Degradation of pentachlorobiphenyl by a sequential treatment using Pd coated iron and an aerobic bacterium (H1)

The reductive dechlorination and biodegradation of 2,2^′4,5,5^′-pentachlorobiphenyl (PCB#101) was investigated in a laboratory-scale. Palladium coated iron (Pd/Fe) was used as a catalytic reductant for the chemical degradation of 2,2^′4,5,5^′-pentachlorobiphenyl, and an aerobic bacteria was used for biodegradation following the chemical reaction in this study. Dechlorination was affected by several factors such as Pd loading, initial soil pH and the amount of Pd/Fe used. The results showed that higher Pd loading, higher dosage of Pd/Fe and slightly acid condition were beneficial to the catalytic dechlorination of 2,2^′,4,5,5^′-pentachlorobiphenyl. In laboratory batch experiments, 2,2^′4,5,5^′-pentachlorobiphenyl was reduced in the presence of Pd/Fe bimetal, which was not further degraded by aerobic bacteria. 2,2^′,4-trichlorobiphenyl (PCB#17), a reduction product from 2,2^′4,5,5^′-pentachlorobiphenyl, was readily biodegraded in the presence of a aerobic bacterial strain. It is suggested that an integrated Pd/Fe catalytic reduction-aerobic biodegradation process may be a feasible option for treating PCB-contaminated soil.     

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.     

Generator column determination of aqueous solubilities for non-ortho and mono-ortho substituted polychlorinated biphenyls

Aqueous solubilities of four non-ortho and eight mono-ortho substituted PCBs were determined using a generator-column technique followed by subsequent off-line GC/ECD analysis of the aqueous solutions. The method is based on pumping water through a column containing glass beads coated with the congener being studied and has been used to measure solubilities at room temperature. The method circumvents many of the experimental difficulties encountered with the traditional shake-flask system. Aqueous solubility of 3,3′,4,4′-tetrachlorobiphenyl determined by this procedure is compared with data obtained from the shake-flask method and the computational method. The precision of replicate measurements is better than ±6.5%. Aqueous solubilities determined for 12 congeners ranged from 6.07 × 10⁻¹¹ to 4.47 × ⁻⁹ mol/L and generally decreased with molecular weight and increased with degree of ortho-chlorine substitution within a molecular-weight class.     

Global baseline pollution studies XI: Congener specific determination of polychlorinated biphenyls (PCB) and occurrence of alpha- and gamma-hexachlorocyclohexane (HCH), 4,4′-DDE and 4,4′-DDT in continental air

The hexachlorocyclohexane-isomers (HCH), hexachlorobenzene (HCB), the polychlorinated biphenyls (PCB), 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (4,4′-DDT) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (4,4′-DDE) have been measured in urban and rural air around the city of Ulm (F. R. G., 48.4° N, 10.0° E). The sampling stations are typical for continental air in the westerlies of the northern hemisphere including local and regional influences. The analytical method consists of adsorptive sampling of large volumes (1000 m³) of air on silica gel, solvent desorption with CH₂Cl₂, preseparation of the collected chlorinated C₆/C₁₄ hydrocarbons by liquid adsorption chromatography on silica gel, and high resolution capillary gas chromatography with electron capture-(HRGC/ECD) or mass-selective detection (HRGC/MSD). The concentrations found in the lower troposphere under different meteorological conditions reflect regional input and long range transport. The levels found range from 1 pg/m³ for 4,4′-DDT to 10 ng/m³ for gamma HCH.     

Development of steady-state phosphate concentrations in septic system plumes

Long-term monitoring of PO₄⁻³ behaviour in a well-defined septic system plume on calcareous sand (Cambridge site) shows that, after 17 yr of system operation, a distinct PO₄⁻³ plume (PO₄⁻³−P > 1 mg L⁻¹) is present extending 20 m downgradient from the infiltration bed. The PO₄³⁻ plume migration velocity is 1 m yr⁻¹, reflecting retardation by a factor of 20 compared to the groundwater velocity. During monitoring between years 10 to 17, an expanding steady-state zone was noted below the infiltration bed where PO₄³⁻ −P levels remained consistently near 4 mg L⁻¹, a value 25% lower than the average effluent value (6.3 mg L⁻¹). The pattern of attenuation — a 25% mass loss in the 2-m-thick vadose zone, then little further attenuation along the flowpath — is suggestive of a condition of equilibrium with a controlling phosphate mineral phase. Chemical equilibrium modelling shows supersaturation with respect to hydroxylapatite and variscite. Four other field sites are identified from the literature and from our work where similar steady-state PO₄³⁻ zones are present in septic system plumes. In these, steady-state levels range from 15% to 68% of effluent values, with lower concentrations observed in the more acidic plumes, again indicative of a mineral solubility control, possibly variscite.PO₄³⁻ behaviour in these plumes suggests that, although P migration velocity is controlled by the processes of sorption, the magnitude of PO₄³⁻ that is present is governed by the constraints of phosphate mineral solubility. When septic systems on sands are located relatively close to sensitive surface water bodies and when long-term downgradient impact is the primary concern, more attention should be focused on the geochemical conditions that control PO₄³⁻ mineral solubility rather than only on the sorption characteristics of the sediment.     

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.     

Uptake and bioaccumulation of three PCBs by Chlorellafusca

This paper reports the bioaccumulation of three PCBs (2,4′-dichlorobiphenyl, 2,4,6,2′-tetrachlorobiphenyl and 2,4,6,2′,4′-pentachlorobiphenyl) by the green alga $\text{Chlorella}$$\text{fusca}$ under various conditions. A probable pattern of the bioconcentration mechanism is suggested. No metabolites were extracted from algae or water 6 days after incubation with PCBs.     

A simple dermal absorption model: Derivation and application

This paper deals with the derivation of a QSAR for the estimation of:

• the skin permeation coefficient from aqueous solutions in cm h⁻¹,

• the stratum corneum/water partition coefficient.

These QSARs enable the estimation of:

• the aqueous permeation coefficient in cm h⁻¹,

• the maximum dermal absorption in mg cm⁻² h⁻¹ from a saturated aqueous solution at steady state,

• the lag time in hours (h),

• the diffusivity of a substance in the stratum corneum in cm² h⁻¹

By using the independent variables:

• the log(octanol/water partition coefficient),

• the molecular weight,

• the water solubility.

The estimated maximum dermal absorption and the lag time were compared with some recent measured data of substances, which were not used for developing the QSARs. The estimates were generally in the same order of magnitude as the measured absorption and lag time. These QSARs are recommended for risk assessment of chemicals in the scope of the European REACH legislation.     

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.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Time course of isocyanate emission from curing polyurethane adhesives

The time course of isocyanate emission from curing polyurethane (PUR) resins and adhesives was studied in two different emission test chambers. The measured emissions were strongly dependent on the type of experiment. The adhesives under investigation contained different types of diisocyanates and are used for different applications, e.g. for fixing of textile floor coverings. The influence of the curing mechanism on emission was studied by comparing the emission curves of one-component adhesives (OCA) and two-component adhesives (TCA). For TCA, the decrease in isocyanate emission was found to follow a two-step process during curing. In the first step, the emission is dominated by surface evaporation, and the decay of emission is mainly caused by the decrease in monomer content due to reaction. In the second step, the release is limited by internal diffusion. The influence of monomer reactivity on the emission profile could be demonstrated for 2,4′- and 4,4′-MDI. The less-reactive 2,4′-MDI caused prolonged emission. A strong dependence of emission rates on temperature and adhesive viscosity was also obvious. The evaluation of emission rates of different commercially available PUR adhesives showed the highest emission from systems that are applied at high temperatures. The high reactivity of diisocyanates requires special techniques for sampling and analysis. Therefore, an analytical method using HPLC–MS/MS was developed that enables limits of quantitation of <5 ng/m³ with a sampling volume of 100 l.     

Impact of earthworms on trace element solubility in contaminated mine soils amended with green waste compost

The common practice of remediating metal contaminated mine soils with compost can reduce metal mobility and promote revegetation, but the effect of introduced or colonising earthworms on metal solubility is largely unknown. We amended soils from an As/Cu (1150 mgAs kg⁻¹ and 362 mgCu kg⁻¹) and Pb/Zn mine (4550 mgPb kg⁻¹ and 908 mgZn kg⁻¹) with 0, 5, 10, 15 and 20% compost and then introduced Lumbricus terrestris. Porewater was sampled and soil extracted with water to determine trace element solubility, pH and soluble organic carbon. Compost reduced Cu, Pb and Zn, but increased As solubility. Earthworms decreased water soluble Cu and As but increased Pb and Zn in porewater. The effect of the earthworms decreased with increasing compost amendment. The impact of the compost and the earthworms on metal solubility is explained by their effect on pH and soluble organic carbon and the environmental chemistry of each element.     

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p,p′-DDE, and p,p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL⁻¹ for PCBs and from 0.12 to 0.36 ng mL⁻¹ for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.     

Chemical compositions and radiative properties of dust and anthropogenic air masses study in Taipei Basin, Taiwan, during spring of 2004

Asia is one of the major sources of not only mineral dust but also anthropogenic aerosols. Continental air masses associated with the East Asian winter monsoon always contain high contents of mineral dust and anthropogenic species and transported southeastward to Taiwan, which have significant influences on global atmospheric radiation transfer directly by scattering and absorbing solar radiation in each spring. However, few measurements for the long-range transported aerosol and its optical properties were announced in this area, between the Western Pacific and the southeastern coast of Mainland China. The overall objective of this work is to quantify the optical characteristics of different aerosol types in the Eastern Asian. In order to achieve this objective, meteorological parameters, concentrations of PM₁₀ and its soluble species, and optical property of atmospheric scattering coefficients were measured continuously with 1 h time-resolved from 11 February to 7 April 2004 in Taipei Basin (25°00′N, 121°32′E). In this work, the dramatic changes of meteorological parameters such as temperature and winds were used to determine the influenced period of each air mass. Continental, strong continental, marine, and stagnant air masses defined by the back-trajectory analysis and local meteorology were further characterized as long-range transport pollution, dust, clean marine, and local pollution aerosols, respectively, according to the diagnostic ratios. The aerosol mass scattering efficiency of continental pollution, dust, clean marine, and local pollution aerosols were ranged from 1.3 to 1.6, 0.7 to 1.0, 1.4 and 1.4 to 2.3 m² g⁻¹, respectively. Overall, there are two distinct populations of aerosol mass scattering efficiencies, one for an aerosol chemical composition dominated by dust (<1.0 m² g⁻¹) and the other for an aerosol chemical composition dominated by anthropogenic pollutants (1.3–2.3 m² g⁻¹), which were similar to the previous measurements with high degree of temporal resolution.     

DDT residues in water, sediment, domestic and indigenous biota from a currently DDT-sprayed area

DDT is used for indoor residual spraying (IRS) in Limpopo Province, northern South Africa to control malaria. Through IRS, DDT may reach the outdoor environment via dust and air and from possible spillages during application. In this area the local people consume domestic chickens, wild fish or birds. Fish from the river catchment and impoundments seem to be the major source of protein intake. Water, sediment and tissue samples from two such fish species, domestic chickens and wild birds (terrestrial and aquatic) from this DDT-sprayed area were analysed for DDT and metabolite residues. The samples contained p,p′-DDT, p,p′-DDD and p,p′-DDE residues, with the latter the most ubiquitous and in the highest concentrations. These findings raise concern that both water and food may be major routes of human exposure to DDT and metabolites, thereby posing possible adverse human health implications to the local communities.     

Synthesis of 4,4′-dichloro-3,5,3′,5′-tetramethylbiphenyl by the sandmeyer reaction

4,4′-Dichloro-3,5,3′,5′-tetramethylbiphenyl was prepared by -diazotization of 3,5,3′,5′-tetramethylbenzidine followed by the Sandmeyer reaction. The starting material is a noncarcinogenic analogue of benzidine, and the product may be of interest as a model compound for studying the metabolism of chlorinated biphenyls.     

Shift in ectomycorrhizal community composition in Scots pine (Pinus sylvestris L.) seedling roots as a response to nickel deposition and removal of lichen cover

Scots pine seedlings were exposed to wet-deposited nickel (Ni) and removal of lichen cover in a dry heath Scots pine forest. Ni deposition affected the colonization of roots by indigenous ectomycorrhizal fungi in contrasting ways in intact and skimmed quadrats. Highest frequencies of tubercle morphotypes of ectomycorrhiza were found in quadrats exposed to 100 mg m⁻² year⁻¹ Ni in lichen covered treatment, while in skimmed quadrats these peaked after the treatment with 10 mg Ni m⁻² year⁻¹. Removal of the lichen layer increased the value of diversity index (H′) of ectomycorrhizal fungal community, probably due to the increase in the evenness of the morphotype distribution. Lichen removal seemed also to improve the condition of the short roots, as the frequencies of poor and senescent short roots were decreased by the removal.     

Impact of the Saharan dust outbreaks on the ambient levels of total suspended particles (TSP) in the marine boundary layer (MBL) of the Subtropical Eastern North Atlantic Ocean

Six years (1998–2003) of measurements of ambient air concentrations of total suspended particulate (TSP) measured at a rural background monitoring station in Tenerife (Canary Islands), the El Río station (ER, 28°08′35″N, 16°39′20″W, 500 m a.s.l.) were studied. African dust outbreaks were objectively identified using a new quantitative tool, called the African Index. This index indicates the percentage of time that an air mass remained over an African region at one of three possible height intervals of the lower troposphere. After identifying these episodes, a study of the background TSP levels at the ER station and of direct and indirect (those which cause vertical deposition of dust) African air mass intrusion impacts was performed. Taking into account both direct and indirect episodes, a total of 322 days of African dust intrusion were objectively identified (a mean of 54 episodes per year) in the period 1998–2003, some of them caused by “transition episodes” or “return African air masses”. A subjective method confirmed that 256 of these days were caused by direct impacts of African dust on the ER station. A mean TSP value of 21.6 μg m⁻³ was found at the station during this period. All the episodes occurred when the TSP concentration was >28.5 μg m⁻³. The TSP background (14 μg m⁻³) can be assumed to be representative of the MBL of the Eastern North Atlantic subtropical region. The highest number of dust gravitational settlement (or indirect) episodes occurs in summer, but the highest contribution of these episodes to the TSP levels is in March with a monthly mean TSP contribution of up to 30.5 μg m⁻³.     

Bioconcentration kinetics of 2,4,5- tri- and 3,3′,4,4′-tetrachlorobiphenyl and 2,4,5- tri- and 3,3′,4,4′-tetrachlorodiphenylether in fish

The rates of uptake and elimination of 2,4,5 tri- and 3,3′,4,4′-tetrachlorodiphenylether in fish after aqueous exposure are comparable to those of similarly substituted chlorobiphenyls. Mass balance data suggest that 2,4,5- trichlorobiphenyl and 2,4,5- trichlorodiphenylether are metabolized with rates approximately twice as high as the rates of elimination of the parent compounds.The bioconcentration factors of the 3,3′,4,4′-tetrachloro- biphenyl and 3,3′,4,4′- tetrachlorodiphenyl ether are only determined by the hydrophobic nature of these chemicals and are not influenced by metabolism. Congener specific uptake and elimination processes as have been reported for chlorinated dibenzo-p-dioxins and dibenzofurans does not seem to be important for chlorinated biphenyls and diphenylethers.     

Water and solute movement in soil as influenced by macropore characteristics: 2. Macropore tortuosity

The paper describes the results of a laboratory study on the effects of macropore tortuosity on breakthrough curves BTCs and solute distribution in a Forman loam (fine loamy-mixed Udic Haploborolls) soil. BTC were obtained using 2-D columns (slab) containing artificial macropores of five different tortuosity levels. The BTCs were run under a constant hydraulic head of 0.08 m over an initially air dry soil. The input solutions contained 1190 mg l⁻¹ of potassium bromide, 10 mg l⁻¹ of Rhodamine WT, and 100 mg l⁻¹ of FD&C Blue #1. A soil column without macropores served as a control. The displacement of a non-adsorbed tracer was not affected by the tortuosity level. An increase in macropore tortuosity progressively increased the breakthrough time, increased the apparent retardation coefficient (R′), decreased the depth to the center of mass of a given adsorbed tracer, and increased the anisotropy in tracer distribution profile. The relative importance of macropore tortuosity increased with an increase in the adsorption coefficient of the tracer. Compared to macropore continuity, the macropore tortuosity had greater impact on solute distribution profile than in its leaching.