Irene Wittmer

Significance of urban and agricultural land use for biocide and pesticide dynamics in surface waters

Biocides and pesticides are designed to control the occurrence of unwanted organisms. From their point of application, these substances can be mobilized and transported to surface waters posing a threat to the aquatic environment. Historically, agricultural pesticides have received substantially more attention than biocidal compounds from urban use, despite being used in similar quantities. This study aims at improving our understanding of the influence of mixed urban and agricultural land use on the overall concentration dynamics of biocides and pesticides during rain events throughout the year. A comprehensive field study was conducted in a catchment within the Swiss plateau (25 km(2)). Four surface water sampling sites represented varying combinations of urban and agricultural sources. Additionally, the urban drainage system was studied by sampling the only wastewater treatment plant (WWTP) in the catchment, a combined sewer overflow (CSO), and a storm sewer (SS). High temporal resolution sampling was carried out during rain events from March to November 2007. The results, based on more than 600 samples analyzed for 23 substances, revealed distinct and complex concentration patterns for different compounds and sources. Five types of concentration patterns can be distinguished: a) compounds that showed elevated background concentrations throughout the year (e.g. diazinon >50 ng L(-1)), indicating a constant household source; b) compounds that showed elevated concentrations driven by rain events throughout the year (e.g. diuron 100-300 ng L(-1)), indicating a constant urban outdoor source such as facades; c) compounds with seasonal peak concentrations driven by rain events from urban and agricultural areas (e.g. mecoprop 1600 ng L(-1) and atrazine 2500 ng L(-1) respectively); d) compounds that showed unpredictably sharp peaks (e.g. atrazine 10,000 ng L(-1), diazinon 2500 ng L(-1)), which were most probably due to improper handling or even disposal of products; and finally, e) compounds that were used in high amounts but were not detected in surface waters (e.g. isothiazolinones). It can be safely concluded that in catchments of mixed land use, the contributions of biocide and pesticide inputs into surface waters from urban areas are at least as important as those from agricultural areas.

How a Complete Pesticide Screening Changes the Assessment of Surface Water Quality

A comprehensive assessment of pesticides in surface waters is challenging due to the large number of potential contaminants. Most scientific studies and routine monitoring programs include only 15-40 pesticides, which leads to error-prone interpretations. In the present study, an extensive analytical screening was carried out using liquid chromatography-high-resolution mass spectrometry, covering 86% of all polar organic pesticides sold in Switzerland and applied to agricultural or urban land (in total 249 compounds), plus 134 transformation products; each of which could be quantified in the low ng/L range. Five medium-sized rivers, containing large areas of diverse crops and urban settlements within the respective catchments, were sampled between March and July 2012. More than 100 parent compounds and 40 transformation products were detected in total, between 30 and 50 parent compounds in each two-week composite sample in concentrations up to 1500 ng/L. The sum of pesticide concentrations was above 1000 ng/L in 78% of samples. The chronic environmental quality standard was exceeded for 19 single substances; using a mixture toxicity approach, exceedances occurred over the whole measurement period in all rivers. With scenario calculations including only 30-40 frequently measured pesticides, the number of detected substances and the mixture toxicity would be underestimated on average by a factor of 2. Thus, selecting a subset of substances to assess the surface water quality may be sufficient, but a comprehensive screening yields substantially more confidence.

Relevance of urban glyphosate use for surface water quality.

Relative contributions of agricultural and urban uses to the glyphosate contamination of surface waters were studied in a small catchment (25 km(2)) in Switzerland. Monitoring in four sub-catchments with differing land use allowed comparing load and input dynamics from different sources. Agricultural as well as urban use was surveyed in all sub-catchments allowing for a detailed interpretation of the monitoring results. Water samples from the river system and from the urban drainage system (combined sewer overflow, storm sewer and outflow of wastewater treatment plant) were investigated. The concentrations at peak discharge during storm events were elevated throughout the year with maximum concentrations of 4.15 μg L(-1). Glyphosate concentrations mostly exceeded those of other commonly used herbicides such as atrazine or mecoprop. Fast runoff from hard surfaces led to a fast increase of the glyphosate concentration shortly after the beginning of rainfall not coinciding with the concentration peak normally observed from agricultural fields. The comparison of the agricultural application and the seasonal concentration and load pattern in the main creek from March to November revealed that the occurrence of glyphosate cannot be explained by agricultural use only. Extrapolations from agricultural loss rates and from concentrations found in the urban drainage system showed that more than half of the load during selected rain events originates from urban areas. The inputs from the effluent of the wastewater treatment plant, the overflow of the combined sewer system and of the separate sewer system summed up to 60% of the total load.

Loss rates of urban biocides can exceed those of agricultural pesticides.

Biocides and pesticides are used to control unwanted organisms in urban and agricultural areas. After application, they can be lost to surface waters and impair water quality. Several national consumption studies have shown that urban and agricultural use may be in the same range. It is difficult to judge whether this results in similar loadings of surface waters because there is a lack of sound, comparative studies addressing urban and agricultural losses simultaneously. The aim of this study is thus to relate the biocide and pesticide loads found in surface waters to their respective urban and agricultural usage (loss rates). To simultaneously assess the loss rates, we conducted a comprehensive field study in a catchment of mixed land use on the Swiss Plateau. The study area was divided into four sub-catchments with different degrees of urban and agricultural land use. In addition, we studied the only wastewater treatment plant, a combined sewer overflow and a storm sewer within the area. Rain events were sampled at high temporal resolution from March to November, 2007. Information on agricultural applications was gained from local farmers. For urban uses, consumption estimations were conducted based on statistical and product information. Despite substantially lower amounts used, the measured loads of urban biocides were in the same range as the most widely-used agricultural pesticides. The lower usage was compensated by urban loss rates that were up to ten times higher than agricultural ones (0.6 to 15% for urban, 0.4 to 0.9% for agricultural compounds). For most biocides and pesticides, the loads were controlled by rain events. Besides the rain-controlled losses, some urban-used biocides (e.g. diazinon) showed a continuous load independent of rain events and season. This study demonstrates that in catchments with mixed land use, mitigation strategies have to pay sufficient attention to the urban sources.

Modelling biocide leaching from facades

Biocides leach from facades during rain events and subsequently enter the aquatic environment with storm water. Little is known about the losses of an entire settlement, since most studies referred to wash-off experiments conducted under laboratory conditions. Their results show a fast decrease of concentrations in the beginning, which subsequently slows down. The aim of this study is to develop a simple model to understand the mechanisms leading to these losses as well as to simulate losses under various rainfall and application conditions. We developed a four-box model based on the knowledge gained from fits of an exponential function to an existing experimental data set of a wash-off experiment. The model consists of two mobile stocks from which biocides are washed off during a rain event. These mobile stocks are supplied with biocides from storage stocks by diffusion-type processes. The model accurately reproduced the measured data of wash-off during single cycles as well as peak wash-offs over all cycles. Our model results for diuron losses showed that a large proportion (∼ 70%) of the applied biocides are still in the stocks even after a rain volume corresponding to several years (1100 mm y(-1), Swiss Plateau). Applications to realistic outdoor conditions showed that losses can not be neglected for urban environments and that knowledge about the amount of rainfall turned into runoff and the decay constants of the biocides in the facades are crucial. The model increased our understanding of the processes leading to the observed dynamic in laboratory experiments and was used to simulate losses for various rainfall and application conditions.

Environmental risk assessment of fluctuating diazinon concentrations in an urban and agricultural catchment using toxicokinetic-toxicodynamic modeling

Temporally resolved environmental risk assessment of fluctuating concentrations of micropollutants is presented. We separated the prediction of toxicity over time from the extrapolation from one to many species and from acute to sublethal effects. A toxicokinetic–toxicodynamic (TKTD) model predicted toxicity caused by fluctuating concentrations of diazinon, measured by time-resolved sampling over 108 days from three locations in a stream network, representing urban, agricultural and mixed land use. We calculated extrapolation factors to quantify variation in toxicity among species and effect types based on available toxicity data, while correcting for different test durations with the TKTD model. Sampling from the distribution of extrapolation factors and prediction of time-resolved toxicity with the TKTD model facilitated subsequent calculation of the risk of undesired toxic events. Approximately one-fifth of aquatic organisms were at risk and fluctuating concentrations were more toxic than their averages. Contribution of urban and agricultural sources of diazinon to the overall risk varied. Thus using fixed concentrations as water quality criteria appears overly simplistic because it ignores the temporal dimension of toxicity. However, the improved prediction of toxicity for fluctuating concentrations may be small compared to uncertainty due to limited diversity of toxicity data to base the extrapolation factors on.

Pesticide Risks in Small Streams – How to Get as Close as Possible to the Stress Imposed on Aquatic Organisms

The risks associated with pesticides in small streams remain poorly characterized. The challenges reside in understanding the complexities of (1) the highly dynamic concentration profiles of (2) several hundred active substances with (3) differing seasonality. The present study addressed these three challenges simultaneously. Five small streams in catchments under intensive agricultural land use were sampled using half-day composite samples from March to August 2015. Of 213 active substances quantified using liquid chromatography-high resolution mass spectrometry, a total of 128 was detected at least at one of the sites. Ecotoxicological acute and/or chronic quality criteria were exceeded for a total of 32 different active substances. The evaluation of risks over time revealed the necessity to evaluate the sequences of different active substances that are imposed on aquatic organisms. In contrast, a substance-specific perspective provides only a very limited assessment. Scenarios for reduction of either temporal resolution, number of substances or seasonal coverage were defined. It could be shown that risks can be underestimated by more than a factor of 10 in vulnerable catchments and that an increased temporal resolution is essential to cover acute risks but that a focused selection of substances is a possibility to reduce expenditures.