Aerosols formed from the chemical reaction of monoterpenes and ozone

Chamber experiments were conducted to study the aerosol products from the ozonolysis of the major atmospheric monoterpenes; α-pinene, β-pinene and limonene. It was found that the α-pinend–O₃ reaction produced mainly 2′. 2′-dimethyl-3′-acetyl cyclobutyl ethanal (pinonaldehyde), the β-pinene–O₃ reaction, mainly 6,6-dimethyl-bicyclo [3.1.1] heptan-2-one and the limonene–O₃ reaction, several unidentified products. These products were sought in forest aerosols and pinonaldehyde was detected in the atmosphere.     

植物对Cd-B[α]P复合污染土壤的修复

为了研究植物对Cd-B[α]P复合污染土壤的修复效果,本研究采取实验室模拟实验的方法,通过种植黑麦草、芥菜、苜蓿和高羊茅,进行Cd、B[α]P污染土壤修复植物的筛选。结果表明,芥菜和黑麦草对土壤中有效态Cd均有富集能力。黑麦草对B[α]P污染土壤修复效果比苜蓿、高羊茅的修复效果强,75 d时,平均富集系数最高为1.1。在Cd-B[α]P复合污染土壤植物修复效果的研究中,选择在土壤中种植黑麦草,结果表明,黑麦草对Cd-B[α]P复合污染土壤中Cd和B[α]P 有良好地去除作用,75 d时,分别达到58.55%和89.95%。     

Some Improvements in the Determination of Benzo [α] Pyrene in Air Samples

The earliest measurements of benz[α]pyrene (BαP) in air samples were almost exclusively based on chroma-tography on alumina columns followed by ultraviolet absorption, in spite of the fact that the original discovery and isolation of BαP in coal tar was based on its fluorescence properties. With the increasing use of fluorescence techniques, the vastly increased sensitivity over ultraviolet measurements has become generally apparent. In air sample extracts containing the four polycyclics, benzo[a]pyrene (BαP) benzo[k]-fluoranthene (BkF), benzo[g,h,i]perylene, (BghiP), and BαP, ultraviolet measurements for BαP are particularly, inaccurate. Fluorescence measurements of BαP are much more accurate, but some improvement in accuracy seems desirable. The present work deals with improvement of the fluorescence measurement of BαP. It now is possible to measure BαP in the presence of BkF with greatly increased accuracy. Interferences resulting from the presence of benzo[k]fluoranthene are now much lower.     

Gene expression of heat shock protein 70, interleukin-1β and tumor necrosis factor α as tools to identify immunotoxic effects on Xenopus laevis: a dose-response study with benzo[a]pyrene and its degradation products

The exposure to benzo[a]pyrene (B[a]P) results in an alteration of immune function in mammals and fish, and the analysis of cytokine mRNA levels has been suggested for predicting the immunomodulatory potential of chemicals. To obtain evidence of the innate immune responses to B[a]P in Xenopus laevis, the present study monitored the mRNA expression of interleukin 1-β (IL-1β), tumor necrosis factor α (TNF-α) and heat shock protein 70 (HSP70) in a laboratorial exposure. Tadpoles exposed to 8.36, 14.64, 89.06 and 309.47 μg/L of B[a]P,were used for detecting hsp70, IL-1β and TNF-α mRNA induction. A dose-response increase in the expression of hsp70 and IL-1β mRNA was found. The results of this study confirmed the use of hsp70 and IL-1β, but not TNF-α, as sensitive indicators of immunotoxic effect of B[a]P in X. laevis. Further research would be required for the validation of these endpoints.     

Metabolism of DDT in Different Tissues of Young Rats

The bioconcentration and distribution pattern of p,p′-DDT 1,1,1-1trichloro-2,2-bis(2-chlorophenyl-4-chlorophenyl)-ethane] and its main metabolites (p,p′-DDD [1,1-dichloro-2,2-bis (4-chlorophenyl) ethane] and p,p′-DDE [1,1-dichloro-2,2-bis (4-chlorophenyl) in adipose tissue, liver, brain, kidney, thymus, and testis were examined in young rats after 10 days of intraperitoneal injection of 50 and 100 mg of p,p′-DDT/kg of body weight. Analyses were performed by high-resolution gas chromatography. p,p′-DDT was found to be accumulated in a dose-dependent manner with the highest concentration in adipose tissue. However, in brain, the accumulation of pesticide was low and remained unchanged at the higher dose. This difference may relate to the protective role of the blood-brain barrier, which limits the access of the xenobiotic in the cerebral compartment, and to the differential tissue lipid composition. Although tissues concentration of p,p′-DDE and p,p′-DDD correlated positively to total p,p′-DDT levels, the active role in detoxification of pollutants may explain why p,p′-DDD is more abundant in liver than in the rest of organs. On the contrary, in brain, the concentration of p,p′-DDE is higher than that of p,p′-DDD, suggesting that the metabolism of the parent insecticide proceeds via more than one pathway.     

Simultaneous detection and degradation patterns of kresoxim-methyl and trifloxystrobin residues in citrus fruits by HPLC combined with QuEChERS

This study aimed to investigate the residues, kinetics and dissipation patterns of kresoxim-methyl, (E)-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate, and trifloxystrobin, methyl(E)-methoxyimino-{(E)-α[1-(α,α,α-trifluoro-m-tolyl)ethylideneaminooxy]-o-tolyl}acetate”. A simple and sensitive liquid chromatography-ultraviolet detection (LC-UV) method combined with the ‘Quick Easy Cheap Effective Rugged and Safe' (QuEChERS) protocol was developed to quantify the levels of kresoxim-methyl and trifloxystrobin residues in citrus. More than 97% of the kresoxim-methyl and trifloxystrobin deposists gradually dissipated from the citrus peels within 15 days. The half-lives of kresoxim-methyl and trifloxystrobin in the peels were in the ranges of 2.63–2.66 d and 3.12–3.15 d, respectively, and the pattern of decline in the peels followed first-order kinetics. The kresoxim-methyl and trifloxystrobin residues in the pulp dissipated below the detectable level of 0.01 mg kg^?1 after 9 days. Kresoxim-methyl and trifloxystrobin were easily decomposed (T_1/2 < 30 d), and the observed dissipation patterns could support the application of these two fungicides in the postharvest storage of citrus fruits.     

Removal of Aldrin,Dieldrin, Heptachlor,and Heptachlor Epoxide Using Activated Carbon and/or Pseudomonas fluorescens Free Cell Cultures

Degradation of aldrin (1,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro-1,4:5-8-dimethanonaphthalene), heptachlor (1H-1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methano indene), dieldrin (1aα,2β,2aα,3β,6β,6aα,7β,7aα)-3,4,5,6,9,9-Hexachloro-1a,2,2a,3,6,6a,7,7a-octahydro-2,7:3,6-d-methanonaphtha[2,3-b]oxirene, and heptachlor epoxide (1aα, 1bβ,2α,5α,5αβ,6β,6aα-2,3,4,5,6,7,7-Heptachloro-1a,1b,5,5a,6,6a-hexahydro-2,5-methano-2H-inden[1,2-b]-oxirene) was tested using free cultures of Pseudomonas fluorescens under controlled conditions. Pesticide concentrations were monitored by gas chromatography during 120 h. Percentages of degradation and biodegradation rates (BDR) were calculated. Data showed a trend suggesting a relation between chemical structure and degradability. Degradation kinetics for each pesticide tested showed that the highest degradation rates were found in the first 24 h. Kinetics data were adjusted to an empirical equation in order to predict their behavior, and the correlation coefficients obtained were satisfactory. Gas chromatography/mass spectrometry (GC/MS) analysis of the final extracts allowed the identification of chlordene and monodechlorodieldrin, which have been reported as final metabolite produced in the biodegradation of this kind of compounds. Regarding adsorption of pesticides on activated vegetal carbon, we concluded that removal efficiencies between 95.45 and 97.18% can be reached, depending on the pesticide and the carbon dose applied. The values for K from the Freundlich equation were quite similar for the four pesticides (between 1.0001 and 1.04), whereas the n values were quite different for each pesticide in the following order of affinity: dieldrin > aldrin > heptachlor epoxide > heptachlor. Equilibrium times, very important for scaling up the process, were between 43 min and 1 h, for the heptachlor epoxide and the heptachlor, respectively.     

Aerobic and anaerobic degradation of profluralin and trifluralin

Abstract

The degradation of profluralin [N‐(cyclopropylmethyl)‐α,α,α‐trifluoro‐2,6‐dinitro‐N‐propyl‐]p‐toluidine] and trifluralin (α,α,α‐trifluoro‐2,6‐dinitro‐N,N‐dipropyl‐p‐toluidine) was studied under aerobic and anaerobic soil conditions. Three soils (Goldsboro loamy sand, Cecil loamy sand, Drummer clay loam) were each treated with 1 ppmw herbicide; anaerobic conditions were maintained by flooding. Soil samples were extracted monthly and subjected to TLC analysis. No degradation was detected in sterile controls. Aerobic degradation of both herbicides was greatest in the Cecil loamy sand soil over the entire incubation period. Degradation of profluralin in Cecil soil under aerobic conditions was 86 percent after 4 months with three products detected; 83 percent of the trifluralin was degraded with two products detected. Anaerobic degradation accounted for 72 percent of the profluralin and 78 percent of the trifluralin after 4 months. Degradation of both herbicides increased with incubation time for the first 3 months and decreased slightly thereafter. Generally there was more extensive degradation (percent and in number of products formed) of profluralin than trifluralin under the conditions tested. More degradation products were detected for both herbicides under aerobic conditions than under anaerobic conditions.     

Aerosols formed from the chemical reaction of monoterpenes and ozone

Chamber experiments were conducted to study the aerosol products from the ozonolysis of the major atmospheric monoterpenes; α-pinene, β-pinene and limonene. It was found that the α-pinene-O₃ reaction produced mainly 2′, 2′-dimethyl-3′-acetyl cyclobutyl ethanal (pinonaldehyde), the β-pinene-O₃ reaction, mainly 6,6-dimethyl-bicyclo [3.1.1] heptan-2-one and the limonene-O₃ reaction, several unidentified products. These products were sought in forest aerosols and pinonaldehyde was detected in the atmosphere.     

Minor crops for export: A case study of boscalid,pyraclostrobin, lufenuron and lambda-cyhalothrin residue levels on green beans and spring onions in Egypt

Dissipation rates of boscalid [2-chloro-N-(4′ -chlorobiphenyl-2-yl)nicotinamide], pyraclostrobin [methyl 2-[1-(4-chlorophenyl) pyrazol-3-yloxymethyl]-N-methoxycarbanilate], lufenuron [(RS)-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-3-(2,6-difluorobenzoyl)urea] and λ-cyhalothrin [(R)-cyano(3-phenoxyphenyl)methyl (1S,3S)-rel-3-[(1Z)-2-chloro-3,3,3-trifluoro-1-propenyl]-2,2-dimethylcyclopropanecarboxylate] in green beans and spring onions under Egyptian field conditions were studied. Field trials were carried out in 2008 in a Blue Nile farm, located at 70 kilometer (km) from Cairo (Egypt). The pesticides were sprayed at the recommended rate and samples were collected at pre-determined intervals. After treatment (T₀) the pesticide residues in green beans were 7 times lower than in spring onions. This is due to a different structure of vegetable plant in the two crops. In spring onions, half-life (t_1/2) of pyraclostrobin and lufenuron was 3.1 days and 9.8 days respectively. At day 14th (T₁₄) after treatment boscalid residues were below the Maximum Residue Limit (MRL) (0.34 versus 0.5 mg/kg), pyraclostrobin and λ -cyhalothrin residues were not detectable (ND), while lufenuron residues were above the MRL (0.06 versus 0.02 mg/kg). In green beans, at T₀, levels of boscalid, lufenuron and λ -cyhalothrin were below the MRL (0.28 versus 2 mg/kg; ND versus 0.02 mg/kg; 0.06 versus 0.2 mg/kg, respectively) while, after 7 days treatment (T₇) pyraclostrobin residues were above the MRL (0.03 versus 0.02 mg/kg). However, after 14 days the residue level could go below the MRL (0.02 mg/kg), as observed in spring onions.     

Surfactant effect on persistence of oxadiazolyl 3(2H)-pyridazinones against Pseudaletia separata walker

The photodynamic decomposition of two new insect-growth inhibitors (IGRs), 2-tert-butyl-5-[5′-aryl-2′-(1′,3′,4′-oxadiazolyl)methoxy]-3(2H)-pyridazinones (OPB) and its 4-chloro substituted derivative (OPC), and effect of surfactants on persistence of their bioactivity were taken into investigation. Both chemicals were significantly induced to photolysis by ultraviolet light at 365 nm wavelength and their inhibitory activities against Pseudaletia separata larvae decreased with the increasing irradiation time. However, irradiation at 254 nm wavelength didn't cause their photodegradation. Triton X-100 and Succinic-sulfonie acidic sodium but not Tween 60 possessed strong capability to slow down the decomposition and obviously prolonged the half life of OPC in laboratory and field whilst effects of the three surfactants almost did not preserve the inhibitory activity of OPB. Data suggested that electron-withdrawing halogen (?Cl) on the π electron system in planar benzene-oxadialyl structures might reduce the efficiency of OPC on ultraviolet (UV) photoabsorption, and its hydrophobic interaction with the surfactants might be beneficial for forming stable micellar solubilization, thus sustaining the chemical's bioactivity.     

Toxicity of imidazolium salt with anion bromide to a phytoplankton Selenastrum capricornutum: effect of alkyl-chain length

Room-temperature ionic liquids are regarded as environmentally benign alternatives to volatile organic solvents. However, the product designs for this promising group of compounds should take account, not only the technological needs, but also the eco-toxicological hazards. Therefore, this study aimed to evaluate the toxicity of some important ionic liquids on the growth of the freshwater alga, Selenastrum capricornutum. The ionic liquids examined in this study included 1-propyl-3-methylimidazolium [PMIM], 1-butyl-3-methylimidazolium [BMIM], 1-hexyl-3-methylimidazolium [HMIM] and 1-octyl-3-methylimidazolium [OMIM] with a bromide anion. The susceptibility of alga to ionic liquids was strongly dependent on the alkyl-chain length. According to our results, a longer alkyl-chain resulted in stronger inhibition of algal growth. In general, the toxicity could be summarized as decreasing in the following order: [OMIM]>[HMIM]>[BMIM]>or=[PMIM]. Among the ionic liquids examined, [OMIM] [Br] was found to be most toxic to S. capricornutum, with EC(50) values ranging from 26.3 microM to 54.9 microM after an incubating time of 96 h. Although [BMIM] [Br] and [PMIM] [Br] was relatively less toxic than [OMIM] and [HMIM], their toxicity increased as increasing the incubation time from 48 h to 96 h. This fact indicates that these kinds of ionic liquids may become more toxic after being released and contacted to freshwater ecosystem.     

Photodechlorination of polychlorinated biphenyls in the presence of hydroquinone in aqueous alcoholic media

On exposure to sunlight or photolysis at λ >300nm, the dechlorination of a polychlorinated biphenyl mixture (Aroclor 1254) in the H donor alcohol 2-propanol under neutral conditions is enhanced by the presence of the photosensitizer hydroquinone. Dechlorination is strongly promoted by an increasingly aqueous solvent (1:1 water:alcohol) and by maintaining neutral conditions (pH 7.0 buffer) both in the presence and absence of sensitizer. Atmospheric oxygen (continuous aeration) retards the hydroquinone induced dechlorination less than the direct photolysis process.     

Isolation and identification of chlorpropham and two of its metabolites in potatoes by GC-MS

Chloropropham [(3-chlorophenyl)carbamic acid 1-methylethyl ester] (CPP) and two of its metabolite/degradation products, 3-chloroaniline (3-CA) and 3,3′-dichloroazobenzene (3,3′-DCAB), were analyzed in potato peels obtained from market potatoes from several geographic regions. Residues were screened for by capillary EC-GLC and quantitated by capillary GC-MS using single ion monitoring. This permitted the simultaneous analysis of all three compounds in peel extracts, with minimal cleanup, at the ppb level. Residue levels of 21–166 ppb (CPP), 0.18–0.36 ppb (3-CA) and 2–39 ppb (3,3′-DCAB) were found in several samples.     

Leaching of azoxystrobin and its degradation product R234886 from Danish agricultural field sites

The objective was to estimate leaching of the fungicide azoxystrobin (methyl (αE)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]-α-(methoxymethylene)benzene-acetate) and one of its primary degradation products R234886 ([(E)-2-(2-[6-cyanophenoxy)-pyrimidin-4-yloxyl]-phenyl-3-methoxyacrylic acid], major fraction) at four agricultural research fields (one sandy and three loamy) in Denmark. Water was sampled from tile drains, suction cups and groundwater wells for a minimum period of two years after application of azoxystrobin. Neither azoxystrobin nor R234886 were detected at the sandy site, but did leach through loamy soils. While azoxystrobin was generally only detected during the first couple of months following application, R234886 leached for a longer period of time and at higher concentrations (up to 2.1 μg L⁻¹). Azoxystrobin is classified as very toxic to aquatic organisms and R234886 as very harmful. Our study shows that azoxystrobin and R234886 can leach through loamy soils for a long period of time following application of the pesticide and thereby pose a potential threat to vulnerable aquatic environments and drinking water resources. We thus recommend the inclusion of azoxystrobin and R234886 in pesticide monitoring programmes and further investigation of their long-term ecotoxicological effects.     

Carcinogenicity of Organic Extracts of Atmospheric Pollutants

The carcinogenicity of atmospheric pollutants from various urban sources in the U.S.A. has been demonstrated by the subcutaneous injection of trace quantities of organic extracts in newborn mice. The incidence of tumors, which included hepatomas, multiple pulmonary adenomas, and lymphomas, varied widely with the source of the pollutant. The results of these experiments indicate that, besides benzo[α] pyrene, other major classes of carcinogens are also present in polluted air. These experiments also indicate a high potential carcinogenic hazard of polluted air to man.     

Degradation of fipronil under laboratory conditions in a tropical soil from sirinhaém pernambuco,Brazil

The objective of this research was to assess the degradation of fipronil [5-amino-1-(2,6-dichloro-α,α,α -trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile] in soils from sugar cane fields in Northeastern Brazil. Degradation experiments were carried out under laboratory conditions (controlled temperature and in the dark), where sterile and non-sterile soils (Ustoxs) were incubated [under moisture content of 55% of the water holding capacity (WHC)] and analyzed for fipronil disappearance and metabolite formation. Microbial communities present in the soil degrade fipronil. However, biodegradation seems to be dependent on the bioavailability of the fipronil and the half-life according to the zero-order model. Fipronil degradation rate appeared to be biphasic. Degradation fipronil ranged from 83 days (initial concentration = 978 ng g^{? 1}; short-term experiment) to 200 days (initial concentration = 689 ng g^{? 1}; long-term experiment). This an initial slower rate followed by a faster rate after 90 days of incubation may lead to shorter half-life than that calculated with the zero-order model. The sulfone derivative (an oxidation product) was the predominant metabolite, but the sulfide (a reduction product) and amide (a hydrolysis product) derivatives were also formed under non-sterile conditions after 120 days of incubation. The metabolites underwent further biodegradation, particularly the sulfone derivative. Bioavailability appears to affect fipronil degradation in soils with an effective capacity to adsorb fipronil (such as Ustoxs), while redox potential was important for the formation of metabolites. Despite the fine texture, more aerobic sites were present, thus favoring the formation of the sulfone metabolite over that of the sulfide metabolite. Therefore, microaggregation of Ustoxs, with high clay content, played a very important role in determining the types of metabolites formed.     

Synthesis of [14C]biphenyl and of some chlorinated [14C]biphenyls containing 4-chloro-, 2,4-dichloro- and 2,3,6-trichlorophenyl nuclei from the corresponding labelled anilines

The preparation of ¹⁴C-labelled biphenyl, 2,5-dichlorobiphenyl, 2,4′,5-trichlorobiphenyl, 2,2′,4,5′-tetrachlorobiphenyl, 2′,3,4,4′,5-pentachlorobiphenyl, 2,2′,3,4,4′-pentachlorobiphenyl, 2,3,3′,4′,6-pentachlorobiphenyl and 2,2′,3,3′,6-pentachlorobiphenyl is described [¹⁴C]Aniline hydrogen sulfate used as a starting material was acetylated, chlorinated and deacetylated followed by coupling to benzene or an appropriate chlorobenzene to give the biphenyls labelled in the phenyl nuclei having chlorine atoms at the 4-, 2,4- or 2,3,6-positions, respectively. The structures of the labelled compounds were established by comparison with authentic samples among which 2′,3,4,4′,5- and 2,2′,3,4,4′-pentachlorobiphenyl were not earlier described.A simple method for the preparation of 2,3,6-trichloroacetanilide, unlabelled and labelled, was worked out. 2,6-Dichloroacetanilide in concentrated hydrochloric acid gave the $\text{meta}$ substituted product when treated with chlorine.An improved thin layer chromatographic technique utilizing plates impregnated with certain tetraalkylammonium salts was used for separation of some of the labelled compounds prepared.     

Anaerobic testosterone degradation in Steroidobacter denitrificans - Identification of transformation products

The transformation of the androgenic steroid testosterone by gammaproteobacterium Steroidobacter denitrificans was studied under denitrifying conditions. For the first time, growth experiments showed that testosterone was mineralized under consumption of nitrate and concurrent biomass production. Experiments with cell suspensions using [4-¹⁴C]-testosterone revealed the intermediate production of several transformation products (TPs). Characterisation of ten TPs was carried out by means of HPLC coupled to high resolution mass spectrometry with atmospheric pressure chemical ionization as well as ¹H and ¹³C NMR spectroscopy. 3β-hydroxy-5α-androstan-17-one (trans-androsterone) was formed in the highest amount followed by 5α-androstan-3,17-dione. The data suggests that several dehydrogenation and hydrogenation processes take place concurrently in ring A and D because no consistent time-resolved pattern of TP peaks was observed and assays using 2 TPs as substrates resulted in essentially the same TPs. The further transformation of testosterone in S. denitrificans seems to be very efficient and fast without formation of detectable intermediates.     

Mitigating nitrous oxide and methane emissions from soil in rice-wheat system of the Indo-Gangetic plain with nitrification and urease inhibitors

Mitigation of methane (CH4) and nitrous oxide (N2O) emissions from soil is important to reduce the global warming. Efficacy of five nitrification inhibitors, i.e. neem (Azadirachta melia) cake, thiosulphate, coated calcium carbide, neem oil coated urea and dicyandiamide (DCD) and one urease inhibitor, hydroquinone, in mitigating N2O and CH4 emissions from fertilized soil was tested in rice-wheat system in the Indo-Gangetic plains. The closed chamber technique was used for the collection of gas samples, which were analyzed using gas chromatography. Reduction in N2O emission on the application of nitrification/urease inhibitors along with urea ranged from 5% with hydroquinone to 31% with thiosulphate in rice and 7% with hydroquinone to 29% with DCD in wheat crop. The inhibitors also influenced the emission of CH4. While application of neem coated urea, coated calcium carbide, neem oil and DCD reduced the emission of CH4; hydroquinone and thiosulphate increased the emission when compared to urea alone. However, the global warming potential was lower with the inhibitors (except hydroquinone) as compared to urea alone, suggesting that these substances could be used for mitigating greenhouse gas emission from the rice-wheat systems.