Sources and distribution of polychlorinated-dibenzo-p-dioxins and -dibenzofurans in soil and sediment from the Yellow Sea region of China and Korea

Polychlorinated-dibenzo-p-dioxins and -dibenzofurans (PCDD/Fs) were measured in soils and sediments from the Yellow Sea region. Korean soils and sediments mostly contained detectable PCDD/Fs and showed a widespread distribution among locations. Soil and sedimentary PCDD/Fs from China were comparable to or less than those in Korea. The patterns of relative concentrations of individual congeners in soils were different between the two countries, but similar in sediments. Sources of PCDD/Fs in China and Korea were found to be independent of each other and their distributions reflected matrix-dependent accumulation. Spatial distribution indicated some point sources in Korea while Chinese sources were more widespread and diffuse. PCDD/Fs measured in the coastal areas of the Yellow Sea were comparable to or less than those previously reported in for eastern Asia. However, ∑TEQs in soils and sediments were near to or, in some cases exceeded environmental quality guidelines.     

Measurements and modelling of cloudwater deposition to moorland and forests

The objective of the study was to measure the size dependence of cloudwater deposition and associated average ionic fluxes to vegetated surfaces. Measurements were made over a forest canopy at Dunslair heights in south Scotland and a moorland site, Great Dun Fell, in northern England. Measurements were made using the gradient and eddy correlation techniques. Eddy correlation measurements were made using an ultrasonic anemometer, a Knollenberg forward scattering spectrometer probe (to measure liquid water fluxes and fluxes of droplets in 1 microm size intervals) and a GSI particulate volume monitor (to measure liquid-water fluxes). Measurements were made at Great Dun Fell of the size dependence of droplet deposition velocity, using the gradient technique with two Knollenberg probes. Simultaneous gradient and eddy correlation measurements were also made at Great Dun Fell of average cloud-water fluxes, together with chemical analysis of cloud water composition, using a continuous analysis system. At Dunslair Heights, eddy correlation measurements were made using both the Knollenberg and Gerber Scientific Instruments (GSI) probes, while simultaneous gradient measurements using two GSI probes were also attempted. Samples of cloud water were collected at Dunslair Heights, using passive string collectors for chemical analysis by ion chromatography. The major findings of the study were: 1. The droplet deposition velocities measured by the two techniques were similar. 2. The deposition velocities were a strong function of droplet size. Considerable resistance to deposition was evident for droplets of less than 5 microm radius. Deposition velocities for particles from about 6 to 8 microm exceeded those for momentum. 3. Except when the droplets were very small or the winds very light, bulk cloud-water deposition velocities were about 80% or more of the momentum deposition velocities to forests.     

Participate and Gaseous Emissions from Natural Gas Furnaces and Water Heaters

Three furnaces and one hot water heater were tested for particulate and gaseous emissions. The effects of fuel, stoichiometry, operating conditions, and appliance type on emission levels were studied. The filterable particulate levels from a properly operating furnace were very low. However, condensable particulate emissions were considerably greater, approximately the same as predicted by EPA estimates of furnace particulate emissions. Carbon emissions comprised about 12% of filterable particulate emissions. However, when operated highly fuel-rich, copious amounts of elemental carbon particles were emitted with a mass median diameter of less than 0.4 μm. Gaseous emissions were dependent on cycling of the furnace and stoichiometry.

An estimate was made of the daily furnace emissions compared to daily emissions from a 1980 catalyst-equipped automobile. While gaseous emissions were less than the corresponding vehicle emissions, the particle emissions from the furnace were three times greater than particle emissions from a 1980 vehicle.     

Lead and cadmium in indoor air and the urban environment

The present study was conducted to find potential terrestrial biomonitors for heavy metals in indoor air in an urban environment. TSP, PM(10), and PM(2.5) were collected in three retirement facilities in the urban area of Vienna. In addition, particulate matter and soil, vegetation, and isopods (Porcellio scaber L.) were collected in the adjacent garden areas. Aerosols were sampled with a low-volume air sampler. The sampled materials were wet ashed and total lead and cadmium contents were determined. Water-soluble heavy metal concentrations were measured in aqueous extracts from air exposed filters, soil, and vegetation. Lead and cadmium were analyzed by graphite furnace AAS. Lead contents in the vegetation were inferred from water-soluble lead in soils. Lead in isopods generally reflected the contents in vegetation. Cadmium in plants probably derived from soil solutions as well as from atmospheric input. Isopods reflected the total cadmium contents in soils. Particulate matter was dominated by PM(2.5), both with respect to mass concentrations and to heavy metal contents. The indoor aerosol was found to be influenced by human activity, indoor sources, and outdoor particles. Relationships between indoor airborne heavy metals and the contents in vegetation (lead and cadmium: positive) and isopods (lead: negative) were identified to have the potential for biomonitoring indoor air quality.     

Dissipation of phosalone and diazinon in fresh and dried alfalfa

The objectives of this study were to determine the persistence of phosalone (S-6-chloro-2,3-dihydro-2-oxobenzoxazol-3-ylmethyl O, O-diethyl phosphorodithioate) and diazinon (O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate) residues in fresh and baled alfalfa under field conditions. Plots of alfalfa were sprayed with each insecticide. Fresh alfalfa was sampled up to 20 days after treatment, and dried alfalfa was sampled up to 25 weeks after baling. Samples were analyzed for residues using high performance liquid chromatography (HPLC) equipped with a UV detector. The half-lives of diazinon and phosalone in fresh alfalfa were 1.8 and 3.3 days, respectively. In baled alfalfa the half-life of diazinon and phosalone were 2.8 and 16.7 weeks, respectively. No diazinon residues were detected in baled alfalfa, sampled after week 9, although the concentration of phosalone found at week 25 was 5.51 mg/kg.     

青霉菌对印染废水吸附脱色及深度处理的研究

利用青霉菌P 1(Penicilliumsp )对 2种染浴废水中的染料进行吸附去除 ,研究结果表明 ,吸附处理 3h ,黑色和红色染浴废水色度基本被去除 ,去除率分别达 98 0 %和 74 5 % ,但去色处理后废水的CODCr值仍偏高。对去除色度的废水进一步用活性污泥进行深度处理 ,黑色和红色废水的CODCr去除率分别为 75 9%和 89 7%。青霉菌菌丝通过吸附作用从废水中抽提出的染料分子在有染料降解细菌L 1和L 2的降解池中脱色降解 ,菌丝吸附脱色能力得到再生。     

Identification and level estimation of chlorinated neutral aromatic sulfur compounds and their alkylated derivatives in pulp mill effluents and sediments

Seven effluent samples from a modern pulp mill, in which chlorine and chlorine dioxide bleaching is used, and five sediment samples from the recipient watercourse were investigated for polychlorinated dibenzothiophenes (PCDBTs), polychlorinated thianthrenes (PCTAs), polychlorinated diphenylsulfides (PCDPSs) and for alkylated derivatives of these. Mainly di-, tri-, tetra- and pentachlorinated congeners were studied. Particles and filtrates from the effluents were analyzed separately. The concentration levels of the nonalkylated compounds were found to be higher in the filtrates than in the particles. Trichlorinated dibenzothiophenes and thianthrenes were found as the major congeners. Pentachlorinated derivatives were not found. Alkylated di- and trichlorodibenzothiophenes were detected in some samples, while alkylated chlorinated thianthrenes and diphenylsulfides were nondetectable. The estimated concentration levels of the compounds detected were in the range of 40–2700 pg/L in the pulp mill effluents and in the range of 2–40 pg/g dry weight in the sediments. Mixtures of methylated di- and trichlorodibenzothiophenes used as references in analyses were prepared from methylchlorobiphenyls. Some new pure model compounds were obtained by HPLC fractionation of the chlorination mixture of dibenzothiophene. Structures of these were determined by ¹H NMR.     

Dissipation of Phosalone and Diazinon in Fresh and Dried Alfalfa

The objectives of this study were to determine the persistence of phosalone (S-6-chloro-2,3-dihydro-2-oxobenzoxazol-3-ylmethyl O, O-diethyl phosphorodithioate) and diazinon (O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate) residues in fresh and baled alfalfa under field conditions. Plots of alfalfa were sprayed with each insecticide. Fresh alfalfa was sampled up to 20 days after treatment, and dried alfalfa was sampled up to 25 weeks after baling. Samples were analyzed for residues using high performance liquid chromatography (HPLC) equipped with a UV detector. The half-lives of diazinon and phosalone in fresh alfalfa were 1.8 and 3.3 days, respectively. In baled alfalfa the half-life of diazinon and phosalone were 2.8 and 16.7 weeks, respectively. No diazinon residues were detected in baled alfalfa, sampled after week 9, although the concentration of phosalone found at week 25 was 5.51 mg/kg.     

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.     

Identification of selected hormonally active agents and animal mammary carcinogens in commercial and residential air and dust samples

In order to characterize typical indoor exposures to chemicals of interest for research on breast cancer and other hormonally mediated health outcomes, methods were developed to analyze air and dust for target compounds that have been identified as animal mammary carcinogens or hormonally active agents and that are used in commercial or consumer products or building materials. These methods were applied to a small number of residential and commercial environments to begin to characterize the extent of exposure to these classes of compounds. Phenolic compounds, including nonylphenol, octylphenol, bisphenol A, and the methoxychlor metabolite 2,2-bis(p-hydroxyphenyl)-1,1,1-trichloroethane (HPTE), were extracted, derivatized, and analyzed by gas chromatography/mass spectrometry (GC/MS)-selective ion monitoring (SIM). Selected phthalates, pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) were extracted and analyzed by GC/MS-SIM. Residential and workplace samples showed detectable levels of twelve pesticides in dust and seven in air samples. Phthalates were abundant in dust (0.3-524 micrograms/g) and air (0.005-2.8 micrograms/m3). Nonylphenol and its mono- and di-ethoxylates were prevalent in dust (0.82-14 micrograms/g) along with estrogenic phenols such as bisphenol A and o-phenyl phenol. In this 7-sample pilot study, 33 of 86 target compounds were detected in dust, and 24 of 57 target compounds were detected in air. In a single sample from one home, 27 of the target compounds were detected in dust and 15 in air, providing an indication of chemical mixtures to which humans are typically exposed.     

Effects of compositional heterogeneity and nanoporosity of raw and treated biomass-generated soot on adsorption and absorption of organic contaminants

A biomass-generated soot was sequentially treated by HCl-HF solution, organic solvent, and oxidative acid to remove ash, extractable native organic matter (EOM), and amorphous carbon. The compositional heterogeneity and nano-structure of the untreated and treated soot samples were characterized by elemental analysis, thermal gravimetric analysis, BET-N₂ surface area, and electron microscopic analysis. Sorption properties of polar and nonpolar organic pollutants onto the soot samples were compared, and individual contributions of adsorption and absorption were quantified. The sorption isotherms for raw sample were practically linear, while were nonlinear for the pretreated-soot. The removal of EOM enhanced adsorption and reduced absorption, indicating that EOM served as a partitioning phase and simultaneously masked the adsorptive sites. By drastic-oxidation, the outer amorphous carbon and the inner disordered core of the soot particles were completely removed, and a fullerene-like nanoporous structure (aromatic shell) was created, which promoted additional π-π interaction between phenanthrene and the soot.     

Identification of Selected Hormonally Active Agents and Animal Mammary Carcinogens in Commercial and Residential Air and Dust Samples

ABSTRACT

In order to characterize typical indoor exposures to chemicals of interest for research on breast cancer and other hormonally mediated health outcomes, methods were developed to analyze air and dust for target compounds that have been identified as animal mammary carcinogens or hormonally active agents and that are used in commercial or consumer products or building materials. These methods were applied to a small number of residential and commercial environments to begin to characterize the extent of exposure to these classes of compounds. Phenolic compounds, including nonylphenol, octylphenol, bisphenol A, and the methoxychlor metabolite 2,2-bis (p-hydroxyphenyl)-1,1,1-trichloroethane (HPTE), were extracted, derivatized, and analyzed by gas chromatography/mass spectrometry (GC/MS)–selective ion monitoring (SIM). Selected phthalates, pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) were extracted and analyzed by GC/MS-SIM. Residential and workplace samples showed detectable levels of twelve pesticides in dust and seven in air samples. Phthalates were abundant in dust (0.3524 μg/g) and air (0.005-2.8 μg/m³). Nonylphenol and its mono- and di-ethoxylates were prevalent in dust (0.82-14 μg/g) along with estrogenic phenols such as bisphenol A and o-phenyl phenol. In this 7-sample pilot study, 33 of 86 target compounds were detected in dust, and 24 of 57 target compounds were detected in air. In a single sample from one home, 27 of the target compounds were detected in dust and 15 in air, providing an indication of chemical mixtures to which humans are typically exposed.     

Chlorinated fluorenes and alkylfluorenes in bleached kraft pulp and pulp mill discharges

The occurrence and levels of polychlorinated fluorenes (PCFLs), methylfluorenes (C₁-PCFLs) and dimethylfluorenes (C₂-PCFLs) were studied by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) in hardwood and softwood pulp, effluent and biosludge from a bleached kraft mill. Semiquantitative concentrations of these compounds were estimated using selected ion monitoring and a mass spectral resolution of 10,000. The identification of PCFLs and C₁-PCFLs was confirmed by the chlorination mixtures of fluorene and 2-methylfluorene.

Several congeners were found for each compound groups studied and isomer patterns were similar in bleached pulp and biosludge. The approximated sum levels of di- and trichloro isomers of PCFLs, C₁-PCFLs and C₂-PCFLs in the biosludge were about 2, 5 and 4 ng/g dry weight (dw), respectively. The levels of the corresponding compounds in the softwood pulp were 0.5, 0.8 and 0.2 ng/g dw, respectively. Of the studied compounds, only C₁-diCFLs (0.01 ng/g dw) were detected in the hardwood pulp. In the effluent, PCFLs were non-detectable, but traces of C₁-diCFLs (0.5 ng/L) and C₂-pentaCFLs (0.06 ng/L) were found. These were observed mainly as dissolved in the filtrate and not as particle-bound.     

Combined effects of soil moisture and carbaryl to earthworms and plants: simulation of flood and drought scenarios

Studying tolerance limits in organisms exposed to climatic variations is key to understanding effects on behaviour and physiology. The presence of pollutants may influence these tolerance limits, by altering the toxicity or bioavailability of the chemical. In this work, the plant species Brassica rapa and Triticum aestivum and the earthworm Eisenia andrei were exposed to different levels of soil moisture and carbaryl, as natural and chemical stressors, respectively. Both stress factors were tested individually, as well as in combination. Acute and chronic tests were performed and results were discussed in order to evaluate the responses of organisms to the combination of stressors. When possible, data was fitted to widely employed models for describing chemical mixture responses. Synergistic interactions were observed in earthworms exposed to carbaryl and drought conditions, while antagonistic interactions were more representative for plants, especially in relation to biomass loss under flood-simulation conditions.     

RDX and TNT residues from live-fire and blow-in-place detonations

Snow was used as a collection medium to examine 1,3,5-hexahydro-1,3,5-trinitrotriazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues post-detonation of 60-, 81-, and 120-mm mortar rounds, 105- and 155-mm howitzer rounds, M67 hand grenades, 40-mm rifle grenades, and blocks of C4. Residue-covered snow samples were collected, processed, and analyzed for explosives without cross-contamination from previous detonations and other potential matrix interferences. Detonation trials were performed following standard military live-fire and blow-in-place techniques. When possible, replicate munitions were detonated under similar conditions to provide a more reliable estimation of the mass of unconsumed high explosive residues. Overall the amount of energetic residues deposited from live-fire detonations were considerably less than the energetic residues deposited by blow-in-place detonations.     

PCBs and chlorinated hydrocarbon pesticides in Antarctic atmosphere and hydrosphere

PCBs and chlorinated hydrocarbon pesticides such as DDTs and HCHs (BHCs) were measured in air, water, ice and snow samples collected around the Japanese research stations in Antarctica and adjacent oceans during December 1980 to March 1982. The atmospheric concentrations of chlorinated hydrocarbons decreased in the transport process from northern lands to Antarctica, but the compositions of PCBs, DDT compounds and HCH isomers were relatively uniform throughout this process. Regional and seasonal variations were found in aerial concentrations of these pollutants at Syowa Station and adjacent seas in Antarctica. Chlorinated hydrocarbons were also detected in snow, ice, lake water and sea water samples, in which rather high concentrations were found in snow and ice samples. This suggests that snow and ice serve as media of supply of these pollutants into Antarctic marine environment. Most interestingly, the concentrations of DDTs and higher chlorinated biphenyls were much lower in sea water under fast ice than in that from outer margin of pack ice. This indicates that the active removal of these pollutants is occurred in the sea under fast ice, and that is strongly associated with high primary productivity. It is, therefore, presumed that the concentrations of PCBs and DDTs in marine organisms living under fast ice in Antarctica could be lower than those in other oceans.     

Particulate and Nicotine Sampling in Public Facilities and Offices

Abstract

The purpose of this study was to characterize and measure indoor air quality in public facilities and office buildings. The pollutants of interest were particulate matter smaller than 2.5 μm in diameter, PM-2.5, and environmental tobacco smoke (ETS). Integrated PM- 2.5 samples were taken on Teflon membrane filters using Harvard Aerosol Impactors as a pre-size selector. Filters were analyzed by gravimetric analysis. Nicotine, which was used as a marker for ETS, was collected on sodium-bisulfate-impregnated, glass-fiber filters and was analyzed by gas chromatography. Twenty-one structures were monitored in Metropolitan Boston. Measured particle concentrations ranged from 6.0 μg/m³ to about 550 μg/m³. Nicotine concentrations were as high as 26 μg/m³ in a designated smoking room. Real-time measurements were also taken using two types of nephelometers; a Handheld Aerosol Monitor (HAM) and a Miniature Real-Time Aerosol Monitor (MINIRAM). Short-term field measurements with these instruments correlated better with the integrated PM-2.5 concentrations in smoking locations than with concentrations in non-smoking areas.     

Reaction rates and intermediates of chlorinated organic compounds in water and soil

Degradation reactions of thirteen chlorinated organic compounds were investigated in a water system and a water-soil system. Three compounds were degraded following the first order rate equation regardless of pH, and five compounds were degraded following the second order rate equation with a concentration of hydroxide ion in alkaline solution.The reaction rate constants and the activation energies of the reactions were obtained, and the intermediates were determined quantitatively for the eight compounds.From the result of the degradation of 1,1,1-trichloroethane in the water-soil system, it was found that 1,1,1 trichloroethane did not react on the soil surface and only reacted in the water phase.     

Spatial and temporal trends of metals and arsenic in German freshwater compartments

Cadmium, lead, mercury, copper, nickel, zinc, and arsenic were analyzed in suspended particulate matter (SPM), zebra mussels, and bream sampled yearly under the program of the German Environmental Specimen Bank (ESB) in the rivers Rhine, Elbe, Danube, Saar, Mulde, and Saale and in Lake Belau. Temporal and spatial trends were analyzed, correlations between metal levels in different specimen types assessed, and sampling sites ranked according to their metal levels by calculating a Multi-Metal Index (MMI) for every specimen type and site. SPM: Highest metal loads were detected in Mulde, Saale, and Elbe right downstream of the Saale confluence. In the Elbe, metal loads in SPM were mostly highest in the upper and middle section of the river while in Rhine and Saar concentrations increased downstream. Temporal trends since 2005 were detected only at three sites. Zebra mussel: MMIs were highest in the tidal section of the Elbe and the lower Rhine and lowest in Lake Belau and the upper Danube. Different temporal trends were detected since the early 1990s depending on site and metal. Bream: As, Pb, Cu, and Hg were analyzed in muscle tissue and Pb, Cd, Cu, and Zn in liver. For both tissues, MMIs were highest in Mulde and Saale and the lower and middle Elbe. Since the early 1990s, Hg, Pb, and Cu decreased in bream muscle at many sites while As increased at 6 of the 17 sites. The findings indicate that Hg, Pb, and Cu have obviously decreased in many freshwater ecosystems in recent years, whereas As and Ni levels have increased at several sites. Metal levels and temporal trends mostly differed between the specimen types under investigation and only few correlations between specimen types were detected. This underlines the importance of including different components of an ecosystem when assessing its environmental quality.     

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment.