Laboratory studies of dissipation of 14C‐DDT from soil and plywood surfaces

Abstract

The effects of temperature and solar radiation on dissipation of ¹⁴C‐p,p'‐DDT from a latosol soil were studied under laboratory conditions. Volatilization was measured by trapping organic volatiles during 6 weeks and was found to increase with rise of temperature from 3.8% of initial amount at ambient temperature to 5.9% at 45°C.

Studies on the effect of solar radiation using quartz tubes under sterilized and non‐sterilized conditions have shown that volatilized organics were highest in quartz tubes, with soil microflora presumably playing a very minor role in volatilization. Mineralization was shown to be low in sterilized systems and highest in non‐sterilized quartz systems. Studies on binding suggest that soil bioactivity may be involved in the formation of a portion of the bound residue. These laboratory experiments seem to support data from the field, where it is maintained that volatilization is a major mechanism for dissipation. Degradation in soil and to a lesser extent solar irradiation contribute also substantially to the dissipation mechanisms. Radiocarbon dissipated from plywood surfaces under indoor conditions in a biphasic fashion. Loss of 50% occurred after 5.5 weeks while the remainder dissipated at a very slow rate.     

Laboratory studies on volatilization and mineralization of 14c‐p,p'‐DDT in soil,release of bound residues and dissipation from solid surfaces

Abstract

In support of field data, laboratory studies were conducted on volatilization, mineralization and binding of ¹⁴C‐p,p'‐DDT in soils at Sao Paulo. Incubation of soil for 6 weeks did not result in volatilized organics or mineralization; with >95% extractable radiocarbon in the form of p,p'‐DDT. Small amounts of bound residues (1.8%) were detected in soil. These data confirm the very slow dissipation of DDT in the field which presumably relates to the acidic pH of soil (4.5–4.8).

Bound ¹⁴C‐residues in soils treated with ¹⁴C‐p,p'‐DDT at Praia Grande and Sao Paulo could be released (5–21%) by sulphuric acid treatment. The released residue had the composition: 69–90% DDT, 7–32% DDD and 0–3% DDE. Incubation of soil bound ¹⁴C‐residues with fresh inoculum for 3 months did not result in release of ¹⁴C.

Dissipation from wooden surfaces was fairly slow. After 20 weeks, 74% of the applied radioactivity could be recovered; 44% hexane‐non‐extractable.     

Chemical and biological release of 14C‐bound residues from soil treated with 14C‐p,p'‐DDT

Abstract

¹⁴C‐p,p'‐DDT‐bound residues in soil can be released by treatment with concentrated sulphuric acid at ambient temperatures. Within 6 days, about 70% of the bound residues was released. Bound residues released after 9 months incubation with ¹⁴C‐DDT showed the presence of DDT and DDE only while bound residues released after 18 months, contained in addition 13% DDD.

Release of bound ¹⁴C‐residues also occurs readily following inoculation of the soil‐bound residues with fresh soil or with individual microorganisms. Almost complete release of bound residues was observed after incubation for 45 days. The rate of release was rapid during the first two weeks and decreased thereafter. TLC and HPLC analysis showed that the released residues contained DDE (about 80%) and a smaller amount of DDD. The disappearance of DDT from the released residues may be attributed to its microbiological degradation to DDE and DDD, shortly after its release.     

Metabolism of 14C‐carbaryl and 14C‐1‐naphthol in moist and flooded soils

Abstract

The metabolism of ¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol in moist and flooded soils was studied in a continuous flow‐through system over a period of 28 days permitting ¹⁴C‐mass balance. The percent distribution of radiocarbon in organic volatiles, carbon dioxide, extractable and non‐extractable (bound) fractions of soils were determined. Organic volatiles could not be detected in both carbaryl and 1‐naphthol treated soils. More of ¹⁴CO₂ (25.6%) was evolved from moist than flooded soil (15.1%) treated with carbaryl. However, the mineralization of ¹⁴C‐1‐naphthol was negligible. The extractable radiocarbon was more in flooded soil (28.9%) than moist soil (5.5%) from carbaryl treatment. Less than one percent was present as parent compound, whereas carbaryl was mainly metabolized to 5‐hydroxy carbaryl in moist soil and to 4‐ and 5‐hydroxy carbaryl in flooded soil. The extractable radiocarbon amounted to 18.2 and 24.3% in moist and flooded soils respectively and the parent compound was less than one percent with 1‐naphthol treatment. Most of the radiocarbon was found as soil bound residues; the formation being more with 1‐naphthol than carbaryl. Humin fraction of the soil organic matter contributed most to soil bound residues of both carbaryl and 1‐naphthol.     

Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

Fate and residues of 14C‐chloramphenicol in laying chickens 1

Abstract

Studies were conducted to determine the metabolic fate of chloramphenicol (CAP) in White Leghorn using the ^l4C‐labelled compound. In one experiment birds were administered orally via intra‐crop, a single dose of 100 mg (equivalent to 66 mg kg^‐1 body weight) of CAP containing 14 μCi ¹⁴C‐CAP, and its absorption, elimination and distribution in plasma were recorded. Orally dosed ¹⁴C‐compound was rapidly absorbed, efficiently distributed in plasma and eliminated in excreta (>70% in 5 hr). After 5 h, CAP equivalent residues in tissues were lower than 15 μg g^‐1 for this treatment. In a second experiment birds were given intra‐crop dose of either 0.5 or 5 mg of CAP (each dose contained 2.5 μCi ¹⁴C‐CAP) daily for five consecutive days followed by a seven day withdrawal period and elimination of ¹⁴C in excreta and eggs was monitored. More than 95% of the administered ¹⁴C was eliminated within the first 24 h after dosing. Radiocarbon (¹⁴C) was deposited preferentially in yolks compared to albumen or other tissues. Residues declined when feeding was stopped. Various metabolites were isolated and identified by a combination of TLC, LC, and LC‐MS. The main metabolic route of CAP in laying hens appears to be the glucuronidation. Cleavage of the dichloroacetate moiety was only a minor route.     

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.     

Hydrotalcites and organo‐hydrotalcites as sorbents for removing pesticides from water

Abstract

This paper reports on the adsorption of different organic pesticides by hydrotalcite, hydrotalcite heated to 500°C and organo‐hydrotalcite in aqueous medium by employing adsorption isotherms, and using X‐ray diffraction and infrared spectroscopy techniques. The results suggest that the adsorption capacity of the different materials depends on their nature as well as on the structure, polarity and hydrophobic or anionic nature of the pesticides. The results also show that hydrotalcite, both natural and after calcination at 500°C, is not a good sorbent of hydrophobic pesticides. The data demonstrated that both types of hydrotalcite, however, are very good sorbents of glyphosphate. Furthermore, the organo‐hydrotalcites may be as good sorbents as organo‐montmorillonites for hydrophobic pesticides.     

Biological activity and bioavailability of grain bound 14C‐malathion residues in rats

Abstract

Paddy (unmilled rice), milled rice and maize‐bound ¹⁴C residues were prepared using ¹⁴C‐succinate‐labelled malathion at 10 and 152 ppm. After 3 months, the bound residues accounted for 12%, 6.5% and 17.7% of the applied dose in paddy, milled rice and maize respectively in the grains treated at 10 ppm. The corresponding values for the 152 ppm were 16.6%, 8.5% and 18.8%. Rats fed milled rice ‐ bound ¹⁴C‐residues eliminated 61% of the ¹⁴C in the faeces and 28% in the urine. The corresponding percentages for paddy and maize were 72%, 9% and 53%, 41% respectively; indicating that bound residues from milled rice and maize were moderately bioavailable. When rice‐bound malathion residues (0.65 ppm in feed) were administered to rats in a 5 week feeding study, no signs of toxicity were observed. Plasma and RBC cholinesterase activities were slightly inhibited: blood urea nitrogen was significantly elevated in the test animals. Other parameters examined showed no or marginal changes.     

Vertical profiles of air pollutants in a spruce forest — analysis of adherent water,throughfall and deposits on surrogate surfaces

Vertical profiles of air pollutants were studied in a spruce forest, which is damaged mainly in the upper parts of the canopy. The sampling included plant surface water, throughfall and surrogate surfaces at five different heights. For most components a low amount of precipitation after a dry period yielded in vertical profiles of the plant surface water shaped by the wind speed. If there was enough precipitation to start wash-off, the maximum of the concentrations shifted downwards. An exception was the acidity, which increased continuously from the top to the bottom of the trees. The deposition on vertically orientated surfaces and face up orientated surfaces were in the same order of magnitude, but the deposition on face down orientated surfaces was negligible.     

Removal and biosorption of C₆₀ from water by an aquatic plant, Ceratophyllum sp

The fate of fullerene water suspension (FWS) in an aquatic system of Ceratophyllum sp., a rootless submerged plant, under non-sterile sediment-free conditions was investigated. Fast removal of FWS from water by the plants was observed and irreversible adsorption of C₆₀ onto plants and increasing C₆₀ mass on the plant surface with prolonged exposure durations were confirmed. An intact plant extraction procedure was developed and the majority (>80%) of C₆₀ removed from water was extracted from the plants. C₆₀ remained aggregated after being associated with the plants, which was verified by ¹³C NMR spectroscopy. Light micrographs showed association of FWS on and in the cuticle layers.     

Fate of 14C‐lindane in a rice‐fish model ecosystem*

Abstract

A model ecosystem has been used to evaluate the impact of ¹⁴C‐lindane on rice‐fish agricultural system. The distribution of ¹⁴C‐residues among the constituents of the model ecosystem was studied over a period of 90 days. The insecticide was found to be readily absorbed by the roots and translocated to all parts of the rice plant. The peak level in the shoots (26 ppm) and roots (105 ppm) of plants was reached to within three weeks. Lindane was concentrated in fish and residues as high as 90 ppm could be detected after 30 days.

The major part of the residues present in the different constituents of the ecosystem could be extracted with hexane and proved to contain soley the parent compound. The data obtained show that lindane possesses a relatively low biodegradability in fish and in rice plant. The insecticide accumulates in fish and rice plant to considerable extent.     

Relevance of the Paraná River hydrology on the fluvial water quality of the Delta Biosphere Reserve

The increasing frequency of extreme events in large rivers may affect not only their flow, but also their water quality. In the present study, spatial and temporal changes in fluvial physico-chemical variables were analyzed in a mega-river delta during two extreme hydrological years (La Niña-El Niño) and related to potential explanatory factors. Basic water variables were evaluated in situ at 13 points (distant 2–35 km from each other) in watercourses of the Delta Biosphere Reserve (890 km²) in the Lower Paraná River (Argentina) in nine surveys (October 2008–July 2010) without meteorological tides. Samples for laboratory analyses were collected from each main river. Multivariate tests by permutations were applied. The period studied was influenced by a drought, within a long period dominated by low flows combined with dry weather and wildfires, and a large (10 years of recurrence) and prolonged (7 months) flood. The hydrological phase, followed by the season and the hydrological year (according to the ENSO event) were the principal explanatory factors of the main water quality changes, whereas the drainage sub-basin and the fluvial environment (river or stream) were secondary explanatory factors. During the drought period, conductivity, turbidity, and associated variables (e.g., major ions, silicon, and iron concentrations) were maximal, whereas real color was minimal. In the overbanking flood phase, pH and dissolved oxygen concentration were minimal, whereas real color was maximal. Dissolved oxygen saturation was also low in the receding flood phase and total major ion load doubled after the arrival of the overbanking stage. The water quality of these watercourses may be affected by the combination of several influences, such as the Paraná River flow, the pulses with sediments and solutes from the Bermejo River, the export of the Delta floodplain properties mainly by the flood, the season, and the saline tributaries to the Lower Paraná River. The high influence of the hydrology of this large river on the Delta fluvial water quality emphasizes the relevance of changes in its flow regime in recent decades, such as the seasonality attenuation. Considering that the effects of extreme events differ among and within fluvial systems, specific ecohydrological evaluations and powerful appropriate statistics are key tools to gain knowledge on these systems and to provide bases for suitable management measures in a scenario of climate change and increasing human alterations and demands.     

Evaluation of the genotoxic and cytochrome P450 monooxygenase‐inhibitory potential of dicuran on procaryotic and eucaryotic test systems

Abstract

The effect of the herbicide Dicuran 500 FL (formulated product) on the phenotypical and genotypical changes in procaryotic and eucaryotic organisms was investigated using short‐term tests for detecting genotoxins. Since pesticides discharged in the water environment can modulate the mixed‐function monooxygenases (MFO) detoxification system of water organisms, the in vivo and in vitro effects of Dicuran on hepatic cytochrome P450 (cyt P450) monooxygenase activities were also examined in juvenile carp (Cyprinus carpio L.). By measuring the activities of MFO in experimental carp exposed to Dicuran an attempt was made to establish whether Dicuran could be bioactivated by MFO into ultimate mutagens. Our results on the bacterial strains Salmonella typhimurium TA100 and TA98 show that Dicuran does not possess either mutagenic or premutagenic characteristics. The micronucleus test on the erythrocytes of experimental carp did not establish any clastogenic effect either. However, Dicuran significantly inhibited the MFO activity of 7‐ethoxyresorufin‐O‐deethylase (EROD) and benzo[a]pyrene monooxygenase (BaPMO) in the liver of experimental carp in vitro, as well as in in vivo conditions. These findings demonstrate the potentially damaging effect of Dicuran on the xenobiotic metabolizing enzyme systems of fish, and suggest the applicability of described methods for the prediction of the ecotoxicological significance of the presence of pesticides in the water environment.     

Effect of fatty acids and oils on photodegradation of azadirachtin‐A

Abstract

Azadirachtin‐A on exposure to UV‐light (254 nm) as a thin film on glass surface gave a isomerised (Z)‐2‐ methylbut‐2‐enoate product. Half‐life of azadirachtin‐A as thin film under UV light was found to be 48 min. Azadirachtin ‐A was irradiated along with saturated and unsaturated fatty acids, and fatty oils under ultra‐violet light as thin film. Saturated fatty acid increased the rate of photodegradation of azadirachtin‐A, whereas unsaturated fatty acids such as oleic, linoleic and elaidic acid reduced the rate of degradation. Castor, linseed and olive oil accelerated the rate of degradation, whereas neem oil showed no or little change in the rate of degradation of azadirachtin‐A. None of these fatty acids and fatty oils were effective in controlling the rate of degradation of azadirachtin‐A under UV‐light as thin film.     

Effect of agricultural activities on surface water quality from páramo ecosystems

Environmental Science and Pollution Research - Páramos are high mountain ecosystems strategic for water provision in South America. Currently, páramos are under threat due to agricultural...     

Production of OH radicals from the reactions of C4–C6 internal alkenes and styrenes with ozone in the gas phase

OH formation from the ozonolysis reactions of seven internal alkenes with 4–6 carbons, styrene, trans-β-methyl styrene, and α-methyl styrene was studied using complementary techniques. A small-ratio relative-rate technique in which small quantities of OH tracers are added to monitor OH formation yields provided the following results: trans-2-butene, 0.64±0.12; cis-2-butene, 0.33±0.05; trans-2-pentene, 0.46±0.08; cis-2-pentene, 0.29±0.06; trans-3-hexene, 0.53±0.08; cis-3-hexene, 0.36±0.07; and 2-methyl-2-butene, 0.98±0.24. For styrene, trans-β-methyl styrene, and α-methyl styrene, OH yields of 0.07±0.04, 0.22±0.09, and 0.23±0.12 were measured, respectively. A second method, which monitors product formation from the OH reaction with 2-butanol was used to derive OH formation yields from 2,3-dimethyl-2-butene, 2-methyl-2-butene and cis-2-pentene, and provided yields of 0.91±0.14, 0.80±0.12, and 0.27±0.07, respectively. The results are briefly discussed in terms of the relationship between structures of these alkenes and OH formation.     

Impact of financial development and technological innovation on the volatility of green growth—evidence from China

Environmental Science and Pollution Research - China’s green growth has shown a trend of fluctuation year by year. Simultaneously, Chinese local governments have pursued simple economic...     

Evidence of the water-cage effect on the photolysis of NO3− and FeOH2+. Implications of this effect and of H2O2 surface accumulation on photochemistry at the air–water interface of atmospheric droplets

Experiments are conducted to determine the effect of a cage of water molecules on the photolysis quantum yields of nitrate, FeOH²⁺, and H₂O₂. Results suggest that the quantum yields of nitrate and FeOH²⁺ are decreased by the recombination of photo-fragments ( OH +  NO₂ and Fe²⁺ +  OH, respectively) before they leave the surrounding cage of water molecules. However, no evidence is found for an enhanced quantum yield for H₂O₂. Therefore, the photolysis of nitrate and FeOH²⁺ could be enhanced if the cage of the solvent molecules is incomplete, as is the case at the air–water interface of atmospheric droplets. The photolysis rate constant distribution within nitrate, FeOH²⁺, and H₂O₂ aerosols is calculated by combining the expected quantum yield data in the bulk and at the interface with Mie theory calculations of light intensity. The photolysis rate constant of nitrate and FeOH²⁺ would be significantly higher at the surface than in the bulk if quantum yields are enhanced at the surface. In the case of H₂O₂, the photolysis rate constant would be enhanced by surface accumulation. The results concerning the expected rates of photolysis of these photoactive species are applied to the assessment of the reaction between benzene and OH in the presence of OH scavengers in an atmospherically relevant scenario. For a droplet of 1 μm radius, a large fraction of the total OH-benzene reaction (15% for H₂O₂, 20% for nitrate, and 35% for FeOH²⁺) would occur in the surface layer, which accounts for just 0.15% of the droplet volume.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in a sediment–water system

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (¹⁴C-CfP) was studied for 28 days in lab assays using a sediment–water system derived from a German location. Mineralization was 5.21% of applied ¹⁴C after 28 days exhibiting a distinct lag phase until day 14 of incubation. Portions of radioactivity remaining in water phases decreased at moderate rate to 18.48% after 28 days; 62.46% were still detected in water after 14 days. Soxhlet extraction of the sediment using acetonitrile released 35.56% of applied ¹⁴C with day 28, while 33.99% remained as non-extractable residues. A remarkable increase of bound ¹⁴C was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with microbial activity of the sediment as determined by dimethyl sulfoxide reduction. Dissolved oxygen and pH value of water phases remained almost constant for 28 days. Analyses of Soxhlet extracts of the sediment and ethyl acetate extracts of water phases by radio-TLC and radio-HPLC revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed. DT₅₀ values (based on radio-HPLC) were below 1 day (CfP) and slightly above 28 days (Cf). Further metabolites were not detected. Fractionation of humic and non-humic components of the sediment demonstrated that CfP's non-extractable residues were predominantly associated with fulvic acids up to 14 days of incubation (3.36%), whereas after 28 days, the majority of radioactivity was found in the humin/mineral fraction (13.30% of applied ¹⁴C). Due to high-performance size-exclusion chromatography of the fulvic acids fraction derived from assays incubated for 28 days, this portion of ¹⁴C was firmly, possibly covalently bound to fulvic acids and did not consist of CfP or Cf. Using an isolation strategy comprising preincubation of sediment with CfP and mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the sediment examined. It grew on ¹⁴C-CfP as sole carbon source with evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and 16S rDNA sequence analysis. Its sequence exhibited high similarity with that of Nocardioides aromaticivorans strain H-1 (98.85%; DSM 15131, JCM 11674).