Investigating adsorption performance of heavy metals onto humic acid from sludge using Fourier-transform infrared combined with two-dimensional correlation spectroscopy.

Efforts to improve sludge resource utilization have become increasingly important. In this study, humic acid (HA) was extracted from sludge samples collected from a sewage treatment plant, and then used for the adsorption of heavy metals. We used two-dimensional correlation spectroscopy (2D-COS) integrated with Fourier-transform infrared spectroscopy (FTIR) to explore the adsorption between sludge HA (HA) and three metal ions (Cu, Ni, and Pb). The resulting adsorbing data conformed to the isotherm of Langmuir adsorption. The maximum capacity values (qm) were 5.34, 1.49, and 26.29.8 mg/g for Cu, Ni, and Pb, respectively. The data from 2D-FTIR-COS analysis showed that the susceptibility of the functional group followed the order 2300 → 1130 → 1330 → 1480 → 1580 cm-1 for Cu(II) and Ni(II), and 2300 → 1130 → 1330 → 1480 → 1200 → 1580 cm-1 for Pb(II). The sludge HA with Pb(II) showed more adsorption sites than sludge HA with Cu(II) and Ni(II), and these adsorption sites could preferentially bond with Pb(II) at × 1 compared with Cu(II) and Ni(II). Our findings indicate that 2D-FTIR-COS technology has great potential for application as a useful tool for understanding the adsorption mechanism between adsorbents with heavy metals.

The binding properties of copper and lead onto compost-derived DOM using Fourier-transform infrared, UV-vis and fluorescence spectra combined with two-dimensional correlation analysis.

Three dissolved organic matter (DOM) samples were obtained from municipal solid wastes at the initial (C0), high-temperature (C7) and mature (C51) period during composting. Two-dimensional correlation spectroscopy (2D-COS) analysis on Fourier-transform infrared (FTIR), ultraviolet visible (UV-vis), and synchronous fluorescence spectra (SFS) were used to investigate the metal binding properties of compost-derived DOM. Synchronous and asynchronous maps of 2D-FTIR-COS of DOM-Cu(II) and DOM-Pb(II) were similar, however, the susceptibility and binding sequence of the corresponding spectral region was different. The N-H (amide I), phenolic OH, and C-O of alcohols, ethers, and esters were the most susceptive in the C0, C7, and C51 samples, respectively. 2D absorption COS indicated that the preferential binding with Cu(II) was shown to be at 305 nm for C0, at 236 nm for C7 and C51, and with Pb(II) at 247 nm for C0, at 233 nm for C7 and C51. 2D-SFS-COS indicated that protein-like matter showed a higher susceptibility and preferential binding with Cu(II) than humic-like substances. DOM showed a higher complexing affinity with Cu(II) than Pb(II) on the basis of the log K values. Spectral techniques combined with 2D-COS are useful to understand the binding heterogeneities of ligand sites within DOM-Cu(II) or Pb(II) during the composting.

Insights into the pollutant-removal performance and DOM characteristics of stormwater runoff during grassy-swales treatment.

The water purification performance of grassy swales for treating stormwater road runoff was evaluated using a simulated experimental device in two different seasons. The results showed that the removal rates for total suspended solids (TSS), chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP) reached 89.90%, 56.71%, 32.37%, and 19.67%, respectively, in summer, and 34.09%, 7.75%, 56.71%, and 13.33%, respectively, in winter, suggesting that grassy swales showed higher water purification performance in summer than in winter. Soil filtration in grassy swales also showed high removal rates of TSS, COD, TN and TP in summer (98.13%, 59.10%, 33.82%, and 24.59% respectively). The structure, composition and source of dissolved organic matter (DOM) were investigated using ultraviolet visible (UV-Vis) spectra and fluorescence spectra. The spectral parameters indicated a relatively high humification and aromaticity of DOM, and a relatively higher contribution of organic matter derived from microbial substances in summer than in winter. In addition, grassy-swale treatment showed a slight decrease in metal-ion concentrations at the surface, while the removal rates in the bottom samples were 38.42%, 40.59%, 33.81%, and 40.06% for Cu2+, Cd2+, Pb2+, and Zn2+, respectively. The results of 2D-COS suggested that grass swales treatment can change the binding sites and binding sequencing of DOM with heavy metals and further influence the metal speciation, mobility and biotoxicity.

Experimental and visual research on the microbial induced carbonate precipitation by Pseudomonas aeruginosa.

Microbial induced carbonate precipitation (MICP) is a common occurrence of geochemistry influences in many fields, such as biological, geographical, and engineering systems. However, the processes that control interactions between carbonate biomineralization and biofilm properties are poorly understood. We develop a method for real time, in situ and nondestructive imaging with confocal scanning microscopy. This method provides a possible way to observe biomineralization process and the morphology of biomineralized deposits within biofilms. We use this method to show calcite biominerals produced by Pseudomonas aeruginosa biofilms which extremely change biofilm structures. The distribution of calcite precipitation produced in situ biomineralization is highly heterogeneous in biofilms and also to occur primarily on the bottom of biofilms. It is distinct from those usual expectations that mineral started to precipitate from surface of biofilm. Our results reveal that biomineralization plays a comprehensive regulation function on biofilm architecture and properties.

Changes and characteristics of dissolved organic matter in a constructed wetland system using fluorescence spectroscopy.

Domestic wastewater was treated by five constructed wetland beds in series. Dissolved organic matter (DOM) collected from influent and effluent samples from the constructed wetland was investigated using fluorescence spectroscopy combined with fluorescence regional integration (FRI), parallel factor (PARAFAC) analysis, and two-dimensional correlation spectroscopy (2D-COS). This study evaluates the capability of these methods in detecting the spectral characteristics of fluorescent DOM fractions and their changes in constructed wetlands. Fluorescence excitation-emission matrix (EEM) combined with FRI analysis showed that protein-like materials displayed a higher removal ratio compared to humic-like substances. The PARAFAC analysis of wastewater DOM indicated that six fluorescent components, i.e., two protein-like substances (C1 and C6), three humic-like substances (C2, C3 and C5), and one non-humic component (C4), could be identified. Tryptophan-like C1 was the dominant component in the influent DOM. The removal ratios of six fluorescent components (C1-C6) were 56.21, 32.05, 49.19, 39.90, 29.60, and 45.87 %, respectively, after the constructed wetland treatment. Furthermore, 2D-COS demonstrated that the sequencing of spectral changes for fluorescent DOM followed the order 298 nm → 403 nm → 283 nm (310-360 nm) in the constructed wetland, suggesting that the peak at 298 nm is associated with preferential tryptophan fluorescence removal. Variation of the fluorescence index (FI) and the ratio of fluorescence components indicated that the constructed wetland treatment resulted in the decrease of fluorescent organic pollutant with increasing the humification and chemical stability of the DOM.

Detection of Copper (II) and Cadmium (II) binding to dissolved organic matter from macrophyte decomposition by fluorescence excitation-emission matrix spectra combined with parallel factor analysis.

Fluorescence excitation-emission matrix (EEM) spectra coupled with parallel factor analysis (PARAFAC) was used to characterize dissolved organic matter (DOM) derived from macrophyte decomposition, and to study its complexation with Cu (II) and Cd (II). Both the protein-like and the humic-like components showed a marked quenching effect by Cu (II). Negligible quenching effects were found for Cd (II) by components 1, 5 and 6. The stability constants and the fraction of the binding fluorophores for humic-like components and Cu (II) can be influenced by macrophyte decomposition of various weight gradients in aquatic plants. Macrophyte decomposition within the scope of the appropriate aquatic phytomass can maximize the stability constant of DOM-metal complexes. A large amount of organic matter was introduced into the aquatic environment by macrophyte decomposition, suggesting that the potential risk of DOM as a carrier of heavy metal contamination in macrophytic lakes should not be ignored.

Electrokinetic removal of Cu and Zn in anaerobic digestate: interrelation between metal speciation and electrokinetic treatments.

In recent years, a potential controversy has arisen that whether the metal speciation in solid matrix determined its electrokinetic (EK) removal efficiency or by contrast. In present study, Cu and Zn in anaerobic digestate were selected as candidates to investigate the relation between the species of metal and EK treatment. The obtained results show that the removal efficiency for each fraction decreased in the order as follows: exchangeable ≥ bound to carbonates > bound to Fe-Mn oxides>bound to organic matters >> residual. For both Cu and Zn, their total removal performance was dependent on their dominant fraction in the digestate. A constant pH maintenance around the digestate via circulation of acid electrolyte is an optional operation because a strong acid atmosphere (pH < 2) around the digestate can be formed automatically as EK time elapses. Despite that many reactions occurred during EK process, the species distribution of Cu and Zn in the digestate determined their total EK removal efficiency essentially.

Nutrition potential of biogas residues as organic fertilizer regarding the speciation and leachability of inorganic metal elements.

Biogas residues (BRs) are prospective organic fertilizer sources for agricultural cultivation. Besides N and P, however, other inorganic metal elements, such as K, Fe, Cu, Zn and so on, also affect the nutritional level of BRs significantly. In this study, a sequential extraction procedure (SEP) combined with a toxicity characteristic leaching procedure (TCLP) was conducted to investigate the speciation and leachability of metal components in BRs. The results showed that element K was the most effective nutrient component due to its largest available fraction and highest mobility factor (MF) of 78.4, whereas phytotoxic Al was the most stable and inert element in terms of its 96.68% residual fraction. Ca and Mg could be viewed as potential nutrient sources because their MFs exceeded 60. TCLP results revealed that these BRs could be classed as non-toxic organic waste but Cu and Zn should be paid more attention in that their total contents were beyond the permissible values. Meanwhile, more concerns should be given to Ni and Pb due to their large TCLP extractable fraction. In conclusion, these BRs can be used as a prospective nutrient pool for agricultural cultivation. SEP combined with TCLP can be effectively applied for assessing the nutrient level of the BRs as organic fertilizer for agricultural use.

Influence of the composition and removal characteristics of organic matter on heavy metal distribution in compost leachates.

Compost leachates were collected to investigate the influence of the composition and removal of volatile fatty acids (VFAs), humic-like substances (HSs), and dissolved organic nitrogen (DON) on heavy metal distribution during the leachate treatment process. The results showed that acetic and propionic acids accounted for 81.3 to 93.84% of VFAs, and that these acids were removed by the anaerobic-aerobic process. Humic- and fulvic-like substances were detected by excitation-emission matrix spectroscopy coupled with parallel factor analysis, and their content significantly decreased after the anaerobic and membrane treatments. DON in compost leachates ranged from 26.53 mg L(-1) to 919.46 mg L(-1), comprised of dissolved free amino acids and the protein-like matter bound to humic- and fulvic-like substances, and was removed by the aerobic process. Correlation analysis showed that Mn, Ni, and Pb were bound to VFAs and protein-, fulvic-, and humic-like substances in the leachates. Co was primarily bound to fulvic- and humic-like matter and inorganic sulfurs, whereas Cu, Zn, and Cd interacted with inorganic sulfur.

Sequential extraction of anaerobic digestate sludge for the determination of partitioning of heavy metals.

In China, agricultural use of anaerobic digestate sludge is considered a concern due to high heavy metal content of the sludge. In this study, sequential extraction procedure (SEP) was conducted to determine metal speciation which affects release and mobility of metal significantly. The results of SEP showed that each heavy metal possessed different distribution characteristics. Cu mainly reacted with carboxyl functional group to form the fraction bound to organic matter. Zn and Mn were dominated in the fraction bound to Fe-Mn oxides and carbonates, respectively. Pb, Ni, Cr, Cd and As were present as the residual fraction. Examination of mobility factors (MFs) indicated that Zn, Pb, Ni, Mn and Cd were more mobile whereas Cr and As were immobilized in anaerobic digestate. Based on the results, it can be stated that Cu, Zn, Mn, Ni and Cd may be grouped as toxic and active components in sludge and should be regarded as the priority pollutants for elimination. Pb should be monitored in terms of its high mobility factors (MF). Cr and As, nevertheless, were the most stable components in sludge.

Changes in spectral characteristics and copper (II)-binding of dissolved organic matter in leachate from different water-treatment processes.

The aim of the present study was to investigate the fluorescence properties of dissolved organic matter (DOM) from four leachate samples, which were disposed by regulating tank (RTK), anaerobic treatment (ATT), oxidation ditch (ODH), and membrane bioreactor and to assess their binding capacities and stability constants by Cu(II). The results showed that five fluorescent peaks, including three humic-like peaks (peaks A, C, and E) and two protein-like peaks (peaks B and D), were identified. Most fluorescent components can be degraded after ODH. Fluorescence-quenching titration showed that the modified Stern-Volmer model can be used to fit the quenching data and calculate conditional stability constants (log K) and the % of fluorophores (f %) between DOM and Cu(II). DOM-Cu(II) complexes had relatively high log K values in the RTK and ATT disposals. After the ODH-treatment process, log K values showed a marked decrease. The f % values of protein-like materials were evidently greater than those of humic-like substances. The results showed the impact of the water treatment on the metal-binding ability of various fractions.

Detection of dissolved organic matter in saline-alkali soils using synchronous fluorescence spectroscopy and principal component analysis.

Dissolved organic matter (DOM) is attributed a key role in soil major biogeochemical processes. Its molecular characteristics can reflect both its source and its biogeochemical history. Saline-alkali soil samples were collected from a field in desert and semi-desert region. DOM was analyzed by synchronous fluorescence spectroscopy. Principal Components Analysis (PCA) of synchronous fluorescence spectra was used to detect and describe changes in the DOM in different soil profiles. The analysis of PCA yielded 2 PCs that account for 97% of the variance. DOM is characterized by a dominant tyrosine-like fluorophore in the Region I (PC1>0.9, PC2<0.3), including soils Ke02, Ke03, Ke04, Rh02, Rh03, Rh04, Sa04 and Sc04. The region II including Kf02, Sa01, Yb01, Yzd01 and Yzd02 obtain higher PC2 (>0.9) and lower PC1 (<0.3) loading, which is dominated humic-like fluorophore. Hierarchical cluster analysis (HCA) identified five main clusters. The results of hierarchical cluster analysis (HCA) were consistent with the PCA. The ratio of fluorescence intensity of humic substances at long wavelengths and short wavelengths was used to indicate the humification of organic matter. Two ratios (I(345/318) and I(362/318).) can be used to indicate the humification of DOM. The humification degree of the remaining soils has no systematic trend because of land use, agricultural irrigation, soil erosion and salinization. Soils obtained a relatively high humification degree in the region II and a relatively low humification degree in the region I.

Spectroscopic techniques for quantitative characterization of Cu (II) and Hg (II) complexation by dissolved organic matter from lake sediment in arid and semi-arid region.

Dissolved organic matter (DOM) was extracted from six sediment samples in arid and semi-arid region, which was characterized by fluorescence excitation-emission matrices (EEMs). The results showed that four fluorescent peak, fulvic-like (peak A), humic-like (peak C) and two tryptophan-like (peaks B and D), were identified in lake sediment DOM. Fluorescence quenching titration showed that peaks B and D were quenched gradually by adding additional Cu (II) and Hg (II), whereas humic-like substances had no systematic trend of the change of fluorescence intensity. Increasing fluorescence intensity value of humic-like substances can also be found. The modified Stern-Volmer model was used to calculate conditional stability constants (logK) and the percent of fluorophores (f %) which participate in the complexation between DOM and Cu (II), and Hg (II). The results showed that DOM-Cu (II) and DOM-Hg (II) complexes had higher logK values of 4.21-5.23 and the logK values of DOM-Cu (II) are much larger than the corresponding values for Hg (II). Peak B showed relatively low logK and high f % values than those of peak D. Different pollution sources which are mainly obtained from the upstream industrial wastewater, domestic sewage and return water of farmland irrigation tend to affect the stability constants and complexing capacities of Cu (II) and Hg (II).

The structure and origin of dissolved organic matter studied by UV-vis spectroscopy and fluorescence spectroscopy in lake in arid and semi-arid region.

To develop a proper indicator which could predict water quality and trace pollution sources is critically important for the management of sustainable aquatic ecosystem. In our study, seven water samples collected from Wuliangsuhai Lake in Inner Mongolia were used. UV-visible spectra and synchronous fluorescence spectra were applied to investigate the humification degree and aromatic structure of dissolved organic matter (DOM) extracted from water samples. The results showed that both samples from W1 site and W3 site display lower humification degree and less aromatic structure, where industrial wastewater and domestic sewage, and reclaimed water of farmland irrigation, were accepted respectively. After computing the values of SUVA(254), A(280), A(250/365), A(253/203) and A(226-400), we reached the conclusion that they have a consistent trend (W4> W6> W5> W2> W7> W1> W3). Fluorescence index (f(450/500)) was always utilised to interpret the origin of organic matter in a complex aquatic environment system. Values of f(450/500) are closer to 1.60, indicating that humic substances derived from terrestrial sources and biological sources. Our study demonstrated that reclaimed water of farmland irrigation, industrial wastewater and domestic sewage will definitely influence the humification degree and amount of the aromatic structure of DOM.

[Study on solid surface fluorescence characteristic of saline soils around lakes in arid and semiarid regions].

Fluorescence spectroscopy relies on the fluorescence emitted by rigid conjugated systems and thus has been increasingly used to assess the soil organic matter (SOM) humification. This technique is widely applied to solution samples of humic substances, and so far no information exists about its applicability to solid-phase soil samples. Composite soil samples of different depths (0-20, 20-40 and 40-60 cm) were collected from four different halophyte communities along a saline-impact gradient, namely, Comm. Salicornia europaea (CSE), Comm. Suaeda glauca (CSG), Comm. Kalidium foliatum (CKF) and Comm. Sophora alopecuroides (CSA) located around Wuliangsuhai Lake. A humification index based on solid surface fluorescence spectroscopy (HIX(SSF)) was proposed, and compared with conventional humification indices I400/I360, I470/I360, I465/I399 and A4 /Al. There were close positive linear correlations between HIXass and 1400/1360, 145/I399 and A4/A1, but a poor positive linear correlation existed between the HIX(SSF) and I470/I360. The results indicated that HIX(SSF) can be taken as a tool to assess the soil humi fication. The HIX(SSF) of the CSE and CSG varied inappreciably within soil profiles and there was no trend with depth. However the HIX(SSF) varied appreciably in the CKF and CSA, and the HIX(SSF) of the bottom soil profile was higher than that of the other profiles. As a whole, the soil humification degree was low around Wuliangsuhai Lake, and the ecological environment was relatively fragile. The salinity showed a strong negative linear relationship with the I400/I360, I470/I360, I465/I399 and A4/A1, but a good negative linear relationship with the HIX(SSF). The results indicated that the degree of the SOM humification increased with the drop in the salinity. The HIX(SSF) can be an indicator not only of the degree of SOM humification, but also of the process of the salinisation.