Quantification of pendimethalin in soil and garlic samples by microwave-assisted solvent extraction and HPLC method

A method for the residual pendimethalin in soil and vegetable samples was developed. The method is based on extraction of pendimethalin from samples using microwave-assisted solvent extraction (MASE) with acetone, ethanol, and water as extraction solvent. Extracted pendimethalin samples were analyzed by high-performance liquid chromatography with ultraviolet detector at 240 nm. The MASE parameters, temperature, heating time, and solvent types were optimized with the feasibility of MASE application in the determination of pendimethalin extraction efficiency of pendimethalin from soil and vegetable samples. The maximum temperature that can be used during the heating for MASE is 60°C, where the recovery percentages reached 97%. Linearity for pendimethalin was found in the range of 2?C20 ??g mL^???1 with limits of detection and limits of quantification of 0.059 and 0.17 ??g mL^???1, respectively.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

A study on the phytoaccumulation of waste elements in wetland plants of a Ramsar site in India

Some wetland plant species are adapted to growing in the areas of higher metal concentrations. Use of such vegetation in remediation of soil and water contaminated with heavy metals is a promising cost-effective alternative to the more established treatment methods. Throughout the year, composite industrial effluents bringing various kinds of heavy metals contaminate our study site, the East Calcutta Wetlands, a Ramsar site at the eastern fringe of Kolkata city (formerly Calcutta), India. In the present study, possible measures for remediation of contaminated soil and water (with elements namely, Ca, Cr, Cu, Pb, Zn, Mn, and Fe) of the ecosystem had been investigated. Ten common regional wetland plant species were selected to study their efficiency and diversity in metal uptake and accumulation. Results showed that Bermuda grass (Cynodon dactylon) had the highest total Cr concentration (6,601 ± 33 mg kg^???1 dw). The extent of accumulation of various elements in ten common wetland plants of the study sites was: Pb (4.4?C57 mg kg^???1 dw), Cu (6.2?C39 mg kg^???1 dw), Zn (59?C364 mg kg^???1 dw), Mn (87?C376 mg kg^???1 dw), Fe (188?C8,625 mg kg^???1 dw), Ca (969?C3,756 mg kg^???1 dw), and Cr (27?C660 mg kg^???1 dw) indicating an uptake gradient of elements by plants as Ca>Fe>Mn>Cr>Zn>Cu>Pb. The present study indicates the importance of identification and efficiency of metal uptake and accumulation capabilities by plants in relation to their applications in remediation of a contaminated East Calcutta Wetland ecosystem.     

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.     

Selenium in surface and irrigation water in the Kendrick irrigation district, Wyoming

High selenium (Se) concentrations have been found in surface waters in the Kendrick Reclamation Project, Wyoming. Precipitation and irrigation water moving over seleniferous soils are contributing causes, and drought may exacerbate this. This study surveyed Se concentrations and discharges in local surface streams, irrigation drains, and the delivery canal. Sites were sampled monthly and analyzed for Se and total suspended solids (TSS). A completely randomized design with two factors (soil parent material and location, inside or outside irrigation district) was used. Mean Se concentrations were 64 μg L^???1 inside the irrigation district on shale soils, 17 μg L^???1 inside the district off shale soils, 5 μg L^???1 outside the district on shale soils, and 3 μg L^???1 outside the district off shale soils. Correlations between discharge and Se concentrations were generally negative, while correlations between discharge and Se load were generally positive. There was little correlation between load and concentration, and little correlation between TSS and Se. A comparison of Se concentrations in streams and drains showed Se concentrations were significantly higher (p?<?0.001) in streams during the irrigation season, but not in the off-season (p?=?0.515). We conclude that higher discharges decrease Se concentration, but increase load. Conversion from flood to sprinkle irrigation may increase Se concentrations by reducing discharge, but decrease Se loads going into the N. Platte River, and will likely alter the timing and magnitude of flows. Both load and concentration should be considered when implementing Se regulations and standards.     

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.     

A study of background radioactivity level for Canakkale, Turkey

This study assesses the level of background radiation for Canakkale province of northwestern Turkey. Radon concentrations in indoor air were determined using CR-39 nuclear track detectors and ²²²Rn activity was found to be 167 Bq m^???3 (equivalent to an annual effective dose of 4.2 mSv). Measurements of outdoor gamma radiation (of terrestrial and cosmic origin) in air were performed using plastic scintillators, and the average absorbed gamma dose rate was found to be 66.4 nGy h^???1 (corresponding to an annual effective dose of 81.4 μSv). The radionuclide activity concentrations in soil samples collected from the study area were measured through gamma-ray spectrometry, and the average activities were determined as 94.55, 110.4, and 1,273 Bq kg^???1 for the natural radionuclides ²³⁸U, ²³²Th, and ⁴⁰K, respectively, and 19.39 Bq kg^???1 for the fission product ¹³⁷Cs. The natural radioactivity sources resulted in an annual effective dose of 184 μSv. The radioactivity levels of drinking water samples were measured as 0.0599 Bq l^???1 for gross-alpha activity and 0.0841 Bq l^???1 for gross-beta activity using a low-background counting technique (equivalent to an annual effective dose of 12.25 μSv). The results of this study show that the activity levels of radon in air, radionuclides in soil, and alpha activities in drinking water are higher compared to the data available for other Turkish cities and the world averages. On the other hand, the outdoor gamma dose rates in air and beta activities in drinking water are within natural limits.     

Development and application of microwave assisted extraction (MAE) for the extraction of five polycyclic aromatic hydrocarbons in sediment samples in Johannesburg area, South Africa

A microwave-assisted extraction (MAE) method was verified and applied for the extraction of polycyclic aromatic hydrocarbons (PAHs) in sediment samples. Soxhlet extraction was used as the reference method. The optimum MAE was carried out with 20 mL of hexane/acetone (1:1, v/v) mixture in a 1-g sample at 250 W for 20 min. Soxhlet extraction was carried out with 250 mL of dichloromethane:hexane (1:1, v/v) mixture in a 15-g sample for 24 h in a water bath maintained at 60 °C. The collected extracts were both cleaned up, reduced to 1 mL under nitrogen and then injected into an HPLC fluorescence. To increase the sample throughput, simultaneous MAE was performed. The obtained percentage recoveries ranged from 61 to 93 and 88–98 for MAE and SE, respectively. The optimised MAE method was validated using certified reference material. It was then applied to real sediment samples from in and around the greater Johannesburg area. The sediments from Jukskei River were found to be the most polluted while Hartbeespoort Dam sediments were found to be least polluted. The overall order of concentrations for the studied PAHs per site was as follows: Jukskei River?>?Kempton Park?>?Centurion Dams?>?Natalspruit River (PIT)?>?Hartbeespoort Dam.     

Physicochemical characteristics of paper industry effluents��a case study of South India Paper Mill (SIPM)

Pulp and paper mills generate varieties of pollutants depending upon type of the pulping process being used. This paper presents the characteristics of wastewater from South India Paper Mill, Karnataka, India which is using recycled waste paper as a raw material. The raw wastewater consists of 80?C90 mg L^???1 suspended solid and 1,010?C1,015 mg L^???1 dissolved solid. However, pH varied from 5.5?C6.8. The biochemical oxygen demand and chemical oxygen demand ranged from 200?C210 and 1,120?C1,160 mg L^???1, respectively. Aerobic treatment of raw effluent attribute to significant reduction in suspended solid (range between 25 to 30 mg L^???1) and total dissolved solid (range between 360 to 390 mg L^???1). However, pH, temperature, and electrical conductivity were found superior after treatment. Copper, cadmium, iron, lead, nickel, and zinc were found in less quantity in raw effluent and were almost completely removed after treatment. The dendrogram of the effluent quality parameters clearly indicate that South India Paper Mill does not meet Minimal National Standard set by central Pollution Control Board to discharge in agricultural field.     

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.     

Spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Nansi Lake, China

Polycyclic aromatic hydrocarbons (PAHs) were measured in surface sediments and dated core sediments from the Nansi Lake of China to investigate the spatial and temporal distribution characteristics. The concentrations of 16 kinds priority PAH compounds were determined by GC-MS method. And ²¹⁰Pb isotope dating method was used to determine the chronological age of the sediment as well as the deposition rate. The results indicated that the total PAHs concentration ranges in surface and core sediment samples were 160 ~32,600 and 137 ~ 693 ng/g (dry wt.), respectively. The sediment rate and the average mass sedimentation were calculated to be 0.330 cm·year^???1 and 0.237 g·cm^???2·yr^???1 and the sediment time of the collected core sample ranged from 1899 to 2000. The peak of PAH concentrations came at recent years. The source analysis showed PAHs mainly came from the contamination of low temperature pyrogenic processes, such as coal combustion. The PAHs concentrations were lower than ERL and LEL values for most collected samples. However, in several surface sediment samples especially in estuary sites, the PAHs concentrations were not only higher than ERL and LEL values, but also higher than ERM values.