Herbicide residues in Australian grain cropping soils at sowing and their relevance to crop growth.

Herbicides are used extensively in Australian grain cropping systems. Despite occasional observations of herbicide-induced phytotoxicity, there is little information on the persistence and carryover of multiple herbicide classes in cropping soils and the risk to subsequent crops. Two soil surveys were conducted, in 2015 (n = 40) and 2016 (n = 42), across different Australian grain cropping fields prior to sowing of winter crops, and soil samples analysed for herbicide residues (16 analytes in 2015 and 22 analytes in 2016). Samples in 2015 were taken at two depths (0-10 cm and 10-30 cm), whilst samples in 2016 were taken in topsoil (0-10 cm) only, but from two discrete locations in each field. Our research in both years found at least one herbicide (or herbicide metabolite) residue at all sites, with a median of 6 analytes detected in 2015 and 7 analytes detected in 2016. The most frequently detected residues were glyphosate and its primary breakdown product aminomethylphosphonic acid (AMPA), in 87 and 100%, respectively, of topsoil (0-10 cm) samples in 2015, and 67 and 93% of samples in 2016. The median concentration of glyphosate in 2015 was 0.12 mg kg-1, while AMPA was 0.41 mg kg-1. In 2016, median concentrations of glyphosate and AMPA were 0.22 mg kg-1 and 0.31 mg kg-1. Residues of 2,4-dichlorophenoxyacetic acid, trifluralin and diflufenican were also detected in >40% of topsoil samples in both seasons, but with median concentrations of <0.05 mg kg-1. A literature review found limited availability of phytotoxicity thresholds for major grain crops exposed to soilborne herbicide residues. A risk assessment using available thresholds suggested that although up to 29% of fields contained trifluralin residues that could constrain cereal crop growth, and 24% of fields contained residues of phenoxy or sulfonylureas that could affect dicotyledonous crops, the majority of these fields when planted with tolerant crops would be unlikely to be affected by herbicide residues. More work is required to ascertain the spatial distribution, bioavailability and phytotoxicity of residues and residue mixtures to enable a more accurate agronomic risk assessment.

Tetraphenylethene Functionalized Polyhedral Oligomeric Silsesquioxane Fluorescent Probe for Rapid and Selective Trifluralin Sensing in Vegetables and Fruits.

A novel fluorescent probe was designed and synthesized from tetraphenylethene (TPE) and polyhedral oligomeric silsesquioxanes (POSS) via Heck-palladium catalyzed cross-coupling reaction. The as-synthesized TPE functionalized probe performed good solvent stability and selectively preconcentration capability towards target analyte due to its stable structure and the adsorption property. The morphology as well as the physical and chemical properties of the POSS@TPE were carefully characterized. The POSS@TPE was employed to develop an effective fluorescent probe for trifluralin, with a response range of 0.1-80 mg/kg and a detection limit of 0.102 mg/kg. The mixed mechanisms of inner-filter effect (IFE) and photoinduced electron transfer (PET) explain the selectivity of POSS@TPE. Rapid detection for trifluralin in tomato and celery has been achieved with recoveries between 99.4-120.7% (RSD≤3.4%), and the results were verified compared with GC-MS method.

Trifluralin recognition using touch-based fingertip: Application of wearable glove-based sensor toward environmental pollution and human health control.

Monitoring of herbicides and pesticides in water, food, and the environment is essential for human health, and this requires low-cost, portable devices for widespread deployment of this technology. For the first time, a wearable glove-based electrochemical sensor based on conductive Ag nano-ink was developed for the on-site monitoring of trifluralin residue on the surface of various substrates. Three electrode system with optimal thicknesses was designed directly on the finger surface of a rubber glove. Then, fabricated electrochemical sensor used for the direct detection of trifluralin in the range of 0.01 µM to 1 mM on the surface of tomato and mulberry leaves using square wave voltammetry (SWV) and difference pulse voltammetry technique. The obtained LLOQ was 0.01 µM, which indicates the suitable sensitivity of this sensor. On the other hand, this sensor is portable, easy to use, and has a high environmental capability that can be effective in detecting other chemical threats in the soil and water environment.

A stretchable glove sensor toward rapid monitoring of trifluralin: A new platform for the on-site recognition of herbicides based on wearable flexible sensor technology using lab-on-glove.

In this study, a flexible glove-based electrochemical sensor as a wearable point-of-use screening tool has been fabricated for defense and food security applications. To design the wearable glove-based sensor, we drew conductive patterns on the fingers of a rubber glove via gold@silver-modified graphene quantum dots (Au@Ag core-shell/graphene quantum dots [GQDs]) nano-ink with optimal thickness. Then, this platform is combined with a portable electrochemical analyzer for on-site detection of trifluralin pesticide in the range of 10 nM to 1 mM with the low limit of quantification (LLOQ) of 10 nM. The high efficiency and distinction of the trifluralin at specified concentrations in real leaf and apple samples were performed by simply touching with the glove and in spikes solution by immersing of fingertips. With their high sensitivity, selectivity, rapid, and easy operation pesticide analysis, these glove-embedded sensors can also be engaged in on-site monitor of other chemical threats and can be expanded to water and environmental samples.

Persistence of atrazine and trifluralin in a clay loam soil undergoing different temperature and moisture conditions.

Dissipation kinetics of atrazine and trifluralin in a clay loam soil was investigated in a laboratory incubation experiment under different temperature and moisture conditions. The soil was spiked with diluted atrazine and trifluralin concentrations at 4.50 and 4.25 mg/kg soil, respectively, the moisture content adjusted to 40, 70, and 100% of field capacity (FC) and then incubated in three climatic chambers at 10, 20, and 30 °C. For each of the herbicides, soil samples were collected at 0, 7, 21, 42, 70, and 105 days and analysed by Gas Chromatography-Electron Capture Detector (GC-ECD). A stochastic gamma model was used to model the dissipation of herbicides from the clay loam soil by incorporating environmental factors as covariates to determine half-life and days to complete dissipation. Results showed that temperature played a greater role on atrazine persistence than soil moisture; while the interaction effect of temperature and moisture was significant on the persistence of trifluralin over time. Atrazine dissipated more rapidly at 30 °C compared to 10 and 20 °C, with a half-life of 7.50 days and 326.23 days to reach complete dissipation. Rapid loss of trifluralin was observed at 70% moisture content when incubated at 30 °C, with a half-life of 5.80 days and 182.01 days to complete dissipation. It was observed that the half-life of both herbicides tended to double with every 10 °C decreases of temperature over the range tested. The model indicated that both atrazine and trifluralin have the potential to persist in clay loam soil for several years at temperature ≤20 °C; which could potentially affect following crops in rotation.

Simultaneous determination of 79 pesticides in pigeonpea grains using GC-MS/MS and LC-MS/MS.

Pigeonpea grains are important sources of vegetarian proteins. It is the paramount importance to check the pesticide residues due to their frequent use during production. The LC-MS/MS and GC-MS/MS analytical method was developed and validated for the simultaneous determination of 79 pesticide residues in pigeonpea. The LOD and LOQ of the analytical method were in the range of 0.53 to 3.97 and 1.60 to 10.05 µg kg-1, respectively, with a correlation coefficient of more than 0.997. Average recoveries were in the range of 80 to 118.8%, with the RSD of less than 15%. Measurement uncertainty (Ux) for pesticides was in the range of 3.42 to 12.76 µg kg-1 evaluated at 50 µg kg-1. The method was applied to analyze the sample collected from the farmer's field. This method could be useful for routine analysis of selected pesticide residue for monitoring purposes.

Biodegradation and Abiotic Degradation of Trifluralin: A Commonly Used Herbicide with a Poorly Understood Environmental Fate.

Trifluralin is a widely used dinitroaniline herbicide, which can persist in the environment and has substantial ecotoxicity, especially to aquatic organisms. Trifluralin is very insoluble in water (0.22 mg/L at 20 °C) and highly volatile (vapor pressure of 6.7 mPa at 20 °C); these physicochemical properties determine a large part of its environmental fate, which includes rapid loss from soils if surface-applied, strong binding to soil organic matter, and negligible leaching into water. The trifluralin structure contains a tertiary amino group, two nitro-groups and a trifluoromethyl- group. Despite the strongly xenobiotic character of some of these substituents, biodegradation of trifluralin does occur, and pure cultures of bacteria and fungi capable of partially degrading the molecule either by dealkylation or nitro-group reduction have been identified. There are many unanswered questions about the environmental fate and metabolism of this herbicide; the genes and enzymes responsible for biodegradation are largely unknown, the relative roles of abiotic processes vs growth-linked biodegradation vs cometabolism are unresolved, and the impact of different environmental factors on the rates and extents of biodegradation are not clear. Here, we summarize the relevant literature on the persistence and environmental fate of trifluralin with a focus on biodegradation pathways and mechanisms, and we identify the current major knowledge gaps for future research.

Fates and ecological effects of current-use pesticides (CUPs) in a typical river-estuarine system of Laizhou Bay, North China.

Current-use pesticides (CUPs) are widely applied in agriculture; however, little is known about their environmental behaviors, especially in the freshwater-seawater transitional zone. Water and sediment samples were collected in an intensively human impacted river (Xiaoqing River) from the headwaters to Laizhou Bay to investigate the distributions and environmental fates of four CUPs: trifluralin, chlorothalonil, chlorpyrifos, and dicofol. These CUPs were frequently detected in water and sediment samples. ∑CUPs in water and sediment samples ranged from 1.20 to 100.2 ng L-1 and 6.6-2972.5 ng g-1 dry weight (dw), respectively. Chlorpyrifos and chlorothalonil were the most abundant CUPs in water and sediment samples, respectively. Spatial distribution of CUPs in the Xiaoqing River aquatic ecosystem was mainly influenced by point sources, agricultural activities, the dilution effect by seawater, and environmental parameters. Field-based sediment water partitioning coefficients, normalized by organic carbon (log Koc), were calculated. Interestingly, temperature and salinity exhibited significant impacts on the distribution of log Koc of the four CUPs. The effect of temperature on the distribution of log Koc of the four CUPs varied between the CUPs. In most water samples, the levels of chlorpyrifos exceed the freshwater screening benchmarks. Hence, urgent control measures need to be devised and implemented.

Effect of crop residues on interception and activity of prosulfocarb, pyroxasulfone, and trifluralin.

Crop residue retention on the soil surface in no-tillage system can intercept pre-emergent herbicides and reduce their efficacy. Three experiments were conducted to investigate the effect of crop residue amount (0, 1, 2 and 4 t ha-1), moisture (wet versus dry), type (wheat, barley, canola, chickpea and lupin) and age (fresh or aged for one year) on the interception and subsequent leaching of prosulfocarb, pyroxasulfone, and trifluralin from the residue into soil. Bioassays, using cucumber and annual ryegrass as indicator plants, were used to assess herbicide activity/availability in the soil and on the residue. Herbicide interception increased considerably as residue quantity increased from 2 to 4 t ha-1. After simulated rainfall, which washed herbicide into the soil, complete control of ryegrass occurred for trifluralin with 0 t ha-1 residue, for prosulfocarb with 0 and 1 t ha-1 residue, and for pyroxasulfone with all residue rates. Therefore, with rain or irrigation, pyroxasulfone was the herbicide least affected by high residue loads. Less chemical leached from the crop residue into the soil after rainfall, when prosulfocarb and trifluralin were applied to wet residue compared with dry residue, but the initial moisture condition had no effect on the leaching of pyroxasulfone from residue. If practically possible, farmers should minimise spraying prosulfocarb and trifluralin onto wet crop residue. Barley and wheat residues intercepted more herbicide than an equivalent mass of canola, chickpea or lupin residue, which was largely due to the increased ground cover with cereal residues. The effect of residue age on herbicide interception and leaching was relatively small and variable. Overall, more herbicide reached the soil when sprayed on one-year old residue than new residue, which was largely due to reduced ground cover with aged residue. A strong positive linear relationship existed between ground cover percentage and growth of bioassay species (r2 = 0.75). This means that there was little difference in the ability of residue to adsorb and retain herbicide between crop residue types and ages, such that farmers can simply use the ground cover of the crop residue to assess interception.

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices.

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9 mg O3 L-1 h-1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20 min. Treatment at 5 min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20 min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025-0.1 mg kg-1) were conducted with ozonation at 20 min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.

Grab and passive sampling applied to pesticide analysis in the São Lourenço river headwater in Campo Verde - MT, Brazil.

In this study, the quality of surface water in the headwaters of São Lourenço River in Mato Grosso, Brazil, was evaluated in relation to contamination by pesticides. For this purpose, samples were collected between December 2015 and June 2016 by grab sampling and by passive sampling using an integrative polar organic compound sampler installed in the field during four 14-day cycles between March and June 2016. The analyses were performed by gas chromatography (CG/MS) and by liquid chromatography (UPLC-MS/MS). The results showed the detection of two pesticides (atrazine and pyraclostrobin) of the five analyzed by passive sampling and eight active principles among the 20 analyzed (malathion, diuron, carbofuran, carbendazim, trifluralin, imidacloprid, metolachlor, and acetamiprid) by grab sampling. The detection of 10 pesticides, even almost a decade after the beginning of a recovery process of the ciliary forest, confirms the headwaters' vulnerability to these contaminants and passive sampling proved to be an important tool in capturing small concentrations of pesticides constituting an interesting complement to grab sampling.

Leachability and potential ecotoxic impact of trifluralin-impregnated mulch.

The leachability, potential ecotoxicity, and photolysis of trifluralin-impregnated mulch, a popular retail consumer gardening product, were investigated under environmentally realistic conditions. Leachability of trifluralin from impregnated mulch was low (< 1% of total extractable compound) and in the range of reported values for agricultural soils. No trifluralin transformation products were detected in mulch leachate. Yeast-based estrogenicity and androgenicity screens indicated that aqueous trifluralin is not estrogenic but is moderately androgenic at concentrations ~ 1e - 5 M. Impregnated mulch leachate was not hormonally active, even at undiluted concentrations, but it did exert nonspecific toxicity at dilutions of ~ 1:10. Photolysis of trifluralin was investigated in acetonitrile and water and on mulch surfaces. Degradation on mulch surfaces was diffusion-limited; it was ~ 17 times slower than in aqueous solution, but faster than has been reported on kaolinite. An array of trifluralin transformation products was identified, but in no case did they exceed 10% of the parent compound. Using industry-recommended application guidelines, it is estimated that as much as 1400 µg/m2 of trifluralin may leach from impregnated mulch upon the first rainfall. However, provided that consumers are aware that such mulch products contain trifluralin and are properly educated about its use, the potential for direct ecotoxic impact is likely to be small.

Voltammetric detection of trifluralin in tap water, fruit juice, and vegetable extracts in the presence of surfactants.

This study describes a novel electrochemical method to determine the herbicide trifluralin in samples of water, fruit juice, and vegetable extracts in the presence of surfactants, using a glassy carbon electrode (GCE). In acidic media, trifluralin was irreversible on the glassy carbon electrode surface at -0.5 V vs. Ag/AgCl. Surfactant presence on the electrode-solution interface modified current intensities and shifted the reduction peak potential of trifluralin. Different types of surfactant and their concentrations were investigated. The anionic surfactant significantly enhanced the peak current intensity of trifluralin. Under optimal analytical conditions, an analytical curve was obtained in the concentration range of 0.48-32.20 µM. The limits of detection and quantification were estimated at 0.031 and 0.104 µM, respectively. The method was successfully applied to quantify trifluralin in samples of water, orange and tomato juice, and green pepper, carrot, and onion extracts, with recovery rates of 97.9-102.1%. The results were in good agreement with those obtained using high-performance liquid chromatography, indicating that the proposed electrochemical method can be employed to quantify trifluralin in various types foods, with sensitivity, specificity, selectivity and reproducibility.

Occurrence and distribution of trifluralin, ethalfluralin, and pendimethalin in soils used for long-term intensive cotton cultivation in central Greece.

In the present study, a soil monitoring program was undertaken in Greek cotton cultivated areas in 2012. Twenty-seven soil samples were collected from the entire Thessaly plain in early summer of 2012, corresponding to approximately three months (current use of pendimethalin), up to one year (for the banned ethalfluralin), and three years (for the also banned trifluralin), after the last dinitroaniline application. Low but not negligible levels of dinitroanilines were detected, ranging from 0.01 to 0.21 µg g-1 d.w. for trifluralin and 0.01-0.048 µg g-1 d.w. for pendimethalin, respectively. Trifluralin was the herbicide most frequently detected (44.4%). The high historic application of trifluralin and its high persistence and accumulation potential is in line with the abundance of the detected residues. The present data indicate that soil samples contain extractable residues of banned trifluralin, but based on the comparison of the theoretical PECplateau for trifluralin (0.277 µg g-1) and the maximum Measured Environmental Concentration, it was concluded that the detected residues should be attributed to previous years' application. The latter suggested the need for continual monitoring of the dinitroaniline family of pesticides, including the banned substances, aiming thus to an improved environmental profile for agricultural areas.

Legacy and currently used pesticides in the atmospheric environment of Lake Victoria, East Africa.

The Lake Victoria watershed has extensive agricultural activity with a long history of pesticide use but there is limited information on historical use or on environmental levels. To address this data gap, high volume air samples were collected from two sites close to the northern shore of Lake Victoria; Kakira (KAK) and Entebbe (EBB). The samples, to be analyzed for pesticides, were collected over various periods between 1999 and 2004 inclusive (KAK 1999-2000, KAK 2003-2004, EBB 2003 and EBB 2004 sample sets) and from 2008 to 2010 inclusive (EBB 2008, EBB 2009 and EBB 2010 sample sets). The latter sample sets (which also included precipitation samples) were also analyzed for currently used pesticides (CUPs) including chlorpyrifos, chlorthalonil, metribuzin, trifluralin, malathion and dacthal. Chlorpyrifos was the predominant CUP in air samples with average concentrations of 93.5, 26.1 and 3.54 ng m(-3) for the EBB 2008, 2009, 2010 sample sets, respectively. Average concentrations of total endosulfan (ΣEndo), total DDT related compounds (ΣDDTs) and hexachlorocyclohexanes (ΣHCHs) ranged from 12.3-282, 22.8-130 and 3.72-81.8 pg m(-3), respectively, for all the sample sets. Atmospheric prevalence of residues of persistent organic pollutants (POPs) increased with fresh emissions of endosulfan, DDT and lindane. Hexachlorobenzene (HCB), pentachlorobenzene (PeCB) and dieldrin were also detected in air samples. Transformation products, pentachloroanisole, 3,4,5-trichloroveratrole and 3,4,5,6-tetrachloroveratrole, were also detected. The five most prevalent compounds in the precipitation samples were in the order chlorpyrifos>chlorothalonil>ΣEndo>ΣDDTs>ΣHCHs with average fluxes of 1123, 396, 130, 41.7 and 41.3 ng m(-2)sample(-1), respectively. PeCB exceeded HCB in precipitation samples. The reverse was true for air samples. Backward air trajectories suggested transboundary and local emission sources of the analytes. The results underscore the need for a concerted regional vigilance in management of chemicals.

Contribution to the food products' analysis: A research and evaluation on the hemolytic effect of some pesticides used in Lebanon.

Pesticides are a real concern for the society as their use has become critical, leading sometimes to their accumulation as residues in fruits and vegetables. After examining the pesticides sold in Northern Lebanon, this study is focused on the analysis and identification of pesticides residues in fruits and vegetables that are harvested in this region and treated with the locally sold pesticides. Results show: first, (i) a use of Zineb by the name of another pesticide Micronized Sulfur to avoid prosecution; (ii) a significant presence of Metalaxyl in lemons and oranges; (iii) a significant presence of Trifluralin in strawberries; and (iv) a significant presence of Zineb in lemons and tomatoes. Second, with the use of hemolytic tests on human blood results show: (i) a critical concentration and a significant hemolytic effect of some pesticides used in Lebanon; and (ii) an absence of hemolytic effect in the collected fractions of the different analyzed fruit extracts containing pesticides. Finally, this work is the first step for pesticides' analysis in vegetables and fruits in Lebanon, initiating a wider analytical study in order to control and examine the use of pesticides which, according to our results, could have an adverse effect on human health over a long term.

Genotoxicity evaluation of environmental pollutants using analysis of nucleolar alterations.

Nucleolar alterations resulting from the action of either chemical or physical agents can serve as important genotoxicity biomarkers. In this study, the efficiency of AgNOR banding technique to identify the presence of nucleoli in micronucleus and assess nucleolar alterations in aberrant cells of Allium cepa was evaluated. Seeds of this plant were exposed to both water samples from a river that receives untreated urban effluent and to the trifluralin herbicide (0.84 mg/L concentration), both analyzed in two different seasons (summer and winter seasons). Samples induced significant frequencies of chromosomal and nuclear aberrations and micronuclei, as observed in cells submitted to conventional chromosomal staining. The herbicide caused a significant increase in the number of nucleoli and micronuclei, interpreted as due to the elimination of excessive nucleolar material resulting from polyploidization. The use of the AgNOR technique enabled the identification of both the presence of the nucleolus in some micronuclei and the nucleolar organizer region (NOR) behavior of aberrant cells. The NOR-banding technique showed to be an efficient tool for studying the genotoxic effects caused by a xenobiotics and a complex environmental sample.

The spatial distribution of organochlorine pesticides and halogenated flame retardants in the surface sediments of an Arctic fjord: the influence of ocean currents vs. glacial runoff.

Selected organochlorine pesticides (OCs) and halogenated flame retardants (HFRs) were analyzed in surficial fjord sediments collected down the length of Kongsfjorden, Svalbard in the Norwegian high Arctic. Hexachlorocyclohexane (α-HCHs) was found to be the most abundant OC in the sediment, followed by BDE-209>chlordane>α-endosulfan>Dechlorane Plus (anti-DP)>trifluralin concentration ranges were high over the relatively small study area of the fjord (e.g. ∑HCH: 7.2-100 pg g(-1) dry weight (dw)), with concentrations broadly similar to, or lower than, measurements conducted in other parts of the Arctic. Concentrations of legacy OCs, including both HCH isomers and chlordane showed a decreasing trend from the outer, seaward end of the fjord to the inner, glacier end of the fjord. Conversely, sediment concentrations of α- and ß-endosulfan (0.1-12.5 pg g(-1) dw) increased from the outer fjord to the inner fjord. This contrasting pattern may be attributed to the influence of historical vs. contemporary sources of these chemicals to the fjord area, whereby the North Atlantic/West Spitzbergen oceanic current dominates the transport and input of the legacy OCs, whereas atmospheric deposition and meltwater runoff from the glaciers influence the inner fjord sediments for endosulfan. Interestingly, BDE-209 and Dechlorane Plus did not reveal any clear spatial trend. It is plausible that both glacial runoff and oceanic current end members are playing a role in introducing these chemicals to the fjord sediments. The relatively low fractional abundance of the syn-DP isomer (fsyn), however, indicates the long-range transport of this chemical to this Arctic site.

[Determination of trifluralin residue in aquatic products and edible oils by gas chromatography-negative chemical ionization mass spectrometry].

A confirmatory method was established for the determination of trifluralin residue in aquatic products and edible oils with the technique of offline disperse solid phase extraction and gas chromatography-negative chemical ionization mass spectrometry (DSPE-GC-MS/NCI). Trifluralin was extracted from aquatic products and edible oils with acetonitrile, and liquid-liquid partitioning formed by adding anhydrous magnesium sulfate followed by a simple cleanup step known as dispersive solid-phase extraction. The aliquot was analyzed by GC-MS/NCI using isotope internal standard method. The method was reliable and stable. The recoveries of trifluralin were in the range from 80% to 100% at three spiked levels of 1.0, 2.0, and 3.0 microg/kg, and the RSDs were not more than 10.3%. The linearity of method was good from 1 to 40 microg/L, and the LOD was 0.02 microg/kg. This method can be used as a conclusive evidence method for the determination of trifluralin residue in aquatic products and edible oils.

Assessment of riverine load of contaminants to European seas under policy implementation scenarios: an example with 3 pilot substances.

An evaluation of conventional emission scenarios is carried out targeting a possible impact of European Union (EU) policies on riverine loads to the European seas for 3 pilot pollutants: lindane, trifluralin, and perfluorooctane sulfonate (PFOS). The policy scenarios are investigated to the time horizon of year 2020 starting from chemical-specific reference conditions and considering different types of regulatory measures including business as usual (BAU), current trend (CT), partial implementation (PI), or complete ban (PI ban) of emissions. The scenario analyses show that the model-estimated lindane load of 745 t to European seas in 1995, based on the official emission data, would be reduced by 98.3% to approximately 12.5 t in 2005 (BAU scenario), 10 years after the start of the EU regulation of this chemical. The CT and PI ban scenarios indicate a reduction of sea loads of lindane in 2020 by 74% and 95%, respectively, when compared to the BAU estimate. For trifluralin, an annual load of approximately 61.7 t is estimated for the baseline year 2003 (BAU scenario), although the applied conservative assumptions related to pesticide use data availability in Europe. Under the PI (ban) scenario, assuming only small residual emissions of trifluralin, we estimate a sea loading of approximately 0.07 t/y. For PFOS, the total sea load from all European countries is estimated at approximately 5.8 t/y referred to 2007 (BAU scenario). Reducing the total load of PFOS below 1 t/y requires emissions to be reduced by 84%. The analysis of conventional scenarios or scenario typologies for emissions of contaminants using simple spatially explicit GIS-based models is suggested as a viable, affordable exercise that may support the assessment of implementation of policies and the identification or negotiation of emission reduction targets.