Photodegradation of organophosphorus insecticides - investigations of products and their toxicity using gas chromatography-mass spectrometry and AChE-thermal lens spectrometric bioassay

Four organophosphorus compounds: azinphos-methyl, chlorpyrifos, malathion and malaoxon in aqueous solution were degraded by using a 125 W xenon parabolic lamp. Gas chromatography-mass spectrometry (GC-MS) was used to monitor the disappearance of starting compounds and formation of degradation products as a function of time. AChE-thermal lens spectrometric bioassay was employed to assess the toxicity of photoproducts. The photodegradation kinetics can be described by a first-order degradation curve C=C0e(-kt), resulting in the following half lives: 2.5min for azinphos-methyl, 11.6 min for malathion, 13.3 min for chlorpyrifos and 45.5 min for malaoxon, under given experimental conditions. During the photoprocess several intermediates were identified by GC-MS suggesting the pathway of OP degradation. The oxidation of chlorpyrifos results in the formation of chlorpyrifos-oxon as the main identified photoproduct. In case of malathion and azinphos-methyl the corresponding oxon analogues were not detected. The formation of diethyl (dimethoxy-phosphoryl) succinate in traces was observed during photodegradation of malaoxon and malathion. Several other photoproducts including trimethyl phosphate esters, which are known to be AChE inhibitors and 1,2,3-benzotriazin-4(3H)-one as a member of triazine compounds were identified in photodegraded samples of malathion, malaoxon, and azinphos-methyl. Based on this, two main degradation pathways can be proposed, both result of the (P-S-C) bond cleavage taking place at the side of leaving group. The enhanced inhibition of AChE observed with the TLS bioassay during the initial 30 min of photodegradation in case of all four OPs, confirmed the formation of toxic intermediates. With the continuation of irradiation, the AChE inhibition decreased, indicating that the formed toxic compounds were further degraded to AChE non-inhibiting products. The presented results demonstrate the importance of toxicity monitoring during the degradation of OPs in processes of waste water remediation, before releasing it into the environment.     

Genotoxicity screening of the river Rasina in Serbia using the Allium anaphase–telophase test

Evaluation of the presence of genotoxic substances is especially important in rivers that serve as a source of drinking water. Nine water samples collected along the river Rasina in Serbia were analyzed for potential toxic and genotoxic effects using the Allium anaphase-telophase test. Inhibition of root growth relative to the negative control (synthetic water) was observed in all samples. Analysis of the genotoxic potential, through scoring anaphase and telophase aberrations, showed that in seven of the nine samples the level of aberrations was significantly increased relative to the negative control but was lower than that obtained for the positive control (methyl methanesulfonate). Changes in the relation between spindle and chromosome types of aberrations were found in some samples, indicating differences in the potential genotoxic substances present at the analyzed sites. The data, which were obtained from samples collected at the highest level of river water, warn that during periods of low flow the values could reach genotoxic activity. The Allium anaphase-telophase test can be recommended as an monitoring system, that can serve as the first alert for the presence of genotoxic environmental pollutants.     

Determination of selected neonicotinoid insecticides by liquid chromatography with thermal lens spectrometric detection

We studied the analysis of trace amounts of neonicotinoid insecticides by liquid chromatography coupled with a thermal lens spectrometric detector (TLS). This multi-residue analysis method is based on the reversed phase separation on C₁₈ column, isocratic elution and collinear dual beam TLS detection. The insecticides thiamethoxam, imidacloprid, acetamiprid and thiacloprid were detected with retention times of 4.4, 5.7, 6.5 and 8.5 min and limits of quantifications of 50, 89, 10, and 25 μg/L, respectively. The retention times agreed well with those obtained by the same chromatographic method but using a diode-array detector (DAD). The limits of quantifications for imidacloprid were identical in both techniques. However, the limits of quantifications for thiamethoxam, acetamiprid and thiacloprid were up to 8.5 times lower using the TLS detector compared to the diode-array detector. The applicability of the developed procedure was tested on spiked river water and potato samples.     

The Role of Suspended Matter in Assessing the Assimilative Capacity Case Study of Two Estuaries in the Adriatic Sea

Suspended particulate matter has been studied in two Adriatic river mouths to assess its role as a transport vehicle for waste disposal into the Adriatic sea.

The larger of the two, the Adige River (northwestern Adriatic coast, Italy), carries large quantities of solids and builds up a prodelta. the Krka River (eastern Adriatic coast, Croatia, Yugoslavia) is a typical karst river, and carries small quantities of suspended matter, since it drains carbonate terrains.

The resulting disposal of contaminants into the Adriatic sea is largely governed by the adsorption/desorption processes occurring in the estuarine mixing region. Surface adsorption properties, the specific surface area, and the nature and reactivity of the organic film coating determine the partitioning of pollutants between the dissolved and particulate state.

The observations reported point to the key role of particulates in transport of pollutants from land to sea. the concept of the assimilative capacity of the estuarine area requires detailed scientific knowledge on the geochemical behaviour of particulates.

In the Adige River mouth, lead, chromium, zinc, and nickel are accumulated in the prodelta sediments, and thus the loading of the sea with these metals is diminished, whereas in the Krka River estuary, desorption and mobilization of some trace metals occurs.     

LCA of tomato greenhouse production using spatially differentiated life cycle impact assessment indicators: an Albanian case study

The increasing attention to agricultural exports and sustainability issues is driving a surge of interest in the life cycle assessment (LCAs) of greenhouse crop production in Albania. Meanwhile, most of the reported agricultural LCAs tend to be generic without considering regionalized environmental sensitivities. In this study, ReCiPe 2016, covering 18 midpoint indicators and 3 endpoint indicators was used to generate a full-fledged cradle-to-farm gate LCA of greenhouse tomatoes in a typical Albanian farm including spatial differentiation and indicators not covered by contemporary LCAs. The most important midpoint categories per 1 ha identified from foreground–background analysis were global warming (2660.4 kg CO2-eq), stratospheric ozone depletion (0.0308 kg CFC11-eq), particulate matter formation (7.99 kg PM2.5-eq), human health and ecosystem ozone formation (8.47 and 14.95 kg NOx-eq), water consumption (2293.23 m3), and terrestrial acidification (42.28 kg SO2-eq). The application of spatial differentiation resulted in higher impacts with about 21% for particulate matter formation, 12% for human health ozone formation, 134% for ecosystem ozone formation, 19% for terrestrial acidification, and 13% for water consumption. The impacts primarily originated from nitrogen-based fertilizer emissions and diesel fuel with the origin of the impact from nitrous oxide (N2O), ammonia volatilization (NH3), nitrogen oxides (NOx), and non-methane volatile organic compounds (NMVOCs). Water consumption was dominated by irrigation water use. Overall, at the endpoint level, 9% and 24% less cumulative damage to human health and ecosystem quality were calculated with respect to the site-generic analysis primarily from the cause-and-effect chain of water consumption (mainly lower water stress index). This affirms the importance of regional considerations in LCA calculations to reflect the impacts accordingly (i.e., the magnitude of impacts, the most relevant midpoint categories, and their relevance on endpoint level) and increase the possibility of making correct conclusions and sub-optimizations, i.e., increase the discriminating power of LCA.     

Minimization of blank values of the miniature silica gel column

Several methods involving silica gel separations of polychlorinated biphenyls from chlorinated insecticides are already described in literature. Our intention was to find a system of solvent and silica gel of the lowest blank values. The first step was to find a solvent mixture which will keep the homogenity of a silica gel column. PCBs elution was performed with pentane, while the chlorinated insecticides eluated with diethylether, acetone, methanol, and benzene. The elution of pesticides gave the best results for the following solvent systems: diethylether + hexane (1:1), acetone + hexane (1:4), methanole + pentane (1:8) and benzene.Separation of pesticides from polychlorinated biphenyls found in a synthetic mixture was also examined. It was found that all solvent systems used gave similar results of separation. However, only if benzene is used as eluant, the silica gel column can be used for four successive separations after the “on column” regeneration. In order to obtain the lowest blank values silica gel was cleaned with several solvents. The eluates after the silica gel separation were also cleaned up by means of deactivation alumina and concentrated sulphuric acid.     

Oxidation of organophosphorus pesticides with chloroperoxidase enzyme in the presence of an ionic liquid as co-solvent

Effects of selected ionic liquids on the efficiency of CPO oxidation of methyl-parathion were studied. In general, the activity of CPO decreases with the increased concentration of ionic liquid. For ionic liquids with the same cation, those with PF₆ ^? exhibit strongest inhibition toward CPO, while those with either BF₄ ^? or metSO₄ ^? show relatively lesser inhibition. It was further demonstrated that even for buffer solutions containing up to 30% concentration of ionic liquids such as EAN, BMIMmetSO₄, and EtPyTFA, CPO still can retain high activity (70–100% compared to that in citrate buffer) for oxidation of methyl-parathion. Photothermal enhancement factors of 3.5 times and corresponding improvements of sensitivity in the determination of organophosphates by the FIA-TLS method are predicted in 30% ionic liquids.     

Validation of the CANDY model with Russian long-term experiments

The CANDY model has been qualitatively assessed for simulating long-term dynamics of soil organic carbon and tested against different long-term experiments representing various land uses and geographical sites, but never before against conditions of the Former Soviet Union (FSU). Our goal was to simulate long-term trends in soil organic carbon for the long-term experiments of Barybino (Moscow region, Russia), Grakov (Kharkow region, Ukraine) and Yachenka (Minsk region, Belarus) representing the predominant arable soil types, climate conditions and typical management strategies for the investigated arable areas. The fit of modelled results to the observed data was evaluated to assess the suitability of the model for further applications in the FSU. The crop parameters of the CANDY model had to be adapted to the low yields observed under the Russian site conditions resulting in a higher sensitivity to crop-derived carbon input as a function of yield. The results show that the approach of treating the organic carbon situated in micro pores as inert, is an applicable solution for simulating soil carbon dynamics under Russian conditions. This evaluation of CANDY, against long-term experiments from Russia, gives confidence for its wider application in this region.     

Photolytic and photocatalytic degradation of 6-chloronicotinic acid

This work describes for the first time the photolytic and photocatalytic degradation of 6-chloronicotinic acid (6CNA) in double deionised water, which is a degradation product of neonicotinoid insecticides imidacloprid and acetamiprid, and it is known to appear in different environmental matrices. Photolytic experiments were performed with three UVA (ultraviolet A) polychromatic fluorescent lamps with broad maximum at 355 nm, while photocatalytic experiments were performed using immobilised titanium dioxide (TiO₂) on six glass slides in the spinning basket inside a photocatalytic quartz cell under similar irradiation conditions. Photolytic degradation revealed no change in concentration of 6CNA within 120 min of irradiation, while the photocatalytic degradation within 120 min, obeyed first-order kinetics. The observed disappearance rate constant was k = 0.011 ± 0.001 min⁻¹ and t_1/2 was 63.1 ± 5.5 min. Mineralisation rate was estimated through total organic carbon (TOC) and measurements revealed no carbon removal in case of photolysis after 120 min of exposure. However in photocatalytic experiments 46 ± 7% mineralisation was achieved within 120 min of irradiation. Nevertheless, the removal of total nitrogen (TN) was not observed across all experiments. Ion chromatographic analyses indicated transformation of chlorine atoms to chloride and increase of nitrate(V) ions only via photocatalytic experiments. Efficiency of selected advanced oxidation process (AOP) was investigated through toxicity assessment with Vibrio fischeri luminescent bacteria and revealed higher adverse effects of treated samples on bacteria following photocatalytic degradation in spite of the fact that higher mineralisation was achieved. New hydroxylated product generated in photocatalytic experiments with TiO₂, was confirmed with liquid chromatography-electro spray ionisation mass spectrometry (LC-ESI-MS/MS) analyses, gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (¹H NMR).     

Evaluation of modifications of the simple spectrofluorometry method for estimating petroleum hydrocarbon levels in fresh and waste water samples

The monitoring of petroleum hydrocarbons in the water environment is very often performed using complicated methods. There are many difficulties encountered in analyzing a long number of samples in the monitoring programme. In such cases, a simpler though less precise and specific technique using inexpensive equipment to monitor a large number of water samples, might be more desirable.

This idea was realized in the assessment of the state of pollution of the Mediterranean Sea by petroleum hydrocarbons where the pollution of sea water with oil (dissolved and/or dispersed in sea water) was measured by spectrofluorometry. The paper describes an analytical evaluation of three modifications of simple the spectrofluorometry method, applied on numerous river and waste water samples collected from various areas of Croatia.