Artificial sweat enhances dermal transfer of chlorpyrifos from treated nylon carpet fibers

The dermal transfer and absorption of 14C-ring-chlorpyrifos from nylon carpet fibers was measured in skin penetration-evaporation cells with excised pig skin. Prior to application, synthetic sweat was applied to skin in half of the cells. Radioactivity was measured in receptor fluid, dermis, epidermis, tape stripping samples, and vapor trap samples during a 24-h period. The sum of radiolabel recovered from the dermis and receptor fluid represented the absorbed dose. There was no significant difference (p > 0.05) in percutaneous absorption between cells that received the synthetic sweat application and "dry" cells (1.3 +/- 0.3% of applied dose). There was significantly more (p < 0.05) radiolabel recovered from tape stripping (5.4 +/- 2.1 vs. 2.8 +/- 0.6%) and in the epidermis (4.5 +/- 0.8 vs. 3.1 +/- 0.3%) from cells that received the synthetic sweat application, which indicated synthetic sweat facilitated transfer of chlorpyrifos from a treated substrate to the skin surface. The measured value for percutaneous absorption of chlorpyrifos agreed with the value predicted from an empirical model previously developed for nitro compound-containing soil.     

Heavy and toxic metals in staple foodstuffs and agriproduct from contaminated soils

This article presents basic data on the content of Cr, Fe, Ni, Cu, Zn, As, Cd, Sb, Hg, and Pb in staple foodstuffs and agriproduct grown in Russia (Astrakhan region and the town of Belovo) and Egypt (Helwan region). The dependence of the concentration of metals in agriproducts on the content and chemical form of existence in irrigation water and soils is indicated.     

Methods for sampling and analysis of tropospheric ethanol in gaseous and aqueous phases

In this paper, we report on techniques for sampling and measuring ethanol in both the gas and aqueous phases of the lower troposphere. In the gas phase, the best sampling conditions were ensured by adsorption on Hayesep Q with a Chromosorb W AW coated with LiCl dryer (method 1) or by cryogenic trapping (method 2). An intercomparison campaign showed good agreement between both methods under various conditions. Method 1 (adsorption on Hayesep Q with dryer) is easier to set up and to carry away from the laboratory. Method 2 (cryogenic trapping) requires longer sampling time (up to 60 min while method 1 requires only 10-15 min). Method 1 is adapted to high concentrations of ethanol (>20 ppb) and low relative humidity (<30%). Method 2 gives more accurate results than method 1 for low ethanol concentrations (1-20 ppb). Comparing these results to previous studies, it is clear that sampling with appropriate solid adsorbents or with stainless steel canisters (with appropriate humidified air and short storage time) is adapted to urban or industrial environments where ethanol concentrations are high. Cryogenic sampling must be preferred for remote places where ethanol concentrations are low. Three techniques were tested for sampling ethanol in the liquid phase, namely solid phase microextraction, purge and trap injection, and direct injection. Among those, the latter was chosen for field measurements of ethanol in rain samples at an urban location. These first ever results at an urban location show concentrations ranging from <1 to 5 microM in rains, which agree with the expected range of concentrations. However, the purge and trap method showed detection limits that were 50 times lower and should be preferred for liquid phase ethanol measurements in rural and remote locations. Combining cryogenic trapping for the gas phase (method 2) and direct injection for the liquid phase is convenient and well adapted for a multiphase study of ethanol in the atmosphere, where simultaneous measurements in both phases are needed.     

Inclusion complexes of alpha- and gamma-cyclodextrins and the herbicide norflurazon: I. Preparation and characterisation. II. Enhanced solubilisation and removal from soils

The interaction of norflurazon with alpha- and gamma-cyclodextrins (CDs) yielded the formation of inclusion complexes at a 1:1 stoichiometric ratio in solution and in the solid state. Apparent stability constants of 50.7+/-1.6 and 37+/-1.7 M(-1) and an increase in herbicide solubility by up to five and fourfold for alpha- and gamma-CD, respectively, were determined from the phase solubility diagrams at 25 degrees C in water. Three processing methods (kneading, spray-drying and vacuum evaporation) were used to prepare norflurazon-CD solid inclusion complexes, which were characterised by infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy. A high increase in the norflurazon dissolution rate was obtained with all the solid complexes with gamma-CD, but when alpha-CD was used, only the solid system obtained after the vacuum evaporation process showed a higher dissolution rate. This finding is a first step in the development of new, environmentally sound formulations of norflurazon (NFL), due to the capacity for increasing its dissolution rate and hydrosolubility, and thus diminishing the use of organic solvents. On the other hand, the effect of alpha- and gamma-cyclodextrin on the solubility of norflurazon in solution was also considered as a way of modifying its behaviour in the soil environment. Desorption studies of NFL from soils in the presence of alpha- and gamma-cyclodextrin were carried out using a batch equilibration method. The results obtained showed that alpha- and gamma-cyclodextrin greatly increased the removal of norflurazon previously adsorbed, proving the potential use of these CDs for in situ remediation of pesticide-contaminated soils.     

Detection of polycyclic aromatic hydrocarbons in skin oil obtained from roofing workers

Twelve polycyclic aromatic hydrocarbons have been analyzed in blood serum and skin oil collected from roofing workers. Although a range of 0.05–36 ng was observed in skin oil samples, none was detected in serum, at detection limits of 1–175 pg/ml.     

Tributyltin contamination around an oil terminal in Sullom Voe (Shetland)

This report provides clear evidence of tributyltin (TBT) contamination of coastal waters close to an oil terminal handling large tankers. Dogwhelk populations from Sullom Voe, Shetland, have been examined for the development by females of certain male sexual characteristics (e.g. a penis and vas deferens). This condition, termed imposex, is a response to exposure to tributylin compounds, and can be quantified by use of the relative penis size index (RPSI). Dogwhelk populations throughout Sullom Voe were strongly affected by TBT (RPSI 34 to 81%), and up to 90% of the females in the oil terminal area were sterile. Queen scallops collected in the Voe contained enhanced concentrations of tin in adductor muscle and gonad tissue (0.02 to 0.23 mg kg(-1) wet weight), but it is considered unlikely that their growth and development is adversely affected. Tin was rarely detected in scallops, queens, or dogwhelks outside the Voe, although the development of a vas deferens in many of the female dogwhelks indicated a degree of contamination of the open waters of Yell Sound. TBT was detectable (2 ng litre(-1) as tin) in only two sea water samples taken from the terminal area.     

Nonlinearities in source receptor relationships for sulfur and nitrogen compounds

The relationship between emissions and deposition of air pollutants, both spatially and in time forms an important focus for science and for policy makers. In practice, this relationship may become nonlinear if the underlying processes change with time, or in space. Nonlinearities may also appear due to errors in emission or deposition data, and careful scrutiny of both data sources and their relationship provides a means of picking up such deficiencies. Nonlinearities in source receptor relationships for sulfur and nitrogen compounds in Europe have been identified in measurement data for the UK. In the case of sulfur, the dry deposition process has been shown to be strongly influenced by ambient concentrations of NH3, leading to substantial increases in deposition rate as SO2 concentrations decline and the ratio SO2/NH3 decreases. The field evidence extends to measurements over three different surfaces in three countries across Europe. A mechanistic understanding of the cause of this nonlinearity has been provided. Apparent nonlinearities also exist in the sulfur deposition field through the influence of shipping emissions. The effect is clear at west coast locations, where during a period in which land-based sulfur emissions declined by 50%, no significant decline in concentrations of SO(2-) in precipitation were observed. The sites affected are primarily the coastal regions of southwestern UK, where shipping sources contribute a substantial fraction of the deposited sulfur, but the effect is not detectable elsewhere. Full quantification of the spatially disaggregated emission and their changes in time will eliminate this apparent nonlinearity in the source-receptor data. For oxidized nitrogen emission and deposition in the UK, there is strong evidence of nonlinearity in the source-receptor relationship. The concentrations and deposition of NO(3-) in precipitation have declined little following a reduction in emissions of 45% during the period 1987 to 2001. The data imply a significant decrease in the average transport distance for oxidized nitrogen and most probably an increase in the average oxidation rate. However, the net effect of changes in aerosol chemistry due to changes in sulfur emissions and less competition for the main oxidants as a consequence of reductions in sulfur emission have not been separated. A quantitative explanation of the cause of this nonlinearity is lacking and the effects are therefore identified as an important uncertainty for the development of further protocols to control acidification, eutrophication and photochemical oxidants in Europe.     

Atp-measurements in soil: A combination between the TCA and NRB ® extraction methods

The extraction of ATP from soils with the TCA- and NRB ®-methods shows qualitative and quantitative differences. A combination of both methods results in a higher yield of extracted ATP and in a solution of low optical quenching.     

Plasma ALP activity and blood PCV value changes in chick fetuses due to exposure of the egg to different xenobiotics

The effects of two polycyclic aromatic hydrocarbon (PAH) compounds (benz(k)fluoranthene and fluoranthene) and two heavy metals (cadmium and lead) were studied on the alkaline phosphatase (ALP) enzyme activity and hematocrit (PCV) values in chick fetuses. Eggs were exposed to one of the four compounds before incubation, by applying two exposure methods: injection (into the air cell) or immersion. Fluoranthene, cadmium and lead injection significantly decreased ALP activity compared to the control, while none of the compounds caused significant reduction in ALP activity in the immersion groups; however, a decreasing tendency was seen in these groups as well. Hematocrit values were increased after benz(k)fluoranthene immersion, fluoranthene immersion and cadmium injection. However, the doses in this study are relatively low (compared to other ecotoxicological studies in birds), the alteration in ALP enzyme activity and PCV values was apparent in each treatment group and is indicative of the high sensitivity of chick fetuses.     

Radiocarbon content of synthetic and natural semi-volatile halogenated organic compounds

Some halogenated organic compounds, such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polybrominated diphenyl ethers (PBDEs), have been suggested to have natural sources but separating these compounds from their commercially synthesized counterparts is difficult. Molecular-level 14C analysis may be beneficial since most synthetic compounds are manufactured from petrochemicals (14C-free) and natural compounds should have "modern" or "contemporary" 14C levels. As a baseline study, we measured, for the first time, the 14C abundance in commercial PCB and PBDE mixtures, a number of organochlorine pesticides, as well as one natural product 2-(3',5'-dibromo-2'-methoxyphenoxy)-3,5-dibromoanisole. The latter compound was isolated from a marine sponge and is similar in structure to a PBDE. All of the synthetic compounds were 14C-free except for the pesticide toxaphene. which had a modern 14C abundance, as did the brominated natural compound. The result for toxaphene was not surprising since it was commercially synthesized by the chlorination of camphene derived from pine trees. These results suggest that measuring the 14C content of halogenated organic compounds may be quite useful in establishing whether organic compounds encountered in the environment have natural or synthetic origins (or both) provided that any synthetic counterparts derive from petrochemical feedstock.