Uni-Tübingen

The glyphosate puzzle

Scientists have long explained the presence of the herbicide glyphosphate in our water to have been washed from fields by strong rain. But Professor Carolin Huhn and her team have now discovered another important source of the substance.

In the summer of 2022, we wade with shovels and sampling tubes into rivers around Tübingen, crawl over wooden boards that have been laid over a drained lake and shovel sediment samples from its muddy bottom. We want to know what happens to glyphosate washed from fields by rain. Where do deposits form? We are surprised by the laboratory analysis: Some sediment samples contain as much glyphosate as farmland a few days after spraying the herbicide. 

Could the sediment in the lakebed form a reservoir for glyphosate? We want to drill deeper and extract further sediment cores. This time we take palaeontologist Annett Junginger with us for sampling. She also arranged dating the sediment cores. Now we are puzzled: We find glyphosate at high concentrations all over the core dating back to the 1960s – to a time when the substance was not even approved. Has it really seeped down that deep over the years?

We would not have expected so much glyphosate in these layers. The concentrations also don't match the sales figures for the herbicide in agriculture. It is equally astonishing that we can detect the most important degradation product of glyphosate, aminomethylphosphonic acid, AMPA for short, in much higher concentrations throughout the core. How do both substances get there? 

To understand the conundrum, I turn to the State Institute for the Environment in Baden-Württemberg and ask for data on glyphosate and AMPA, ideally from the neighboring Neckar. Monthly measurements have taken place at several points in the Neckar since 2004. This is impressive for glyphosate as it can only be detected by special analysis. 

When I receive the data, I see a clear seasonal trend over almost 20 years. Every year, glyphosate concentrations rise in April and May, reaching a maximum in late summer, and fall again from October. Concentrations are low in winter. But how can this keep on happening? The increase in spring could be expected from preparing the seedbeds around this time. But why do the concentrations go down again in autumn, during the main period of glyphosate use, when harvesting is over and only stubble remains in the fields? And why are they still measurable throughout the winter when herbicides are not sprayed? AMPA and glyphosate occur in almost the same ratio over the entire time, which is even more surprising for us chemists. This is hardly to be expected with the different rates of degradation of the two substances, which we had already demonstrated in our work on agricultural soils. Looking for answers, I see that the data from a measuring station in Mannheim are almost identical. 

I attend a workshop in Tübingen on the contamination of arable soils. It makes me think: What if the glyphosate and its degradation product AMPA are produced anew from another substance? A logical thought for a chemist. I now recall studies that mention another source for AMPA: Aminopolyphosphonates, which are used in detergents, among other things. Could these also be producing the glyphosate? They are chemically related. 

I write to my colleague Professor Stefan Haderlein from the Center for Applied Geoscience. His answer: “Perhaps far-fetched but not implausible.” Our glyphosate task force 
now has two investigative approaches: We continue looking at river water data and start our laboratory work. We receive a larger data set for Germany via contacts with authorities. It quickly becomes clear that the seasonal trend, which does not at all correspond to the use of glyphosate, occurs in almost all larger and smaller rivers. We see the same picture emerging from a huge dataset from France and later examine data from Luxembourg, Italy, the Netherlands, the United Kingdom and Sweden. Everywhere we look, it’s the same story, although the land use is so different. 


The seasonal trend arises from an entry point such as a sewage treatment plant. At some measuring points, there are even clear indications of households as a source.


Dr. Marc Schwientek, hydrologist at the University of Tübingen, who also helped us with the sampling, looks at the water data with his many years of experience and confirms:The seasonal trend arises from an entry point such as a sewage treatment plant. The entry remains approximately constant throughout the year and changes seasonally during the lower dilution in summer, when rivers carry less water due to evaporation. 

In meticulous detail, we now compare the patterns of glyphosate and AMPA with those of other agricultural herbicides, but also with wastewater markers such as pharmaceuticals. Carbamazepine, for example, is used all year round as an anti-epileptic and is poorly degraded in sewage treatment plants. It therefore clearly indicates the significance of wastewater inputs in a body of water.

And indeed: In Europe, the similarity of glyphosate and AMPA entry with sewage treatment plant substances is unmistakable. At some measuring points, there are even clear indications of households as a source.

Meanwhile back in the laboratory: Our suspicion falls on DTPMP, a phosphonate like glyphosate, with the long name diethylenetriamine pentakis(methylene phosphonic acid). Today, the substance is widely used in household detergents and cleaning agents and in industrial cleaning, but also in the textile and paper industry and in the production of drinking water. On paper, the chemistry is right – but can it be confirmed in the laboratory? Astonishingly little is known about phosphonates. After much research, we cautiously estimate the amount of DTPMP used in Germany per year at 1,500 to 2,500 tons. Like all phosphonates, DTPMP is hardly biodegradable. Photolysis by sunlight is often investigated to understand its transformation to other substances. We consider this option briefly, but reject it again, as the transformation process is too slow. We continue to experiment and find glyphosate formation from DTPMP for the first time in a reaction with manganese dioxide, which is a component of many minerals: Stefan Haderlein’s group has experience with phosphonates and they succeed in this proof. The first step has been taken: We have established a relationship between DTPMP and glyphosate in a reaction that can occur in nature. 

We chemists go back out into the field to a sewage treatment plant. We add DTPMP to sewage sludge and watch anxiously over a few days to see what happens. And indeed: Glyphosate and AMPA are produced in a relatively constant ratio, as we have also observed in the river water data. And not just in a single experiment, but in every single one. Although we only find small quantities, less than one percent, projections for the whole of Germany already yield relevant quantities. The results also show that it is not bacteria that break down DTPMP but chemical processes that are presumably triggered by manganese dioxide. Now we have significant proof and many pieces of the puzzle have been discovered and put into place. The bigger picture is now more visible and we will hopefully close the remaining gaps in the next few years. And we are curious to see how citizens, politicians and industry will react.

Professor Carolin Huhn and Professor Stefan Haderlein first published the solution to the glyphosate puzzle on a preprint server in the summer of 2024 so that authorities could quickly access the results. In the meantime, the first article has also been reviewed by independent researchers and published in the journal Water Research.

Text: Carolin Huhn


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