Value of biochars from Miscanthus x giganteus cultivated on contaminated soils to decrease the availability of metals in multicontaminated aqueous solutions

The objective of this study was to evaluate the sorption efficiency of eight biochars, made from Miscanthus x giganteus cultivated on contaminated agricultural soil, in aqueous solutions contaminated with metals alone or mixed with polycyclic aromatic hydrocarbons. These biochars were produced in different pyrolysis conditions (temperature, 400/600 °C; heating rate, 5/10 °C min⁻¹; duration, 45/90 min) and compared with an uncontaminated commercialized biochar made of wood. The physicochemical characterization of the Miscanthus biochars confirmed the impact of the pyrolysis on the biochar parameters with substantial differences between the biochars in terms of pH, cation exchange capacity, and specific surface area. The sorption experiment showed higher sorption efficiency of Cd, Pb, and Zn for the Miscanthus biochars produced at 600 °C compared with the biochars produced at 400 °C when the aqueous solutions were mono- or multicontaminated. Furthermore, the desorption study showed that the sorption process was largely irreversible. Therefore, the high sorption capacity of Miscanthus biochars and the low sorption reversibility confirmed that these biochars are a suitable sorbent for metals.

     

Effect of Pinus radiata derived biochars on soil sorption and desorption of phenanthrene

Biochars are anthropogenic carbonaceous sorbent and their influences on the sorption of environmental contaminants need to be characterized. Here we evaluated the effect of Pinus radiata derived biochars on soil sorption and desorption of phenanthrene. Two biochars separately produced at 350 °C and 700 °C and three soils were tested. Biochar amendment generally enhanced the soil sorption of phenanthrene. The biochar produced at 700 °C generally showed a greater ability at enhancing a soil’s sorption ability than that prepared at 350 °C. The single-step desorption measurement showed an apparent hysteresis in biochar-amended soils. After 28 d equilibration, the sorptive capacity of biochar-amended soil (with an organic carbon content of 0.16%) significantly decreased. This study clearly suggested that biochar application enhanced soil sorption of hydrophobic organic compounds, but the magnitude of enhancement depended on the preparation of biochars, the indigenous soil organic carbon levels, and the contact time between soil and biochar.     

Maize,switchgrass, and ponderosa pine biochar added to soil increased herbicide sorption and decreased herbicide efficacy

Biochar, a by-product of pyrolysis made from a wide array of plant biomass when producing biofuels, is a proposed soil amendment to improve soil health. This study measured herbicide sorption and efficacy when soils were treated with low (1% w/w) or high (10% w/w) amounts of biochar manufactured from different feedstocks [maize (Zea mays) stover, switchgrass (Panicum vigatum), and ponderosa pine (Pinus ponderosa)], and treated with different post-processing techniques. Twenty-four hour batch equilibration measured sorption of ¹⁴C-labelled atrazine or 2,4-D to two soil types with and without biochar amendments. Herbicide efficacy was measured with and without biochar using speed of seed germination tests of sensitive species. Biochar amended soils sorbed more herbicide than untreated soils, with major differences due to biochar application rate but minor differences due to biochar type or post-process handling technique. Biochar presence increased the speed of seed germination compared with herbicide alone addition. These data indicate that biochar addition to soil can increase herbicide sorption and reduce efficacy. Evaluation for site-specific biochar applications may be warranted to obtain maximal benefits without compromising other agronomic practices.     

Sorption and desorption kinetics of diuron,fluometuron, prometryn and pyrithiobac sodium in soils

Abstract

The sorption and desorption characteristics of four herbicides (diuron, fluometuron, prometryn and pyrithiobac‐sodium) in three different cotton growing soils of Australia was investigated. Kinetics and equilibrium sorption and desorption isotherms were determined using the batch equilibrium technique. Sorption was rapid (> 80% in 2 h) and sorption equilibrium was achieved within a short period of time (ca 4 h) for all herbicides. Sorption isotherms of the four herbicides were described by Freundlich equation with an r² value > 0.98. The herbicide sorption as measured by the distribution coefficient (K_d) values ranged from 3.24 to 5.71 L/kg for diuron, 0.44 to 1.13 L/kg for fluometuron, 1.78 to 6.04 L/kg for prometryn and 0.22 to 0.59 L/kg for pyrithiobac‐sodium. Sorption of herbicides was higher in the Moree soil than in Narrabri and Wee Waa soils. When the K_d values were normalised to organic carbon content of the soils (K_oC), it suggested that the affinity of the herbicides to the organic carbon increased in the order: pyrithiobac‐sodium < fluometuron < prometryn < diuron. The desorption isotherms were also adequately described by the Freundlich equation. For desorption, all herbicides exhibited hysteresis and the hysteresis was stronger for highly sorbed herbicides (diuron and prometryn) than the weakly sorbed herbicides (fluometuron and pyrithiobac‐sodium). Hysteresis was also quantified as the percentage of sorbed herbicides which is not released during the desorption step ω = [n_ad / n_de ‐1] x 100). Soil type and initial concentration had significant effect on ω. The effect of sorption and desorption properties of these four herbicides on the off‐site transport to contaminate surface and groundwater are also discussed in this paper.     

Sorption-Desorption of Atrazine and Diuron in Soils from Southern Brazil

The objective of this study was to investigate the behavior of sorption and desorption of the herbicides atrazine (6-chloro-N ²-ethyl-N ⁴-isopropyl-1,3,5-triazine-2,4-diamine) and diuron [3-(3,4-dichlorophenyl)-1,1-dimethyleurea] in soil samples from a typical lithosequence located in the municipality of Mamborê (PR), southern Brazil. Five concentrations of ¹⁴C-atrazine and ¹⁴C-diuron were used for both herbicides (0.48, 0.96, 1.92, 3.84, and 7.69 mg L^?1). Sorption of both herbicides correlated positively with the organic carbon and clay content of the soil samples. Sorption isotherms were well described by the Freundlich model. The slope values of the isotherm (N) ranged from 0.84 to 0.90 (atrazine) and from 0.75 to 0.79 (diuron) for the lithosequence samples. Sorption of diuron was high regardless of the soil texture or the concentration added. The desorption isotherms for atrazine and diuron showed good fit to the Freundlich equation (R ² ≥ 0,87). Atrazine slope values for the desorption isotherms were similar for the different concentrations and were much lower than those observed for the sorption isotherms. Significant hysteresis was observed in the herbicide desorption. When the two herbicides were compared, it was found that diuron (N = 0.06–0.22) presented more pronounced hysteresis than atrazine. The results showed that, quantitatively, a greater atrazine fraction applied to these soils remains available to be leached in the soil profile, as compared to diuron.     

Adsorption of hydrogen sulfide by biochars derived from pyrolysis of different agricultural/forestry wastes

The characteristics and mechanisms of hydrogen sulfide (H₂S) adsorption on three different biochars derived from agricultural/forestry wastes through pyrolysis at various temperatures (100 to 500 ºC) were investigated. In this study, the H₂S breakthrough capacity was measured using a laboratory-characterized using pH and Fourier transform infrared spectroscopy analysis. The results obtained demonstrate that all biochars were effective in H₂S sorption. The sorption capacity of the biochar for H₂S removal is related to the pyrolysis temperature and pH of the surface. Certain threshold ranges of the pyrolysis temperature (from 100 to 500 ºC) and pH of the surface are presented. It also concluded that the sorption capacity (for removing H₂S) of rice hull-derived biochar is the largest in three biochars (camphor-derived biochar, rice hull-derived biochar, and bamboo-derived biochar). These observations will be helpful in designing biochar as engineered sorbents for the removal of H₂S.Implications: This paper focuses on the adsorption of hydrogen sulfide (H₂S) by biochars derived from wastes. The characteristics and mechanisms of hydrogen sulfide (H₂S) adsorption on three different boichars derived from agricultural/forestry wastes through pyrolysis at various temperatures were investigated. In this study, the H₂S breakthrough capacity was measured using laboratory characterization with pH and Fourier-transform infrared spectroscopy analysis. The results obtained demonstrate that all biochars were effective in H₂S sorption. The sorption capacity of the biochar for H₂S removal is related to the pyrolysis temperature and pH of the surface.     

Behavior of Two Phenyl Urea Herbicides in Clayey Soils and Effect of Alternating Dry-Wet Conditions on their Availability

Adsorption and mobility of linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea) and diuron (3-(3,4-dichlorophenyl)-1, 1-dimethylurea) were studied in clayey soils from the Gharb area (Morocco). Soils A and B were planted with sun flower (Helianthus annuus) while soil C was planted with sugar cane (Saccharum offcinarum). Adsorption was studied for linuron in soils A and B, while mobility was studied only in soil B. Adsorption data were found to fit the Freundlich equation with correlation coefficients r² > 0.9. Freundlich coefficients (K_f, n_f) were in agreement with L and S isotherm types for soils A and B, respectively. Values of K_oc (195 and 102) indicate moderate adsorption. Desorption isotherms for linuron showed hysteresis for both soils. The pesticide would be more bound to soil A (H = 8.44) than to soil B (H = 4.01). The effect of alternating wet and dry conditions was tested for soils A and B. Results showed that retention would increase in soil subject to an additional wet and dry cycle. In the case of diuron isotherm was of type L in soil C. Desorption was noticeable at high concentrations and tended to decrease when concentrations diminished. Mobility of linuron was tested in polyvinyle chloride (PVC) columns, which received different treatments before their percolation. The pesticide was more mobile in a previously saturated column. In columns subject to a drying step after saturation with water, linuron mobility was greatly reduced.     

Effect of biochar amendment on sorption and leaching of nitrate,ammonium, and phosphate in a sandy soil

When applied to soils, it is unclear whether and how biochar can affect soil nutrients. This has implications both to the availability of nutrients to plants or microbes, as well as to the question of whether biochar soil amendment may enhance or reduce the leaching of nutrients. In this work, a range of laboratory experiments were conducted to determine the effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil. A total of thirteen biochars were tested in laboratory sorption experiments and most of them showed little/no ability to sorb nitrate or phosphate. However, nine biochars could remove ammonium from aqueous solution. Biochars made from Brazilian pepperwood and peanut hull at 600 °C (PH600 and BP600, respectively) were used in a column leaching experiment to assess their ability to hold nutrients in a sandy soil. The BP600 biochar effectively reduced the total amount of nitrate, ammonium, and phosphate in the leachates by 34.0%, 34.7%, and 20.6%, respectively, relative to the soil alone. The PH600 biochar also reduced the leaching of nitrate and ammonium by 34% and 14%, respectively, but caused additional phosphate release from the soil columns. These results indicate that the effect of biochar on the leaching of agricultural nutrients in soils is not uniform and varies by biochar and nutrient type. Therefore, the nutrient sorption characteristics of a biochar should be studied prior to its use in a particular soil amendment project.     

Metabolites of the phenylurea herbicides chlorotoluron, diuron, isoproturon and linuron produced by the soil fungus Mortierella sp.

Phenylurea herbicides are used worldwide, and often pollute surface- and groundwater in concentrations exceeding the limit value for drinking water (0.1 μg l⁻¹). Bacteria degrade phenylurea herbicides by successive N-dealkylation to substituted aniline products. Little is known about the corresponding fungal pathways, however. We here report degradation of chlorotoluron, diuron, isoproturon and linuron by the soil fungus Mortierella sp. Gr4. Degradation was fastest with linuron and resulted in successively dealkylated metabolites and 3,4-dichloroaniline. A major new metabolite was detected that has not yet been fully identified. Thin layer chromatography and nuclear magnetic resonance spectroscopy indicate that it is a non-aromatic diol. Degradation of isoproturon, chlorotoluron and diuron involved successive N-demethylation and, in the case of isoproturon and chlorotoluron, additional hydroxylation. A new hydroxylated isoproturon metabolite was detected. The study thus shows that the fungal pathways differ from the bacterial pathways and yield new metabolites of possible environmental concern.     

Effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil

When applied to soils, it is unclear whether and how biochar can affect soil nutrients. This has implications both to the availability of nutrients to plants or microbes, as well as to the question of whether biochar soil amendment may enhance or reduce the leaching of nutrients. In this work, a range of laboratory experiments were conducted to determine the effect of biochar amendment on sorption and leaching of nitrate, ammonium, and phosphate in a sandy soil. A total of thirteen biochars were tested in laboratory sorption experiments and most of them showed little/no ability to sorb nitrate or phosphate. However, nine biochars could remove ammonium from aqueous solution. Biochars made from Brazilian pepperwood and peanut hull at 600 °C (PH600 and BP600, respectively) were used in a column leaching experiment to assess their ability to hold nutrients in a sandy soil. The BP600 biochar effectively reduced the total amount of nitrate, ammonium, and phosphate in the leachates by 34.0%, 34.7%, and 20.6%, respectively, relative to the soil alone. The PH600 biochar also reduced the leaching of nitrate and ammonium by 34% and 14%, respectively, but caused additional phosphate release from the soil columns. These results indicate that the effect of biochar on the leaching of agricultural nutrients in soils is not uniform and varies by biochar and nutrient type. Therefore, the nutrient sorption characteristics of a biochar should be studied prior to its use in a particular soil amendment project.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

Biochar as low-cost sorbent of volatile fuel organic compounds: potential application to water remediation

Pyrolysis of waste materials to produce biochar is an excellent and suitable alternative supporting a circular bio-based economy. One of the properties attributed to biochar is the capacity for sorbing organic contaminants, which is determined by its composition and physicochemical characteristics. In this study, the capacity of waste-derived biochar to retain volatile fuel organic compounds (benzene, toluene, ethylbenzene and xylene (BTEX) and fuel oxygenates (FO)) from artificially contaminated water was assessed using batch-based sorption experiments. Additionally, the sorption isotherms were established. The results showed significant differences between BTEX and FO sorption on biochar, being the most hydrophobic and non-polar contaminants those showing the highest retention. Furthermore, the sorption process reflected a multilayer behaviour and a relatively high sorption capacity of the biochar materials. Langmuir and Freundlich models were adequate to describe the experimental results and to detect general differences in the sorption behaviour of volatile fuel organic compounds. It was also observed that the feedstock material and biochar pyrolysis conditions had a significant influence in the sorption process. The highest sorption capacity was found in biochars produced at high temperature (>?400 °C) and thus rich in aromatic C, such as eucalyptus and corn cob biochars. Overall, waste-derived biochar offers a viable alternative to be used in the remediation of volatile fuel organic compounds from water due to its high sorption capacity.

     

Leaching potential of phenylurea herbicides in a calcareous soil: comparison of column elution and batch studies

The transfer of eleven phenylurea herbicides through soil columns was investigated in laboratory conditions in order to determine leaching properties in a calcareous soil. Elution curves with distilled water were plotted after herbicide application on the soil column. Phenylurea retention by the soil indicating interactions with soil can be classified as follows: fenuron < fluometron ≤ isoproturon = monuron < metoxuron < monolinuron < metobromuron < chlorotoluron < linuron = diuron < chlorbromuron. The number and nature of halogen atoms on the phenyl ring had an important influence on leaching. Retention was higher for molecules with higher number of halogen, and it was also higher for bromine than chlorine. Column elution experiments were compared to batch experiments from which the distribution coefficients K _d were determined. According to Kendall correlation coefficients, parameter m/m _0max from column experiments was relatively well linked to K _d. In case of phenylurea, a linear relationship between K _d and m/m _0max was established.     

Insights into aqueous carbofuran removal by modified and non-modified rice husk biochars

Biochar has been considered as a potential sorbent for removal of frequently detected pesticides in water. In the present study, modified and non-modified rice husk biochars were used for aqueous carbofuran removal. Rice husk biochars were produced at 300, 500, and 700 °C in slow pyrolysis and further exposed to steam activation. Biochars were physicochemically characterized using proximate, ultimate, FTIR methods and used to examine equilibrium and dynamic adsorption of carbofuran. Increasing pyrolysis temperature led to a decrease of biochar yield and increase of porosity, surface area, and adsorption capacities which were further enhanced by steam activation. Carbofuran adsorption was pH-dependant, and the maximum (161 mg g^?1) occurred in the vicinity of pH 5, on steam-activated biochar produced at 700 °C. Freundlich model best fitted the sorption equilibrium data. Both chemisorption and physisorption interactions on heterogeneous adsorbent surface may involve in carbofuran adsorption. Langmuir kinetics could be applied to describe carbofuran adsorption in a fixed bed. A higher carbofuran volume was treated in a column bed by a steam-activated biochar versus non-activated biochars. Overall, steam-activated rice husk biochar can be highlighted as a promising low-cost sustainable material for aqueous carbofuran removal.     

Poor efficacy of herbicides in biochar-amended soils as affected by their chemistry and mode of action

We evaluated wheat straw biochar produced at 450 °C for its ability to influence bioavailability and persistence of two commonly used herbicides (atrazine and trifluralin) with different modes of action (photosynthesis versus root tip mitosis inhibitors) in two contrasting soils. The biochar was added to soils at 0%, 0.5% and 1.0% (w/w) and the herbicides were applied to those soil-biochar mixes at nil, half, full, two times, and four times, the recommended dosage (H₄). Annual ryegrass (Lolium rigidum) was grown in biochar amended soils for 1 month. Biochar had a positive impact on ryegrass survival rate and above-ground biomass at most of the application rates, and particularly at H₄. Within any given biochar treatment, increasing herbicide application decreased the survival rate and fresh weight of above-ground biomass. Biomass production across the biochar treatment gradient significantly differed (p < 0.01) and was more pronounced in the case of atrazine than trifluralin. For example, the dose-response analysis showed that in the presence of 1% biochar in soil, the value of GR₅₀ (i.e. the dose required to reduce weed biomass by 50%) for atrazine increased by 3.5 times, whereas it increased only by a factor of 1.6 in the case of trifluralin. The combination of the chemical properties and the mode of action governed the extent of biochar-induced reduction in bioavailability of herbicides. The greater biomass of ryegrass in the soil containing the highest biochar (despite having the highest herbicide residues) demonstrates decreased bioavailability of the chemicals caused by the wheat straw biochar. This work clearly demonstrates decreased efficacy of herbicides in biochar amended soils. The role played by herbicide chemistry and mode of action will have major implications in choosing the appropriate application rates for biochar amended soils.     

Influence of Al-oxide on pesticide sorption to woody biochars with different surface areas

Biochars’ properties will change after application in soil due to the interactions with soil constituents, which would then impact the performance of biochars as soil amendment. For a better understanding on these interactions, two woody biochars of different surface areas (SA) were physically treated with aluminum oxide (Al-oxide) to investigate its potential influence on biochars’ sorption property. Both the micropore area and mesopore (17～500 Å in diameter) area of the low-SA biochar were enhanced by at least 1.5 times after treatment with Al-oxide, whereas the same treatment did not change the surface characteristics of the high-SA biochar due partly to its well-developed porosity. The enhanced sorption of the pesticide isoproturon to the Al-oxide-treated low-SA biochar was observed and is positively related to the increased mesopore area. The desorption hysteresis of pesticide from the low-SA biochar was strengthened because of more pesticide molecules entrapped in the expanded pores by Al-oxide. However, no obvious change of pesticide sorption to the high-SA biochar after Al-oxide treatment was observed, corresponding to its unchanged porosity. The results suggest that the influence of Al-oxide on the biochars’ sorption property is dependent on their porosity. This study will provide valuable information on the use of biochars for reducing the bioavailability of pesticides.     

Comparison of various advanced oxidation processes for the degradation of phenylurea herbicides

Various types of advanced oxidation processes (AOPs), such as UV photolysis, ozonation, heterogeneous photocatalysis and their combinations were comparatively examined at the same energy input in a home-made reactor. The oxidative transformations of the phenylurea herbicides fenuron, monuron and diuron were investigated. The initial rates of transformation demonstrated that UV photolysis was highly efficient in the cases of diuron and monuron. Ozonation proved to be much more effective in the transformation of fenuron than in those of the chlorine containing monuron and diuron. In heterogeneous photocatalysis, the rate of decomposition decreased with increase of the number of chlorine atoms in the target molecule. Addition of ozone to UV-irradiated solutions and/or TiO₂-containing suspensions markedly increased the initial rates of degradation. Dehalogenation of monuron and diuron showed that each of these procedures is suitable for the simultaneous removal of chlorinated pesticides and their chlorinated intermediates. Heterogeneous photocatalysis was found to be effective in the mineralization.     

Sorption of simazine to corn straw biochars prepared at different pyrolytic temperatures

Simazine sorption to corn straw biochars prepared at various temperatures (100-600 °C) was examined to understand its sorption behavior as influenced by characteristics of biochars. Biochars were characterized via elemental analysis, BET-N₂ surface area (SA), FTIR and ¹³C NMR. Freundlich and dual-mode models described sorption isotherms well. Positive correlation between log K_oc values and aromatic C contents and negative correlation between log K_oc values and (O + N)/C ratios indicate aromatic-rich biochars have high binding affinity to simazine (charge transfer (π-π*) interactions) and hydrophobic binding may overwhelm H-bonding, respectively. Dual-mode model results suggest adsorption contribution to total sorption increases with carbonization degree. Positive correlation between amounts of adsorption (Q_ad) and SA indicates pore-filling mechanism. Comparison between our results and those obtained with other sorbents indicates corn straw biochars produced at higher temperature can effectively retain simazine. These observations will be helpful for designing biochars as engineered sorbents to remove triazine herbicides.     

Effect of wheat and rice straw biochars on pyrazosulfuron-ethyl sorption and persistence in a sandy loam soil

The objective of this research was to investigate the effect of wheat and rice biochars on pyrazosulfuron-ethyl sorption in a sandy loam soil. Pyrazosulfuron-ethyl was poorly sorbed in the soil (3.5–8.6%) but biochar amendment increased the herbicide adsorption, and the effect varied with the nature of the feedstock and pyrolysis temperature. Biochars prepared at 600°C were more effective in adsorbing pyrazosulfuron-ethyl than biochars prepared at 400°C. Rice biochars were better than wheat biochars, and higher herbicide adsorption was attributed to the biochar surface area/porosity. The Freundlich constant 1/n suggested nonlinear isotherms, and nonlinearlity increased with increase in the level of biochar amendment. Desorption results suggested sorption of pyrazosulfuron-ethyl was partially irreversible, and the irreversibility increased with increase in the level of biochar. Both sorption and desorption of pyrazosulfuron-ethyl correlated well with the content of biochars. The free energy change (ΔG) indicated that the pyrazosulfuron-ethyl sorption process was exothermic, spontaneous and physical in nature. Persistence studies indicated that biochar (0.5%) amendment did not have significant effect on herbicide degradation, and its half-life values in the control, 0.5% WBC600- and RBC600-amended rice planted soils were 7, 8.6, and 10.4 days, respectively.     

Monitoring of Triazine and Phenylurea Herbicides in the Surface Waters of Greece

A large-scale study was implemented to monitor triazine and phenylurea herbicides in the main surface water bodies of continental Greece from October 1998 to September 1999. Samples from 10 rivers and 7 lakes were analyzed for the presence of five triazine (atrazine, cyanazine, prometryne, simazine, terbuthylazine) and five phenylurea (chlorotoluron, diuron, linuron, metobromuron, monolinuron) herbicides. The samples were extracted with C18 cartridges and analyzed by high-performance liquid chromatography–diode array detection (HPLC-DAD). The most frequently detected herbicides were atrazine, followed by prometryne, cyanazine, and simazine. The concentrations of the compounds were generally low (< 0.78 μ g/L) and are not considered harmful for the freshwater ecosystem. Most of the positive samples were taken from the water bodies of northern Greece where agricultural activity is more intense.