Sorption of alpha and beta hydrophobic endosulfan in a Vertisol from southeast region of Turkey

Endosulfan has been applied to control numerous insects in a variety of food and non-food crops. Limited information is available on dynamics of this pesticide in the soil. The objective of this research was to determine the adsorption–desorption behavior of the alpha (α) and beta (β) endosulfan in a Vertisol from the southeast region of Turkey, where cotton is the main crop in the large irrigated lowlands. The α and β endosulfan were adsorbed considerably and Freundlich adsorption–desorption isotherms fitted the α and β endosulfan data (R² > 0.98). Freundlich adsorption coefficients (K_f) for the α endosulfan ranged between 21.63 and 16.33 while for the β endosulfan they were between 14.01 and 17.98 for the Ap and Bw2 horizons. The difference of K_f values of α and β endosulfan for two horizons were explained with the slight difference in the amount of organic matter and clay, but considerable difference in Fe contents of the two horizons. Alpha and β endosulfan K_fd values were 118.03 and 45.81 for the Ap and 48.08 and 68.71 for the Bw2 horizons. Higher adsorption and desorption behavior of the endosulfan isomers for the same horizon was attributed to poor physical bonding between the endosulfan molecule and the surfaces of fundamental soil particles. This fact is thought to increase the effective use of endosulfan in agriculture with a possibility of its movement to the surface and groundwater in the Vertisol studied.     

Organochlorine pesticides in Avicennia marina from the Mumbai mangroves, India

This paper examines the concentration levels of organochlorine pesticides (OCPs) such as hexachlorocyclohexane (HCH) (α, β and γ), Aldrin, Endosulfan (α, β), DDE, DDD, and DDT in the leaf, root and sediment part of Avicennia marina, a dominantly distributed mangrove species in Mumbai. The overall pattern of accumulation of OCPs was observed as ∑HCH > ∑DDT > ∑Endosulfan > Aldrin. The occurrence of αHCH was found to be frequent in all the samples. The leaf and root samples showed better uptake of organochlorine pesticides whereas lower concentration levels of OCPs was observed in case of sediment samples. The mean concentration of OCPs was observed highest in case of root samples. This study indicated towards the capability of A. marina in bioaccumulation of the OCPs. The present data will serve as the baseline against which future study of OCPs uptake in the mangrove plant species may be assessed.     

Determination of flame-retardant hexabromocyclododecane diastereomers in textiles

To establish a concise and rapid procedure to analyze hexabromocyclododecane (HBCD) diastereomers in flame-retarded textiles, three different methods of extraction—Soxhlet, ultrasonic, and soaking extractions with toluene and dichloromethane (DCM)—were compared. During Soxhlet extraction using toluene, the percent contribution of α-HBCD to total HBCDs increased slightly and that of γ-HBCD decreased, indicating that γ-HBCD was isomerized to some extent at the boiling point of toluene (110.6 °C). For ultrasonic extraction, the temperature of the water bath can easily increase over time during the procedure, which might lead to undesirable effects. Therefore, we considered soaking extraction with DCM to be the most facile procedure to analyze HBCD diastereomers in textiles. Using the method established in this study, commercially available textiles in Japan (n = 10) were analyzed to understand the actual composition of HBCD contents and its diastereomer profiles. With the exception of one textile sample, HBCDs were detected in all the samples analyzed, with concentrations ranging from 22 000 to 43 000 mg kg⁻¹ (i.e. 2.2–4.3%). We found a higher proportion of the α-diastereomer in most textile products compared with that of commercial HBCD mixtures, indicating that γ-HBCD isomerized to α-diastereomer by heating processes to incorporate the commercial formulation into treated materials or that the α-diastereomer preferentially absorbed onto textile materials during the manufacturing of flame-retarded consumer products.     

Occurrence and distribution of atmospheric organic micropollutants in conifer needles

The distribution of some chlorinated hydrocarbons(p,p′-DDT, p,p′-DDE,α-HCH,γ-HCH,HCB) in spruce (Picea abies) needles was investigated. A comparision of concentrations in the wax with that of the remaining needle and time-resolved washing of the needle-surface shows the distribution behaviour of these substances.     

Converging hydrostatic and hydromechanic concepts of preferential flow definitions

The boundary between preferential flow and Richards-type flow is a priori set at a volumetric soil water content θ at which soil water diffusivity D (θ) = η (= 10^− 6 m² s^− 1), where η is the kinematic viscosity. First we estimated with a hydrostatic approach from soil water retention curves the boundary, θ^K, between the structural pore domain, in which preferential flow occurs, and the matrix pore domain, in which Richards-type flow occurs. We then compared θ^K with θ that was derived from the respective soil hydrological property functions of same soil sample. Second, from in situ investigations we determined 96 values of θ^G as the terminal soil water contents that established themselves when the corresponding water-content waves of preferential flow have practically ceased. We compared the frequency distribution of θ^G with the one of θ that was calculated from the respective soil hydrological property functions of 32 soil samples that were determined with pressure plate apparatuses in the laboratory. There is support of the notion that θ^K ≈ θ^G ≈ θ, thus indicating the potential of θ to explain more generally what constitutes preferential flow. However, the support is assessed as working hypothesis on which to base further research rather than a procedure to a clear-cut identification of preferential flow and associated flow paths.     

Application of simple soil-water flow models to the transfer of surface-applied solutes to streams

In the context of leaching of surface-applied nitrate fertilizer to runoff, this paper evaluates the performance of five simple predictive models, based upon: (1) field capacity; (2) uniform displacement; (3) wetting front; (4) by-passing (preferential) flow; and (5) soil-water domains. Predicted behaviour and observed on an 85-cm depth soil are compared for leaching depth and outflow response. Predictive success of outflow by the models for 40 monitored rainfall events were: (1) 60%; (2) 52%; and (3) 76%. For the by-passing flow model (4), simple prediction of pedal excess flow (4a) gave a success of 80%; where calculations of the operational volume in preferential flow were involved (4b), variations from 20 to 100% success occurred for a range of operational volumes, the lowest volumes giving the greatest success (4c). The soil-water domain model (5) is a simple, predictive scheme involving the classification of outflow events according to antecedent soil moisture (θ_a); the method uses the mobile: retained water content (θ_r) at 2 bars and field capacity (θ_fc). Using soil-water domains alone was of limited success but when the domains were combined with rainfall intensity, the scheme specified outflow exactly. Thus, for θ_a < θ_r, no soil-water outflow occurred, even at high rainfall intensity; for θ_a >θ_fc outflow always occurred, even at low rainfall intensity and for θ_a >θ_r < θ_fc the simple by-passing model (4a) achieved 100% predictive success. The implications for fertilizer application are discussed.     

Large outdoor chamber experiments and computer simulations: (I) Secondary organic aerosol formation from the oxidation of a mixture of d-limonene and α-pinene

This work merges kinetic models for α-pinene and d-limonene which were individually developed to predict secondary organic aerosol (SOA) formation from these compounds. Three major changes in the d-limonene and α-pinene combined mechanism were made. First, radical–radical reactions were integrated so that radicals formed from both individual mechanisms all reacted with each other. Second, all SOA model species from both compounds were used to calculate semi-volatile partitioning for new semi-volatiles formed in the gas phase. Third particle phase reactions for particle phase α-pinene and d-limonene aldehydes, carboxylic acids, etc. were integrated. Experiments with mixtures of α-pinene and d-limonene, nitric oxide (NO), nitrogen dioxide (NO₂), and diurnal natural sunlight were carried out in a dual 270 m³ outdoor Teflon film chamber located in Pittsboro, NC. The model closely simulated the behavior and timing for α-pinene, d-limonene, NO, NO₂, O₃ and SOA. Model sensitivities were tested with respect to effects of d-limonene/α-pinene ratios, initial hydrocarbon to NO_x (HC₀/NO_x) ratios, temperature, and light intensity. The results showed that SOA yield (Y_SOA) was very sensitive to initial d-limonene/α-pinene ratio and temperature. The model was also used to simulate remote atmospheric SOA conditions that hypothetically could result from diurnal emissions of α-pinene, d-limonene and NO_x. We observed that the volatility of the simulated SOA material on the aging aerosol decreased with time, and this was consistent with chamber observations. Of additional importance was that our simulation did not show a loss of SOA during the daytime and this was consistent with observed measurements.     

Organochlorine pesticides and polybrominated diphenyl ethers in irrigated soils of Beijing, China: Levels, inventory and fate

Limited information on the levels, inventory and fate of Organochlorine pesticides (OCPs) and Polybrominated diphenyl ethers (PBDEs) in the soils irrigated by sewage or wastewater is available. In this study, variation in concentrations, profiles and fate of OCPs and PBDEs were investigated using soil samples collected from a region irrigated by sewage, mixed water and clean water in the east of Beijing, China. No significant variation was observed among groups, except for penta-BDEs. The measured ΣOCPs and ΣPBDEs residues ranged from 6.4 to 171.2 ng g⁻¹ (dw) and 501.9 to 3310.7 pg g⁻¹ (dw), respectively. ΣDDTs and BDE-209 were the most abundant congeners accounting for about 76% of ΣOCPs and 93% of ΣPBDEs. Concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane (DDTs) and its major degradation products, and hexachlorobenzene (HCB) ranged from 1.2 to 11.4 ng g⁻¹ (dw), 4.0 to 155.6 ng g⁻¹ (dw) and 0.3 to 3.4 ng g⁻¹ (dw), respectively. The major DDT degradation products were p,p′-DDT and p,p′-DDE. The major hexachlorocyclohexane (HCH) isomer in irrigated soils is β-HCH, reflecting its higher affinity to solids and resistance to degradation than other isomers. Both α-HCH/β-HCH and p,p′-DDT/p,p′-DDE ratios were log-normally distributed and negatively correlated to log(ΣHCHs) and log(ΣDDTs), respectively, suggesting no significant recent application of OCPs. Individual BDE congeners, ΣPBDEs and ΣOCPs were significantly correlated with total organic carbon (TOC). Moreover, a good correlationship between ΣPBDEs and black carbon (BC) was obtained but not between ΣOCPs and BC. Sewage irrigation did not have obvious effect on their contaminant levels and inventory of OCPs and PBDEs.     

Iron isotopic fractionation in industrial emissions and urban aerosols

A study on tropospheric aerosols involving Fe particles with an industrial origin is tackled here. Aerosols were collected at the largest exhausts of a major European steel metallurgy plant and around its near urban environment. A combination of bulk and individual particle analysis performed by SEM–EDX provides the chemical composition of Fe-bearing aerosols emitted within the factory process (hematite, magnetite and agglomerates of these oxides with sylvite (KCl), calcite (CaCO₃) and graphite carbon). Fe isotopic compositions of those emissions fall within the range (0.08‰ < δ⁵⁶Fe < +0.80‰) of enriched ores processed by the manufacturer (−0.16‰ < δ⁵⁶Fe < +1.19‰). No significant evolution of Fe fractionation during steelworks processes is observed. At the industrial source, Fe is mainly present as oxide particles, to some extent in 3–4 μm aggregates. In the close urban area, 5 km away from the steel plant, individual particle analysis of collected aerosols presents, in addition to the industrial particle type, aluminosilicates and related natural particles (gypsum, quartz, calcite and reacted sea salt). The Fe isotopic composition (δ⁵⁶Fe = 0.14 ± 0.11‰) measured in the close urban environment of the steel metallurgy plant appears coherent with an external mixing of industrial and continental Fe-containing tropospheric aerosols, as evidenced by individual particle chemical analysis. Our isotopic data provide a first estimation of an anthropogenic source term as part of the study of photochemically promoted dissolution processes and related Fe fractionations in tropospheric aerosols.     

Organochlorine pesticides in surface sediments and suspended particulate matters from the Yangtze estuary, China

Total HCHs' and total DDTs' levels in surface sediments (SS) ranged from 0.5 to 17.5 ng g⁻¹ and from 0.9 to 33.1 ng g⁻¹, averaged 6.0 and 8.2 ng g⁻¹, respectively. Total HCHs' and total DDTs' levels in suspended particulate matters (SPM) varied from 6.2 to 14.8 ng g⁻¹ with a mean value of 12.3 ng g⁻¹ and were from 3.4 to 25.7 ng g⁻¹ with an average of 16.4 ng g⁻¹, respectively. Lindane is the main HCHs' source and continuing use in the Yangtze Delta areas of ‘pure’ γ-HCH (lindane) rather than technical HCH (a mix of largely α- and some γ-HCH). DDTs in SS are mainly accumulated in history. However, high DDT fractions in SPM are indicators of new input of typical dicofol type DDT from 2002 to 2004. It can be seen that most samples from the Yangtze estuary were in ranges where adverse biological effects are expected, either occasionally or frequently.     

Processes affecting the movement of organochlorine pesticides (OCPs) between soil and air in an industrial site in Turkey

Soil and atmospheric concentrations, dry deposition and soil-air gas exchange of organochlorine pesticides (OCPs) were investigated at an industrial site in Aliaga, Izmir, Turkey. Current-use pesticides, endosulfan and chlorpyrifos, had the highest atmospheric levels in summer and winter. Summertime total (gas + particle) OCP concentrations in air were higher, probably due to increased volatilization at higher temperatures and seasonal local/regional applications of current-use pesticides. Particle deposition fluxes were generally higher in summer than in winter. Overall average dry particle deposition velocity for all the OCPs was 4.9 ± 4.1 cm s⁻¹ (average ± SD). ΣDDXs (sum of p,p′-DDT, p,p′-DDD, and p,p′-DDE) were the most abundant OCPs in Aliaga soils (n = 48), probably due to their heavy historical use and persistence. Calculated fugacity ratios and average net gas fluxes across the soil-air interface indicated volatilization for α-CHL, γ-CHL, heptachlorepoxide, cis-nonachlor, trans-nonachlor, and p,p′-DDT in summer, and for α-CHL, γ-CHL, trans-nonachlor, endosulfan sulfate, and p,p′-DDT in winter. For the remaining OCPs, soil acted as a sink during both seasons. Comparison of the determined fluxes showed that dry particle, gas-phase, and wet deposition are significant OCP input mechanisms to the soil in the study area.     

Bioaccumulative characteristics of hexabromocyclododecanes in freshwater species from an electronic waste recycling area in China

Hexabromocyclododecanes (HBCDs) are now emerging ubiquitous contaminants due to their wide usage, persistence and toxicities. To investigate the bioaccumulative characteristics of HBCDs, sediments, Winkle (Littorina littorea), crucian carp (Carassius carassius) and loach (Misgurnus anguillicaudatus) were collected from two streams near an E-waste dismantling site in China, and HBCD exposure test was then conducted on Chinese rare minnow. The concentration of HBCDs was 14 ng g⁻¹ dry weight in sediments, 186, 377 and 1791 ng g⁻¹ lipid weight in winkle, crucian carp and loach, respectively. γ-HBCD was found to be the dominant diastereoisomer in the sediments (63% of total HBCDs). However, α-HBCD was selectively accumulated in the biotic samples and contributed to 77%, 63% and 63% of total HBCDs in winkle, crucian carp and loach, respectively. Moreover, an enrichment of (−)-enantiomers of α- and γ-HBCD were found in the winkle. The reverse results were observed in the crucian carp and loach. Similar observations of diastereoisomeric and enantiomeric composition were obtained in Chinese rare minnow with those found in the crucian carp and loach. These results indicate that the freshwater species from the streams are contaminated by HBCDs. α-HBCD can be selectively accumulated in organisms and the accumulative characteristics are enantioselective among species.     

Suppression of estrogenic activity of 17-beta-estradiol by beta-cyclodextrin

The suppressive effects of cyclodextrins (CDs) on the strong estrogenic activity of 17β-estradiol (E2) in water environments were investigated in this study. Cyclodextrins are doughnut-shaped molecules that possess a hydrophobic cavity and a hydrophilic exterior. The cavity can incorporate nonpolar molecules as guests to form inclusion complexes. β-CD and 2-hydroxypropyl-β-CD (HP-β-CD) were the most successful in forming a complex with E2 and improving its low aqueous solubility. The E2/CDs complexes bound to the estrogen receptor in a cell-free system as determined by ELISA and suppressed the hormone activities as measured by a yeast two-hybrid assay. These results indicate that hydrophobic E2 is easily transported through the lipid zone of the plasma membrane into the target cell and can bind to the nuclear receptor. However, the hydrophilic E2/β-CD and E2/HP-β-CD complexes do not penetrate the membrane. Therefore, these CDs are able to suppress the hormone activity of E2 through complex formation.     

Global environmental cycling of γ-HCH and DDT in the 1980s – A study using a coupled atmosphere and ocean general circulation model

A coupled atmosphere–ocean general circulation model, ECHAM5-MPIOM, was used to study the multicompartmental cycling and long-range transport of persistent and semivolatile organics. Multiphase systems in air and ocean are covered by submodels for atmospheric aerosols, HAM, and marine biogeochemistry, HAMOCC5, respectively. The model, furthermore, encompasses 2D surface compartments, i.e. top soil, vegetation surfaces and sea-ice. The total environmental fate of γ-hexachlorocyclohexane (γ-HCH, lindane) and dichlorophenyltrichloroethane (DDT) in agriculture were studied.DDT is mostly present in the soils, the water-soluble γ-HCH in soils and ocean. DDT has the longest residence time in almost all compartments. Quasi-steady state with regard to substance accumulation is reached within a few years in air and vegetation surfaces. In seawater the partitioning to suspended and sinking particles contributes to the vertical transport of substances. On the global scale deep water formation is, however, found to be more efficient. Up to 30% of DDT but only less than 0.2% of γ-HCH in seawater are stored in particulate matter.On the time scale studied (1 decade) and on global scale substance transport in the environment is determined by the fast atmospheric circulation. The meridional transport mechanism, for both compounds, is significantly enhanced by multi-hopping. Net meridional transport in the ocean is effective only regionally, mostly by currents along the western boundaries of Africa and the Americas. The total environmental burdens of the substances experience a net northward migration from their source regions, which is more pronounced for DDT than for γ-HCH. Due to the application distribution, however, after 10 years of simulation 21% of the global environmental burden of γ-HCH and 12% of DDT have accumulated in the Arctic.     

Carbonyl products of the gas-phase reaction of ozone with 1-alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas-phase reaction of ozone with the 1-alkenes (RCH = CH 2) 3-methyl-l-butene (R = i-propyl), 4-methyl-l-pentene (R = i-butyl), 3-methyl-l-pentene (R= s-butyl), 3,3-dimethyl-l-butene (R = t-butyl) and styrene (R = C₆H₅) at ambient T and p = 1 atm of air. Sufficient cyclohexane was added to scavenge OH in order to minimize reactions of OH with the alkenes and with their carbonyl products. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃ + RCH = CH₂ → α(HCHO + RCHOO) + (1 - α) (H₂COO + RCHO), where formaldehyde and RCHO are the primary carbonyls and H₂COO and RCHOO are the biradicals. Measured sums of the primary carbonyl formation yields were 1.006 ± 0.053 (1 S.D.) for formaldehyde + methylpropanal from3-methyl-l-butene(α = 0.494 ± 0.049), 1.025 ± 0.017 for formaldehyde + 2-methylbutanal from 3-methyl-l-pentene (α = 0.384 ± 0.013),1.147 ± 0.050 for formaldehyde + 3-methylbutanal from 4-methyl-l-pentene (α = 0.384 ± 0.020), 0.986 ± 0.014 for formaldehyde + 2,2-dimethylpropanal from 3,3-dimethyl-l-butene (α = 0.320 ± 0.012) and 0.980 ± 0.086 for formaldehyde + benzaldehyde from styrene (α = 0.347 ± 0.059). Carbonyls other than the primary carbonyls were identified; formation pathways are proposed that involve subsequent reactions of the monosubstituted biradicals RCHOO. Similarities and differences between branched-chain 1-alkenes and n-alkyl-substituted 1-alkenes are discussed.     

Chlorinated hydrocarbons in sediments of the Elbe River and the Elbe Estuary

Eight sediment samples collected between Hamburg and Cuxhaven were analysed for organic micropollutants. Using three different methods the following compounds were determined: α-HCH, γ-HCH, HCB, PCB, DDT-family, pentachlorobenzene and octachlorostyrene.     

Serum levels of organochlorine pesticides in healthy adults from five regions of Spain

The aim of this study was to measure of serum levels of p,p′-dichlorodiphenyl trichloroethane (p,p′-DDT), p,p′-dichlorodiphenyl dichlorethylene (p,p′-DDE), β-hexachlorocyclohexane (β-HCH), and hexachlorobenzene (HCB) in healthy adults in Spain. Furthermore, we also analyzed these levels according to dietary, other lifestyle factors and anthropometric characteristics. We measured the concentrations of such organochlorine pesticides (OCPs) in serum samples collected during 1992–1996 from 953 subjects aged 35–64 years, they were residents of five Spanish regions, they were randomly selected from the European Prospective Investigation into Cancer and Nutrition (EPIC) cohort. OCPs were determined by means of gas chromatography with electron-capture detection (GC-ECD). The most frequent compound found in serum was p,p′-DDE, present in 98% of the samples, followed by HCB and β-HCH, found in 89% and 77% of samples, respectively, while p,p′-DDT could be measured only in 26% of subjects. The geometric means of serum concentrations (ng/g lipid) were 822 for p,p′-DDE, 167 for β-HCH, and 379 for HCB. The concentrations of all OCPs were positively associated with age and body mass index, and decreased along the period of blood collection. No association was found between OCPs levels and dietary factors. The concentrations of p,p′-DDE and β-HCB were higher in Murcia, one of southern regions, most likely associated with intensive past use of pesticides related to agricultural practices, while higher levels of HCB were found in Navarra, located in the north, maybe due to industrial use rather than agricultural application.