Distribution, fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, (14)C- and (13)C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied (14)C was mineralized. The bioavailable, water extractable portion was low (9 % of applied (14)C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied (14)C was incorporated into organo-clay complexes as NER, whereas 9 % of applied (14)C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.     

Dietary exposure to dioxin-like compounds in three age groups: results from the Flemish environment and health study

Lipophilic contaminants are present in the environment and bioaccumulate in the food chain. Therefore, their intake via animal fat of various sources was assessed for three age groups of the Flemish population, participating in a large biomonitoring program of the Flemish government. In total, 1636 adolescents (14-15 years), 1186 mothers (18-44 years), and 1586 adults (50-65 years) participated in the study and completed a semi quantitative food frequency questionnaire. Individual consumption data were combined, via a so-called simple distribution approach, with recent data on polychlorinated dibenzo-p-dioxins/furans and dioxin-like polychlorinated biphenyls, measured via the chemical-activated luciferase gene expression (CALUX) bio-assay in food items available on the Flemish market. The median (95th percentile) estimated intakes of dioxin-like contaminants were 2.24 (4.61), 2.09 (4.26), and 1.74 (3.53) pg CALUX-TEQ kg(-1) bw d(-1) for, respectively adolescents, mothers and adults. These data are in the same range as those found in other European studies. The CALUX-TEQ results of respectively 59.8%, 53.7% and 36.2% of the adolescent, mother and adult population exceed the tolerable weekly intake (TWI) of 14 pg WHO-TEQ kg(-1) bw w(-1), as derived by the Scientific Committee on Food [Scientific Committee on Food, 2001. Opinion of the Scientific Committee on Food on the Risk Assessment of Dioxins and Dioxin-like PCBs in Food, CS/CNTM/DIOXIN/20 final Brussels, Belgium]. The main contributors of dioxin-like substances are fish and seafood (25-43% of the total intake), added fats (22-25% of the total intake) and dairy products (17-20% of the total intake).     

Placental transfer of polychlorinated biphenyls, their hydroxylated metabolites and pentachlorophenol in pregnant women from eastern Slovakia

The aim of the present study was to understand the placental transfer of polychlorinated biphenyls (PCBs), specific hydroxylated PCB metabolites (OH-PCBs), and pentachlorophenol (PCP) in blood serum, in a birth cohort from eastern Slovakia. During the period 2002-2004, cord blood specimens were collected in parallel with maternal specimens from women delivering in the two eastern Slovak districts of Michalovce and Svidnik/Stropkov. A total of 92 pairs of mother-cord specimens at delivery were selected for this study. 4-OH-CB107, 3-OH-CB153, 4-OH-CB146, 3'-OH-CB138, 4-OH-CB187, and 4'-OH-CB172 were quantified. The median concentrations of Sigma(17)PCBs, Sigma(6)OH-PCBs, and PCP in cord serum were 0.92, 0.33, and 0.69 ng/g wet wt., respectively and highly correlated with the corresponding maternal serum levels (correlations were R(2)=0.61, 0.78, and 0.82, respectively). The median cord to mother ratios of the Sigma(17)PCBs, Sigma(6)OH-PCBs, and PCP were 0.18, 0.75, and 1.10, respectively. The median ratio of the Sigma(6)OH-PCBs to the Sigma(17) PCBs in the cord serum was 0.38 from wet weight based concentrations, which was about four times higher than the ratio of these compounds in maternal serum (0.09). PCP was more abundant than any PCB or OH-PCB congener measured in cord serum. The higher cord to maternal ratios of OH-PCB metabolites as compared with the parent compounds suggests either a higher placental transfer rate or greater metabolism in the fetus as compared with the maternal compartment. These findings are consistent with their preferential binding to TTR that can cross the placenta. The cord to maternal ratio varies by congener (e.g., 4-OH-CB107=0.58, 4-OH-CB146=0.74, 3'-OH-CB138=1.01).     

Manipulation of snow in small headwater catchments at Storgama, Norway: effects on leaching of total organic carbon and total organic nitrogen

Projected increases in winter temperature due to future climate change may cause decreased snow accumulation at lower and intermediate altitudes in northern temperate regions. The resulting changes in soil temperature and water regime may affect the leaching of total organic carbon (TOC) and total organic nitrogen (TON). We manipulated the snow cover of small headwater catchments in a montane heathland area of southern Norway to quantify its effect on concentrations and fluxes of TOC and TON in runoff. Manipulations included snow removal, to promote soil frost, and insulation, to prevent soil frost. Snow removal resulted in increased TOC and TON concentrations, but decreased fluxes. Insulation caused a slight decrease in concentrations and fluxes of TOC. Our experiments show that a change in snow depth, and thus soil temperature, is not likely to have serious effects on TOC and TON leaching in the montane heathland area studied.     

Manipulation of precipitation in small headwater catchments at Storgama, Norway: effects on leaching of organic carbon and nitrogen species

Projected changes in climate in Southern Norway include increases in summer and autumn precipitation. This may affect leaching of dissolved organic matter (DOM) from soils. Effects of experimentally added extra precipitation (10 mm week) during the growing season of 3 years (2004-2006) to small headwater catchments at Storgama (59 degrees 0'N, 550-600 m a.s.l.) on leaching of total organic carbon (TOC) and total organic nitrogen (TON) were assessed. Extra precipitation did not have a significant effect on average TOC and TON concentrations in runoff. Thus, fluxes of TOC and TON increased nearly proportionally with water fluxes. This suggests that a store of adsorbed and potentially mobile TOC and TON in catchment soils buffers the concentration of DOM in runoff. The size and dynamics of the pool of TOC and TON depends on the balance between production and leaching rates. Infrequent short droughts had only small effects on TOC and TON fluxes in runoff from the reference catchments.     

Comparison of naphthalene bioavailability determined by whole-cell biosensing and availability determined by extraction with Tenax

A rapid biological method for the determination of the bioavailability of naphthalene was developed and its value as an alternative to extraction-based chemical approaches demonstrated. Genetically engineered whole-cell biosensors are used to determine bioavailable naphthalene and their responses compared with results from Tenax extraction and chemical analysis. Results show a 1:1 correlation between biosensor results and chemical analyses for naphthalene-contaminated model materials and sediments, but the biosensor assay is much faster. This work demonstrates that biosensor technology can perform as well as standard chemical methods, though with some advantages including the inherent biological relevance of the response, rapid response time, and potential for field deployment. A survey of results from this work and the literature shows that bioavailability under non-equilibrium conditions nonetheless correlates well with K_oc or K_d. A rationale is provided wherein chemical resistance is speculated to be operative.     

Performance change during long-term ozonation aimed at augmenting denitrification and decreasing waste activated sludge

Partial ozonation of return activated sludge for waste sludge minimization and soluble COD production was examined. Two nitrifying sequencing batch reactors, one control and one ozonated, were operated under alternating anoxic/aerobic conditions. During the first steady-state period of 95-136 d of ozonation, the amount of wasted solids decreased with the ozone dose up to 25%, generating soluble COD by cell lysis. However, during a subsequent period of 190-232 d of continuous ozonation, the effect of solids destruction and COD production decreased by 50%. The investigations of extracellular polymers content and floc shape analyses showed that, after prolonged daily ozone treatment, sludge floc structure becomes stronger, denser, and more ozone-resistant. The findings suggest that, for prolonged operation of partial sludge ozonation, an increase in ozone doses may be required to continuously maintain the expected solids destruction level. This in turn will increase the operational costs of the treatment.     

Enhanced biological phosphorus removal and recovery

Activated sludge systems designed for enhanced nutrient removal are based on the principle of altering anaerobic and aerobic conditions for growth of microorganisms with a high capacity of phosphorus accumulation. Most often, filamentous bacteria constitute a component of the activated sludge microflora. The filamentous microorganisms are responsible for foam formation and activated sludge bulking. The results obtained confirm unanimously that the filamentous bacteria have the ability of phosphorus uptake and accumulation as polyphosphates. Hydrodynamic disintegration of the foam microorganisms results in the transfer of phosphorus and metal cations and ammonium-nitrogen into the liquid phase. It was demonstrated that the disintegration of foam permits the removal of a portion of the nutrients in the form of struvite.     

Effect of humic substances on the Fenton treatment of wastewater at acidic and neutral pH

This paper describes results of treatability studies of the effect of humic substances (humate, HS, at the concentration 500-5000 mg l-1) on the Fenton (Fe2+/H2O2) treatment of industrial wastewater at pH 3.5 and 7.0. Without humate, the removal of all contaminants was significantly higher at pH 3.5 than at pH 7. At pH 7.0, the removal of all compounds in the presence of HS (3000 mg l-1) was comparable to that at pH 3.5 without HS. At pH 3.5, humate had no effect on the removal of arsenic, thiocyanate and cyanide, but the removal of all organic compounds (phenol, 2,4-dimethylphenol, benzene, toluene, o-xylene, m- & p-xylene and dichloromethane) was significantly inhibited. Mechanisms of the processes are discussed. It is suggested that, in the presence of HS, acidification of the treated wastewater may not only be unnecessary but it can even hinder the degradation of organic pollutants.