Electrochemical study of the fungicide acibenzolar-s-methyl and its voltammetric determination in environmental samples

The electrochemical behavior of new generation fungicide acibenzolar-s-methyl (S-methyl 1,2,3-benzothiadiazole-7-carbothioate, ASM) on the hanging mercury drop electrode (HMDE) was investigated using square wave adsorptive stripping voltammetry. This method of determination is based on the irreversible reduction of ASM at the HMDE. The well-defined ASM peak was observed at ?0.4 V (vs. Ag/AgCl) in BR buffer at pH 2.2. The reduction peak current was proportional to concentration of ASM from 1.0 × 10^?8 to 6.0 × 10^?8 mol L^?1 with detection and quantification limit 3.0 × 10^?9 and 1.0 × 10^?8 mol L^?1, respectively. The applicability of the developed method for analysis of spiked samples of tap water, river water, and soil is illustrated. The effect of adsorption on the mercury electrode was studied in detail using the AC impedance method. Possible interferences with other common pesticides and heavy metal ions were examined. Clarification of the electrode mechanism was made using cyclic voltammetry (CV) technique.     

Distribution and relationships of trace metals in soft tissue,byssus and shells of Mytilus edulis trossulus from the southern Baltic

Concentrations of Hg, Cd, Pb, Ag, Cu, Zn, Cr, Ni, Co, Mn, and Fe in soft tissues, shells and byssus of blue mussel (Mytilus edulis trossulus) from 23 sites along the Polish coast of the Baltic Sea were determined by AAS method. Byssus, as compared with the soft tissue, concentrated more effectively Pb, Cu, Cr, and especially Ag, Ni, Mn and Fe, moderately Hg and Zn and less effectively Cd. Significant inter-regional and inter-size differences in metal concentrations in both soft tissues and byssus were recorded. Highly significant correlations (P<0.01, P<0.05) were observed between tissue and byssal concentrations of Cd, Pb, Ni and Ag. Factor analysis showed clear separation of both the tissue and byssi samples based on their geographic distribution, possibly reflecting a different rate of deposition of clay minerals at the head of the Pomeranian Bay and the Gulf of Gdańsk. The Pomeranian Bay differs from the Gulf of Gdańsk in respect to geological structure of bottom sediments as a substrata for the M. edulis trossulus as well as in relation to various sources of metallic pollutants. From the data obtained in the present study and those reported previously the soft tissue and especially byssus of M. edulis, in contrast to shells, appear to be a significantly better bioindicator for identification of coastal areas exposed to metallic contaminants.     

Relationships and bioaccumulation of chemical elements in the Baikal seal (Phoca sibirica)

Concentrations of Al, Ba, Cd, Cu, Fe, Mn, Mo, Si, Sr, Zn, Ca, K, Mg, Na and P in the livers of Baikal seal, plankton, zoobenthos, and fish, constituting the food sources for the seals, were determined by ICP-MS and ICP-AES. The accumulation of elements in the liver of seals, affected by internal and external (environmental) factors, was assessed by multidimensional (ANOVA, FA) and correlation analyses. FA has enabled identification of abiotic and biotic factors responsible for the accumulation of elements in the livers of Baikal seals. Significant influence of sex and development stage of the seals analysed on hepatic concentrations of some elements was found. The observed differences in element concentrations between pups, males and females could be attributable to the reproductive cycle of this species. ANOVA showed differences in concentrations of Fe, Zn, Cu and Cd in seals from the three separate basins of the lake. BMFs suggest biomagnification of Fe and Zn in the fish-seal trophic link.     

Blood clinical-chemical parameters and feeding history in growing Japanese quail (Coturnix japonica) chicks exposed to Tris(1,3-dichloro-2-propyl) phosphate and Dechlorane Plus in ovo

Blood clinical-chemical parameters (BCCPs) are used to investigate physiological consequences attributed to exposure to anthropogenic stressors, such as exposure to Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and Dechlorane Plus (DP), which are flame retardants (FRs), on avian health. Japanese quail (Coturnix japonica) were used as a model species to investigate individual and mixture effects of both FRs by injecting different concentrations (5, 50, or 500 ng/µL) of either of these compounds as well as a 1:1 mixture of both into fertilized eggs. To estimate post-hatching effects, 18 BCCPs were evaluated from 101 chicks at day 14. Albumin levels were found to be significantly elevated in the groups exposed to high doses of TDCIPP alone as well as a mixture of TDCIPP and DP. However, during the course of the study, the initial corn-based feed had to be substituted by a fishmeal-based feed. The 8 days consuming the new feed played a significant role on 12 of 18 BCCPs measured. Consequently, it is recommended that dietary habits need to be considered when investigating the physiological impact of contaminants using BCCPs as biomarkers in growing nestlings both in controlled in vivo and field experiments.     

Square wave adsorptive stripping voltammetric determination of diazinon in its insecticidal formulations

The pesticide diazinon was determined in its insecticidal formulations by square wave adsorptive stripping voltammetry. The method of its determination is based on the irreversible reduction reaction at the hanging mercury drop electrode. The optimal signal was detected at -1.05?V vs. Ag/AgCl in Britton-Robinson buffer at pH?4.4. Various parameters such as pH, buffer concentration, frequency, amplitude, step potential, accumulation time, and potential were investigated to enhance the sensitivity of the determination. The highest response was recorded at an accumulation potential -0.4?V, accumulation time 60?s, amplitude 75?mV, frequency 100?Hz, and step potential 5?mV. The pesticide electrochemical behavior was considered under experimental conditions. The electroanalytical procedure enabled diazinon determination in the concentration range 4.0?×?10(-8)-3.9?×?10(-7)?mol?L(-1) in supporting electrolyte. The detection and quantification limit were found to be 1.1?×?10(-8) and 3.7?×?10(-8)?mol?L(-1), respectively. The method was applied successfully in the determination of the active ingredients in the insecticidal formulations Diazinon 10GR and Beaphar 275.     

Removal of petroleum pollutants and monitoring of bacterial community structure in a membrane bioreactor

The long-term operational stability (159 d) in removal of organics and ammonia from synthetic wastewater was investigated. The experiment was carried out in two identical plug flow membrane bioreactors (MBR) (each with a submerged A4 Kubota membrane) operated under aerobic conditions. The vacuum distillate of a crude oil fraction in the emulsified state, which was used to model the petroleum pollutants, was added into the feed medium. The performance of biological treatment was evaluated by physicochemical analyses such as nitrogen forms, COD, and BOD. Additionally, monitoring of PAHs in the wastewaters was performed using HPLC-diode array detector. Moreover, the community structure of bacteria was analyzed by polymerase chain reaction-denaturing gradient gel electrophoresis. The MBR treatment was very effective with reduction by more than 90% of COD and Total Organic Carbon. Nearly complete removal of petroleum originated non-polar micropollutants was observed. The influence of the highest dosage of petroleum pollutants (1000 μLL(-1)) on the bacterial community was noted.     

Interspecific distribution and co-associations of chemical elements in the liver tissue of marine mammals from the Polish Economical Exclusive Zone, Baltic Sea

Concentrations of Al, B, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hg, Li, Mn, Mo, Ni, Pb, Se, Si, Sr, Tl, V, Zn, Ca, K, Mg, Na and P in the livers of marine mammals obtained from by-catches or stranded on beaches on the Polish Baltic coast were determined by ICP-MS or ICP-AES and CV AAS. Interspecific diversity with respect to the contents of these elements was found in cetaceans and pinnipeds. The diverse Cd contents in the livers of these mammals can be attributed to the variable concentrations of this element in their food. Mercury was correlated with age and can reach high concentration associated with higher level of Se in older specimens. No significant relationships were found between concentration of the chemical elements studied and nutritional status/condition of the Baltic harbour porpoises as well as between their concentration in specimens from the Gulf of Gdańsk and open Baltic. It seems that the nutritional and health status of the specimens studied is generally enough good since the specimens studied were not stranded on beach because of starvation but almost incidentally caught in salmon gill nets. Strong correlations were found between the macroelements analysed, i.e. for the Ba-Ca-Sr, Ca-K, Ca-Mg, Mg-P, Zn-Mg and Zn-P assemblies. Significantly higher content of Al was found in males of harbour porpoises.     

Do salmon farms increase the concentrations of mercury and other elements in wild fish?

Earlier assessments have suggested that salmon farms may act as a source of mercury (Hg) and other elements in local marine environments. In this study, we measured 30 elements in the livers of demersal Atlantic cod (Gadus morhua) and pelagic saithe (Pollachius virens) caught in association with salmon farms (farm associated [FA]; n = 75) or at reference locations (control; n = 80) in three regions throughout the latitudinal extent of Norway (59-70° N). Concentrations of most elements (24 of 30) were higher (20-70%) in cod compared to saithe. In particular, Hg was 6.8 times higher in cod than saithe. Nine elements were significantly different between FA saithe and control saithe, but only four (Hg, U, Cr and Mn) were highest in FA saithe, and this pattern was only detected consistently across all locations for Hg. Thirteen elements differed in concentration between FA cod and control cod, but only three elements (U, Al and Ba) were higher in FA cod than controls, and this pattern was only detected consistently across all locations for Al. After controlling for a set of potentially confounding variables, the estimated concentrations of Hg in saithe livers were ～80% higher in FA fish compared to controls. In contrast, Hg concentrations were ～40% higher in control cod compared to FA cod. Our results do not support the notion that salmon farms in general increase the concentrations of potentially harmful elements in wild fish, and the distribution of Hg and other elements in cod and saithe in Norwegian coastal waters may be more influenced by habitat use, diet, geochemical conditions and water chemistry.     

Near-road multipollutant profiles: associations between volatile organic compounds and a tracer gas surrogate near a busy highway

This research characterizes associations between multiple pollutants in the near-road environment attributed to a roadway line source. It also examines the use of a tracer gas as a surrogate of mobile source pollutants. Air samples were collected in summa canisters along a 300 m transect normal to a highway in Raleigh, North Carolina for five sampling periods spanning four days. Samples were subsequently measured for volatile organic compounds (VOCs) using an electron capture gas chromatograph. Sulfur hexafluoride (SF6) was released from a finite line source adjacent to the roadway for two of the sampling periods, collected in the canisters and measured with the VOCs. Associations between each VOC, and between VOCs and the tracer, were quantified with Pearson correlation coefficients to assess the consistency of the multi-pollutant dispersion profiles, and assess the tracer as a potential surrogate for mobile source pollutants. As expected, benzene, toluene, ethylbenzene, and m,p- and o-xylenes (collectively, BTEX) show strong correlations between each other; further BTEX shows a strong correlation to SF6. Between 26 VOCs, correlation coefficients were greater than 0.8, and 14 VOCs had coefficients greater than 0.6 with the tracer gas. Even under non-downwind conditions, chemical concentrations had significant correlations with distance. Results indicate that certain VOCs are representative of a larger multi-pollutant mixture, and many VOCs are well-correlated with the tracer gas.     

Analysis and DNA interaction of the profluralin herbicide

Environmental Chemistry Letters - The increasing use of pesticides is a major health issue. There is therefore a need for improved analytical methods and more knowledge on the interaction of...