The effects of alkalinity and acidity of process water and hydrochar washing on the adsorption of atrazine on hydrothermally produced hydrochar

Hydrothermal carbonization of simulated food waste was performed at 250 °C for 20 h using deionized water (DI) and 0.01 N solutions of HCl, NaCl, and NaOH. The hydrochars produced were washed with acetone and the adsorptive capacity of the washed and unwashed hydrochars for atrazine were characterized. Using a generalized linear model, it was shown that the adsorptive capacity of the washed hydrochar was significantly higher than that of the unwashed hydrochars. The HCl processed unwashed hydrochar has a slightly higher adsorptive capacity compared to the DI processed hydrochar while both the NaOH processed washed and unwashed hydrochars were slightly lower than the corresponding DI processed hydrochars. ¹³C solid-state NMR results showed no discernible differences in surface functional groups among the washed hydrochars and among the unwashed hydrochars. A clear decrease in alkyl groups and an increase in aromatic/olefinic-C groups were observed after acetone washing. ¹H liquid-phase NMR showed carbon alkyl chains were present in the acetone wash. Interaction energies calculated using dispersion corrected density functional theory show that atrazine is more strongly adsorbed to surfaces without weakly associated alkyl groups.     

Recirculation of activated sludge for coagulant synthesis under hydrothermal conditions

Environmental Science and Pollution Research - A hypothesis was proposed that the activated sludge was converted into hydrochar full of phenolic hydroxyl and then was made into coagulant by graft...     

Removal and recovery of uranium (VI) from aqueous solutions by residual sludge and its biochars

Environmental Science and Pollution Research - The removal and recovery of uranium (VI) from water solutions are critical for energy and environmental security. In this study, hydrochar at 100,...     

Catalytic CO2 gasification of rubber seed shell-derived hydrochar: reactivity and kinetic studies

In this study, hydrothermal carbonization (HTC) of a biomass was used as a means to improve the physicochemical properties of rubber seed shell (RSS) and enhance its reactivity in the char-CO₂ gasification reaction, known as the Boudouard reaction (C + CO₂ ? 2CO). Hydrochar samples were developed by hydrothermal treatment of RSS, without separating the solid residue from the liquid product, at 433, 473, 513, and 553 K under autogenous pressure. The CO₂ gasification reactivity of the developed hydrochars was then investigated at different heating rates (5, 10, 20, and 30 K/min) by the non-isothermal thermogravimetric method. The hydrochars revealed higher reactivity and improved gasification characteristics compared to the untreated biomass, while the hydrochar which was filtered from the liquid slurry showed lower reactivity compared to the untreated biomass. This was due to the chemical and structural evolutions of the biomass during hydrothermal treatment as indicated by various analyses. The gasification reactivity of the hydrochar was substantially enhanced by introduction of a catalyst (NaNO₃) during HTC. Kinetic analysis of the char-CO₂ gasification reaction was carried out by applying Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starink isoconversional methods, and thermodynamic parameters were also determined. The activation energy of the Na-loaded RSS hydrochar in CO₂ gasification (120–154 kJ/mol) was considerably lower than that of the untreated biomass (153–172 kJ/mol). Thermodynamic studies also confirmed the promoting effect of hydrothermal treatment and catalyst impregnation on enhancement of reactivity of the virgin biomass and reduction of gasification temperature.

     

Dissipation pathways of organic pollutants during the composting of organic wastes

The organic pollutants (OPs) present in compostable organic residues can be recovered in the final composts leading to environmental impacts related to their use in agriculture. However, the composting process may contribute to their partial dissipation that is classically evaluated through the concentration decrease in extractable OPs, without identification of the responsible mechanisms as mineralization or stabilization of OP as non-extractable residues (NER) or bound residues. The dissipation of four (14)C-labeled OPs (fluoranthene; 4-n-nonylphenol, NP; sodium linear dodecylbenzene sulfonate, LAS; glyphosate) was assessed during composting of sewage sludge and green waste. The dissipation of LAS largely resulted from its mineralization (51% of initial LAS), whereas mineralization was intermediate for NP (29%) and glyphosate (24%), and negligible for fluoranthene. The NER pathway mostly concerned NP and glyphosate, with 45% and 37% of the recovered (14)C being found as NER at the end of composting, respectively. In the final composts, the proportions of water soluble residues of OPs considered as readily available were <11% of recovered (14)C-OPs. However, most fluoranthene remained solvent extractable (72%) and potentially available, whereas only 18% of glyphosate and less than 7% of both NP and LAS remained solvent extractable in the final compost.     

Complexation-flocculation of organic contaminants by the application of oxyhumolite-based humic organic matter

Control of hazardous organic micropollutants is a challenging water quality issue. Dissolved humic organic matter (DOM) isolated from oxyhumolite coal mined in Bohemia was investigated as a complexation agent to remove polycyclic aromatic hydrocarbons (PAHs) and functionalized phenols from water by a two-stage process involving complexation and flocculation. After the formation of humic-contaminant complexes, ferric salts were added resulting in the precipitation and flocculation of the DOM and the associated pollutants. Flocculation experiments with ferric ion coagulants indicated that precipitation of oxyhumolite DOM together with the complexed contaminants occurred at lower ferric ion concentrations than with the reference DOM in acidic environments (pH approximately 3.5). The complexation-flocculation removal rates for non-reactive PAHs characterized by small localization energies of pi-electrons correlated well with the complexation constants. On the other hand, the combined complexation-flocculation removal rates for activated PAHs including trans-stilbene, anthracene and 9-methyl anthracene, as well as functionalized polar phenols, were higher than predicted from the complexation coefficients. Methodological studies revealed for the first time that the ferric ion coagulant contributed to enhanced removal rates, most probably due to ferric ion-catalyzed pollutant degradation resulting in oxidized products.     

Impact of dry deposition of semi-volatile organic compounds on secondary organic aerosols

Dry deposition of semi-volatile organic compounds (SVOC) is not currently treated in most chemical transport models of air quality and this omission has been identified as a possible major source of uncertainty. The effect of dry deposition of SVOC on the concentration of secondary organic aerosols (SOA) is investigated in summertime with the chemical transport model CHIMERE that simulates SOA concentrations by means of molecular SOA surrogate species. Omitting dry deposition could overestimate SOA concentrations by as much as 50%. This overestimation is larger during nighttime due to higher relative humidity.     

Hair-biomonitoring of organic pollutants

This report reviews past research on hair analysis development for organic contaminants from the point of view of analytical procedures, successful applications and their limitations. For the past 20 years, hair analysis for organic pollutants has received more and more attention, since it is non-invasive, easily available and ethically not prioritized. New methods such as SFE, SPME and INAA have been developed to make the analysis more accurate and reliable. Furthermore, the correlation of contamination levels between hair samples and ambient air or internal tissues has been found by hair analysis and short-term and long-term exposure assessment in combination. However, there are still some limitations of hair analysis to be a validated risk assessment tool for many compounds. Some limitations had been of the past, some have not been fully investigated and need still further study. In this way, hair analysis can be the key to successfully biomonitor organic contaminations.     

Cosorption study of organic pollutants and dissolved organic matter in a soil

In this study we have evaluated the effects of dissolved organic matter (DOM) on sorption of imidacloprid, 3,4-dichloroaniline (3,4-DCA) and 4-bromoaniline (4-BA) on a typical calcareous soil (Luvic Xerosol) from south-eastern Spain. Two different types of DOM were used, that is to say, dissolved natural organic matter extracts from a commercial peat (DNOM) and a high-purity tannic acid (TA) solution. The experiments were carried out in a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results indicated that the presence of both DNOM and TA, over a concentration range of 15-100 mg L(-1), produced an increase in the amount of 3,4-DCA and 4-BA sorbed and a decrease in the amount of imidacloprid retained on the soil studied. A modified distribution coefficient, K(doc), has been proposed as a safer parameter for soil sorption predictions of organic pollutants and it could be of help to model the fate of these in the environment.     

Effect of dissolved organic carbon on the environmental distribution of nonpolar organic compounds

The effect of dissolved organic carbon on the process of pollutant sorption to aquatic sediments was studied using sediments from the Boonton Reservoir/Rockaway River system in northern New Jersey. Addition of DOC to the aqueous phase reduced the sorption of DDT to sediments, but had no effect on the sorption of Lindane. The effect of the DOC is to increase the amount of DDT in the soluble phase and enable transport of the compound throughout an aquatic system. The apparent influence of DOC on the equilibrium distribution of organic compounds is illustrated by modifying an existing environmental model.     

Changes in soil organic matter chemical properties after organic amendments

Organic inputs are used to improve soil physical and chemical properties, but the corresponding changes in soil organic matter (SOM) chemical properties are not well known. In this study, we compared some characteristics of the SOM of a soil receiving either no organic inputs, or two different amendments during 15 years (straw or conifer compost). Quantities of organic carbon and C/N values were determined on particle size fractions after physical soil fractionation to localize changes due to amendments. Contents in reactive functional groups, acid-base properties and copper binding affinities were determined by titration experiments for the soluble fraction of SOM: the fulvic acid fraction (FA). Data of FA extracted from the bulk soil were compared to data of FA extracted from the <20 microm size fraction with the help of either a discrete or a continuous model (fit of data with FITEQL or NICA, respectively). Copper binding characteristics of FA extracted from the <20 microm size fraction did not change significantly after organic inputs, while those of FA extracted from the bulk organic-amended soils were found different from the ones with no amendment. Minor effects observed in the finer soil fractions were ascribed to their low turn-over of organic carbon and/or to a greater homogeneity in the nature of the organic carbon entering these fractions. Our results show major chemical changes in coarser soil organic fractions after organic amendments.     

Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples

The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low.     

Influence of the organic complex concentration on adsorption of herbicide in organic modified montmorillonite

This study was undertaken to determine the impact of the organic complex concentration on the adsorption of herbicide (acetochlor) at the surface of the organic modified montmorillonite. In this work, natural montmorillonite from Bogovina (Boljevac municipality, Serbia) was used for organic modification. Cation-exchange capacity of this montmorillonite was determined using a methylene blue method (86 mmol/100 g of clay). Montmorillonite has been modified first with NaCl and then with hexadecyltrimethylammonium bromide (HDTMA-bromide) organic complex. Saturation of cation exchange capacity (CEC) was 50%, 100%, and 150%. Changes in the properties of the inorganic and organic montmorillonite have been examined using the X-ray diffraction, Fourier transform infrared spectroscopy, and batch equilibrium method. Montmorillonite modified with HDTMA-bromide demonstrated higher uptake of the herbicide, compared to the inorganic montmorillonite. Comparing the values Freundlich coefficients in batch equilibrium method, it can be seen that the adsorption of acetochlor decreased in the series: 0.5 CEC HM > 1 CEC HM > 1.5 CEC HM > NaM.     

Effect of organic fertilizers derived dissolved organic matter on pesticide sorption and leaching

Incorporation of organic fertilizers/amendments has been, and continues to be, a popular strategy for golf course turfgrass management. Dissolved organic matter (DOM) derived from these organic materials may, however, facilitate organic chemical movement through soils. A batch equilibrium technique was used to evaluate the effects of organic fertilizer-derived DOM on sorption of three organic chemicals (2,4-D, naphthalene and chlorpyrifos) in USGA (United States Golf Association) sand, a mixed soil (70% USGA sand and 30% native soil) and a silt loam soil (Typic Fragiochrept). DOM was extracted from two commercial organic fertilizers. Column leaching experiments were also performed using USGA sand. Sorption experiments showed that sorption capacity was significantly reduced with increasing DOM concentration in solution for all three chemicals. Column experimental results were consistent with batch equilibrium data. These results suggest that organic fertilizer-derived DOM might lead to enhanced transport of applied chemicals in turf soils.     

Hydrophobicity of complex organic mixtures

Hydrophobicity is an important property in risk assessment of chemicals. A group parameter that reflects the hydrophobicity of technical mixtures is not yet available. However, many substances are complex organic mixtures, for which it is practically impossible to determine each component separately. An experimental procedure to measure the hydrophobicity of organic mixtures without knowledge of the individual components was developed and tested for a mixture of benzene and twelve chlorobenzenes. This procedure is based on separation of the mixture into fractions of increasing hydrophobicity by reversed-phase HPLC, after which the total molar concentration in each fraction is determined by vapour pressure osmometry. The obtained information on hydrophobicity can be used for assessing bioaccumulation and sediment sorption after emission of the mixture to water has occurred.     

Comparison of capillary pressure relationships of organic liquid-water systems containing an organic acid or base

The presence of surface-active solutes such as organic acids and bases may have a profound influence on the transport of organic liquid contaminants through their impact on the constitutive relationship of capillary pressure vs. saturation. This relationship is a function of the interfacial tension and wettability of the system, which, in turn, depend on the pH and the concentration of organic acids and bases that are present. This study examines the impact of pH and the concentration on the interfacial tension, contact angle, and capillary pressure of systems consisting of tetrachloroethylene, water, and quartz containing either octanoic acid or dodecylamine. In general, the ionic form of the solute tended to remain in the aqueous phase and reduced the capillary pressure through its impact on the interfacial tension and contact angle; on the other hand, the neutral form of the solute partitioned into the organic liquid phase and had a lesser impact on the capillary pressure for the same total mass of solute. A comparison of these data with data generated in previous research in similar systems where o-xylene was the organic liquid showed that the trends are analogous. Thus, the behavior of these two solvent systems seems to be driven primarily by the aqueous phase speciation of the solute, and the differences between the capillary pressure relationships for the two systems could be attributed to the pure system interfacial tension.     

A new approach for estimating emissions of organic solutes and organic solvents under wind speeds

A new approach is developed to predict the volatilization loss of the pure liquid and the volatilization rates of organic solutes with different Henry's law constants (H) under wind speed. The tested compounds include eight volatile organic compounds for pure liquid and the forty-one organic solutes with different H compounds are divided into three groups that span seven H orders. The wind speed is set from 0 to 6.0 ms^?1. A characteristic parameter ε was established to estimate volatilization loss of pure organic compounds. The mass transfer coefficient (K_OL) ratios of the organic solutes, under both wind speed and still conditions, are applied to describe the volatilization characteristics of the selected solutes. The curve profile for K_OL ratios and ε values relative to the selected wind speed can be divided into two stages, the sharp-rise stage and the stable-linearity stage. The critical finding is the ε values for the different organic compounds under a specific wind speed approach a constant. The changes in the curve profile of the K_OL ratios are similar to the ε values of the pure organic compounds. It is also found the relatively lower H compounds exhibit a sensitive wind effect on the K_OL ratios. The K_OL ratios of the relatively higher H compounds indicate a similar linear increase with the increasing wind speed in the two stages. Accordingly, concentrations of the organic compounds at the interface are thought to the primary factor. The obtained results could be a good reference to estimate volatilization loss of the organic solutes or the organic solvents under different wind speed conditions.     

Sorption of organic pollutants by marine sediments: implication for the role of particulate organic matter

The objective of this study was to quantify sorption properties for kerogen/black carbon (BC)-bearing sediments. Single-solute sorption isotherms were measured for five pristine marine sediments using phenanthrene, naphthalene, 1,3,5-trichlorobenzene, and 1,4-dichlorobenzene as the sorbates. The results showed that the sorption isotherms were nonlinear and that the organic carbon normalized single point K_OC values were comparable to those reported in the literature for the purified keorgen and BC, but are much higher than the data reported for HA and kerogen/BC-containing terrestrial soils and sediments. It is likely that koergen and BC associated with these pristine marine sediments may not be encapsulated with humic acids or Fe and Mn oxides and hydroxides as often do in terrestrial soils and sediments. As a result, they may be fully accessible to sorbing molecules, exhibiting higher sorption capacities. The study suggests that competition from background HOCs and reduced accessibility when kerogen and BC are associated with terrestrial sediments may dramatically increase variability of sorption reactivities of geosorbents. Such variability may lead to large uncertainties in the prediction of sorption from the contents of kerogen and/or BC along with TOC.     

Temperature dependence of secondary organic aerosol

Temperature was found to have a dramatic effect on secondary organic aerosol formation from two ozonolysis systems, cyclohexene and α-pinene. Isothermal experiments were conducted for both systems where the lowest temperature, 278 K, formed approximately 2.5–3 times and 5–6 times the SOA formed at 300 K and 318 K, respectively. Changing the cyclohexene system temperature to a different isothermal experimental set point after completion of SOA formation did not lead to sufficient condensation/evaporation to reproduce the SOA formation at other temperature set points. When the system temperature was cycled between two set points at the end of an experiment, the α-pinene system showed reversibility between the initial temperature 318 K and 300 K. For temperature cycles between the initial temperature of 300 K–318 K, an irreversible loss of mass is observed after the first heating cycle with reversibility observed between subsequent temperature cycles. The SOA formed at 278 K was reversible over a 22 K range but was unable to evaporate sufficiently to match the SOA mass formed at 300 K. Hygroscopicity measurements, taken after the completion of SOA formation, indicate that hygroscopicity of the aerosol is also a function of temperature and that the aerosol does not continue to be oxidized after initial growth is complete. The differing hygroscopicity of the semi-volatile component of the aerosol is evident during system temperature changes after completion of the experiment.