Persistence of metsulfuron‐methyl in two soils

Abstract

The persistence of metsulfuron‐methyl in sandy loam and clay soil incubated at different temperatures and moistures contents was investigated under laboratory conditions using longbean (Vigna sesquipedalis L.) as bioassay species. A significant degradation of metsulfuron‐methyl was observed in non‐autoclaved soil rather than the autoclaved soil sample. At higher temperature, the degradation rate in non‐autoclaved soil improved with increasing soil moisture content. In non‐autoclaved sandy loam and clay soil, the half‐life was reduced from 9.0 to 5.7 and from 11.2 to 4.6 days, respectively when moisture level of sandy loam increased from 20 to 80% field capacity at 35°C. In the autoclaved soil, herbicide residue seems to have been broken down by non‐biological process. The rate of dissipation was slightly increased after the second application of the herbicide to non‐autoclaved soils but not in autoclaved soil, indicating the importance of microorganisms in the breakdown process.     

Biomonitoring of polychlorinated biphenyls in Bavaria/Germany—long-term observations and standardization

In the 1980s, it was demonstrated that semi-volatile organic compounds (SVOCs) like polychlorinated biphenyls (PCBs) accumulate in plant leaves. Plants are at the base of the food chain, and therefore a starting point for transfer of PCBs to animals and related human exposure. For two decades, the Environment Agency of the German federal state of Bavaria (LfU) has been operating long-term monitoring stations to measure the impact of organic air pollutants. Standardized ryegrass, curly kale, and spruce needles are used as bioindicators for the atmospheric entries of PCBs into vegetation. From the end of 1990s to 2009, there was a marked decline in the concentrations of indicator PCBs (i-PCBs) and a minor decline in PCB-TEQ levels. After 2009, the concentrations leveled off. In rural areas, the median concentrations of Σ6 i-PCB in ryegrass and curly kale were about 3 and 4 μg/kg dm in 2000, and have been about 0.5 and 1 μg/kg dm since 2009, respectively. Concentrations in spruce needles fell from 0.9 to 0.4 μg/kg dm. Median PCB-TEQ concentrations in the bioindicator plants ranged from 0.05 to 0.23 ng/kg dm between 2002 and 2009 and from 0.15 to 0.05 ng/kg dm after 2009. Indicator PCB and PCB-TEQ concentrations were several times higher at the urban station in Munich than at the rural areas, reflecting the emissions from in-use PCB stocks in the building sector. The likely reason of the slower decrease of PCB-TEQ compared to i-PCBs is the formation of PCB-126 by dechlorination of industrial PCBs in open applications.     

Carbofuran degradation by the application of MW-assisted H₂O₂ process

Carbofuran removal performance of a microwave (MW)-assisted H?O? system under different MW-power levels (300-900 W) was investigated. Batch experiments were conducted at 100 mg/L carbofuran concentration using a modified-MW reactor with 2450 MHz of fixed frequency. As a precursor, control experiments were carried out with H?O? alone, MW alone and conventional heating (CH). A maximum carbofuran removal of 14 % was observed in both H?O? alone and CH systems. On the other hand, only 2 % removal was observed in the MW alone system irrespective of the operation-mode, i.e. continuous or pulsed. The combination of MW and H?O? produced 100 % carbofuran removal in all the MW-assisted experiments. The MW-assisted system operated under continuous-mode and at 750 W has showed rapid carbofuran degradation, i.e. 30 sec, with the highest first-order removal rate constant of 25.82/min. However, 97 % carbon oxygen demand (COD) removal was observed in the same system only after 30 min. On the other hand, 100 % carbofuran removal and 49 % COD removal were observed in the pulsed-mode MW-assisted H?O? system after 10 and 30 min, respectively. Carbofuran mineralization in the system was evidenced by the formation of ammonium and nitrate, and carbofuran intermediates.     

Concentrations and accumulation rates of polychlorinated biphenyls in soil along an urban–rural gradient in Shanghai

Environmental Science and Pollution Research - This study proposed an in situ soil experimental system to quantify concentration and accumulation rates of polychlorinated biphenyl (PCB) congeners...     

Comparison of levels of polychlorinated biphenyls in edible oils and oil-based products—possible link to environmental factors

Food consumption has been widely reported to be the main source of human exposure to PCBs. A total of 47 samples of food products on sale in supermarkets in the United Kingdom were thus analyzed for PCBs to determine residual levels in oil and oil-based products. The objective was to compare the measured levels of total PCBs (ΣPCBs) in food products to those reported in various environmental compartments. Combined extraction and online clean up was achieved using Accelerated Solvent Extraction? (ASE) to recover target analytes for analysis by GC-MSD (gas chromatography mass spectrometry). Σ PCBs (ng/g) in each product were in the ranges of 4.73–44.38 edible oil; 1.40–6.18 mayonnaise; 1.21–6.25 salad cream; 1.28–5.64 seafood sauce, and 0.97–15.08 exotic dressing. The level of human exposure to PCBs in all products was < 1 μg/kg body weight/day when considering a 70 kg male or 57 kg female, possibly reflecting the reported decline of PCBs in the environment.     

Effect of phenobarbital and polychlorinated biphenyls on the toxicity and disposition of 1,2,4,5‐tetrachlorobenzene in the rat

Soil avoidance by earthworms has been generally considered a relevant and sensitive endpoint for assessing soil contamination by xenobiotics. However, when pesticide ecotoxicological assessment is concerned, the sensitivity of the recently standardized avoidance assay has been questioned. We hypothesized that this controversy may be due to the specific pesticide mode of action of the chemicals used rather than reveal inconsistencies in the test feasibility, i.e. provided that no pesticides interfering with neuronal pathways are tested, this bioassay should keep expected high levels of sensitivity. In this study, the avoidance behaviour of the earthworm Eisenia andrei under exposure to the carbamate insecticide methomyl [S-methyl N-(methylcarbamoyloxy)thioacetimidate] was linked to the corresponding acetylcholinesterase (AChE) inhibition. Significant AChE inhibition occurred at lower concentrations (from 0.86 mg Kg^?1 onwards) than significant avoidance of spiked soil (from 5.62 mg Kg^?1 onwards). This indicates that assessments regarding pesticides that have neurotoxic activity may be biased if behavioral endpoints are selected. Despite theoretical hypothesis that have been raised, this should be the first study providing preliminary experimental evidence on such a link between avoidance behavior and neuronal impairment levels in earthworms. Further studies are ongoing that should refine conclusions of this study.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State, Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.     

H₂S abatement in a biotrickling filter using iron(III) foam media

Airstreams polluted with H(2)S at inlet loads ranging from 2.4 to 40.9 g H(2)Sm(-3)h(-1) were treated in a biotrickling reactor packed with hematite bearing, open pore foam units, at Empty Bed Residence Times (EBRT) ranging from 20 to 60s over a period of 80 d, with almost complete removal of the pollutant from the startup of the system. The media had been seeded with sludge from a local water works facility, and removal efficiencies in excess of 80% were consistently observed along the operation of the reactor, with an average of 98%. Based on section performance, being a section one third of the bed length, observed elimination capacities (EC) reached up to 88.7 g H(2)Sm(-3)h(-)(1) and 72.0 g H(2)Sm(-3)h(-1) at section EBRT of 10 and 7s, respectively. The observed EC values compared much better than data reported on other packed bed reactors using biological iron oxidization to treat H(2)S airstreams indirectly, and so did it when comparing the EC per unit of specific area in a similar study using polyurethane (PU) foams. Further, and unlike PU packed biofilters, no compaction occurred due to the iron foam rigidity, which translated in much better observed gas phase pressure drop as opposed to other conventional biofilters. Denaturing gel gradient electrophoresis was performed on the biomass collected in the packing after the biofilter service, and it was found that though a multi bacterial colony was seeded in the system via the sludge, the only surviving genus was the iron oxidizing Alicyclobacillus spp.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State,Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.     

Determination of indicator polychlorinated biphenyls (PCBs) by gas chromatography–electron capture detector

An effective method for determination of indicator polychlorinated biphenyls (PCBs) has been validated using gas chromatography (GC) equipped with electron capture detector (ECD). The GC–ECD method was validated by determining the linear range (working range) for determination of the compounds, minimum detectable quantities (MDQ), the precision and accuracy of the method for the analysis of the compounds. MDQ obtained for the compounds ranges from 0.0005 to 0.002 ng. Indeed the method was found to be more sensitive as the number of chlorine atoms attached to the biphenyl increases. The precision and accuracy of the GC method validated ranges from 2.4% to 14.5% and −7.0% to 14.6% respectively. Coefficient of variation associated with the repeatability of the retention times and corresponding peak areas was found to be 0.0001–0.0007 for the retention times and 0.0014–0.059 for the peak areas. Percentage recoveries for the compounds were in the range of 95.7–101.0%. The validated method was then applied to determine levels of indicator PCBs in sediments sampled from eleven sampling points along the Lake Bosuntwi in Ghana and the highest PCB load of 19.17 ng g⁻¹ was recorded at Pipie No. 2. PCB 52 and PCB 101 were found to be the most ubiquitous indicator PCBs in the study area, both with 90.91% occurrence.     

Enantiomeric fractions and congener specific determination of polychlorinated biphenyls in eggs of predatory birds from Doñana National Park (Spain)

The content of 30 polychlorinated biphenyls (PCBs) and the enantiomeric fractions of 10 chiral PCBs were determined in 17 infertile eggs from three different predatory bird species collected in Do?ana National Park (DNP, Spain) in the period 1999-2000. The highest PCB concentration was found in eggs from red kites (0.52-110 microg/g on a fresh weight basis, f.w.) followed by buzzard (0.08-13 microg/g f.w.) and booted eagle (0.10-1.5 microg/g f.w.). Seventy-five percent of the red kite eggs had PCB levels above 4.7 microg/g f.w., which is associated in the literature with reproductive failure. This could be related to the fact that red kite populations have decreased by more than 50% in the last five years in DNP. PCBs # 138, 153, and 180 were the most abundant in all cases. This is the first time that atropisomers of 10 chiral PCBs (PCBs # 45, 84, 91, 95, 132, 135, 136, 149, 174, and 176) in predatory bird eggs have been performed. The enantiomeric fractions (EFs) for most PCBs investigated were non-racemic (EF not = 0.5), ranging from 0.05 to 0.95. The results suggested that predatory birds, mainly red kite species, are highly polluted by PCBs, and PCBs # 95, 132, 135, 136, and 174 strongly deviate from the racemic-mixture values.     

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH

A new Vis-Fe⁰-H₂O₂-citrate-O₂ system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L⁻¹ of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L⁻¹ of H₂O₂, 12.6 g of Fe⁰ and 1.0 mmol L⁻¹ of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe⁰ surface was found to be at a very low level as <5.4 μmol L⁻¹. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe⁰-H₂O₂-citrate-O₂ system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe⁰ > H₂O₂ > citrate > Vis > O₂. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.     

Evaluation of the mobility of c14‐labelled pesticides in soils by thin layer chromatography using a linear analyser

Abstract

The mobility of seven pesticides in a chromic cambisol soil was studied by soil thin layer chromatography. Pesticide mobilities were determined by means of conventional autoradiographs of the chromatograms, as well as from sequential series of curves and images of the pesticide spots provided by a linear analyser. The R _f values obtained from the autoradiographs and those provided by the linear analyser were quite consistent. Based on such values, pesticide mobility decreased in the following order: acephate > fluometuron > atrazine > ethofumesate > metolachlor > diazinon > glyphosate. According to the mobility scale proposed by Helling and Turner (1968), acephate is highly mobile; atrazine, fluometuron, ethofumesate and metolachlor are moderately mobile; diazinon is slightly mobile; and glyphosate is immobile. The images provided by the linear analyser allow to determine the R _f values for the zones of maximum activity in the pesticide spots (R _f ^max), as well as the activities of different spot zones and those corresponding to R _f and R _f ^max. The results obtained show the image analyser to provide more expeditious R _f measurements from the chromatograms and open up new prospects for using soil TLC to investigate pesticide mobility.     

Redistribution of free tropospheric chemical species over West Africa: radicals (OH and HO₂), peroxide (H₂O₂) and acids (HNO₃ and H₂SO₄)

The purpose of this paper is to study the redistribution of chemical species (OH, HO₂, H₂O₂, HNO₃ and H₂SO₄) over West Africa, where the cloud cover is ubiquitously present, and where deep convection often develops. In this area, because of these cloud systems, chemical species are redistributed by the ascending and descending flow, or leached if they are soluble. So, we carry out a mesoscale study using the Regional Atmospheric Modelling System (RAMS) coupled to a code of gas and aqueous chemistry (RAMS_Chemistry). It takes into account all processes under mesh. We examine several cases following the period (November and July), with inputs emissions (anthropogenic, biogenic and biomass burning). The radicals OH and HO₂ are an indicator of possibilities for chemical activity. They characterize the oxidizing power of the atmosphere and are very strong oxidants. The acids HNO₃ and H₂SO₄ are interesting in their transformation into nitrates and sulfates in precipitation. In November, when photochemistry is active during an event of biomass burning, concentrations of chemical species are higher than those of November in the absence of biomass burning. The concentrations of nitric acid double and sulfuric acid increases 70 times. In addition, the concentrations are even lower in July if there is a deep convection. Compared to measures of the African Monsoon Multidisciplinary Analysis (AMMA), the results and observations of radicals OH and HO₂ are the same order of magnitude. Emissions from biomass burning increase the concentrations of acid and peroxide, and a deep convection cloud allows the solubility and the washing out of species, reducing their concentration. Rainfalls play a major role in solubility and washing out acids, peroxides and radicals in this region.     

Sorption–desorption of indaziflam and its three metabolites in sandy soils

Indaziflam is a relatively new herbicide for which sorption–desorption information is lacking, and nothing is available on its metabolites. Information is needed on the multiple soil and pesticide characteristics known to influence these processes. For four soils, the order of sorption was indaziflam (N-[1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: K_f = 5.9, 1/n_f = 0.7, K_foc = 447; sandy loam: K_f = 3.9, 1/n_f = 0.9, K_foc = 276) > triazine indanone metabolite (N-[(1R,2S)-2,3-dihydro-2,6-dimethyl-3-oxo-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: K_f = 2.1, 1/n_f = 0.8, K_foc = 177; sandy loam: K_f = 1.7, 1/n_f = 0.9, K_foc = 118) > fluoroethyldiaminotriazine metabolite (6-[(1R-1-Fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: K_f = 0.3, 1/n_f = 0.9, K_foc = 28; sandy loam: K_f = 0.3, 1/n_f = 0.9, K_foc = 22) = indaziflam carboxylic acid metabolite (2S,3R)-3-[[4-amino-6-[(1R)-1-fluoroethyl]-1,3,5-triazin-2-yl]amino]-2,3-dihydro-2-methyl-1H-indene-5-carboxylic acid) (sandy clay loam: K_f = 0.3, 1/n_f = 0.9, K_foc = 22; sandy loam: K_f = 0.5, 1/n_f = 0.8, K_foc = 32). The metabolites being more polar than the parent compound showed lower sorption. Desorption was hysteretic for indaziflam and triazine indanone metabolite, but not for the other two metabolites. Unsaturated transient flow K_d's were lower than batch K_d's for indaziflam, but similar for fluoroethyldiaminotriazine metabolite. Batch K_d's would overpredict potential offsite transport if desorption hysteresis is not taken into account.     

Photocatalytic mineralization of hydroperfluorocarboxylic acids with heteropolyacid H₄SiW₁₂O₄₀ in water

The decomposition of hydroperfluorocarboxylic acids [H-PFCAs; HC_nF_2nCOOH (n = 4 and 6)] induced by heteropolyacid photocatalyst H₄SiW₁₂O₄₀ in water was investigated, and the results are compared with the results for the corresponding perfluorocarboxylic acids (PFCAs; C_nF_2n+1COOH). This is the first report on the photochemical decomposition of H-PFCAs, which are being developed as alternative surfactants to environmentally persistent and bioaccumulative PFCAs. H-PFCAs were not decomposed by irradiation with UV-Visible light (>290 nm) in the absence of H₄SiW₁₂O₄₀. In contrast, UV-Visible light irradiation of H-PFCAs in the presence of H₄SiW₁₂O₄₀ efficiently decomposed H-PFCAs to F⁻ and CO₂. The decomposition reactions showed pseudo-first-order kinetics, and the decomposition rate constants were 1.8-2.5 times higher than those for the corresponding PFCAs. The reaction mechanism can be explained by elimination of H⁺ from the ω-H atom of the H-PFCAs by the excited catalyst, followed by formation of perfluorodicarboxylic acids.     

Acute effects of Fe₂O₃, TiO₂, ZnO and CuO nanomaterials on Xenopus laevis

Metal oxide nanomaterials have exhibited toxicity to a variety of aquatic organisms, especially microbes and invertebrates. To date, few studies have evaluated the toxicity of metal oxide nanomaterials on aquatic vertebrates. Therefore, this study examined effects of ZnO, TiO₂, Fe₂O₃, and CuO nanomaterials (20-100 nm) on amphibians utilizing the Frog Embryo Teratogenesis Assay Xenopus (FETAX) protocol, a 96 h exposure with daily solution exchanges. Nanomaterials were dispersed in reconstituted moderately hard test medium. These exposures did not increase mortality in static renewal exposures containing up to 1000 mg L⁻¹ for TiO₂, Fe₂O₃, CuO, and ZnO, but did induce developmental abnormalities. Gastrointestinal, spinal, and other abnormalities were observed in CuO and ZnO nanomaterial exposures at concentrations as low as 3.16 mg L⁻¹ (ZnO). An EC₅₀ of 10.3 mg L⁻¹ ZnO was observed for total malformations. The minimum concentration to inhibit growth of tadpoles exposed to CuO or ZnO nanomaterials was 10 mg L⁻¹. The results indicate that select nanomaterials can negatively affect amphibians during development. Evaluation of nanomaterial exposure on vertebrate organisms are imperative to responsible production and introduction of nanomaterials in everyday products to ensure human and environmental safety.