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%.     

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.     

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.     

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.     

Autocenosis and democenosis as individual- and population-level ecological categories in terms of symbiogenesis and systems approach

According to the basic concept of the theory dealt with in this study, autocenosis, i.e., a self-regulatory host-symbiont system, rather than an individual, is the individual-level unit. Then, democenosis, which is a system of autocenoses, corresponds to the population level. Therefore, natural selection of autocenoses rather than individuals occurs in a democenosis, and auto- and democenoses, rather than “individuals” and “populations,” are components of food chains and webs. However, the symbiotic approach does not exclude the population paradigm and will be developed in parallel with it.     

Polybrominated diphenyl ethers and organochlorine compound levels in brown trout (Salmo trutta) from Andean Patagonia, Argentina

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), DDTs and endosulfan residues were analyzed in muscle, liver, gonads, gills and stomach content of brown trout (Salmo trutta) from the Andean Patagonia. PBDEs, PCBs and DDTs levels were positively correlated with lipid content, while less hydrophobic endosulfans showed a poor correlation. Endosulfan levels were about 99.9% of total contaminant (highest levels in liver 500 × 10³ ng g⁻¹ lipid weight), with α-/β-isomers ratio >1 in all organs. These results are in agreement to the current-use of the technical endosulfan and also suggest acute exposure to this insecticide. Conversely, DDT/DDE ratio reflects fish exposure to old DDT sources, showing a DDE predominance. Gills had the highest levels of DDTs, PCBs and PBDEs, indicating they represent the main uptake pathway for such hydrophobic compounds from water column. PCBs showed the lowest levels in all organs and the PBDEs/PCBs ratios >1 agree with worldwide trends. PBDEs levels in gonads, gills, liver and muscle exceeded 80 ng g⁻¹ (lipid weight) and were higher than other values reported in the Southern Hemisphere. BDE-47 was the predominant congener, suggesting higher bioaccumulation potential and possible brown trout metabolism of higher congeners. Since there is no point source of PBDEs in the region and residues were dominated by lower brominated congeners, atmospheric transport could be the main source of these compounds. This first report of PBDEs levels in fish from Argentina contributes to the knowledge about environmental trends of these persistent organic pollutants (POPs) in remote areas such as the Andean Patagonia.     

Carry-over of dietary organochlorine pesticides, PCDD/Fs, PCBs, and brominated flame retardants to Atlantic salmon (Salmo salar L.) fillets

Information on carry-over of contaminants from feed to animal food products is essential for appropriate human risk assessment of feed contaminants. The carry-over of potentially hazardous persistent organic pollutants (POPs) from feed to fillet was assessed in consumption sized Atlantic salmon (Salmo salar). Relative carry-over (defined as the fraction of a certain dietary POP retained in the fillet) was assessed in a controlled feeding trial, which provided fillet retention of dietary organochlorine pesticides (OCPs), dioxins (PCDD/Fs), polychlorinated biphenyls (PCBs), and brominated flame retardants (BFRs). Highest retention was found for OCPs, BFRs and PCBs (31-58%), and the lowest retentions were observed for PCDD/Fs congeners (10-34%). National monitoring data on commercial fish feed and farmed Atlantic salmon on the Norwegian market were used to provide commercially relevant feed-to-fillet transfer factors (calculated as fillet POP level divided by feed POP level), which ranged from 0.4 to 0.5, which is a factor 5-10 times higher than reported for terrestrial meat products. For the OCP with one of the highest relative carry-over, toxaphene, uptake and elimination kinetics were established. Model simulations that are based on the uptake and elimination kinetics gave predicted levels that were in agreement with the measured values. Application of the model to the current EU upper limit for toxaphene in feed (50 μg kg⁻¹) gave maximum fillet levels of 22 μg kg⁻¹, which exceeds the estimated permissible level (21 μg kg⁻¹) for toxaphene in fish food samples in Norway.