Effect of Sediment Humic Substances on Sorption of Selected Endocrine Disruptors

Characterizing sorption processes is essential to understand the environmental distribution and toxicity potential of endocrine disruptors in terrestrial and aquatic systems. The sorption behaviors of three endocrine disruptors (bisphenol A (BPA), 17β-estradiol (E2), and 17α-ethynylestradiol (EE2)) on sediments were investigated using batch techniques. Samples were taken from some representative reaches in several major Chinese rivers. More attention has been paid to the effect of sediment organic components on the sorption of BPA, E2, and EE2. The results show that the sediment organic carbon-normalized partition coefficients (K _oc (sed)) for three endocrine disruptors are in the order of EE2 > E2 > BPA, which corresponds to the octanol-water partitioning coefficients (logK _ow) of the compounds. Moreover, the K _oc values for humic substances (K _oc (hs)) are comparable with the K _oc (sed) values and highly dependent on the physico-chemical properties of humic substances in sediments. The UV absorptivity at 272 nm (A ₂₇₂), which suggests the abundance of aromatic rings in humic substance structure, correlates well with the K _oc (hs) values. In addition, the infrared spectra of the humic substances extracted from sediments show four strong bands centered at 3,400 cm⁻¹, 1,625 cm⁻¹, 1,390 cm⁻¹, and 1,025 cm⁻¹. The K _oc (hs) values have a positive linear relation with the peak area ratio for peak at 1,025 cm⁻¹ and a negative linear relation with the peak area ratio between peaks at 1,625 cm⁻¹ and 1,025 cm⁻¹. Hence, the hydrogen bonds play a critical role to the sorption of selected endocrine disruptors.     

Recycling of ‘waste’ FE(III)/CR(III) hydroxide for the removal of nickel from wastewater: Adsorption and equilibrium studies

Effects of Ni(II) concentration, agitation time, temperature and pH on adsorption of Ni(II) on Fe(III)/Cr(III) hydroxide, a waste by-product from fertilizer industry, have been investigated. The percent adsorption increased from 55 to 69% with increase in temperature from 20 to 40°C and from 32 to 77% with increase in pH from 3.7 to 7.5 and from 38 to 79% with decrease in Ni(II) concentration from 100 to 25 mg/L. The equilibrium data fit well with the Langmuir isotherm and the adsorption capacity was found to be 21.0 mg/g at 30°C. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were evaluated. The adsorption rate constant was higher at lower concentration of Ni(II) and at higher temperature. Desorption studies show that 70% of Ni(II) can be desorbed from the adsorbent at pH 4.0. The adsorbent was tested using nickel plating industry wastewater and the maximum percent removal was 97.     

Thermal behavior characteristics of Adhesive residue

Solid wastes from organic Adhesive production are identified as toxicant hazardous wastes in China’s National Catalogue of Hazardous Wastes. The aim of this study is analyzing the thermal behavior of Adhesive residue. Its pyrolysis and combustion characteristics were investigated using thermogravimetric analysis (TGA). Experiments were carried out in the temperature range of 50–950 °C in both nitrogen and air. The results indicate that combustion under these experimental conditions largely occurs between 210 and 410 °C, whereas pyrolysis proceeds between 260 and 430 °C. Almost all weight lost takes place before 430 °C during both pyrolysis and combustion of the residue. Fourier transform infrared spectroscopy (FTIR) was used to characterize the emission characteristics during pyrolysis. When the sample is heated in an inert atmosphere, the evolution of volatiles starts around 260 °C, and reaches a peak rate at 394 °C. Most organic products evolve in a narrow temperature range during pyrolysis. The evolving gaseous products were identified as Butyraldehyde, Ether, Acetonitrile and CO₂, accompanied with some CO.     

Moisture Sorption Characteristics of Microbially Produced Polysaccharide and Polyvinyl Alcohol Blends

Moisture sorption characteristics of microbial polysaccharide (Ps.C101) from Pseudomonas caryophilli and polyvinyl alcohol (PVA) blends have been carried out at 27°C for water activity from 0.1 to 0.9. The sorption data was used to fit six different sorption isotherm models proposed in literature. The model constants were determined by linear fitting of the sorption equations. The ranges of applicability of water activity for isotherm models reported in this paper lie in between 0.1 and 0.4 for Brunaur–Emmet–Teller (BET) model (monolayer), and in between 0.2 and 0.9 for other models. The value of the coefficient of determination (R² = 0.97 ± 0.02) confirms the applicability of the equations studied.     

Monitoring degradation of poly(hydroxybutyrate) by fracture toughness measurements

The fracture behavior of poly(hydroxybutyrate) is described in terms of classical fracture mechanics. The fracture toughness (measured byG _c, the strain energy release rate, andK _c, the stress intensity factor) was monitored during physical aging and during chemical degradation with methylamine. A change in the measuredK _c value was found after degradation by methylamine which does not seem to be due solely to the measured thickness changes. The work lays the foundation for studies monitoring changes in fracture behavior during environmental degradation.Presented at the 4th International Workshop on Biodegradable Plastics and Polymers, October 11–14, 1995. Durham, New Hampshire.     

The release of nitrous oxide from the intertidal zones of two European estuaries in response to increased ammonium and nitrate loading

Nitrous oxide (N₂O) release and denitrification rates were investigated from the intertidal saltmarsh and mudflats of two European river estuaries, the Couesnon in Normandy, France and the Torridge in Devon, UK. Sediment cores and water were collected from each study site and incubated for 72 h in tidal simulation chambers. Gas samples were collected at 6 and 12 h intervals from the chambers during incubation. From these N₂O emission rates were calculated. The greatest rates for both N₂O production and denitrification were measured from saltmarsh cores. These were 1032 mol N₂O m^–2 day^–1 and 2518 mol N₂ m^–2 day^–1, respectively, from the Couesnon and 109 mol N₂O m^–2 day^–1 and 303 mol N₂ m^–2 day^–1 from the Torridge. A strong positive correlation was apparent with N₂O emission rates and ammonium concentration in the sediment, nitrate concentration in floodwater and sediment aerobicity.     

Novel Biobased Polyurethanes Synthesized from Soybean Phosphate Ester Polyols: Thermomechanical Properties Evaluations

Biobased polyurethanes from soybean oil–derived polyols and polymeric diphenylmethane diisocyanate (pMDI) are prepared and their thermomechanical properties are studied and evaluated. The cross-linked biobased polyurethanes being prepared from soy phosphate ester polyols with hydroxyl contents ranging from 122 to 145 mg KOH/g and pMDI within 5 min of reaction time at 150°C in absence of any catalyst show cross-linking densities ranging from 1.8 × 10³ to 3.0 × 10³ M/m³, whereas glass transition temperatures vary from approximately 69 to 82°C. The loss factor (tan ) curves show single peaks for all these biobased polyurethanes, thus indicating a single-phase system. The storage moduli (G) at 30°C range from 4 × 10⁸ to 1.3 × 10⁹ Pa. Upon postcure at 150°C, the thermomechanical properties can be optimized. Cross-link densities are improved significantly for hydroxyl content of 139 and 145 mg KOH/g at curing time of 24 h. Similarly, glass transition temperature (T_g) and storage moduli around and after T_g are increased. Meanwhile, tan intensities decrease as result of restricted chain mobility. Longer exposure time (24 h) induces thermal degradation, as evidenced by thermogravimetric analysis (TGA). The dynamic mechanical (DMA) analysis shows that postcure at 100°C for times exceeding 24 h also leads to improved properties. However, cross-linking densities are lower compared to postcure carried out at 150°C.     

A Retrospective Isotopic Study of Spruce Decline in the Vosges Mountains (France)

The objective of this study was to assess the time variation of mineral and water stress levels across the life of a declining, Mg-deficient, spruce stand, in order to clarify the factors that caused the decline. Since 1985, strong soil acidification linked to a large leaching of nitrate and base cations was measured at the study site. In 1994, 5 trees were felled and tree rings were measured and analysed for Ca, Mg, K, Sr, ¹³C¹²C and ⁸⁷Sr/⁸⁶Sr isotopic ratios. Strontium pools and fluxes as well as root Sr isotope ratio in relation to depth were also measured. Wood chemical concentrations and isotope ratios were strongly related to the dominance status of each tree. On average during the study period, the ⁸⁷Sr/⁸⁶Sr ratio of spruce wood decreased. Using a mechanistic model computing long term variations of ⁸⁷Sr/⁸⁶Sr ratio in trees and soils, we reproduced the observed trend by simulating soil acidification – increasing Sr drainage from the whole profile, and particularly from the organic horizon –, and root uptake becoming more superficial with time. Between 1952 and 1976, tree ring ¹³C decreased strongly and continuously, which, in addition to other factors, might be related to an increase in water stress. Thus, a decrease in rooting depth, possibly related to soil acidification, appeared as a possible cause for the long term increase in water stress. The extreme drought event of 1976 appears to have revealed and triggered the decline.     

Remediation of petroleum-contaminated soils by fluidized thermal desorption

A novel type of fluidized bed desorber was developed for the remediation of petroleum-contaminated soils at low temperature with high efficiency. Cahn balance® was utilized to investigate the thermal desorption behavior of soils contaminated by various hydrocarbons. The performance of the fluidized-bed desorber was investigated at different operating modes. Batch operation of the fluidized-bed desorber exhibited 99.9% desorption efficiency at temperatures of ca. 300°C within a half hour. Continuous operation of the fluidized-bed indicated that Q/F (the ratio of the mass flow rate of fluidizing gas to feeding rate of contaminated soils) is less important at higher temperature (>300°C), if proper fluidization is ensured. The periodic operation of the fluidized bed desorber shows the possibility to reduce off-gas volume significantly.     

Air Pollution Zones and Harmful Pollution Levels of Alkaline Dust for Plants

For characterisation of landscapes in north-eastern Estoniaaffected by alkaline oil shale fly ash and cement dust the zonation-method based on average annual (C _y) and short-termconcentrations of pollutants in the air was used, as well as on deposition loads of dust and Ca²⁺. In the overground layer of atmosphere the zones with different air pollution loads were distinguished. A comparative analysis of pollution zones characteristics and biomonitoring data revealed that for sensitive lichen the dangerous level of alkaline dust in the air, introducingthe degradation of Sphagnum sp. at the level of C _y of dust 10–20 g m^-3 and at 0.5–1 hr maximums 100–150 g m^-3. For Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L.) Karst.) this limited concentration (decline of growth parameters) of cement dust is correspondingly following: 30–50 g m^-3 and 150–500 g m^-3, in case of fly ash the limit level of C _y amounting 100 g m^-3. Daily deposition load of Ca²⁺ should not exceed approximately 4.5–15 mg m^-2 for lichen; for conifers the harmful pollution load is higher – >22 mg m^-2.     

Miscibility and Biodegradability of Poly(Butylene Succinate)/Poly(Butylene Terephthalate) Blends

As one of the biodegradable polymers, the blend of poly(butylene succinate) and poly(butylene terephthalate) is dealt with in this study. In our previous work, it was demonstrated that PBS and PBT are immiscible not only from the changes of T _g but also from logG–log G plots. It is expected that the biodegradability of the blends could be improved by enhancing the miscibility. We tried to induce the transesterification reaction between two polyesters with various time intervals to enhance the miscibility of the blends. The extent of transesterification reaction was examined by ¹H-NMR. We utilized a dynamic mechanical thermal analyzer and a rotational rheometer to investigate the changes in miscibility. We also verified the biodegradability of PBS/PBT blends after the transesterification reaction by the composting method.     

Moisture Sorption Characteristics of Chitosan/Polyethylene Oxide Blended Films

Studies on the moisture sorption characteristics of chitosan/polyethylene oxide (PEO) blended films have been carried out at 27 °C for water activity (a _w) from 0.1 to 0.9. The sorption data at different a _w were used to fit 12 different sorption isotherm models proposed in the literature. The model constants were determined by linear fitting of the sorption equations. The ranges of applicability of water activity for the isotherms reported in the article lie between 0.11 to 0.44 (monomolecular layer) for the BET model and between 0.11 to 0.86 (monolayer & multilayer’s) for Smith, Caurie, Bradley and Oswin. The water activity for Halsey and Chung & Pfost models lies between 0.44 to 0.86 (multilayer) and 0.33 to 0.86 for Henderson and Freundlich models and 0.11 to 0.65 for Kuhn, Linear and Iglesias & Chirife models. The high coefficient of determination R ² (ranges from 0.82 to 1) confirms the applicability of the equations employed. The study on the application of such water activity data of chitosan/PEO blended films on different model equations will be helpful in prediction of durability and functional behavior of moisture sensitive biopolymeric films     

The effect of bed properties on methane removal in an aerated biofilter--model studies

The capacity of laboratory-scale aerated biofilters to oxidize methane was investigated. Four types of organic and mineral-organic materials were flushed with a mixture of CH₄, CO₂ and air (1:1:8 by volume) during a six-month period. The filter bed materials were as follows: (1) municipal waste compost, (2) an organic horticultural substrate, (3) a composite of expanded perlite and compost amended with zeolite, and (4) the same mixture of perlite and compost amended with bentonite. Methanotrophic capacity during the six months of the experiment reached maximum values of between 889 and 1036 g m⁻² d⁻¹. Batch incubation tests were carried out in order to determine the influence of methane and oxygen concentrations, as well as the addition of sewage sludge, on methanotrophic activity. Michaelis constants K_M for CH₄ and O₂ were 4.6-14.9%, and 0.7-12.3%, respectively. Maximum methanotrophic activities V_max were between 1.3 and 11.6 cm³ g⁻¹ d⁻¹. The activity significantly increased when sewage sludge was added. The main conclusion is that the type of filter bed material (differing significantly in organic matter content, water-holding capacity, or gas diffusion coefficient) was not an important factor in determining methanotrophic capacity when oxygen was supplied to the biofilter.     

Characterization of Environmentally Friendly Polymers by Inverse Gas Chromatography: I Amylopectin

Amylopectin, as a potato starch based polymer, with a molecular weight of six million gram/mol was characterized using the Inverse Gas Chromatography Method (IGC). DSC method was also used to measure the glass and melting temperatures. Both DSC and IGC agreed well on a T_g of 105°C and T_m of 160–166°C. Nineteen solutes (solvents) were injected onto a chromatographic column containing amylopectin. These solutes revealed the interaction of alkanes with AP, and the wettability and water intake of AP. Alkanes showed exothermic values of interaction parameters which were increased as the temperature increased and as the number of carbons in the alkane series decreased. Retention diagrams of these solutes in a temperature range of 80–200°C revealed two zones, crystalline and amorphous. T_g and T_m were measured using these zones which complimented the DSC values. The two zones were used to calculate the degree of crystallinity below the melting temperature which ranged from 85% at 104°C to 0% at 161°C. The dispersive component of the surface energy of amylopectin was measured using alkanes which ranged from 25.35 mJ/m² at 80°C to 8.47 mJ/m² at 200°C. This is attributed to the weak crystalline surface of AP at 80°C and when the surface melted at 160°C the surface energy decreased due to the thermal expansion of the surface.     

Linking field experiments to long-term simulation of impacts of nitrogen deposition on heathlands and moorlands

The results from three long-term field manipulation studies of the impacts of increased nitrogen deposition (0–120 kg N ha^–1 yr^–1) on lowland and upland heathlands in the UK were compared, to test if common responses are observed. Consistent increases in Calluna foliar N content and decreases in litter C:N ratios were found across all sites, while increases in N leaching were not observed at any site over the range 0–80 kg ha^–1 yr^–1. However, the response of Calluna biomass did vary between sites, possibly reflecting site differences in nutrient status and management histories. Five versions of a simulation model of heathland responses to N were developed, each reflecting different assumptions about the fate and turnover of soil N. Model outputs supported the deduction from mass balance calculations at two of the field sites that N additions have resulted in an increase in immobilisation; the latter was needed to prevent the model overestimating measured N leaching. However, this version of the model significantly underestimated Calluna biomass. Model versions, which included uptake of organic N by Callunaand re-mobilisation of N from the soil organic store provided some improvement in the fit between modelled and field biomass data, but re-mobilisation also led to an overestimation of N leaching. Quantification of these processes and their response to increased N deposition are therefore critical to interpreting experimental data and predicting the long-term impacts of atmospheric deposition on heathlands and moorlands.     

An Automated Wet Deposition System to Compare the Effects of Reduced and Oxidised N on Ombrotrophic Bog Species: Practical Considerations

Critical N loads for ombrotrophic bogs, which often contain rare and N-sensitive plants (especially those in lower plant groups: lichens, mosses and liverworts), are based on very few experimental data from measured, low background N deposition areas. Additionally the relative effects of reduced versus oxidised N are largely unknown. This paper describes an automated field exposure system (30 km S. of Edinburgh, Scotland) for treating ombrotrophic bog vegetation with fine droplets of oxidised N (NaNO₃) and reduced N (NH₄Cl). Whim Moss exists in an area of low ambient N deposition (ca. 8 kg N ha^–1 y^–1), the sources and quantification of which are described. The wet N treatment system is run continuously, and is controlled/activated by wind speed and rainfall to provide a unique simulation of real world treatment patterns (no rain=no treatment). Simulated precipitation is supplied at ionic concentrations below4mMin rainwater collected on site. Treatments provide a replicated dose response to 16, 32 and 64 kg N ha^–1 y^–1 adjusted for ambient deposition (8 kg N ha^–1 y^–1). The 16 and 64 kg N ha^–1 y^–1 are duplicated with a P+K supplement. Baseline soil chemistry and foliar nutrient status was established for all 44 plots for Calluna vulgaris, Sphagnum capillifolium, Hypnum jutlandicum and Cladonia portentosa.     

Trends in Water Chemistry in a Maple Forest on a Steep Slope

Year-to-year variation in SO₄ ^2-,NO₃ ^-, Ca²⁺, K⁺, and Mg²⁺concentrations in forest floor and mineral soil percolatefrom a forested, podzolic soil at the Turkey Lakes Watershedon the Precambrian Shield was assessed for monotonic trendsbetween 1986 and 1995. Our objective was to examine howrapidly ion concentrations in soil percolate equilibratedafter stabilization of SO₄ ^2- concentrations inprecipitation. Significant negative trends were detected inmonthly Ca²⁺, and Mg²⁺ concentrations in forestfloor and SO₄ ^2-, Ca²⁺, and Mg²⁺ inmineral soil percolate during the 10-year-period. Thedecline in Ca²⁺ and Mg²⁺ was greater than annualdecreases in SO₄ ^2- and NO₃ ^- in forestfloor percolate and proportional to the reduction inSO₄ ^2- in mineral soil percolate. Response ofmineral soil percolate to a 15 mol_c L^-1SO₄ ^2- decrease in wet-only precipitation between1985 and 1986 was a gradual decline in SO₄ ^2-concentration through 1995. The five-year meanSO₄ ^2- concentration in bulk precipitation, forestfloor percolate, and mineral soil percolate decreased 8, 9and 18 mol_c L^-1 from 1986–90 to 1991–95.Microbial (mineralization of organic S) and sorption(release from and/or retention in the pool of insolubleSO₄ ^2-) processes in the soil were logicalexplanations for the observed changes in SO₄ ^2- inmineral soil percolate.     

Metabolic and Environmental Control on Methane Emission from Soils: Mechanistic Studies of Mesotrophic Fen in West Siberia

The biological mechanisms regulating methane emission fromnatural wetlands are the focus of this article. A novel techniqueprovides estimates of the distribution of CH₄ sources withinan undisturbed soil profile by recording the transient gasdynamics after soil enclosure by deep (50 cm) chamber. Thecombined use of conventional surface and soil chambers across a200-m fen transect allowed us to relate the observed methaneemission to its instant generation and uptake. Surprisingly, themethane generation was relatively constant (9–12 mg CH₄-C hr^-1 m^-2) and highly variable net emission (0.2–20 mg CH₄-C hr^-1 m^-2) was closely correlated (r = –0.809)with methane uptake. In laboratory incubations, CH₄ uptakefollowed Michaelis-Menten kinetics. Added chloride and nitrateirrespective of the cation's nature suppressed uptake as a strongnoncompetitive inhibitors (K _i 0.5 mM). The methaneformation turned out to be unstable and under anaerobicincubation, the formation of CH₄, CO₂ andH₂displayed sustained weekly oscillations. We conclude that effectsof environmental factors alone are not sufficient topredict the variation in emission, which depends also on metabolic control of respective soil organisms. The multitude ofsuch controls is dependent on diversity of respective soilorganisms and could be grouped into a limited number ofcategories considerably simplifying large-scale simulations.     

Protozooplankton in the Deep Oligotrophic Traunsee (Austria) Influenced by Discharges of Soda and Salt Industries

Traunsee is a deep oligotrophic lake in Austria characterised by an artificial enrichment of chloride in the hypolimnion (up to 170 mg L^-1) caused by waste disposal of soda and salt industries. Protists were collected monthly over one year, observed alive and after Quantitative Protargol Staining (ciliates) or via epifluorescence microscopy (heterotrophic flagellates). Three sites within the lake (0–40 m depths) were compared to deeper water layers from 60–160 m depths where chloride concentrations and conductivity were increased. In addition, we observed the protozooplankton of two neighbouring lakes, i.e. reference systems, during one sampling occasion. In Traunsee the abundance of ciliates was low (200–36 600 cells L^-1) in contrast to high species diversity (at least 60 different species; H_S = 2.6) throughout the year. The main pelagic species in terms of abundance were small oligotrichs and prostomatids like Rimostrombidium brachykinetum/hyalinum, Balanion planctonicum and Urotricha spp. throughout the investigation period. Among free-living heterotrophic flagellates, which occurred at densities of 40–2800 cells mL^-1, small morphotypes dominated in the pelagial. No differences at the community level between the three lakes could be observed and pelagic ciliates and flagellates seemed not to be affected by increased chloride concentrations or by enhanced conductivity.