Pesticide Impact Rating Index – A Pesticide Risk Indicator for Water Quality

Pesticide users, natural resource managers, regulators, government agencies and many others are concerned about the off-site impact of pesticides on the environment. Systematic methods of the assessment of potential risk of pesticides to environmental components can serve as valuable tools in decision making and policy formulation. Simple risk indicators have been developed which cover a range of scenarios such as toxicity to organisms, health of farm workers, consumer health, and residues in harvested produce. The authors have developed a software package named Pesticide Impact Rating Index (PIRI) that outputs an improved pesticide risk indicator for water quality. PIRI is a standalone, user-friendly, platform-independent program. It can be used to (i) rank pesticides in terms of their relative pollution potential to groundwater or surface water, and (ii) to compare different land uses in a catchment or at a regional scale in terms of their relative impact on water quality. It is based on pesticides use; the pathway through which the pesticides are released to the water resources (drift, runoff, erosion, leaching) and the value of the water resources threatened. Each component is quantified using pesticide characteristics (including toxicity to organisms at different trophic levels, i.e. fish, daphnia, algae, etc.), environmental and site conditions (e.g. organic carbon content of soil, water input, slope of land, soil loss, recharge rate, depth of water table, etc.). This paper describes two case studies of the application of PIRI in Australia. The comparison of the risk assessment by PIRI on these revealed that PIRI correctly estimated the pollution potential of pesticides in greater than 80% of cases. A GIS version of PIRI is described in a companion paper in this volume. An erratum to this article is available at .     

A conceptual model of spatially heterogeneous nitrogen leaching from a welsh moorland catchment

Soil- and stream-water data from the Plynlimon research area, mid-Wales, have been used to develop a conceptual model of spatial variations in nitrogen (N) leaching within moorland catchments. Extensive peats, in both hilltop and valley locations, are considered near-complete sinks for inorganic N, but leach the most dissolved organic nitrogen (DON). Peaty mineral soils on hillslopes also retain inorganic N within upper organic horizons, but a proportion percolates into mineral horizons as nitrate (NO^? ₃), either through incomplete immobilisation in the organic layer, or in water bypassing the organic soil matrix via macropores. This NO^? ₃ reaches the stream where mineral soilwaters discharge (via matrix throughflow or pipeflow) directly to the drainage network, or via small N-enriched flush wetlands. NO^? ₃ in hillslope waters discharging into larger valley wetlands will be removed before reaching the stream. A concept of catchment ‘nitrate leaching zones’ is proposed, whereby most stream NO^? ₃ derives from localised areas of mineral soil hillslope draining directly to the stream; the extent of these zones within a catchment may thus determine its overall susceptibility to elevated surface water NO^? ₃ concentrations.     

Modelling Pesticide and Nutrient Transport in the Cameron Highlands, Malaysia Agro-Ecosystems

Cameron Highlands has a long history of intensive horticulture especially vegetable and flower cultivation. This industry uses large amounts of nutrients and pesticides. Several simulation models were used to assess the movement of pesticides and nutrients in relation to agronomic practices in farm plots cultivated with cabbage and chrysanthemum. It was shown that most of the pesticides are absorbed by the topsoils which are enriched by organic fertiliser, and are not leached beyond the top 10 cm layer. Methamidophos, dazomet, cyromazine, triforine and NO₃N were predicted to cause soil contamination. The application of high amounts of fertilisers can cause nitrate contamination to the groundwater in Cameron Highlands.     

In-situ application of colloidal activated carbon for PFAS-contaminated soil and groundwater: A Swedish case study

Soil and groundwater contamination by per- and polyfluoroalkyl substances (PFAS) has been a significant concern to human health and environmental quality. Remediation of contaminated sites is crucial to prevent plume expansion but can prove challenging due to the persistent nature of PFAS combined with their high aqueous mobility. In this case study, we investigated the potential of colloidal activated carbon (CAC) for soil stabilization at the pilot scale, aiming to entrap PFAS and prevent their leaching from soil into groundwater. Monitoring of the site revealed the presence of two potential sources of PFAS contamination at concentrations up to 23 μg L⁻¹ for ∑₁₁PFAS in groundwater. After CAC application, initial results indicated a 76% reduction of ∑₁₁PFAS and high removal rates for long-chain PFAS, such as perfluorooctane sulfonic acid and perfluorooctanoic acid. A spike in concentrations was noticed 6 months after injection of CAC, showing a rebound of the plume and a reduction of treatment effectiveness. Based on long-term monitoring data, the treatment effectiveness for ∑₁₁PFAS dropped to 52%. The rebound of concentrations was attributed to the plume bypass of the barrier due to the presence of high conductivity zones, which likely occurred because of seasonal changes in groundwater flow directions or the CAC application at the site. This demonstrates the need for a detailed and accurate hydrogeological understanding of contaminated sites before designing and applying stabilization techniques, especially at sites with high geologic and hydrologic complexity. The results herein can serve as a guideline for treating similar sites and help avoid potential pitfalls of remedial efforts.     

Effects of Nitrogen Deposition on Bryophyte Species Composition of Calcareous Grasslands

Regular additions of NH₄NO₃ (35–140 kg N ha⁻¹ yr⁻¹) and (NH₄)₂SO₄ (140 kg N ha⁻¹ yr⁻¹) to a calcareous grassland in northern England over a period of 12 years have resulted in a decline in the frequency of the indigenous bryophyte species and the establishment of non-indigenous calcifuge species, with implications for the structure and composition of this calcareous bryophyte community. The lowest NH₄NO₃ additions of 35 kg N ha⁻¹ yr⁻¹ produced significant declines in frequency of Hypnum cupressiforme, Campylium chrysophyllum, and Calliergon cuspidatum. Significant reductions in frequency at higher NH₄NO₃ application rates were recorded for Pseudoscleropodium purum, Ctenidum molluscum, and Dicranum scoparium. The highest NH₄NO₃ and (NH₄)₂SO₄ additions provided conditions conducive for the establishment of two typical calcifuges – Polytrichum spp. and Campylopus introflexus, respectively. Substrate-surface pH measurements showed a dose-related reduction in pH with increasing NH₄NO₃ deposition rates of 1.6 pH units between the control and highest deposition rate, and a further significant fall in pH, of >1 pH unit, between the NH₄NO₃ and (NH₄)₂SO₄ treatments. These results suggest that indigenous bryophyte composition may be at risk from nitrogen deposition rates of 35 kg N ha⁻¹ yr⁻¹ or less. These effects are of particular concern for rare or endangered species of low frequency.     

Nitrate Leaching From a Mountain Forest Ecosystem with Gleysols Subjected to Experimentally Increased N Deposition

Nitrate leaching was measured over seven years of nitrogen (N) addition in a paired-catchment experiment in Alptal, central Switzerland (altitude: 1200 m, bulk N deposition: 12 kg ha^-1 a^-1). Two forested catchments (1500 m² each) dominated by Picea abies) were delimited by trenches in the Gleysols. NH₄NO₃ was added to one of the catchments using sprinklers. During the first year, the N addition was labelled with ¹⁵N. Additionally, soil N transformationswere studied in replicated plots. Pre-treatment NO₃ ^--N leaching was 4 kg ha^-1 a^-1 from both catchments, and remained between 2.5 and 4.8 kg ha^-1 a^-1 in the control catchment. The first year of treatment induced an additional leaching of 3.1 kg ha^-1, almost 90% of which was labelled with ¹⁵N, indicating that it did not cycle through the large N pools of the ecosystem (soil organic matter and plants). These losses partly correspond to NO₃ ^- from precipitation bypassing the soil due to preferential flow. During rain or snowmelt events, NO₃ ^- concentration peaks as the water table is rising, indicating flushing from the soil. Nitrification occurs temporarily along the water flow paths in the soil and can be the source of NO₃ ^- flushing. Its isotopic signature however, shows that this release mainly affects recently applied N, stored only between runoff events or up to a few weeks. At first, the ecosystem retained 90% of the added N (2/3 in the soil), but NO₃ ^- losses increased from 10 to 30% within 7 yr, indicating that the ecosystem became progressively N saturated.     

Controls on leaching of N species in upland moorland catchments

Spatial and temporal changes in mobility of N species have been studied for three UK upland river networks, the Etherow in the South Pennines, the Nether Beck in the Lake District and the Dee in NE Scotland. The catchments are subject to N deposition at 35.1, 22.0 and 10.8–15.6 kg N ha^?1 yr^?1, respectively. The NH⁺ ₄ leaching appears to be predominantly regulated by flow path in more polluted upland catchments. It is greatest where water draining acidified peaty soils contributes more to total discharge. Soluble organic matter may provide the dominant counter anion. In the Etherow and Dee catchments, which are dominated by acid mineral and organic soils, at high discharge NO^? ₃ also appears to be associated with greater input of water from acidified soils. In contrast, for the Nether Beck, higher NO^? ₃ concentrations are associated with tributaries draining soils contributing water with higher alkalinity, suggesting nitrification is important. For the Etherow and Dee, dissolved organic N (DON) appears to originate predominantly from acidified, peaty soils. Spiking experiments with peat soil from the Etherow catchment confirmed the limited capacity of these soils to utilize inorganic N inputs, favouring equilibration with NH⁺ ₄ inputs and leaching losses of inorganic N throughout the year.     

Integration of the Pesticide Impact Rating Index with a Geographic Information System for the Assessment of Pesticide Impact on Water Quality

The pesticide impact rating index (PIRI) has been integrated with a Geographic Information System (GIS) to enable regional assessment of pesticide impact on groundwater and surface water resources. The GIS version of PIRI (PIRI-GIS) was used to assess the impact of pre-planting atrazine use in the pine plantations on the Gnangara Mound, Western Australia. The impact on groundwater was found to be spatially variable, mainly dependent on soil type and depth to groundwater, because land use variables were spatially constant. Areas with the greatest impact on groundwater were those where the soil had a low sorption capacity for atrazine. Knowledge of the spatial distribution of the sorption coefficient based on organic carbon (K _oc) for atrazine was found to significantly improve the results from PIRI-GIS. Average values for K _oc (i.e. based on overseas data) were too low for most of the local soil types, resulting in a general overestimation of pesticide impact on groundwater resources, but an underestimation of impact in areas that should be of greatest concern (i.e. where the soil has a low sorption capacity for atrazine).     

Integrated Nitrogen and Flow Modelling (INCA) in a Boreal River Basin Dominated by Forestry: Scenarios of Environmental Change

A new version (v1.7) of the Integrated Nitrogen in CAtchments model(INCA) was applied to the northern boreal Simojoki river basin (3160 km²) in Finland. The INCA model is a semi-distributed, dynamic nitrogen (N) process model which simulates N transport and processes in catchments. The INCA model was applied to model flow and seasonal inorganic N dynamics of the river Simojoki basin over the period 1994–1996, and validated for two more years. Both calibration and validation of the model were successful. The model was able to simulate annual dynamics of inorganic N concentrations in the river. The effects of forest management and atmospheric deposition on inorganic N fluxes to the sea in 2010 were studied. Three scenarios were applied for forestry practices and two for deposition. The effects of forest cutting scenarios and atmospheric deposition scenarios on inorganic N flux to the sea were small. The combination of the maximum technically possible reduction of N deposition and a decrease of 100% in forest cutting and peat mining areas decreased NO₃ ^--N flux by 6.0% and NH₄ ⁺-N flux by 3.1%.     

Hydrogeomorphological Controls on Groundwater Quality in the Rattaphum Catchment (Songkhla Lake Basin), Thailand

The Rattaphum Catchment comprises four major hydrogeomorphic units: mountains, footslopes, plains and inland swamps around a lake system. The area accommodates three main agro-ecosystems: vegetable, rubber and fruits. During the high-rainfall period, groundwater levels rise near to the soil surface in all agro-ecosystems. The high water levels remain for 3–4 months in the coastal plain, while in other areas the groundwater level fluctuates according to the intensity of rainfall events during the 2–3 months of the rainy season. Groundwater salinity is higher near Songkhla Lake and decreases rapidly inland. It is generally lower near streams. Salinity is also lower during periods of higher recharge, increasing slightly during the dry season due to leaching of chemicals from the agricultural areas. In the saturated sandy soils with high hydraulic conductivity and in the vegetable agro-ecosystem areas with high water levels, the NO₃ level in groundwater always exceeds the WHO standard. Variations in NO₃ levels are closely related to patterns of landuse, with higher nitrate levels commonly found in vegetable areas and lower levels associated with fruit and rubber tree plantations. Nearly all groundwater and surface water is contaminated by coliform bacteria, with the level of contamination controlled by groundwater levels, the amount of rainfall and farm activities. Vegetable agro-ecosystems, which have the most intensive cropping system, were found to be the most polluted. In all of the agro-ecosystems, the most polluted period coincided with the first series of rainfall events.     

Acidification Trends and the Evolution of Neutralization Mechanisms through Time at the Bear Brook Watershed in Maine (BBWM), U.S.A.

The paired catchment study at the forested Bear Brook Watershed in Maine (BBWM) U.S.A. documents interactions among short- to long-term processes of acidification. In 1987–1989, runoff from the two catchments was nearly identical in quality and quantity. Ammonium sulfate has been added bi-monthly since 1989 to the West Bear catchment at 1800 eq ha^-1 a^-1; the East Bear reference catchment is responding to ambient conditions. Initially, the two catchments had nearly identical chemistry (e.g., Ca²⁺, Mg²⁺, SO₄ ^2-, and alkalinity ≈82, 32, 100, and 5 μeq L^-1, respectively). The manipulated catchment responded initially with increased export of base cations, lower pH and alkalinity, and increased dissolved Al,NO₃ ^- and SO₄ ^2-. Dissolved organic carbon and Si have remained relatively constant. After 7 yr of treatment, the chemical response of runoff switched to declining base cations, with the other analytes continuing their trends; the exports of dissolved and particulate Al, Fe, and P increased substantially as base cations declined. The reference catchment has slowly acidified under ambient conditions, caused by the base cation supply decreasing faster than the decrease of SO₄ ², as pollution abates. Export of Al, Fe and, P is mimicking that of the manipulated watershed, but is lower in magnitude and lags in time. Probable increasing SO₄ ^2- adsorption caused by acidification has moderated the longer-term trends of acidification of both watersheds. The trends of decreasing base cations were interrupted by the effects of several short-term events, including severe ice storm damage to the canopy, unusual snow pack conditions, snow melt and rain storms, and episodic input of marine aerosols. These episodic events alter alkalinity by5 to 15 μeq L^-1 and make it more difficult to determine recovery from pollution abatement.     

Simulation of Nitrogen Dynamics and Fluxes in Contrasting Catchments in Norway by Applying the Integrated Nitrogen Model for Catchments (INCA)

The process-based INCA model was applied to Dalelva Brook (3.2 km²) and the Bjerkreim River (685 km²) including several subcatchments, in order to test the model's ability to simulate streamwater nitrate (NO₃ ^-) dynamics and output fluxes under highly contrasting climatic conditions and nitrogen (N) loading. The simulated runoff volumes and mean NO₃ ^- concentrations at Dalelva and Bjerkreimwere within +2 to +10% of the measured average during 1993–1995 (–19 to +31% within individual years). INCA to a great extent also reproduced the observed streamwater flow dynamics at both study sites (coefficient of determination, r ² > 0.70). Temporal variation of streamwater NO₃ ^- during 1993–1995 was captured quite well by the model, especially at small catchments with a distinct seasonal NO₃ ^- pattern (r ² = 0.46–0.68). At the Bjerkreim River outlet, the relationship were somewhat weaker (r ² = 0.26, p < 0.01). Despite a few situations where the model failed to capturethe streamwater NO₃ ^- dynamics, INCA proved to be a quite robust tool for simulating NO₃ ^- dynamics and output fluxes in the two study catchments.     

The Use of Zero‐Valent Iron (ZVI) Technology to Promote DDT and Dieldrin Degradation at Point Pelee National Park

Point Pelee National Park (PPNP) is highly contaminated with dichlorodiphenyltrichloroethane (DDT) and dieldrin due to the historical use of these two persistent organochlorine pesticides. Zero‐valent iron (ZVI) technology with and without amendments has been successfully used in the past to promote organochlorine pesticides degradation in several locations in North America and Europe. In this study, the use of two commercially available ZVI products, DARAMEND^® and EHC^®, to promote DDT and dieldrin degradation in PPNP's soil and groundwater were investigated. DARAMEND^® was applied to PPNP's soil in a laboratory experiment and in an in situ pilot‐scale plot. In both cases, DARAMEND^® did not significantly increase DDT or dieldrin degradation in treated soils. The effectiveness of EHC^® was tested in a laboratory experiment that simulated the park's groundwater environment using PPNP's pesticide contaminated soil. The result was consistent with the one reported for DARAMEND^®, in that there was no significant increase in DDT or dieldrin degradation in any of the samples treated with EHC^®. These results demonstrate that both of these ZVI commercially available products are not suitable for in situ remediation at PPNP.  ©2017 Wiley Periodicals, Inc.     

Fate and distribution of nitrogen in soil and plants irrigated with landfill leachate

Landfill leachate contains a high concentration of ammoniacal substances which can be a potential supply of N for plants. A bioassay was conducted using seeds of Brassica chinensis and Lolium perenne to evaluate the phytotoxicity of the leachate sample. A soil column experiment was then carried out in a greenhouse to study the effect of leachate on plant growth. Two grasses (Paspalum notatum and Vetiver zizanioides) and two trees (Hibiscus tiliaceus and Litsea glutinosa) were irrigated with leachate at the EC50 levels for 12 weeks. Their growth performance and the distribution of N were examined and compared with columns applied with chemical fertilizer. With the exception of P. notatum, plants receiving leachate and fertilizer grew better than those receiving water alone. The growth of L. glutinosa and V. zizanioides with leachate irrigation did not differ significantly from plants treated with fertilizer. Leachate irrigation significantly increased the levels of NH_x-N in soil. Although NO_x-N was below 1 mg N L⁻¹ in the leachate sample, the soil NO_x-N content increased by 9-fold after leachate irrigation, possibly as a result of nitrification. Leachate irrigation at EC50 provided an N input of 1920 kg N ha⁻¹ over the experimental period, during which up to 1050 kg N ha⁻¹ was retained in the soil and biomass, depending on the type of vegetation. The amount of nutrient added seems to exceed beyond the assimilative capability. Practitioners should be aware of the possible consequence of N saturation when deciding the application rate if leachate irrigation is aimed for water reuse.     

Matrix stability and leaching behaviour in ettringite-based stabilization systems doped with heavy metals

A stabilizing matrix able to generate ettringite from calcium sulphoaluminate in the presence of CaSO₄·2H₂O and Ca(OH)₂ has been studied. Ten series of stabilized samples have been produced, each containing 10% of one of the following heavy metal salts: Cd(NO₃)₂, Cr(NO₃)₃ Cu(NO₃)₂, Fe(NO₃)₃, Mn(NO₃)₃, Ni(NO₃)₂, Pb(NO₃)₂, Zn(NO₃)₂, K₂CrO₄ and K₂MoO₄. The study has been directed towards the matrix stability and metal release behaviour in three different dynamic leaching tests carried out with the following media: distilled water, pH 4 HNO₃ solution and pH 4.74 acetic acid/sodium acetate buffer solution. It has been found that the matrix stability and leaching behaviour strongly depend on the nature of the dopant salt, as well as on the nature of the leaching medium. In many cases the leaching medium attack causes disaggregation of the matrix but this does not imply complete dissolution of the dopant metal. When the leaching medium is the acetate buffer the chemical resistance to dissolution increases as the physico-mechanical resistance to disgregation decreases. This apparently contradictory result has been explained in terms of microstructure of the stabilized samples.     

A Conceptual Model of Spatially Heterogeneous Nitrogen Leaching from a Welsh Moorland Catchment

Soil- and stream-water data from the Plynlimon research area, mid-Wales, have been used to develop a conceptual model of spatial variations in nitrogen (N) leaching within moorland catchments. Extensive peats, in both hilltop and valley locations, are considered near-complete sinks for inorganic N, but leach the most dissolved organic nitrogen (DON). Peaty mineral soils on hillslopes also retain inorganic N within upper organic horizons, but a proportion percolates into mineral horizons as nitrate (NO ₃ ^– ), either through incomplete immobilisation in the organic layer, or in water bypassing the organic soil matrix via macropores. This NO ₃ ^– reaches the stream where mineral soilwaters discharge (via matrix throughflow or pipeflow) directly to the drainage network, or via small N-enriched flush wetlands. NO ₃ ^– in hillslope waters discharging into larger valley wetlands will be removed before reaching the stream. A concept of catchment nitrate leaching zones is proposed, whereby most stream NO ₃ ^– derives from localised areas of mineral soil hillslope draining directly to the stream; the extent of these zones within a catchment may thus determine its overall susceptibility to elevated surface water NO ₃ ^– concentrations.     

Re-cycling of remediated soil - Evaluation of leaching tests as tools for characterization

In Sweden, leaching tests with deionized water (D.W.) are utilized in risk assessment of materials entering landfills, but implementation of these results to evaluate the risk of spreading of pollutants in the environment is difficult. One problem is that most leaching procedures only consider heavy metals release, whereas organic pollutants are left out. The aim of the present study was to assess the possible pollutant mitigation in four remediated soils, three with heavy metals and one with polycyclic aromatic hydrocarbons (PAH) contamination. The mitigation was evaluated by standardized batch and column leaching tests utilizing three different leaching solutions: D.W., a weak ionic solution (0.001 M CaCl₂) and an artificially made soil water (ASW). In general, batch leaching tests implied larger contaminant removal than column leaching test, possibly due to the more rough treatment of the soil particles, and guidelines would at times be exceeded by the batch leaching test but not by column leaching tests. Utilization of CaCl₂ was found to release less heavy metal than D.W., whereas the metals mobilized by ASW were removed from solution by the filtration of soil leachates. Low molecular weight PAH was most efficiently mobilized by CaCl₂, while D.W. worked better for high molecular weight PAH. Despite very low initial PAH-concentrations, tap- and groundwater criteria were exceeded by all leaching solutions.     

Landfill leachate treatment with willows and poplars – Efficiency and plant response

Irrigation of willow and poplar short-rotation coppice with landfill leachate is an increasingly interesting treatment option. Minimal leaching to groundwater and disturbance to plant growth must be ensured, but in such systems, where various site-specific factors interact, a case-specific approach is needed to determine potential hazards. This paper compares the effect of leachate irrigation on willow grown in clay lysimeters and poplar grown in sand lysimeters. Leachate irrigation increased willow biomass production, but not that of poplar. Near-zero nitrate-N concentrations were found in drainage water for both species after 2 years of irrigation. Ability to retain total N and P, and TOC was relatively high for willow, taking into account the large amounts supplied, and better than for poplar. To reduce environmental risks the irrigation load should be reduced, but if leachate concentrations are reduced, the irrigation load can be as high as 6 mm/day.     

Nutrients on Asphalt Parking Surfaces in an Urban Environment

Amounts of readily soluble nutrients on asphalt parking lot surfaceswere measured at four locations in metropolitan Phoenix, Arizona, U.S.A. Using a rainfall simulator, short intense rainfall events were generated to simulate `first flush' runoff. Samples were collected from 0.3 m² sections of asphalt at 8 to 10 sites on each of four parkinglots, during the pre-monsoon season in June-July 1998 and analyzed for dissolved NO₃ ^--N, NH₄ ⁺-N, soluble reactive phosphate (SRP), and dissolved organic carbon (DOC). Runoff concentrations varied considerably for NO₃ ^--N and NH₄ ⁺-N (between 0.1 and 115.8 mg L^-1) and DOC (26.1 to 295.7 mg L^-1), but less so for SRP (0.1 to 1.0 mg L^-1), representing average surface loadings of 191.3, 532.2, and 1.8 mg m^-2 respectively. Compared with similar data collected from undeveloped desert soil surfaces outside the city, loadings of NO₃ ^--N and NH₄ ⁺-N on asphalt surfaces were greater by factors of 91 and 13, respectively. In contrast, SRP loads showed little difference between asphalt and desert surfaces. Nutrient fluxes in runoff from a storm that occurred shortly after the experiments were used to estimate input-output budgets for 3 of the lots under study. Measured outputs of DOC and SRP were similar to those predicted using rainfall and experimentally determined surface loadings, but for NH₄ ⁺-N and particularly for NO₃ ^--N, estimated rainfall inputs and surface runoff were significantly higher than exports in runoff. This suggests that parking lots may be important sites for nutrient accumulation and temporary storage in arid urban catchments.