Experimental study of 60Co behaviour in Tejo River sediments

The objective of this study was to obtain information on the transfer of radiocobalt in freshwater environments that can be used to predict its environmental distribution. The sediment-water behaviour of ⁶⁰Co in freshwater systems was studied through adsorption and desorption experiments undertaken using sediments and water from Fratel Reservoir in the Tejo River. The suspended sediment concentrations (C_s: 500–2000 mg 1^–1) and Co distribution coefficient (K_d) were inversely related: K_d = 2211–2001 ln [C_s]; K_d ranged from 4000 to 8000 ml g^–1. With a suspended sediment concentration of 1000 mg 1^–1, the ⁶⁰Co concentration remaining in solution (C_t) was given by: C_t = 49.4 e^–0.584t + 46.3 e^–0.014t; where t is the time in days and the half-life periods are 1.2 and 50 days. In a closed system, desorption of ⁶⁰Co could be described by a one-component relation with a half-life of 104 days, and a two component relation (half-life 5 hours and 45 days) in an open system. In river water the ⁶⁰Co was found to be almost 100% in cationic forms, however, in the presence of sediment there was a decrease in the proportion of cationic forms (to 50%), with some anionic forms appearing.     

Norfloxacin Sorption to Different Fractions in Sediments from Typical Water Systems in China

Sorption isotherms of Norfloxacin (NOF) to different fractions from six typical sediments in China were determined to compare the NOF sorption behavior and contribution of different fractions to total sorption. All sorption isotherms were nonlinear and fitted well with the Freundlich model. Sorption coefficients (K _f) by original sediments changed in larger magnitude, from 114 (mg/g)/(mg/L)ⁿ to 5271 (mg/g)/(mg/L)ⁿ, and black carbon with more aromatic carbon has more sorption capacity and nonlinearity. The sorption capacity K _f values were found to significantly correlate with SSA (specific surface area), OC (organic carbon), BC (black carbon), and TON (total organic nitrogen) (p < 0.05), but had no obvious relation with pH, CEC (cation exchange capacity), TOC/TON, and BC/TOC. The DOC removed, NaOH extracted, and 375°C heated fractions showed more nonlinear sorption than the original sediments, suggesting more heterogeneous sorption sites in these fractions. Among different sediment fractions, the 375°C heating fractions were responsible for >50% of the total NOF sorption over the whole concentration range. The contribution of DOC removed fractions to the total sorption was the highest at higher NOF concentration.     

Comparative Sorption of Phenanthrene and Benzo[α]pyrene to Soil Humic Acids

Sorption of phenanthrene (Phen) and benzo[α]pyrene (BaP) by humic acids (HAs) extracted from four typical soils in China, including cinnamon soil, fluvo-aquic soil, red soil, and mountain meadow soil were investigated. All sorption data were fitted well by the Freundlich model, but BaP exhibited stronger and more nonlinear sorption than Phen by a given HA. For Phen isotherms, there was a positive relation between K _oc values and aliphaticity of HAs, whereas a negative correlation was observed between n values and aliphaticity. This indicated the importance of aliphatic groups in Phen sorption capacity and nonlinearity. Compared to Phen, a similar trend was obtained between n values of BaP and aliphaticity or aromatic carbon. However, no correlation existed between K _oc values for BaP and aliphaticity or aromatic carbon.     

Importance of Environmental Black Carbon to Dissolved Petroleum Hydrocarbons Sorption on Soil

Importance of environmental black carbon (BC) to sorption of dissolved petroleum hydrocarbons (DPH) on two soils with high BC:TOC ratios (33% and 11%, respectively) was evaluated at a relatively high concentrations (mg/L ～ μ g/L range). Sorption isotherms of DPH were determined for the two original soils and soils combusted at 375°C (only BC). The sorption isotherms of the original soils were linear, whereas the isotherms of the combusted soils were highly nonlinear (n _F = 0.45, 0.60). It is indicated that intrinsic BC-water sorption coefficient is not possible to be used to estimate total sorption to the original soil, even in our relatively high concentrations. From the sorption isotherms, Freundlich coefficient of environmental BC sorption, K _F,BC ^env of 10 ^{2.55 ± 0.21} was calculated and could be used as a generic starting point for environmental modeling purposes. From the data, it could be deduced that BC was responsible for 50% of the total sorption at concentrations of 45 and 4 μ g/L (μ g/L range), which were significantly higher than literature concentrations (ng/L range). These results demonstrate that in soil with high BC:TOC ratio BC is the most important geosorbent constituent with respect to sorption of DPH at relatively high concentrations ranged in μ g/L.     

Decomposition and sorption characterization of plant cuticles in soil

The sorption of organic compounds by plant cuticular matter has been extensively investigated; however, little has been studied regarding the effect of plant cuticle degradation on their role in the sorption of organic compounds in soils. The sorption of phenanthrene was studied in soil samples which had been incubated for up to 9 months with three different types of plant cuticle isolated from tomato fruits, pepper fruits and citrus leaves. The main change in the diffuse reflectance Fourier-transform infrared (DRIFT) spectra during incubation of the cuticles was related to cutin decomposition. The peaks assigned to methyl and ethyl vibration and C=O vibration in ester links decreased with decomposition. In general, with all samples, the phenanthrene sorption coefficients calculated for the whole incubated soils (K _d) decreased with incubation time. In contrast, the carbon-normalized K _d values (K _oc) did not exhibit a similar trend for the different cuticles during incubation. The origin of the cuticle also affected the linearity of the sorption isotherms. With the tomato and citrus cuticle samples, the Freundlich N values were close to unity and were stable throughout incubation. However with the green pepper cuticle, the N values exhibited a significant decrease (from 0.98 to 0.70). This study demonstrates that the structural composition of the plant cuticle affects its biodegradability and therefore its ability to sorb organic compounds in soils. Of the residues originating from plant cuticular matter in soils, the cutan biopolymer and lignin-derived structures appear to play a dominant role in sorption as decomposition progresses. Responsible Editor: Alfonso Escudero.     

Sorption of Glyphosate on Soil Components: The Roles of Metal Oxides and Organic Materials

Predicting the behavior, fate, and transport potential of a herbicide in any soil involves understanding the sorption characteristics. The sorption characteristics of glyphosate (GPS) on soil and their main components were investigated, indicating that the mineral phase is more important than the organic carbon in adsorption of GPS. Sorption isotherms were determined from each component using the batch equilibrium method at various concentrations (5, 10, 15, 20, 25, and 30 mg L^?1) and sorption affinity of GPS was approximated by the Freundlich equation. The sorption strength K _f [mg kg^?1 (L mg^?1)^?n] across the various components ranged from 2.1–134.9 while the organic carbon-normalized Freundlich sorption capacity values, K _foc, ranged from 1.28–3.53 mg kg^?1-OC/(mg L^?1)ⁿ. Infrared Fourier transform spectroscopy (FTIR) of the components showed significant structural differences. The results suggest that the presence of the oxides and hydroxides iron, in particular in soil solutions, enhanced GPS adsorption. They also suggest that reduction in OC% due to various treatments may enhance the remobilization of GPS into the aqueous phase (i.e., groundwater), though at different rates. Comparatively, contribution of surface area to the adsorption of GPS on the various components proved more significant than contents of organic carbon.     

Characteristics of Copper Sorption by Various Agricultural Soils in China and the Effect of Exogenic Dissolved Organic Matter on the Sorption

To explore the effect of exogenic dissolved organic matter (DOM) on Cu(II) sorption in agricultural soils, 26 agricultural soils were collected across China. Exogenic dissolved organic matter, extracting from wheat straw (DOM_W) and swine manure (DOM_S), respectively, were added to the soils to conduct a series of batch sorption and characterization experiments. The solid-liquid partition coefficient (K_d) ranged from 0.02 to 76.46 L g^?1, suggesting different Cu(II) sorption on various soils. PCA analysis indicated that pH, free Fe/Al oxides, carbon, and total Cu content had a significant positive relationship with the Cu(II) sorption, respectively. And the contribution rate of pH was the highest (38.15%). Moreover, DOM markedly inhibited the Cu(II) sorption in alkaline soils while promoted the Cu(II) sorption in acidic soils, which were interacted by the soil properties and DOM characteristics. The effect of DOM_S on Cu(II) sorption were more obvious than DOM_W, which were further confirmed by Fourier transform infrared (FTIR) spectroscopy. FTIR also showed Cu(II) was primarily adsorbed on the specific functional groups, such as CO, OH, and CO, providing direct evidences for the binding of Cu(II) with DOM. This study can guide the rational use of organic fertilizers, and also provide baseline knowledge for the prevention and control of soil pollution.     

Adsorption of linuron and metamitron on soil and peats at two different decomposition stages

We studied the adsorption of two herbicides of different polarity, linuron and metamitron, by a mineral soil and two peats at different decomposition stages and determined Freundlich and distribution coefficients per unit of organic matter. The Freundlich adsorption constant (K₁) was 20‐to 30‐fold higher in the case of linuron and 40‐to 90‐fold higher for metamitron for the organic materials (peats) than for the mineral soil, reflecting adsorption dependence on both organic matter content and type. The well‐decomposed peat showed the highest affinity for both herbicides. Hydro‐phobic bonding is suggested as a possible explanation. For linuron, the variation in K, was reduced to less than a twofold variation in K_oc by normalizing adsorption to organic carbon, whereas for metamitron, K_oc values were not constant, confirming that this parameter may be of little meaning for polar compounds.     

Phosphorus sorption characteristics of sediment in the Simiyu and Kagera River basins: implications for phosphorus loading into Lake Victoria

As part of a larger study to assess the influence of land use on riverine and atmospheric phosphorus (P) loading to Lake Victoria, P sorption characteristics of eight composite bottom sediment samples from the Simiyu and Kagera rivers were determined using the Langmuir equation. The samples had low to medium Langmuir adsorption maxima (Γ_m), ranging from 107 to 201μg g^?1. Langmuir binding energy co-efficient (K) ranged from 60 to 181μg l^?1 and the equilibrium P concentration at zero sorption (EPC₀) from 0.1 to 2.75μg g^?1. By using Langmuir co-efficients derived from P sorption experiments and soluble reactive phosphorus (SRP) concentrations measured in rivers as well as the in-shore waters of Lake Victoria, it was possible to determine the potential release of SRP into the lake by sediment from the two catchments. For the 2000 water-year, it was estimated that about 28.65 ± 0.89 (mean ± SD) and 66 ± 6.76 tons of SRP were released into Lake Victoria by sediment deposited by the Simiyu and Kagera rivers, respectively. The implications of these results to future management of cultural eutrophication in Lake Victoria are also discussed.     

Adsorption and Degradation of Metolachlor and Metribuzin in a No-Till System Under Three Winter Crop Covers

The objective of this study was to quantify adsorption and degradation of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1 -methylethyl) acetamide] and metribizun [4-amino-6-(1,1 -dimethylethyl)-3-(methylthio)-1,2,4-trazine-5(4H)-one] in a soil planted to winter covers clover (Trifolium sp.), vetch (Vicia villosa), and wheat (Triticum aestivum). Surface soil samples (0 to 5?cm) from Memphis silt loam (fine-silty, mixed, thermic Typic Hapludalf) were collected and equilibrated with herbicide at initial concentrations ranging from 0 to 20?mg L^?1 that were then applied for a batch experiment. Soils were treated either with a single herbicide or a mixture of the two herbicides. For the degradation experiments, herbicides at a concentration of 10?mg kg^?1 soil were applied and incubated for 21?d at ～23°C. Metolachlor and metribuzin adsorptions were described by the Freundlich isotherm. Average Freundlich distribution coefficient (K_f) for metolachlor was significantly higher (p≥0.05) than that of metribuzin in soils under the three crop covers irrespective of method of application. The K_f for metolachlor ranged from 18.38 to 11.18?L kg^?1, and K_f for metribuzin ranged from 1.80 to 0.93?L kg^?1. Average normalized distribution coefficient (K_oc) for metolachlor was significantly higher (p≥0.05) than average K_oc for metribuzin irrespective of crop cover. After 21 days of incubation, average half-life of metolachlor across soil under the three crop covers was significantly higher than the average half-life of metribuzin (p≥0.05). Half-life values ranged from 20.6 to 24.9 days for metolachlor, and 4.4 to 12.4 days for metribuzin. In soils treated with metribuzin, the half-life was highest for soil under wheat and lowest for soil under clover (p≥0.05).     

Biodegradation kinetic constants and sorption coefficients of micropollutants in membrane bioreactors

In order to elucidate the capability of biomass developed in membrane bioreactors (MBR) to degrade and sorb emerging micropollutants, biodegradation (k_biol) and sorption (k_sor) kinetic constants as well as solid–liquid partition coefficients (K_d) of 13 selected pharmaceutical and personal care products (PPCPs) were determined with MBR heterotrophic biomass adding a pulse (100 ppb of each compound) and following the liquid and solid phase concentrations over time. The results obtained were compared to literature data referring to conventional activated sludge (CAS) systems. Two experiments were performed: one in the MBR itself and the second one in a batch reactor with the same type and concentration of biomass as in the MBR. Overall, both biodegradation and sorption coefficients were in the same range as previously reported by other studies in CAS systems, indicating that MBR biomass does not show better capabilities for the biological degradation and/or sorption of PPCPs compared to the biomass developed in CAS reactors. Therefore, the higher PPCPs removal efficiencies found in MBRs are explained by the high biomass concentrations obtained at the long sludge retention times at which this type of reactors are usually operated.     

Gas Exchange and Chlorophyll Fluorescence of C3 and C4 Saltmarsh Species

Spartina maritima (Curtis) Fernald, Spartina densiflora Brong, Arthrocnemum perenne (Miller) Moss, and Arthrocnemum fruticosum (L.) Moq are very frequent halophytes on the coasts of SW Europe. The first two are perennial Gramineae with C₄ metabolism; the last two are perennial Chenopodiaceae with C₃ metabolism. Controlled garden experiments were carried out with the four species to compare their physiological response, i.e., water potential (Ψ), net photosynthetic rate (P_N), transpiration rate (E), stomatal conductance (g_s), intercellular CO₂ concentration (Ci), and chlorophyll fluorescence of photosystem (PS) 2 under saline and non-saline conditions. S. maritima behaves as an osmoconformer species, the other three as osmoregulators. In the four species, P_N, E, and g_s improved following freshwater irrigation. The variations in P_N might be related with biochemical changes (which appear not to affect PS2), but not with significant stomatal fluctuations, which are associated with a lower water use efficiency in the case of Arthrocnemum. The species were segregated into two groups (not depending on their C₃ or C₄ photosynthetic pathway), in relation with the topographic level of this species in natural conditions: the relative responses of P_N in S. maritima and A. perenne were lower than those of S. densiflora and A. fruticosum. The salt-tolerance index supports such segregation. S. densiflora demonstrated the best competitive possibilities against salt-tolerant glycophytes, with its more flexible response in saline or brackish environments, which explains its spreading along the rivers draining into the estuaries of the SW Iberian Peninsula. This revised version was published online in June 2006 with corrections to the Cover Date.     

Regulation of mesophyll photosynthesis in intact wheat leaves by cytoplasmic phosphate concentrations

The effect of D-(+)-mannose, inorganic phosphate (Pi) and mannose-6-phosphate on net mesophyll CO₂ assimilation rate (A) and stomatal conductance (g_s) of wheat (Triticum aestivum L.) leaves was studied. The compounds were supplied through the transpiration stream of detached leaves from plants grown in sand in growth cabinets or glasshouses, with different concentrations of Pi (0.25, 1.0 and 4.0 mM) supplied during growth. In all cases, 10 mM D-(+)mannose caused 40–60% reduction of A within 30 min, though the time courses differed for flag leaves and the sixth leaf on the mainstem of glasshouse- and cabinet-grown plants. D-(+)Mannose had a similar effect on A in leaves having a fourfold range in total phosphate content. Effects of D-(+)mannose in reducing g_s were always slower than on A. When the CO₂ concentration in the leaf chamber was adjusted to maintain intercellular CO₂ concentration (C_i) constant as A declined after mannose supply, g_s still declined indicating that stomatal closure was not caused by changing C_i. Supplying mannose-6-phosphate at 10 and 1 mM and Pi at 5 and 10 mM concentrations caused rapid reductions in g_s and also direct reductions in A. The observed effects of mannose and Pi on assimilation are consistent with the proposed regulatory role of cytoplasmic Pi in determining mesophyll carbon assimilation that has been derived previously using leaf discs, protoplasts and chloroplasts.Abbreviations and symbols A net mesophyll CO₂-assimilation rate - C_a, C_i external (assimilation-chamber) and intercellular CO₂ concentration, respectively - g_s stomatal conductance - Man6P mannose-6-phosphate - Pi orthophosphate     

Sorption of Methylene Blue by an Oscillatoria sp.–Dominated Cyanobacterial Mat

The ability of an Oscillatoria sp.–dominated cyanobacterial mat in sorbing methylene blue (MB), a cationic dye, was investigated using the batch contact method. The sorption of MB onto the powdered biomass was not significantly influenced by initial pH (2–10) and temperature (5–45°C) of the solution. MB sorption occurred slowly, requiring 1–8 h for the establishment of equilibrium. A slow attainment of equilibrium seems to be related with the large size of MB ions. The isotherm data of MB sorption by the mat biomass could effectively fit to Langmuir and Freundlich models. The maximum MB sorption capacity (q _max) of the test biomass was 78.43 mg g^?1, which changed little with variation in biomass concentration. Moreover, the test biomass could efficiently sorb MB from solution in presence of Na⁺, K⁺, and Ca²⁺, which usually occur at high concentrations in natural waters, and also in presence of Cd²⁺. These particular characteristics together with pH and temperature independence of the sorption process make the mat biomass an ideal MB sorbent.     

Observations and model simulations link stomatal inhibition to impaired hydraulic conductance following ozone exposure in cotton

Ozone (O₃) inhibits plant gas exchange and productivity. Vapour phase (g_s) and liquid or hydraulic phase (K) conductances to water flux are often correlated as both change with environmental parameters. Exposure of cotton plants to tropospheric O₃ reduces g_s through reversible short-term mechanisms and by irreversible long-term disruption of biomass allocation to roots which reduces K. We hypothesize that chronic effects of O₃ on gas exchange can be mediated by effects on K without a direct effect of O₃ on g_s or carbon assimilation (A). Experimental observations from diverse field and exposure chamber studies, and simulations with a model of mass and energy transport, support this hypothesis. O₃ inhibition of K leads to realistic simulated diurnal courses of g_s that reproduce observations at low ambient O₃ concentration and maintain the positive correlation between midday g_s and K observed experimentally at higher O₃ concentrations. Effects mediated by reduced K may interact with more rapid responses of g_s and A to yield the observed suite of oxidant impacts on vegetation. The model extends these physiological impacts to the extensive canopy scale. Simulated magnitudes and diurnal time courses of canopy-scale fluxes of H₂O and O₃ match observations under low ambient concentrations of O₃. With greater simulated concentrations of O₃ during plant development, the model suggests potential reductions of canopy-scale water fluxes and O₃ deposition. This could represent a potentially unfavourable positive feedback on tropospheric O₃ concentrations associated with biosphere–atmosphere exchange.     

Acetate synthesis from 2 CO2 in acetogenic bacteria: is carbon monoxide an intermediate?

Cultures of Acetobacterium woodii and Clostridium thermoaceticum growing on fructose or glucose, respectively, were found to produce small, but significant amounts of carbon monoxide. In the gas phase of the cultures up to 53 ppm CO were determined. The carbon monoxide production was completely inhibited by 1 mM cyanide. Cultures and cell suspensions of both acetogens incorporated ¹⁴CO specifically into the carboxyl group of acetate. This CO fixation into C₁ of acetate was unaffected by cyanide (1 mM). The findings are taken to indicate that CO (in a bound form) is the physiological precursor of the C₁ of acetate in acetate synthesis from CO₂. The cyanide inhibition experiments support the hypothesis that the cyanide-sensitive carbon monoxide dehydrogenase may serve to reduce CO₂ to CO rather than to incorporate the carbonyl into C₁ of acetate.     

Influence of Matrix Composition on the Bioaccessibility of Copper,Zinc, and Nickel in Urban Residential Dust and Soil

This study examines factors affecting oral bioaccessibility of metals in household dust, in particular metal speciation, organic carbon content, and particle size, with the goal of addressing risk assessment information requirements. Investigation of copper (Cu) and zinc (Zn) speciation in two size fractions of dust (< 36 μ m and 80–150 μ m) using synchrotron X-ray absorption spectroscopy (XAS) indicates that the two metals are bound to different components of the dust: Cu is predominately associated with the organic phase of the dust, while Zn is predominately associated with the mineral fraction. Total and bioaccessible Cu, nickel (Ni), and Zn were determined (on dry weight basis) in the < 150 μ m size fraction of a set of archived indoor dust samples (n = 63) and corresponding garden soil samples (n = 66) from the City of Ottawa, Canada. The median bioaccessible Cu content is 66 μ g g^?1 in dust compared to 5 μ g g^?1 in soil; the median bioaccessible Ni content is 16 μ g g^?1 in dust compared to 2 μ g g^?1 in soil; and the median bioaccessible Zn content is 410 μ g g^?1 in dust compared to 18 μ g g^?1 in soil. For the same data set, the median total Cu content is 152 μ g g^?1 in dust compared to 17 μ g g^?1 in soil; the median total Ni content is 41 μ g g^?1 in dust compared to 13 μ g g^?1 in soil; and the median total Zn content is 626 μ g g^?1 in dust compared to 84 μ g g^?1 in soil. Organic carbon is elevated in indoor dust (median 28%) compared to soil (median 5%), and is a key factor controlling metal partitioning and therefore bioaccessibility. The results show that house dust and soil have distinct geochemical signatures and should not be treated as identical media in exposure and risk assessments. Separate measurements of the indoor and outdoor environment are essential to improve the accuracy of residential risk assessments.     

Evaluating the Adsorption Potential of Alachlor and Its Subsequent Removal from Soils via Activated Carbon

Alachlor, a globally used aniline herbicide, has great agronomic interest for controlling the development of broadleaved weeds and grasses. This research aspires to evaluate the sorption attributes of Alachlor through batch equilibrium method and its successive removal through biomass based activated carbon prepared from Sawdust (Cedrus deodara). Six soil samples were collected from selected regions of Pakistan to assess the adsorption and removal phenomena. Adsorption capacity for Alachlor varied in soils depending upon their physicochemical properties. Adsorption coefficient (K_d) values ranged from 12 to 31 µg ml^?1 with the highest K_d value observed in soil sample with highest organic content (1.4%) and least pH (5.62). The Gibbs free energy values ranged from ?17 to ?20 kJ mol^?1 proposing physio-sorption and exothermic interaction with soils. Values of R² (0.96–0.99) exhibited the best fit to linear adsorption model. Adsorption coefficient displayed a negative correlation (r = ?0.97) with soil pH and positive correlation with organic matter (r = 0.87). The effect of contact time and pesticide concentration on the removal efficiency by activated carbon was investigated. The highest removal percentages observed through activated carbon were 66% and 64% at concentrations of 5 and 7.5 ppm respectively. Activated carbon from sawdust (Cedrus deodara) was investigated as a suitable adsorbent for the removal of Alachor from selected soils. Biomass based activated carbon can prove to be an effective and a sustainable mean to remove pesticides from soil.     

Ethylene Directly Inhibits Foliar Gas Exchange in Glycine max

Gas exchange of individual attached leaves of soybean, Glycine max (L.) Merr cv Davis, was monitored during exposure to exogenous ethylene (C₂H₄) to test the hypothesis that the effects of C₂H₄ on net photosynthesis (P_N) and stomatal conductance to H₂O vapor (g_s) are direct and not mediated by changes in leaf orientation to light. Leaflets were held perpendicular to incident light in a temperature-controlled cuvette throughout a 5.5 hour exposure to 10 microliters per liter C₂H₄. Declines in both P_N and g_s were evident within 2 hours and became more pronounced throughout the exposure period. In C₂H₄ treated plants, P_N and g_s decreased to 80 and 62%, respectively, of the rates in control plants. Because epinastic movement of the leaflets was prohibited by the cuvette, the observed declines in P_N and g_s were a direct effect of C₂H₄ rather than the result of reduced light interception caused by changing leaf angle.