Influence of relative humidity on carbon dioxide sorption in wheat gluten films

The influence of relative humidity (RH) on carbon dioxide sorption at 10⁵ Pa in wheat gluten films (WGF) was investigated in the range of 0–96% RH at 25 °C. The amount of water sorbed by these protein based films reached up to 60% of the dry weight at 96% RH. Carbon dioxide sorption increased with water content, ranging from 2.8 × 10⁻⁴ to 1.9 × 10⁻² mol Pa⁻¹ m⁻³ respectively at 0% and 96% RH. This behavior was tentatively explained on the grounds that sorbed water enhanced carbon dioxide accessibility to protein active sorption sites. The dependence of both the solubility and the diffusivity coefficients of CO₂ and O₂ on WGF water content explains the very good permselectivity of these films observed at high RH values (22 at 93% RH and 25 °C).     

Assessing the effect of humic acid redox state on organic pollutant sorption by combined electrochemical reduction and sorption experiments

Natural Organic Matter (NOM) is a major sorbent for organic pollutants in soils and sediments. While sorption under oxic conditions has been well investigated, possible changes in the sorption capacity of a given NOM induced by reduction have not yet been studied. Reduction of quinones to hydroquinones, the major redox active moieties in NOM, increases the number of H-donor moieties and thus may affect sorption. This work compares the sorption of four nonionic organic pollutants of different polarities (naphthalene, acetophenone, quinoline, and 2-naphthol), and of the organocation paraquat to unreduced and electrochemically reduced Leonardite Humic Acid (LHA). The redox states of reduced and unreduced LHA in all sorption experiments were stable, as demonstrated by a spectrophotometric 2,6-dichlorophenol indophenol reduction assay. The sorption isotherms of the nonionic pollutants were highly linear, while paraquat sorption was strongly concentration dependent. LHA reduction did not result in significant changes in the sorption of all tested compounds, not even of the cationic paraquat at pH 7, 9, and 11. This work provides the first evidence that changes in NOM redox state do not largely affect organic pollutant sorption, suggesting that current sorption models are applicable both to unreduced and to reduced soil and sediment NOM.     

Effect of dissolved organic carbon on sorption of pyrethroids to sediments

Despite their strong hydrophobicity, recent studies showed widespread occurrence of pyrethroid in downstream surface waters bodies. In this work, the effect of dissolved organic carbon (DOC) on the sorption and desorption of pyrethroids in sediment was evaluated to understand the role of DOC in facilitating pyrethroid transport. Presence of DOC from three sources at 38 ± 2 mg L?1 in the aqueous phase decreased pesticide sorption to a sediment by 1.7 to 38.9 times and increased their desorption by 1.2 to 41.4 times. The effect on pyrethroid sorption to the sediment was linear. In addition, interactions between DOC and pyrethroids, when taking place prior to the contact with sediment, decreased sorption of some pyrethroids even further, implying that DOC-pyrethroid complexs were relatively stable in solution. DOC sources with higher contents of carboxylic and phenolic groups were found to have a higher potential to associate with pyrethroids. The DOC-water partition coefficients (K(DOC)) obtained by solid-phase microextraction measurement were significantly correlated (P < 0.01) with K(d) values measured for the sediment. These results provide evidence that DOC increases the distribution of pyrethroids from the sediment to the solution phase and plays an important role in mobilizing pyrethroids in runoff and surface streams.     

Importance of unburned coal carbon, black carbon, and amorphous organic carbon to phenanthrene sorption in sediments

The aim of this paper was to estimate the contribution to total phenanthrene sorption from unburned coal and black carbon (BC; soot and charcoal) in sediment. We determined sorption isotherms for five Argonne Premium Coal standards over a wide concentration interval (0.01-10 000 ng/L). The coals showed strong and nonlinear sorption (carbon-normalized K(F) = 5.41-5.96; nF = 0.68-0.82). Coal sorption appeared to become more nonlinear with increasing coal maturity. The coal's specific surface area appeared to influence K(F). On the basis of the current coal sorption observations combined with earlier petrographic analyses and BC sorption experiments, we calculated for one particular sediment that coal, BC, and "other" OC were all important to PHE sorption in the environmentally relevant nanogram per liter range. This indicates that it is important to consider strong sorption to coal in the risk assessment of coal-impacted geosorbents (e.g., river beds) where coal is mined/shipped and manufactured gas plant sites.     

羊毛等离子体改性对超临界CO2染色效果的影响

研究了羊毛经等离子体改性后，在超临界CO2状态下利用分散染料染色的方法。研究发现，在功率为150W，压强为30Pa的条件下处理羊毛10min，染料在纤维上的固着率可达89．4％。     

Investigation of sorption behavior between pyrene and colloidal organic carbon from activated sludge processes

The sorption behavior of pyrene for different size fractions of colloidal organic carbon (COC) originating from two biological wastewater treatment facilities (a full-scale activated sludge system (FSAS) and a membrane bioreactor (MBR)) was investigated by fluorescence quenching. Fluorescence lifetime measurements demonstrated a dynamic quenching component in all samples, including the colloidal-free filtrates. COC sorption coefficients (Kcoc) for pyrene ranged from <1 x 10(3) L/kgcoc to 80 x 10(3) L/kgcoc and were comparable to values obtained in the literature for natural organic matter. Both linear and nonlinear behaviors were observed in the Freundlich-described converted isotherms (n = 0.89-2.1). The aromatic content of COC was quantified by the molar extinction coefficient at 280 nm (e280). Good correlations were observed between COC-pyrene sorption coefficients and e280 coefficients, suggesting that e280 may be a useful tool for predicting colloidal transport of hydrophobic organic compounds (HOCs) from activated sludge systems. The removal of COC from treated effluents may appreciably reduce the concentrations of HOCs discharged to receiving streams.     

Effect of heavy metals on the sorption of hydrophobic organic compounds to wood charcoal

Black carbon (BC) is believed to be an important adsorbent of organic pollutants. A complex suite of heavy metals and organic pollutants is commonly present in many situations. An issue that has received little direct attention is the effect of heavy metals on sorption of organic compounds to BC. We found that coadsorption of Cu2+ at an environmentally relevant, comparable concentration (50 mg L-1) decreases sorption of both the polar compound, 2,4-dichlorophenol (DCP), and nonpolar compounds, 1,2-dichlorobenzene (DCB) and naphthalene (NAP), by 30-60%, as measured bythe change in the distribution coefficient (Kd). This was attributed to surface complexation of CU2+ to form hydration shells of dense water that directly compete with organics for adsorption surface area. In contrast, coadsorption of Ag+ increases sorption of the organic solutes, which was accounted for by the decline in hydrophilicity of the local region around Ag+-complexed functionalities due to softness of the cation, leading to mitigated competitive sorption of water. Coadsorption of heavy metal ions to nonporous graphite, a model of the BC graphene (polycyclic aromatic) structure that has no 0-containing groups, however, only slightly inhibits organic adsorption due to the low affinities of metal ions to graphite surface. The results of the present study showed that the presence of coexisting heavy metals greatly affects sorption of organic pollutants on BC and thereby their fate and transport.     

Influence of dissolved organic carbon on methylmercury bioavailability across Minnesota stream ecosystems

Stream ecosystems are widely contaminated by mercury (Hg) via atmospheric transport and deposition in watersheds. Dissolved organic carbon (DOC) is well-known to be the dominant ligand for aqueous methylmercury (MeHg), the bioaccumulative form of Hg in aquatic food webs. However, it is less clear if and how the concentration and character (e.g., aromaticity) of DOC influences the availability of dissolved MeHg to stream food webs. In this work, we analyzed total-Hg and/or MeHg concentrations in water, seston, and macroinvertebrates (filter-feeding hydropsychid caddisflies), and other physiochemical properties in 30 streams along a south-north geographic gradient in eastern Minnesota that corresponds to substantial changes in dominant land cover (i.e., agriculture, urban, wetland, and forest). In general, MeHg concentrations in seston and hydropsychids were higher in watersheds with more forest and wetland coverage, and increased with dissolved MeHg concentration. However, we found that the efficiency of MeHg incorporation into the stream food webs (i.e., bioconcentration factors of MeHg in both seston and hydropsychids, BCF(MeHg) = solid MeHg ÷ dissolved MeHg) decreased significantly with DOC concentration and aromaticity, suggesting that MeHg bioavailability to the base of food webs was attenuated at higher levels of terrestrial DOC. Therefore, our findings suggest that there is a dual role of DOC on MeHg cycling in streams: terrestrial DOC acts as the primary carrier ligand of dissolved MeHg for transport into surface waters, yet this aromatic DOC also attenuates dissolved MeHg uptake by aquatic food webs. Thus, consideration of MeHg bioavailability and its environmental regulation could help improve predictive models of MeHg bioaccumulation in stream ecosystems.     

夹带剂和鞣制时间对二氧化碳超临界流体条件下铬鞣的影响

利用自制的二氧化碳超临界流体制革设备,考察了夹带剂A用量和鞣制时间,对二氧化碳超临界流体代替水 作介质铬鞣的影响。通过对鞣制后坯革的收缩温度、铬含量和感观等的比较,得出了二氧化碳超临界流体条 件下,铬鞣夹带剂A最佳用量为8%,最佳鞣制时间为1h。     

Influence of sorption to dissolved humic substances on transformation reactions of hydrophobic organic compounds in water. I. Chlorination of PAHs

The effect of sorption to dissolved humic acids (HAs) on the chlorination of PAHs in aqueous solution was studied. The addition of HA accelerated the chlorination of fluoranthene and naphthalene in hypochlorite solutions at pH 5, the stronger effect being observed for fluoranthene that is sorbed to a higher extent than naphthalene. Sorption coefficients (K(DOC)) of the analytes were determined by solid-phase microextraction (SPME). The observed rate constant for fluoranthene chlorination is, for example, larger by a factor of 5 in the presence of 10 mg L(-1) of an aquatic HA as compared to HA-free solution (k' = 0.02 h(-1) at 60 mg L(-1) active chlorine, pH 5, without HA). While Cl2 is the dominant reactive species in pure aqueous solution for both PAHs, the reaction of fluoranthene seems to involve an additional pathway of chlorination by HOCl in the presence of HA. It was found that not only did HA not protect PAHs from the electrophilic attack of the chlorinating species, but the sorption of PAHs on the hydrophobic domains of the HA favored instead the extent of the chlorination reaction.     

Influence of calcite and dissolved calcium on uranium(VI) sorption to a hanford subsurface sediment

The influence of calcite and dissolved calcium on U(VI) adsorption was investigated using a calcite-containing sandy silt/clay sediment from the U. S. Department of Energy Hanford site. U(VI) adsorption to sediment, treated sediment, and sediment size fractions was studied in solutions that both had and had not been preequilibrated with calcite, at initial [U(VI)] = 10(-7)-10(-5) mol/L and final pH = 6.0-10.0. Kinetic and reversibility studies (pH 8.4) showed rapid sorption (30 min), with reasonable reversibility in the 3-day reaction time. Sorption from solutions equilibrated with calcite showed maximum U(VI) adsorption at pH 8.4 +/- 0.1. In contrast, calcium-free systems showed the greatest adsorption at pH 6.0-7.2. At pH > 8.4, U(VI) adsorption was identical from calcium-free and calcium-containing solutions. For calcite-presaturated systems, both speciation calculations and laser-induced fluorescence spectroscopic analyses indicated that aqueous U(VI) was increasingly dominated by Ca2UO2(CO3)3(0)(aq) at pH < 8.4 and thatformation of Ca2UO2(CO3)3(0)(aq) is what suppresses U(VI) adsorption. Above pH 8.4, aqueous U(VI) speciation was dominated by UO2(CO3)3(4-) in all solutions. Finally, results also showed that U(VI) adsorption was additive in regard to size fraction but not in regard to mineral mass: Carbonate minerals may have blocked U(VI) access to surfaces of higher sorption affinity.     

高压二氧化碳处理中几种因素对苹果浊汁中大肠杆菌杀菌效果的影响

主要研究处理介质pH、循环处理和卸压速率对高压二氧化碳处理对苹果浊汁中大肠杆菌杀菌效果的影响。结果表明:在32℃、10MPa和37℃、20MPa下处理30min,通过降低处理介质苹果浊汁的初始pH能提高杀菌效果;在32～42℃、10～30MPa下以15min为一个周期来循环处理也能提高杀菌效果,主要是由于循环处理中因多次升、降压造成CO2与微生物细胞接触时间延长,且多次升、降压提高了CO2渗透入细胞的能力,卸压速率对HPCD杀菌效果影响不显著。      

Dispersion state and humic acids concentration-dependent sorption of pyrene to carbon nanotubes

Sonication and humic acids (HA) are known to disperse carbon nanotube (CNT) suspensions, but potential effects on sorption of chemicals to CNTs remain poorly understood. We applied a passive sampling method to investigate the influence of dispersion/aggregation on sorption of pyrene to CNTs. Sonication broke down CNT aggregates and increased pyrene sorption affinity by up to 1.39 orders of magnitude. Sorption surfaces newly exposed by sonication remained available to pyrene even after reaggregation occurred, suggesting an irreversible effect of sonication. The presence of HA decreased sorption of pyrene to CNTs, but at the highest HA concentration investigated (200 mg/L), sorption affinity was still 1.90 orders of magnitude larger than sorption of pyrene to HA alone. Specific interactions between pyrene and CNTs were thus still taking place, in spite of the presence of a HA coating on the CNTs' surface. A greater suppression of sorption by CNTs occurred when the HA addition was combined with a sonication pretreatment. Sorption isotherm fitting indicated that the maximum sorption capacity, sorption affinity, and heterogeneity of the CNT surface were all affected by sonication and the presence of HA at a concentration as low as 1 mg/L. The present results contribute to an improved understanding of the sorption behavior of CNTs in both natural and wastewater systems.     

Influence of sediment bioreduction and reoxidation on uranium sorption

The influence of sediment bioreduction and reoxidation on U(VI) sorption was studied using Fe(II) oxide-containing saprolite from the U.S. Department of Energy (DOE) Oak Ridge site. Bioreduced sediments were generated by anoxic incubation with a metal-reducing bacterium, Shewanella putrefaciens strain CN32, supplied with lactate as an electron donor. The reduced sediments were subsequently reoxidized by air contact. U(VI) sorption was studied in NaNO3-HCO3 electrolytes that were both closed and open to atmosphere and where pH, U(VI), and carbonate concentration were varied. M?ssbauer spectroscopy and chemical analyses showed that 50% of the Fe(III)-oxides were reduced to Fe(II) that was sorbed to the sediment during incubation with CN32. However, this reduction and subsequent reoxidation of the sorbed Fe(II) had negligible influence on the rate and extent of U sorption or the extractability of sorbed U by 0.2 mol/L NaHCO3. Various results indicated that U(VI) surface complexation was the primary process responsible for uranyl sorption by the bioreduced and reoxidized sediments. A two-site, nonelectrostatic surface complexation model best described U(VI) adsorption under variable pH, carbonate, and U(VI) conditions. A ferrihydrite-based diffuse double layer model provided a better estimation of U(VI) adsorption without parameter adjustment than did a goethite-based model, even though a majority of the Fe(III)-oxides in the sediments were goethite. Our results highlight the complexity of the coupled U-Fe redox system and show that sorbed Fe(II) is not a universal reductant for U(VI) as commonly assumed.     

Influence of calcium carbonate on U(VI) sorption to soils

The high stability of calcium uranyl carbonate complexes in the circumneutral pH range has a strong impact on U(VI) sorption in calcareous soils. To quantify this influence, sorption of U(VI) to soils in the presence of naturally occurring calcium carbonate was investigated by conducting batch experiments in which either U(VI) concentration or solution pH was varied. Two soils containing different calcium carbonate concentrations were selected, one from Oak Ridge, TN, and another from Altamont Pass, CA. The results show that the presence of calcium carbonate in soils strongly affects U(VI) sorption. Higher concentrations of soil calcium carbonate lead to a pronounced suppression of the pH-dependent sorption curve in the neutral pH range because of the formation of a very stable neutral complex of calcium uranyl carbonate in solution. A surface complexation model considering both strong and weak sites for ferrihydrite and ionizable hydroxyl sites for clay minerals was compared with experimental results, and U(VI) binding parameters were reasonably estimated. Fair agreement was found between the model predictions and sorption data, which span a wide range of U(VI) concentrations and pH. The results also show that appropriate solution-to-solid ratios need to be used when measuring distribution coefficients in calcareous soils to avoid complete CaCO3 dissolution and consequent dilution of calcium uranyl carbonate complexes.     

添加CO2对原料乳物理性质及稳定性的影响

在实验室条件下研究了添加CO2的原料乳在脱气前后的物理性质和稳定性,以确定适宜的CO2添加量。试验设计分为CO2处理组和脱气处理组2组,4个水平,以未处理的原料乳做对照组,检测每组样品CO2浓度、感官性质、pH值、酸度和稳定性。结果表明,二氧化碳浓度为39.86 mmol/L时,原料乳开始产生酸味,脱气后,感官性质正常,pH值为6.61,滴定酸度18.6 T°,酒精稳定性68%,热稳定时间8.2 min,符合正常原料乳标准;二氧化碳浓度为49.43 mmol/L时,脱气后的原料乳pH值为6.58,滴定酸度20.7 T°,酒精稳定性66%,热稳定时间6.9 min,已不能用于生产。因此,原料乳中二氧化碳添加量以不高于39.86 mmol/L为宜。     

Influence of total organic carbon and UV-B radiation on zinc toxicity and bioaccumulation in aquatic communities

The effects of total organic carbon (TOC) and UV-B radiation on Zn toxicity and bioaccumulation in a Rocky Mountain stream community were assessed in a 10-d microcosm experiment. We predicted that TOC would mitigate Zn toxicity and that the combined effects of Zn and UV-B would be greater than Zn alone. However, TOC did not mitigate Zn toxicity in this study. In fact, treatments with TOC plus Zn had significantly lower community respiration as compared with the controls and Zn concentrations associated with the periphyton increased in the presence of TOC. UV-B had no additive effect on periphyton Zn accumulation or community respiration. Heptageniid mayflies (Ephemeroptera) were particularly sensitive to Zn, and reduced abundances were observed in all Zn treatments. UV-B did not additionally impact Heptageniid abundances; however UV-B did have a greater effect on macroinvertebrate drift than Zn alone. Ephemeroptera, Plecoptera, and Trichoptera (groups typically classified as sensitive to disturbance) were found in highest numbers in the drift of UV-B + Zn treatments. Measures of Zn accumulation in the caddisfly Arctopsyche grandis, periphyton biomass, and total macroinvertebrate abundance were not sufficiently sensitive to differentiate effects of TOC, UV-B, and Zn. These results indicate that UV-B and TOC affect Zn bioavailability and toxicity by impacting species abundance, behavior, and ecosystem processes.     

Black carbon and kerogen in soils and sediments. 2. Their roles in equilibrium sorption of less-polar organic pollutants

The first paper of this series reported that soil/sediment organic matter (SOM) can be fractionated into four fractions with a combined wet chemical procedure and that kerogen and black carbon (BC) are major SOM components in soil/sediment samples collected from the industrialized suburban areas of Guangzhou, China. The goal of this study was to determine the sorptive properties forthe four SOM fractions for organic contaminants. Sorption isotherms were measured with a batch technique using phenanthrene and naphthalene as the sorbates and four original and four Soxhlet-extracted soil/sediment samples, 15 isolated SOM fractions, and a char as the sorbents. The results showed that the sorption isotherms measured for all the sorbents were variously nonlinear. The isolated humic acid (HA) exhibited significantly nonlinear sorption, but its contribution to the overall isotherm nonlinearity and sorption capacity of the original soil was insignificant because of its low content in the tested soils and sediments. The particulate kerogen and black carbon (KB) fractions exhibited more nonlinear sorption with much higher organic carbon-normalized capacities for both sorbates. They dominate the observed overall sorption by the tested soils and sediments and are expected to be the most important soil components affecting bioavailability and ultimate fate of hydrophobic organic contaminants (HOCs). The fact that the isolated KB fractions exhibited much higher sorption capacities than when they were associated with soil/sediment matrixes suggested that a large fraction of the particulate kerogen and BC was not accessible to sorbing HOCs. Encapsulation within soil aggregates and surface coverage by inorganic and organic coatings may have caused large variations in the accessibility of fine kerogen and BC particles to HOCs and hence lowered the sorption capacity of the soil. This variability posts an ultimate challenge for precisely predicting HOC sorption by soils from the contents of different types of SOM.     

Influence of smectite hydration and swelling on atrazine sorption behavior

Smectites, clay minerals commonly found in soils and sediments, vary widely in their ability to adsorb organic chemicals. Recent research has demonstrated the importance of surface charge density and properties of exchangeable cations in controlling the affinity of smectites for organic molecules. In this study, we induced hysteresis in the crystalline swelling of smectites to test the hypothesis that the extent of crystalline swelling (or interlayer hydration status) has a large influence on the ability of smectites to adsorb atrazine from aqueous systems. Air-dried K-saturated Panther Creek (PC) smectite swelled less (d(001) = 1.38 nm) than never-dried K-PC (d(001) = 1.7 nm) when rehydrated in 20 mM KCl. Correspondingly, the air-dried-rehydrated K-PC had an order of magnitude greater affinity for atrazine relative to the never-dried K-PC. Both air-dried-rehydrated and never-dried Ca-PC expanded to approximately 2.0 nm in 10 mM CaCl2 and both samples had similar affinities for atrazine that were slightly lower than that of never-dried K-PC. The importance of interlayer hydration status in controlling sorption affinity was confirmed by molecular modeling, which revealed much greater interaction between interlayer water molecules and atrazine in a three-layer hydrate relative to a one-layer hydrate. The entropy change on moving atrazine from a fully hydrated state in the bulk solution to a partially hydrated state in the smectite interlayers is believed to be a major factor influencing sorption affinity. In an application test, choice of background solution (20 mM KCl versus 10 mM CaCl2) and air-drying treatments significantly affected atrazine sorption affinities for three-smectitic soils; however, the trends were not consistent with those observed for the reference smectite. Further, extending the initial rehydration time from 24 to 240 h (prior to adding atrazine) significantly decreased the soil's sorption affinity for atrazine. We conclude that interlayer hydration status has a large influence on the affinity of smectites for atrazine and that air-drying treatments have the potential to modify the sorption affinity of smectitic soils for organic molecules such as atrazine.