Remediation of alachlor and atrazine contaminated water with zero-valent iron nanoparticles

Zero-valent iron nanoparticles (nZVI, diameter < 90 nm, specific surface area = 25 m² g^?1) have been used under anoxic conditions for the remediation of pesticides alachlor and atrazine in water. While alachlor (10, 20, 40 mg L^?1) was reduced by 92–96% within 72 h, no degradation of atrazine was observed. The alachlor degradation reaction was found to obey first-order kinetics very closely. The reaction rate (35.5 × 10^?3–43.0 × 10^?3 h^?1) increased with increasing alachlor concentration. The results are in conformity with other researchers who worked on these pesticides but mostly with micro ZVI and iron filings. This is for the first time that alachlor has been degraded under reductive environment using nZVI. The authors contend that nZVI may prove to be a simple method for on-site treatment of high concentration pesticide rinse water (100 mg L^?1) and for use in flooring materials in pesticide filling and storage stations.     

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO₂) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO₂ nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO₂ by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO₂-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO₂?+?monodisperse TiO₂ (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO₂-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO₂-P25. Using NF-TiO₂ layer-by-layer with monodisperse TiO₂ (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10^?3?min^?1 for caffeine, 12.5 and 9.0?×?10^?3?min^?1 for carbamazepine, and 10.9 and 5.8?×?10^?3?min^?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO₂-based films compared to the direct addition of nanoparticles into the sol.     

Herbicide movement and dissipation at four midwestern sites

Abstract

This study was conducted to evaluate atrazine (2‐chloro‐4‐ethylamino‐6‐isopropyl‐1, 3, 5‐triazine) and alachlor (2‐chIoro‐N‐(methoxymethyl)acetamide) dissipation and movement to shallow aquifers across the Northern Sand Plains region of the United States. Sites were located at Minnesota on a Zimmerman fine sand, North Dakota on Hecla sandy loam, South Dakota on a Brandt silty clay loam, and Wisconsin on a Sparta sand. Herbicide concentrations were determined in soil samples taken to 90 cm four times during the growing season and water samples taken from the top one m of aquifer at least once every three months. Herbicides were detected to a depth of 30 cm in Sparta sand and 90 cm in all other soils. Some aquifer samples from each site contained atrazine with the highest concentration in the aquifer beneath the Sparta sand (1.28 μg L^‐1). Alachlor was detected only once in the aquifer at the SD site. The time to 50% atrazine dissipation (DT₅₀) in the top 15 cm of soil averaged about 21 d in Sparta and Zimmerman sands and more than 45 d for Brandt and Hecla soils. Atrazine DT₅₀ was correlated positively with % clay and organic carbon (OC), and negatively with % fine sand. Alachlor DT₅₀ ranged from 12 to 32 d for Zimmerman and Brandt soils, respectively, and was correlated negatively with % clay and OC and positively with % sand.     

Phytotoxicity of atrazine and alachlor in soil amended with sludge,manure and activated carbon

Abstract

Greenhouse studies were conducted to determine the influence of waste‐activated carbon (WAC), digested municipal sewage sludge (DMS), and animal manure on herbicidal activity of atrazine [2‐chloro‐4‐(ethylamino)‐6‐(isopropylamino)‐s‐trazine] and alachlor [2‐chloro‐2’,6'‐diethyl‐N‐(methoxymethyl)acetanilide] in a Plainfield sandy soil. Amendments generally reduced bioactivity against oat (Avena sativa L.) and Japanese millet (E. crus‐galli frumentacea). The extent to which herbicide phytotoxicity was inhibited depended upon the application rate and the kind of soil amendment. WAC, applied at the loading rate of 2.1 mt C/ha, showed a significant inhibitory effect on both herbicides. In DMS‐ and manure‐amended soil, the reduction of atrazine activity was not significant at the rate of 8.4 mt C/ha, but reduction of alachlor activity was significant at the rate of 4.2 mt C/ha. Despite inhibition of herbicidal activity, the ED₅₀ of atrazine and alachlor was below 2 ppm in most of the amendment treatments. Before adopting carbon‐rich waste amendments as management practices for controlling pesticide leaching in coarse‐textured soils, further studies are needed to characterize how alterations in sorption, leaching and degradation may affect herbicidal activity.     

Photolysis of atrazine in aqueous solution: role of process variables and reactive oxygen species

Photochemical advanced oxidation processes have been considered for the treatment of water and wastewater containing the herbicide atrazine (ATZ), a possible human carcinogen and endocrine disruptor. In this study, we investigated the effects of the photon emission rate and initial concentration on ATZ photolysis at 254 nm, an issue not usually detailed in literature. Moreover, the role of reactive oxygen species (ROS) is discussed. Photon emission rates in the range 0.87?×?10¹⁸–3.6?×?10¹⁸ photons L^?1 s^?1 and [ATZ]₀?=?5 and 20 mg L^?1 were used. The results showed more than 65 % of ATZ removal after 30 min. ATZ photolysis followed apparent first-order kinetics with k values and percent removals decreasing with increasing herbicide initial concentration. A fivefold linear increase in specific degradation rate constants with photon emission rate was observed. Also, regardless the presence of persistent degradation products, toxicity was efficiently removed after 60-min exposure to UV radiation. Experiments confirmed a noticeable contribution of singlet oxygen and radical species to atrazine degradation during photolysis. These results may help understand the behavior of atrazine in different UV-driven photochemical degradation treatment processes.     

Degradation kinetics of tebufenozide in model aquatic systems under controlled laboratory conditions

Abstract

The hydrolysis of the insecticide tebufenozide was studied in the dark at 20 to 40°C in buffered (pH 4 to 10) distilled water, and at 20°C in unbuffered, sterilized and unsterilized stream water. Tebufenozide was very stable in acidic and neutral buffers at 20°C and the corresponding pseudo‐first‐order rate constants (k_obsd) and half‐lives (T_1/2) were 5.946 × 10^‐4 and 13.10 × 10^‐4 d^‐1, and 1166 and 529 d, respectively. The hydrolytic degradation was dependent on pH and temperature. At pH 10 and at 20,30 and 40°C, the k_obsd (10^‐4 d^‐1) and T_1/2 (d) values were 34.22, 66.72 and 130.0; and 203, 104 and 53.3, respectively. The energy of activation (E_a) values for the hydrolysis of tebufenozide at pH 4, 7 and 10, calculated from the Arrhenius plots, were 83.50, 66.71 and 50.87 kJ/mol, respectively. Tebufenozide was stable in sterilized stream water in the dark (T_1/2 = 734 d) but it degraded fairly rapidly in unsterilized stream water (T_1/2 = 181 d). Sunlight photodegradation of the chemical was slower (T_1/2 = 83.0 h) than the photolysis by ultraviolet radiations (T_1/2 values at 254 and 365 nm were 9.92 and 27.6 h, respectively); nevertheless, it was still appreciable during the summer months at 46°31’ N latitude. The differences in degradation rates between the unsterilized and sterilized stream water and the degradation of the chemical in the sterile, distilled water in sunlight, suggests that microbial processes and photolysis are the two main degradative routes for tebufenozide in natural aquatic systems.     

Inhibition kinetics of acid and alkaline phosphatases by atrazine and methomyl pesticides

The main objective of this work was to investigate the kinetic characteristics of acid and alkaline phosphatases isolated from different sources and to study the effects of the herbicide atrazine and insecticide methomyl on the activity and kinetic properties of the enzymes. Acid phosphatase (ACP) was isolated from the tomato plant (Solanum lycopersicum L. var. lycopersicum); alkaline phosphatase (ALP) was isolated from two sources, including mature earthworms (Aporrectodea caliginosa) and larvae of the Egyptian cotton leafworm (Spodoptera littoralis). The specific activities of the enzymes were 33.31, 5.56 and 0.72 mmol substrate hydrolyzed per minute per milligram protein for plant ACP, earthworms ALP and cotton leafworm ALP, respectively. The inhibition kinetics indicated that atrazine and methomyl caused competitive–non-competitive inhibition of the enzymes. The relationships between estimates of K_m and V_max calculated from the Michaelis–Menten equation have been explored. The extent of the inhibition was different, as estimated by the values of the inhibition constant K_i that were found to be 3.34 × 10^?3, 1.12 × 10^?2 and 1.07 × 10^?2 mM for plant ACP, earthworms ALP and cotton leafworm ALP, respectively, with methomyl. In the case of atrazine, K_i were found to be 8.99 × 10^?3, 3.55 × 10^?2 and 1.36 × 10^?2 mM for plant ACP, earthworms ALP and cotton leafworm ALP, respectively.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH^? · pH^?1. The sediments were spiked with atrazine at 7.25-36.23 mg kg^?1 (6.21 × 10^?7–3.09 × 10^?6 mol atrazine · g^?1 sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 × 10^?2?7.04 × 10^?2 d^?1 for the atrazine-spiked sediments.     

Persistence of seven pesticides as influenced by soil moisture1

Abstract

Pesticides are often applied in combination, but less‐often is soil persistence measured this way. The present field and laboratory study determined relative persistence of five herbicides and two insecticides, co‐applied, as a function of three soil water contents. Losses were modeled adequately by first‐order dissipation, with no significant improvement by using a two‐compartment model. The order of persistence in a silt loam, at 25% moisture, was carbofuran < cyanazine < metribuzin = alachlor < atrazine < ethoprop < metolachlor (t_½ ranged from 7–91 days). Carbofuran degradation increased greatly from 12–25% soil moisture; atrazine was unaffected by 12–35%, whereas the remaining compounds showed limited increasing loss in wetter soil. Field‐based persistence was more variable, but generally similar to lab rankings.     

Field calibration of surface: A model of agricultural chemicals in surface waters

Abstract

Agricultural chemicals sporadically occur at detectable levels in the surface waters of intensively farmed watersheds. HSPF, a previously released model of agricultural chemicals in surface water, had been used to predict concentrations which were much higher (10 X) than those actually observed during monitoring studies. A new model, SURFACE, is described here which is much simpler than HSPF and gives better predictions of surface water concentrations. SURFACE uses PRZM, an EPA model, to calculate edge‐of‐field runoff losses and simple hydraulic routing algorithms to determine concentrations at the bottom of large river basins. In water systems sampled during 1985 and 1986, SURFACE predictions of annualized mean concentrations for alachlor, atrazine, cyanazine and metolachlor were within 0.09 ppb half of the time.     

Runoff and leaching of atrazine and alachlor on a sandy soil as affected by application in sprinkler irrigation

Abstract

Rainfall simulation was used with small packed boxes of soil to compare runoff of herbicides applied by conventional spray and injection into sprinkler‐irrigation (chemigation), under severe rainfall conditions. It was hypothesized that the larger water volumes used in chemigation would leach some of the chemicals out of the soil surface rainfall interaction zone, and thus reduce the amounts of herbicides available for runoff. A 47‐mm rain falling in a 2‐hour event 24 hours after application of alachlor (2‐chloro‐N‐(2,6‐diethylphenyl)‐N‐(methoxymethyl)‐acetamide) and atrazine (6‐chloro‐N‐ethyl‐N‐(1‐methylethyl)‐1,3,5‐triazine‐2,4‐diamine) was simulated. The design of the boxes allowed a measurement of pesticide concentrations in splash water throughout the rainfall event. Initial atrazine concentrations exceeding its’ solubility were observed. When the herbicides were applied in 64000 L/ha of water (simulating chemigation in 6.4 mm irrigation water) to the surface of a Tifton loamy sand, subsequent herbicide losses in runoff water were decreased by 90% for atrazine and 91% for alachlor, as compared to losses from applications in typical carrier water volumes of 187 L/ha. However, this difference was not due to an herbicide leaching effect but to a 96% decrease in the amount of runoff from the chemigated plots. Only 0.3 mm of runoff occurred from the chemigated boxes while 7.4 mm runoff occurred from the conventionally‐treated boxes, even though antecedent moisture was higher in the former. Two possible explanations for this unexpected result are (a) increased aggregate stability in the more moist condition, leading to less surface sealing during subsequent rainfall, or (b) a hydrophobic effect in the drier boxes. In the majority of these pans herbicide loss was much less in runoff than in leachate water. Thus, in this soil, application of these herbicides by chemigation would decrease their potential for pollution only in situations where runoff is a greater potential threat than leaching.     

Speciation and persistence of doxycycline in the aquatic environment: Characterization in terms of steady state kinetics

The aim of the present work was to establish the kinetics for the degradation of doxycycline in the aquatic environment with a view to arriving at a kinetic model that can be used to predict the persistence of antibiotic with confidence. The degradation of doxycycline in both water and sediment phases of aquatic microcosm experiments, as well as in distilled water control experiments, was studied over a period of 90 days. An initial 21% loss due to adsorption by the sediment was observed in the microcosm experiment soon after charging. Biphasic zero-order linear rates of degradation, attributed to microbial degradation of the free and sediment or colloidal particle-adsorbed antibiotic, were observed for both water phase (2.3 × 10^?2 and 4.5 × 10^?3 μgg^?1 day^?1) and sediment phase (7.9 × 10^?3 and 1.5 × 10^?3 μgg^?1 day^?1) of the microcosm experiment. The covered distilled water control experiment exhibited a monophasic zero-order linear rate (1.9 × 10^?3 μgg^?1 day^?1) attributed to hydrolysis, while the distilled water experiment exposed to natural light exhibited biphasic liner rates attributed to a combination of hydrolysis and photolysis (2.9 × 10^?3 μgg^?1 day^?1) and to microbial degradation (9.8 × 10^?3 μgg^?1 day^?1). A kinetic model that takes into account hydrolysis, photolysis, microbial degradation as well as sorption/desorption by colloidal and sediment particles is presented to account for the observed zero-order kinetics. The implications of the observed kinetics on the persistence of doxycycline in the aquatic environment are discussed.     

Effect of ozonation on the biodegradability of atrazine in GAC columns

Abstract

The biodegradation of atrazine as influenced by preozonation was studied in biological GAC columns. Metabolism of isopropyl‐¹⁴C atrazine produced more ¹⁴CO₂ than ring‐UL‐¹⁴C atrazine, indicating dealkylation was more rapid than ring cleavage. Preozonation increased mineralization of ring‐UL‐¹⁴C atrazine and, consequently, enhanced the performance of the GAC columns. Sixty‐two percent of the influent atrazine was converted to ¹⁴CO₂ in columns that received ozonated atrazine and ozonated surface water, while 50% of the influent atrazine was converted to ¹⁴CO₂ in columns that received untreated atrazine and ozonated surface water, and only 38% of the influent atrazine was converted to ¹⁴CO₂ in columns with untreated influent.     

声电协同氧化氯酚的实验研究

采用超声波-电催化联合技术处理2-氯酚(2-CP)和4-氯酚(4-CP),探讨了电催化氧化和超声氧化的协同效应,考察了影响声电联合降解氯酚化合物的条件因数.结果表明,超声波-电催化联合技术处理效率明显优于电催化氧化技术,2-CP和4-CP的增强因子f分别为1.325和1.509.高电流密度有助于氯酚降解,2-CP和4-CP的表观反应速率常数随电流密度上升分别增加了1.28×10-5 s-1和1.82×10-5 s-1;高pH值也有利于氯酚降解,pH为9.08时,2-CP和4-CP的表观反应速率常数分别为9.22×10-5 s-1和11.02×10-5 s-1;高电解质浓度促进了2-CP的降解,而对4-CP的降解影响不大,2-CP表观反应速率常数从7.70×10-5 s-1上升到16.03×10-5 s-1.总之,超声波-电催化联合技术能够协同降解氯酚.     

Bioremediation model for atrazine contaminated agricultural soils using phytoremediation (using Phaseolus vulgaris L.) and a locally adapted microbial consortium

The objective of the present study was to examine a biological model under greenhouse conditions for the bioremediation of atrazine contaminated soils. The model consisted in a combination of phytoremediation (using Phaseolus vulgaris L.) and rhizopheric bio-augmentation using native Trichoderma sp., and Rhizobium sp. microorganisms that showed no inhibitory growth at 10,000 mg L^?1 of herbicide concentration. 33.3 mg of atrazine 50 g^?1 of soil of initial concentration was used and an initial inoculation of 1 × 10⁹ UFC mL^?1 of Rhizobium sp. and 1 × 10⁵ conidia mL^?1 of Trichoderma sp. were set. Four treatments were arranged: Bean + Trichoderma sp. (B+T); Bean + Rhizobium sp. (BR); Bean + Rhizobium sp. + Trichoderma sp. (B+R+T) and Bean (B). 25.51 mg of atrazine 50 g^?1 of soil (76.63%) was removed by the B+T treatment in 40 days (a = 0.050, Tukey). This last indicate that the proposed biological model and methodology developed is useful for atrazine contaminated bioremediation agricultural soils, which can contribute to reduce the effects of agrochemical abuse.     

Behavior of atrazine in soils of tropical zone

Abstract

Movement and degradation of ¹⁴C‐atrazine (2‐chloro 4‐(ethylamino)‐6‐(isopropylamino)‐s‐triazine, was studied in undisturbed soil columns (0.50m length × 0.10m diameter) of Gley Humic and Deep Red Latosol from a maize crop region of Sao Paulo state, Brazil. Atrazine residues were largely confined to the 0–20cm layers over a 12 month period Atrazine degraded to the dealkylated metabolites deisopropylatrazine and deethylatrazine, but the major metabolite was hydroxyatrazine, mainly in the Gley Humic soil. Activity detected in the leachate was equivalent to an atrazine concentration of 0.08 to 0.11μg/1.

The persistence of ¹⁴C‐atrazine in a maize‐bean crop rotation was evaluated in lysimeters, using Gley Humic and Deep Red Latosol soils. Uptake of the radiocarbon by maize plants after 14‐days growth was equivalent to a herbicide concentration of 3.9μg/g fresh tissue and was similar in both soils. High atrazine degradation to hydroxyatrazine was detected by tic of maize extracts. After maize harvest, when beans were sown the Gley Humic soil contained an atrazine concentration of 0.29 μg/g soil and the Deep Red Latosol, 0.13 μg/g soil in the 0–30 cm layer. Activity detected in bean plants corresponded to a herbicide concentration of 0.26 (Gley Humic soil) and 0.32μg/g fresh tissue (Deep Red Latossol) after 14 days growth and 0.43 (Gley Humic soil) and 0.50 μg/g fresh tissue (Deep Red Latossol) after 97 days growth. Traces of activity equivalent to 0.06 and 0.02μg/g fresh tissue were detected in bean seeds at harvest. Non‐extractable (bound) residues in the soils at 235 days accounted for 66.6 to 75% (Gley Humic soil and Deep Red Latossol) of the total residual activity.     

Size-segregated particulate matter and its association with respiratory deposition doses among outdoor exercisers in Dhanbad City,India

Regular exercise improves physiological processes and yields positive health outcomes. However, it is relatively less known that particulate matter (PM) exposure during outdoor exercises may increase several respiratory health problems depending on PM levels. In this study, the respiratory deposition doses (RDDs) in head airway (HD), tracheobronchial (TB), and alveolar (AL) regions of various PM size fractions (<10, <2.5, and <1 μm; PM₁₀, PM_2.5, and PM₁) were estimated in healthy male and female exercisers in urban outdoors and within house premises. The highest RDDs were found for PM during morning hours in winter compared with remaining periods. RDDs in AL region for males and females, respectively, were 34.7 × 10^?2 and 28.8 × 10^?2 µg min^?1 for PM₁₀, 65.7 × 10^?2 and 56.9 × 10^?2 µg min^?1 for PM_2.5, and 76.5 × 10^?2 and 66.3 × 10^?2 µg min^?1 for PM₁. The RDD values in AL region were significantly higher in PM₁ (27%) compared with PM_2.5 (13%) and PM₁₀ (2%) during exercise in all periods. This result showed that the morning peak hours in winter are more harmful to urban outdoor exercisers compared with other periods. This study also showed that the AL region would have been the main affected zone through fine particle (PM₁) to all the exercisers.

Implications: Size-segregated particle concentrations in urban outdoors and within house premises were measured. The highest respiratory deposition doses (RDDs) were found for PM during morning hours in winter compared with remaining periods. During light exercise, the RDD values in alveolar (AL) region for PM₁₀, PM_2.5, and PM₁ for male exercisers were significantly higher, 20.4%, 15.5%, and 15.4%, respectively, compared with female exercisers during morning peak hours in winter.     

Toxicity of atrazine and its bioaccumulation and biodegradation in a green microalga,Chlamydomonas mexicana

This study evaluated the toxicity of herbicide atrazine, along with its bioaccumulation and biodegradation in the green microalga Chlamydomonas mexicana. At low concentration (10 μg L^?1), atrazine had no profound effect on the microalga, while higher concentrations (25, 50, and 100 μg L^?1) imposed toxicity, leading to inhibition of cell growth and chlorophyll a accumulation by 22 %, 33 %, and 36 %, and 13 %, 24 %, and 27 %, respectively. Atrazine 96-h EC50 for C. mexicana was estimated to be 33 μg L^?1. Microalga showed a capability to accumulate atrazine in the cell and to biodegrade the cell-accumulated atrazine resulting in 14–36 % atrazine degradation at 10–100 μg L^?1. Increasing atrazine concentration decreased the total fatty acids (from 102 to 75 mg g^?1) and increased the unsaturated fatty acid content in the microalga. Carbohydrate content increased gradually with the increase in atrazine concentration up to 15 %. This study shows that C. mexicana has the capability to degrade atrazine and can be employed for the remediation of atrazine-contaminated streams.     

Observation de la fluorescence sur feuille entiere et mise en evidence de la resistance chloroplastique a l'atrazine chez Chenopodium album L. et Poa annua L.

Within two plant species, Chenopodium album L. generally susceptible to atrazine, and Poa annua L. always reported as susceptible, atrazine tolerant populations were observed.This resistance is due to lower atrazine susceptibility of chloroplastic electron transfert. Oxygen evolution in isolated chloroplasts was mesured to determine the concentrations required for 50 % inhibition. They are similar in the two species for the susceptible and the tolerant chloroplasts 2 × 10^?7 M and 10^?4 M respectively.Differential chlorophyll fluorescence observed on whole leaf was used as a simple mean for detection of chloroplastic resistance.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at λ = 254 nm. The photolysis of (α + β: 2 + 1) endosulfan, α-endosulfan and β-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 × 10^?4 s^?1; 1 × 10^?4 s^?1; and 2 × 10^?5 s^?1, respectively, and the calculated quantum yields (φ) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.