Jenny Kreuger

Pesticides in stream water within an agricultural catchment in southern Sweden, 1990–1996

Pesticide loss to stream water was studied in a small agricultural catchment in southern Sweden during the period 1990-1996. A total of 38 pesticides were detected in water samples, including 30 herbicides, four fungicides, three insecticides and one metabolite of one of the herbicides. Concentrations of pesticides in stream water were observed throughout the sampling periods. Peak concentrations occurred during the spraying seasons and following runoff events. Daily average concentrations sometimes varied by one order of magnitude from one day to another. Pesticides were also found in water samples as a result of incautious actions during handling and application procedures. Concentrations were lower at the outlet of the catchment area when the water had passed an open part of the stream, compared to concentrations detected in discharge from a culvert system upstream. This was largely a result of dilution from groundwater intrusion during low-flow periods. Sampling at different sites along the culvert demonstrated that the small village situated in the catchment did not contribute to pesticide findings in the culvert discharge. Wind drift had little influence on stream-water quality. Pesticide application for weed control in farmyards resulted in a substantial contribution to the pesticide load in stream water. Pesticide were persistent in the discharge throughout the winter and originated from both autumn and spring applications, as well as from farmyard application. Some autumn applied pesticides prevailed in stream flow during the following summer. Total amounts of pesticides lost in stream flow during May-September each year varied between 0.5 and 2.8 kg during the 7-year period, corresponding to approximately 0.1% of the applied amount. Losses of single pesticides were generally less than 0.3% of the applied amount during individual years. Pesticides from agricultural applications in the catchment constituted, on average, 82% of the total transported amount lost during May-September each year, of which 2% was from autumn application the previous year. There was an overall correlation between amounts used in the catchment and occurrence in the water samples. The total pesticide load in water decreased markedly during the course of the investigation, in accordance with decreased amounts applied during spring and early summer. The results indicate that concentrations of some pesticides entering head-water streams in agricultural areas are close to, and during certain time periods even above those levels demonstrated as having an impact on the aquatic flora and fauna.

Evaluation of pesticide monitoring strategies in agricultural streams based on the toxic-unit concept — Experiences from long-term measurements

The European Water Framework Directive requires surface water bodies to have a good chemical and ecological status. Although relatively few pesticides are included in the list of priority pollutants, they pose, due to their intrinsic biological activity, a significant risk for the integrity of aquatic ecosystems. In this context, the pesticide (up to 128 pesticides including some transformation products) exposure pattern in four agricultural streams and two rivers was determined from 2002 to 2011 under the umbrella of the Swedish national monitoring program employing time-proportional and grab sampling strategies, respectively. After transforming the measured pesticide concentrations into toxic units, the European Uniform Principles for algae (chronic), invertebrates and fish (both acute), which are partly employed as benchmark for pesticide regulation, were only occasionally (<2%) exceeded. Moreover, this evaluation showed no long-term trends over the years. However, recent publications suggested that those thresholds are not protective for ecosystem structure and function, indicating a risk of up to 20% and 35% of the samples from the agricultural streams and the rivers, respectively. Moreover, the monitoring data show a continuous but rather low toxic potential of pesticides for all three trophic levels throughout the year, which suggests pesticides as an evolutionary force in agriculturally impacted aquatic ecosystems. However, the flow-triggered sampling, which was implemented as an additional sampling strategy in one of the agricultural streams starting in 2006, displayed an up to 7-fold underestimation of the maximum concentration in terms of toxic units for daphnids and fish during run-off events. The present study thus underpins that the optimal sampling design for pesticide monitoring strongly depends on its overall purpose. If the long-term exposure pattern is of concern a time-proportional composite sampling strategy is recommended, while for an assessment of peak exposures a flow-event-triggered high-resolution sampling strategy is superior.

Toxicity of 15 veterinary pharmaceuticals in zebrafish (Danio rerio) embryos.

Extensive use of veterinary pharmaceuticals may result in contamination of water bodies adjacent to pasture land or areas where animal manure has been applied. In order to evaluate the potential risk to fish embryos 15 veterinary pharmaceuticals were investigated by use of an extended zebrafish embryo toxicity test. Chemical analysis of the exposure medium was performed by solid phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) for 11 of the compounds and potential metabolism by the embryos was studied for albendazole, febantel, fenbendazole and oxfendazole. Newly fertilized zebrafish eggs were exposed under static conditions in 96-well plates for 6 days to the pharmaceuticals: 5 antibacterials and 10 antiparasitics. Endpoints including mortality, malformations and other sublethal responses were recorded at 24, 48 and 144 h post fertilization (hpf). The pharmaceuticals causing the highest toxicity were antiparasitics whereas the tested antibacterials, danofloxacin, enrofloxacin, tylosine, trimethoprim and oxytetracyclin had a much lower toxic potency in zebrafish embryos. Most toxic were fenbendazole, albendazole and flumethrin with no observed effect concentrations (NOECs) around 0.02 mg/L. The overall NOEC was determined by lethality for the following pharmaceuticals: albendazole, fenbendazole and oxfendazole. Sublethal endpoints, including malformations, side-laying embryos, tremors, reduced movements and altered heart rate increased the sensitivity of the tests and determined the overall NOECs for febantel, doramectin, ivermectin, flumethrin and toltrazuril. Exposure to doramectin and ivermectin caused a decrease in movements at 24 hpf and a decrease in heart rate at 48 hpf. Flumethrin exposure resulted in decreased time to hatching, except at the highest concentrations, and caused an increase in heart rate at 48 hpf. In contrast, toltrazuril caused an increased time to hatching and a decrease in heart rate. Chemical analysis of the exposure medium after the tests revealed great differences between nominal and measured concentrations, emphasizing the need of including analysis of the actual exposure concentrations. The results indicated that metabolism of albendazole into its sulfoxide protected the embryos from toxicity. Albendazole was metabolized efficiently into albendazole sulfoxide at lower exposure concentrations, resulting in reduced toxicity. At higher concentrations, an increasing proportion of albendazole remained unmetabolized and embryo mortality occurred. Metabolism by the embryos of febantel into fenbendazole and oxfendazole and of fenbendazole into oxfendazole was demonstrated. It is suggested that the toxic effect of febantel in zebrafish embryos is due to metabolism into fenbendazole.

Spray drift as influenced by meteorological and technical factors

BACKGROUND The objective of this study was to investigate spray drift from a conventional field sprayer as influenced by meteorological and technical factors, and to provide spray operators with data on which to base sound judgements when applying pesticides. The study was conducted in grazing fields and cereal crops. RESULTS Interpreting the results from 15 field trials under varying meteorological conditions using different boom heights and driving speeds indicates that, during normal spraying conditions, the most decisive factors influencing the total spray drift (TSD) will be boom height and wind speed, followed by air temperature, driving speed and vapour pressure deficit. One important finding was that TSD (within the encompassed range of meteorological conditions and a boom height of 0.4 m) could be expressed as a simple function of the fraction of droplets ≤ 100 µm. In cereal crops: TSD = 0.36 + 0.11× [fr. (d ≤ 100 µm)] and in grazing fields, TSD = 1.02 + 0.10× [fr. (d ≤ 100 µm)]. In most cases a fraction of the airborne drift passed over the 6 m sampling mast located 5 m downwind of the spray swath. CONCLUSIONS Under specified conditions, the present results indicate a simple relation between the total spray drift and volume fractions of droplets ≤ 100 µm. Given the nozzle type, it was concluded that the most decisive factors determining TSD are wind speed and boom height. Evaluating the relative importance of the meteorological and technical factors contributes to increasing knowledge in this field of research.

Multiple regression analysis of pesticide occurrence in streamflow related to pesticide properties and quantities applied

Abstract Monitoring data of 25 pesticides in surface water from a small agricultural catchment in southern Sweden during 1990–1994 were subjected to stepwise multiple linear regression analyses to express concentration, transported amount and loss rate as functions of different pesticide intrinsic properties (or a combination of these) and quantities applied. The single most significant variable was quantities applied, accounting for ca . 50–85% of the variability in concentration and transported amount during individual years. Model performance was slightly improved by adding intrinsic properties of the pesticides as explanatory variables, thus explaining between 70 and 95 percent of the variability of the two dependent variables. Evaluation of loss rate, in percent of applied quantities, using simple linear regression analysis identified log P ow as the most significant variable for pesticide loss to surface water accounting for 26% of the variance when monitoring results from four individual years were pooled. Using the best model equations in a crossvalidation procedure, surface water concentrations, transported amount and loss rates were calculated that compared well to monitoring results for 80–100% of the compounds measured. This study demonstrated that quantities of pesticides used in the catchment area was the most important estimator of level and amount of pesticides occurring in the stream and that log P ow was the most significant intrinsic property estimating relative loss of pesticides from the catchment.

The legacy of pesticide pollution: An overlooked factor in current risk assessments of freshwater systems

We revealed a history of legacy pesticides in water and sediment samples from 19 small streams across an agricultural landscape. Dominant legacy compounds included organochlorine pesticides, such as DDT and lindane, the organophosphate chlorpyrifos and triazine herbicides such as terbutylazine and simazine which have long been banned in the EU. The highest concentrations of legacy pesticides were found in streams draining catchments with a large proportion of arable farmland suggesting that they originated from past agricultural applications. The sum of toxic units (SumTUD.magna) based on storm water samples from agriculturally impacted streams was significantly higher when legacy pesticides were included compared to when they were omitted. Legacy pesticides did not significantly change the predicted toxicity of water samples to algae or fish. However, pesticide concentrations in bed sediment and suspended sediment samples exceeded safety thresholds in 50% of the samples and the average contribution of legacy pesticides to the SumTUC.riparius was >90%. Our results suggest that legacy pesticides can be highly significant contributors to the current toxic exposure of stream biota, especially macroinvertebrate communities, and that those communities were primarily exposed to legacy pesticides via the sediment. Additionally, our results suggest that neglecting legacy pesticides in the risk assessment of pesticides in streams may severely underestimate the risk of ecological effects.

Characterization of five passive sampling devices for monitoring of pesticides in water

Five different passive sampler devices were characterized under laboratory conditions for measurement of 124 legacy and current used pesticides in water. In addition, passive sampler derived time-weighted average (TWA) concentrations were compared to time-integrated active sampling in the field. Sampling rates (RS) and passive sampler-water partition coefficients (KPW) were calculated for individual pesticides using silicone rubber (SR), polar organic chemical integrative sampler (POCIS)-A, POCIS-B, Chemcatcher(®) SDB-RPS and Chemcatcher(®) C18. The median RS (Lday(-1)) decreased as follows: SR (0.86)>POCIS-B (0.22)>POCIS-A (0.18)>Chemcatcher(®) SDB-RPS (0.05)>Chemcatcher(®) C18 (0.02), while the median logKPW (Lkg(-1)) decreased as follows: POCIS-B (4.78)>POCIS-A (4.56)>Chemcatcher(®) SDB-RPS (3.17)>SR (3.14)>Chemcatcher(®)C18 (2.71). The uptake of the selected compounds depended on their physicochemical properties, i.e. SR showed a better uptake for more hydrophobic compounds (log octanol-water partition coefficient (KOW)>5.3), whereas POCIS-A, POCIS-B and Chemcatcher(®) SDB-RPS were more suitable for hydrophilic compounds (logKOW<0.70). Overall, the comparison between passive sampler and time-integrated active sampler concentrations showed a good agreement and the tested passive samplers were suitable for capturing compounds with a wide range of KOWs in water.

Direct and indirect effects of climate change on herbicide leaching - A regional scale assessment in Sweden

Climate change is not only likely to improve conditions for crop production in Sweden, but also to increase weed pressure and the need for herbicides. This study aimed at assessing and contrasting the direct and indirect effects of climate change on herbicide leaching to groundwater in a major crop production region in south-west Sweden with the help of the regional pesticide fate and transport model MACRO-SE. We simulated 37 out of the 41 herbicides that are currently approved for use in Sweden on eight major crop types for the 24 most common soil types in the region. The results were aggregated accounting for the fractional coverage of the crop and the area sprayed with a particular herbicide. For simulations of the future, we used projections of five different climate models as model driving data and assessed three different future scenarios: (A) only changes in climate, (B) changes in climate and land-use (altered crop distribution), and (C) changes in climate, land-use, and an increase in herbicide use. The model successfully distinguished between leachable and non-leachable compounds (88% correctly classified) in a qualitative comparison against regional-scale monitoring data. Leaching was dominated by only a few herbicides and crops under current climate and agronomic conditions. The model simulations suggest that the direct effects of an increase in temperature, which enhances degradation, and precipitation which promotes leaching, cancel each other at a regional scale, resulting in a slight decrease in leachate concentrations in a future climate. However, the area at risk of groundwater contamination doubled when indirect effects of changes in land-use and herbicide use, were considered. We therefore concluded that it is important to consider the indirect effects of climate change alongside the direct effects and that effective mitigation strategies and strict regulation are required to secure future (drinking) water resources.

Spatial variation in herbicide leaching from a marine clay soil via subsurface drains.

Background Subsurface transport via tile drains can significantly contribute to pesticide contamination of surface waters. The spatial variation in subsurface leaching of normally applied herbicides was examined together with phosphorus losses in 24 experimental plots with water sampled flow-proportionally. The study site was a flat, tile-drained area with 60% marine clay in the topsoil in southeast Sweden. The objectives were to quantify the leaching of frequently used herbicides from a tile drained cracking clay soil and to evaluate the variation in leaching within the experimental area and relate this to topsoil management practices (tillage method and structure liming). Results In summer 2009, 0.14, 0.22 and 1.62%, respectively, of simultaneously applied amounts of MCPA, fluroxypyr and clopyralid were leached by heavy rain five days after spraying. In summer 2011, on average 0.70% of applied bentazone was leached by short bursts of intensive rain 12 days after application. Peak flow concentrations for 50% of the treated area for MCPA and 33% for bentazone exceeded the Swedish no-effect guideline values for aquatic ecosystems. Approximately 0.08% of the glyphosate applied was leached in dissolved form in the winters of 2008/2009 and 2010/2011. Based on measurements of glyphosate in particulate form, total glyphosate losses were twice as high (0.16%) in the second winter. The spatial inter-plot variation was large (72–115%) for all five herbicides studied, despite small variations (25%) in water discharge. Conclusions The study shows the importance of local scale soil transport properties for herbicide leaching in cracking clay soils.

Particulate-facilitated leaching of glyphosate and phosphorus from a marine clay soil via tile drains

Abstract Losses of commonly used chemical pesticides from agricultural land may cause serious problems in recipient waters in a similar way to phosphorus (P). Due to analytical challenges concerning determination of glyphosate (Gly), transport behaviour of this widely used herbicide is still not well known. The objective of the present study was to quantify and evaluate leaching of Gly in parallel with P. Leaching losses of autumn-applied Gly (1.06 kg ha−1) via drainage water were examined by flow-proportional sampling of discharge from 20 drained plots in a field experiment in eastern Sweden. Samples were analysed for Gly in particulate-bound (PGly) and dissolved (DGly) form. The first 10 mm water discharge contained no detectable Gly, but the following 70 mm had total Gly (TotGly) concentrations of up to 6 µg L−1, with 62% occurring as PGly. On average, 0.7 g TotGly ha−1 was leached from conventionally ploughed plots, compared with 1.7 g TotGly ha−1 from shallow-tilled plots (cultivator to 12 cm working depth). Higher Gly losses occurred in snowmelt periods in spring, but then with the majority (60%) as DGly. All autumn concentrations of PGly in drainage water were significantly correlated (p<0.001) to the concentrations of particulate-bound phosphorus (PP) lost from the different plots (Pearson correlation coefficient 0.84), while PP concentrations were in turn significantly correlated to water turbidity (Pearson correlation coefficient 0.81). Leaching losses of TotGly were significantly lower (by 1.3 g ha−1; p<0.01) from plots that had been structure-limed three years previously and ploughed thereafter than from shallow-tilled plots. Turbidity and PP concentration also tended to be lowest in discharge from structure-limed plots and highest from shallow-tilled plots. This difference in TotGly leaching between soil management regimes could not be explained by differences in measured pH in drainage water or amount of discharge. However, previously structure-limed plots had significantly better aggregate stability, measured as readily dispersed clay (RDC), than unlimited plots. The effects of building up good soil structure, with strong soil aggregates and an appropriate pore system in the topsoil, on mitigating Gly and P losses in particulate and dissolved form should be further investigated.