Sixty years of research on bracken fern (Pteridium spp.) toxins: Environmental exposure, health risks and recommendations for bracken fern control.

Bracken fern (Pteridium spp.) is a highly problematic plant worldwide due to its toxicity in combination with invasive properties on former farmland, in deforested areas and on disturbed natural habitats. The carcinogenic potential of bracken ferns has caused scientific and public concern for six decades. Its genotoxic effects are linked to illudane-type glycosides (ITGs), their aglycons and derivatives. Ptaquiloside is considered the dominating ITG, but with significant contributions from other ITGs. The present review aims to compile evidence regarding environmental pollution by bracken fern ITGs, in the context of their human and animal health implications. The ITG content in bracken fern exhibits substantial spatial, temporal, and chemotaxonomic variation. Consumption of bracken fern as food is linked to human gastric cancer but also causes urinary bladder cancers in bovines browsing on bracken. Genotoxic metabolites are found in milk and meat from bracken fed animals. ITG exposure may also take place via contaminated water with recent data pointing to concentrations at microgram/L-level following rain events. Airborne ITG-exposure from spores and dust has also been documented. ITGs may synergize with major biological and environmental carcinogens like papillomaviruses and Helicobacter pylori to induce cancer, revealing novel instances of chemical and biological co-carcinogenesis. Thus, the emerging landscape from six decades of bracken research points towards a global environmental problem with increasingly complex health implications.

Ptaquiloside in Irish Bracken Ferns and Receiving Waters, with Implications for Land Managers.

Ptaquiloside, along with other natural phytotoxins, is receiving increased attention from scientists and land use managers. There is an urgent need to increase empirical evidence to understand the scale of phytotoxin mobilisation and potential to enter into the environment. In this study the risk of ptaquiloside to drinking water was assessed by quantifying ptaquiloside in the receiving waters at three drinking water abstraction sites across Ireland and in bracken fronds surrounding the abstraction sites. We also investigated the impact of different management regimes (spraying, cutting and rolling) on ptaquiloside concentrations at plot-scale in six locations in Northern Ireland, UK. Ptaquiloside concentrations were determined using recent advances in the use of LC-MS for the detection and quantification of ptaquiloside. The results indicate that ptaquiloside is present in bracken stands surrounding drinking water abstractions in Ireland, and ptaquiloside concentrations were also observed in the receiving waters. Furthermore, spraying was found to be the most effective bracken management regime observed in terms of reducing ptaquiloside load. Increased awareness is vital on the implications of managing land with extensive bracken stands.

Highly variable soil dissipation of metaldehyde can explain its environmental persistence and mobility.

There are increasing concerns about the hazard posed to drinking water resources by persistent, mobile, and toxic (PMT) substances in the environment. For example, the extensive use of metaldehyde-based molluscicide to control slug populations in agricultural fields has frequently led to pollution of surface waters and contamination of drinking water at levels exceeding the statutory limit. Regulatory environmental fate assessments and studies in the literature did not predict that metaldehyde would be persistent in the environment, contrary to observations from monitoring schemes. To understand the reasons for this disparity, this study conducted a suite of degradation experiments, covering different soil types and environmentally realistic conditions in Northern Europe, and generated a distribution of DT50 values for metaldehyde to examine whether degradation rates are underestimated by current risk assessments. The results were found to vary, showing DT50 values ranging from 3.0 to 4150 days, which indicated that metaldehyde had the potential to become persistent. Lack of prior metaldehyde exposure, high moisture content, low temperature, and locally high metaldehyde concentration under pellets were identified as high-risk conditions for low pesticide biodegradation in UK soils.

Analytical method development and validation for the quantification of metaldehyde in soil.

Previously published methods for the analysis of metaldehyde were adapted for its reliable quantification in soil extracts. Varied methanol-water extraction solvents were trialed, but the use of pure methanol proved to be the most reliable approach for the scaled down methodology. Analysis of metaldehyde was done using LC-MS. Initially the method had problems with matrix suppression of the signal. The method was therefore further developed to overcome this challenge to avoid the costs and time demands of laborious clean-up protocols. This modification to the method involved use of the BEH Phenyl column instead of the C18 column initially used, and optimization of the gradient flow of the mobile phase. The optimized LC-MS method was validated and used for further research applications. In brief,•We investigated the recovery of metaldehyde from spiked soil samples.•The optimized LC-MS method achieved acceptable metaldehyde recoveries (100-132%, 109% on average) for a range of soil types.•The optimized method was suitable for high through-put analyzes.

Pesticide prioritization approaches and limitations in environmental monitoring studies: From Europe to Latin America and the Caribbean.

Assessment and management of issues related to pesticide residues, such as environmental fate, monitoring and toxicity, are complex and, in many cases, require costly studies. The early establishment of a priority list of pesticides that should be monitored and assigned to a restricted-use policy is an important issue of post-registration Risk Assessment (RA). Various pesticide registration approaches have been adopted by different countries with those from Europe and the USA being the most popular, constituting the major prototypes for registration approaches in other countries. Adoption of pesticide registration and monitoring systems developed in Europe or USA by Latin American and Caribbean countries may underestimate factors affecting the environmental fate and toxicity of pesticides in their own countries. Incentive for this short review was the activities undertaken during the three KNOWPEC workshops held in Costa Rica, Argentina and Bolivia where European pesticide experts met Latin American experience in the form of Costa Rica's exceptional environmental conditions and ecology, Argentina's and Uruguay's soyisation and Bolivia's contrasting climate and agricultural zones. During the parallel activities of the workshop - including scientific presentations, field trips, interviews and meetings among European partners and pesticide stakeholders in Latin America, - the whole pesticide chain (import-export, trade, application, plant protection-efficacy, residues, monitoring, remediation and risk) was studied and clarified. Recently-published chemical prioritization studies were reviewed to consider their use as a tool to support risk assessments. Differences in regional practices are highlighted as regards to the establishment of RA or prioritization strategy in European and Latin American regimes. General guidance of establishing a cost-effective pesticide monitoring scheme in water bodies of Latin America and the Caribbean (LAC) is also proposed. Moreover, we summarize the most important factors that should be taken into consideration for prioritization approaches and categorization used in pesticide environmental monitoring studies. Consideration of current RA approaches and limitations, and pesticide prioritization exercises highlighted in this Commentary could assist in the management of pesticides in Latin America and Caribbean.

Assessment of occupational exposure to pesticide mixtures with endocrine-disrupting activity.

Occupational exposure to pesticide mixtures comprising active substance(s) and/or co-formulant(s) with known/possible endocrine-disrupting activity was assessed using long-term activity records for 50 professional operators representing arable and orchard cropping systems in Greece, Lithuania, and the UK. Exposure was estimated using the harmonised Agricultural Operator Exposure Model, and risk was quantified as a point of departure index (PODI) using the lowest no observed (adverse) effect level. Use of substances with known/possible endocrine activity was common, with 43 of the 50 operators applying at least one such active substance on more than 50% of spray days; at maximum, one UK operator sprayed five such active substances and 10 such co-formulants in a single day. At 95th percentile, total exposure was largest in the UK orchard system (0.041 × 10-2 mg kg bw-1 day-1) whereas risk was largest in the Greek cropping systems (PODI 0.053 × 10-1). All five cropping systems had instances indicating potential for risk when expressed at a daily resolution (maximum PODI 1.2-10.7). Toxicological data are sparse for co-formulants, so combined risk from complex mixtures of active substances and co-formulants may be larger in reality.

Assessment of exposure of professional agricultural operators to pesticides.

This study investigates how field practices in handling and applying pesticides influence the long-term patterns of professional agricultural operators' exposure to pesticides. It presents the first use of a comprehensive pesticide application dataset collected on behalf of the European Food Safety Authority with 50 operators selected to cover arable and orchard cropping systems in Greece, Lithuania and the UK. Exposure was predicted based on the harmonised Agricultural Operator Exposure Model (AOEM) and compared with Acceptable Operator Exposure Levels (AOELs). The amount of pesticides handled by individual operators across a cropping season was largest in the UK arable and orchard systems (median 580 and 437kg active substance, respectively), intermediate for the arable systems in Greece and Lithuania (151 and 77kg, respectively), and smallest in the Greek orchard system (22kg). Overall, 30 of the 50 operators made at least one application within a day with predicted exposure greater than the AOEL. The rate of AOEL exceedance was greatest in the Greek cropping systems (8 orchard operators, 2.8-16% of total applications; 7 arable operators, 1.1-14% of total applications), and least for the Lithuanian arable system (2 operators, 2.9-4.5% of total applications). Instances in Greece when predicted exposure exceed the AOEL were strongly influenced by the widespread use of wettable powder formulations (>40% of the total pesticide active substance handled for 11 of the 20 Greek operators). In contrast, the total area of land treated with an active substance on a single day was more important in the UK and Lithuania (95th percentile observed value was 132 and 19haday-1 for UK arable and orchard systems, respectively). Study findings can be used to evaluate current assumptions in regulatory exposure calculations and to identify situations with potential risk that require further analysis including measurements of exposure to validate model estimations.

The potential environmental impact of pesticides removed from sprayers during cleaning.

BACKGROUND: There is concern that pesticide residues on the external surfaces of sprayers could have an adverse impact on the environment if they are washed off, yet there is a need to remove these residues for health reasons. The aim of this study was to quantify pesticide residues contained in washings from cleaning discrete parts of a sprayer and to assess their likely environmental impact. RESULTS: The boom/rear of the sprayer and the spray tank accounted for 80% of the total pesticide load in the washings. Predicted environmental pesticide concentrations from sprayer washings were lower than predictions from the FOCUS surface water model for pesticides used under normal agricultural conditions, although for tebuconazole this difference was smaller than for the other compounds investigated. The field area over which the residues may need to be uniformly deposited to avoid overdosing during infield cleaning was typically less than 0.5 m(2), with a maximum value of 4 m(2). CONCLUSIONS: It is unlikely that infield cleaning will lead to overdosing. External residues are not insignificant, so any adverse impact on the environment must be mitigated. Appropriate measures include cleaning in the field away from surface waters and other sensitive areas, and cleaning machines over bunded areas or similar.

How does exposure to pesticides vary in space and time for residents living near to treated orchards?

This study investigated changes over 25 years (1987-2012) in pesticide usage in orchards in England and Wales and associated changes to exposure and risk for resident pregnant women living 100 and 1000 m downwind of treated areas. A model was developed to estimate aggregated daily exposure to pesticides via inhaled vapour and indirect dermal contact with contaminated ground, whilst risk was expressed as a hazard quotient (HQ) based on estimated exposure and the no observed (adverse) effect level for reproductive and developmental effects. Results show the largest changes occurred between 1987 and 1996 with total pesticide usage reduced by ca. 25%, exposure per unit of pesticide applied slightly increased, and a reduction in risk per unit exposure by factors of 1.3 to 3. Thereafter, there were no consistent changes in use between 1996 and 2012, with an increase in number of applications to each crop balanced by a decrease in average application rate. Exposure per unit of pesticide applied decreased consistently over this period such that values in 2012 for this metric were 48-65% of those in 1987, and there were further smaller decreases in risk per unit exposure. All aggregated hazard quotients were two to three orders of magnitude smaller than one, despite the inherent simplifications of assuming co-occurrence of exposure to all pesticides and additivity of effects. Hazard quotients at 1000 m were 5 to 16 times smaller than those at 100 m. There were clear signals of the impact of regulatory intervention in improving the fate and hazard profiles of pesticides used in orchards in England and Wales over the period investigated.

Ptaquiloside from bracken in stream water at base flow and during storm events.

The bracken fern (Pteridium spp.) densely populates both open and woodland vegetation types around the globe. Bracken is toxic to livestock when consumed, and a group of potent illudane-type carcinogens have been identified, of which the compound ptaquiloside (PTA) is the most abundant. The highly water soluble PTA has been shown to be leachable from bracken fronds, and present in the soil and water below bracken stands. This has raised concerns over whether the compound might pose a risk to drinking water sources. We investigated PTA concentrations in a small stream draining a bracken-infested catchment at base flow and in response to storm events during a growth season, and included sampling of the bracken canopy throughfall. Streams in other bracken-dominated areas were also sampled at base flow for comparison, and a controlled pulse experiment was conducted in the field to study the in-stream dynamics of PTA. Ptaquiloside concentrations in the stream never exceeded 61 ng L-1 in the base flow samples, but peaked at 2.2 µg L-1 during the studied storm events. The mass of PTA in the stream, per storm event, was 7.5-93 mg from this catchment. A clear temporal connection was observed between rainfall and PTA concentration in the stream, with a reproducible time lag of approx. 1 h from onset of rain to elevated concentrations, and returning rather quickly (about 2 h) to base flow concentration levels. The concentration of PTA behaved similar to an inert tracer (Cl-) in the pulse experiment over a relative short time scale (minutes-hours) reflecting no PTA sorption, and dispersion and dilution considerably lowered the observed PTA concentrations downstream. Bracken throughfall revealed a potent and lasting source of PTA during rainfall, with concentrations up to 169 µg L-1, that did not decrease over the course of the event. In the stream, the throughfall contribution to PTA cannot be separated from a possible below-ground input from litter, rhizomes and soil. Catchment-specific factors such as the soil pH, topography, hydrology, and bracken coverage will evidently affect the level of PTA observed in the receiving stream, as well as the distance from bracken, but time since precipitation seems most important. Studying PTA loads and transport in surface streams fed by bracken-infested catchments, simply taking occasional grab samples will not capture the precipitation-linked pulses. The place and time of sampling governs the findings, and including event-based sampling is essential to provide a more complete picture of PTA loads to surface water.

Herbicide sorption to concrete and asphalt.

In order to accurately predict the fate and behaviour of herbicides following application to hard surfaces, an understanding of the processes involved is required. Previous studies have demonstrated that herbicides with a low soil organic carbon partition coefficient (K(oc)) are preferentially removed from concrete and asphalt surfaces. It is possible, therefore, that sorption may play a role in retaining herbicides to hard surfaces. This study provides an indication of the extent to which herbicides may sorb to concrete and asphalt, and examines the results in the light of other research to identify the significance of sorption in describing herbicide losses after application. There was measurable sorption of herbicides to concrete and asphalt although this was limited compared with that to soils, especially for concrete. An exponential relationship between experimentally derived values of K(p) and literature values of K(oc) for asphalt was established (r(2) = 0.931); there was a weaker relationship for concrete (r(2) = 0.606). The experimentally derived K(p) values could be used to enhance the prediction of herbicide loss to receiving waters following application. It is probable that the fate of herbicides applied to concrete and asphalt surfaces depends more heavily on physical processes than is the case in soils.

Herbicide loss following application to a roadside.

Risk assessments for herbicides applied to roads are limited by the lack of knowledge on the fate and behaviour of the compounds in the urban environment. This study was designed to address this deficiency by quantifying the percentage loss of six herbicides following application to a roadside. Herbicides were applied on two occasions to a 16-m length of roadside and kerb edge. An automatic water sampler was used to collect run-off, draining to a single gulley pot, until 25 mm of rain had fallen. Samples were analysed for glyphosate, atrazine, diuron, oxadiazon and oryzalin, and peak concentrations were 650, 2210, 1810, 390 and 70 micrograms litre-1 respectively. Isoxaben was also applied, but concentrations in run-off were below the limit of detection (10 micrograms litre-1). Herbicide concentrations all followed a similar pattern of rapid decline throughout the first rain event following application, with the majority of loss occurring within the first 10 mm of accumulated rainfall, but compounds of high solubility and low Koc produced the highest peak concentrations. For those compounds of relatively low solubility and moderate Koc, application rate may be an influential factor in determining herbicide loss for these compounds. The percentage loss of the active substances applied differed between compounds, ranging from < 10% to 73%. The ecotoxicological significance of the results is discussed.

Herbicide loss following application to a railway.

Railways have been identified as a potential source of herbicides detected in surface and groundwaters, but there are few data to support this theory. Two studies were undertaken to investigate the fate of herbicides applied to railway trackbeds: a pilot study in a section of a disused, but intact, cutting where runoff and throughflow were sampled from trenches adjacent to the treated area, and a larger scale study on 0.75 km of embankment where surface water from the drainage ditch at the base of the embankment and groundwater were sampled. In the pilot study, peak concentrations of atrazine, diuron and glyphosate (1280, 210 and 15 microg litre(-1) respectively) were detected 6days after treatment (DAT). Oxadiazon, oryzalin and isoxaben were not detected above their limits of quantification. Lower concentrations were detected 81 DAT (10 and 0.8 microg litre(-1) of atrazine and glyphosate respectively). In the larger scale study, herbicides were not detected, in either the surface water or groundwater, at concentrations above the limit of detection that could be attributed to application to the railway. Rainfall volume and depth to sampling point may partly explain the different results obtained from the two studies. The findings are compared with herbicide losses from other 'hard surfaces'.

Pesticide residues on the external surfaces of field-crop sprayers: environmental impact.

There is increased awareness of the need to clean the external surfaces of sprayers, but the extent to which the washings may impact on the environment is not known. Quantification of the levels of external residues on sprayers could give an indication of the potential environmental impact of sprayer cleaning. The presence of azoxystrobin, carbendazim, chlorothalonil, cyanazine, cypermethrin, epoxiconazole, flusilazole, isoproturon, kresoxim-methyl, metazachlor, pendimethalin, pirimicarb and tebuconazole on thirteen sprayers, sampled on two occasions was investigated. Composite samples were taken from the boom, nozzles and spray tank (delivery system) and the mudguard, cab door, rear window and windscreen (tractor body). Despite being subject to some form of cleaning, pesticides were detected on all sprayers. Residues were found at higher quantities and with greater frequency on the nozzles and booms, but the mean dose on the spray tank was equal to that on the mudguard (7.2 mg m(-2)). Isoproturon, pendimethalin, metazachlor, chlorothalonil and azoxystrobin were all detected above 1000 mg m(-2) on the delivery system, whereas on the tractor body the highest concentrations were between 100 and 1000 mg m(-2) (isoproturon, pendimethalin, chlorothalonil and carbendazim). On the whole, azoxystrobin was detected on the least number of occasions. However, there was great variation within and between compounds and sampling sites. Generally sprayers were not cleaned frequently or efficiently, enabling residues to accumulate on the external surfaces where they can remain for years. The findings here indicate that the quantity of these residues may be sufficient to be harmful to aquatic organisms should the residues enter a watercourse. In addition, if all the residues were removed by cleaning in the field and the washings catchment area was 15 m2 or less, overdosing could occur. Further work is required to assess whether a more frequent cleaning regime would reduce the overall environmental impact of cleaning sprayers. Implications for potential occupational exposure are considered elsewhere.

Contribution of household herbicide usage to glyphosate and its degradate aminomethylphosphonic acid in surface water drains.

BACKGROUND: It is necessary to understand the extent to which different sources of pesticides contribute to surface water contamination in order to focus preventive measures appropriately. The extent to which glyphosate use in the home and garden sector may contribute to surface water contamination has not previously been quantified. The aim of this study was to quantify the widely used herbicide glyphosate and its degradation product aminomethylphosphonic acid (AMPA) in surface water drains (storm drains) that could be attributed to amateur, non-professional usage alone. RESULTS: Maximum glyphosate and AMPA concentrations in surface water drains were 8.99 and 1.15 µg L(-1) respectively after the first rain event following the main application period, but concentrations rapidly declined to <1.5 and <0.5 µg L(-1) . The AMPA:glyphosate ratio was typically 0.35. Less than 1% of the applied glyphosate was recovered in drain water. CONCLUSION: Glyphosate and AMPA losses from urban areas that arise solely from amateur usage have been quantified. In spite of overdosing occurring, glyphosate concentrations in drain flow were lower than concentrations reported elsewhere from professional use in urban areas.

Transferability of six pesticides from agricultural sprayer surfaces.

Secondary exposure to pesticide residues on the external surfaces of sprayers does not currently form part of the risk assessment process. A measure of the ease with which residues may be transferred from the sprayer surface to the operator would enhance the accuracy of any such assessment. This study quantified the dislodgeability of six pesticides from sprayer surfaces in order to calculate the transfer efficiencies. The transfer efficiency was compound dependent, ranging from 80% for azoxystrobin to <25% for flusilazole and tebuconazole. When the washed and unwashed surfaces were analysed separately, more pendimethalin and isoproturon residues were removed from the wet surface compared with the dry surface. The variation in results for the different compounds highlights the need to consider a range of compounds to form generic statements to support guidelines regarding operator exposure to pesticide residues on sprayers.

Pesticide residues on the external surfaces of field crop sprayers: occupational exposure.

There is a general perception, amongst farmers and researchers, that post-application residues on the external surfaces of sprayers are negligible compared with residues remaining on the internal surfaces, although there have been few attempts to verify this assumption. The aim of this study was to investigate, using cotton glove sampling, operator exposure resulting from three typical operations: entering and working in the cab, general handling of the sprayer and maintenance practices. Samples were analysed for azoxystrobin, carbendazim, chlorothalonil, cyanazine, cypermethrin, epoxiconazole, flusilazole, isoproturon, kresoxim-methyl, metazachlor, pendimethalin, pirimicarb and tebuconazole. Isoproturon, pendimethalin, chlorothalonil and carbendazim were detected >1 mg per glove pair on the cotton gloves, but on the whole there was variability in residue levels between and within compounds. Comparison of results with occupational exposure limits indicated that residues were such that they may not necessarily be considered insignificant. It may therefore be prudent to develop more efficient methods for the external decontamination of sprayers and/or raise awareness of the findings.