Residual behavior of quizalofop ethyl on onion (Allium cepa L.)

Quizalofop ethyl, a phenoxy propionate herbicide, is used for postemergence control of annual and perennial grass weeds in broad-leaved crops in India. The experiments were designed to study the dissipation kinetics of quizalofop ethyl on onion for two seasons. A simple, rapid, and sensitive method for estimation of quizalofop ethyl residues in onion and soil was developed and validated. The recoveries of quizalofop ethyl residues from onion and soil at different spiking level range from 84.81 to 92.68 %. The limit of quantification of this method was found to be 0.01 μg g^?1. The risk assessment through consumption of the onion in comparison to its acceptable daily intake which is an important parameter for the safety of the consumer was also evaluated. Standardized methodology supported by recovery studies was adopted to estimate residues of quizalofop ethyl on onion and soil. The average initial deposits of quizalofop ethyl on onion were observed to be 0.25 and 0.33 mg kg^?1, following single application of the herbicide at 50 g active ingredient (a.i.) ha^?1 during 2009 and 2010, respectively. The half-life values (T _1/2) of quizalofop ethyl on onion crop were worked out to be 0.85 and 0.79 days, respectively, during 2009 and 2010. At harvest time, the residues of quizalofop ethyl on onion and soil were found to be below the determination limit of 0.01 mg kg^?1 following single application of the herbicide at 50 and 100 g a.i. ha^?1 for both the periods.     

Assessment of trace metal concentration in feathers of seabird (Larus dominicanus) sampled in the Florianópolis, SC, Brazilian coast

Cd, Co, Cr, Cu, Mn, Ni, Zn, and Pb were measured in feather samples of adult, subadult, and juvenile of Larus dominicanus, sampled in the Florianólis, SC, in the south of Brazil in December 2005, by flame atomic absorption spectrophotometry. The average of the distribution of Cd concentration in adult feathers (0.072 μg g^???1) was significantly different than that found in juvenile feathers (0.021 μg g^???1). Cu concentration averages were not significantly different between adults (13.30 μg g^???1), subadults (9.67 μg g^???1), and juveniles (13.76 μg g^???1). For adults and juveniles there was significant difference in feather concentrations for Cd, Co, Cr, Ni, and Pb. The distribution of Mn concentration averages in feathers differs between adults (11.36 μg g^???1) and juveniles (1.184 μg g^???1). Ni concentration averages of adults (5.92 μg g^???1) were significantly higher than those of juveniles (2.23 μg g^???1). For Pb, concentration averages were significantly higher in adults (7.53 μg g^???1) than in juveniles (1.47 μg g^???1). The concentration of Co and Cr in juvenile and subadults are statistically different when compared with the adults. In the present study, levels of Cd, Co, Cr, Mn, Ni, Zn, and Pb increased with age. The concentrations of essential trace elements in L. dominicanus were generally comparable to values reported in other studies. With non-essential metals (Cd, Pb, and Ni), in our study, L. dominicanus had lower values than those reported for their northern Atlantic counterparts.     

Occurrence of organochlorine pesticide residues in green mussel (Perna viridis L.) and water from Ennore creek, Chennai, India

Green mussel (Perna viridis) and water samples were collected from Ennore creek, Chennai by seasonal sampling and analyzed for organochlorine pesticide residues (OCPs) like dichloro-diphenyl-trichloroethane (DDT) and its metabolites, isomers of hexachlorocyclohexane (HCH) and endosulfan. These residues were analyzed by using gas chromatograph (GC) with μECD. In the present study, mussel samples showed very low concentrations of OCPs in the statistical order of DDT (5.83 ng g^???1 wet tissue) > endosulfan (2.84 ng g^???1 wet tissue) > HCH (2.34 ng g^???1 wet tissue). Concentrations of OCPs in water samples were in the statistical order of endosulfan (29.21 ng L^???1)?> HCH (17.14 ng L^???1)?> DDT (14.63 ng L^???1). To our knowledge, this is the first report on the seasonal variation of OCPs and especially the quantification of endosulfan in Ennore Creek. The present study recommends that continuous monitoring in Ennore creek is necessary to assess possible impact on human health.     

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.     

Dissipation of flubendiamide residues in/on cabbage (Brassica oleracea L.)

Residues of fubendiamide and its metabolite desiodo flubendiamide were estimated in cabbage and soil using high-performance liquid chromatography with UV–vis detector. The initial deposits of flubendiamide residues on cabbage were found to be 0.16 and 0.31 μg g^?1 following two applications of flubendiamide 20 WG at 12.5 (standard dose) and 25 (double dose) g a.i. ha^?1 respectively at 10-days interval. The half-life values (t _1/2) of flubendiamide on cabbage ranged from 3.4 to 3.6 days. When flubendiamide applied at both the standard and double dose, no detectable residues were found in cabbage and soil at harvest. Thus, a waiting period of 1.63 days was suggested for the safe consumption of flubendiamide-treated cabbage. These data could provide guidance for the proper and safe use of this pesticide on cabbage crops in India.     

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.     

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.     

Mercury accumulation in caged Corbicula: rate of uptake and seasonal variation

The uptake and seasonal fluctuations of total mercury were followed in caged and uncaged Asiatic clams, Corbicula fluminea, over a 1-year period in South River, Virginia. Mercury was rapidly accumulated in clams transplanted from a nominally uncontaminated site into cages on the contaminated South River, reaching 0.99 μg g^???1 dry mass within the first month. Resident clams moved to cages had higher mercury contents after the first month (2.04 μg g^???1 dry mass) and at all subsequent times in the study. Large monthly fluctuations in mercury were noted for both resident caged and transplant caged clams with a notable peak occurring in early spring (4.31 μg g^???1 dry mass in resident caged clams). Tissue mass of caged clams steadily increased through the winter and early spring. Adjustment of mercury concentrations for tissue mass changes indicated that the changes in mercury contents were primarily due to uptake/release rather than changes in tissue mass (concentration/dilution). The present study demonstrates the utility of using caged Corbicula as mercury biomonitors and illustrates the importance of accounting for large, short-term changes of mercury content in Corbicula when designing long-term biomonitoring studies.     

Dissipation kinetics and assessment of processing factor for chlorpyrifos and lambda-cyhalothrin in cardamom

The dissipation kinetics and method for estimation of residues of chlorpyrifos and lambda-cyhalothrin in cardamom were studied and developed. The limit of detection and limit of quantitation arrived for the compounds were 0.01 and 0.025 μg?g^?1, respectively. Gas chromatographic response of chlorpyrifos and lambda-cyhalothrin residues was linear in the range of 0.01–0.50 μg?g^?1 and the mean recovery obtained was 97.3 % for chlorpyrifos and 98.9 % for lambda-cyhalothrin with satisfactory relative standard deviation values. The mean initial residues of chlorpyrifos applied at a concentration of 0.05 % in cardamom was 2.5 μg?g^?1 and the residue was 8.1 μg?g^?1 after processing, with a processing factor of 3.24, while lambda-cyhalothrin when applied at 0.0025 % resulted in initial residues of 1.63 μg?g^?1 that magnified to 4.86 μg?g^?1 on curing, with a processing factor of 2.98. The half-life of chlorpyrifos was in the range of 5.1–5.24 days while that of lambda-cyhalothrin was in the range of 4.40–4.55 days. The processing factor arrived at in the above experiment lead to the conclusion that the residues of chlorpyrifos got magnified to 3.24–3.68 times and that of lambda-cyhalothrin got magnified to 2.98–3.46 times of initial residues, consequent to loss of weight due to dehydration during curing.     

Determination of imazosulfuron persistence in rice crop and soil

Imazosulfuron is a new post-emergence sulfonylurea herbicide. It is highly active at low application rates to control annual and perennial broad-leaf weeds and sedges in rice. There is increasing concerned about the persistence of pesticide residues in soils, crop produce and subsequent contamination of groundwater. Thus persistence of imazosulfuron residues under field condition was evaluated. Imazosulfuron was applied at 30, 40, 50 and 60 a. i. g ha ⁻¹ rates, 4 days after transplanting of rice as post-emergence herbicide. Soil and plant samples treated with imazosulfuron were collected at 60, 90 and 120 days after herbicide application and analyzed for residues. Rice grains and straw samples were sampled at harvest (120 days). Residues of imazosulfuron in soil were not found after 90 and 120 DAS (days after spraying). Rice grains contained 0.006, 0.009 μg g⁻¹ residues at 50 and 60 g ha ⁻¹ application rates. 0.009 and 0.039 μg g⁻¹ residues of imazosulfuron were detected at 50 and 60 g/ha rates respectively in rice straw. Residues of imazosulfuron were not detected applied at 30 and 40 g ha⁻¹ in rice grains and straw, respectively and can be safely applied to the transplanted rice.     

Determination of some organochlorine pesticide residues in honeys from Konya, Turkey

In this study, 24 organochlorine pesticide residues in 109 different honey samples collected from stores and open markets in Konya, Turkey were analyzed by gas chromatography-electron capture detection. Aldrin, cis-chlordane, trans-chlordane, oxy-chlordane, 2,4^′ -DDE, and 4,4^′ -DDE were found in all honey samples. The mean value was 0.0540 μg g^???1 for oxy-chlordane. In the 55 samples of 109, levels of organochlorine pesticide residues of oxy-chlordane were determined as higher than those of Turkish Alimentarius Codex maximum residual limits (MRLs). Other organochlorine pesticide residues also exceeded MRLs except for cis-heptachlor epoxide and α-hexachlorocyclohexane. Since all of the honey samples are found contaminated and most of these samples exceeded MRLs, a control of organochlorine pesticide residues in honey is necessary for consumer health.     

Mercury in freshwater, estuarine, and marine fishes from Southern Brazil and its ecological implication

In this study, we measured the mercury concentration in 27 different fish species with high commercial value. Samples were taken from a region characterized by the diversity of aquatic environments. Mercury concentration in marine fish species varied from 30.4 to 216 ng g^???1, while in estuarine species, it varied from 12.4 to 60.3 ng g^???1. Compared to mercury concentration in marine species, none of the specimens from estuarine environment has reached a mercury concentration of 100 ng g^???1. However, mercury concentrations in species from the freshwater Patos lagoon are remarkably higher (15.3 to 462 ng g^???1) than those from the estuarine or marine region. Even though mercury concentrations in these fish species did not exceed the maximum level (500 ng g^???1) allowed by WHO for human consumption, they represent the main food source for sea birds and mammals coming from South Pole during their migration period.     

Comparative study based on sediment characteristics and macrobenthic communities in two Italian lagoons

The aims of this study were to analyse sediment characteristics and macrobenthic assemblages in two very close Italian coastal lagoons (Lesina and Varano) and to assess the different behaviour between the two basins and the relationship between sediment matrix and benthic organisms within and between the two lagoons. The comparative study was performed in July 2007 at 13 sampling sites in Lesina lagoon and 15 sites in Varano basin for sediment grain size, total organic carbon (TOC), total nitrogen (TN), total phosphorus (TP) and macrobenthic structure analyses. Both lagoons were generally dominated by fine-grained sediments (clay and silt components). The average contents of TOC and TN measured in Lesina was higher than in Varano (3.31% vs 2.52% for TOC and 5,200 μg·g^???1 vs 3,713 μg·g^???1 for TN); in contrast, the TP was lower (540 μg·g^???1 vs 620 μg·g^???1). Based on macrobenthic community patterns, the central zone in Varano lagoon and the eastern area in Lesina lagoon were characterised by the lowest abundance (168.7 ind·m^???2 and 503.2 ind·m^???2, respectively) and by the lowest number of species, as highlighted by the diversity indices (Shannon–Wiener, H ^′ range was 0.47–1.45 for Lesina and 0.00–1.68 for Varano; Margalef species richness, d range was 0.00–1.67 for Lesina lagoon and 0.00–2.38 for Varano basin). Ordination diagrams suggested an influence of marine and freshwater inputs on the sediment distribution in Varano lagoon and on macrobenthic assemblages in Lesina lagoon.     

Presence, distribution, and origins of polycyclic aromatic hydrocarbons (PAHs) in sediments from Bahía Blanca estuary, Argentina

This paper is the first comprehensive survey of polycyclic aromatic hydrocarbons (PAHs) in coastal sediments in Bahia Blanca, Argentina, and provides useful information on their levels of concentration, composition, and sources of these pollutants. The total concentrations of PAHs ranged from 15 to 10,260 ng g^???1. The highest contents (mean 3,315 ng g^???1) of total PAHs in marine sediments were found in the inner channels of the estuary, while the lower ones (204 ng g^???1) belong to samples collected far away from contamination sources. The global average recorded in this study (1,500 ng g^???1) indicates that the studied area lies within the referenced category of industrialized coastal zones under chronic pollution. The diagenetic PAH contribution was found to be negligible at all sampled locations; however, the calculation of molecular ratios determined an overimposition of pyrolitic PAHs over the petrogenic input. Further, the use of principal components analysis (PCA) clearly separated ring group compounds and enabled the determination of pyrolitic/combustion PAHs dominancy.     

Arsenic accumulation in lichens of Mandav monuments, Dhar district, Madhya Pradesh, India

Total arsenic in four different growth forms of lichens growing on old monuments in the city of Mandav, Dhar district of Madhya Pradesh, India was analyzed. Among the different growth forms, foliose lichens were found to accumulate higher amounts of arsenic followed by leprose form. The squamulose and crustose form accumulates the lower concentration of arsenic and ranged between 0.46 ± 0.03 and 20.99 ± 0.58 μg g^???1 dry weight, while the foliose and leprose lichens have ranges from 10.98–51.95 and 28.63–51.20 μg g^???1 dry weight, respectively. The substrate having high arsenic ranges also exhibit higher ranges of arsenic on lichens growing on them. The cyanolichens exhibit higher concentration of arsenic than the green photobiont-containing squamulose form. The higher concentration of arsenic was found at site having past mining activities. LSD (1%) shows significant difference for As concentration in lichens thallus between the selected sites and species both.     

Safety evaluation of flubendiamide and its metabolites on cabbage and persistence in soil in different agroclimatic zones of India

Supervised field trials following good agricultural practices were conducted at the research farms of four agricultural universities located at four different agroclimatic zones of India to evaluate the persistence and dissipation of flubendiamide and its metabolite, des-iodo flubendiamide, on cabbage. Two spray applications of flubendiamide 480 SC of standard and double dose at the rate of 24 and 48 g a.i. ha^?1 were given to the crop at a 15-day interval, and the residues of flubendiamide 2 h after spray were found in the range of 0.107–0.33 and 0.20–0.49 mg kg^?1 at respective doses. Residue of des-iodo flubendiamide was not detected in any cabbage sample during study period. No residues were found in the soil samples collected from all treated fields after 15 days of application. On the basis of data generated under All India Network Project on Pesticide Residues, a preharvest interval (PHI) of 10 days has been recommended, and the flubendiamide 480 SC has been registered for its use on cabbage by Central Insecticide Board and Registration Committee, Ministry of Agriculture, Government of India. The maximum residue limit (MRL) of flubendiamide on cabbage has been fixed by the Ministry of Health and Family Welfare, Government of India, under Food Safety Standard Authority of India as 0.05 μg/g after its risk assessment.     

Persistence and effect of processing on reduction of fipronil and its metabolites in chilli pepper (Capsicum annum L.) fruits

A single laboratory UPLC-MS/MS method was developed and validated for the estimation of fipronil and its metabolites in fresh and dry chilli pepper fruits. Dissipation of fipronil on chilli fruits was studied following the application of fipronil (Jump 80 WG) at 40 and 80 g active ingredient (a.i.) ha^?1 in the fruiting stage of the crop. The initial deposits of total fipronil on fresh chilli fruits at single and double dose application were 0.69 and 1.43 μg g^?1, respectively, and were dissipated to below quantitation level at 27 days after application. The half-life of fipronil at single and double dose in fresh chilli pepper was 4.22 and 4.32 days and the waiting period was 25.9 and 30.6 days, respectively. Processing factor due to sun drying was calculated by measuring fipronil residues in dry chilli fruits, and it ranged from 2.96 to 3.50 during 0 to 21st day after application. Among the metabolites of fipronil, fipronil desulfenyl and fipronil sulfone had maximum residues in fresh and dried chilli, respectively, followed by fipronil sulfide. Dipping in solutions of tamarind, turmeric, vinegar and slaked lime and wet scrubbing could remove more than 90 % of fipronil residues in fruits.     

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.     

Occurrence and distribution of organochlorine pesticides (DDT and HCH) in sediments from the middle and lower reaches of the Yellow River, China

Sediments used in this study were selected from 23 stations in the middle and lower reaches of the Yellow River and its tributaries in November 2005. The levels and distribution patterns of selected organochlorine pesticides (OCPs = p,p ^′-DDT, o,p ^′-DDT, p,p ^′-DDE, p,p ^′-DDD, α-, β-, γ-, and δ-HCH) in samples were investigated by analysis of gas chromatography coupled with micro-electronic capture detector. Concentration of OCPs in the sediments from the Yellow River ranged from 0.05 to 5.03 ng g^???1 (mean, 1.02 ng g^???1) for ∑DDT, 0.09–12.89 ng g^???1 (mean, 1.08 ng g^???1) for ∑HCH. The concentration distribution of ∑DDT and ∑HCH varied significantly with different sampling station, indicating their different contamination sources. Composition analyses demonstrated that residues of DDTs in sediments came from the previous inputs of organochlorine pesticides, while β-HCH and γ-HCH significantly dominated in the sediments for HCHs.     

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.