Complex behaviour of trivalent rare earth elements by humic acids

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Complex behaviour of trivalent rare earth elements by humic acids

The complexation behaviours of trivalent rare earth elements (La, Ce, Ho and Yb) by two types of humic acids were investigated under a specified set of conditions. Humic acids show quite different complexation capacities an conditional formation constants with the REEs. Apparently there are two types of binding sites in the functional groups of humic acid, in which the first binding sites have stronger ability than the second. Cerium shows the largest complexation capacities and highest formation constants among the four REEs with two humic acids, this anomaly may be relative to the distribution pattern of the REEs in seawater. The experimental results were comparable to the values of other metals reported and provided the basic data for environmental geochemistry of rare earth elements.     

Determination of haloacetic acids in hospital effuent after chlorination by ion chromatography

The ion chromatography combined solid phase extraction (SPE) method was developed for the analysis of low concentration haloacetic acids (HAAs), a class of disinfection by-products formed from chlorination of hospital wastewater. The monitored HAAs included monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, dibromoacetic acid and trichloroacetic acid. The method employed a sodium hydroxide eluent at a flow rate of 0.8 mlmin, electrolytically generated gradients, and suppressed conductivity detection. To analyze the HAAs in real hospital wastewater samples, C18 pretreatment cartridge was utilized to reduce samples' turbidity. Preconcentration with SPE and matrix elimination with treatment cartridges were investigated and found to be able to obtain acceptable detection limits. Linearity, repeatability and detection limits of the above method were evaluated. The detection limits of monobromoacetic acid and dibromoacetic acid were 2.61 μgL and 1.30 μgL, respectively, and the other three acids are ranging from 0.48 to 0.82 μgL under 25-fold preconcentration. When the above optimization procedure was applied to three hospital wastewater samples with different treatment processes in Tianjin, it was found that the dichloroacetic acid was the major compound, and the growth ratios of the HAAs after disinfection by sodium hypochlorite were 91.28%, 63.61% and 79.50%, respectively.     

Study on the action and mechanism of humic acids in Kaschin-Beck disease

Humic acids, especially FA in fractions, contain more oxygen functional groups. In this experiment, on the basis of confirming the action of humic acids on KBD, what was studied is the biological effects of one of main oxygen functional groups, hydroxy group (-OH). The results indicate that inducing pathologic process of KBD, obviously decrease the GSH-Px activity and induce peroxidation membrane injury of tissue. The SOD activity increase in the tissues caused by oxygen functional groups showed that enhancing of free radical reaction should not be neglected.     

Chlorination of para-substituted phenols: Formation of α, β-unsaturated C4-dialdehydes and C4-dicarboxylic acids

Despite the widespread occurrence of phenols in anthropogenic and natural compounds, their fate in reactions with hypochlorous acid (HOCl), one of the most common water treatment disinfectants, remains incompletely understood. To close this knowledge gap, this study investigated the formation of disinfection by-products (DBPs) in the reaction of free chlorine with seven para-substituted phenols. Based on the chemical structures of the DBPs and the reaction mechanisms leading to their formation, the DBPs were categorized into four groups: chlorophenols, coupling products, substituent reaction products, and ring cleavage products. In contrast to previous studies that investigated the formation of early-stage chlorophenols, the primary focus of this study was on the elucidation of novel ring cleavage products, in particular α, β-unsaturated C₄-dialdehydes, and C₄-dicarboxylic acids, which, for the first time, were identified and quantified in this study. The molar yields of 2-butene-1,4-dial (BDA), one of the identified α, β-unsaturated C₄-dialdehydes, varied among the different phenolic compounds, reaching a maximum value of 10.4% for bisphenol S. Molar yields of 2-chloromaleic acid (Cl-MA), one of the identified C₄-dicarboxylic acids, reached a maximum value of 30.5% for 4-hydroxy-phenylacetic acid under given conditions. 2,4,6-trichlorophenol (TCP) was shown to be an important intermediate of the parent phenols and the C₄-ring cleavage products. Based on the temporal trends of α, β-unsaturated C₄-dialdehydes and C₄-dicarboxylic acids, their formation is likely attributable to two separate ring cleavage pathways. Based on the obtained results, an overall transformation pathway for the reaction of para-substituted phenols with free chlorine leading to the formation of novel C₄ ring cleavage products was proposed.     

Electrokinetic chemical characteristics of humic and dannic acids effecting on the natural water and its coagulation

Taking streaming current(SC)as the electrokinetic parameter,this paper demonstrated the electrokinetic chemical characteristics of humic and dannic acids(HA and DA)in suspensions including turbid water,coagulated water and HA or DA contained water.Accordingly, the studies were carried out for determining the relationship between streaming current and zeta potential ζ(expressed by eleetrophoretie mobility EM)in above water conditions.In addition,the mechanisms of HA effecting on streaming current within or after coagulant addition and the electrokinetic detection principles for HA or DA were also investigated on experiments and theoretical analysis.The results indicated that the change of SC like ζ presented meaningful information concerning the degree for destabilization of a particulate suspension,and HA or DA in water could remarkably decrease the effect of inorganic coagulant upon streaming current,which is in accordance with their influence on coagulation.     

Determining short chain fatty acids in sewage sludge hydrolysate：A comparison of three analytical methods and investigation of sample storage effects

In anaerobic digestion, the production of short-chain fatty acids （SCFAs） can be beneficial or harmful to the overall process, depending on the concentration of accumulated acids. Therefore, the accurate determination of the SCFA concentration in both fresh and stored sludge hydrolysates is important. To select a suitable method for monitoring SCFAs during the anaerobic digestion of sewage sludge, the accuracy of three available analytical methods, including 5 pH point acid titration （TITRA5）, gas chromatography （GC）, and spectrophotometry, were compared in the present study. The results revealed that TITRA5 and GC displayed better agreement in the achieved measurements and higher precision and accuracy than the spectrophotometric assay, as supported by the application of different statistical models. TITRA5 excelled in titrating unfiltered hydrolysate while simultaneously measuring the alkalinity, whereas the GC method provided detailed information on the contribution of different fatty acids to the total acidity. In contrast, the spectrophotometric assay suffered from many forms of interference, depending on the sample＇s matrix. SCFA production followed the pattern of enzymatic reactions and fitted the Michaelis-Menten model. In addition to promoting TITRA5 as an accurate and robust analytical tool for routine SCFA analyses, this comparative study also demonstrated the possibility of storing hydrolysate samples at different temperatures and durations without altering the SCFA measurements.     

Dssimilatory Fe(Ⅲ) reduction characteristics of paddy soil extract cultures treated with glucose or fatty acids

Dissimilatory Fe(Ⅲ) reduction is a universal process with irreplaceable biological and environmental importance in anoxic environments. Our knowledge about Fe(Ⅲ) reduction predominantly comes from pure cultures of dissimilatory Fe(Ⅲ) reducing bacteria (DFRB). The objective of this study was to compare the effects of glucose and a selection of short organic acids (citrate, succinate, pyruvate, propionate, acetate, and formate) on Fe(Ⅲ) reduction via the anaerobic culture of three paddy soil solutions with Fe(OH)3 as the sole electron acceptor. The results showed significant differences in Fe(Ⅲ) reduction among the three paddy soil solutions and suhstrate types. Bacteria from the Sichuan paddy soil responded quickly to substrate supply and showed higher Fe(Ⅲ) reducing activity than the other two soil types. Bacteria in the Jiangxi paddy soil culture solution could not use propionate as a source of electrons for Fe(Ⅲ) reduction. Similarly, bacteria in the Jilin paddy soil culture could not use succinate effectively. Pyruvate was readily used by cultures from all three paddy soil solutions, thus indicating that there were some similarities in substrate utilization by bacteria for Fe(Ⅲ) reduction. The use of glucose and citrate as substrate for dissimilatory Fe(Ⅲ) reduction indicates important ecological implications for this type of anoxic respiration.     

Dissimilatory Fe(Ⅲ) reduction characteristics of paddy soil extract cultures treated with glucose or fatty acids

Dissimilatory Fe(Ⅲ) reduction is a universal process with irreplaceable biological and environmental importance in anoxic environments. Our knowledge about Fe(Ⅲ) reduction predominantly comes from pure cultures of dissimilatory Fe(Ⅲ) reducing bacteria (DFRB). The objective of this study was to compare the effects of glucose and a selection of short organic acids (citrate, succinate, pyruvate, propionate, acetate, and formate) on Fe(Ⅲ) reduction via the anaerobic culture of three paddy soil solutions with Fe...     

Volatile fatty acids carbon source for biological denitrification

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Simultaneous elution of polycyclic aromatic hydrocarbons and heavy metals from contaminated soil by two amino acids derived from β-cyclodextrins

Two highly water-soluble amino acids, which derived from -CDs, i.e., glutamic acid- -cyclodextrin (GluCD) and ethylene-diamine- -cyclodextrin (EDCD), were synthesized and were examined for their e ect on solubilization of anthracene (ANT), complexation of cadmium (Cd2+), and elution removal of ANT and Cd2+ in soil. The results showed that GluCD and EDCD were powerful complexant for ANT and Cd2+. In the presence of 10 g/L GluCD and EDCD, the solubilization of ANT increased by 47.04 and 23.85 times compared to the control, respectively. GluCD resulted in approximately 90% complexation of Cd2+ while 70% complexation was observed for EDCD. Simultaneously, GluCD and EDCD could greatly enhance the elution removal of ANT and Cd2+ from soil. GluCD resulted in the highest elution e ciency of ANT and Cd2+.With the addition of 10 g/L GluCD, 53.5% of ANT and 85.6% of Cd2+ were eluted, respectively. The ANT had a negligible e ect on the Cd2+ removal due to di erent complexing sites of ANT and Cd2+, while Cd2+ enhanced the ANT removal under the addition of GluCD because Cd2+ neutralized the –COOH group of GluCD. Adversely, the removal of ANT was decreased with Cd2+ under the addition of EDCD, this was due to the fact that Cd2+ enhanced the polarity of EDCD molecule and inhibited the complexation between ANT and EDCD. The study suggested that GluCD could be preferred and be successfully applied to remediation of heavy metals or organic compounds in contaminated soil.     

Simultaneous elution of polycyclic aromatic hydrocarbons and heavy metals from contaminated soil by two amino acids derived from β-cyclodextrins

Two highly water-soluble amino acids,which derived from β-CDs,i.e.,glutamic acid-β-cyclodextrin (GluCD) and ethylene-diamineβ-cyclodextrin (EDCD),were synthesized and were examined for their effect on solubilization of anthracene (ANT),complexation of cadmium (Cd2+),and elution removal of ANT and Cd2+ in soil.The results showed that GluCD and EDCD were powerful complexant for ANT and Cd2+.In the presence of 10 g/L GluCD and EDCD,the solubilization of ANT increased by 47.04 and 23.85 times compared to the control,respectively.GluCD resulted in approximately 90% complexation of Cd2+ while 70% complexation was observed for EDCD.Simultaneously,GluCD and EDCD could greatly enhance the elution removal of ANT and Cd 2+ from soil.GluCD resulted in the highest elution efficiency of ANT and Cd2+.With the addition of 10 g/L GluCD,53.5% of ANT and 85.6% of Cd2+ were eluted,respectively.The ANT had a negligible effect on the Cd2+ removal due to different complexing sites of ANT and Cd2+,while Cd2+ enhanced the ANT removal under the addition of GluCD because Cd2+ neutralized the-COOH group of GluCD.Adversely,the removal of ANT was decreased with Cd2+ under the addition of EDCD,this was due to the fact that Cd2+ enhanced the polarity of EDCD molecule and inhibited the complexation between ANT and EDCD.The study suggested that GluCD could be preferred and be successfully applied to remediation of heavy metals or organic compounds in contaminated soil.     

Perfluoroalkyl acids(PFAAs) in urban surface water of Shijiazhuang,China: Occurrence,distribution,sources and ecological risks

It is extremely important to analyze the contaminative behaviors of Perfluoroalkyl acids(PFAAs) due to their serious threats to urban environments which are closely related to humans. Current study aimed to explore the distribution, source apportionment and ecological risk assessment of PFAAs in surface water from Shijiazhuang, China. The concentrations of ΣPFAAs ranged from 19.5 to 125.9 ng/L in the investigation area. Perfluorobutanesulfonic acid(PFBS) and perfluoropentanoic acid(PFPeA) were t...     

Evaluation of adsorption capacities of humic acids extracted from Algerian soil on polyaniline for application to remove pollutants such as Cd(Ⅱ), Zn(Ⅱ) and Ni(Ⅱ) and characterization with cavity microelectrode

The adsorption capacities of new humic acids isolated from Yakouren forest (YHA) and Sahara (Tamenrasset: THA) soils (Algeria) and commercial humic acid (PFHA) on polyaniline emeraldine base (PEB) were studied at pH 6.6. Also the adsorption of heavy metals such as Cd2+, Zn2+ and Ni2+ on humic acid-polyaniline systems (HA-PEB) was investigated at the same conditions. HA-PEB compounds were characterized by scanning electron microscopy (SEM), infrared spectrometry and cavity microelectrode. In addition, batch adsorption and cavity microelectrode were used in the adsorption study of Cd2+, Zn2+ and Ni2+ on HA-PEB. To develop biocaptors of polluting metals using a cavity microelectrode modified by HA-PEB systems, the adsorption kinetic and adsorption capacity were investigated. The SEM analysis showed that the presence of humic acid affected the PEB surface and caused the formation of a granular morphology. The maximum adsorption capacities (qmax) of PFHA, THA and YHA determined by adsorption isotherms were 91.31, 132.1 and 151.0 mg/g, respectively. Batch adsorption results showed that qmax of Cd2+, Zn2+ and Ni2+ on HA-PEB followed the order: THA-PEB > YHA-PEB > PFHA-PEB. The voltammograms obtained with HA-PEB modified cavity microelectrode showed the appearance of new redox couples reflecting the adsorption of HA on PEB. Metal-humic acid-polyaniline voltammograms were characterized by appearance of oxidation-reduction couples or reduction wave corresponding to metal. Finally, the result may be exploited to develop a biocaptor based on the cavity microelectrode amended by THA-PEB and YHA-PEB.     

Relating Cd2 + binding by humic acids to molecular weight: A modeling and spectroscopic study

Molecular weight(Mw) is a fundamental property of humic acids(HAs), which considerably affect the mobility and speciation of heavy metals in the environment. In this study, soil humic acid(HA) extracted from Jinyun Mountain, Chongqing was ultra-filtered into four fractions according to the molecular weight, and their properties were characterized.Complexation of cadmium was investigated by titration experiments. For the first time,Langmuir and non-ideal competitive adsorption-Donna(NICA-Donnan) models combined with fluorescence excitation-emission matrix(EEM) quenching were employed to elucidate the binding characteristics of individual Mw fractions of HA. The results showed that the concentration of acidic functional groups decreased with increasing Mw, especially the phenolic groups. The humification degree and aliphaticity increased with increasing Mw as indicated by elemental composition analysis and FT-IR spectra. The binding capacity of Cd~(2+) to Mw fractions of HA followed the order UF1( 5 kDa) UF2(5–10 kDa) UF4( 30 kDa) UF3(10–30 kDa). Moreover, the distribution of cadmium speciation indicated that the phenolic groups were responsible for the variations in binding of Cd~(2+) among different Mw fractions. The results of fluorescence quenching illustrated that the binding capacity of Cd~(2+) to Mw fractions was controlled by the content of functional groups, while the binding affinity was largely influenced by structural factors. The results provide a better understanding of the roles that different HA Mw fractions play in heavy metal binding,which has important implications in the control of heavy metal migration and bio-toxicity.     

Characteristics of distribution of heavy metals insediment of Le An River

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Effects of elevated CO_2 on sensitivity of six species of algae and interspecific competition of three species of alga

Introduction The atm ospheric C O 2 concentration increases at a rate of 1.5 滋 m ol/(m ol·a) and w ill double com pared to pre-industrial levels around the year 2050 (W atson et al., 1990). Its effects and m echanism by elevated CO 2 on global clim ate,…     

Modelling of water quality of Minjiang estuary

In order to establish economic development region at Mawei districtwhich is nearby downstream of Minjiang river and to answer the question of impact of economic development on water quality of Minjiang estuary, the analyses of hydrologic and hydraulic characteristics of Mawei reach of Minjiang tidal river, a two-dimensional mathematical model has been established and simulation of water quality was studied. The results show that the flushing time of a conservative pollutant during dry and raining period are 12 and 7 days respectively from Mawei to Minjiang mouth, the decay rate constants of BOD and NH3-N are 0.1 to 0.4 and 0.18 to 0.45 d-1 respectively. The capacity of dilution and assimilation for pollutants is larger.