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.     

Evaluation of groundwater contamination in a coastal area of south-eastern Sicily

This investigation was under taken to evaluate the groundwater resources contamination due to intensive agricultural practices (particularly greenhouses). The study-area is located in the coastal area of the Ragusa province (South-East Sicily), where numerous existing greenhouses may cause the contamination of groundwater systems (unconfined and confined aquifers) beneath the cropped land. The pollution risk is mainly related with the seepage process of macro-elements nitrogen (N), phosphorus (P), potassium (K), held in the irrigation water and the massive use of fertilizers and pesticides, that may pass through the unsaturated zone of the soil profile. Moreover, the area is characterized by the presence of several wells (about 15 wells/km2) for agricultural use that cause the aquifer overexploitation and the consequent risk of seawater intrusion. The agriculture practices adopted in the study area (irrigation volumes, fertilizer concentrations, use of pesticides…) were monitored since February 2009; moreover, the pollution risk of the aquifers was evaluated through the analysis of groundwater water samples collected (monthly) in the monitoring wells; in particular, nitrogen compounds, soluble phosphorous (PO?2?), potassium, as well as the main pesticides commonly used in the study area, were measured.The results show that electrical conductivity and chloride concentration values can cause reduction of production and leaf damage problems, respectively, for most of the monitored farm systems. The high nitrogen compounds concentrations observed in the monitored wells can cause health and environmental problems. Moreover high pesticide contamination of groundwater was found in two of the five monitored wells.     

Pesticide contamination of ground water in the United States--a review

Over 70 pesticides have been detected in ground water. Aldicarb and atrazine along with the soil fumigants EDB and DCP and DBCP have been the pesticides most frequently detected in ground water. Atrazine concentrations have been correlated with high nitrate concentrations. The triazine herbicides, simazine and cyanazine, have also been detected in ground water. The annual amount of recharge, soil type, depth of aquifer from the surface, nitrate contamination and soil pH are important field parameters in determining ground-water contamination potential by pesticides. Pesticide leaching is reduced by proper choice of crop rotation, increasing pesticide application efficiency, and integrated pest management.     

Seasonal exposures to triazine and other pesticides in surface waters in the western Highveld corn-production region in South Africa

The objective of this study was to characterize concentrations of atrazine, terbuthylazine, and other pesticides in amphibian habitats in surface waters of a corn-production area of the western Highveld region (North-West Province) of South Africa. The study was conducted from November 2001 to June 2002, coinciding with the corn-production season. Pesticide residues were measured at regular intervals in surface water from eight ponds, three in a non-corn-growing area (NCGA) and five within the corn-growing area (CGA). Measured atrazine concentrations differed significantly among sites and between samples. In the five CGA sites, the maximum atrazine concentrations measured during the study ranged from 1.2 to 9.3 microg/L. Although no atrazine was recorded as being applied in the catchment of the three NCGA sites, maximum concentrations from 0.39 to 0.84 microg/L were measured during the study, possibly as a result of atmospheric transport. Maximum measured concentrations of terbuthylazine ranged from 1.22 to 2.1 microg/L in the NCGA sites and from 1.04 to 4.1 microg/L in the CGA sites. The source of terbuthylazine in the NCGA sites may have been in use other than in corn. The triazine degradation products, deisopropylatrazine (DIA) and deethylatrazine (DEA) and diaminochlorotriazine (DACT) were also found in water from both the CGA and NCGA sites. Concentrations of DIA were > or = 1 microg/L throughout the season, while DEA concentrations were mostly <0.5 microg/L before planting but increased after planting and application of herbicides to concentrations >2 microg/L in some locations. Concentrations of DACT were highly variable (LOD to 8 microg/L) both before and after planting and application, suggesting that they resulted from historical use of triazines in the area. Other herbicides such as simazine and acetochlor were only detected infrequently and pesticides such as S-metolachlor, cypermethrin, monocrotophos, and terbuphos, known to be used in the CGA, were not detected in any of the samples. Because of dilution by higher than normal rainfall in the study period, these concentrations may not be predictive of those in years of normal rainfall.     

Herbicide leaching on a recharge area of the Guarany aquifer in Brazil

The region of Ribeir?o Preto City, located in Southeast of Brazil, S?o 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 microg/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 microg/L, which is above the allowable 0.1 microg/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.     

Exposure assessment of pesticides in a shallow groundwater of the Tagus vulnerable zone (Portugal): a multivariate statistical approach (JCA)

Purpose

To assess groundwater exposure to pesticides, in agricultural areas of ??Ribatejo?? region (Portugal), and the influence of some key factors in that exposure, field, laboratory and modelling studies were carried out.

Methods

The study was performed in maize, potato, sugar beet, tomato and vegetables agricultural areas, located in a shallow aquifer, with pesticides use and, in most cases, with irrigation practices. Pesticides used in the studied agricultural areas and having leaching potential were selected, being considered also other pesticides included in priority lists, defined in Europe. Evaluation of groundwater exposure to pesticides was carried out by successively: (1) groundwater sampling in seven campaigns over the period 2004?C2006; (2) pesticide analysis [including isolation and concentration from the groundwater samples and further determination by gas chromatography?Cmass spectrometry (GC?CMS) of 14 herbicides, four insecticides and two metabolites]; and (3) analysis and discussion of the results by applying joint correspondence analysis (JCA).

Results

From the 20 pesticides and metabolites selected for the study, 11 were found in groundwater. Pesticides and metabolites most frequently detected were atrazine, alachlor, metolachlor, desethylatrazine, ethofumesate, ??-endosulfan, metribuzine, lindane and ??-endosulfan. The results showed that groundwater exposure to pesticides is influenced by local factors??either environmental or agricultural, as precipitation, soil, geology, crops and irrigation practices. Spring and autumn were more associated with the detection of pesticides being more likely to observe mixtures of these compounds in a groundwater sample in these transition seasons.

Conclusions

This work evidences the importance of models, which evaluate pesticides environmental behaviour, namely their water contamination potential (as Mackay multicompartimental fugacity model) and, specially, groundwater contamination potential (as GUS and Bacci and Gaggi leaching indices), in pesticide selection. Moreover, it reveals the importance to adapt proper statistical methods according to level of left-censored data. Using JCA was still possible to establish relations between pesticides and their temporal trend in a case study where there were more than 80% of data censored. This study will contribute to the Tagus river basin management plan with information on the patterns of pesticide occurrence in the alluvial aquifer system.     

A modelling approach to determine the origin of urban ground water

A simple modelling approach was developed to link patterns of urban land-use with ground water flow and chemistry in three dimensions and was applied to characterize the origin of recharge in the aquifer beneath the old industrial city of Nottingham, UK. The approach involved dividing land uses into types, and times into periods, and assigning the recharge from each an individual tracer-solute with a unit concentration. The computer code MT3DMS was used to track the multiple tracer-solutes in transient, three-dimensional simulations of the important urban aquifer. A depth-specific hydrochemical dataset collected in parallel supported the model predictions. At depth under the industrial area studied, a large component of ground water originated of older agricultural origin, with relatively low nitrate concentrations. Shallower ground water originated mainly from residential and industrial areas, with higher nitrate concentrations probably arising from leaking sewers and contaminated land. The results highlighted the spectrum of ground water from different origins that amalgamate even at short well screens in a non-pumped borehole and remind us that the non-point-source pollution of ground water from anthropogenic activities will involve more years of slow degradation of quality.     

The status of pesticide pollution in surface waters (rivers and lakes) of Greece. Part I. Review on occurrence and levels

This review evaluates and summarizes the results of long-term research projects, monitoring programs and published papers concerning the pollution of surface waters (rivers and lakes) of Greece by pesticides. Pesticide classes mostly detected involve herbicides used extensively in corn, cotton and rice production, organophosphorus insecticides as well as the banned organochlorines insecticides due to their persistence in the aquatic environment. The compounds most frequently detected were atrazine, simazine, alachlor, metolachlor and trifluralin of the herbicides, diazinon, parathion methyl of the insecticides and lindane, endosulfan and aldrin of the organochlorine pesticides. Rivers were found to be more polluted than lakes. The detected concentrations of most pesticides follow a seasonal variation, with maximum values occurring during the late spring and summer period followed by a decrease during winter. Nationwide, in many cases the reported concentrations ranged in low ppb levels. However, elevated concentrations were recorded in areas of high pesticide use and intense agricultural practices. Generally, similar trends and levels of pesticides were found in Greek rivers compared to pesticide contamination in other European rivers. Monitoring of the Greek water resources for pesticide residues must continue, especially in agricultural regions, because the nationwide patterns of pesticide use are constantly changing. Moreover, emphasis should be placed on degradation products not sufficiently studied so far.     

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.     

A screening method for preliminary assessment of risk to groundwater from land-applied chemicals

A simple mathematical model for initial screening is presented that can aid in evaluating the relative risk to groundwater from applying nonpolar synthetic organic chemicals to soil. The basic premise is that the magnitude of the quotient of the chemical concentration of the water entering the aquifer and the maximum allowable concentration (as established by EPA or Health Departments) represents the health risk of a chemical. The chemical concentration of the soil water is estimated based on conservative, simplifying assumptions and requires only readily available data such as: basic soil properties (organic matter and saturated hydraulic conductivity), organic chemical properties (octanol-water partition coefficient and degradation rate) and environmental factors (recharge rate and depth to groundwater).The methodology was applied to assess the relative risk of organic chemicals in municipal sewage sludge and pesticides applied to agricultural land. The results are realistic.     

Dynamic factor analysis of groundwater quality trends in an agricultural area adjacent to Everglades National Park

The extensive eastern boundary of Everglades National Park (ENP) in south Florida (USA) is subject to one of the most expensive and ambitious environmental restoration projects in history. Understanding and predicting the water quality interactions between the shallow aquifer and surface water is a key component in meeting current environmental regulations and fine-tuning ENP wetland restoration while still maintaining flood protection for the adjacent developed areas. Dynamic factor analysis (DFA), a recent technique for the study of multivariate non-stationary time-series, was applied to study fluctuations in groundwater quality in the area. More than two years of hydrological and water quality time series (rainfall; water table depth; and soil, ground and surface water concentrations of N-NO3-, N-NH4+, P-PO4(3-), Total P, F-and Cl-) from a small agricultural watershed adjacent to the ENP were selected for the study. The unexplained variability required for determining the concentration of each chemical in the 16 wells was greatly reduced by including in the analysis some of the observed time series as explanatory variables (rainfall, water table depth, and soil and canal water chemical concentration). DFA results showed that groundwater concentration of three of the agrochemical species studied (N-NO3-, P-PO4(3-)and Total P) were affected by the same explanatory variables (water table depth, enriched topsoil, and occurrence of a leaching rainfall event, in order of decreasing relative importance). This indicates that leaching by rainfall is the main mechanism explaining concentration peaks in groundwater. In the case of N-NH4+, in addition to leaching, groundwater concentration is governed by lateral exchange with canals. F-and Cl- are mainly affected by periods of dilution by rainfall recharge, and by exchange with the canals. The unstructured nature of the common trends found suggests that these are related to the complex spatially and temporally varying land use patterns in the watershed. The results indicate that peak concentrations of agrochemicals in groundwater could be reduced by improving fertilization practices (by splitting and modifying timing of applications) and by operating the regional canal system to maintain the water table low, especially during the rainy periods.     

Trace organic chemicals contamination in ground water recharge

Population growth and unpredictable climate changes will pose high demands on water resources in the future. Even at present, surface water is certainly not enough to cope with the water requirement for agricultural, industrial, recreational and drinking purposes. In this context, the usage of ground water has become essential, therefore, their quality and quantity has to be carefully managed. Regarding quantity, artificial recharge can guarantee a sustainable level of ground water, whilst the strict quality control of the waters intended for recharge will minimize contamination of both the ground water and aquifer area. However, all water resources in the planet are threatened by multiple sources of contamination coming from the extended use of chemicals worldwide. In this respect, the environmental occurrence of organic micropollutants such as pesticides, pharmaceuticals, industrial chemicals and their metabolites has experienced fast growing interest. In this paper an overview of the priority and emerging organic micropollutants in the different source waters used for artificial aquifer recharge purposes and in the recovered water is presented. Besides, some considerations regarding fate and removal of such compounds are also addressed.     

Part I: Temporal and spatial distribution of multiclass pesticide residues in lake waters of Northern Greece: application of an optimized SPE-UPLC-MS/MS pretreatment and analytical method

The present work describes the application of an analytical procedure, utilizing ultra performance liquid chromatography (UPLC) coupled with mass spectrometry instrumentation, for the determination of 253 multiclass pesticides, classified in six different groups. Solid phase extraction was applied for the isolation and pre-concentration of target compounds in water samples. Surface waters of the lakes located in Northern Greece (Volvi, Doirani, and Kerkini), were collected in two time periods (fall/winter 2010 and spring/summer 2011) and analyzed, applying the developed analytical methods. Spatial distribution of detected pesticides was visualized using interpolation methods and geographical information systems (GIS). Pesticides with maximum concentrations were amitrole, propoxur, simazine, chlorpyrifos, carbendazim, triazophos, disulfoton-sulfone, pyridaben, sebuthylazine, terbuthylazine, atrazine, atrazine-desethyl, bensulfuron-methyl, metobromuron, metribuzin, rotenone, pyriproxyfen, and rimsulfuron. In Lake Kerkini, mainly carbamates and triazines were determined at elevated concentrations, near the coastal point of the NW side of the lake. Seasonal variations were strong among the applied pesticide classes and determined concentrations, indicating the contribution of pesticide application patterns and rainfall. Lake Doirani exhibited organophosphate pesticides at higher concentrations mainly at coastal points, while triazines emerged as the main pollutant during spring sampling. Lake Volvi exhibited the highest pesticide concentrations, mostly triazines and ureas at the central part of the lake. The occurrence of extreme values and nonconstant seasonal variations indicated that the concentrations were increased disproportionately during the second sampling, as a result of the varying contribution of pollution sources right after the application period. In all cases, the total concentration of pesticides increased during the second sampling period.     

Determination of herbicides in stemflow and throughfall of beeches (Fagus sylvatica L.) and in rainfall

The pesticide contamination of water samples collected in and nearby a beech forest in northern Germany was evaluated. For this purpose, a method for the collection of water samples from stemflow and throughfall of beeches (Fagus sylvatica L.) and rainfall was developed in response to the demands for the analysis of organic contaminants in water samples. Furthermore a sensitive and selective multiresidue method was developed to determine 18 pesticides, frequently used in Germany, in aqueous samples. The samples collected were taken from the stemflow, the crown throughfall and the rainfall between May and November 2001. Analysis based on reversed-phase liquid chromatography with a pneumatically assisted electrospray mass spectrometer followed a solid phase extraction using C-18 extraction cartridges. Isoproturon, metolachlor, prosulfocarb and terbuthylazine were found during and shortly after their application period. In rainfall metolachlor, terbuthylazine and prosulfocarb were detectable in concentrations between 5 and 65 ng l(-1) and isoproturon in concentrations between 20 and 360 ng l(-1) respectively. In most of the samples, concentrations of those four pesticides were higher and detectable for a longer time in stemflow than in rainfall. Crown throughfall samples were collected from the end of August to November. Absolute deposition of isoproturon to forest soil were up to 70 times higher in comparison to rainwater samples.     

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 micro 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.     

Enhanced transport of pesticides in a field trial with treated sewage sludge

This study was designed to provide high-density data on spatial distribution of three herbicides with different physiochemical characteristics in a sludge-amended and non-amended control field over the course of an irrigation season. The field experiment was carried out on a sandy loam Hamra Red Mediterranean soil (Rhodoxeralf) at Bet Dagan, Israel. After a single 50 mm irrigation event, the mean centers of mass (COM) in the control field were at 15.6, 14.9, and 17 cm for bromacil, atrazine and terbuthylazine, respectively; in the sludge-amended field, mean COMs were at 28.8, 31.2, and 34.1 cm, respectively. After 500 mm of irrigation in the control field, the COM depth distribution of the three pesticides was inversely correlated with octanol-water (Kow) distribution coefficients and soil sorption coefficients (Koc), and positively correlated with aqueous solubilities. After 500 mm irrigation in the sludge-amended field, the mean terbuthylazine COM was at 19.8 cm versus 13.8 cm for the control field, demonstrating a sustained enhanced effect on terbuthylazine transport. Downward transport of atrazine was also enhanced by sludge amendment, albeit less than terbuthylazine. Bromacil was preferentially accumulated in the upper soil layers of the sludge-amended field as compared with the control field after 500 mm irrigation. The enhanced transport of all three pesticides in the sludge-amended field after a single irrigation event is attributed to development of preferential flow pathways around hydrophobic clods of sludge. Enhanced transport of terbuthylazine, and to a lesser extent, atrazine, throughout the irrigation season, is attributed to their transport as complexes with dissolved, colloidal and suspended organic matter derived from sludge degradation.     

Anthropogenic contaminants as tracers in an urbanizing karst aquifer

Karst aquifers are uniquely vulnerable to contamination. In the Barton Springs segment of the karstic Edwards aquifer (Texas, U.S.A.), urban contaminants such as pesticides and volatile organic compounds frequently are detected in spring base flow. To determine whether contaminant concentrations change in response to storms, and if they therefore might act as tracers of focused recharge, samples were collected from Barton Springs at closely spaced intervals following three storms. Two herbicides (atrazine and simazine), two insecticides (carbaryl and diazinon), and a solvent (tetrachloroethene) described breakthrough curves over a 1-week period following one or more storms. The breakthrough curves were decomposed into two to five log-normal subcurves, which were interpreted as representing pulses of contaminants moving through the aquifer. Each subcurve could be used in the same way as an artificial tracer to determine travel time to and recovery at the spring. The contaminants have several advantages over artificial tracers: they represent the actual compounds of interest, they are injected essentially simultaneously at several points, and they are injected under those conditions when transport is of the most interest, i.e., following storms. The response of storm discharge, specific conductance, and contaminant loading at the spring depended on initial aquifer flow conditions, which varied from very low (spring discharge of 0.48 m3/s) to high (spring discharge of 2.7 m3/s): concentrations and recovery were the highest when initial aquifer flow conditions were low. This behavior provides information about aquifer structure and the influence of aquifer flow condition on transport properties.     

Occurrence of currently used pesticides in ambient air of Centre Region (France)

Ambient air samples were collected, from 2006 to 2008 at three rural and two urban sites in Centre Region (France) and analyzed for 56 currently used pesticides (CUPs), of which 41 were detected. The four CUPs most frequently detected were the herbicides trifluralin, acetochlor and pendimethalin and the fungicide chlorothalonil, which were found with frequencies ranging between 52 and 78%, and with average concentrations of 1.93, 1.32, 1.84 and 12.15 ng m^?3, respectively. Among the detected pesticides, concentrations of eight fungicides (spiroxamine, fenpropimorph, cyprodinil, tolyfluanid, epoxiconazole, vinchlozolin, fluazinam, fludioxinil), two insecticides (propargite, ethoprophos), and one herbicide (oxyfluorfen) are, to our knowledge, reported for the first time in the literature.The majority of the CUPs showed a seasonal trend, with most of the detections and the highest concentrations occurring during the spring and early summer. The most important pesticides detected were related to arable crops and fruit orchards, the main cultures in this region, highlighting the fact that the main sources come from local applications. Minor differences were found in the profiles of pesticides within rural areas and between rural and urban areas.     

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.