Teratologic assessment of maleic hydrazide and daminozide,and formulations of ethoxyquin,thiabendazole and naled in rats

Abstract

Teratogenicity studies were conducted in rats treated orally from days 6–15 of gestation with single daily doses of 400–1600 mg/kg of maleic hydrazide, 300–1000 mg/kg daminozide, 125–500 mg/kg ethoxyquin or thiabendazole, or 25–100 mg/kg naled. Dams were killed on the 22nd day of gestation, and fetuses were evaluated by routine teratologic methods. No adverse effect was related to any treatment other than an increased incidence of anomalous fetuses at the highest dose (500 mg/kg) of thiabendazole.     

Toxicity assessment of the maize herbicides S-metolachlor,benoxacor, mesotrione and nicosulfuron,and their corresponding commercial formulations,alone and in mixtures,using the Microtox® test

The Microtox® test, using the prokaryote Vibrio fischeri, was employed to assess the toxicity of the maize herbicides S-metolachlor, benoxacor, mesotrione and nicosulfuron, and their formulated compounds: Dual Gold Safeneur®, Callisto® and Milagro®; alone and in mixtures. For each compound we obtained original IC₅₀ values, with consistent higher toxicities for formulated compounds compared to active ingredients alone. Mixtures of the four herbicides, prepared according to application doses encountered in agriculture, were found to be toxic at a lower concentration than single molecules. Mesotrione and nicosulfuron mixture appeared to be highly toxic to V. fischeri, however, this recommended post-emergence combination for maize crops got its toxicity decreased in formulated compound mixtures, suggesting that chemical interactions could potentially reduce the toxicity. Data comparisons to theoretical models showed a good prediction of mixture toxicity by Concentration Addition concept. Results seemed to exclude any synergistic effects on V. fischeri for the tested herbicide mixtures. Additional work coupling these bioassay data to ecosystemic level studies (aquatic and soil compartments) and data on additives and degradation products toxicity, will help to fill the gap in our knowledge of the environmental impact of these xenobiotics and in the choice of a more sustainable use of pesticides.     

Mixture of paraquat and linuron formulations examined for genotoxicity in Wistar rats by the in vivo micronucleus test--evaluation by different statistical tests

The purposes of the present study were the evaluation of the genotoxic effect of mixture of paraquat and linuron commercial formulations. the evaluation of the possible interaction between the two pesticides and the comparison of different statistical tests used for the data analysis. For this purposes the bone marrow micronucleus test was used. Dose levels were determined in the base of the LD50 of each component. According the experimental design, three dose levels of the mixture were administered at groups of five Wistar rats from each sex. Sampling time was 24 h for all groups plus 48 h for the highest dose and the positive control groups. In addition, the formulations were studied separately at two dose levels. Cyclophosphamide was used as positive control. For the statistical analysis of the results different parametric and nonparametric tests were used. The mixture of the two pesticides under the study conditions was not proven to be genotoxic. However, cytotoxicity and no signs of interaction were indicated. Minor declinations between the statistical tests used for data analysis observed.     

The effect of fluorescent tracers on droplet spectrum,viscosity, and density of pesticide formulations

The most important factor affecting efficacy and drift of pesticide applications is the droplet spectrum. To measure pesticide drift, researchers utilize fluorescent tracers to rapidly quantify spray deposition. Although fluorescent tracers have been used for more than 50 years, no experiments have been performed on the effect they have on the properties of pesticide formulations (density and viscosity) or droplet spectrum, which affect the drift of pesticides. Therefore, we examined the effect of an oil- and water-based tracer on the volume median diameter (VMD), viscosity, and density of oil- and water-based pesticide formulations. In addition, we experimentally fit and demonstrate the utility of using distributions to characterize pesticide droplet spectra. The addition of tracers to both water- and oil-based formulations did not significantly alter the VMD, viscosity, and density. Lognormal distributions provided the best fit for the water- and oil-based formulations with and without tracer. Our results demonstrated that the addition of oil- and water-based tracers do not significantly alter pesticide formulations properties and droplet spectrum, and most likely do not alter the movement of pesticide droplets in the environment.     

Simultaneous analysis of thiabendazole,carbendazim and 2-aminobenzimidazole in concentrated fruit juices by liquid chromatography after a single mix-mode solid-phase extraction cleanup

A method using liquid chromatography and a single mix-mode solid-phase extraction cleanup for the simultaneous analysis of thiabendazole [2-(1,3-thiazol-4-yl)-1H-benzoimidazole], carbendazim [(methyl N-(1H-benzoimidazol-2-yl)-carbamate)] and 2-aminobenzimidazole (1H-benzimidazol-2-amine) in concentrated fruit juices is described. The three fungicides were isolated from the samples and concentrated by solid-phase extraction on Oasis MCX cartridges. The determination was performed by liquid chromatography with a diode array, detecting at 288 nm. In this method, the average recoveries from blank control juice samples spiked in a concentration range of 0.01–0.10 mg/kg were in the range of 81–95%, with relative standard deviations below 8%. Detection limits and limits of quantification were 4 μ g/kg and 10 μ g/kg, respectively, for each fungicide. Real juice samples were analyzed by the proposed method. The results were compared to those from liquid chromatography-tandem mass spectrometry.     

Distribution and persistence of aminocarb in stream water, sediment and fish after application of three Matacil formulations

Three aminocarb formulations, water-based Matacil 180F, oil-based Matacil 180F and oil-based Matacil 180D, were applied separately to the surface of a stream at 2.40 g a.i./min for 5 minutes. The highest aminocarb concentration in the top 1 cm of water was found 5 min after application of oil-based 180F (5000 ppb). The next highest concentration was 1862 ppb found in the top 1 cm layer of water 3 min after application of oil-based 180D, followed by 1306 ppb found 5 min after application of water-based 180F. Residue accumulations were first observed in sediment at 3 min and in fish tissues 0.5 h after application. The levels of accumulation were in the order of water-based 180F greater than oil-based 180F greater than oil-based 180-D. After the application of water-based 180F, the highest concentrations were 20.2 ppb in sediment after 5 min and 127 ppb in fish tissues after 3 h. Residues disappeared rapidly from all three matrices and could not be detected after a period of 3-25 h.     

Effect of additives in the Neem formulations on deposition,volatilization and persistence of Azadirachtin in spruce foliage

Abstract

Foliar deposits, volatilization and persistence of azadirachtin‐A (AZ‐A) were investigated after application of four spray mixes prepared from a wettable powder (WP) and three emulsifiable concentrate (EC) formulations of neem. They were applied at the dosage rate of 50 g AI in 4 L/ha onto potted spruce seedlings in a laboratory spray chamber. Droplet‐size spectra and deposits were assessed using Kromekote^® card/glass plate collection units. Foliar residues [dislodgeable residues (DR), penetrated residues (PR) and total residues (TR)] of AZ‐A and their volatilization were measured by HPLC at different intervals of time up to 60 h after treatment. Differences in the droplet‐size spectra and deposit levels were observed among the four spray mixes due to the influence of additives present in them. Dissipation half‐lives (DT₅₀) of the DR, PR and TR in the foliage were low (range, 19.5 to 38.9 h) and varied according to the residue type and the spray mix used. The DT₅₀ values of the DR were consistently lower (range, 19.5 to 31.9 h) than those of the PR (range, 30.5 to 38.9 h) due to preferential loss of the surface residues. The low DT₅₀ values observed for the DR and TR in the foliage sprayed with the WP spray mix were attributed to the particulate nature of the deposit. AZ‐A volatilized appreciably from the DR rather than from the PR. The variations found in the amounts of AZ‐A volatilized (42 to 58%) and unaccountable (38 to 46%) from the initial TR values in spruce foliage, after 60 h, were attributed to the physical form of the deposits on the target surface and the influences of additives present in the different spray mixes.     

Contents and sources of DDT impurities in dicofol formulations in Turkey

Background, aim, and scope  Dicofol is widely used as a pesticide in agriculture applications. Since dicofol is mainly synthesized from dichlorodiphenyltrichlorethane (DDT), it contains DDT as an impurity. The European Community has forced Prohibition Directive 79/117/EEC to reduce DDT in dicofol formulations. Specifically, DDT content in a dicofol formulation cannot exceed 0.1%. The goal of this project was to determine the DDT content in dicofol formulations used in Turkey. Materials and methods  Samples of all the dicofol formulations in Turkey were collected to quantify DDT and DDT-related compounds. Four replicates were used for each sample. GC/MS/MS was used to analyze p,p′ and o,p′ isomers of DDT, DDD, and DDE. A HPLC was used to determine p,p′-Cl-DDT concentrations. Results  The total DDT content of the formulated dicofol was found between 0.3% and 14.3%. The concentration of p,p′-DDE ranged from 167 to 1,042 mg kg⁻¹ in dicofol samples. p,p′-DDT concentrations were found to be 32 to 183 mg kg⁻¹. The o,p’-DDT level ranged from 2 to 34 mg kg⁻¹ in the dicofol formulations analyzed. Discussion  It was estimated that 617.8 kg of DDT was released from dicofol. The main impurity was identified as p,p-Cl-DDT. Based on these results, dicofol serves as a continuing source of DDT contamination. Conclusions  All DDT concentrations in dicofol samples analyzed were higher than the permitted 0.1% level of Prohibition Directive 79/117/EEC. The reduction of dicofol is critical since it serves as a continual source of DDT contamination. Recommendations and perspectives  DDT has been found in soil, water, and air samples. Dicofol has been identified as a contributor to continued DDT contamination in soil and water. More studies are needed to ascertain the source of DDT in the air.     

Quinoa value chain,adoption, and market assessment in Morocco

Environmental Science and Pollution Research - Agriculture faces many challenges such as climate change, droughts, and salinity, which requires urgent interventions for fast adaptation and...     

Effects of salinity, DOM and metals on the fate and microbial toxicology of propetamphos formulations in river and estuarine sediment

Toxicity studies tend to use pure pesticides with single organisms. However, natural systems are complex and biological communities diverse. The organophosphate pesticide propetamphos (PPT) has been found exceeding regulatory limits (100 ng L⁻¹) in rivers. We address whether solution properties affect the fate of Analar (Analar-PPT) or industrial PPT (PPT-Ind) propetamphos formulations and whether propetamphos and metal toxicant effects are additive, antagonistic or synergistic? The sorption, desorption, biodegradation and microbial toxicology of Analar-PPT and PPT-Ind were investigated in Conwy River and estuary sediment. Results showed elevated salinity enhanced PPT sorption, while higher salinities increased PPT-Ind retention. Higher dissolved organic matter (DOM) and low salinity slowed Analar-PPT biodegradation (1.9 × 10⁻³ h⁻¹). Analar-PPT and PPT-Ind biodegradation was further reduced by low salinity, high DOM and dissolved Zn and Pb (6.3 × 10⁻⁴ h⁻¹, 1100 h t_½ for Analar-PPT; 7.5 × 10⁻⁴ h⁻¹, 924 h t_½ for PPT-Ind). Toxicity effects of PPT, Zn and Pb in equitoxic ratio were higher for PPT-Ind (4.7 μg PPT-Ind g⁻¹; 581 μg Zn g⁻¹; 395 μg Pb g⁻¹) than for Analar-PPT (34.6 μg PPT g⁻¹; 312 μg Zn g⁻¹; 212 μg Pb g⁻¹) whilst a toxicant ratio 1:100:10 suggested small quantities of Analar-PPT (EC₁₀ = 0.06 μg g⁻¹) affected microbial communities. The combined toxicity effect was more than additive. Thus, industrial formulations and pollutant mixtures should be considered when assessing environmental toxicity.     

Controlled release formulations of metribuzin: Release kinetics in water and soil

Controlled release (CR) formulations of metribuzin in Polyvinyl chloride [(PVC) (emulsion)], carboxy methyl cellulose (CMC), and carboxy methyl cellulose-kaolinite composite (CMC-KAO), are reported. Kinetics of its release in water and soil was studied in comparison with the commercial formulation (75 DF). Metribuzin from the commercial formulation became non-detectable after 35 days whereas it attained maxima between 35–49 days and became non-detectable after 63 days in the developed products. Amongst the CR formulations, the release in both water and soil was the fastest in CMC and slowest in PVC. The CMC-KAO composite reduced the rate of release as compared to CMC alone. The diffusion exponent (n value) of metribuzin in water and soil ranged from 0.515 to 0.745 and 0.662 to 1.296, respectively in the various formulations. The release was diffusion controlled with half release time (t_1/2) from different controlled release matrices of 12.98 to 47.63 days in water and 16.90 to 51.79 days in soil. It was 3.25 and 4.66 days, respectively in the commercial formulation. The period of optimum availability of metribuzin in water and soil from controlled released formulations ranged from 15.09 to 31.68 and 17.99 to 34.72 days as against 5.03 and 8.80 days in the commercial formulation.     

Concentration,sources and risk assessment of PAHs in bottom sediments

Environmental Science and Pollution Research - The aims of the study were to investigate the concentration, sources and ecological risk of PAHs (polycyclic aromatic hydrocarbons) in bottom...     

Occurrence,distribution, and risk assessment of antibiotics in the Songhua River in China

The occurrence, distribution, and risk assessment of antibiotics in freshwater systems are receiving global attention, because of their impact on the environment and human health. However, few studies have focused on this topic in Northeast China and its Songhua River, the third-largest river in China. This study investigated the occurrence and distribution of 12 antibiotics, including three cephalosporins (cefazolin, cefmetazole, cefotaxime), three macrolides (azithromycin, clarithromycin, roxithromycin), three fluoroquinolones (ofloxacin, norfloxacin, flumequine), and three sulfonamides (sulfadiazine, sulfapyridine, sulfamethoxazole) in the mainstream and tributaries of the Songhua River. A total of 152 surface water samples were collected in January, May, July, and October 2016. These samples were analyzed using solid-phase extraction (SPE) and ultra-high-performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The results indicated the wide use of all 12 antibiotics in the mainstream of the Songhua River. Sulfamethoxazole and cefazolin were the dominant antibiotics, with maximum concentrations of 73.1 and 65.4 ng L^?1, respectively. Other antibiotics were present at mean concentrations below 15 ng L^?1, except cefmetazole, present at a mean concentration of 35.6 ng L^?1. The spatial distribution of antibiotics showed that unbalanced regional development may lead to the distribution pattern of the antibiotics in the tributaries and the mainstream. Thus study also assessed the seasonal variation of antibiotics in urban surface water; cephalosporin, sulfonamide, fluoroquinolone, and macrolide concentrations were significantly higher during the icebound season than during non-icebound season. This may be due to the low temperature and water flow of the river in winter. Risk assessment showed that azithromycin, clarithromycin, roxithromycin, flumequine, and sulfamethoxazole posed a low or median risk to the aquatic organisms in the mainstream. The potential risks created by antibiotics to the aquatic environment should not be neglected in the Songhua River. The potential risks created by antibiotics to the aquatic environment should not be neglected in the Songhua River.

     

Distribution,fate, and risk assessment of antibiotics in five wastewater treatment plants in Shanghai,China

The project studied the occurrence, fate, and seasonal variation of 14 antibiotics, from five wastewater treatment plants (WWTPs) in Shanghai. The results indicated that ofloxacin, sulfamethoxazole, and oxytetracycline were the predominant antibiotics, with maximum concentrations of 1208.20, 959.13, and 564.30 ng/L in influents, while 916.88, 106.60, and 337.81 ng/L in effluents, respectively. The level of antibiotics in WWTPs obviously varied with seasonal changes, and higher detectable frequencies and concentrations were found in winter. The daily mass loads per capita of amoxicillin, enrofloxacin, and oxytetracycline in the study were all higher than those in other regions/countries, such as Hong Kong, Australia, and Italy. The elimination of antibiotics through these WWTPs was incomplete, and a wide range of removal efficiencies during the different treatment process and seasons were observed (?500.56 to 100 % in winter and ?124.24 to 94.21 % in summer). Sulfonamides were relatively easy to be removed in WWTPs and the ultraviolet (UV) process can effectively improve the removal efficiency. Risk assessment of antibiotics in effluents was estimated. Only AMOX’s hazard quotient (HQ) was higher than 0.01. Even though the environmental risks in the study were estimated to be low, the potential negative effects on aquatic ecosystems should call our attention as continually discharge in the long term.     

Metal fractionation in soils and assessment of environmental contamination in Vallecamonica, Italy

Metal contamination was investigated in soils of the Vallecamonica, an area in the northern part of the Brescia province (Italy), where ferroalloy industries were active for a century until 2001. The extent in which emissions from ferroalloy plants affected metal concentration in soils is not known in this area. In this study, the geogenic and/or anthropogenic origin of metals in soils were estimated. A modified Community Bureau of Reference sequential chemical extraction method followed by inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses were employed to evaluate the potential bioavailability of Al, Cd, Mn, Fe, Cr, Zn, and Pb in soils. Principal component analysis (PCA) was used to assess the relationships among metal sources in soil samples from different locations. This approach allowed distinguishing of different loadings and mobility of metals in soils collected in different areas. Results showed high concentrations and readily extractability of Mn in the Vallecamonica soils, which may suggest potential bioavailability for organisms and may create an environmental risk and potential health risk of human exposure.     

Distributions,origins, and health-risk assessment of nitrate in groundwater in typical alluvial-pluvial fans,North China Plain

Environmental Science and Pollution Research - High concentration of nitrate (NO3?) in groundwater is a major concern because of its complex origin and harmful effects on human health. This...     

Chemical,biological, and ecotoxicological assessment of pesticides and persistent organic pollutants in the Bahlui River,Romania

Background, aim, and scope

Current knowledge on environmental impacts of industrial activities in Romania, particularly persistent organic pollutants (POPs), indicates that environmental standards of the European Union are not systematically met. In our study area, additional sources of POPs are agriculture and domestic wastes. Very scarce information is available upon environmental contaminations and effects. In the present study, we investigated the chemical pollution and their eventual impact on the ecosystem by measuring POPs and by using biological indicators of pollution.

Materials and methods

The survey was carried out at six main sample sites along the Bahlui River. Sediments were chemically analysed for their content in polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs)—hexachlorocyclohexanes (HCHs) isomers and the dichlorodiphenyl trichloroethane (DDT) family. River water was biologically monitored at the level of phytoplankton and benthic invertebrates’ communities. Water samples from six locations have been analyzed for algal species composition and correspondence to various water quality indices. Biological samples have been taken from the same locations so as to calculate the macroinvertebrate indices. In the most polluted areas, as revealed by previous methods, toxicity was tested by exposing the green alga Pseudokirchneriella subcapitata and the cladoceran Daphnia magna to various dilutions of water sample.

Results

Important concentrations of POPs were identified only in sediments at river mouths (sites S5 and S6). Along the year, the sum of PCB concentrations ranged between 3 and 10 ng/g dw (S5), and between 4 and 26 ng/g dw (S6). Concentration of HCHs ranged between 0.4 and 3 ng/g dw (both S5 and S6) with a higher contribution of the gamma-HCH (30–70%), followed by beta-HCH (20–50%). The beta-HCH isomer was found at lower concentrations or even not detected in outer city sites. DDTs were found at higher concentrations than HCHs and ranged between 0.18 and 4 ng/g dw (S5) and between 0.56 and 18 ng/g dw (S6). The parent compound, p,p′-DDT, could be detected only in low concentrations (up to 5 ng/g dw) and contributed with less than 30% to the sum of DDTs in sediment. The principal contributors of the ΣDDTs in sediment were p,p′-DDE, and p,p′-DDD. The o,p′-DDD and DDT isomers were minor contributors to the sum of DDT. PAHs were found at higher concentrations than DDTs and ranged between 6 and 36 ng/g dw (S5) and between 36 and 155 ng/g dw (S6). Fluoranthene was predominant (up to 40%), followed by phenantrene (up to 30%), naphthalene (up to 35%), and benzo-(g,h,i)-perylene (up to 23%). The saprobity index and the diatom index increased from springs to river mouth, indicating a decrease in the water quality, but within the limits of moderate pollution. The saprobity index varied between 1.99 at spring to 2.70 at mouth. The diatom index varied from 3.48 to 3.14. The species’ richness in phytoplankton has a less clear pattern along the river, but in general, it appears to be negatively influenced by pollution. At the level of biological consumer species, the analyses of the macroinvertebrates confirm the situation and the tendency shown with algae. In addition, the Shannon–Wiener index, the Pielou evenness index, and the McNaughton dominance index indicate a peculiar pattern: invertebrate communities appear to a have a more stable structure along the river, with visible shifts at springs and at river mouths. Water toxicity testing indicates low toxicity of river waters around the city of Iasi, with two notable exceptions: the point pollution at the domestic wastewater treatment discharge and at the old open-air deposit of domestic solid wastes. Another important result was that tested algae appeared to be more readily affected than tested cladoceran: EC₅₀ (percent effluent) was 16 in algae and 28 in cladocerans. The slope of toxic effect was also much steeper in cladocerans (6) than in algae (1.8), which means that the toxic effect is more sudden on the tested invertebrates than on the tested algae.

Discussion

Pollutant concentrations reported herein are lower or similar than those reported for the sediments by earlier studies (RIZA 2000; Dragan et al., Int J Environ Anal Chem 86:833–842, 2006). Ratios of individual PAH compounds indicate important pyrolytic inputs and suggest that PAHs in the area are derived from the combustion of fossil fuels. Biologically, the waters appear to be beta-mesosaprobic towards alpha-mesosaprobic according to the saprobic index classification and undergo moderate pollution according to the diatom index classification. Water quality decreases from springs to river mouths. Algal species richness index has a less clear pattern along the river. Water toxicity is low, but certain sources of point pollution require increased attention.

Conclusions

The water quality is better than expected, probably because of the drop in pollution intensity following the collapse of local agricultural and industrial activity following the fall of communism in 1989. Nevertheless, further studies will be needed to confirm and refine our results. While this study draws no strident alarm, it appeals for high attention, particularly because the economic activity in the area is expected to increase.

Recommendations and perspectives

Future close monitoring will be necessary for insuring compliance with the Water Framework Directive, and for refining standards and understanding of the local situation, but with relevance for the wider international community. On the basis of the situation described in the present study, we recommend that future studies dedicate specific efforts to point pollution and effluent toxicity, particularly around the city of Iasi. For a better understanding of pollution and its effects, we recommend pursuing the type of multidisciplinary investigations proposed by the present study: chemical, ecotoxicological, and ecological. We also recommend that new methods should be developed and/or refined, like the empirical determination of partitioning coefficients in water and soils, process-based toxicity methods in ecotoxicological assessments, searching for interactions between pollution, producers, and consumers in aquatic ecosystems. We also recommend preference for cheaper survey methods, as these will be more applicable locally.