Electrochemical Monitoring of Methylparathion Degradation in an Acid Aqueous Medium in Presence of Cu(II)

Abstract

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o, 4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2–7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH ≤ 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 × 10^?3 s^?1 at pH 2, 5.5 × 10^?3 s^?1 at pH 4 and 9.0 × 10^?3 s^?1 at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

Genotypic Differences in Effects of Cadmium Exposure on Plant Growth and Contents of Cadmium and Elements in 14 Cultivars of Bai Cai

Abstract

Fourteen cultivars of bai cai (Brassica campestris L. ssp. chinensis var. communis) were grown in the nutrient solutions containing 0–0.5 μg mL^?1 of cadmium (Cd) to investigate genotypic differences in the effects of Cd exposure on the plant growth and uptake and distribution of Cd in bai cai plants. The Cd exposure significantly reduced the dry and fresh weights of roots and shoots, the dry weight ratio of shoot/root (S/R), total biomass, and chlorophyll content (SPAD value). Cd concentrations in bai cai ranged from 13.3 to 74.9 μg g^?1 DW in shoots and from 163.1 to 574.7 μg g^?1 DW in roots under Cd exposure, respectively. The considerable genotypic differences of Cd concentrations and accumulations in both shoots and roots were observed among 14 bai cai cultivars. Moreover, Cd mainly accumulated in the roots. Cd also caused the changes of uptake and distribution of nutrients in bai cai and under the influence of cadmium, the concentration of potassium (K) decreased in shoot and increased in root. However, the concentrations of magnesium (Mg), phosphorus (P), manganese (Mn), boron (B), and iron (Fe) increased in shoots and decreased in roots. In addition, Cd exposure resulted in an increase in calcium (Ca), sulphur (S), and zinc (Zn) concentrations in both shoots and roots but had no significant effects on the whole uptake of the examined mineral nutrients except for S.     

Biodegradation of α and β Endosulfan in Soil as Influenced by Application of Different Organic Materials

Abstract

A laboratory pot experiment was conducted to study the effect of amending soil with four different sources of organic matter on the degradation rate of α and β endosulfan isomers. Poultry by-product meal, poultry manure, dairy manure, and municipal solid waste compost were cured, dried, ground (<1 mm) and thoroughly mixed with a calcareous soil at a rate of 2% and placed in plastic pots. Endosulfan was added at the rate of 20 mg kg^?1. The moisture level was kept near field capacity and the pots were kept at room temperature. Soil sub-samples, 100 g each, were collected from every pot at days 1, 8, 15, 22, 29, 43, and 57 for the measurement of endosulfan isomers. Endosulfan residues were extracted from the soil samples with acetone. The supernatant was filtered through anhydrous sodium sulphate, 5 mL aliquot was diluted to 25 mL with hexane, mixed well, and then two sub-samples from the filtrates were analyzed for α and β endosulfan isomers by gas chromatography. The results indicated that the half-life (T _½) of α-endosulfan in the poultry by-product meal treatment was 15 days compared to about 22 days in the other treatments. The T _½ of β-endosulfan was 22 days in the poultry by-product meal treatment and followed a bi-phasic pattern, 57 days in the municipal solid waste compost treatment and the extrapolated T _½ was about 115 days for the other three treatments.     

Method Development for Determination of Fluroxypyr in Soil

Abstract

Four methods were developed for the analysis of fluroxypyr in soil samples from oil palm plantations. The first method involved the extraction of the herbicide with 0.05 M NaOH in methanol followed by purification using acid base partition. The concentrated material was subjected to derivatization and then cleaning process using a florisil column and finally analyzed by gas chromatography (GC) equipped with electron capture detector (ECD). By this method, the recovery of fluroxypyr from the spiked soil ranged from 70 to 104% with the minimum detection limit at 5 µg/kg. The second method involved solid liquid extraction of fluroxypyr using a horizontal shaker followed by quantification using high performance liquid chromatography (HPLC) equipped with UV detector. The recovery of fluroxypyr using this method, ranged from 80 to 120% when the soil was spiked with fluroxypyr at 0.1–0.2 µg/g soil. In the third method, the recovery of fluroxypyr was determined by solid liquid extraction using an ultrasonic bath. The recovery of fluroxypyr at spiking levels of 4–50 µg/L ranged from 88 to 98% with relative standard deviations of 3.0–5.8% with a minimum detection limit of 4 µg/kg. In the fourth method, fluroxypyr was extracted using the solid liquid extraction method followed by the cleaning up step with OASIS® HLB (polyvinyl dibenzene). The recovery of fluroxypyr was between 91 and 95% with relative standard deviations of 4.2–6.2%, respectively. The limit of detection in method 4 was further improved to 1 µg/kg. When the weight of soil used was increased 4 fold, the recovery of fluroxypyr at spiking level of 1–50 µg/kg ranged from 82–107% with relative standard deviations of 0.5–4.7%.     

Salmonella Enterica Serovar Typhimurium HilA-LacZY Fusion Gene Response to Iron Chelation or Supplementation in Rich and Minimal Media

Abstract

Virulence expression of Salmonella enterica serovar Typhimurium under iron limited condition was measured by β-galactosidase (β-gal) assay using a hilA-lacZY fusion strain and calculated as Miller units. hilA-lacZY β-galactosidase assays were performed in brain heart infusion (BHI) and minimal media (M9), after iron chelation with 2, 2-dipridyl and iron-supplementation respectively. Before performing virulence assays, concentrations of iron in the media were estimated using ferrozine. Iron content was found to be more in BHI (42.6 µg dL^?1) as compared to M9 (10.03 µg dL^?1). β-gal activity of Salmonella Typhimurium in BHI was generally less than that observed in M9. After exposure to various combinations of iron chelator in BHI, hilA-lacZY activity only increased at the highest concentration of chelator (200 µM) but decreased in M9 media for all iron concentrations when compared to controls with no iron amendment. These results indicate that iron availability may influence S. Typhimurium hilA expression.     

Detection of transfluthrin and metofluthrin genotoxicity in the ST cross of the Drosophila Wing Spot Test

In this study, different concentrations of transfluthrin and metofluthrin have been assayed for genotoxicity by using the Wing Spot Test on Drosophila melanogaster. Standard cross was used in the experiment. Third-instar larvae that were trans-heterozygous for the two genetic markers mwh and flr³ were treated at different concentrations (0.0103 mg mL⁻¹, 0.103 mg mL⁻¹ for transfluthrin and 6 μg mL⁻¹, 60 μg mL⁻¹ for metofluthrin) of the test compounds. Feeding ended with pupation of the surviving larvae and the genetic changes induced in somatic cells of the wing’s imaginal discs lead to the formation of mutant clones on the wing blade. Results indicated that two experimental concentrations of transfluthrin and 60 μg mL⁻¹ metofluthrin showed mutagenic and recombinogenic effects in both the marker-heterozygous (MH) flies and the balancer-heterozygous (BH) flies.     

Simulation of a Hazardous and Noxious Substances (HNS) spill in the marine environment: Lethal and sublethal effects of acrylonitrile to the European seabass

Despite the extensive maritime transportation of Hazardous and Noxious Substances (HNS), there is a current lack of knowledge on the effects posed by HNS spills on the marine biota. Among the HNS identified as priority, acrylonitrile was selected to conduct ecotoxicological assays. We assessed the acute and subletal effects of acrylonitrile in seabass, followed by a recovery phase to simulate the conditions of a spill incident. The work aimed at testing a broad range of biological responses induced by acrylonitrile. Sublethal exposure to the highest two doses increased the fish mortality rate (8.3% and 25% mortality in 0.75 and 2 mg L⁻¹ acrylonitrile concentrations), whereas no mortality were observed in control and 0.15 mg L⁻¹ treatments. Additionally, important alterations at sub-individual level were observed. Acrylonitrile significantly induced the activities of Catalase– CAT and Glutathione S-Transferase – GST; and the levels of DNA damage were significantly increased. Conversely, Superoxide Dismutase– SOD – activity was found to be significantly inhibited and no effects were found on Lipid Peroxidation– LPO and ethoxyresorufin O-deethylase – EROD – activity. Following a 7 d recovery period, the levels of CAT, GST and EROD fell to levels at or below those in the control. In the 2 mg L⁻¹ group, SOD remained at the levels found during exposure phase. This study has gathered essential information on the acute and subletal toxicity of acrylonitrile to seabass. It also demonstrated that 7 d recovery allowed a return of most endpoints to background levels. These data will be useful to assist relevant bodies in preparedness and response to HNS spills.     

Evaluation of food chain transfer of the antibiotic oxytetracycline and human risk assessment

There has been recent concern regarding the possibility of antibiotics entering the aquatic food chain and impacting human consumers. This work reports experimental results of the bioconcentration of the antibiotic oxytetracycline (OTC) by the Asian watermeal plant (Wolffia globosa Hartog & Plas) and bioaccumulation of OTC in watermeal and water by the seven-striped carp (Probarbus jullieni). They show, for the first time, the extent to which OTC is able to transfer from water to plant to fish and enter the food chain. The mean bioconcentration factor (dry weight basis) with watermeal was 1.28 × 10³ L kg⁻¹. Separate experiments were undertaken to characterize accumulation of OTC by carp from water and watermeal. These showed the latter pathway to be dominant under the conditions employed. The bioconcentration and biomagnification factors for these processes were 1.75 L kg⁻¹ and 2 × 10⁻⁴ kg g⁻¹ respectively. Using an aqueous concentration range of 0.34–3.0 μg L⁻¹, hazard quotients for human consumption of contaminated fish of 1.3 × 10⁻² to 1.15 × 10⁻¹ were derived.     

Quantification of the interactions between Ca,Hg and extracellular polymeric substances (EPS) of sludge

The interactions between metals (Ca²⁺ and Hg²⁺) and extracellular polymeric substances (EPS) extracted from the aerobic and anaerobic sludge in wastewater treatment reactors were investigated using a combination of zeta potential measurement and 3-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy with parallel factor (PARAFAC) analysis. Results show that Ca²⁺ had no substantial effects on the EEM fluorescence spectra of the EPS, but their zeta potentials increased with the increasing Ca²⁺ dosage. However, Hg²⁺ had a significant effect on the EEM fluorescence spectra of the EPS, while their zeta potentials seemed not to be affected by the dose of Hg²⁺. The interactions between Hg²⁺ and EPS were elucidated using the fluorescence quenching with PARAFAC analysis, while the interactions between Ca²⁺ and EPS were evaluated by the zeta potential technique. The binding constants for Hg²⁺ and EPS were two orders of magnitude higher than those for Ca²⁺ and EPS, suggesting that the binding mechanisms between Ca²⁺ and EPS were different from those between Hg²⁺ and EPS. The results might be useful for understanding the roles of EPS in bacterial self-protection against heavy metals and the aggregate formation mechanisms through ionic bridging interactions.     

Residues of persistent organic pollutants in frequently-consumed vegetables and assessment of human health risk based on consumption of vegetables in Huizhou,South China

Concentrations of 16 polycyclic aromatic hydrocarbons (PAHs), 16 phthalate esters (PAEs), eight organochlorine pesticides (OCPs) and seven polychlorinated biphenyls (PCBs) in 17 frequently-consumed varieties of vegetables collected from 48 sites in Huizhou were measured. Concentrations of PAHs and PAEs of leafy vegetables were higher than those of gourd and fruit vegetables but it was the opposite for OCPs and PCBs. A questionnaire of 450 local residents on vegetable consumption showed that the total vegetable ingested rates of females and males were 278.80 g person⁻¹ d⁻¹ and 282.92 g person⁻¹ d⁻¹, respectively. The weight-specific daily intakes of pollutants by females were higher than those by males because of differences in body weight. Twenty-seven pollutants were used to assess the potential risk to human health by calculating target hazard quotient (THQ) values. Results showed that the risk to females was higher than for males. OCPs were the major contributors to the risk for both females and males. The main risks were from consumption of eggplant, Chinese lettuce and luffa and were significantly related to the contents of di-nonyl phthalate, β-hexachlorocyclohexane, γ-hexachlorocyclohexane, p,p-dichlorodiphenyltrichloroethane and p,p-dichlorodiphenyl dichloroethane in vegetables. Although the THQ values induced by individual pollutants were relatively low, the total THQ values induced by 27 pollutants were above 1 in some administrative regions of Huizhou, which might give cause for concern.