In situ formation of environmental endocrine disruptors from phytosterol degradation: a temporal model for agricultural soils.

We propose a conceptual model that describes the in situ formation of androstenedione in agricultural soil from a phytosterol, ß-sitosterol, released after crop harvest and soil fertiliser amendment. Based on the recorded agricultural practice at a spring barley field, ß-sitosterol and androstenedione concentrations were modelled over the year. While decomposition of crop residues created low soil levels, the application of pig slurry led to an androstenedione soil concentration of 54 µg kg-1. The elevated soil concentration of androstenedione is not due to the introduction of the endocrine disruptor in the fertiliser, but a result of the addition of large concentrations of ß-sitosterol as a natural precursor. The limited available data on ß-sitosterol and androstenedione concentration in soil prohibited their accurate prediction by our model. However, the potential implication of endocrine-disrupting steroid hormones being formed in situ from currently little considered phytosterols justifies a conceptual description and further research.

Mapping monthly rainfall erosivity in Europe.

Rainfall erosivity as a dynamic factor of soil loss by water erosion is modelled intra-annually for the first time at European scale. The development of Rainfall Erosivity Database at European Scale (REDES) and its 2015 update with the extension to monthly component allowed to develop monthly and seasonal R-factor maps and assess rainfall erosivity both spatially and temporally. During winter months, significant rainfall erosivity is present only in part of the Mediterranean countries. A sudden increase of erosivity occurs in major part of European Union (except Mediterranean basin, western part of Britain and Ireland) in May and the highest values are registered during summer months. Starting from September, R-factor has a decreasing trend. The mean rainfall erosivity in summer is almost 4 times higher (315MJmmha-1h-1) compared to winter (87MJmmha-1h-1). The Cubist model has been selected among various statistical models to perform the spatial interpolation due to its excellent performance, ability to model non-linearity and interpretability. The monthly prediction is an order more difficult than the annual one as it is limited by the number of covariates and, for consistency, the sum of all months has to be close to annual erosivity. The performance of the Cubist models proved to be generally high, resulting in R2 values between 0.40 and 0.64 in cross-validation. The obtained months show an increasing trend of erosivity occurring from winter to summer starting from western to Eastern Europe. The maps also show a clear delineation of areas with different erosivity seasonal patterns, whose spatial outline was evidenced by cluster analysis. The monthly erosivity maps can be used to develop composite indicators that map both intra-annual variability and concentration of erosive events. Consequently, spatio-temporal mapping of rainfall erosivity permits to identify the months and the areas with highest risk of soil loss where conservation measures should be applied in different seasons of the year.

Degradation and enantiomeric fractionation of mecoprop in soil previously exposed to phenoxy acid herbicides - New insights for bioremediation.

Phenoxy acid-contaminated subsoils are common as a result of irregular disposal of residues and production wastes in the past. For enhancing in situ biodegradation at reducing conditions, biostimulation may be an effective option. Some phenoxy acids were marketed in racemic mixtures, and biodegradation rates may differ between enantiomers. Therefore, enantio-preferred degradation of mecoprop (MCPP) in soil was measured to get in-depth information on whether amendment with glucose (BOD equivalents as substrate for microbial growth) and nitrate (redox equivalents for oxidation) can stimulate bioremediation. The degradation processes were studied in soil sampled at different depths (3, 4.5 and 6m) at a Danish urban site with a history of phenoxy acid contamination. We observed preferential degradation of the R-enantiomer only under aerobic conditions in the soil samples from 3- and 6-m depth at environmentally relevant (nM) MCPP concentrations: enantiomer fraction (EF)<0.5. On the other hand, we observed preferential degradation of the S-enantiomer in all samples and treatments at elevated (µM) MCPP concentrations: EF>0.5. Three different microbial communities were discriminated by enantioselective degradation of MCPP: 1) aerobic microorganisms with little enantioselectivity, 2) aerobic microorganisms with R-selectivity and 3) anaerobic denitrifying organisms with S-selectivity. Glucose-amendment did not enhance MCPP degradation, while nitrate amendment enhanced the degradation of high concentrations of the herbicide.

When does the fluazifop-P-butyl degradate, TFMP, leach through an agricultural loamy soil to groundwater?

In intensely cultivated regions, it is crucial to have knowledge of the leaching potential related to pesticides in agricultural production. This is especially true in countries, like Denmark, that base its drinking water supply on untreated groundwater. Since fluazifop-P-butyl (FPB) is applied to control perennial and annual weed grasses in agricultural fields, the objective of this study was to evaluate leaching of its two degradation products - fluazifop-P (FP; free acid; (R)-2-(4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)propionic acid) and TFMP (5-(trifluoromethyl)-2(1H)-pyridinone) - through an agricultural field consisting of loamy soil. Drainage and groundwater samples were collected over a five-year period following four spring/summer applications of FPB, and analysed for both FP and TFMP. FP was only detected once in groundwater, whereas TFMP within the first year after the first and fourth application was detected in concentrations exceeding the value of 0.1µgL(-1) in 100% and 24% of the drainage samples and 9% and 14% of the groundwater samples, respectively. Detections of TFMP up to 18months after application were obtained both in the drainage and groundwater. What differentiated the first and fourth FPB applications from the two others were heavy precipitation events within one week of FPB application, which resulted in rapid transport of TFMP through the discontinuities in the soil and contributed to relatively high TFMP detections in drainage and groundwater. This study indicated that pesticide degradates like TFMP, often being more soluble than the pesticide, have a relatively high leaching potential especially associated with heavy precipitation events shortly after the application. Hence, such pesticide degradates should like in Denmark be considered "relevant" meaning that the EU value for drinking water applies to them, having its leaching potential regulatory assessed based on high quality estimations of their persistence, and be exposed to an assessment of the risk to consumers of drinking contaminated groundwater.

Environmental Fate of the Herbicide Fluazifop-P-butyl and Its Degradation Products in Two Loamy Agricultural Soils: A Combined Laboratory and Field Study.

The herbicide fluazifop-P-butyl (FPB) is used against grasses in agricultural crops such as potato, oilseed rape, and sugar beet. Limited information is available in scientific literature on its environmental fate, therefore extensive monitoring at two agricultural test fields was combined with laboratory studies to determine leaching and the underlying degradation and sorption processes. Water samples from drains, suction cups, and groundwater wells showed leaching of the degradation products fluazifop-P (FP) and 2-hydroxy-5-trifluoromethyl-pyridin (TFMP) following FPB treatment. Laboratory experiments with soil from each field revealed a rapid degradation of FPB to FP. The degradation was almost exclusively microbial, and further biodegradation to TFMP occurred at a slower rate. Both degradation products were sorbed to the two soils to a small extent and were fairly persistent to degradation during the two-month incubation period. Together, the field and laboratory results from this study showed that the biodegradation of FPB in loamy soils gave rise to the production of two major degradation products that sorbed to a small extent. In this study, both degradation products leached to drainage and groundwater during precipitation. It is therefore recommended that these degradation products be included in programs monitoring water quality in areas with FPB use.

Reply to the comment on "Rainfall erosivity in Europe" by Auerswald et al.

Recently, in the Auerswald et al. (2015) comment on "Rainfall erosivity in Europe", 5 criticisms were addressed: i) the neglect of seasonal erosion indices, ii) the neglect of published studies and data, iii) the low temporal resolution of the data, especially of the maximum rain intensity, iv) the use of precipitation data instead of rain data and the subsequent deviation of the R-factor in Germany and Austria compared with previous studies, and v) the differences in considered time periods between countries. We reply as follows: (i) An evaluation of the seasonal erosion index at the European scale is, to our knowledge, not achievable at present with the available data but would be a future goal. Synchronous publication of the seasonal erosion index is not mandatory, specifically because seasonal soil loss ratios are not available at this scale to date. We are looking forward to the appropriate study by the authors of the comment, who assert that they have access to the required data. (ii) We discuss and evaluate relevant studies in our original work and in this reply; however, we cannot consider what is not available to the scientific community. (iii) The third point of critique was based on a misunderstanding by Auerswald et al. (2015), as we did indeed calculate the maximum intensity with the highest resolution of data available. (iv) The low R-factor values in Germany and the higher values in Austria compared with previous studies are not due to the involvement of snow but are rather due to a Pan-European interpolation. We argue that an interpolation across the borders of Austria creates a more reliable data set. (v) We agree that the use of a short time series or time series from different periods is generally a problem in all large-scale studies and requires improvement in the future. However, because this affects countries with a rather low variability of the R-factor in our study, we are confident that the overall results of the map are not biased. In conclusion, the Pan-European rainfall data compilation (REDES) was a great success and yielded data from 1541 stations with an average length of 17.1years and a temporal resolution of <60min. However, a Pan-European data collection will never be complete without the help and supply of data from its users. Thus, we invite the authors of the comment to share their data in the open REDES to help build even better rainfall-erosivity maps at regional or European scales.

Pesticide leaching through sandy and loamy fields - long-term lessons learnt from the Danish Pesticide Leaching Assessment Programme.

The European Union authorization procedure for pesticides includes an assessment of the leaching risk posed by pesticides and their degradation products (DP) with the aim of avoiding any unacceptable influence on groundwater. Twelve-year's results of the Danish Pesticide Leaching Assessment Programme reveal shortcomings to the procedure by having assessed leaching into groundwater of 43 pesticides applied in accordance with current regulations on agricultural fields, and 47 of their DP. Three types of leaching scenario were not fully captured by the procedure: long-term leaching of DP of pesticides applied on potato crops cultivated in sand, leaching of strongly sorbing pesticides after autumn application on loam, and leaching of various pesticides and their DP following early summer application on loam. Rapid preferential transport that bypasses the retardation of the plow layer primarily in autumn, but also during early summer, seems to dominate leaching in a number of those scenarios.

Rainfall erosivity in Europe.

Rainfall is one the main drivers of soil erosion. The erosive force of rainfall is expressed as rainfall erosivity. Rainfall erosivity considers the rainfall amount and intensity, and is most commonly expressed as the R-factor in the USLE model and its revised version, RUSLE. At national and continental levels, the scarce availability of data obliges soil erosion modellers to estimate this factor based on rainfall data with only low temporal resolution (daily, monthly, annual averages). The purpose of this study is to assess rainfall erosivity in Europe in the form of the RUSLE R-factor, based on the best available datasets. Data have been collected from 1541 precipitation stations in all European Union (EU) Member States and Switzerland, with temporal resolutions of 5 to 60 min. The R-factor values calculated from precipitation data of different temporal resolutions were normalised to R-factor values with temporal resolutions of 30 min using linear regression functions. Precipitation time series ranged from a minimum of 5 years to a maximum of 40 years. The average time series per precipitation station is around 17.1 years, the most datasets including the first decade of the 21st century. Gaussian Process Regression (GPR) has been used to interpolate the R-factor station values to a European rainfall erosivity map at 1 km resolution. The covariates used for the R-factor interpolation were climatic data (total precipitation, seasonal precipitation, precipitation of driest/wettest months, average temperature), elevation and latitude/longitude. The mean R-factor for the EU plus Switzerland is 722 MJ mm ha(-1) h(-1) yr(-1), with the highest values (>1000 MJ mm ha(-1) h(-1) yr(-1)) in the Mediterranean and alpine regions and the lowest (<500 MJ mm ha(-1) h(-1) yr(-1)) in the Nordic countries. The erosivity density (erosivity normalised to annual precipitation amounts) was also the highest in Mediterranean regions which implies high risk for erosive events and floods.

Comparative mapping of soil physical-chemical and structural parameters at field scale to identify zones of enhanced leaching risk.

Preferential flow and particle-facilitated transport through macropores contributes significantly to the transport of strongly sorbing substances such as pesticides and phosphorus. The aim of this study was to perform a field-scale characterization of basic soil physical properties like clay and organic carbon content and investigate whether it was possible to relate these to derived structural parameters such as bulk density and conservative tracer parameters and to actual particle and phosphorus leaching patterns obtained from laboratory leaching experiments. Sixty-five cylindrical soil columns of 20-cm height and 20-cm diameter and bulk soil were sampled from the topsoil in a 15-m × 15-m grid in an agricultural loamy field. Highest clay contents and highest bulk densities were found in the northern part of the field. Leaching experiments with a conservative tracer showed fast 5% tracer arrival times and high tracer recovery percentages from columns sampled from the northern part of the field, and the leached mass of particles and particulate phosphorus was also largest from this area. Strong correlations were obtained between 5% tracer arrival time, tracer recovery, and bulk density, indicating that a few well-aligned and better connected macropores might change the hydraulic conductivity between the macropores and the soil matrix, triggering an onset of preferential flow at lower rain intensities compared with less compacted soil. Overall, a comparison mapping of basic and structural characteristics including soil texture, bulk density, dissolved tracer, particle and phosphorus transport parameters identified the northern one-third of the field as a zone with higher leaching risk. This risk assessment based on parameter mapping from measurements on intact samples was in good agreement with 9 yr of pesticide detections in two horizontal wells and with particle and phosphorus leaching patterns from a distributed, shallow drainage pipe system across the field.

Leaching of azoxystrobin and its degradation product R234886 from Danish agricultural field sites.

The objective was to estimate leaching of the fungicide azoxystrobin (methyl (αE)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]-α-(methoxymethylene)benzene-acetate) and one of its primary degradation products R234886 ([(E)-2-(2-[6-cyanophenoxy)-pyrimidin-4-yloxyl]-phenyl-3-methoxyacrylic acid], major fraction) at four agricultural research fields (one sandy and three loamy) in Denmark. Water was sampled from tile drains, suction cups and groundwater wells for a minimum period of two years after application of azoxystrobin. Neither azoxystrobin nor R234886 were detected at the sandy site, but did leach through loamy soils. While azoxystrobin was generally only detected during the first couple of months following application, R234886 leached for a longer period of time and at higher concentrations (up to 2.1µgL(-1)). Azoxystrobin is classified as very toxic to aquatic organisms and R234886 as very harmful. Our study shows that azoxystrobin and R234886 can leach through loamy soils for a long period of time following application of the pesticide and thereby pose a potential threat to vulnerable aquatic environments and drinking water resources. We thus recommend the inclusion of azoxystrobin and R234886 in pesticide monitoring programmes and further investigation of their long-term ecotoxicological effects.

Transport modes and pathways of the strongly sorbing pesticides glyphosate and pendimethalin through structured drained soils.

Leaching of the strongly sorbing pesticides glyphosate and pendimethalin was evaluated in an 8-month field study focussing on preferential flow and particle-facilitated transport, both of which may enhance the leaching of such pesticides in structured soils. Glyphosate mainly sorbs to mineral sorption sites, while pendimethalin mainly sorbs to organic sorption sites. The two pesticides were applied in equal dosage to a structured, tile-drained soil, and the concentration of the pesticides was then measured in drainage water sampled flow-proportionally. The leaching pattern of glyphosate resembled that of pendimethalin, suggesting that the leaching potential of pesticides sorbed to either the inorganic or organic soil fractions is high in structured soils. Both glyphosate and pendimethalin leached from the root zone, with the average concentration in the drainage water being 3.5 and 2.7 µg L(-1), respectively. Particle-facilitated transport (particles >0.24 µm) accounted for only a small proportion of the observed leaching (13-16% for glyphosate and 16-31% for pendimethalin). Drain-connected macropores located above or in the vicinity of the drains facilitated very rapid transport of pesticide to the drains. That the concentration of glyphosate and pendimethalin in the drainage water remained high (>0.1 µg L(-1)) for up to 7d after a precipitation event indicates that macropores between the drains connected to underlying fractures were able to transport strongly sorbing pesticides in the dissolved phase. Lateral transport of dissolved pesticide via such discontinuities implies that strongly sorbing pesticides such as glyphosate and pendimethalin could potentially be present in high concentrations (>0.1 µg L(-1)) in both water originating from the drainage system and the shallow groundwater located at the depth of the drainage system.

Long-term leaching of rimsulfuron degradation products through sandy agricultural soils.

The objective was to quantify leaching of the widely used low-dosage sulfonylurea herbicides rimsulfuron and its primary degradation products IN70941 ([N-(4,6-dimethoxypyrimidin-2-yl)-N-((3-ethylsulfonyl)-2-pyridinyl)urea]) and IN70942 ([N-((3-ethylsulfonyl)-2-pyridinyl)-4,6-dimethoxy-2-pyrimidineamine]) at two sandy research fields in Denmark. Water was sampled monthly from the vadose and groundwater zones at the two sites (Tylstrup and Jyndevad) over a 4-6-year period following application of rimsulfuron. No rimsulfuron was detected in the water samples. At the Jyndevad site, IN70941 was detected in the vadose zone at a depth of 1m for as long as three years in annual average concentrations exceeding the EU limit value for drinking water of 0.1microgL(-1). At the Tylstrup site, IN70941 was detected at a depth of 2m in concentrations just below 0.1microgL(-1). The groundwater concentration of IN70941 occasionally exceeded 0.1microgL(-1) at the Jyndevad site, but is only detected on one occasion (and at a low concentration) at the Tylstrup site. At both sites IN70941 was relatively stable and persisted in the soil water for several years, with relatively little degrading further to IN70942. Thus, the concentration of IN7092 was much lower and apart from four samples from the Jyndevad site, never exceeded 0.1microgL(-1). Nevertheless, our findings show that degradation products of rimsulfuron can leach through sandy soils in relatively high concentrations and could potentially contaminate vulnerable aquatic environments. In view of this risk, IN70941 and IN70942 should be included in pesticide monitoring programmes, and their long-term ecotoxicological effects should be investigated further.

Ability of the MACRO model to predict long-term leaching of metribuzin and diketometribuzin.

In a regulatory context, numerical models are increasingly employed to quantify leaching of pesticides and their metabolites. Although the ability of these models to accurately simulate leaching of pesticides has been evaluated, little is known about their ability to accurately simulate long-term leaching of metabolites. A Danish study on the dissipation and sorption of metribuzin, involving both monitoring and batch experiments, concluded that desorption and degradation of metribuzin and leaching of its primary metabolite diketometribuzin continued for 5-6 years after application, posing a risk of groundwater contamination. That study provided a unique opportunity for evaluating the ability of the numerical model MACRO to accurately simulate long-term leaching of metribuzin and diketometribuzin. When calibrated and validated with respect to water and bromide balances and applied assuming equilibrium sorption and first-order degradation kinetics as recommended in the European Union pesticide authorization procedure, MACRO was unable to accurately simulate the long-term fate of metribuzin and diketometribuzin; the concentrations in the soil were underestimated by many orders of magnitude. By introducing alternative kinetics (a two-site approach), we captured the observed leaching scenario, thus underlining the necessity of accounting for the long-term sorption and dissipation characteristics when using models to predict the risk of groundwater contamination.

Bevacizumab plus irinotecan in the treatment patients with progressive recurrent malignant brain tumours.

MATERIAL AND METHODS: We retrospectively determined the efficacy and safety of a combination of bevacizumab and irinotecan in a consecutive series of 52 heavily pre-treated patients with recurrent high-grade brain tumours. Patients received bevacizumab (10 mg/kg) and irinotecan [340 mg/m(2) for those receiving enzyme-inducing antiepileptic drugs (EIAEDs) and 125 mg/m(2) for those not receiving EIAEDs] every 2 weeks. Fifty-two patients were included and 47 were evaluable for response. RESULTS: Complete or partial response was observed in 25% of all cases (30% response in grade IV glioma and 15% in grade III glioma). Estimated median progression-free survival (PFS) for both grade IV and grade III glioma was 22 weeks. The 6-month PFS was 32% for all patients, 40% for grade IV glioma and 33% for grade III glioma. Estimated median overall survival was 30 weeks for all patients, 28 weeks for grade IV glioma and 32 weeks for grade III glioma. Four patients discontinued treatment because of unmanageable toxicity: cerebral haemorrhage, cardiac arrhythmia, intestinal perforation and diarrhoea, the latter resulting in death. DISCUSSION: We conclude that the combination of bevacizumab and irinotecan shows acceptable safety and is a clinically relevant choice of therapy in heavily pre-treated patients with recurrent high-grade brain tumours.

Mitochondrial uncouplers with an extraordinary dynamic range.

We have discovered that some weak uncouplers (typified by butylated hydroxytoluene) have a dynamic range of more than 10(6) in vitro: the concentration giving measurable uncoupling is less than one millionth of the concentration causing full uncoupling. They achieve this through a high-affinity interaction with the mitochondrial adenine nucleotide translocase that causes significant but limited uncoupling at extremely low uncoupler concentrations, together with more conventional uncoupling at much higher concentrations. Uncoupling at the translocase is not by a conventional weak acid/anion cycling mechanism since it is also caused by substituted triphenylphosphonium molecules, which are not anionic and cannot protonate. Covalent attachment of the uncoupler to a mitochondrially targeted hydrophobic cation sensitizes it to membrane potential, giving a small additional effect. The wide dynamic range of these uncouplers in isolated mitochondria and intact cells reveals a novel allosteric activation of proton transport through the adenine nucleotide translocase and provides a promising starting point for designing safer uncouplers for obesity therapy.

Leaching of estrogenic hormones from manure-treated structured soils.

The threat to the aquatic environment posed by root zone leaching of estrogens from manure-treated fields has hitherto been overlooked. The steroid hormones 17beta-estradiol (E2) and its degradation product estrone (E1) are of particular environmental concern as both are abundant in slurryfrom pregnant and cycling pigs and both are potential endocrine disruptors (lowest observable effect level (LOEL) 14 and 3.3 ng/L, respectively). The present one-year study examines the transport of E1 and E2 from manure to tile drainage systems at two field sites on structured, loamy soil. The estrogens leached from the root zone to tile drainage water in concentrations exceeding the LOEL for as long as 3 months after application, with the maximum recorded concentration of E1 and E2 being 68.1 and 2.5 ng/ L, respectively. Transport of estrogens from the soil to the aquatic environment was governed by pronounced macropore flow and consequent rapid movement of the estrogens to the tile drains. These findings suggest that the application of manure to structured soils poses a potential contamination risk to the aquatic environment with estrogen, particularly when manure is applied to areas where the majority of streamwater derives from drainage water.

Leaching of metribuzin metabolites and the associated contamination of a sandy Danish aquifer.

As degradation products of metribuzin have received little attention as potential groundwater contaminants, we evaluated leaching of metribuzin and its primary metabolites desaminometribuzin (DA), desaminodiketometribuzin (DADK), and diketometribuzin (DK) at a sandy test site in Denmark. Soil water and groundwater were sampled monthly over a four-year period. Leaching of metribuzin and DA was negligible. DK and DADK leached from the root zone (1 meter below ground surface (mbgs)) in average concentrations considerably exceeding the EU limit value for drinking water (0.1 microg/L). Both metabolites appear to be relatively stable and persisted in soil water and groundwater several years after application. Past application of metribuzin at the site had contaminated the groundwater with both DK and DADK, which were detected in 99% and 48%, respectively, of the groundwater samples analyzed. Except for three of the groundwater samples, the DADK concentration never exceeded the EU limit value. In contrast, the annual concentration of DK exceeded 0.1 microg/L at 90% of the screens analyzed. The present findings suggest that as the degradation products of metribuzin can leach through sandy soil in high concentrations, they could potentially contaminate the groundwater. In view of this risk DK and DADK should both be included in monitoring programs and their ecotoxicological effects should be further investigated.

Leaching of glyphosate and amino-methylphosphonic acid from Danish agricultural field sites.

Pesticide leaching is an important process with respect to contamination risk to the aquatic environment. The risk of leaching was thus evaluated for glyphosate (N-phosphonomethyl-glycine) and its degradation product AMPA (amino-methylphosphonic acid) under field conditions at one sandy and two loamy sites. Over a 2-yr period, tile-drainage water, ground water, and soil water were sampled and analyzed for pesticides. At a sandy site, the strong soil sorption capacity and lack of macropores seemed to prevent leaching of both glyphosate and AMPA. At one loamy site, which received low precipitation with little intensity, the residence time within the root zone seemed sufficient to prevent leaching of glyphosate, probably due to degradation and sorption. Minor leaching of AMPA was observed at this site, although the concentration was generally low, being on the order of 0.05 microg L(-1) or less. At another loamy site, however, glyphosate and AMPA leached from the root zone into the tile drains (1 m below ground surface [BGS]) in average concentrations exceeding 0.1 microg L(-1), which is the EU threshold value for drinking water. The leaching of glyphosate was mainly governed by pronounced macropore flow occurring within the first months after application. AMPA was frequently detected more than 1.5 yr after application, thus indicating a minor release and limited degradation capacity within the soil. Leaching has so far been confined to the depth of the tile drains, and the pesticides have rarely been detected in monitoring screens located at lower depths. This study suggests that as both glyphosate and AMPA can leach through structured soils, they thereby pose a potential risk to the aquatic environment.