): their strong sorption to soil minerals requires harsh extraction conditions. Coextracted matrix compounds impair downstream analysis and must be removed before analysis. RESULTS A new extraction method combined with subsequent capillary electrophoresis‐mass spectrometry for derivatization‐free analysis of glyphosate and AMPA in soil and sediment was developed and applied to a suite of environmental samples. It was compared to three extraction methods from literature. We show that no extraction medium reaches 100% recovery. The new phosphate‐supported alkaline extraction method revealed (1) high recoveries of 70–90% for soils and aquatic sediments, (2) limits of detections below 20 μg kg⁻¹, and (3) a high robustness, because impairing matrix components (trivalent cations and humic acids) were precipitated prior to the analysis. Soil and sediment samples collected around Tübingen, Germany, revealed maximum glyphosate and AMPA residues of 80 and 2100 μg kg⁻¹, respectively, with residues observed along a core of lake sediments. Glyphosate and/or AMPA were found in 40% of arable soils and 57% of aquatic sediment samples. CONCLUSION In this work, we discuss soil parameters that influence (de)sorption and thus extraction. From our results we conclude that residues of glyphosate in environmental samples are easily underestimated. With its possible high throughput, the method presented here can resolve current limitations in monitoring campaigns of glyphosate by addressing soil and aquatic sediment samples with critical sorption characteristics.

In this study, we developed and validated a CE-TOF-MS method for the quantification of glyphosate (N-(phosphonomethyl)glycine) and its major degradation product aminomethylphosphonic acid (AMPA) in different samples including beer, media from toxicological analysis with Daphnia magna, and sorption experiments. Using a background electrolyte (BGE) of very low pH, where glyphosate is still negatively charged but many matrix components become neutral or protonated, a very high separation selectivity was reached. The presence of inorganic salts in the sample was advantageous with regard to preconcentration via transient isotachophoresis. The advantages of our new method are the following: no derivatization is needed, high separation selectivity and thus matrix tolerance, speed of analysis, limits of detection suitable for many applications in food and environmental science, negligible disturbance by metal chelation. LODs for glyphosate were < 5 μg/L for both aqueous and beer samples, the linear range in aqueous samples was 5–3000 μg/L, for beer samples 10–3000 μg/L. For AMPA, LODs were 3.3 and 30.6 μg/L, and the linear range 10–3000 μg/L and 50–3000 μg/L, for aqueous and beer samples, respectively. Recoveries in beer samples for glyphosate were 94.3–110.7% and for AMPA 80.2–100.4%. We analyzed 12 German and 2 Danish beer samples. Quantification of glyphosate and AMPA was possible using isotopically labeled standards without enrichment, purification, or dilution, only degassing and filtration were required for sample preparation. Finally, we demonstrate the applicability of the method for other strong acids, relevant in food and environmental sciences such as N-acetyl glyphosate, N-acetyl AMPA (present in some glyphosate resistant crop), trifluoroacetic acid, 2-methyl-4-chlorophenoxyacetic acid, glufosinate and its degradation product 3-(methylphosphinico)propionic acid, oxamic acid, and others.