Fate of the herbicide glyphosate and its metabolite AMPA in soils and their transfer to surface waters: A multi-scale approach in the Lavaux vineyards, western Switzerland

The use of herbicides in agriculture may lead to environmental problems, such as surface water pollution, with a potential risk for aquatic organisms. The herbicide glyphosate is the most used active ingredient in the world and in Switzerland. In the Lavaux vineyards it is nearly the only molecule applied. This work aimed at studying its fate in soils and its transfer to surface waters, using a multi-scale approach: from molecular (10-9 m) and microscopic scales (10-6 m), to macroscopic (m) and landscape ones (103 m). First of all, an analytical method was developed for the trace level quantification of this widely used herbicide and its main by-product, aminomethylphosphonic acid (AMPA). Due to their polar nature, their derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) was done prior to their concentration and purification by solid phase extraction. They were then analyzed by ultra performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The method was tested in different aqueous matrices with spiking tests and validated for the matrix effect correction in relevant environmental samples. Calibration curves established between 10 and 1000ng/l showed r2 values above 0.989, mean recoveries varied between 86 and 133% and limits of detection and quantification of the method were as low as 5 and 10ng/l respectively. At the parcel scale, two parcels of the Lavaux vineyard area, located near the Lutrive River at 6km to the east of Lausanne, were monitored to assess to which extent glyphosate and AMPA were retained in the soil or exported to surface waters. They were equipped at their bottom with porous ceramic cups and runoff collectors, which allowed retrieving water samples for the growing seasons 2010 and 2011. Results revealed that the mobility of glyphosate and AMPA in the unsaturated zone was likely driven by the precipitation regime and the soil characteristics, such as slope, porosity structure and layer permeability discrepancy. Elevated glyphosate and AMPA concentrations were measured at 60 and 80 cm depth at parcel bottoms, suggesting their infiltration in the upper parts of the parcels and the presence of preferential flow in the studied parcels. Indeed, the succession of rainy days induced the gradual saturation of the soil porosity, leading to rapid infiltration through macropores, as well as surface runoff formation. Furthermore, the presence of more impervious weathered marls at 100 cm depth induced throughflows, the importance of which for the lateral transport of the herbicide molecules was determined by the slope steepness. Important rainfall events (>10 mm/day) were clearly exporting molecules from the soil top layer, as indicated by important concentrations in runoff samples. A mass balance showed that total loss (10-20%) mainly occurred through surface runoff (96%) and, to a minor extent, by throughflows in soils (4%), with subsequent exfiltration to surface waters. Observations made in the Lutrive River revealed interesting details of glyphosate and AMPA dynamics in urbanized landscapes, such as the Lavaux vineyards. Indeed, besides their physical and chemical properties, herbicide dynamics at the catchment level strongly depend on application rates, precipitation regime, land use and also on the presence of drains or constructed channels. Elevated concentrations, up to 4970 ng/l, observed just after the application, confirmed the diffuse export of these compounds from the vineyard area by surface runoff during main rain events. From April to September 2011, a total load of 7.1 kg was calculated, with 85% coming from vineyards and minor urban sources and 15% from arable crops. Small vineyard surfaces could generate high concentrations of herbicides and contribute considerably to the total load calculated at the outlet, due to their steep slopes (~10%). The extrapolated total amount transferred yearly from the Lavaux vineyards to the Lake of Geneva was of 190kg. At the molecular scale, the possible involvement of dissolved organic matter (DOM) in glyphosate and copper transport was studied using UV/Vis fluorescence spectroscopy. Combined with parallel factor (PARAFAC) analysis, this technique allowed characterizing DOM of soil and surface water samples from the studied vineyard area. Glyphosate concentrations were linked to the fulvic-like spectroscopic signature of DOM in soil water samples, as well as to copper, suggesting the formation of ternary complexes. In surface water samples, its concentrations were also correlated to copper ones, but not in a significant way to the fulvic-like signature. Quenching experiments with standards confirmed field tendencies in the laboratory, with a stronger decrease in fluorescence intensity for fulvic-like fluorophore than for more aromatic ones. Lastly, based on maximum concentrations measured in the river, an environmental risk for these compounds was assessed, using laboratory tests and ecotoxicity data from the literature. In our case and with the methodology applied, the risk towards aquatic species was found negligible (RF<1).

Reconstruction of the recent history of a large deep prealpine lake (Lake Bourget, France) using subfossil chironomids, diatoms, and organic matter analysis: towards the definition of a lake-specific reference state

This paper presents the recent history of a large prealpine lake (Lake Bourget) using chironomids, diatoms and organic matter analysis, and deals with the ability of paleolimnological approach to define an ecological reference state for the lake in the sense of the European Framework Directive. The study at low resolution of subfossil chironomids in a 4-m-long core shows the remarkable stability over the last 2.5 kyrs of the profundal community dominated by a Micropsectra-association until the beginning of the twentieth century, when oxyphilous taxa disappeared. Focusing on this key recent period, a high resolution and multiproxy study of two short cores reveals a progressive evolution of the lake's ecological state. Until AD 1880, Lake Bourget showed low organic matter content in the deep sediments (TOC less than 1%) and a well-oxygenated hypolimnion that allowed the development of a profundal oxyphilous chironomid fauna (Micropsectra-association). Diatom communities were characteristic of oligotrophic conditions. Around AD 1880, a slight increase in the TOC was the first sign of changes in lake conditions. This was followed by a first limited decline in oligotrophic diatom taxa and the disappearance of two oxyphilous chironomid taxa at the beginning of the twentieth century. The 1940s were a major turning point in recent lake history. Diatom assemblages and accumulation of well preserved planktonic organic matter in the sediment provide evidence of strong eutrophication. The absence of profundal chironomid communities reveals permanent hypolimnetic anoxia. From AD 1995 to 2006, the diatom assemblages suggest a reduction in nutrients, and a return to mesotrophic conditions, a result of improved wastewater management. However, no change in hypolimnion benthic conditions has been shown by either the organic matter or the subfossil chironomid profundal community. Our results emphasize the relevance of the paleolimnological approach for the assessment of reference conditions for modern lakes. Before AD 1900, the profundal Micropsectra-association and the Cyclotella dominated diatom community can be considered as the Lake Bourget reference community, which reflects the reference ecological state of the lake.

Field Instrumentation, Testing, and Long-Term Monitoring of High-Mast Lighting Tower No. 1 at the I-35/US 18 Interchange Near Clear Lake in the State of Iowa Phase 3, TR-562, 2009

The current study was initiated to quantify the stresses induced in critical details on the reinforcing jacket and the tower itself through the use of field instrumentation, load testing, and long-term monitoring. Strain gages were installed on the both the tower and the reinforcing jacket. Additional strain gages were installed on two anchor rods. Tests were conducted with and without the reinforcing jacket installed. Data were collected from all strain gages during static load testing and were used to study the stress distribution of the tower caused by known loads, both with and without the reinforcing jacket. The tower was tested dynamically by first applying a static load, and then quickly releasing the load causing the tower to vibrate freely. Furthermore, the tower was monitored over a period of over 1 year to obtain stress range histograms at the critical details to be used for a fatigue evaluation. Also during the long-term monitoring, triggered time-history data were recorded to study the wind loading phenomena that excite the tower.

Evidence for morphological and adaptive genetic divergence between lake and stream habitats in European minnows (Phoxinus phoxinus, Cyprinidae).

Natural selection drives local adaptation, potentially even at small temporal and spatial scales. As a result, adaptive genetic and phenotypic divergence can occur among populations living in different habitats. We investigated patterns of differentiation between contrasting lake and stream habitats in the cyprinid fish European minnow (Phoxinus phoxinus) at both the morphological and genomic levels using geometric morphometrics and AFLP markers, respectively. We also used a spatial correlative approach to identify AFLP loci associated with environmental variables representing potential selective forces responsible for adaptation to divergent habitats. Our results identified different morphologies between lakes and streams, with lake fish presenting a deeper body and caudal peduncle compared to stream fish. Body shape variation conformed to a priori predictions concerning biomechanics and swimming performance in lakes vs. streams. Moreover, morphological differentiation was found to be associated with several environmental variables, which could impose selection on body and caudal peduncle shape. We found adaptive genetic divergence between these contrasting habitats in the form of 'outlier' loci (2.9%) whose genetic divergence exceeded neutral expectations. We also detected additional loci (6.6%) not associated with habitat type (lake vs. stream), but contributing to genetic divergence between populations. Specific environmental variables related to trophic dynamics, landscape topography and geography were associated with several neutral and outlier loci. These results provide new insights into the morphological divergence and genetic basis of adaptation to differentiated habitats.

Climatic and anthropogenic influence on the stable isotope record from bulk carbonates and ostracodes in Lake Neuchatel, Switzerland, during the last two millennia

Lake Neuchatel is a medium sized, hard-water lake, lacking varved sediments, situated in the western Swiss Lowlands at the foot of the Jura Mountains. Stable isotope data (delta(18)O and delta(13)C) from both bulk carbonate and ostracode calcite in an 81 cm long, radiocarbon-dated sediment core represent the last 1500 years of Lake Neuchatel's environmental history. Comparison between this isotopic and other palaeolimnologic data (mineralogical, geochemical, palynological, etc.) helps to differentiate between anthropogenic and natural factors most recently affecting the lake. An increase in lacustrine productivity (450-650AD ca), inferred from the positive trend in delta(13)C values of bulk carbonate, is related to medieval forest clearances and the associated nutrient budget changes. A negative trend in both the bulk carbonate and ostracode calcite delta(18)O values between approximately 1300 and 1500AD, is tentatively interpreted as due to a cooling in mean air temperature at the transition from the Medieval Warm Period to the Little Ice Age. Negative trends in bulk carbonate delta(18)O and delta(13)C values through the uppermost sediments, which have no equivalent in ostracode calcite isotopic values, are concomitant with the recent onset of eutrophication in the lake. Isotopic disequilibrium during calcite precipitation, probably due to kinetic factors in periods of high productivity is postulated as the mechanism to explain the associated negative isotopic trends, although the effect of a shift of the calcite precipitation towards the warmer months cannot be excluded.

Lake Restoration 2007 Report and 2008 Plan, December 28, 2007

The Department of Natural Resources (IDNR) Lake Restoration Program focuses on restoring impaired lakes to improve the quality of life for Iowans. Communities are rallying around their water resources as they seek population growth and economic success. Communities of the Iowa Great Lakes Region, Storm Lake, Crystal Lake, Creston and Clear Lake are obvious examples, but other communities including Lake View and Brighton are identifying the importance of lakes for their futures as well. The distribution and nature of Vision Iowa grants, Community Attraction and Tourism grants, and now, Great Places, all further emphasize the importance of water to community, quality of life and economic growth.

Lake Restoration 2008 Report and 2009 Plan, December 30, 2008

The Department of Natural Resources (IDNR) Lake Restoration Program focuses on restoring impaired lakes to improve the quality of life for Iowans. Communities are rallying around their water resources as they seek population growth and economic success. Communities of the Iowa Great Lakes Region, Storm Lake, Crystal Lake, Creston and Clear Lake are obvious examples, but other communities including Lake View and Brighton are identifying the importance of lakes for their futures as well. The distribution and nature of Vision Iowa grants, Community Attraction and Tourism grants, and now, Great Places, all further emphasize the importance of water to community, quality of life and economic growth.

Lake Restoration 2009 Report and 2010 Plan, December 30, 2009

The Department of Natural Resources (IDNR) Lake Restoration Program focuses on restoring impaired lakes to improve the quality of life for Iowans. Communities are rallying around their water resources as they seek population growth and economic success. Communities of the Iowa Great Lakes Region, Storm Lake, Crystal Lake, Creston and Clear Lake are obvious examples, but other communities including Lake View and Brighton are identifying the importance of lakes for their futures as well. The distribution and nature of Vision Iowa grants, Community Attraction and Tourism grants, and now, Great Places, all further emphasize the importance of water to community, quality of life and economic growth.

Lake Restoration 2010 Report and 2011 Plan, December 30, 2010

The Department of Natural Resources (IDNR) Lake Restoration Program focuses on restoring impaired lakes to improve the quality of life for Iowans. Communities are rallying around their water resources as they seek population growth and economic success. Communities of the Iowa Great Lakes Region, Storm Lake, Crystal Lake, Creston and Clear Lake are obvious examples, but other communities including Lake View and Brighton are identifying the importance of lakes for their futures as well. The distribution and nature of Vision Iowa grants, Community Attraction and Tourism grants, and now, Great Places, all further emphasize the importance of water to community, quality of life and economic growth.

Lake Restoration 2011 Report and 2012 Plan, December 30, 2011

The Department of Natural Resources (IDNR) Lake Restoration Program focuses on restoring impaired lakes to improve the quality of life for Iowans. Communities are rallying around their water resources as they seek population growth and economic success. Communities of the Iowa Great Lakes Region, Storm Lake, Crystal Lake, Creston and Clear Lake are obvious examples, but other communities including Lake View and Brighton are identifying the importance of lakes for their futures as well. The distribution and nature of Vision Iowa grants, Community Attraction and Tourism grants, and now, Great Places, all further emphasize the importance of water to community, quality of life and economic growth.

Lake Restoration 2012 Report and 2013 Plan, December 31, 2012

The Department of Natural Resources (IDNR) Lake Restoration Program focuses on restoring impaired lakes to improve the quality of life for Iowans. Communities are rallying around their water resources as they seek population growth and economic success. Communities of the Iowa Great Lakes Region, Storm Lake, Crystal Lake, Creston and Clear Lake are obvious examples, but other communities including Lake View and Brighton are identifying the importance of lakes for their futures as well. The distribution and nature of Vision Iowa grants, Community Attraction and Tourism grants, and now, Great Places, all further emphasize the importance of water to community, quality of life and economic growth.

Lake Restoration 2013 Report and 2014 Plan, December 31, 2013

The Department of Natural Resources (IDNR) Lake Restoration Program focuses on restoring impaired lakes to improve the quality of life for Iowans. Communities are rallying around their water resources as they seek population growth and economic success. Communities of the Iowa Great Lakes Region, Storm Lake, Crystal Lake, Creston and Clear Lake are obvious examples, but other communities including Lake View and Brighton are identifying the importance of lakes for their futures as well. The distribution and nature of Vision Iowa grants, Community Attraction and Tourism grants, and now, Great Places, all further emphasize the importance of water to community, quality of life and economic growth.

Lake Restoration 2014 Report and 2015 Plan, December 31, 2014

The Department of Natural Resources (IDNR) Lake Restoration Program focuses on restoring impaired lakes to improve the quality of life for Iowans. Communities are rallying around their water resources as they seek population growth and economic success. Communities of the Iowa Great Lakes Region, Storm Lake, Crystal Lake, Creston and Clear Lake are obvious examples, but other communities including Lake View and Brighton are identifying the importance of lakes for their futures as well. The distribution and nature of Vision Iowa grants, Community Attraction and Tourism grants, and now, Great Places, all further emphasize the importance of water to community, quality of life and economic growth.

1102-001 Twelve Mile Lake Final Report

Twelve-Mile Lake is an 800-acre man-made lake in central Union County. The watershed has 13,964 land acres that are used by farmers for row crops and pasture. This lake is used as a water supply source for the City of Creston and the Southern Iowa Rural Water Association. In total approximately 40,000 people are affected by this project. Developed over 20 years ago, the lake and fishery was renovated and restocked and much of the shoreline was riprapped about six years ago. During its history, extensive watershed efforts have been ongoing. However, as farmland for cropland has become more valuable and demand has increased, hilly land once used for dairy farming, grazing, and CRP has been put into row crop production. Consequently, sediment loss has become an increasing issue for farmers, conservation professionals, and the Creston Waterworks Department, which owns the water treatment facility at the lake. In 2011, the Creston Water Board received a WIRB grant to implement a sedimentation structure at the north end of the main channel flowing into the lake. The WIRB funds were used for land acquisition, with the IDNR actually constructing the facility. This report depicts work performed as part of the WIRB project.