胶体TiO2颗粒对不同来源溶解性有机质光降解的影响:基于分子量差异分析

溶解性有机质(DOM)广泛存在于多种水环境介质,其光降解过程显著影响水体污染物的化学形态及生态风险.本文以典型陆源天然有机质(NOM)和藻源有机质(AlgOM)为研究对象,采用切向超过滤技术将初始DOM样品(Bulk,0.45μm)分为高分子量(HMW, 1 kDa～0.45μm)和低分子量(LMW,1 kDa)组分,研究胶体TiO2颗粒存在下不同分子量有机组分的光降解行为差异.表征结果表明,DOM样品的有机质均相对较多地分布在LMW组分中(55.3%～57.8%),但HMW的芳香性比LMW组分高;三维光谱结果表明AlgOM富含类蛋白和类腐殖物质,而NOM只含类腐殖物质;进一步分析发现类蛋白物质主要分布于HMW组分,类腐殖物质则主要分布于LMW组分.胶体颗粒的存在通过吸附作用抑制AlgOM中有机质及芳香性物质的光降解,而通过催化作用促进NOM中有机质及芳香性物质的光降解.胶体颗粒不改变不同分子量DOM中有机质的光降解效率顺序,均为HMWBulkLMW,说明HMW有机质更易光降解.但无胶体颗粒时AlgOM和NOM芳香物质的光降解效率为LMWBulkHMW,且胶体颗粒的存在改变不同分子量NOM芳香性物质的光降解顺序.另外,无胶体颗粒存在时陆源类腐殖物质比藻源类腐殖物质更易光降解,而胶体颗粒的存在均可促进藻源和陆源类腐殖质物质光降解;相比于HMW类腐殖质,LMW类腐殖物质具有较高的光敏性和优先降解特性.     

Abundance, size distribution, and stable carbon and nitrogen isotopic compositions of marine organic matter isolated by tangential-flow ultrafiltration

Tangential-flow ultrafiltration was used to isolate particulate and high-molecular-weight dissolved material from seawater collected at various depths and geographic regions of the Pacific and Atlantic Oceans. Ultrafiltration proved to be a relatively fast and efficient method for the isolation of hundreds of milligrams of material. Optical and electron microscopy of the isolated materials revealed that relatively fragile materials were recovered intact. Depth-weighted results of the size distribution of organic matter in seawater indicated that ˜ 75% of marine organic carbon was low-molecular-weight (LMW) dissolved organic carbon (< 1 nm), ˜ 24% was high-molecular-weight (HMW) dissolved organic carbon (1–100 nm), and ˜ 1% was particulate organic carbon (> 100 nm). The distribution of carbon in surface water was shifted to greater relative abundances of larger size fractions, suggesting a diagenetic sequence from macromolecular material to small refractory molecules. The average C:N ratios of particulate organic matter (POM) and HMW dissolved organic matter (DOM) were 7.7 and 16.7, respectively. Differences in C:N ratios between POM and HMW DOM were large and invariant with depth and geographic region, indicating that the aggregation of HMW DOM to form POM must be of minor significance to overall carbon dynamics. The stable carbon isotope composition (δ¹³C) of POM averaged −22.7%. in surface water and −25.2%. in subsurface water. Several possible explanations for the observed isotopic shift with depth were explored, but we were unable to discern the cause. The δ¹³C of HMW DOM samples was relatively constant and averaged −21.7%., indicating a predominantly marine origin for this material. The δ¹⁵N values of POM were highly variable (5.8–15.4%.), and the availability of nitrate in surface waters appeared to be the major factor influencing δ¹⁵N values in the equatorial Pacific. In the upwelling region nitrate concentrations were relatively high and δ¹⁵N values of POM were low, whereas to the north and south of the upwelling nitrate concentrations were low and δ¹⁵N values were high. The δ¹⁵N values of HMW DOM reflected the same trends observed in the POM fraction and provided the first such evidence for biological cycling of dissolved organic nitrogen (DON). Using the observed δ¹⁵N values and an estimate of meridional advection velocity, we estimated a turnover time of 0.3 to 0.5% day⁻¹ for HMW DON. These results suggest a major role for DON in the upper ocean nitrogen cycle.     

Size fractionation and optical properties of colloids in an organic-rich estuary (Thurso, UK)

The optical characteristics of a black water river estuary from the north coast of Scotland were examined in the filtered (0.4 µm), ultrafiltered (5 kDa) and colloid-enriched fractions of estuarine samples. The samples were collected over the full salinity range during a period when the pH was relatively constant (8.2–8.5) throughout the estuary, allowing the influence of salinity on estuarine colloidal processes to be distinguished. The properties examined in the bulk, the low molecular weight (LMW) and the colloidal fraction (HMW) were UV–visible absorption, 3-D fluorescence excitation–emission matrix (EEM) spectrum, inorganic and organic carbon, mean size (by dynamic light scattering), and size distribution by flow field-flow fractionation analysis (FlFFF). The combined results of these analyses support the view that river-borne, humic-rich colloids underwent two types of transformation upon mixing with the seawater end member. The first one resulted in an apparent increase in the abundance of LMW constituents and may be explained by coiling of the individual humic macromolecules. The second one resulted in an increase in the mean size measured in both the lower and higher colloidal size ranges, and may be explained by aggregation of colloids to form entities that were still mostly colloidal i.e., smaller than 0.4 µm. The LMW contribution to the bulk optical properties increased with increasing salinity. Very similar findings were obtained from simulated mixing experiments using a Nordic Reference NOM extract as a source of freshwater colloids. This indicates that changes in the molecular architecture and molar mass of river-borne colloids—not changes in their chemical nature—were responsible for the observed variations in the spectral characteristics of CDOM in this estuary.     

Isolation of colloidal monomethyl mercury in natural waters using cross-flow ultrafiltration techniques

A series of experiments was conducted to evaluate the appropriateness of cross-flow ultrafiltration (CFUF) techniques for the determination of the phase speciation of monomethyl mercury (MeHg) in natural waters. Spiral-wound cartridge (Amicon S1Y1) and Miniplate (Amicon) were evaluated for their nominal molecular weight cut-offs of 1 and 10 kDa, respectively. The ultrafiltration behavior of standard macromolecules showed that the permeation of high molecular weight (HMW) organic macromolecules was not significant when a concentration factor (CF)>15 was used. The retention of low molecular weight (LMW) molecules was significant, especially at a low CF<5, suggesting that the use of a high CF (15) will minimize the retention of LMW molecules. Sorptive losses of MeHg in the solution phase to the 1 kDa membrane were negligible, but MeHg bound to HMW macromolecules was still retained (20%), even with a preconditioned membrane. The mass balance recovery of MeHg during ultrafiltration averaged 101±15% (n=7) and 105±14% (n=5) for the 1 and 10 kDa membranes, respectively. Sample storage over 24 h caused significant coagulation (47%) of the <10 kDa MeHg into the 10 kDa–0.45 μm colloidal or the particulate MeHg pool. The 1 kDa–0.45 μm colloidal MeHg in Galveston Bay and the Trinity River water samples accounted for 40–48% of the filter-passing MeHg, although the most abundant fraction (52–60%) of MeHg was the truly dissolved fraction (<1 kDa). The partition coefficient between the colloidal (1 kDa–0.45 μm) and truly dissolved MeHg (average log K_C=5.2) was higher than the partition coefficient based on particle/filter-passing (average log K_D=4.6) or particle/truly dissolved MeHg (average log K_P=4.8), suggesting that MeHg has stronger affinity for natural colloids than macroparticulate materials (>0.45 μm).     

海水中胶体有机碳的测定──高温燃烧法和紫外/过硫酸钾法的比较

利用切向超滤(cross-flow ultrafiltration)技术对海水中胶体有机碳(COC)和真溶解有机碳(UOC)进行了分离,并分别用高温燃烧法和紫外/过硫酸钾法对胶体有机碳和真溶解有机碳进行了测定。测定结果表明,切向超滤能定量分离海水中的胶体有机碳,高温燃烧法和紫外/过硫酸钾法对胶体有机碳和真溶解有机碳的测定结果没有明显的系统误差,表明这两种方法的氧化效率基本相同,胶体粒子的存在,对紫外/过硫酸钾法的氧化效率没有显着影响。     

Flow dynamics inside the rotor of a three straight bladed cross-flow turbine

In this work we study experimentally the flow dynamics inside the rotor of a three straight-bladed Cross-Flow Turbine (CFT). The CFT model used in the experiments is based on symmetric NACA-0015 profiles, with a chord to rotor diameter ratio of 0.16. The turbine model was designed in order to quantify the flow inside and around the rotor using planar Digital Particle Image Velocimetry (DPIV). Tests were made by forcing the rotation of the turbine with a DC motor, which provided precise control of the Tip Speed Ratio (TSR), while being towed in a still-water tank at a constant turbine diameter Reynolds number of 6.1 × 10⁴. The range of TSRs covered in the experiments went from 0.7 to 2.3.The focus is given to the analysis of the blade-wake interactions inside the rotor. The investigation has allowed us to relate the interactions with the performance differences in this type of turbines, as a function of the operational tip speed ratio.     

Comparison of HTC method and UV/persulphate method to determine colloidal organic carbon in seawater

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Fe–Al–organic Colloids Control of Trace Elements in Peat Soil Solutions: Results of Ultrafiltration and Dialysis

Size fractionation of ~40 major and trace elements (TE) in peat soil solutions from the Tverskaya region (Russia) has been studied using frontal filtration and ultrafiltration through a progressively decreasing pore size (5, 2.5, 0.22 μm, 100, 10, 5, and 1 kD) and in situ dialysis through 6–8 and 1 kD membranes with subsequent analysis by ICP-MS. In (ultra) filter-passed permeates and dialysates of soil solutions, Fe, Al, and organic carbon (OC) are well correlated, indicating the presence of mixed organo-mineral colloids. All major anions and silica are present in “dissolved” forms passed through 1 kD membrane. According to their behavior during filtration and dialysis and association with mineral or organic components, three groups of elements can be distinguished: (i) species that are weakly affected by size separation operations and largely (>50–80%) present in the form of dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, As, Mn) with some proportion of small (1–10 kD) organic complexes (Ca, Mg, Sr, Ba), (ii) biologically essential elements (Co, Ni, Zn, Cu, Cd) mainly present in the fraction smaller than 1 kD and known to form strong organic complexes with fulvic acids, and, (iii) elements strongly associated with aluminum, iron and OC in all ultrafiltrates and dialysates with 30–50% being concentrated in large (>10 kD) colloids (Ga, Y, REEs, Pb, Cd, V, Nb, Sn, Ti, Zr, Hf, Th, U). For most trace metals, the proportion in the colloidal fraction correlates with their first hydrolysis constant. This implies a strong control of negatively charged oxygen donors present in inorganic/organic colloids on TE distribution between aqueous solution and colloid particles. It is suggested that these colloids are formed during plant uptake of Al, Fe, and TE from mineral matrix of deep soil horizons and their subsequent release in surface horizons after litter degradation and oxygenation on redox or acid/base fronts. Dissolved organic matter stabilizes Al/Fe colloids and thus enhances trace elements transport in soil solutions.     

土壤腐殖质提取和分组综述

土壤腐殖质的定量提取、分离与纯化是深入研究土壤腐殖质的重要前提。本文详细综述了国内外腐殖质提取和分组的实验手段和研究进展;以国际腐殖质协会提供的标准方法为参考,对比论述了提取剂种类,提取次数、提取剂用量等的选择;对比讨论了两种主要的土壤腐殖质的分组方法。超滤分离和体积排阻色谱是腐殖质物理化学表征研究中的两种新兴技术,笔者认为组合使用两种实验手段对土壤腐殖质进行细致的分离与分组研究有助于深化理解土壤腐殖质的化学性质和分子结构。     

Optical properties of estuarine dissolved organic matter isolated using cross-flow ultrafiltration

Dissolved organic matter(DOM) from freshwater, mid-salinity, and seawater endmember samples in the Jiulong River Estuary, China were fractionated using cross-flow ultrafiltration with a 10-kDa membrane. The colloidal organic matter(COM; 10 kDa–0.22 μm) retentate, low molecular weight(LMW) DOM(10 kDa) permeate, and bulk samples were analyzed using absorption spectroscopy and three-dimensional fluorescence excitation-emission-matrix spectroscopy. The UV-visible spectra of COM were very similar to those obtained for permeate and bulk samples, decreasing monotonically with increasing wavelength. Most of the chromophoric DOM(CDOM, expressed as the absorption coefficient a355) occurred in the LMW fraction, while the percentage of CDOM in the colloidal fraction was substantially higher in the freshwater endmember(13.4% of the total) than in the seawater endmember(6.8%). The bulk CDOM showed a conservative mixing behavior in the estuary, while there was removal of the COM fraction and a concurrent addition of the permeate fraction in the mid-salinity sample, implying that part of the colloidal CDOM was transformed into LMW CDOM. Two humic-like components(C1: 250, 325/402 nm; and C2: 265, 360/458 nm) and one protein-like component(C3: 275/334 nm) were identified using parallel factor analysis. The contributions of the C1, C2, and C3 components of the COM fraction to the bulk sample were 2.5%–8.7%, 4.8%–12.6%, and 7.4%–14.7%, respectively, revealing that fluorescent DOM occurred mainly in the LMW fraction in the Jiulong River Estuary. The C1 and C2 components in the retentate and permeate samples showed conservative mixing behavior, but the intensity ratio of C2/C1 was higher in the retentate than in the permeate fractions for all salinity samples, showing that the humic component was more enriched in the COM than the fulvic component. The intensity ratio of C3/(C1+C2) was much higher in the retentate than in the permeate fraction for mid-salinity and seawater samples, revealing that the protein-like component was relatively more enriched in COM than the humic-like component. The contribution of the protein-like component(C3) to the total fluorescence in the retentate increased from 14% in the freshwater endmember to 72% for the seawater endmember samples, clearly indicating the variation of dominance by the humic-like component compared to the protein-like component during the estuarine mixing process of COM.