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Part-per-trillion level determination of antifouling pesticides and their byproducts in seawater samples by off-line solid-phase extraction followed by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

A new method for the simultaneous determination of antifouling pesticides and some of their byproducts such as dichlofluanid, diuron and its byproducts [demethyldiuron and 1-(3,4-dichlorophenyl)urea], (2-thiocyanomethylthio)ben: zothiazole, chlorothalonil, Sea-nine 211, Irgarol 1051 and one of its byproducts (2-methylthio-4-tert.-butylamino-s-triazine) in seawater was developed. The extraction of these compounds from the filtered seawater samples was performed off-line with different solid-phase extraction sorbents using (I) a 500 mg graphitized carbon black cartridge (ENVI-Carb) and (II) 200 mg polymeric cartridges (LiChrolut EN and Isolute ENV+) and passing 500 ml of the sample through these cartridges. The detection was carried out by reversed-phase high-performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry both in the negative and positive ion modes. The recovery ranged from 76 to 96% for the whole antifouling group with the ENVI-Carb cartridges and the detection limit was at the part-per-trillion level except for TCMTB. The method utilizing the polymeric cartridge proved to be very useful, time saving and with good recoveries when only Irgarol and its byproduct, Sea-nine 211 and diuron and its byproducts, have to be analyzed. The different cartridges were applied to the analysis of these pesticides in different marinas of the Catalan coast; diuron, dichlofluanid, Sea-nine 211, Irgarol as well as demethyldiuron and the Irgarol byproduct being the must ubiquitous pollutants. Maximum concentration levels were 2-3.5 microg/l of diuron and Sea-nine 211, respectively.

Atmospheric Pressure↗

Antifouling paint booster biocides in UK coastal waters: inputs, occurrence and environmental fate.

This study considered the inputs of antifouling paint booster biocides into the aquatic environment directly from painted hulls and high pressure hosing operations, the occurrence of booster biocides in marinas, harbours and docks, and the influence of degradation and water-sediment partition on their environmental fate. Irgarol 1051, the Irgarol 1051 degradation product GS26575, diuron, and the diuron degradation products 1-(3-chlorophenyl)-3,1-dimethylurea (CPDU), 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU) and 1-(3,4-dichlorophenyl)urea (DCPU) were all detected at measurable concentrations in surface waters. Irgarol 1051, GS26575 and diuron were also detected in bottom sediments. A preliminary study of biocide input during both normal use and foreshore hull hosing showed that hosing may be a significant point source input and also be a cause for future concern since much of this input is in the form of paint particles. Field based measurements and laboratory experiments showed that Irgarol 1051 and diuron persist in the water column, due to a low affinity to partition onto sedimentary material and high resistance to degradation. Other biocides such as chlorothalonil, dichlofluanid, and Sea-Nine 211 were all found to be rapidly removed from the water column and be less persistent.

Animals↗

Outward photocurrent component in chloroplasts of Peperomia metallica and its assignment to the 'closed thylakoid' recording configuration.

The photoinduced electrical events at energy-conserving chloroplast membranes can be studied in whole plastids using suction electrodes. In chloroplasts of Peperomia metallica the kinetic profile of photocurrent contains a minor outward component that occurs prior to and differs in polarity from the main component. The origin of this outward current was analyzed using single-turnover flashes in combination with prolonged light exposures and differential physicochemical treatments of tip-located (internal) and the exposed parts of a chloroplast. The outward current signal was higher after 10- to 20-s preillumination and gradually reduced in darkness. The relative amplitude of the outward peak current was enhanced when photosystem II (PS II) was excited by flashes given in the presence of far-red background light (lambda = 712 nm). The outward current was small or absent under conditions promoting activity of photosystem I (cyclic electron transport supported by artificial redox mediators in the presence of diuron) and was particularly high in the presence of PS II electron acceptors (e.g., p-phenylenediamine). This indicates the predominant association of the outward current with activity of PS II. The external application of diuron strongly inhibited the inward current, giving rise to a temporal increase in the outward current. On the contrary, when diuron was added into the suction pipette, the outward current was inhibited soon after sealing. The data suggest that the outward current originated in the tip-located portions of the thylakoid membrane that have orientation opposite to the exposed part of 'whole thylakoid'. These tip-located membrane portions are least accessible for inhibitors added into the outer medium and are highly sensitive to inhibitors (diuron), ionophores (gramicidin D), and detergents (Triton X-100) added into the pipette. Differential involvement of two photosystems in generation of the outward current may be caused by uneven structural distribution of photosystems I and II between appressed (granal) and nonappressed (stromal) thylakoids and by different recording configurations for these thylakoids.

Chloroplasts↗

Heterogeneity of Photosystem I reaction centers in barley leaves as related to the donation from stromal reductants.

The light-response curves of P700 oxidation and time-resolved kinetics of P700(+) dark re-reduction were studied in barley leaves using absorbance changes at 820 nm. Leaves were exposed to 45 degrees C and treated with either diuron or diuron plus methyl viologen (MV) to prevent linear electron flow from PS II to PS I and ferredoxin-dependent cyclic electron flow around PS I. Under those conditions, P700(+) could accept electrons solely from soluble stromal reductants. P700 was oxidized under weak far-red light in leaves treated with diuron plus MV, while identical illumination was nearly ineffective in diuron-treated leaves in the absence of MV. When heat-exposed leaves were briefly illuminated with strong far-red light, which completely oxidized P700, the kinetics of P700(+) dark reduction was fitted by a single exponential term with half-time of about 40 ms. However, two first-order kinetic components of electron flow to P700(+) (fast and slow) were found after prolonged leaf irradiation. The light-induced modulation of the kinetics of P700(+) dark reduction was reversed following dark adaptation. The fast component (half time of 80-90 ms) was 1.5 larger than the slow one (half time of about 1 s). No kinetic competition occurred between two pathways of electron donation to P700(+) from stromal reductants. This suggests the presence of two different populations of PS I.

Journal Article↗

Passive sampling of herbicides combined with effect analysis in algae using a novel high-throughput phytotoxicity assay (Maxi-Imaging-PAM).

We propose to combine a passive sampler for polar organic compounds (POS) with a specific bioassay for phytotoxicity to assess the hazard of herbicidal compounds in surface waters. The POS consisted of an Empore disk coated with styrenedivinylbenzene deployed in a Teflon housing, which has relatively high sampling rates (e.g., approximately 1 L d(-1) for diuron). POS were deployed for 5 days in a small-scale field study in South East Queensland, Australia, in a relatively pristine environment and an urban environment to explore sensitivity towards herbicides and potential influences of non-herbicidal pollutants. Besides chemical analysis of 8 herbicides, a novel bioassay (Maxi-Imaging-PAM, IPAM) was employed to assess the phytotoxic effects of water samples and POS extracts. The IPAM allows rapid assessment of photosynthetic quantum yields of a large number of samples via chlorophyll-fluorescence imaging and the saturation pulse method. Sampling rates for several herbicides from laboratory calibrations were found to be applicable under field conditions. Toxic equivalent concentrations (with reference to the herbicide diuron) were computed from the concentrations determined by chemical analysis and the relative potency (also termed toxic equivalence factor) of the detected herbicides. There was good agreement between diuron equivalent concentrations from chemical analysis and diuron equivalent concentrations determined with the IPAM.

Chlorophyll↗

[Effect of pyridazinone herbicides on the photosynthetic electron transport chain of chloroplasts and Chlorella].

In order to establish the site of pyridazinone herbicides action on the photosynthetic electron transport chain, their effect on the photochemical activity of chloroplasts and Chlorella was studied. It was shown that these compounds similar to diuron inhibit the delta F of chloroplasts but enhance the delta F and cause the disappearance of slow transient processes in Chlorella and change the light-off time course of delta F both in Chlorella and in the chloroplasts. The inhibiting effect is observed at herbicide concentration of 5 x 10(-6) M and is maximal at 10(-4) M. However, in contrast to diuron the herbicides enhance the msec afterglow in Chlorella cells; besides, even at concentration as high as 10(-4) M they only partly block photosynthetic oxygen evolution and the light-induced change of pH. Pyridazinone herbicides retard the delay of light-off delta F at-196 degrees C more efficiently than diuron. It is suggested that the herbicides under study inhibit the photosynthetic electron transport chain, however less efficiently than diuron; the inhibiting effect is decreased in the following order: SAN 9785, SAN 6706, SAN 9789. The herbicides affect mainly the acceptor part of the photosystem 2, retarding the electron transport from the intermediary acceptor to plastoquinone. In addition these herbicides may also have other sites of action in the region of photosystem 2.

Chlorella↗

Rainfastness and adsorption of herbicides on hard surfaces.

Herbicides are still used to control weeds on hard surfaces, including municipal, private and industrial sites. Used under unfavourable conditions, especially when rain occurs shortly after application, herbicides may run off to surface waters. Such losses of herbicides from hard surfaces are estimated to be much higher than for herbicides used in arable fields. In this study, three kinds of hard surface were evaluated: asphalt, concrete surface and gravel (fine and coarse). Three herbicides were applied: glyphosate, diuron and diflufenican. Adsorption isotherms of diuron and diflufenican to the three surfaces were determined. At different times after treatment with the herbicides, rainfall was simulated by use of a rain-droplet spray nozzle, and the run-off was collected for analysis. After this run-off event, the materials were immersed in water to measure desorption which, together with the compound in the run-off, gave a measure of the dislodgable residues. The apolar herbicides diuron and especially diflufenican adsorbed strongly to asphalt. The polar herbicide glyphosate lost 75% in run-off from asphalt but was adsorbed strongly to soil and concrete pavement.

Adsorption↗

The effects of three related amides on microecosystem stability.

Three related amides (diuron, 2-(octyloxy) acetanilide, and salicylanilide) were evaluated for toxicity to aquatic microcosm communities. Effects were measured at the ecosystem level using changes in pH, Eh (redox potential), and dissolved oxygen as indicators of toxicity. These values were used to calculate the resistance, resilience, and relative instability of the microecosystems to each compound at comparable dose levels of approximately 2500 micrograms/liter. Such measures have often been used in a theoretical context, but have not received wide practical application. The systems showed low resistance and no resilience to diuron, high resistance and low resilience to 2-(octyloxy) acetanilide, and no response to salicylanilide. At a higher exposure level (9800 micrograms/liter salicylanilide), the systems showed low resistance and high resilience. Both this approach and more traditional dose-response measures of toxicity indicated that diuron was clearly the most toxic compound, followed by 2-(octyloxy) acetanilide and salicylanilide. While microcosm toxicity tests were slightly less sensitive than some single species tests, they provided important additional information on the extent of perturbations and the rate of ecosystem recovery.

Amides↗

Haemotoxic effect of phenylurea herbicides in rats: role of haemoglobin-adduct formation in splenic toxicity.

Three substituted phenylurea herbicides were used for the study of the haemotoxic effects on rats of chronic exposure to these compounds. Female Sprague-Dawley rats were given monuron, diuron or fenuron (250-1000 mg/kg diet) for 14 months. The final body weights were similar to those of controls. No treatment-related effects on organ weights were observed at autopsy, except for a dose-related increase in spleen weights in rats treated with monuron or diuron, but not in those treated with fenuron. The proportion of haemoglobin in the form of methaemoglobin increased in the dosed group and resulted in a secondary anaemia with changes in the morphology of erythrocytes. Haemoglobin adducts of aromatic amines released from the herbicides were present at dose-related levels in rats treated with monuron or diuron. Compound-related lesions were observed histologically in treated rats, with increased pigmentation (haemosiderin) in the spleen, reflecting the response to the haemolytic anaemia and methaemoglobinaemia induced by the herbicides. Pigment deposition consisting of golden brown granules in the cytoplasm of the tubular epithelium in the kidney and in the Kupffer cells in the liver were observed only in rats treated with monuron. The haemotoxic effects that were observed may indicate that the formation of adducts between haemoglobin and the parent aromatic amines released metabolically from these herbicides has a role in the splenic toxicity of these compounds.

Animals↗

Effects of insect growth regulators on the nontarget soil arthropod Folsomia candida (Collembola).

The aim of this study was to assess the effect of several insect growth regulators (IGRs) on the nontarget soil arthropod Folsomia candida (Collembola). The survival and reproduction rates of F. candida were evaluated after 28 days of exposure to six IGRs (methoprene, fenoxycarb, precocene II, tebufenozide, hexaflumuron and teflubenzuron) and to one herbicide (diuron) in artificial soil. The differences in the sensitivity of F. candida to these different substances are high. The chitin synthesis inhibitors teflubenzuron and hexaflumuron were the most toxic compounds with an EC50 of 0.05 mg/kg (dry weight) for teflubenzuron and an EC50 of 0.6mg/kg for hexaflumuron. Teflubenzuron is toxic for F. candida at concentrations that are probably close to environmental levels of this insecticide. Inhibition of reproduction is strongly related to adult survival for the juvenile hormone agonist methoprene and for the antijuvenile hormone precocene II, with an EC50 of 173 mg/kg and a LC50 of 178mg/kg for methoprene and an EC50 of 15 mg/kg and a LC50 of 26 mg/kg for precocene II. Fenoxycarb, another juvenile hormone analog, showed a dose-response curve for mortality different from that of methoprene; at concentrations such as 3052 mg/kg no effect on adult survival was observed. However, the EC50 value of 113mg/kg is of the same order of magnitude as that obtained for methoprene. A test with compressed soil contaminated with fenoxycarb was conducted to observe parameters such as numbers of eggs laid and juveniles hatched. No differences were observed between these two endpoints for fenoxycarb. An EC50 of 109 mg/kg was obtained for the ecdysone agonist tebufenozide. The herbicide diuron showed a relatively high toxicity for F. candida with an EC50 of 20 mg/kg. Our results show that some of the tested IGRs can have effects on Collembola at environmentally relevant concentrations (toxicity/exposure ratios < 5 for teflubenzuron, hexaflumuron, and diuron).

Animals↗

Monitoring of antifouling agents in water samples by on-line solid-phase extraction-liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

An automatic method for determining diuron, irgarol 1051, folpet and dichlofluanid in seawater samples have been developed. This method is based on the on-line coupling of solid-phase extraction (SPE) with a highly crosslinked polymeric sorbent, LiChrolut EN, to liquid chromatography followed by atmospheric pressure chemical ionization (APCI) and mass spectrometry. The operational parameters affecting the APCI interface have been studied in both positive and negative ionization modes. The use of LiChrolut EN in the SPE produced recoveries of over 85% for all the compounds when 100 ml of seawater sample was preconcentrated. Calibration was carried out in both ionization modes and in full-scan and selected-ion monitoring (SIM). The method allowed all the analytes to be detected at 5 ng l(-1) in SIM acquisition mode except folpet, which, because of its low response, could only be detected at 250 ng l(-1). The method was used to analyse water samples taken from five different marina and fishing ports along the coast of Tarragona, Catalonia (Spain), over a 5-month period. Diuron and irgarol 1051 were detected and quantified in most samples at concentration levels ranging from 27 to 420 ng l(-1) for diuron and from 15 to 511 ng l(-1) for irgarol 1051.

Atmospheric Pressure↗

Sorption of pesticides in tropical and temperate soils from Australia and the Philippines.

The sorption behavior of diuron, imidacloprid, and thiacloprid was investigated using 22 soils collected in triplicate from temperate environments in Australia and tropical environments in Australia and the Philippines. Within the temperate environment in Australia, the soils were selected from a range of land uses. The average KOC values (L/kg) for imidacloprid were 326, 322, and 336; for thiacloprid, the values were 915, 743, and 842; and for diuron, the values were 579, 536, and 618 for the Ord (tropical), Mt. Lofty (temperate), and Philippines (tropical) soils, respectively. For all soils, the sorption coefficients decreased in the following order: thiacloprid > diuron > imidacloprid. There were no significant differences in sorption behavior between the tropical soils from the Philippines and the temperate soils from Australia. Sorption was also not significantly related with soil characteristics, namely, organic carbon (OC) content, clay content, and pH, for any of the three chemicals studied. When the data were sorted into separate land uses, the sorption of all three chemicals was highly correlated (P < 0.001) with OC for the rice soils from the Philippines. Sorption coefficients for all three chemicals were highly correlated with OC in temperate, native soils only when one extreme value was removed. The relationships between sorption of all three chemicals and OC in temperate, pasture soils were best described by a polynomial. Sorption coefficients for imidacloprid and thiacloprid determined in the temperate pasture soils remained fairly consistent as the OC content increased from 3.3 to 5.3%, indicating that, although the total OC in the pasture soils was increasing, the component of OC involved with sorption of these two compounds may have been remaining constant. This study demonstrated that the origin of the soils (i.e., temperate vs tropical) had no significant effect on the sorption behavior, but in some cases, land use significantly affected the sorption behavior of the three pesticides studied. The impact of land use on the nature of soil OC will be further investigated by NMR analysis.

Adsorption↗

Predominant protection of D2-protein against photodestruction in isolated D1/D2/cytochrome b559 by K15, a phenolic-type inhibitor of electron transfer in photosystem 2.

A protective action of K15 (4-[methoxy-bis(trifluoromethyl)methyl]-2,6-dinitrophenylhydrazone methyl ketone), an inhibitor of electron transport in photosystem 2 (PS 2), against photoinactivation of the PS 2 reaction center (RC) D1/D2/cytochrome b(559) complex, isolated from pea chloroplasts, by red light (0.7 mmol photons/sec per m(2)) has been investigated under aerobic conditions. The inhibitor K15 causing cyclic electron transfer around PS 2 and thus prohibiting stabilization of separated charges has been shown to effectively protect RC both against the loss of photochemical activity (measured as reversible photoinduced absorbance changes related to photoreduction of pheophytin) and aggregation and degradation of the proteins D2 and D1 during photoinactivation. Comparison of the protective action of K15 and of another inhibitor of electron transfer in PS 2, diuron, against light-induced destruction of proteins D1 and D2 shows that diuron stabilizes protein D1 and K15 stabilizes protein D2. The preferential protection of D2 against photoinduced destruction revealed in our work is in accord with the concept of a specific binding of K15 with this protein. It is proposed that this binding site may be that of the primary quinone electron acceptor Q(A) located on the D2 protein (in contrast to diuron, which is known to replace the secondary electron acceptor Q(B) from its binding site on D1).

Cytochrome b Group↗

Analysis of herbicide Krovar I by liquid chromatography with atmospheric pressure chemical ionization mass spectrometry.

A simple, very efficient method is presented for routine analysis of herbicide Krovar I (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid-liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 microg L(-1) and for diuron 0.03 microg L(-1). Method detection limit for soil samples is 0.01 microg g(-1) dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.

Atmospheric Pressure↗

Effect of phenylurea herbicides on soil microbial communities estimated by analysis of 16S rRNA gene fingerprints and community-level physiological profiles.

The effect of three phenyl urea herbicides (diuron, linuron, and chlorotoluron) on soil microbial communities was studied by using soil samples with a 10-year history of treatment. Denaturing gradient gel electrophoresis (DGGE) was used for the analysis of 16S rRNA genes (16S rDNA). The degree of similarity between the 16S rDNA profiles of the communities was quantified by numerically analysing the DGGE band patterns. Similarity dendrograms showed that the microbial community structures of the herbicide-treated and nontreated soils were significantly different. Moreover, the bacterial diversity seemed to decrease in soils treated with urea herbicides, and sequence determination of several DGGE fragments showed that the most affected species in the soils treated with diuron and linuron belonged to an uncultivated bacterial group. As well as the 16S rDNA fingerprints, the substrate utilization patterns of the microbial communities were compared. Principal-component analysis performed on BIOLOG data showed that the functional abilities of the soil microbial communities were altered by the application of the herbicides. In addition, enrichment cultures of the different soils in medium with the urea herbicides as the sole carbon and nitrogen source showed that there was no difference between treated and nontreated soil in the rate of transformation of diuron and chlorotoluron but that there was a strong difference in the case of linuron. In the enrichment cultures with linuron-treated soil, linuron disappeared completely after 1 week whereas no significant transformation was observed in cultures inoculated with nontreated soil even after 4 weeks. In conclusion, this study showed that both the structure and metabolic potential of soil microbial communities were clearly affected by a long-term application of urea herbicides.

Bacteria↗

Novel derivatives of 9,10-anthraquinone are selective algicides against the musty-odor cyanobacterium Oscillatoria perornata.

Musty "off-flavor" in pond-cultured channel catfish (Ictalurus punctatus) costs the catfish production industry in the United States at least 30 million US dollars annually. The cyanobacterium Oscillatoria perornata (Skuja) is credited with being the major cause of musty off-flavor in farm-raised catfish in Mississippi. The herbicides diuron and copper sulfate, currently used by catfish producers as algicides to help mitigate musty off-flavor problems, have several drawbacks, including broad-spectrum toxicity towards the entire phytoplankton community that can lead to water quality deterioration and subsequent fish death. By use of microtiter plate bioassays, a novel group of compounds derived from the natural compound 9,10-anthraquinone have been found to be much more selectively toxic towards O. perornata than diuron and copper sulfate. In efficacy studies using limnocorrals placed in catfish production ponds, application rates of 0.3 micro M (125 micro g/liter) of the most promising anthraquinone derivative, 2-[methylamino-N-(1'-methylethyl)]-9,10-anthraquinone monophosphate (anthraquinone-59), dramatically reduced the abundance of O. perornata and levels of 2-methylisoborneol, the musty compound produced by O. perornata. The abundance of green algae and diatoms increased dramatically 2 days after application of a 0.3 micro M concentration of anthraquinone-59 to pond water within the limnocorrals. The half-life of anthraquinone-59 in pond water was determined to be 19 h, making it much less persistent than diuron. Anthraquinone-59 appears to be promising for use as a selective algicide in catfish aquaculture.

Animals↗

Toxicity of herbicides in highway runoff.

Previous field monitoring at two highway sites found highway-applied herbicides in storm water runoff at maximum concentrations ranging from 10 microg/L for glyphosate and diuron to as high as 200 microg/L for oryzalin. To determine whether these herbicides at these concentrations can cause any toxicity to aquatic organisms, a standard toxicity study was conducted. Storm water was collected along Highway 37, Sonoma County, California, USA, and the herbicides isoxaben, oryzalin, diuron, clopyralid, and glyphosate were spiked into the storm water at the highest concentrations observed during the five previous field-monitoring campaigns. Three different toxicity studies were conducted and the results showed the following: No significant reduction in reproduction or increase in mortality relative to the control for an 8-d Ceriodaphnia (water flea) toxicity test; no significant increase in mortality or decrease in biomass compared to the control during a 7-d Pimephales (fish) toxicity test; and, in a 96-h Selenastrum (algae) toxicity test, both the 10-microg/L diuron treatment and the combined 50-microg/L isoxaben plus 200-microg/L oryzalin treatment produced significant (p < 0.05) reductions in algal growth compared to the controls, although the 30-microg/L clopyralid or 10-microg/L glyphosate treatments did not exhibit any toxic effects.

Animals↗

Contribution of non-agricultural pesticides to pesticide load in surface water.

Two small creeks, tributaries of the River Ruhr near Schwerte, Federal Republic of Germany, were investigated to reveal the regional agricultural and non-agricultural sources of pesticide inputs and the main pathways to surface water. In addition, the receiving water was monitored for pesticides. The watersheds are situated at the northern margin of the Rhenian Schiefergebirge, a highland landscape in North-Rhine-Westphalia. Solid carboniferous shale is covered by a shallow layer of quaternary unconsolidated rock (porous aquifer thickness <5 m). Occurrence of herbicides such as chlortoluron, isoproturon and terbuthylazine in surface water could be due to their broad agricultural application in regional dominant crops, such as barley, wheat and maize. Occurrence of diuron and glyphosate results from their use in residential settlements and industrial areas as well as from weed control on railway tracks. Atrazine concentrations up to 0.8 microg litre(-1) indicated recent use of this herbicide, which has been banned since 1991, and was also the result of non-agricultural applications. Pathways for pesticide input to the receiving waters were related to both surface run-off and underground passage. Two-thirds of the observed diuron load in the surface water resulted from an input by run-off. This was expected as a result of total herbicide application targets to sealed surfaces infringing current regulations and recommendations. Diuron load varied between 0.6 and 1.2% of the estimated amount applied annually in the investigated catchments. Non-agricultural pesticide use contributed more than two-thirds of the whole observed pesticide load in the tributaries and at least one-third in the River Ruhr.

Environmental Monitoring↗