Sorption Kinetics of Atrazine and Diuron in Soils from Southern Brazil

Abstract

Sorption kinetics of atrazine and diuron was evaluated in soil samples from a typical landscape in Paraná. Samples were collected (0–20 cm) in a no-tillage area from Mamborê, PR, which has been cultivated under a crop rotation for the last six years. Six sampling points of the slope were selected to represent a wide range of soil chemical and physical properties found in this area. Radiolabeled tracers (¹⁴C-atrazine and ¹⁴C-diuron) were used and the radioactivity was detected by liquid scintillation counting (LSC). Sorption was accomplished for increasing equilibration periods (0.5, 1.5, 3, 6, 12, 24, and 48 h). Kinetics data fitted adequately well to Elovich equation, providing evidences that soil reaction occurs in two distinct stages: a fast, initial one followed by a slower one. During the fast phase, 34–42 and 71–79% of total atrazine and diuron applied were sorbed to soil samples. No important differences were found among combinations of soil and herbicide sorption during the slow phase. The unrealistic conditions under batch experiments should be overestimating sorption in the fast phase and underestimating diffusion in the slow phase. Sorption of both herbicides was positively correlated to organic carbon and clay contents of soils, but atrazine was much less sorbed than diuron, showing its higher potential to contaminate groundwater, specially in sandy, low organic carbon soils.     

Atrazine sorption and fate in a Ultisol from humid tropical Brazil

This study combined laboratory based microcosm systems as well as field experiments to evaluate the mobility of atrazine on a Ultisol under humid tropical conditions in Brazil. Results from sorption experiments fit to the Freundlich isotherm model [K(f) 0.99 mg kg(-1)/(mg l(-1))(1/n)], and indicate a low sorption capacity for atrazine in this soil and consequently large potential for movement by leaching and runoff. Microcosm systems using (14)C-atrazine to trace the fate of the applied herbicide, showed that 0.33% of the atrazine was volatilized, 0.25% mineralized and 6.89% was recorded in the leachate. After 60 d in the microcosms, 75% of the (14)C remained in the upper 5 cm soil layer indicating atrazine or its metabolites remained close to the soil surface. In field experiments, after 60 d, only 5% of the atrazine applied was recovered in the upper soil layers. In the field experiments atrazine was detected at a depth of 50 cm indicating leaching. Simulating tropical rain in field experiments resulted in 2.1% loss of atrazine in runoff of which 0.5% was adsorbed onto transported soil particles and 1.6% was in solution. Atrazine runoff was greatest two days after herbicide application and decreased 10 fold after 15 d. The use of atrazine on Ultisols, in the humid tropics, constitutes a threat to water quality, causing surface water and ground water pollution.     

Herbicide Leaching on a Recharge Area of the Guarany Aquifer in Brazil

Abstract

The region of Ribeirão Preto City, located in Southeast of Brazil, São Paulo State, is an important sugarcane, soybean, and corn producing area with a high level of pesticides utilization. This region is also an important recharge area for groundwater supply of the Guarany aquifer. Since the past ten years atrazine, simazine, ametryn, tebuthiuron, diuron, 2,4-D, picloram, and hexazinone are the main herbicides used in this area. In order to study a possible leaching of some of these herbicides into the aquifer, surface, and groundwater samples were collected in a watershed during the years of 1996 to 2003, from different locations. To detect and quantify the herbicides a GC-MS (gas chromatograph/mass spectrometry) method was used. The response of the herbicides analyzed was linear over the concentration range of 0.02 to 2.0 μg/L. Analysis of groundwater revealed that the herbicides tebuthiuron, diuron, atrazine, simazine, and ametryn were not present in the samples. In the surface water collected in 1997, ametryn was present in two out of nine locations with concentrations ranging from 0.17 and 0.23 μg/L, which is above the allowable 0.1 μg/L according to the European safety level. The leaching potential of tebuthiuron, diuron, atrazine, simazine, 2,4-D, picloram, and hexazinone has been evaluated using CMLS-94, “Chemical Movement in Layered Soil,” as simulation model. No leaching into the depth of the water table at 40 m was found.     

从竣工环境保护验收调查分析公路噪声环评的有效性

从所选的40条公路的竣工环境保护验收报告入手,对公路建成后与环境影响评价阶段噪声敏感点的数量变化、噪声实测值与环评预测值的差异、实际的噪声防治措施与环评确定措施的差异进行了对比分析.结果表明,以上3个方面在公路建成后与环评阶段均存在较大变化,公路噪声环境影响评价的有效性亟待提高.造成这一状况的主要原因包括项目投资机制、运营期相关条件变化等.通过分析,提出了实现全过程的环境影响评价与管理、提高预测的准确性及增强防噪措施的可操作性等促进环评有效性的相关对策建议.     

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.     

Pesticide exposure and health conditions among orange growers in Southern Brazil

This study aimed to evaluate the exposure to pesticides through the biomarkers analysis, as well as life habits and use of Personal Protective Equipment (PPE) in a group of farmers who grow citrus in the Vale do Caí region, in Rio Grande do Sul, southern Brazil. The study population consisted of 73 volunteer farmers, 45 males and 28 females, aged between 13 and 69 years old. The control group consisted of 30 individuals who were not exposed to pesticides. Measures of urea, creatinine, aspartate aminotransferase (AST), alanine aminotransferase (ALT), gamma-glutamyltransferase (GGT), plasma cholinesterase (BChE) activity, and hematological parameters were analyzed. The study population also answered a structured questionnaire on life habits and health. The results showed that BChE activity was significantly lower in the exposed group than in the control group. AST, ALT, and creatinine were increased in the group of women exposed to pesticides when compared to the control group. GGT, urea, and hematological parameters did not show statistical differences for both male and female group. The most prevalent symptom reported by farmers after exposure to pesticides was headache. Furthermore, it was verified that the use of complete PPE is only made by 38% of the studied population.     

提高环评报告书质量加快浙江省环境影响评价有效性建设

影响环境影响评价(EIA)有效性的因素较多．如相应的政策法规、管理机制和技术的正确性等。文章从环评技术角度出发,以抽样选取的浙江省1997～2001年间完成的100本环评报告书(EIS)为统计对象．按建设项目环保审批6项原则为依据,从产业政策符合性、选址与总图布局合理性、清洁生产、达标排放、总量控制、区域环境质量可达性等方面进行分析．评估了浙江省EIA有效性,探讨了目前EIA中存在的问题及原冈,提出了一些提高EIS质量、加快浙江省EIA有效性建设的建议     

Bioavailability of diuron,imazapic and isoxaflutole in soils of contrasting textures

This research was aimed at understanding the dynamics of the herbicides diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea], imazapic [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methylnicotinic acid] and isoxaflutole [5-cyclopropyl-4-(2-methanesulfonyl-4-trifluoromethyl benzoyl)isoxazole] in two soils of different physico-chemical properties. To accomplish such intent, several greenhouse experiments were run. The bioavailability of diuron (0; 1.6 and 3.2 kg ha^{? 1}), imazapic (0; 98 and 122.5 g ha^{? 1}) and isoxaflutole (0; 35 and 70 g ha^{? 1}) was measured in samples from a sandy loam soil and a clay soil, by sowing a bioindicator (Brachiaria decumbens), at 0, 25, 50, 75 and 100 days after herbicides application (DAA). Diuron was very stable in clay soil, providing control equal to or higher than 92% of bioindicator, up to 100 DAA, as assumed by biomass accumulation. No differential effect was observed in sandy loam soil, even when 2x labeled rate were applied. Imazapic provided a short bioavailability in relation to B. decumbens, independent of rates applied. The persistence of isoxaflutole was longer in clay soil (28 to 30 days).     

景观影响评价中"景观"的内涵和应用探讨

针对目前不同学科对于景观概念存在多种不同的解释,文章对环境影响评价中所基于的景观概念的内涵进行了探讨,指出了景观科学具有边缘性和开放性的特点。并根据目前中国景观影响评价的实际情况,提出了一些建议。     

Baseline levels of PCDD/Fs in soil and herbage samples collected in the vicinity of a new hazardous waste incinerator in Catalonia,Spain

The construction in Constantí (Catalonia, Spain) of a new hazardous waste incinerator (HWI), which is the first one in Spain, finished in 1999. In order to determine the temporal variation (1996–1998) in the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the vicinity of the new HWI, 40 soil and 40 herbage samples were collected (1998) at the same sampling points in which samples had been taken two years before (1996). Each sample was analyzed for PCDDs and PCDFs by high resolution gas chromatography/high resolution mass spectrometry. In the 1996 survey, PCDD/F concentrations in soils ranged from 0.13 to 24.20 ng I-TEQ/kg (d.m.), with median and mean values of 0.67 and 1.68 ng I-TEQ/kg (d.m.), respectively. In the present study, PCDD/F concentrations ranged from 0.12 to 17.20 ng I-TEQ/kg (d.m.), with a median value of 0.75 ng I-TEQ/kg (d.m.) and a mean value of 1.59 ng I-TEQ/kg (d.m.). In turn, in the present study PCDD/F concentrations in vegetation ranged from 0.14 to 2.01 ng I-TEQ/kg (d.m.) (median and mean values: 0.23 and 0.31 ng I-TEQ/kg, respectively), while in the 1996 survey PCDD/F concentrations ranged from 0.24 to 1.22 ng I-TEQ/kg (d.m.) (median and mean values: 0.53 and 0.61 ng I-TEQ/kg, respectively). According to the present (1998) and the previous (1996) levels of PCDD/Fs found in soils and vegetation, the area under potential influence of the new facility shows a rather low contamination by these compounds. The current results should be useful to establish the environmental impact of the HWI.     

Assessment of metolachlor and diuron leaching in a tropical soil using undisturbed soil columns under laboratory conditions

In the present study, diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-metoxi-1-methylethyl)acetamide] leaching was studied in undisturbed soil columns collected in a cotton crop area in Mato Grosso State, Brazil. The pesticides were applied to the soil surface in dosages similar to those used in a cotton plantation. To assess the leaching process, soil columns were submitted to simulated rain under laboratory conditions at 25 ± 3°C, in the absence of wind and direct solar radiation. During the rain simulations, leachate solutions were collected and herbicide concentrations were determined. At the end of the experiment, the soil columns were cut into 10 cm sections to determine the remaining herbicide concentrations through the soil profile. Metolachlor was detected in all soil sections, and approximately 4% of the applied mass was leached. Diuron was detected only in the upper two soil sections and was not detected in the leachate. A linear correlation (r > 0.94) between the metolachlor soil concentrations and the organic contents of the soil sections was observed. Mass balance suggests that around 56% of diuron and 40% of metolachlor were degraded during the experiments. Measurements of the water table depth in the area where the samples were collected showed that it varied from 2 to 6 m and is therefore vulnerable to contamination by the studied herbicides, particularly metolachlor, which demonstrated a higher leaching potential.     

The war on deciduous forest: Large-scale herbicide treatment in the Swedish boreal forest 1948 to 1984

At the mid-twentieth century the pace of the transformation of the Swedish forest increased. New methods; large-scale clearcutting, mechanization of logging and planting of seedlings were developed. Chemicals were used to control insects and unwanted tree species. The aims of this study were to elucidate the timing, chain of events and the spatial extent of the large-scale spraying of phenoxy acids in Swedish forests and the drivers for this practice. More than 700 000 hectares of productive forest land was sprayed and the main driving force was a strong will to transform the forest into high-yield coniferous forest plantations. We conclude that; (1) the use of herbicides in forestry in Sweden was done on a very large scale in the period 1948–1984, (2) the ecosystem legacy of herbicide spraying must be investigated and (3) a homogenous cadre of like-minded professionals working across commercial companies, state agencies and universities is dangerous.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-021-01660-5.     

Photodegradation of the antifouling compounds Irgarol 1051 and Diuron released from a commercial antifouling paint

The antifouling compound Irgarol 1051 and its degradation product M1 (also known as GS26575), along with another antifouling compound Diuron, have recently been found in Japanese coastal waters. This study was undertaken to find the origin of these chemicals and investigate their aquatic fate. Five glass plates, each coated with 1 g of antifouling paint containing Irgarol and Diuron, were submerged in 250 ml of five different test waters and the plates removed after several months. The aqueous solutions were divided into two groups: one exposed to natural sunlight, and the other kept in the dark as a control. Irgarol and Diuron were detected in all aqueous solutions, suggesting leaching from antifouling paints is the origin of these antifouling biocides found in Japanese coastal waters. Under sunlight conditions, Irgarol underwent a rapid degradation to produce M1, which remained even after Irgarol had disappeared from the system. These compounds were persistent in any aqueous solutions tested under dark conditions, indicating high stability to hydrolysis. Diuron and M1 were more persistent than Irgarol under sunlight irradiation. Since these compounds have high herbicidal activities, their ultimate impact on aquatic ecosystems is closely related to their aquatic fate.     

Environmental impact of flood: the study of arsenic speciation in exchangeable fraction of flood deposits of Warta river (Poland) in determination of "finger prints" of the pollutants origin and the ways of the migration

The paper presents the application of the hyphenated technique - high-performance liquid chromatography with atomic absorption spectrometry detection with hydride generation (HPLC-HG-AAS) - in the determinations of inorganic forms of arsenic: As(III) and As(V) in the exchangeable fraction of flood deposits. The separation of analytical signals of the determined arsenic forms was obtained using an ion-exchange column in a chromatographic system with the atomic absorption spectrometer as a detector, at the determination limits of 5 ng g⁻¹ for As(III) and 10 ng g⁻¹ for As(V). Flood deposits were collected after big flood event in valley of the Warta river which took place in summer 2010. Samples of overbank deposits were taken in Poznań agglomeration and vicinity (NW Poland). The results of determinations of arsenic forms in the exchangeable fraction of flood deposits allowed indication of a hypothetical path of deposits migration transported by a river during flood and environmental threats posed by their deposition by flood.     

汽车制造项目环境影响评价技术要点分析

本文在实际开展汽车制造项目环境影响评价的基础上,对汽车制造项目生产工艺及产污环节进行梳理,重点对废气、废水、固废、噪声源强核算过程和方法进行解析,对污染防治措施论证内容进行探讨,同时从清洁生产水平分析、政策相符性分析等方面的技术要点进行总结整理,梳理了目前汽车制造项目环评文件编制的要点核心,指出汽车整车制造项目环境影响评价中应关注的重点问题,主要在于挥发性有机废气源强和含氮、磷及重金属废水源强核算、物料平衡等,为下阶段汽车制造项目建设和环境管理提供参考。     

大气污染物等浓度曲线画法初探

介绍一种环境影响评价中大气污染物等浓度曲线的画法,可用于绘制任意接近的等浓度曲线而不会相交或相切,运算量较小且与图形大小无关。     

Degradation of Metribuzin in Two Soil Types of Lebanon

The degradation of metribuzin [4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one] as influenced by soil type, temperature, humidity, organic fertilizers, soil sterilization, and ultra-violet radiation was studied in two soil types of Lebanon under laboratory conditions. The two soil types were sandy loam and clay. Deamination of metribuzin in the sandy loam soil to its deaminometribuzin (DA) derivative was basically a result of biological activity. In the clay soil the first metabolite diketometribuzin (DK) was a result of oxidative desulfuration, while diketo-deaminometribuzin (DADK) was the product of reductive deamination. The two soils represented major differences in the pesticide transformation processes. Photodecomposition on the soil surface and in aqueous media was also an important process in the degradation of metribuzin. Furthermore, the increase in soil organic matter enhanced degradation.     

Contributions of Pesticide use to Urban Background Concentrations of Arsenic in Denver,Colorado, U.S.A.

Soil investigations near a former smelter have revealed that historic use of arsenical pesticides has contributed significantly to anthropogenic background concentrations of arsenic on certain residential properties in Denver, Colorado, U.S.A. Remedial investigation data, based on samples collected in relatively undisturbed locations, had previously indicated that the "upper limit" of background arsenic concentrations was 28 mg/kg in the site vicinity. This value compares reasonably well with more regional data, which indicate increasing arsenic concentrations moving from rural to urban land use. Soil sampling during cleanup, however, revealed the presence of arsenic concentrations of a few hundred to more than 1000 mg/kg on a large number of residential lawns due to historic applications of a crabgrass killer, which was missed by the earlier investigation samples because of the sampling bias toward undisturbed land. Data from over 20,000 soil samples now show that several different populations comprise urban background levels of arsenic and that these populations may be stratified by land use and have spatial patterns that should be considered during any background study. A variety of forensic techniques, including spatial analysis, arsenic speciation, and calculation of metals ratios were necessary to separate the smelter impacts from pesticide impacts.     

Effect of sewage amendment on the dissipation of terbuthylazine,its degradation compound desethyl-terbuthylazine,and S-metolachlor in a field study

This study evaluates the effect of sewage amendment (SA) on the dissipation of terbuthylazine, its degradation compound desethyl-terbuthylazine, and S-metolachlor in the soil. The experiment was conducted at Padua Experimental Farm (Italy). Herbicides dissipation was evaluated in soils differently fertilized for three years: with inorganic fertilizer, with sewage sludge, and with a combination of them. Terbuthylazine and S-metolachlor were applied on sorghum as a formulated product at a dose of 2.8?L ha^?1, and their dissipation was followed for 2.5 months. The concentrations of herbicides and one metabolite in soil were analyzed by liquid chromatography-mass spectrometry. The dissipation of terbuthylazine and S-metolachlor followed a pseudo first order kinetics; they dissipated faster in soil amended only with inorganic fertilizer than in soils amended with sewage or sewage?+?inorganic fertilizer. The reduction in mineralization of the herbicides after sewage addition can be attributed to the reduced herbicide availability to microorganisms. The degradation of terbuthylazine led to the formation of desethyl-terbuthylazine. SA slowed down the formation and the degradation of desethyl-terbuthylazine, leading to a higher amount measured at the end of the incubation. These findings have practical implications for the assessment of the environmental fate of terbuthylazine and S-metolachlor in agricultural areas.     

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-N2-ethyl-N4-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 (R2 >or= 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.