Pyrolysis-GC/FID Test for Biogenic Interference in Contaminated Soil

Effects of concentration and chemical composition of natural organic matter on the aggregative behavior of silver nanoparticles

A better understanding of metal ion binding to soil organic substances is of fundamental importance in geochemical modeling of environments. Fulvic acids (FA) and humic acids (HA) make up an important part of soil organic matter, and their binding capacity affects the fate of metal ions and plays an important role in their mobility. Binding constants of Pb(II) to HA and FA were evaluated by anodic stripping square wave voltammetry (ASSWV) where the binding reaction was performed at pH 4.5 in a medium of 0.020 mol L-1 KNO3. Results showed that ASSWV technique was well suited for the estimation of the binding capacity of a natural organic matter towards heavy metals. Based on the voltammetric titration curves, binding constants of Pb(II) complexes formed with HA and FA were 0.78times106 and 0.15times106, which indicated that complex of Pb2+ with HA was more stable than with FA. The average molecular weight of HA and FA prepared from soil samples were also found to be 1821 g mol.L-1 and 805 g mol.L-1, respectively.

The presence of natural organic matter (NOM) in drinking water can increase the levels of copper released from copper pipes to water and inhibit the formation of protective deposits such as malachite. Since adsorption of NOM on copper pipes surfaces is believed to be one of mechanisms that explains this phenomenom, the objective of this study was to determine kinetics and the adsorption equilibrium of main components of NOM, humic acid (HA) and fulvic acid (FA), onto copper surfaces. The kinetics and equilibrium adsorption of HA and FA on copper foils were examined using batch experiments at 22°C. HA and FA followed pseudo second-order kinetics adsorption. Rate constants measured were 2.59 × 10−1 (mgTOC cm−2 h−1) for HA and 3.13 × 10−1 (mgTOC cm−2 h−1) for FA. The adsorption behavior of HA and FA on the copper surface is in accordance with the Langmuir adsorption isotherm. Langmuir adsorption constants measured were 5.98 × 10−2 L mg−1 for HA and 4.78 × 10−2 L mg−1 for FA. The copper foils exposed during five months to FA formed malachite deposits, whereas those exposed to HA did not and just cuprite was found. The results of this study showed that both HA as well as FA adsorption on copper surfaces is favored and no significant differences were found in the adsorption parameters calculated for both compounds. However, the inhibition of the malachite precipitation could be attributed to the HA adsorption.

Productivity of cropland soils, especially in semi-arid to arid zones, is declining due to increasing losses of stable organic matter. Therefore, it was found important to evaluate alternative management systems that can control, and if possible combat, these escalating losses of recalcitrant fractions of soil organic matter (SOM). The aim of this study was to quantify the influence of land use changes on humic substances of the semi-arid Plinthustalfs. Topsoil samples from distinctive agro-ecosystems at Harrismith, Tweespruit and Kroonstad were collected in the virgin, cultivated and restored Plinthustalfs and analysed for C and N in crude humic substances (Cs and Ns), extractable humic substances (Ce and Ne), humic acids (Ch and Nh) and fulvic acids (Cf and Nf). The results indicated that cultivation depleted the former virgin soils of crude humic substances, extractable humic substances, humic acids and fulvic acids across the three agro-ecosystems, with the exception of fulvic acids, which were higher in the cultivated soils than in the virgin soils of Kroonstad. Restored soils had substantial amounts of these humic fractions, except fulvic acids that behaved differently in the Kroonstad agro-ecosystem. Some correlations were observed between climate variables and humic fractions. In general, mean annual rainfall (MAR) and aridity index (AI) contributed to the loss of crude humic substances, extractable humic substances, humic acids and fulvic acids, while mean annual temperature (MAT) did not. These three climate variables did not influence the buildup of humic fractions. No trends were observed regarding the C/N ratios of the examined humic fractions; however, most were found to be closer to a range of 10–12, suggesting that SOM was approaching equilibrium state. Although it is known that humic substances are recalcitrant in nature, our results revealed that management practices that prohibit soil disturbance are needed to complement the refractory nature of humic substances against biological oxidation, and hence reduce C and N losses into the atmosphere.

In this study the influence of water matrix and oxidation treatment by ozone on natural organic matter (NOM) fractionation and corresponding disinfection by-products formation was investigated. Three water types were selected, based on their different NOM contents (5.16–9.85 mg/L dissolved organic carbon (DOC)) and structures (42–79% proportion of hydrophobic NOM fraction). It was determined that increasing the ozone dose (0.2–0.8 mg O3/mg DOC) generally led to reductions in DOC (2–26%) and trihalomethane formation potential values (4–58%). Results of NOM fractionation showed that the reactivity of all the individual NOM fractions towards trihalomethane formation decreased after ozone oxidation (0.8 mg O3/mg DOC) by 47–69%, relative to the raw waters.

Selection of anionic exchange resins for removal of natural organic matter (NOM) fractions

Solid-phase fluorescence excitation-emission matrix spectroscopy of soil, fulvic acid fractions, and clay mineral complexes: Evidence from red shift of fluorescence maxima associated with aggregation.

Tracking natural organic matter (NOM) in a drinking water treatment plant using fluorescence excitation–emission matrices and PARAFAC

An experimental and modeling study of humic acid concentration effect on H + binding: Application of the NICA–Donnan model

To gain a better understanding of the role of charred plant materials, which were produced during the burning of vegetation by human activity and wildfires, in the formation of humic and fluvic acids in Japanese volcanic ash soils, the quantitative contribution of charred and buried plant fragments to their acids in whole soils were investigated using three volcanic ash soil samples. Charred fragments were the main components in the fraction of less than specific gravity 1.6 g cm−3 (< 1.6 fraction), which was isolated after HCl–HF treatment of the soil samples. The percentage contribution of organic C content in the < 1.6 fractions to that of the whole soils ranged from 13.9 to 32.0%. All humic acids obtained from the < 1.6 fractions and whole soils were classified into Type A, which is characterized by a high degree of darkening and the presence of a graphite-like structure. However, the color coefficient (ΔlogK) and relative color intensity (RF) values of the humic acids in the < 1.6 fractions were different from those in whole soils. In all soils studied, the amounts of NaOH-extractable humic (OH-HA) and fulvic acids (OH-FA) were much greater than those of Na4P2O7-extractable humic (SPP-HA) and fulvic acids (SPP-FA), respectively, and the amounts of humic acids were substantially greater than those of fulvic acids. The proportion of the quantitative contribution of humic and fulvic acids in the < 1.6 fractions to those in the whole soils ranged from 12.0 to 43.8% for OH-HA, from 3.80 to 9.56% for OH-FA, and from 2.92 to 22.3% for SPP-HA, respectively. The proportion was very small for SPP-FA. It was assumed that in Japanese volcanic ash soils, parts of charred plant materials are subjected to oxidative degradation over a long period of time after burning, and are converted to fulvic acids and, particularly, humic acids.

The compound nitrapyrin is easily adsorbed by soil organic matter in high-organic matter soils, and this results in its effectiveness reducing significantly. In this study, the adsorption characteristics and mechanisms of nitrapyrin as an adsorptive on humic acid (HA) and fulvic acid (FA) as adsorbents were investigated. The results showed that the kinetics of adsorption of nitrapyrin on both HA and FA followed pseudo-second-order kinetic models (R2 ≥ 0.925, P < 0.05) and the adsorption process included an initial fast-adsorption stage and a slow-adsorption stage thereafter. The adsorption efficiencies of nitrapyrin on HA + FA were higher than that on HA or FA alone, and that of HA was higher than that of FA. The adsorption isotherms of nitrapyrin on HA and FA could be optimally fitted with the Langmuir equation (R2 ≥ 0.982, P < 0.05). The maximum adsorption capacities of nitrapyrin on HA, FA and HA + FA were 4896.49, 3173.70 and 4925.56 mg kg−1, respectively. Synergistic adsorption of nitrapyrin in co-existing systems of HA and FA was also observed. The adsorption mechanism of nitrapyrin on both HA and FA involved hydrogen bonding and hydrophobic interaction. Therefore, HA and FA in the soil environment can adsorb a large amount of nitrapyrin and reduce its effectiveness, and they have a positive synergistic effect.

Purpose The contamination of agricultural soils by heavy metals is a worldwide problem. Organic amendments can be used for the immobilization and binding of heavy metal ions in soils by complexation, adsorption, and precipitation. A field trial was carried out to evaluate the influence of some low-cost organic materials such as rice straw (RS), green manure (GM), and pig manure (PM) on the distribution of Cu and Cd and the retention of these metals by organic matter fractions in heavy metal-polluted soils. Materials and methods The experiment was conducted in Miaoyunao Village, Daye County, Hubei province, China. PM, GM (peanut plants), and RS were obtained from a farm close to the village. Sixteen treatments with three replicates were designed. Soil chemical properties such as soil pH, electrical conductivity (EC), organic matter (OM), and available P were measured by standard methods. Soluble/ exchangeable, organic-bound, inorganic precipitates and residual Cu and Cd in the soil were sequentially extracted and analyzed. The amounts of Cu and Cd bound with soil particulate organic matter (POM) fractions and humic substances were also determined. Results and discussion The addition of organic amendments declined significantly the concentrations of soluble/ exchangeable Cu and Cd, but increased the amounts of these metals in organic-bound and inorganic precipitate forms in the soil. RS was more effective than GM and PM in diminishing the solubility of Cu and Cd. The largest retention for Cu and Cd by humic substances and POM was noticedinRStreatments,whereasthelowestwasfoundinPM treatments. Humic substances showed higher potential in the fixation of Cu and Cd than POM fractions. The conversion of soluble/exchangeable Cu and Cd to other insoluble forms after the application of organic amendments may be ascribed to the increases of soil OM, pH, EC, and available P contents. The highest binding of Cu and Cd with POM fractions and humic substances after the incorporation of RS mainly resulted from the greatest increase of soil OM contents. Conclusions RS, GM, and PM can be employed as good and cheap substances for the immobilization of Cu and Cd in heavy metal-polluted soils. RS was the best amendment in decreasing the solubility of Cu and Cd, and also in enhancing the retention of these metals by humic substances and POM fractions in the soil. Futures studies should focus on the influence of these organic amendments or their mixtures on the phytotoxicity of Cu and Cd for different plants in heavy metal-contaminated soils.

Analysis of the carbohydrates of fulvic and humic acids as their partially methylated alditol acetates

A method was developed for the analysis of humic and fulvic acids by size-exclusion chromatography-electrospray ionization-tandem mass spectrometry using a completely volatile eluent. Humic and fulvic acids were separated into three peaks. These fractions occupied different mass ranges and showed differences in the fine structure of their mass spectra. The low-molecular-weight (LMW) fraction of fulvic acids is most sensitively determined by ESI-MS, and it appears that previous results obtained by infusion-ESI-MS were primarily determined by this fulvic acid fraction. The average molecular weight of this fractions turned out to be lower than that reported from infusion-ESI-MS measurements. Its scan spectra and the product ion spectra of some of its molecular anions perfectly match those previously obtained from whole fulvic acid mixtures. Obviously, a class of well-defined polycarboxylated molecules exist that occurs in all fulvic acid fractions thus far investigated. With decreasing elution time and increasing molecular weight, detection by ESI-MS loses sensitivity as compared to the parallel UV recording, and the fine structure of the scan spectra becomes increasingly uniform for both fulvic and humic acids. The average molecular weight of the HMW fraction exceeds those values calculated from infusion experiments. Scan spectra and product ion spectra of the high-molecular-weight (HMW) fraction of both the humic and the fulvic acids suggest that the HMW fraction consists of several subunits that originate from the LMW fraction.

The present study investigated the potential of surfactant modified magnetic nanoadsorbents (MNPs) for the removal of aromatic and hydrophobic fractions of natural organic matter (NOM), leading to the formation of trihalomethanes (THMs) in chlorinated drinking water. Co-precipitation method was used for the synthesis of MNPs. However, MNPs have a tendency to form an agglomeration. Therefore, polyethylene glycol (PEG) was used as a surface modifier to reduce the agglomeration. The PEG-coated MNPs were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), BET surface area, X-ray diffraction (XRD), Fourier transform spectrometer (FTIR), and zeta (ζ) potential. FESEM observation indicates that PEG-coated MNPs were spherical in shape and 25nm in size. Zeta potential values (- 58.35 to - 74.9mV) indicated excellent stability of PEG-MNPs. FTIR spectra indicated the presence of a -CH2 group, responsible for the chemical interaction between aromatic and humic content. Batch experiments were conducted by studying the effect of pH, contact time, and adsorbent dosage on NOM removal. Excellent removal of DOC (94.49%) and UV254 (89.32%) was observed at the optimum dose of adsorbent (0.75g/L) and at pH7.0. Adsorption kinetics followed pseudo-second-order reaction (R2, 0.973) and occurs by multilayer chemisorption which is due to the chemical interaction between aromatic and humic compounds of NOM with MNPs. Thus, MNPs showed great potential as a novel adsorbent for the removal of aromatic and hydrophobic compounds of NOM and can significantly be used to curtail the problem of THMs in drinking water supplies.