Parts-per-trillion LC-MS(Q) analysis of herbicides and transformation products in surface water

The goal of this study was to develop a robust method of analyzing surface water samples for S-triazine herbicides, chloroacetanilide herbicides, and their transformation products (TPs) using solid-phase extraction (SPE) followed by liquid chromatograph-mass spectrometry (LC-MS) with electrospray ionization (ESI) by in-source collision-induced dissociation (ISCID) capability of an orthogonal electrospray ionization probe on a single quadrupole LC-MS system. The method developed here met the goals of the study and yielded estimated method detection limits (EMDLs) averaging 0.3 ± 0.1 ng L(-1) for S-triazines and their TPs and 0.7 ± 0.4 ng L(-1) for chloroacetanilides and TPs. Spiked filtered river water yielded SPE recoveries ranging from 94.2 % ± 4.8 % for S-triazines and TPs after eliminating three compounds with less that 65 % recovery from analysis and 95.9 % ± 19 % for chloroacetanilides and their TPs. The method was field-tested with filtered water samples collected from four sites over a four-month period. Detectible values of S-triazines and TPs ranged from 0.3 to 1540 ng L(-1) with a mean of 79.3 and a median of 19.4 ng L(-1). Detectible values for chloroacetanilides and TPs ranged from 0.31 to 3780 ng L(-1) with a mean of 252 and a median of 25.6 ng L(-1). An additional goal was to determine if the method was useful for microbial degradation studies using native bacterial communities. The bacteria transformed atrazine (2-chloro-4-ethylamino-6-isopropylamino-S-triazine) solely into 2-hydroxy atrazine (2-hydroxy-4-ethylamino-6-isopropylamino-S-triazine) with concentrations of 78.4, 63.3 and 32.5 ng L(-1) after 12 days of incubation compared with 6.3 and 7.1 ng L(-1) for control dark and control sunlight respectively.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO(4) plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO(4) plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg(-1), respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

A sensitive monoclonal antibody-based enzyme-linked immunosorbent assay for chlorpyrifos residue determination in Chinese agricultural samples

A monoclonal antibody-based competitive antibody-coated enzyme-linked immunosorbent assay (ELISA) was developed and optimized for determining chlorpyrifos residue in agricultural products. The IC(50) and IC(10) of this ELISA were 3.3 ng/mL and 0.1 ng/mL respectively. The average recoveries in six agricultural products were between 79.5% and 118.0%, with the intra-assay coefficient of variation being less than 8 %. The limit of detection for all tested products was 30 ng/g. To the best of our knowledge, this assay has the best specificity among all the published research on ELISAs for chlorpyrifos.     

Impact of soil quality on elemental uptake by, and distribution in, Colocasia esculenta (Amadumbe), an edible root

In this study the elemental distribution of selected essential (Ca, Mg, Al, Mn, Cu, Fe, Co, Cr, Zn, Ni and Se) and the non-essential (Pb, Hg and As) elements were determined in the bulb and peel of Amadumbe (Colocasia esculenta) samples from eight different sites in KwaZulu-Natal, South Africa. The concentration of Se and As in the soil and in the Amadumbe bulbs were below the detection limit of 0.09 μg g?1. The total and bioavailable concentrations of the elements in conjunction with pH, soil organic matter (SOM) and cation exchange capacity (CEC) were determined in the soil samples from the eight sites. Statistical analysis was done to evaluate the impact of soil quality parameters on the chemical composition of the Amadumbe root. The results show accumulation or exclusion of certain elements by the bulb as evidenced by the noticeable increase or decrease of the concentrations of elements, respectively. Ca and Mg were found to be major elements in the range (2000-12000 μg g?1), whilst Mn, Zn, Fe and Al were found to be minor elements in the range (20-400 μg g?1). A general trend observed was that the plant favours the absorption of Zn over Cu. A positive correlation between Mg & Ca, Cu & Fe and Co & Ni was also observed. Statistical analysis revealed that the plant tended to accumulate Mg, Ca, Co, Cr and Pb whilst it excluded Hg and Fe, to a lesser extent.     

Phytoremediation of a sulphonated azo dye Green HE4B by <Emphasis Type="Italic">Glandularia pulchella</Emphasis> (Sweet) Tronc. (Moss Verbena)

Purpose  

The dyes and dye stuffs present in effluents released from textile dyeing industries are potentially mutagenic and carcinogenic. Phytoremediation technology can be used for remediating sites contaminated with such textile dyeing effluents. The purpose of the work was to explore the potential of Glandularia pulchella (Sweet) Tronc. to decolorize different textile dyes, textile dyeing effluent, and synthetic mixture of dyes.     

Chitosan membranes as sorbents for trace elements determination in surface waters

Purpose  

Chitosan membranes (non-crosslinked, crosslinked, and modified with l-cysteine) were evaluated as sorbents prior to electrothermal atomic absorption spectrometry (ETAAS) determination of total dissolved metal content in surface water samples.     

Investigation on gene transfer from genetically modified corn (Zea mays L.) plants to soil bacteria

Knowledge about the prevalence and diversity of antibiotic resistance genes in soil bacteria communities is required to evaluate the possibility and ecological consequences of the transfer of these genes carried by genetically modified (GM) plants to soil bacteria. The neomycin phosphotransferase gene (nptII) conferring resistance to kanamycin and neomycin is one of the antibiotic resistance genes commonly present in GM plants. In this study, we investigated kanamycin-resistant (Km(R)) and neomycin-resistant (Nm(R)) soil bacterial populations in a 3-year field trial using a commercial GM corn (Zea mays L.) carrying the nptII gene and its near isogenic line. The results showed that a portion (2.3 - 15.6 %) of cultivable soil bacteria was naturally resistant to kanamycin or neomycin. However, no significant difference in the population level of Km(R) or Nm(R) soil bacteria was observed between the GM and non-GM corn fields. The nptII gene was not detected in any of the total 3000 Km(R) or Nm(R) isolates screened by PCR. Further, total soil bacterial cells were collected through Nycodenz gradient centrifugation and bacterial community DNA was subjected to PCR. Detection limit was about 500 cells per gram of fresh soil. Our study suggests that the nptII gene was relatively rare in the soil bacterial populations and there was no evidence of gene transfer from a GM corn plant to soil bacteria based on the data from total soil bacterial communities.     

Lead and cadmium accumulation in anuran amphibians of a permanent water body in arid Midwestern Argentina

Purpose

Heavy metals have been detected in water and sediments from the Embalse La Florida, an artificial lake in the arid region of San Luis province, Argentina, representing one of the few sources of permanent water for reproduction of native anuran species. This study assesses lead (Pb) and cadmium (Cd) concentrations in the anuran species found in this water reservoir as well as differences between compounds, species and sites of collection.

Methods

Adult anuran amphibians were collected on the north and south shores of the Embalse La Florida and Pb and Cd concentrations were measured in whole body homogenates digested using wet ashing techniques.

Results

All individuals of the six species assayed had detectable levels of Pb and Cd that ranged from 1.19 to 5.57 ??g/g dry mass and from 1.09 to 6.86 ??g/g dry mass, respectively. Anuran amphibians collected in the more contaminated south shore accumulated 21% more Cd and 40% more Pb than individuals from the less altered north shore. Cd and Pb accumulation was not significantly correlated with the concentration in water at the site of collection.

Conclusions

Amphibians of the Embalse La Florida accumulate Cd and Pb. Between and within species, differences were detected in Cd and Pb concentrations. Differences in metal concentrations between species, metals, and individuals collected on shores of the Embalse La Florida with different contamination, were detected. Therefore, it is crucial to implement adequate policies to protect amphibians from the accelerated urban development experienced in this location.     

Spatial distribution of ciguateric fish in the Republic of Kiribati

Ciguatera is food poisoning caused by human consumption of reef fish contaminated with ciguatoxins (CTXs). The expanding international trade of tropical fish species from ciguatera-endemic regions has resulted in increased global incidence of ciguatera, and more than 50 000 people are estimated to suffer from ciguatera each year worldwide. The Republic of Kiribati is located in the Pacific Ocean; two of its islands, Marakei and Tarawa, have been suggested as high-risk areas for ciguatera. The toxicities of coral reef fish collected from these islands, including herbivorous, omnivorous and carnivorous fish (24% [n = 41], 8% [n = 13] and 68% [n = 117], respectively), were analyzed using the mouse neuroblastoma assay (MNA) after CTX extraction. The MNA results indicated that 156 fish specimens, or 91% of the fish samples, were ciguatoxic (CTX levels >0.01 ng g⁻¹). Groupers and moray eels were generally more toxic by an order of magnitude than other fish species. All of the collected individuals of eight species (n = 3-19) were toxic. Toxicity varied within species and among locations by up to 10 000-fold. Cephalapholis argus and Gymnothorax spp. collected from Tarawa Island were significantly less toxic than those from Marakei Island, although all individuals were toxic based on the 0.01 ng g⁻¹ threshold. CTX concentrations in the livers of individuals of two moray eel species (Gymnothorax spp., n = 6) were nine times greater than those in muscle, and toxicity in liver and muscle showed a strong positive correlation with body weight. The present study provides quantitative information on the ciguatoxicity and distribution of toxicity in fish for use in fisheries management and public health.     

The effects of dietary nickel on the detoxification enzymes, innate immunity and resistance to the fungus Beauveria bassiana in the larvae of the greater wax moth Galleria mellonella

In this study, we tested the effects of dietary nickel on the activity of glutathione S-transferase (GST), esterases, phenoloxidase, and encapsulation in the haemolymph of larvae of the greater wax moth Galleria mellonella. We also explored the effects of dietary nickel on larval resistance to infection by the fungus Beauveria bassiana. Larvae fed a low dose of nickel (10 μg g⁻¹) had significantly higher GST, phenoloxidase activity and encapsulation responses than controls fed on a nickel-free diet. We also found that larvae fed a sublethal dose of nickel (50 μg g⁻¹) had increased GST, esterase activity and encapsulation rates but decreased phenoloxidase activity. Although, a sublethal dose of dietary nickel enhanced innate immunity, we found that this reduced resistance against the real pathogen. Our results suggest that enhanced immunity and detoxification enzyme activity of insects may not be beneficial to resistance to fungal infection. It appears that there is a trade off between different resistance mechanisms in insects under different metal treatments.