Quantification of triazine herbicides in soil by microwave-assisted extraction and high-performance liquid chromatography

A method for the determination of herbicides residues, triazine (atrazine, metribuzin, ametryn, and terbutryn), in soil samples with high-performance liquid chromatography (HPLC)?CUV detection is described. The proposed method is based on microwave-assisted extraction (MAE) of soil samples for 4 min at 80% of 850-W magnetron outputs in the presence of mixture of solvents (methanol/acetonitrile/ethylacetate). Related important factors influencing the MAE efficiency, such as the solvent type and volume, irradiation energy, and time, were optimized in detail. Calibration curve ranges established using HPLC for metribuzin, atrazine, ametryn, and terbutryn are 1.0?C19.0, 0.9?C18.0, 0.6?C11.0, and 0.7?C11.0 µg mL^???1, respectively. The limits of detection of metribuzin, atrazine, ametryn, and terbutryn are 0.30, 0.24, 0.16, and 0.20 µg mL^???1 while limits of quantification are 1.0, 0.80, 0.50, and 0.60 µg mL^???1, respectively. A Plackett?CBurman factorial design was used as a screening method in order to select the variables that influence MAE extraction. The recoveries of the method at three different spiked levels were assessed by analyzing real soil samples and were found to be in the range of 83.33 ± 0.12?C96.33 ± 0.23 with good precision (<8%).     

Adsorption study of 14C-paraquat in two Malaysian agricultural soils

The adsorption equilibrium time and effects of pH and concentration of ¹⁴C-labeled paraquat (1,1^??-dimethyl-4,4^??-bipyridylium dichloride) in two types of Malaysian soil were investigated. The soils used in the study were clay loam and clay soils from rice fields. Equilibrium studies of paraquat in a soil and pesticide solution were conducted. Adsorption equilibrium time was achieved within 2 h for both soil types. The amount of ¹⁴C-labeled paraquat adsorbed onto glass surfaces increased with increasing shaking time and remained constant after 10 h. It was found that paraquat adsorbed by the two soils was very similar: 51.73 (clay loam) and 51.59 ?? g g^???1 (clay) at 1 ?? g/ml. The adsorption of paraquat onto both types of soil was higher at high pH, and adsorption decreased with decreasing pH. At pH 11, the amounts of ¹⁴C-labeled paraquat adsorbed onto the clay loam and clay soil samples were 4.08 and 4.05 ?? g g^???1, respectively, whereas at pH 2, the amounts adsorbed were 3.72 and 3.57 ?? g g^???1, respectively. Results also suggested that paraquat sorption by soil is concentration dependent.     

Assessment and sources of nonaromatic hydrocarbons in surface sediments of three harbors in Santa Catarina State, Brazil

Nonaromatic hydrocarbons and geochemical parameters from 17 sediment?Cwater interface samples were used to assess sources of organic matter in three harbors, located in Santa Catarina State, southern Brazil. The evaluation was based on the molar C/N/P ratios, abundance of resolved nonaromatic hydrocarbons (3.0?C25.9 ??g g^???1), unresolved complex mixture, and two indexes: the carbon preference index (CPI) and the low molecular weight to high molecular weight ratio. The results indicate that the organic matter is predominantly of terrestrial origin (C/N > 10 and CPI > 2). Variations in the total organic carbon from 0.43 to 2.98 mmol g^???1 and total phosphorus from 82.4 to 464.3 ??g g^???1 showed no clear correlation with the silt and clay fractions of the sediments possibly due to anthropogenic input. In contrast to the low level of contamination based on the acyclic hydrocarbon distribution, the results obtained from a series of geologically stable hopanes and steranes reveal the presence of less degradable petroleum derivatives.     

Pesticide concentrations in water and sediment and associated invertebrate toxicity in Del Puerto and Orestimba Creeks, California, 2007�C2008

The California??s San Joaquin River and its tributaries including Orestimba (ORC) and Del Puerto (DPC) Creeks are listed on the 2006 US EPA Clean Water Act §303(d) list for pesticide impairment. From December 2007 through June 2008, water and sediment samples were collected from both creeks in Stanislaus County to determine concentrations of organophosphorus (OP) and pyrethroid insecticides and to identify toxicity to Ceriodaphnia dubia and Hyalella azteca. OPs were detected in almost half (10 of 21) of the water samples, at concentrations from 0.005 to 0.912 ??g L^???1. Diazinon was the most frequently detected OP, followed by chlorpyrifos and dimethoate. Two water samples were toxic to C. dubia; based on median lethal concentrations (LC₅₀), chlorpyrifos was likely the cause of this toxicity. Pyrethroids were detected more frequently in sediment samples (18 detections) than in water samples (three detections). Pyrethroid concentrations in water samples ranged from 0.005 to 0.021 ??g L^???1. These concentrations were well below reported C. dubia LC₅₀s, and toxicity was not observed in laboratory bioassays. Cyfluthrin, bifenthrin, esfenvalerate, and ??-cyhalothrin were detected in sediment samples at concentrations ranging from 1.0 to 74.4 ng g^???1, dry weight. At DPC, all but one sediment sample caused 100% toxicity to H. azteca. Based on estimated toxicity units (TUs), bifenthrin was likely responsible for this toxicity and ??-cyhalothrin also contributed. At ORC, survival of H. azteca was significantly reduced in four of the 11 sediment samples. However, pyrethroids were detected in only two of these samples. Based on TUs, bifenthrin and ??-cyhalothrin likely contributed to the toxicity.     

Environmental vanadium distribution, mobility and bioaccumulation in different land-use Districts in Panzhihua Region, SW China

In order to characterize environmental vanadium distribution, mobility, and bioaccumulation, a total of 55 soil samples and 36 plant samples were collected in four typical land-use districts in Panzhihua region, Southwestern China. Soil samples were analyzed with the modified Community Bureau of Reference (BCR) sequential extraction procedure, and the content of vanadium in soil and plant was determined by ICP-AES. The total content of vanadium was 208.1?C938.4 mg kg^???1 in smelting area, 111.6?C591.2 mg kg^???1 in mining area, 94.0?C183.6 mg kg^???1 in urban park, and 71.7?C227.2 mg kg^???1 in agricultural area, respectively, while the bio-available content of vanadium was characterized that the polluted areas (mining area 18.8?C83.6 mg kg^???1, smelting area 41.7?C132.1 mg kg^???1) and the unpolluted area (agricultural area 9.8?C26.4 mg kg^???1, urban park 9.9?C25.2 mg kg^???1). In addition, the contamination degree of vanadium in soil was smelting area > mining area > agricultural area ?? urban park. Moreover, the fraction of vanadium in each sequential extraction characterized that residual fraction > oxidizable fraction > reducible fraction > acid soluble fraction. The bioaccumulation of vanadium from soil to plant was weak to intermediate absorption. Therefore, some countermeasures such as soil monitoring and remediation should be to take in the sooner future, especially in mining and smelting area.     

Monitoring of copper level in water and soil samples by using liquid–liquid extraction

A new, simple, sensitive, and selective spectrophotometric method for the determination of copper in water and soil samples has been demonstrated. The method is based on the reaction of Cu(I) with neocuproine (2,9-dimethyl-1, 10-phenanothroline) and extracted with N-phenyl benzimidoylthiourea in chloroform. The value of molar absorptivity of the complex in the term of Cu(I) is 1.45 × 10⁵ L mol^???1 cm^???1 at λ _max 460 nm in chloroform. The detection limit of copper in water and soil is 2 ng mL^???1 and 4 ng g^???1, respectively. The method is free from the interference of the ions commonly found to be associated with the copper determination in water and soil samples. The application of the proposed method has been successfully tested for the determination of copper in different types of water and soil samples.     

Silica glass modified with flavonoid derivatives for preconcentration of some toxic metal ions in water samples and their determination with ICP-MS

Quercetin (3,3^′,4^′,5,7-pentahydroxyflavone) chemically bonded through pyran rearrangement on modified controlled pore silica glass (QCPSG) with a capacity 0.213 mmol/g was used for solid phase extraction of some toxic metal and metalloid ions. The newly designed QCPSG quantitatively sorbs As(V), Cd(II), Hg(II), and Pb(II) at the pH range 7.5–8.5 after 10 min of stirring. HCl (1 mol L^???1) instantaneously elutes all the metal ions. The sorption capacity of the ion collector is 0.42, 0.46, 0.53, and 0.49 mmol g^???1 for As(V), Cd(II), Hg(II), and Pb(II), respectively, whereas the preconcentration factor is 200. The effect of NaCl, Na₂SO₄, NaF, NaBr, Na₃PO₄, and other interfering salts on the sorption of metal ions (50 μg L^???1) was reported. Analytical detection limits of As(V), Cd(II), Hg(II), and Pb(II) were 4.18, 2.44, 15.86, and 25.00 pg mL^???1, respectively. QCPSG was used in the separation of the investigated metal ions from some natural water samples collected from diverse origins followed by determination by inductively coupled plasma–mass spectrometry. The data were compared with those obtained by the standard methods of determination using atomic absorption (hydride generation, HGAAS and after solvent extraction with ammonium pyrolidine dithiocarbamate/methyl isobutyl ketone). The suggested solid phase extraction method was found accurate with no random error.     

Persistence and bioaccumulation of oxyfluorfen residues in onion

A field study was conducted to determine persistence and bioaccumulation of oxyflorfen residues in onion crop at two growth stages. Oxyfluorfen (23.5% EC) was sprayed at 250 and 500 g ai/ha on the crop (variety, N53). Mature onion and soil samples were collected at harvest. Green onion were collected at 55 days from each treated and control plot and analyzed for oxyfluorfen residues by a validated high-performance liquid chromatography method with an accepted recovery of 78–92% at the minimum detectable concentration of 0.003 μg g^???1. Analysis showed 0.015 and 0.005 μg g^???1 residues of oxyfluorfen at 250 g a.i. ha^???1 rate in green and mature onion samples, respectively; however, at 500 g a.i.ha^???1 rates, 0.025 and 0.011 μg g^???1 of oxyfluorfen residues were detected in green and mature onion samples, respectively. Soil samples collected at harvest showed 0.003 and 0.003 μg g^???1 of oxyfluorfen residues at the doses 250 and 500 g a.i. ha^???1, respectively. From the study, a pre-harvest interval of 118 days for onion crop after the herbicide application is suggested.     

Spectrophotometric determination of platinum(IV) in alloys, complexes, environmental, and pharmaceutical samples using 4-[N,N-(diethyl)amino] benzaldehyde thiosemicarbazone

4-[N,N-(Diethyl)amino] benzaldehyde thiosemicarbazone (DEABT) is proposed as an analytical reagent for the spectrophotometric determination of platinum(IV). The DEABT forms 1:2 yellow complex with Pt(IV), which is sparingly soluble in water and completely soluble in water–ethanol–DMF medium. The Pt(IV)–DEABT complex shows maximum absorbance at 405 nm. Beer’s law is valid up to 7.80 μg cm^???3, and optimum concentration range for the determination of platinum(IV) is 0.48–7.02 μg cm^???3. The molar absorptivity and Sandell’s sensitivity of the method are found to be 1.755 × 10⁴ dm³ mol^???1 cm^???1 and 0.0012 μg cm^???2, respectively. The relative error and coefficient of variation (n?=?6) for the method does not exceed ±0.43% and 0.35%, respectively. Since the method tolerates a number of metal ions commonly associated with platinum, it can be employed for the determination of platinum in environmental samples, pharmaceutical samples, alloys, catalysts, and complexes. The method is rapid as the Pt(IV)–DEABT complex is soluble in water–ethanol–DMF medium and not requiring any time consuming extraction method for the complex.     

Insecticide residues in soil and water in coastal areas of vegetable production in Togo

Some common organochlorine, organophosphorus and pyrethroid insecticides were analysed in agricultural soil samples (n?=?35) and surface water and groundwater samples (n?=?25) collected from coastal areas of vegetable production in Togo. Analytical methods included solvent extraction of the insecticide residues and their subsequent quantification using GC-ECD. δ-HCH, heptachlor epoxide, 4,4-DDE, endosulphan (α, β and sulphate), lambda-cyalothrin and chlorpyrifos were found in the soil samples with concentrations that varied from non-detectable (ND) to 26.93 μg kg^?1 dry weight. For water samples, heptachlor epoxide, 2,4-DDD, 4,4-DDD, 4,4-DDE and endosulphan (α, β, and sulphate) were found at contamination levels that varied from ND to 0.116 μg L^?1. The concentration of insecticide residues detected in the water samples was below the limits set by the World Health Organization (WHO) and also by the European Union (EU), with the exception of the concentration of endosulphan sulphate at the Aného site, which was 0.116 μg L^?1.     

Quantification of penoxsulam in soil and rice samples by matrix solid phase extraction and liquid-liquid extraction followed by HPLC-UV method

The paper exploits the development of novel, simple and sensitive methodology involving matrix solid phase dispersion (MSPD) and the comparison of MSPD with liquid-liquid extraction (LLE) for the evaluation of residual penoxsulam in soil and rice samples. Extracted samples were analyzed by high-performance liquid chromatography (HPLC) with ultraviolet detector at 230 nm. Both methods were optimized, considering different parameters, and under optimum conditions, the mean recoveries obtained were in the range of 85–104 % for MSPD and 78.8–90.7 % for LLE. Precision values expressed as relative standard deviation (RSD) were ≤10 for MSPD and ≤15 for LLE. Linearity for penoxsulam was in the range of 0.01–20 μg mL^?1 with limits of detection and limits of quantification of 0.01 and 0.03 mg kg^?1, respectively.     

Evaluation of leaching behavior of pendimethalin in sandy loam soil

The mobility of pendimethalin in sandy loam soil was studied in soil columns under laboratory conditions at two application rates, 1.0 and 2.0 kg a.i. ha^???1, with simulated rainfall of 300 mm. The maximum concentration of the herbicide was found in the top 10 cm layer, though it was found distributed in soil at all the depths at both the doses.     

Integrated approach for the quality assessment of freshwater resources in a vineyard area (South Portugal)

An integrated chemical and biological approach for the quality assessment of freshwater resources in a vineyard area of the ??Alentejo?? region (South Portugal) is presented. This includes analysis to 11 pesticide compounds and whole toxicity testing on algae and crustaceans. Simazine, terbuthylazine, terbutryn, desethylatrazine and chlorpyrifos were the most frequently detected pesticides in water collected from wells and drainage channels. Mixtures of up to three compounds in different qualitative combinations were also found. The quality standards for individual pesticides (0.1 ??g L^???1) and pesticides-total (0.5 ??g L^???1) were exceeded in some samples. However, their maximum concentrations were lower than the WHO guidelines, the USEPA health advisory values and the environmental quality standards for priority substances applicable to surface water. In five samples, the herbicides terbuthylazine and terbutryn and the insecticide chlorpyrifos did not pass the toxicity exposure ratio (TER) trigger values specified for aquatic organisms (algae, Daphnia and fish). Maximum toxic effects on Daphnia magna (100%) and Pseudokirchneriella subcapitata (82.56%) were determined in groundwater samples, while in surface water, no toxicity was observed. Concerning effects on Heterocypris incongruens in sediment samples collected at the drainage channels, mortality and growth inhibition values were below 38%. Pro-active management of the use of pesticides is recommended for implementing at the farm and catchment level to reduce inputs into ground- and surface water.     

Temporal-spatial variability and fractal characteristics of soil nitrogen and phosphorus in Xinji District, Hebei Province, China

Traditional statistics, geostatistics, fractal dimensions, and geographic information systems (GIS) were employed to study the temporal?Cspatial variability of soil total nitrogen (TN) and total phosphorus (TP) levels in Xinji District, Hebei Province area of the North China Plain from 1980 to 2007. The results indicate that nutrient levels follow normal or lognormal distributions. The TN content was 0.59 ±0.155 g kg^???1 in 2007, an increase of 0.44 g kg^???1 compared with that of 1980. In 2007, the TP content was 1.21 ±0.227 g kg^???1, an increase of 0.01 g kg^???1 from 1980. The geostatistical analysis showed that the distribution of these soil nutrients in the study area exhibits a trend and anisotropy. The range and [C ₀/(C ₀?+?C)] of TN and TP in 1980 were all less than in 2007. The ordinary kriging interpolation method was used to analyze the nutrient contents differences between 1980 and 2007. The results indicate that soil TN levels have increased over the 27-year period, and the area where the TN level had increased by at least 0.4 g kg^???1 was about 61.7% of the district. The area where the TP content increased covered about 58.4% of the district. The variance analysis indicated that land-use type had a clear influence on the distribution and change in TN and TP content. Using the 3-D box-counting dimension method combined with GIS, the fractal dimension of soil nutrient spatial distribution over the two periods showed that in 27 years, the fractal dimension of TN increased from 1.95 to 2.02, and the fractal dimension of TP increased from 1.89 to 2.01, indicating that the complexity of the spatial distribution of all nutrient contents had increased. This study can provide a basis for accurate fertilizing and to enhance the conversion of soil characteristics under different spatial scales.     

Dissipation and residue of famoxadone in grape and soil

The analytical method of famoxadone residue and its dissipation in grape and soil were investigated. Famoxadone (68.75% water-dispersible granule) was applied at two dosages (1.25 and 2.5 g l^???1). Soil and grape samples were collected at intervals and analyzed for famoxadone residues. The results showed that the degradation rate of famoxadone in grape and soil were similar, and their dynamics could be described by C?=?1.1738e ^???0.0562t with correlation coefficient r?=?0.9044 in grape and C?=?5.6565e ^???0.0515t with r?=?0.9620 in soil, respectively. Half-lives were 12.3 and 13.5 days in grape and soil, respectively. The results indicated that at harvest time, the residues of famoxadone in grape were well below the EU’s maximum residue level (2 mg kg^???1) and was safe to apply in grape.     

Mercury accumulation in fish species from the Persian Gulf and in human hair from fishermen

Total and methylmercury concentrations were assessed in muscle and liver of 141 fish samples from the northern part of the Persian Gulf. All fish samples belonged to five different species: grunt, flathead, greasy grouper, tiger-tooth croaker, and silver pomfret. In addition, Hg and methylmercury were analyzed in scalp hair of 19 fishermen living in the same coastal stations of the Persian Gulf and consuming several fish meals a week. Total mercury concentrations in fish muscle and liver ranged from 0.01 to 1.35 μg g^???1 w.w. and from 0.02 to 1.30 μg g^???1 w.w., respectively. In fish muscle, 3% of the Hg concentrations were higher than 0.5 μg g^???1 w.w., which corresponds to the maximum acceptable WHO level, while 9% were in the range of polluted fish (between 0.3 and 0.5 μg g^???1 w.w.). The highest mercury concentrations in fish muscle were observed in flathead fish at Abadan (average of 0.68 μ g g^???1 w.w.). Methylmercury fractions in fish muscle and liver amount to 34–99% (median 64%) and 24–70% (median 43%), respectively. The mean total Hg concentration in the fishermen’s scalp hair amounted to 2.9 ± 2.2 μ g g^???1, with 68% in the form of methylmercury. Ninety-five percent of the Hg levels in the fishermen’s hair were below 10 μ g g^???1, which is the WHO warning limit. In addition, relationships between the mercury levels in hair, on the one hand, and exposure-related factors such as Hg levels in specific fish species, regional differences, and number of fish meals, on the other hand, are discussed. It appears that a significant correlation for example exists between Hg levels human hair and fish muscle or human hair and age and that mean mercury levels in fish muscle and human hair decreased from western (Abadan) to eastern (Abbas port) coastal sites.     

Identification of sources of elevated concentrations of polycyclic aromatic hydrocarbons in an industrial area in Tianjin, China

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatography equipped with a mass spectrometry detector in 105 topsoil samples from an industrial area around Bohai Bay, Tianjin in the North of China. Results demonstrated that concentrations of PAHs in 104 soil samples from this area ranged from 68.7 to 5,590 ng g^???1 dry weight with a mean of ∑16PAHs 814 ± 813 ng g^???1, which suggests that there exists mid to high levels of PAH contamination. The concentration of ∑16PAHs in one soil sample from Tianjin Port was exceptionally high (48,700 ng g^???1). Ninety-three of the 105 soil samples were considered to be contaminated with PAHs (>200 ng g^???1), and 25 were heavily polluted (>1,000 ng g^???1). The sites with high PAHs concentration are mainly distributed around chemical industry parks and near highways. Two low molecular weight PAHs, naphthalene and phenanthrene, were the dominant components in the soil samples, which accounted for 22.1% and 10.7% of the ∑16PAHs concentration, respectively. According to the observed molecular indices, house heating in winter, straw stalk combustion in open areas after harvest, and petroleum input were common sources of PAHs in this area, while factory discharge and vehicle exhaust were the major sources around chemical industrial parks and near highways. Biological processes were probably another main source of low molecular weight PAHs.     

Coupling of solvent-based de-emulsification dispersive liquid–liquid microextraction with high performance liquid chromatography for simultaneous simple and rapid trace monitoring of 2,4-dichlorophenoxyacetic acid and 2-methyl-4-chlorophenoxyacetic acid

A simple, rapid, and efficient sample pretreatment technique, based on solvent-based de-emulsification dispersive liquid–liquid microextraction (SD-DLLME), followed by high performance liquid chromatography (HPLC) has been developed for simultaneous preconcentration and trace detection of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) in water and urine samples. Some parameters such as acidity of solution, the amount of salt, type, and volume of extraction solvents, type of disperser/de-emulsifier solvent, and its volume were investigated and optimized. Under optimum extraction conditions, the limits of detections (LODs) of this method for MCPA and 2,4-D were 0.2 and 0.6 μg L^?1 (based on 3S_b/m) in water and 0.4 and 1.6 μg L^?1 in urine, respectively. Furthermore, dynamic linear range of this method for MCPA and 2,4-D was 1–300 and 2–400 μg L^?1, repectively. Finally, the applicability of the proposed method was evaluated by extraction and determination of the herbicides in urine and different water samples.     

Occurrence and distribution of polycyclic aromatic carbons in sludges from wastewater treatment plants in Guangdong, China

In this study, the occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) were investigated in six sludge samples collected from Guangdong Province, China. Concentrations of PAHs varying from 2,534.1 to 6,926.6 μg kg^???1 (dry sludge) were observed in three municipal wastewater treatment plants with phenanthrene (Phe), fluoranthene, and pyrene being the main compounds. In addition, 682.6 μg kg^???1 PAHs were detected in one sludge sample from a food processing plant, with fluorene, Phe, and chrysene being the main components. No PAHs were detected in sludge samples obtained from two cosmetic plants. The levels and distributional characteristics of PAHs, polychlorinated biphenyls (PCBs), and polycyclic musks (PMs) from the samples were also compared. The results of this comparison indicated that petrochemical refineries and road traffic played important roles in the PAH loads in sludge, while PMs primarily originated from domestic wastewater and industrial wastewater from cosmetic plants. Finally, the presence of 98.8 μg kg^???1 PCBs in sludge suggested diffusional emission sources from electrical components containing PCBs.     

Natural radioactivity and chemical concentrations in Egyptian groundwater

Measurements of natural radioactivity in drinking water have been performed in many parts of the world, mostly for assessment of the doses and risk resulting from consuming water. A study of the radionuclide and chemical components in groundwater from Beni Suef Governate, Egypt has been carried out. Fifty water samples were analyzed by gamma ray spectroscopy to determine the ²²⁶Ra, ²³²Th, and ⁴⁰K concentrations; major elements, pH, alkalinity, and conductivity were also measured. The specific activity values ranged from 0.008 to 0.040 Bq/l for ²²⁶Ra, from 0.003 to 0.019 Bq/l for ²³²Th, and from 0.025 to 0.344 Bq/l for ⁴⁰K. The annual ingestions of these radionuclides, using local consumption rates (average over the whole population) of 1.5 l day^???1, were estimated to be 8.59, 4.86, and 83.47 Bq year^???1 for ²²⁶Ra, ²³²Th, and ⁴⁰K, respectively. The estimated values and weighted means of these radionuclides compare well with the world average. The estimated effective doses from drinking water were found to be 2.4 ??Sv year^???1 (²²⁶Ra), 1.1 ??Sv year^???1 (²³²Th), and 0.51 ??Sv year^???1 (⁴⁰K). Contribution of these radionuclides to the committed effective dose from 1 year consumption of drinking water is estimated to be only 4%.