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).

Performance Evaluation of Concrete Pavement Granular Subbase - Pavement Surface Condition Evaluation, TR-554, 2008

This research project covered a wide range of activities that allowed researchers to understand the relationship between stability, pavement distress, and recycled portland cement concrete (RPCC) subbase aggregate materials. Detailed laboratory and field tests, including pavement distress surveys, were conducted at 26 sites in Iowa. Findings show that specific gravities of RPCC are lower than those of crushed limestone. RPCC aggregate material varies from poorly or well-graded sand to gravel. A modified Micro-Deval test procedure showed that abrasion losses of virgin aggregate materials were within the maximum Micro-Deval abrasion loss of 30% recommended by ASTM D6028-06. Micro-Deval abrasion loss of RPCC aggregate materials, however, was much higher than that of virgin materials and exceeded 30% loss. Modulus of elasticity of RPCC subbase materials is high but variable. RPCC subbase layers normally have low permeability. The pavement surfaces for both virgin and RPCC subbase across Iowa were evaluated to fulfill the objectives of this study related to field evaluation. Visual distress surveys were conducted to gather the detailed current pavement condition information including the type, extent, and severity of the pavement distresses. The historical pavement condition information for the surveyed field sections was extracted from the Iowa DOT's Pavement Management Information System (PMIS). The current surface condition of existing field pavements with RPCC subbase was compared with the virgin aggregate subbase sections using two different approaches. The changes in pavement condition indices (PCI and IRI) with time for both types of pavements (subbases) were compared.

Hydro-Surface Preparation and Coating for Painted Structural Steel, TR-407, 1999

Cities and counties in Iowa have more than 8,890 steel bridges, most of which are painted with red lead paint. The Iowa Department of Transportation (Iowa DOT) maintains less than 35 bridges coated with red lead paint, including seven of the large border bridges over the Mississippi and Missouri Rivers. Because of the federal and state regulations for bridge painting, many governmental agencies have opted not to repaint, or otherwise maintain, lead paint coatings. Consequently, the paint condition on many of these bridges is poor, and some bridges are experiencing severe rusting of structural members. This research project was developed with two objectives: 1) to evaluate the effectiveness of preparing the structural steel surface of a bridge with high pressure water jetting instead of abrasive blasting and 2) to coat the structural steel surface with a moisture-cured polyurethane paint under different surface preparation conditions.

Identification of Laboratory Techniques to Optimize Superpave HMA Surface Friction Characteristics, TR-450, 2010

Wet pavement friction is known to be one of the most important roadway safety parameters. In this research, frictional properties of flexible (asphalt) pavements were investigated. As a part of this study, a laboratory device to polish asphalt specimens was refined and a procedure to evaluate mixture frictional properties was proposed. Following this procedure, 46 different Superpave mixtures, one stone matrix asphalt (SMA) mixture and one porous friction course (PFC) mixture were tested. In addition, 23 different asphalt and two concrete field sections were also tested for friction and noise. The results of both field and laboratory measurements were used to develop an International Friction Index (IFI)-based protocol for measurement of the frictional characteristics of asphalt pavements for laboratory friction measurements. Based on the results of the study, it appears the content of high friction aggregate should be 20% or more of the total aggregate blend when used with other, polish susceptible coarse aggregates; the frictional properties increased substantially as the friction aggregate content increased above 20%. Both steel slag and quartzite were found to improve the frictional properties of the blend, though steel slag had a lower polishing rate. In general, mixes containing soft limestone demonstrated lower friction values than comparable mixes with hard limestone or dolomite. Larger nominal maximum aggregate size mixes had better overall frictional performance than smaller sized mixes. In addition, mixes with higher fineness moduli generally had higher macrotexture and friction.

Covalent cell surface functionalization of human fetal osteoblasts for tissue engineering.

The chemical functionalization of cell-surface proteins of human primary fetal bone cells with hydrophilic bioorthogonal intermediates was investigated. Toward this goal, chemical pathways were developed for click reaction-mediated coupling of alkyne derivatives with cellular azido-expressing proteins. The incorporation via a tetraethylene glycol linker of a dipeptide and a reporter biotin allowed the proof of concept for the introduction of cell-specific peptide ligands and to follow the reaction in living cells. Tuning the conditions of the click reaction resulted in chemical functionalization of living human fetal osteoblasts with excellent cell survival.

Low-Cost Rural Surface Alternatives: Demonstration Project, TR-664, 2015

The goals of this project were to implement several stabilization methods for preventing or mitigating freeze-thaw damage to granular surfaced roads and identify the most effective and economical methods for the soil and climate conditions of Iowa. Several methods and technologies identified as potentially suitable for Iowa were selected from an extensive analysis of existing literature provided with Iowa Highway Research Board (IHRB) Project TR-632. Using the selected methods, demonstration sections were constructed in Hamilton County on a heavily traveled two-mile section of granular surfaced road that required frequent maintenance during previous thawing periods. Construction procedures and costs of the demonstration sections were documented, and subsequent maintenance requirements were tabulated through two seasonal freeze-thaw periods. Extensive laboratory and field tests were performed prior to construction, as well as before and after the two seasonal freeze-thaw periods, to monitor the performance of the demonstration sections. A weather station was installed at the project site and temperature sensors were embedded in the subgrade to monitor ground temperatures up to a depth of 5 ft and determine the duration and depths of ground freezing and thawing. An economic analysis was performed using the documented construction and maintenance costs, and the estimated cumulative costs per square yard were projected over a 20-year timeframe to determine break-even periods relative to the cost of continuing current maintenance practices. Overall, the sections with biaxial geogrid or macadam base courses had the best observed freeze-thaw performance in this study. These two stabilization methods have larger initial costs and longer break-even periods than aggregate columns, but counties should also weigh the benefits of improved ride quality and savings that these solutions can provide as excellent foundations for future paving or surface upgrades.

Assessment of diesel exhaust particulate exposure and surface characteristics in association with levels of oxidative stress biomarkers

Exposure to PM10 and PM2.5 (particulate matter with aerodynamic diameter smaller than 10 μm and 2.5 μm, respectively) is associated with a range of adverse health effects, including cancer, pulmonary and cardiovascular diseases. Surface characteristics (chemical reactivity, surface area) are considered of prime importance to understand the mechanisms which lead to harmful effects. A hypothetical mechanism to explain these adverse effects is the ability of components (organics, metal ions) adsorbed on these particles to generate Reactive Oxygen Species (ROS), and thereby to cause oxidative stress in biological systems (Donaldson et al., 2003). ROS can attack almost any cellular structure, like DNA or cellular membrane, leading to the formation of a wide variety of degradation products which can be used as a biomarker of oxidative stress. The aim of the present research project is to test whether there is a correlation between the exposure to Diesel Exhaust Particulate (DEP) and the oxidative stress status. For that purpose, a survey has been conducted in real occupational situations where workers were exposed to DEP (bus depots). Different exposure variables have been considered: - particulate number, size distribution and surface area (SMPS); - particulate mass - PM2.5 and PM4 (gravimetry); - elemental and organic carbon (coulometry); - total adsorbed heavy metals - iron, copper, manganese (atomic adsorption); - surface functional groups present on aerosols (Knudsen flow reactor). Several biomarkers of oxidative stress (8-hydroxy-2'-deoxyguanosine and several aldehydes) have been determined either in urine or serum of volunteers. Results obtained during the sampling campaign in several bus depots indicated that the occupational exposure to particulates in these places was rather low (40-50 μg/m3 for PM4). Bimodal size distributions were generally observed (5 μm and <1 μm). Surface characteristics of PM4 varied strongly, depending on the bus depot. They were usually characterized by high carbonyl and low acidic sites content. Among the different biomarkers which have been analyzed within the framework of this study, mean urinary levels of 8-hydroxy-2'-deoxyguanosine increased significantly (p<0.05) during two consecutive days of exposure for non-smoker workers. On the other hand, no statistically significant differences were observed for serum levels of hexanal, nonanal and 4- hydroxy-nonenal (p>0.05). Biomarkers levels will be compared to exposure variables to gain a better understanding of the relation between the particulate characteristics and the formation of ROS by-products. This project is financed by the Swiss State Secretariat for Education and Research. It is conducted within the framework of the COST Action 633 "Particulate Matter - Properties Related to Health Effects".