Use pattern of pesticides and their predicted mobility into shallow groundwater and surface water bodies of paddy lands in Mahaweli river basin in Sri Lanka

Pesticides applied on agricultural lands reach groundwater by leaching, and move to offsite water bodies by direct runoff, erosion and spray drift. Therefore, an assessment of the mobility of pesticides in water resources is important to safeguard such resources. Mobility of pesticides on agricultural lands of Mahaweli river basin in Sri Lanka has not been reported to date. In this context, the mobility potential of 32 pesticides on surface water and groundwater was assessed by widely used pesticide risk indicators, such as Attenuation Factor (AF) index and the Pesticide Impact Rating Index (PIRI) with some modifications. Four surface water bodies having greater than 20% land use of the catchment under agriculture, and shallow groundwater table at 3.0 m depth were selected for the risk assessment. According to AF, carbofuran, quinclorac and thiamethoxam are three most leachable pesticides having AF values 1.44 × 10^?2, 1.87 × 10^?3 and 5.70 × 10^?4, respectively. Using PIRI, offsite movement of pesticides by direct runoff was found to be greater than with the erosion of soil particles for the study area. Carbofuran and quinclorac are most mobile pesticides by direct runoff with runoff fractions of 0.01 and 0.08, respectively, at the studied area. Thiamethoxam and novaluron are the most mobile pesticides by erosion with erosion factions of 1.02 × 10^?4 and 1.05 × 10^?4, respectively. Expected pesticide residue levels in both surface and groundwater were predicted to remain below the USEPA health advisory levels, except for carbofuran, indicating that pesticide pollution is unlikely to exceed the available health guidelines in the Mahaweli river basin in Sri Lanka.     

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.

     

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.     

Oryzalin fate and transport in runoff water in Mediterranean vineyards

An experimental study was conducted in a 91.4-ha Mediterranean vineyard catchment in southern France to characterize the fate and transport of oryzalin in runoff water and thus to assess the risk of contamination of surface waters. Oryzalin concentrations in soil were monitored on two fields, one no-till and one tilled from March 1998 to March 2000. Concentrations in solution and on solid phase of runoff water were measured at the outlets of both fields and the catchment. The droughts in the two summer periods reduced the dissipation of oryzalin and increased its field half-life up to 35 days. Consequently, oryzalin was detected throughout the year in runoff water, with maximum dissolved concentrations > 600 microg l(-1) at the field scale. Oryzalin transport essentially occurred in solution. At the no-till field, seasonal losses were 2.29% and 1.89% of the applied amount in 1998 and 1999, respectively. The corresponding values at the tilled field were 1.56% and 0.29%, since tillage reduced total losses by reducing surface runoff. At the catchment scale, oryzalin concentrations were smaller than those at the field scale, due to dilution effects and staggering of application. Large part of the overland flow from the fields reinfiltrated in the ditches before reaching the outlet of the catchment. As a result, seasonal oryzalin losses were <0.2% of the applied amount.     

Effects of copper fungicide residues on the microbial function of vineyard soils

The use of copper-based fungicides leads to an accumulation of copper (Cu) in vineyard soils, potentially causing adverse effects to the microbial function and fertility of the soil. This study used a soil microcosm approach to assess the effects of Cu accumulation on microbial function in vineyard soils. Surface soil samples were collected from 10 vineyards and a number of un-impacted reference sites in each of three different viticultural regions of Australia. The field-collected soils were transferred to microcosms and maintained for up to 93 days in the laboratory at 20–22 °C and 60 % of their maximum water-holding capacity. The microbial function of the soils was indicated by measuring phosphomonoesterase, arylsulfatase, urease, and phenol oxidase activities. In general, the vineyard soils had greater concentrations of Cu and lower enzyme activities than in the reference soils, although a weak negative relationship between Cu and enzyme activity could only be found for phosphomonoesterase activity. The results show that soil physical–chemical properties (i.e., organic carbon, pH) are greater determinants of soil enzyme activity than increased soil Cu concentration at the Cu concentrations present in vineyard soils.     

The dissipation of three fungicides in a biobed organic substrate and their impact on the structure and activity of the microbial community

Biopurification systems (BPS) have been introduced to minimise the risk for point source contamination of natural water resources by pesticides. Their depuration efficiency relies mostly on the high biodegradation of their packing substrate (biomixture). Despite that, little is known regarding the interactions between biomixture microflora and pesticides, especially fungicides which are expected to have a higher impact on the microbial community. This study reports the dissipation of the fungicides azoxystrobin (AZX), fludioxonil (FL) and penconazole (PC), commonly used in vineyards, in a biomixture composed of pruning residues and straw used in vineyard BPS. The impact of fungicides on the microbial community was also studied via microbial biomass carbon, basal respiration and phospholipid fatty acid analysis. AZX dissipated faster (t _1/2?=?30.1 days) than PC (t _1/2?=?99.0 days) and FL (t _1/2?=?115.5 days). Fungicides differently affected the microbial community. PC showed the highest adverse effect on both the size and the activity of the biomixture microflora. A significant change in the structure of the microbial community was noted for PC and FL, and it was attributed to a rapid inhibition of the fungal fraction while bacteria showed a delayed response which was attributed to indirect effects by the late proliferation of fungi. All effects observed were transitory and a full recovery of microbial indices was observed 60 days post-application. Overall, no clear link between pesticide persistence and microbial responses was observed stressing the complex nature of interactions between pesticides in microflora in BPS.     

Environmental fate of pesticides used in Australian viticulture: Behaviour of dithianon and vinclozolin in the soils of the South Australian Riverland

The red calcareous earth soils of the South Australian Riverland produce more than one-third of the grapes used in Australian winemaking. As part of on-going investigations into pesticide transport in Australian vineyard soils, the movement of the fungicides dithianon and vinclozolin through such strongly alkaline soils was investigated. Small, undisturbed soil cores were extracted from the inter-row topsoil of a vineyard adjacent to the River Murray, approximately 10 km S.W. of Overland Corner, South Australia. The vines were grown in a deep (1 – 4 m) reddish brown, strongly alkaline, sandy loam with a low organic carbon content (1 – 2 %). Surface fluxes of pesticide were applied at the maximum recommended application rates to the surface of the cores, which were then irrigated, and pesticide residues in the leachate determined by HPLC. No leaching of either dithianon or vinclozolin occurred. Dithianon was immobilised in the top 2 cm of the soil. Dithianon concentrations were low ( 0 – 37 % applied dose) suggesting that rapid degradation of this compound occurs in these soils (63 – 100 % degradation in 10 days). Extremely low concentrations of vinclozolin were found throughout the soil core profiles (0.05 – 1.4 % applied dose) suggesting that this fungicide was somewhat mobile, but also that it too was unstable in such alkaline soils (> 98 % degradation in 10 days). These results suggest that the irrigated vineyard soils of this region are unlikely to be prone to leaching of dithianon or vinclozolin, and therefore that groundwater supplies in this area are unlikely to be at any significant risk of contamination through viticultural use of these compounds.     

Transport and attenuation of dissolved glyphosate and AMPA in a stormwater wetland

Glyphosate is an herbicide used widely and increasingly since the early 1990s in production of many crops and in urban areas. However, knowledge on the transport of glyphosate and its degradation to aminomethylphosphonic acid (AMPA) in ecosystems receiving urban or agricultural runoff is lacking. Here we show that transport and attenuation of runoff-associated glyphosate and AMPA in a stormwater wetland differ and largely vary over time. Dissolved concentrations and loads of glyphosate and AMPA in a wetland receiving runoff from a vineyard catchment were assessed during three consecutive seasons of glyphosate use (March to June 2009, 2010 and 2011). The load removal of glyphosate and AMPA by the wetland gradually varied yearly from 75% to 99%. However, glyphosate and AMPA were not detected in the wetland sediment, which emphasises that sorption on the wetland vegetation, which increased over time, and biodegradation were prevailing attenuation processes. The relative load of AMPA as a percentage of total glyphosate increased in the wetland and ranged from 0% to 100%, which indicates the variability of glyphosate degradation via the AMPA pathway. Our results demonstrate that transport and degradation of glyphosate in stormwater wetlands can largely change over time, mainly depending on the characteristics of the runoff event and the wetland vegetation. We anticipate our results to be a starting point for considering degradation products of runoff-associated pesticides during their transfer in wetlands, in particular when using stormwater wetlands as a management practice targeting pesticide attenuation.     

Pesticide Modelling for a Small Catchment Using SWAT-2000

Pesticides in stream flow from the 142 ha Colworth catchment in Bedfordshire, UK were monitored from October 1999 to December 2000. About 47% of the catchment is tile-drained and different pesticides and cropping patterns have recently been evaluated in terms of their effect on nutrient and pesticide losses to the stream. The data from Colworth were used to test soil and water assessment tool (SWAT) 2000 predictions of pesticide concentrations at the catchment outlet. A sound model set-up to carry out pesticide modelling was created by means of hydrological modelling with proper simulation of crop growth and evapotranspiration. The pesticides terbuthylazine, terbutryn, cyanazine and bentazone were modelled. There was close agreement between SWAT-predicted pesticide concentration values and observations. Scenario trials were conducted to explore management options for reducing pesticide loads arriving at the catchment outlet. The results obtained indicate that SWAT can be used as a tool to understand pesticide behavior at the catchment scale.     

Distribution of polybrominated diphenyl ethers and dust particle size fractions adherent to skin in indoor dust,Pretoria, South Africa

In order to determine human exposure to the indoor toxicant, selection of dust fraction and understanding dust particle size distribution in settled indoor dust are very important. This study examined the influence of dust particle size on the concentration of polybrominated diphenyl ethers (PBDEs) congeners, assessed the distribution of dust particle size and characterized the main indoor emission sources of PBDEs. Accordingly, the concentrations of PBDE congeners determined in different indoor dust fractions were found to be relatively higher in the order of dust particle size: 45–106 μm?>?(<45 μm)?>?106–150 μm. The finding shows arbitrary selection of dust fractions for exposure determination may result in wrong conclusions. Statistically significant moderate correlation between the concentration of Σ₉PBDEs and organic matter content calculated with respect to the total dust mass was also observed (r?=?0.55, p?=?0.001). On average, of total dust particle size <250 μm, 93.4 % (m/m%) of dust fractions was associated with less than 150 μm. Furthermore, of skin adherent dust fractions considered (<150 μm), 86 % (v/v%) is in the range of particle size 9.25–104.7 μm. Electronic materials treated with PBDEs were found the main emission sources of PBDE congeners in indoor environment. Based on concentrations of PBDEs determined and mass of indoor dust observed, 150 μm metallic sieve is adequate for human exposure risk assessment. However, research in this area is very limited and more research is required to generalize the fact.     

Herbicides: A new threat to the Great Barrier Reef

The runoff of pesticides (insecticides, herbicides and fungicides) from agricultural lands is a key concern for the health of the iconic Great Barrier Reef, Australia. Relatively low levels of herbicide residues can reduce the productivity of marine plants and corals. However, the risk of these residues to Great Barrier Reef ecosystems has been poorly quantified due to a lack of large-scale datasets. Here we present results of a study tracing pesticide residues from rivers and creeks in three catchment regions to the adjacent marine environment. Several pesticides (mainly herbicides) were detected in both freshwater and coastal marine waters and were attributed to specific land uses in the catchment. Elevated herbicide concentrations were particularly associated with sugar cane cultivation in the adjacent catchment. We demonstrate that herbicides reach the Great Barrier Reef lagoon and may disturb sensitive marine ecosystems already affected by other pressures such as climate change.     

Assessing pesticide concentrations and fluxes in the stream of a small vineyard catchment - Effect of sampling frequency

This study reports on the occurrence and behaviour of six pesticides and one metabolite in a small stream draining a vineyard catchment. Base flow and flood events were monitored in order to assess the variability of pesticide concentrations according to the season and to evaluate the role of sampling frequency on the evaluation of fluxes estimates. Results showed that dissolved pesticide concentrations displayed a strong temporal and spatial variability. A large mobilisation of pesticides was observed during floods, with total dissolved pesticide fluxes per event ranging from 5.7 × 10⁻³ g/Ha to 0.34 g/Ha. These results highlight the major role of floods in the transport of pesticides in this small stream which contributed to more than 89% of the total load of diuron during August 2007. The evaluation of pesticide loads using different sampling strategies and method calculation, showed that grab sampling largely underestimated pesticide concentrations and fluxes transiting through the stream.     

Contamination of marine fauna by chlordecone in Guadeloupe: evidence of a seaward decreasing gradient

Chlordecone is an organochlorine pesticide, used in the Lesser Antilles from 1972 to 1993 to fight against a banana weevil. That molecule is very persistent in the natural environment and ends up in the sea with runoff waters. The objective of the present study is to evaluate the level of contamination in several trophic groups of marine animals according to their distance from the source of pollution. Samples of suspended matter, macroalgae, herbivorous fishes, detrivorous crustaceans, zooplanktivorous fishes, first- and second-order of carnivorous fishes, and piscivorous fishes have been collected in two sites, located downstream the contaminated sites (Goyave and Petit-Bourg), in three marine habitats (coastal mangroves, seagrass beds located 1.5 km from the shoreline, and coral reefs at 3 km offshore). Animals collected in mangroves were the most contaminated (mean concentrations 193 μg kg^?1 in Goyave and 213 μg kg^?1 in Petit-Bourg). Samples from seagrass beds presented intermediate concentrations of chlordecone (85 μg kg^?1 in Goyave and 107 μg kg^?1 in Petit-Bourg). Finally, samples from coral reefs were the less contaminated (71 μg kg^?1 in Goyave and 74 μg kg^?1 in Petit-Bourg). Reef samples, collected 3 km offshore, were two to three times less contaminated than those collected in mangroves.     

Particle size distribution of n-alkanes and polycyclic aromatic hydrocarbons (PAHS) in urban and industrial aerosol of Algiers,Algeria

The distribution of ambient air n-alkanes and polycyclic aromatic hydrocarbons (PAHs) associated to particles with aerodynamic diameters lesser than 10 μm (PM₁₀) into six fractions (five stages and a backup filter) was studied for the first time in Algeria. Investigation took place during September of 2007 at an urban and industrial site of Algiers. Size-resolved samples (<0.49, 0.49–0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2, and7.2–10 μm) were concurrently collected at the two sampling sites using five-stage high-volume cascade impactors. Most of n-alkanes (~72 %) and PAHs (~90 %) were associated with fine particles ≤1.5 μm in both urban and industrial atmosphere. In both cases, the n-alkane contents exhibited bimodal or weakly bimodal distribution peaking at the 0.95–1.5-μm size range within the fine mode and at 7.3–10 μm in the coarse mode. Low molecular weight PAHs displayed bimodal patterns peaking at 0.49–0.95 and 7.3–10 μm, while high molecular weight PAHs exhibited mono-modal distribution with maximum in the <0.49-μm fraction. While the mass mean diameter of total n-alkanes in the urban and industrial sites was 0.70 and 0.84 μm, respectively, it did not exceed 0.49 μm for PAHs. Carbon preference index (~1.1), wax% (10.1–12.8), and the diagnostic ratios for PAHs all revealed that vehicular emission was the major source of these organic compounds in PM₁₀ during the study periods and that the contribution of epicuticular waxes emitted by terrestrial plants was minor. According to benzo[a]pyrene-equivalent carcinogenic power rates, ca. 90 % of overall PAH toxicity across PM₁₀ was found in particles ≤0.95 μm in diameter which could induce adverse health effects to the population living in these areas.     

A qualitative field method for monitoring pesticides in the edge-of-field runoff

A field method is described, which allows the qualitative estimation of pesticide contamination in the edgeof-field runoff. The method employs cheap and easy-to-use runoff sampling bottles, which were installed in an agricultural stream catchment over a period of three growing seasons. During this time 18 runoff events were detected, in nine of which insecticide contamination was measured (maximum concentrations: lindane 0.7 μg l⁻¹ and 12.7 μg kg⁻¹, parathion 20 μg l⁻¹ and 728 μg kg⁻, fenvalerate 18.4 μg 1-1 and 924 μg kg⁻¹). These insecticides were detected mainly as particle-bound chemicals. On about 80 % of the occasions the presence or absence of runoff measured in the field was in agreement with a simulation of runoff presence or absence using the runoff model KINEROS.     

Effects of hydromorphology and riparian vegetation on the sediment quality of agricultural low-order streams: consequences for stream restoration

Intensive agricultural land use imposes multiple pressures on streams. More specifically, the loading of streams with nutrient-enriched soil from surrounding crop fields may deteriorate the sediment quality. The current study aimed to find out whether stream restoration may be an effective tool to improve the sediment quality of agricultural headwater streams. We compared nine stream reaches representing different morphological types (forested meandering reaches vs. deforested channelized reaches) regarding sediment structure, sedimentary nutrient and organic matter concentrations, and benthic microbial respiration. Main differences among reach types were found in grain sizes. Meandering reaches featured larger mean grain sizes (50–70 μm) and a thicker oxygenated surface layer (8 cm) than channelized reaches (40 μm, 5 cm). Total phosphorous amounted for up to 1,500 μg?g^?1 DW at retentive channelized reaches and 850–1,050 μg?g^?1 DW at the others. While N-NH₄ accumulated in the sediments (60–180 μg?g^?1 DW), N-NO₃ concentrations were generally low (2–5 μg?g^?1 DW). Benthic respiration was high at all sites (10–20 g O₂ m^?2?day^?1). Our study shows that both hydromorphology and bank vegetation may influence the sediment quality of agricultural streams, though effects are often small and spatially restricted. To increase the efficiency of stream restoration in agricultural landscapes, nutrient and sediment delivery to stream channels need to be minimized by mitigating soil erosion in the catchment.     

Copper mobilization affected by weather conditions in a stormwater detention system receiving runoff waters from vineyard soils (Champagne, France)

Copper, a priority substance on the EU-Water Framework Directive list, is widely used to protect grapevines against fungus diseases. Many vineyards being located on steep slopes, large amounts of Cu could be discharged in downstream systems by runoff water. The efficiency of stormwater detention basins to retain copper in a vineyard catchment was estimated. Suspended solids, dissolved (Cu_diss) and total Cu (Cu_tot) concentrations were monitored in runoff water, upstream, into and downstream from a detention pond. Mean Cu_tot concentrations in entering water was 53.6 μg/L whereas it never exceeded 2.4 μg/L in seepage. Cu_tot concentrations in basin water (>100 μg/L in 24% of the samples) exceeded LC₅₀ values for several aquatic animals. Copper was principally sequestered by reduced compounds in the basin sediments (2/3 of Cu_tot). Metal sequestration was reversible since sediment resuspension resulted in Cu remobilization. Wind velocity controlled resuspension, explained 70% of Cu_diss variability and could help predicting Cu mobilization.     

Composition and effects of inhalable size fractions of atmospheric aerosols in the polluted atmosphere: Part I. PAHs,PCBs and OCPs and the matrix chemical composition

Atmospheric particulate matter (PM) abundance, mass size distribution (MSD) and chemical composition are parameters relevant for human health effects. The MSD and phase state of semivolatile organic pollutants were determined at various polluted sites in addition to the PM composition and MSD. The distribution pattern of pollutants varied from side to side in correspondence to main particle sources and PM composition. Levels of particle-associated polycyclic aromatic hydrocarbons (PAHs) were 1–30 ng m^?3 (corresponding to 15–35 % of the total, i.e., gas and particulate phase concentrations), of polychlorinated biphenyls (PCBs) were 2–11 pg m^?3 (4–26 % of the total) and of DDT compounds were 2–12 pg m^?3 (4–23 % of the total). The PM associated amounts of other organochlorine pesticides were too low for quantification. The organics were preferentially found associated with particles <0.45 μm of aerodynamic equivalent diameter. The mass fractions associated with sub-micrometer particles (PM_0.95) were 73–90 %, 34–71 % and 36–81 % for PAHs, PCBs and DDT compounds, respectively. The finest particles fraction had the highest aerosol surface concentration (6.3–29.7)_×10^?6 cm^?1 (44–70 % of the surface concentration of all size fractions). The data set was used to test gas-particle partitioning models for semivolatile organics for the first time in terms of the organics' MSD and size-dependent PM composition. The results of this study prove that at the various sites particles with diverse size, matrix composition, amount of contaminants and toxicological effects occur. Legislative regulation based on gravimetric determination of PM mass can clearly be insufficient for assessment.     

Neurotoxic effect and metabolic responses induced by a mixture of six pesticides on the earthworm Aporrectodea caliginosa nocturna

The effects of a mixture of insecticides and/or fungicides at different environmental concentrations were investigated on a Aporrectodea caliginosa nocturna population. This laboratory experiment was carried out in order to reproduce Gaillac (France) vineyard conditions. Neurotoxicity (cholinesterase), metabolisation (glutathione-S-transferase) and oxidative stress (catalase) enzymes were studied as biomarkers in earthworms after short-term exposure in terraria. The aim was to observe the global effects of pesticide exposure, as in a vineyard, rather than focus on each isolated biomarker variation, or on each compound's impact. ChE activity was inhibited after a few days of insecticide and/or fungicide exposure, indicative of a neurotoxic effect in earthworms. The significant increase in GST and CAT activities revealed the metabolisation of these products resulting in the production of reactive oxygen species. After a long period of exposure or high concentrations, earthworms were physiologically damaged: they could not cope with the high toxicity (cellular dysfunction, protein catabolism...). Chemical analysis showed that pesticide bioaccumulation in earthworm tissues, even in those exposed to the highest concentrations and for the longest periods, was very low (under LOD) or absent. However, the study of pesticide residues in terraria after 34 days in a climate chamber suggested that earthworms participate in soil pesticide breakdown.