Behaviour of fenitrothion residues in leaves and soil of vineyard after treatment with microencapsulate and emulsified formulations

The rate of decline of fenitrothion residues was investigated in leaves and soil of vineyard over 2 months after treatment with two different kinds of commercial formulations: emulsifiable concentrate (EC) and microencapsulate (ME). Fenitrothion residues were determined with GC-NPD after acetone extraction of soil and leaves. The measured initial deposits in soil and leaves varied between 2.6 and 3.8?mg?kg^?1 and between 89 and 101?mg?kg^?1, respectively. Fenitrothion residues in soil dropped at 0.1–0.2?mg?kg^?1 after 60 days following application with EC formulation showing a more rapid decline than the ME. Fenitrothion residues in leaves from ME formulation treatment showed a longer persistence and lower decline rate than those from EC formulation. During the experimental period, fenitrothion remaining in leaves from ME application was 10 times more than from the EC one. Mathematically defined decline curves were established by determining optimal relationships between fenitrothion residues and time. The RF1st-order and RF1.5th-order equation achieved the best adjustment to the experimental data of fenitrothion dissipation on leaves for the ME and EC formulation, respectively, giving fenitrothion half-lives of about 2–3 days for ME and <1 day for EC formulation. In vineyard soil, the best adjustment to the experimental data for ME and EC formulation was achieved by the 1st-order and 1.5th-order equations, respectively, giving fenitrothion half-lives in soil of about 17–21 days for ME and 5 days for EC formulation.     

Concentration of arsenic in soil samples collected around the monazite processing facility, Thailand

Arsenic (As) in soil is a contaminant originated from human activities including pesticide use, mining and ore processing operations. In this work, As concentration in soil samples collected around the monazite processing facility, Pathum Thani, Thailand, was investigated. The collections of 24 soil samples were collected from the monazite processing area and 7 soil samples were collected from the control area without the processing activity of the same facility. Soils were digested with the mixture of HNO₃, HClO₄ and HF using a microwave digester. Inductively coupled plasma mass spectrometer (ICP-MS) equipped with an octopole reaction system (ORS) was used to determine the concentration of As in soils after the acid digestion. JB-3 (igneous rock) was the standard reference material used to check the accuracy of the method. It was found that the analytical results showed good agreement with the certified values. As concentration in soils collected from the monazite processing area ranged from 3.85 to 36.01 mg kg^?1 with the mean of 13.06 mg kg^?1. The concentration of As higher than the US EPA cancer soil screening level (22 mg kg^?1) was observed for only one sample. The control area showed As concentration varied from 9.59 to 14.19 mg kg^?1 with the mean of 11.97 mg kg^?1. The obtained results from this work were compared with the contaminated soil data of Amphoe Ron Phibun, Nakhon Si Thammarat, Thailand.     

Application of stripping voltammetry method for the analysis of available copper,zinc and manganese contents in soil samples

Determination of copper (Cu), zinc (Zn) and manganese (Mn) micronutrients in soil samples have been studied for an efficient fertiliser application. Plant-available micronutrients of soils were extracted with DTPA extraction procedure, then differential pulse stripping voltammetry (DPSV) and square wave stripping voltammetry (SWSV) methods were performed with inexpensive and disposable pencil graphite electrode for determination of Cu(II), Zn(II) and Mn(II). Parameters such as deposition potential, deposition time, pH and concentration of the supporting electrolyte were optimised for these ions. Under optimised conditions, the limits of detection were found as 0.01 mg L^?1 for Cu(II) and 0.02 mg L^?1 for Zn(II) and 0.25 mg L^?1 for Mn(II). Relative standard deviation (%RSD) was 6.80, 8.86 and 3.29 for Cu(II), Zn(II) and Mn(II), respectively. The experimental study was conducted using a flame atomic absorption spectroscopy. The described stripping voltammetry methods were successfully applied for the determination of Mn(II), Cu(II) and Zn(II) in soil samples.     

Transfer of Metals from Soil to Crops in an Area near a Coal Gangue Pile in the Guqiao Coal Mine,China

A field survey was conducted to investigate the metal contamination in coal gangue, soils, and crops (rice and soybeans), and to evaluate the possible health risks to the local population through food chain transfer near a coal gangue pile in the Guqiao Coal Mine, China. Contamination levels of zinc, lead, cadmium, and copper in coal gangue, soils, and crops were measured, and bio-accumulation factors from soil to crops were determined; the health risks were calculated accordingly. Results showed that both coal gangue and soil contained high levels of cadmium (0.15 mg kg^?1and 0.20 mg kg^?1) exceeding the background value of the soil. The lead soil concentration was low (9.99 mg kg^?1), but lead in rice (0.38 mg kg^?1) exceeded the maximal permissible limit of 0.2 mg kg^?1. For some tissues of crops studied, there was a significant correlation between the bio-accumulation factor values and the corresponding soil metal concentrations that were best described by a power equation. Oral intake of zinc, cadmium, and copper through crops posed no health risk to local residents, although hazard indices for rice (0.87–2.88) and soybeans (0.06–0.09) suggested that ingestion of rice grains was unsafe for human health. Therefore, rice was inappropriate to be planted in the soil surrounding this coal mine.     

Multielement Analysis of South Serbian Strawberry Cultivars by Inductively Coupled Plasma—Optical Emission Spectrometry

The contents of 17 elements in thirteen strawberry cultivars grown in the five districts of Southern Serbia were determined using inductively coupled plasma optical emission spectrometry (ICP-OES). The most abundant elements are K (875–1148 mg?·?kg^?1 fresh weight), P (307–664 mg?·?kg^?1 fresh weight), Ca (192–256 mg?·?kg^?1 fresh weight), and Mg (111–189 mg?·?kg^?1 fresh weight) in all samples. Strawberries were also found to be a good source of Sr (8.05–18.6 mg?·?kg^?1 fresh weight) and Fe (3.09–10.4 mg?·?kg^?1 fresh weight). The contents of As and Cd were below the detection limit (0.0828 mg?·?kg^?1 and 0.0205 mg?·?kg^?1, respectively) in all strawberry samples, while the contents of Ni, Cr, and Cu were below the recommended tolerable levels proposed by Joint Food and Agriculture Organization of the United Nations and World Health Organization Expert Committee on Food Additives, and did not a pose a health risk for the consumer. The application of Duncan’s test showed significant differences between contents of analyzed elements in all strawberry cultivars. The highest mean levels of analyzed elements were detected in strawberries grown in the Topli?ki, Jablani?ki, and P?injski districts. The spike recovery test was used to verify the accuracy of the method, and the spike recovery was in the range 93.8–107.8%. The contents of the metals in strawberry samples were also comparable with values previously reported in the literature.     

Measurement of activity concentration of primordial radionuclides in soil samples from Thirthahalli taluk and the assessment of resulting radiation dose

The activity concentration of primordial radionuclides ²²⁶Ra, ²³²Th, and ⁴⁰K in soil samples of Thirthahalli taluk were measured systematically by using a low background HPGe detector coupled to 16 K MCA. The measured activity concentration of ²²⁶Ra lies between 5.1?±?0.2 and 79.5?±?1.7 Bq kg^?1with an average activity of 25.99 Bq kg^?1, ²³²Th ranges from 5.1?±?0.3 to 95.3?±?2.2 Bq kg^?1with an average activity of 33.60 Bq kg^?1and that of ⁴⁰K varies from 18.3?±?1.5 to 833.4?±?17.5 Bq kg^?1with an average activity of 175.52 Bq kg^?1. Higher concentration of these radionuclides were found in the soil samples where the regional geology is granites. The consequential gamma dose and the corresponding radiation hazard was also estimated and is found to be within the permissible limits. The possible radiological impact on the public was also determined and these results are presented in this paper.     

Experimental assessment of a large sample cell for laser ablation-ICP-MS, and its application to sediment core micro-analysis

The coupling of laser ablation (LA) to inductively coupled plasma-mass spectrometry (ICP-MS) enables the direct analysis of solid samples with micrometric resolution. Analysis is often restricted to relatively small samples owing to the dimensions of conventional ablation cells. Here, we assess the performance of a large rectangular, commercially-available sample cell which enables analysis over a 10.2?×?5.2 cm² area. Comparison with the conventional cell shows a small to moderate performance decrease for the large cell resulting from the dilution of ablated particles in a larger volume with a 4–31% lower signal output and longer signal tailings. The performance of this cell is however sufficient for the determination of both major and trace elements in many kinds of samples. The applicability of the large cell LA-ICP-MS setup was demonstrated by the determination of Al, Si, Mn, Fe, Cu, Zn Pb and U in sediment core sections at a resolution of 0.6 mm. Detection limits for sediment analysis were 7 mg Al kg^?1, 68 mg Si kg^?1, 0.5 mg Mn kg^?1, 20 mg Fe kg^?1, 0.2 mg Cu kg^?1, 0.3 mg Zn kg^?1, 0.08 mg Pb kg^?1 and 0.003 mg U kg^?1. Cyclic patterns, which would have been overlooked by conventional analysis at cm resolution, were observed in analysed sediments. This study demonstrates the potential of LA-ICP-MS in environmental analysis, with the large sample cell setup offering the possibility to analyse a wider range of samples without sectioning.     

Enantioselective separation and simultaneous determination of fenarimol and nuarimol in fruits, vegetables, and soil by liquid chromatography–tandem mass spectrometry

A method for simultaneous enantioselective determination of fenarimol and nuarimol in apple, grape, cucumber, tomato, and soil was developed using liquid chromatography–tandem mass spectrometry. The enantioseparation results of the two fungicides through three different cellulose-based chiral columns are discussed. The influence of column temperature on the resolution of the enantiomers of the two fungicides was examined. Complete enantioseparation of the two fungicides’ enantiomers was obtained on a cellulose tris(4-methylbenzoate) column (Lux Cellulose-3) at 25?°C using methanol and 0.1?% formic acid solution (80:20, v/v) as mobile phase. The linearity, matrix effect, recovery, and precision were evaluated. Good linearity was obtained over the concentration range of 1–500?μg?L^?1 for each enantiomer in the standard solution and sample matrix calibration solution. There was no significant matrix effect in apple, grape, cucumber, or tomato samples, but signal suppression was typically observed with the soil extracts. The mean recoveries, repeatability, and reproducibility were 76.5–103?%, 2.1–9.0?%, and 4.2–11.8?%, respectively. The limit of quantification for enantiomers of the two fungicides in fruits, vegetables and soil was 5?μg?kg^?1. Moreover, the absolute configuration of the enantiomers of fenarimol and nuarimol was determined from a combination of experimentally determined and predicted electronic circular dichroism spectra.

Application of Dispersive Liquid�CLiquid Microextraction for the Analysis of Six Fungicides in Fruit Samples by GC�CECD

A novel approach for the determination of six fungicides (triadimefon, procymidone, hexaconazole, myclobutanil, diniconazole and iprodione) in fruit samples is presented. Analytes were extracted using the dispersive liquid?Cliquid microextraction technique and determined by GC?CECD. Parameters affecting the dispersive liquid?Cliquid microextraction performance, such as the kind and volume of extraction and dispersive solvents, extraction time and salt concentration, were studied and optimized. Under the optimum extraction conditions, the linearities of the method were obtained in the range of 0.5?C20.0 ??g kg^?1 for triadimefon, hexaconazole, diniconazole and procymidone, and 1.0?C40.0 ??g kg^?1 for myclobutanil and iprodione, with the correlation coefficients ranging from 0.9902 to 0.9995. The enrichment factors ranged from 685 to 820 and the extraction recoveries ranged from 81.3 to 98.4%. The relative standard deviations varied from 3.1 to 7.8%. The limits of detection of the method were in the range of 0.02?C0.12 ??g kg^?1. Results showed that the method we proposed can meet the requirements for the determination of target fungicides in fruit samples. Several compounds considered in this study were found in fruit samples.     

Determination of thorium concentrations in soil and sand samples using instrumental neutron activation analysis

Thorium along with its daughter products present in the soil is one of the major contributors to the external gamma dose in the environment. To establish the dose levels, quantification of thorium contents in soil samples is very important. As a part of pre-operational environmental radiological surveillance, a total of 23 soil and six sand samples were collected from different locations around the proposed nuclear power plant site of Jaitapur, Maharashtra. Thorium concentrations in these samples were determined by instrumental neutron activation analysis (INAA). Samples were irradiated with neutrons in Apsara reactor at a neutron flux of?~5?×?10¹¹ cm^?2 s^?1 and radioactive assay was carried out using high resolution gamma ray spectrometry. Relative method of INAA was used for quantification of thorium utilizing 311.9?keV gamma ray of ²³³Pa, the daughter product of ²³³Th. The concentrations of thorium in the soil and sand samples were in the ranges of 4.0?C18.8 and 1.2?C6.2?mg?kg^?1 respectively.     

Assessment of effective radium content and radon exhalation rates in soil samples

Effective radium content and radon exhalation rates in soil samples have been measured by ??Sealed Can Technique?? using LR-115 type II plastic track detectors. The soil samples were collected from Farrukhabad city of Utter Pradesh, India. The values of effective radium content were found to vary from 5.39 to 34.56?Bq?kg^?1 with an average value of 16.58?Bq?kg^?1 and a standard deviation of 7.16. The mass and surface exhalation rate has been found to vary from 0.41?×?10^?6 to 2.64?×?10^?6?Bq?kg^?1?d^?1 and 1.41?×?10^?6 to 9.10?×?10^?6?Bq?m^?2?d^?1, respectively. All the values of radium content in soil samples of study area were found to be quite lower than the permissible value of 370?Bq?kg^?1 recommended by Organization for Economic Cooperation and Development.     

Retrospective determination of 238Pu, 239,240Pu and 90Sr activities in the outer bark of Norway spruce (Picea abies (L.) Karst.) collected at various sites in the Czech Republic

The activity concentrations of ²³⁸Pu, ^239,240Pu and ⁹⁰Sr were determined in 25 archived spruce outer bark samples collected in coniferous forests across the Czech Republic in 1995. At three sampling sites the radionuclide activity concentrations were determined in forest soil. Data was provided on the cumulative deposition and vertical distribution of ²³⁸Pu, ^239,240Pu and ⁹⁰Sr in forest soil. The median activity concentration of ²³⁸Pu in the spruce bark samples was 0.009 Bq kg^?1. The median activity concentration of ^239,240Pu was 0.212 Bq kg^?1, and the median activity concentration of ⁹⁰Sr was 10.6 Bq kg^?1. The radionuclide activity concentration distribution was not significantly explained by the local long-term (1961–2000) mean annual precipitation totals, by site elevation, by bark acidity, by soil moisture and soil texture. The activity concentrations of the radionuclides in bark were found to be higher than or comparable with the published and measured figures for radionuclide activity concentrations in cultivated and uncultivated soils (0–20 cm layer) in the Czech Republic and abroad. The activity concentration ratio of ⁹⁰Sr/^239,240Pu in the investigated spruce bark samples was higher than in the relevant soil samples. We assume that the crucial radioactive contamination loads in bark occurred in the first half of the 1960s, when the concentration of the investigated radionuclides in the air was highest. Spruce trunk bark has preserved relatively high activity concentrations of these radionuclides. The mechanism governing the long-term radionuclide activity concentrations in outer bark proportional to the local radioactive fallout rates is not correctly known. Our results indicate the suitability of spruce bark for use as an effective monitor of radioactive plume fallout loads even several decades after the contamination episode.     

Influence of Ca(OH)2 on the Extraction Efficiency of Nitroaromatic Compounds from Soils

High concentrations of TNT and related nitroaromatic compounds (NAC) can still be found in the soils. To evaluate the alkaline hydrolysis of NAC as a new remediation technology, two highly contaminated soils were treated under alkaline conditions using Ca(OH)₂ as base. However, instead of the expected decrease, a temporary or even permanent increase was observed for several NAC. The extent of the intensity was affected by Ca(OH)₂ concentration, suggesting the existence of desorption processes in the soil. The extent of the increase also depends on the soil investigated, the highest being observed with 1,3,5-trinitrobenzene (239 mg kg^?1 compared to the baseline concentration of 24 mg kg^?1) in the HTNT2 soil. This indicates incomplete NAC extraction and, hence, too low NAC concentrations measured in soils when conventional extraction procedures are used.     

Evaluation of natural gamma radiation and absorbed gamma dose in soil and rocks of Perambalur district (Tamil Nadu,India)

The activity concentrations and absorbed gamma dose of primordial radionuclides ²³⁸U, ²³²Th and ⁴⁰K were determined employing γ-ray spectrometry in 31 soil samples from the land area earmarked for house construction in Perambalur district and 14 rock samples from quarries that supply stones for the entire district. The soil samples registered relatively a higher mean value of 13.2 Bq kg^?1 for ²³⁸U, 66 Bq kg^?1 for ²³²Th and 340.3 Bq kg^?1 for ⁴⁰K as compared to mean values for rock samples (²³⁸U—8.0 Bq kg^?1; ²³²Th—65.1 Bq kg^?1; ⁴⁰K—199.1 Bq kg^?1). The mean absorbed gamma dose rate for soil (61.4 nGy h^?1) marginally exceeded the prescribed limit of 55 nGy h^?1 while, rocks registered the mean absorbed gamma dose rate of 10.4 nGy h^?1. The mean radium equivalent activity was distinctly higher in soil (130.6 Bq kg^?1) than in rock (20.0 Bq kg^?1). However, these values were lower than the limit (370 Bq kg^?1) set by OECD for building materials. It is evident from the data that the soil and rocks do not pose any radiological risk for house constructions in Perambalur district.     

Determination of Trace Elements in Dendrobium Officinale Cultivated in Various Conditions

Dendrobium officinale is an important medicinal plant in traditional Chinese medicine. The consumption of D. officinale has increased rapidly in recent years due to the health awareness among Chinese people. The present study aimed to determine trace elements levels in 42 D. officinale samples and to utilize the elemental data for identifying the cultivation technique. Eighteen trace elements (B, V, Cr, As, Mn, Fe, Mo, Cu, Zn, Se, Sr, Sn, Ti, Al, Co, As Pb, Cd, and Bi) were determined by inductively coupled plasma–mass spectrometry. Of the 11 essential elements, the mean concentrations ranged from 30.6?µg?kg^?1 (Mo) in D. officinale with greenhouse cultivation to 161?mg?kg^?1 (Fe) in D. officinale with rock cultivation, and the contributions of Mn may exceed the dietary reference intake value by the uptake of 20?g of D. officinale. Of the seven toxic elements, the mean concentrations ranged from 3.29?µg?kg^?1 (Bi) in the D. officinale with greenhouse cultivation to 342?mg?kg^?1 (Al) in the D. officinale with rock cultivation, and the contributions of Al may exceed the provisional tolerable daily intake value by the uptake of 20?g of D. officinale. The concentrations of seven metals (Bi, Pb, Fe, Al, Cr, As, and Mo) were utilized to identify the cultivation technique of the analyzed D. officinale samples through linear discriminant analysis.     

Comparison of microwave-assisted digestion procedures for total trace element content determination in calcareous soils

The aim of the study was to determine total trace (Cd, Co, Cr, Cu, Mn, Pb and Zn) and major (Al and Fe) element concentrations in calcareous soils using microwave-assisted digestion procedures. The literature showing lack of consensus regarding digestion procedures and unsatisfying recoveries for calcareous materials, four procedures using various acid combinations (HCl, HNO₃, H₂O₂, HF) and volumes were tested using a certified reference material (CRM 141R) and natural calcareous soil samples. Digests were analysed by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Repeatability (R.S.D. <5%) and recoveries (82-116%) showed that the procedures were precise and accurate for most elements. Five calcareous soil samples from a Champagne vineyard plot were, then, subjected to these procedures. In calcareous materials, the presence of HF resulted in Al being severely underestimated (recovery <5%) and Co overestimated (recovery >124%) due to complex formation or spectrochemical interferences, respectively. As digestion was not significantly influenced by the addition of H₂O₂, the procedure corresponding to Aqua regia (HCl-HNO₃) appeared as the best compromise and was selected for further multielemental environmental studies on calcareous materials, even if the absence of HF could lead to incomplete digestion of accessory silicate minerals. Results for a vineyard plot showed that the soils were contaminated (3.65 mg kg⁻¹ Cd, 67 mg kg⁻¹ Cr, 278 mg kg⁻¹ Cu, 143 mg kg⁻¹ Pb and 400 mg kg⁻¹ Zn) as a consequence of urban waste and copper-treatment applications.     

Persistence of trifloxystrobin and tebuconazole in banana tissues and soil under the semi-arid climatic conditions of Karnataka,India

Trifloxystrobin and tebuconazole are used for control of Sigatoka leaf spot disease of banana. This study was conducted to evaluate residue persistence of the fungicides in/on banana fruit, other edible parts and soil after spray application of the combination formulation, Nativo 75 WG, at the standard dose, 87.5 + 175 and double dose, 175 + 350 g a.i. ha^?1. The fungicides were extracted from banana and soil with acetone, partitioned into dichloromethane and cleaned-up using activated charcoal for trifloxystrobin and primary/secondary amine (PSA) for tebuconazole samples. The limit of quantification of the method was 0.05 mg kg^?1 for both fungicides. Initial residues of trifloxystrobin were 0.444 and 0.552 mg kg^?1 in/on banana with peel (whole fruit), which reached <0.05 and 0.065 mg kg^?1 after 30 days from treatment at the standard and double doses, respectively. Tebuconazole residues were 0.636 and 960 mg kg^?1 initially and reduced to 0.066 and 0.101 mg kg^?1 after 30 days. Trifloxystrobin and tebuconazole degraded with the half-life of about 11 days. Trifloxystrobin or its metabolite was not detected in the fruit pulp. Tebuconazole being systemic in nature moved to the fruit pulp which was highest on the 3rd day (0.103 and 0.147 mg kg^?1) and remained for 15 days. Matured banana fruit, flower, pseudostem and field soil were free from fungicide residues. For consumption of raw banana 43 days pre-harvest interval (PHI) is required after treatment of the combination formulation. Therefore application of the fungicides towards maturity stage of the fruits may be avoided.     

Extraction-chromatographic method for the determination of plutonium-239,240 and plutonium-238 in soils with high natural radioactivity

A highly selective method is described for the determination of ^239,240Pu and ²³⁸Pu in soils by extraction chromatography with Microthene-710/tri-n-octylamine. The method is especially suitable for volcanic soils containing high concentrations of natural alpha radionuclides (Th, Po, U, etc.). The detection limit by α-spectrometry is 2.2 mBq kg^?1 for 50-g soil samples. The average chemical yield, obtained by adding ²⁴²Pu as the internal standard, is 69.5 ± 17.1%. An IAEA reference soil was analyzed, with a relative error of 6.7% for ²³⁹Pu. The concentration of ^2239,240Pu in thirteen analyzed soils and sediments ranged from 26.6 to 429 mBq kg^?1.     

Lead concentration in soil from an old mining town

Lead concentration in soils has been measured in Vetagrande, an old mining town located at the state of Zacatecas in México. Eighty nine soils samples were analyzed using Energy Dispersive X-ray Fluorescence. The lead concentrations were treated with the Kriging method in order to estimate the lead concentration distribution in the studied area. Pb levels in soils were from 8 to 7730 μg kg⁻¹, where 28.1% of soil samples have less than 400 μg kg⁻¹, 71.9% is above 400 μg kg⁻¹ which is the maximum level recommended by the EPA for residential use of soil. Lead concentration measured around public sites represent a risk of lead intake in the population.     

Distribution of arsenic in the natural environment with emphasis on rocks and soils

Arsenic is ubiquitous in the environment. Although the average arsenic concentrations in rocks (～2 mg kg^?1), soils (～2 mg kg^?1), freshwater (～1 m?g dm^?3), seawater (～2 m?g dm^?3) and organisms is generally low, high arsenic concentrations in limited areas are not uncommon. Whereas terrestrial organisms appear not to accumulate arsenic, marine organisms effectively concentrate arsenic to levels thousand of times higher than in ocean waters. The geochemical cycle and mineralogy of arsenic are reviewed with some emphasis towards Japanese locations and arsenic concentrations (averages, ranges) found in samples from the lithosphere, pedosphere, hydrosphere and biosphere are tabulated and discussed.