A comparison of predicted and measured levels of runoff-related pesticide concentrations in small lowland streams on a landscape level

Short-term pollution events via runoff are typical of streams in agricultural areas. Existing runoff models that simulate pesticide loss from agricultural fields require extensive input of information. There is thus a need for a simple model that can predict runoff-related pesticide concentrations in many streams on a landscape level when only limited data are available. To validate such a model, the runoff-related pesticide load of 18 small lowland streams was predicted with an extended version of the model "simplified formula for indirect loadings caused by runoff" (available from the Organisation for Economic Cooperation and Development, OECD). The authors suggest that the model presented here is suitable for use in routine exposure assessment of pesticides on a landscape level, as all input data (soil, slope, precipitation, pesticide application) are readily available from public authorities or could be generated by simple regional flood hydrograph curves. The predicted concentrations were compared with measured concentrations obtained by runoff-triggered sampling. Fungicides, insecticides and herbicides were detected in 17 streams, with max. concentrations measuring up to 29.7 microg/l for the fungicide azoxystrobin and 0.3 microg/l for the insecticide parathion-ethyl. Herbicides were detected in 16 streams, with max. concentrations between 13.7 and 1.2 microg/l. The linear regression between the predicted and measured concentrations (log-values) shows significant correlations for the following pesticides: azoxystrobin: r2=0.43; p=0.03; epoxiconazole: r2=0.71; por=0.5 microg/l).     

Development and field validation of an indicator to assess the relative mobility and risk of pesticides in the Lourens River catchment,South Africa

A GIS based pesticide risk indicator that integrates exposure variables (i.e. pesticide application, geographic, physicochemical and crop data) and toxicity endpoints (using species sensitivity distributions) was developed to estimate the Predicted Relative Exposure (PREX) and Predicted Relative Risk (PRRI) of applied pesticides to aquatic ecosystem health in the Lourens River catchment, Western Cape, South Africa. Samples were collected weekly at five sites from the beginning of the spraying season (October) till the beginning of the rainy season (April) and were semi quantitatively analysed for relevant pesticides applied according to the local farmers spraying programme. Monitoring data indicate that physicochemical data obtained from international databases are reliable indicators of pesticide behaviour in the Western Cape of South Africa. Sensitivity analysis identified K_OC as the most important parameter influencing predictions of pesticide loading derived from runoff. A comparison to monitoring data showed that the PREX successfully identified hotspot sites, gave a reasonable estimation of the relative contamination potential of different pesticides at a site and identified important routes of exposure (i.e. runoff or spray drift) of different pesticides at different sites. All pesticides detected during a monitored runoff event, were indicated as being more associated with runoff than spray drift by the PREX. The PRRI identified azinphos-methyl and chlorpyrifos as high risk pesticides towards the aquatic ecosystem. These results contribute to providing increased confidence in the use of risk indicator applications and, in particular, could lead to improved utilisation of limited resources for monitoring and management in resource constrained countries.     

Comparison of spray drift- and runoff-related input of azinphos-methyl and endosulfan from fruit orchards into the Lourens River, South Africa.

Spray drift and edge-of-field runoff are regarded as important routes of nonpoint-source pesticide input into aquatic surface waters, with current regulatory risk assessment in Europe focussing largely on spray drift. However, the two routes of entry had rarely been compared directly in the same catchment. To this end, the concentrations and loads of the current-use insecticides azinphos-methyl (AZP) and endosulfan (END) were monitored in the Lourens River, South Africa downstream of a 400-ha fruit orchard area during normal farming practice. Spray drift-related peak pesticide levels in the tributaries were in the range of 95th-percentiles of standard drift values according to regulatory risk assessment procedures. Resulting concentrations in Lourens River water samples (n = 3) at a discharge of 0.28 m3/s were as high as 0.04 +/- 0.01 microg/l AZP and 0.07 +/- 0.02 microg/l END. Pesticide levels at the same site during runoff following 3 storm events varying in rainfall between 6.8 and 18.4 mm/d (discharge: 7.5-22.4 m3/s) were considerably higher: by factors between 6 and 37 for AZP (0.26-1.5 microg/l) and between 2 and 41 for END (0.13-2.9 microg/l). Levels of pesticides associated with suspended particles were increased during runoff only up to 1247 microg/kg AZP and 12082 microg/kg END. A possible reason for the relative importance of runoff is that runoff largely integrates potential pesticide input over both time and space, because the prerequisites for the occurrence of runoff in terms of application and plot characteristics as well as meteorological conditions are far less specific than for spray drift. A probability analysis based on pesticide application patterns and 10-yr rainfall data indicates that the frequencies of rainfall events > or = 10 and > or = 15 mm/d are 3.4 and 1.7 per spraying season, respectively.     

Characteristics of mercury speciation in Minnesota rivers and streams

Patterns of mercury (Hg) speciation were examined in four Minnesota streams ranging from the main-stem Mississippi River to small tributaries in the basin. Filtered phase concentrations of methylmercury (MeHg), inorganic Hg (IHg), and dissolved organic carbon (DOC) were higher in all streams during a major summertime runoff event, and DOC was enriched with MeHg but not with IHg. Particulate-phase MeHg and IHg concentrations generally increased with total suspended solids (TSS) concentrations but the event data did not diverge greatly from the non-event data, suggesting that sources of suspended sediments in these streams did not vary significantly between event and non-event samplings. The dissolved fractions (filtered concentration/unfiltered concentration) of both MeHg and IHg increased with increasing DOC concentrations, but varied inversely with TSS concentrations. While MeHg typically constitutes only a minor portion of the total Hg (THg) in these streams, this contribution is not constant and can vary greatly over time in response to watershed inputs.     

Nitrogen removal from urban stormwater runoff through layered bioretention columns.

Bioretention is a low-impact technology used for the treatment of stormwater runoff in developed areas. The fates of mineral nitrogen compounds in two bioretention columns (RP1 and RP2) with different media-layering characteristics were investigated under multiple loadings of simulated urban runoff. The immediate capture of nitrogen was evaluated, with nitrogen transformation reactions that occurred during the drying periods between rainfall events. A greater proportion of ammonium was removed from runoff in RP2 (68 +/- 16%), which had a high permeability layer over a lower permeability layer, than in RP1 (12 +/- 6%), which had the inverse configuration. Both column systems demonstrated nitrate export (9 +/- 32% and 54 +/- 22% greater than input for RP1 and RP2, respectively), attributed to washout of nitrate resulting from nitrification processes between runoff loading events. Bioretention media with a less permeable bottom soil layer could form an anoxic/anaerobic zone for promoting nitrification/denitrification processes.     

Constructed wetlands for mitigation of atrazine-associated agricultural runoff

Atrazine was amended into constructed wetlands (59-73x14x0.3 m) for the purpose of monitoring transport and fate of the pesticide to obtain information necessary to provide future design parameters for constructed wetlands mitigation of agricultural runoff. Following pesticide amendment, a simulated storm and runoff event equal to three volume additions was imposed on each wetland. Targeted atrazine concentrations were 0 microg/l (unamended control), 73 microg/l, and 147 microg/l. Water, sediment, and plant samples were collected weekly for 35 days from transects longitudinally distributed throughout each wetland and were analyzed for atrazine using gas chromatography. Between 17 and 42% of measured atrazine mass was within the first 30-36 m of wetlands. Atrazine was below detection limits (0.05 microg/kg) in all sediment and plant samples collected throughout the duration of this study. Aqueous half lives ranged from 16 to 48 days. According to these data, conservative buffer travel distances of 100-280 m would be necessary for effective runoff mitigation.     

Bioavailability of zinc in runoff water from roofing materials

Corrosion and runoff from zinc-coated materials and outdoor structures is an important source for the dispersion of zinc in the environment. Being part of a large inter-disciplinary research project, this study presents the bioavailability of zinc in runoff water immediately after release from the surface of 15 different commercially available zinc-based materials exposed to the urban environment of Stockholm, Sweden. Runoff water was analysed chemically and evaluated for its possible environmental impact, using both a biosensor test with the bacteria Alcaligenes eutrophus (Biomet^®) and the conventional 72 h growth inhibition test with the green alga Raphidocelis subcapitata. Chemical speciation modelling revealed that most zinc (94.3–99.9%) was present as the free Zn ion, the most bioavailable speciation form. These findings were confirmed by the results of the biosensor test (Biomet^®) which indicated that all zinc was indeed bioavailable. Analysis of the ecotoxicity data also suggested that the observed toxic effects were due to the presence of Zn²⁺ ions. Finally, regression analysis showed that, for this type of runoff samples, the rapid screening biosensor was capable of predicting (a) the total amount of zinc present in the runoff samples (R² of 0.93–0.98; p<0.05) and (b) the observed 72 h-EbC₅₀s (R² of 0.69–0.97; p<0.05).     

The effect of residential and agricultural runoff on the microbiology of a Hawaiian ahupua'a.

The objective of this project was to study the relationship between environmental runoff and the incidence of antibiotic-resistant microorganisms (ARMO) in freshwater streams. Five water systems along the windward coast of the island of O'ahu were evaluated. Samples were collected from sites upstream of residential or agricultural areas, throughout these areas, and at sites of entrance into oceans or bays. It was hypothesized that the incidence of ARMO would increase as the stream received runoff from residential and agricultural areas. The percentage of ARMO did not increase as the streams passed through residential or agricultural areas. Surprisingly, pristine sites, well upstream from residential or agricultural areas, contained bacteria resistant to at least one antibiotic. Areas most affected by runoff did not show a significant increase in the incidence of antibiotic-resistant organisms, suggesting that the incidence of antibiotic resistance is not simply a function of contamination with agricultural or residential runoff. The correlation of antibiotic resistance with heavy metal resistance was evaluated, because others (Fasim et al., 1999; Lazar et al., 2002; Nies, 1999) have shown that antibiotic and heavy metal resistance are each carried on extrachromosomal plasmids. The vast majority of ARMO were also resistant to concentrations of heavy metals reported in the sediments of indicator streams (Waihee, system III), suggesting that an antibiotic-resistant bacterium has a high probability of having dual resistance to a heavy metal. A 3.2-kb plasmid (pSTAMP) was isolated from a bacterium with dual antibiotic and heavy metal resistance. Further analysis of the plasmid is currently in progress.     

Dynamic modeling of organophosphate pesticide load in surface water in the northern San Joaquin Valley watershed of California

The hydrology, sediment, and pesticide transport components of the Soil and Water Assessment Tool (SWAT) were evaluated on the northern San Joaquin Valley watershed of California. The Nash-Sutcliffe coefficients for monthly stream flow and sediment load ranged from 0.49 to 0.99 over the watershed during the study period of 1992-2005. The calibrated SWAT model was applied to simulate fate and transport processes of two organophosphate pesticides of diazinon and chlorpyrifos at watershed scale. The model generated satisfactory predictions of dissolved pesticide loads relative to the monitoring data. The model also showed great success in capturing spatial patterns of dissolved diazinon and chlorpyrifos loads according to the soil properties and landscape morphology over the large agricultural watershed. This study indicated that curve number was the major factor influencing the hydrology while pesticide fate and transport were mainly affected by surface runoff and pesticide application and in the study area.     

Two sampling strategies for an overview of pesticide contamination in an agriculture-extensive headwater stream

Two headwaters located in southwest France were monitored for 3 and 2 years (Auvézère and Aixette watershed, respectively) with two sampling strategies: grab and passive sampling with polar organic chemical integrative sampler (POCIS). These watersheds are rural and characterized by agricultural areas with similar breeding practices, except that the Auvézère watershed contains apple production for agricultural diversification and the downstream portion of the Aixette watershed is in a peri-urban area. The agricultural activities of both are extensive, i.e., with limited supply of fertilizer and pesticides. The sampling strategies used here give specific information: grab samples for higher pesticide content and POCIS for contamination background noise and number of compounds found. Agricultural catchments in small headwater streams are characterized by a background noise of pesticide contamination in the range of 20–70 ng/L, but there may also be transient and high-peak pesticide contamination (2000–3000 ng/L) caused by rain events, poor use of pesticides, and/or the small size of the water body. This study demonstrates that between two specific runoff events, contamination was low; hence the importance of passive sampler use. While the peak pesticide concentrations seen here are a toxicity risk for aquatic life, the pesticide background noise of single compounds do not pose obvious acute nor chronic risks; however, this study did not consider the risk from synergistic “cocktail” effects. Proper tools and sampling strategies may link watershed activities (agricultural, non-agricultural) to pesticides detected in the water, and data from both grab and passive samples can contribute to discussions on environmental effects in headwaters, an area of great importance for biodiversity.     

Assessment of insecticide contamination in runoff and stream water of small agricultural streams in the main soybean area of Argentina

The first- and second-order streams, Brown and Horqueta, respectively, which are located in the main area of soybean production in Argentina were examined for insecticide contamination caused by runoff from nearby soybean fields. The insecticides most widely used in Argentina (chlorpyrifos, cypermethrin and endosulfan) were detected in sediments, suspended particles and water. Highest concentrations in suspended particles were 318 microg/kg for endosulfan in the stream Horqueta, while 226 microg/kg chlorpyrifos and 13.2 microg/kg cypermethrin were measured in the stream Brown. In the Horqueta stream 150 and 53 microg/kg chlorpyrifos and cypermethrin were detected in runoff sediments, respectively. Whereas cypermethrin concentrations in the suspended particles were relatively low, levels in the floodwater of Brown reached 0.7 microg/l. The highest chlorpyrifos concentration in floodwater was 0.45 microg/l in Brown. However, endosulfan was not detected in the water phase. In runoff water the highest concentrations measured were 0.3 microg/l for chlorpyrifos in Horqueta and 0.49 microg/l for cypermethrin in the Brown stream. On five sampling dates during the pesticide application period in Brown stream (2002/2003) the concentration of chlorpyrifos and cypermethrin in runoff and/or floodwater exceeded the water quality criteria for freshwater mentioned in this study. In three cases this insecticide concentration was measured in stream water, indicating an acute risk to aquatic life. The acute toxicity-exposure-ratio (TER) for chlorpyrifos and cypermethrin also shows an acute risk for aquatic invertebrates in the Brown stream. In the Horqueta chlorpyrifos concentrations in the runoff exceeded the safety levels three times during the application period (2001/2002), potentially endangering the aquatic fauna. Effects on aquatic macroinvertebrates after insecticide contamination were reported in earlier studies in Horqueta stream.     

Impacts of some meteorological parameters on SO2 and TSP concentrations in Erzurum, Turkey

The air pollution is the one of the most important environmental problems in Erzurum, situated in the eastern of Turkey, during winter periods. The unfavorable climate as well as the city’s topography, and inappropriate urbanization cause serious air pollution problems. The air pollutant concentrations in a city have a close relationship with its meteorological parameters. In the present study, the relationship between daily average total suspended particulate (TSP) and sulphur dioxide (SO₂) concentrations with meteorological factors, such as wind speed, temperature, relative humidity, pressure and precipitation, in 1995–2002 winter seasons was statistically analyzed using the stepwise multiple linear regression analysis. According to the results obtained through analysis, higher TSP and SO₂ concentrations are strongly related to colder temperatures, lower wind speed, higher pressure system and weakly lower precipitation and higher relative humidity. The statistical models of SO₂ and TSP including meteorological parameters gave R² of 0.74 and 0.88, respectively. Furthermore, the correlation between the previous day’s SO₂, TSP concentrations and actual concentrations of these pollutants on that day was investigated and found as 0.84 and 0.53, respectively. In order to develop this model, previous day’s SO₂ and TSP concentrations were added to the equations. The new model for SO₂ enhanced considerably (R² = 0.92), but for TSP new model was not enhanced (R² = 0.89).     

SPEAR indicates pesticide effects in streams - Comparative use of species- and family-level biomonitoring data

To detect effects of pesticides on non-target freshwater organisms the Species at risk (SPEAR_pesticides) bioindicator based on biological traits was previously developed and successfully validated over different biogeographical regions of Europe using species-level data on stream invertebrates. Since many freshwater biomonitoring programmes have family-level taxonomic resolution we tested the applicability of SPEAR_pesticides with family-level biomonitoring data to indicate pesticide effects in streams (i.e. insecticide toxicity of pesticides). The study showed that the explanatory power of the family-level SPEAR(fm)_pesticides is not significantly lower than the species-level index. The results suggest that the family-level SPEAR(fm)_pesticides is a sensitive, cost-effective, and potentially European-wide bioindicator of pesticide contamination in flowing waters. Class boundaries for SPEAR_pesticides according to EU Water Framework Directive are defined to contribute to the assessment of ecological status of water bodies.     

PeLM: Modeling of Pesticide-Losses Through Runoff and Sediment Transport

Abstract

A GIS-aided pesticide loss model (PeLM) was developed to simulate pesticide losses through surface runoff and sediment transport in watershed systems. The PeLM could tackle the movement of eroded soil along with surface runoff as well as the pesticide losses in adsorbed and dissolved phases. The contributions of different soil types in the sediment were also examined. The model was applied to the Kintore Creek Watershed of southern Ontario, Canada. The simulation results were verified through observed data, indicating a correlation level of 0.89–0.98. The results also showed that clay particles usually held the largest share of contributions to pesticide losses through soil erosion. This study is significant in the efforts for modeling nonpoint source pollution in watershed systems. It provides useful information and support for the related decisions of watershed management.     

Development of QSARs to investigate the bacterial toxicity and biotransformation potential of aromatic heterocylic compounds

A series of aromatic heterocyclic and hydrocarbon compounds were tested for toxicity and biotransformation potential against two contrasting lux-marked whole-cell microbial biosensors. Toxicity was determined by inhibition of light output of a Pseudomonas fluorescens construct that expresses lux constitutively. Biotransformation was tested by increase in light output of P. fluorescens HK44 (pUTK21), which expresses lux when in the presence of a metabolic intermediate (salicylate). The data were then modelled against physical/chemical properties of the compounds tested to see if quantitative structure–activity relationships (QSARs) could be derived. Toxicity was found to be accurately predicted by log K_ow (R²=0.95, Q²=0.88), with the basic (pyridine-ring containing) heterocycles modelled separately. The biotransformation data were best modelled using lowest unoccupied molecular orbital (LUMO) energies (R²=0.90, Q²=0.87).     

Impacts of lawn-care pesticides on aquatic ecosystems in relation to property value

To determine the potential impacts of lawn-care pesticides on aquatic ecosystems, the macroinvertebrate communities of six streams were assessed using a multimetric approach. Four streams flowed through residential neighborhoods of Peachtree City, GA, USA, with differing mean property values and two reference streams were outside the city limits. A series of correlation analyses were conducted comparing stream rank from water quality and physical stream parameters, habitat assessments, benthic macroinvertebrate metric, pesticide toxicity and metal toxicity data to determine relationships among these parameters. Significant correlations were detected between individual analyses of stream rank for pesticide toxicity, specific conductance, turbidity, temperature and dissolved oxygen with benthic macroinvertebrate metrics.     

PeLM: modeling of pesticide-losses through runoff and sediment transport

A GIS-aided pesticide loss model (PeLM) was developed to simulate pesticide losses through surface runoff and sediment transport in watershed systems. The PeLM could tackle the movement of eroded soil along with surface runoff as well as the pesticide losses in adsorbed and dissolved phases. The contributions of different soil types in the sediment were also examined. The model was applied to the Kintore Creek Watershed of southern Ontario, Canada. The simulation results were verified through observed data, indicating a correlation level of 0.89-0.98. The results also showed that clay particles usually held the largest share of contributions to pesticide losses through soil erosion. This study is significant in the efforts for modeling nonpoint source pollution in watershed systems. It provides useful information and support for the related decisions of watershed management.     

Mitigation of azinphos-methyl in a vegetated stream: comparison of runoff- and spray-drift

The effectiveness of aquatic macrophytes in reducing runoff- and spray-drift-induced azinphos-methyl (AZP) input was compared in a vegetated stream. Water, sediment and plant samples were taken at increasing distances from a point of input during a spray-drift event and two runoff (10 and 22 mm/day) events. Peak concentrations of AZP decreased significantly (R2=0.99; p<0.0001; n=5) from 0.24 microg/l to 0.11 microg/l during the 10mm runoff event. No reduction took place during the 22 mm event. AZP concentrations were reduced by 90% following spray-drift input, with peak concentrations decreasing significantly (R2=0.93; p=0.0084; n=5) from 4.3 microg/l to 1.7 microg/l with increasing distance from the point of input. Plant samples taken after the spray-drift event showed increased AZP concentrations in comparison to before the event indicating sorption of the pesticide to the macrophytes. Although peak concentrations of AZP were as effectively mitigated during the 10mm runoff event as during the spray-drift event, predictive modelling revealed that maximum concentrations expected during a worst-case scenario 10mm runoff event (0 days after application) are an order of magnitude lower than what can be expected for a worst-case spray-drift and 22 mm runoff event, suggesting that spray-drift-derived pesticide concentrations are more effectively mitigated than those of runoff.     

Pesticide concentrations in agricultural storm drainage inlets of a small Swiss catchment

Agricultural pesticides transported to surface waters pose a major risk for aquatic ecosystems. Modelling studies indicate that the inlets of agricultural storm drainage systems can considerably increase the connectivity of surface runoff and pesticides to surface waters. These model results have however not yet been validated with field measurements. In this study, we measured discharge and concentrations of 51 pesticides in four out of 158 storm drainage inlets of a small Swiss agricultural catchment (2.8 km²) and in the receiving stream. For this, we performed an event-triggered sampling during 19 rain events and collected plot-specific pesticide application data. Our results show that agricultural storm drainage inlets strongly influence surface runoff and pesticide transport in the study catchment. The concentrations of single pesticides in inlets amounted up to 62 µg/L. During some rain events, transport through single inlets caused more than 10% of the stream load of certain pesticides. An extrapolation to the entire catchment suggests that during selected events on average 30 to 70% of the load in the stream was transported through inlets. Pesticide applications on fields with surface runoff or spray drift potential to inlets led to increased concentrations in the corresponding inlets. Overall, this study corroborates the relevance of such inlets for pesticide transport by establishing a connectivity between fields and surface waters, and by their potential to deliver substantial pesticide loads to surface waters.