Origin and Distribution of Suspended Organic Matter As Inferred From Carbon Isotope Composition in A Mediterranean Semi-Enclosed Marine System

The origin and distribution of suspended organic matter, the trophic features and the stable carbon isotopic composition of particulate organic carbon (POC) were studied monthly in a Western Mediterranean semi-enclosed basin. Sampling stations were selected as a function of wind-exposure and the degree of vegetation cover and then compared with an adjacent unvegetated site. the predominant vegetation was seagrass (Posidonia oceanica and Cymodocea nodosa) and Caulerpa prolifera. Water samples were analyzed for total suspended matter (inorganic and organic fractions), photosynthetic pigments (chlorophyll-a and phaeopigments), dissolved organic carbon, particulate organic carbon and their isotopic composition. Temperature and salinity were also measured at the same sampling sites within range of Mediterranean limits. the suspended organic matter concentration was 1.77 ± 1.55 mg l^-1; the chlorophyll-a concentration was low (0.35 ± 0.24 μg l^-1); the disolved organic carbon concentration was 2,140 ± 2,010 μg l^-1; the particulate organic carbon concentration was 212 ± 106 μg l^-1 and the isotopic composition was 18.77 ± 2.51%_°. There were significant temporal differences except for phaeopigments, POC and its POC isotopic composition, and there were no spatial differences other than for δ¹³C. This picture highlighted a general seasonal trend and trophical features similar to adjacent sea.

Spatial differences in δ¹³C showed that the source of suspended organic matter was different between stations as that between sources and wind-hydrodynamic constraints. In     

14C and 125I Labelling of Humic Material for Use in Environmental Studies

Humic and fulvic acids are present in nearly all natural waters. These acids are known to affect the transport of environmental contaminants such as metals and hydrophobic organics through the terrestrial environment. an understanding of their role in the transport of contaminants is therefore essential and is facilitated if the acid is labelled with a suitable radioactive label. This paper reports the use of ¹⁴C-methylamine and ¹²⁵I to label humic acid with either ¹⁴C or ¹²⁵I and investigates factors which affect the yield of these reactions. the stability and mobility of the labelled humic material through sand is also reported.     

Changes in nutrient content and stable isotope ratios of C and N during decomposition of seagrasses and mangrove leaves along a nutrient availability gradient in Florida Bay, USA

The decomposition of the mangrove Rhizophora mangle and the seagrass Thalassia testudinum was examined using litterbags along a natural gradient in nutrient availability. Seagrass leaves had a higher fraction of their biomass in the labile pool (57%), compared to mangrove leaves (36%) and seagrass rhizomes (29%); the overall decomposition rates of the starting material reflected the fractionation into labile and refractory components. There was no relationship between the N or P content of the starting material and the decomposition rate.

Nutrient availability had no influence on decomposition rate, and mass was lost at the same rate from litterbags that were buried in the sediment and litterbags that were left on the sediment surface. The dynamics of N and P content during decomposition varied as a function of starting material and burial state. N content of decomposing mangrove leaves increased, but seagrass rhizomes decreased in N content during decomposition while there was no change in seagrass leaf N content. These same general patterns held for P content, but buried seagrass leaves increased in P content while surficial leaves decreased. δ¹³C and δ¹⁵N changed by as much as 2‰ during decomposition.     

δ15N-stable isotope analysis of NHx: An overview on analytical measurements,source sampling and its source apportionment

• Challenges in sampling of NH₃ sources for d¹⁵N analysis are highlighted. • Uncertainties in the isotope-based source apportionment of NH₃ and NH₄⁺ are outlined. • Characterizing dynamic isotopic fractionation may reduce uncertainties of NH_x science. Agricultural sources and non-agricultural emissions contribute to gaseous ammonia (NH₃) that plays a vital role in severe haze formation. Qualitative and quantitative contributions of these sources to ambient PM_2.5 (particulate matter with an aerodynamic equivalent diameter below 2.5 µm) concentrations remains uncertain. Stable nitrogen isotopic composition (δ¹⁵N) of NH₃ and NH₄⁺ (δ¹⁵N(NH₃) and δ¹⁵N(NH₄⁺), respectively) can yield valuable information about its sources and associated processes. This review provides an overview of the recent progress in analytical techniques for δ¹⁵N(NH₃) and δ¹⁵N(NH₄⁺) measurement, sampling of atmospheric NH₃ and NH₄⁺ in the ambient air and their sources signature (e.g., agricultural vs. fossil fuel), and isotope-based source apportionment of NH₃ in urban atmosphere. This study highlights that collecting sample that are fully representative of emission sources remains a challenge in fingerprinting δ¹⁵N(NH₃) values of NH₃ emission sources. Furthermore, isotopic fractionation during NH₃ gas-to-particle conversion under varying ambient field conditions (e.g., relative humidity, particle pH, temperature) remains unclear, which indicates more field and laboratory studies to validate theoretically predicted isotopic fractionation are required. Thus, this study concludes that lack of refined δ¹⁵N(NH₃) fingerprints and full understanding of isotopic fractionation during aerosol formation in a laboratory and field conditions is a limitation for isotope-based source apportionment of NH₃. More experimental work (in chamber studies) and theoretical estimations in combinations of field verification are necessary in characterizing isotopic fractionation under various environmental and atmospheric neutralization conditions, which would help to better interpret isotopic data and our understanding on NH_x (NH₃ + NH₄⁺) dynamics in the atmosphere.     

Light-induced variation in environmentally persistent free radicals and the generation of reactive radical species in humic substances

• Light irradiation increased the concentration of free radicals on HS. • The increased spin densities on HS readily returned back to the original value. • The “unstable” free radicals induced the formation of reactive radical species. • Reactive radicals’ concentration correlated strongly with EPFRs’ concentration. Environmentally persistent free radicals (EPFRs) in humic substances play an essential role in soil geochemical processes. Light is known to induce EPFRs formation for dissolved organic matter in aquatic environments; however, the impacts of light irradiation on the variation of EPFRs in soil humic substances remain unclear. In this study, humic acid, fulvic acid, and humin were extracted from peat soil and then in situ irradiated using simulated sunlight. Electron paramagnetic resonance spectroscopy results showed that with the increasing irradiation time, the spin densities and g-factors of humic substances rapidly increased during the initial 20 min and then gradually reached a plateau. After irradiation for 2h, the maximum spin density levels were up to 1.63 × 10¹⁷, 2.06 × 10¹⁷, and 1.77 × 10¹⁷ spins/g for the humic acid, fulvic acid, and humin, respectively. And the superoxide radicals increased to 1.05 × 10¹⁴–1.46 × 10¹⁴ spins/g while the alkyl radicals increased to 0.47 × 10¹⁴–1.76 × 10¹⁴ spins/g. The light-induced EPFRs were relatively unstable and readily returned back to their original state under dark and oxic conditions. Significant positive correlations were observed between the concentrations of EPFRs and reactive radical species (R² = 0.65–0.98, p<0.05), which suggested that the newly produced EPFRs contributed to the formation of reactive radical species. Our findings indicate that under the irradiation humic substances are likely to be more toxic and reactive in soil due to the formation of EPFRs.     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^-1) on ¹³⁷Cs adsorption-desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26-99.97%) of added ¹³⁷Cs (3.7 × 10³-7.03 × 10⁵ Bq l^-1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K_ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K_ads and soil pH was observed. The ¹³⁷Cs adsorption-desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09-0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

Organophosphate esters in sediment from Taihu Lake,China: Bridging the gap between riverine sources and lake sinks

• Eleven OPEs were detected in river sediment and lake sediment in Taihu Lake. • TnBP dominated in river sediment, while TBEP dominated in lake sediment. • A strong correlation existed between logK_oc and logK_ow of OPEs. • Vertical profiles of OPEs in sediment cores varied according to sampling location. Surface sediment samples from Taihu Lake in China and its inflow rivers, along with two lake sediment core samples, were collected and analyzed for organophosphate esters (OPEs). The concentrations of total OPEs varied from 28.60 ng/g to 158.72 ng/g (median: 54.25 ng/g) in river surface sediment and from 62.57 ng/g to 326.84 ng/g (median: 86.37 ng/g) in lake sediment. Tributyl phosphate (TnBP) was the predominant compound in river surface sediment, and tris(2-butoxyethyl) phosphate was predominant in lake sediment. High contamination occurred in the north-west region, which was related to the high level of urbanization and high usage of OPEs. The sediment–water partition coefficients of OPEs (logK_oc) were calculated, showing a significant correlation with logK_ow (p<0.05). The concentration and composition of OPEs in two sediment cores varied due to the different sampling locations, with more OPE species found in the northern region than in the southern one. Principal component analysis and positive matrix factorization indicated that sewage discharges, vehicle emissions, and atmospheric deposition were the possible sources of OPEs in Taihu Lake sediments. Tris(1-chloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, and TnBP were the main OPEs causing ecological risks.     

Predicting non-carcinogenic hazard quotients of heavy metals in pepper (Capsicum annum L.) utilizing electromagnetic waves

• There was significant absorption of heavy metals by the pepper in contaminated soils. • The target hazard quotient (THQ) indices followed the order of Pb>Zn>>Cd » Ni. • Relationships exist between contaminated plants and electromagnetic wave. • PCA and random search can select the main spectra and predict THQ for each element. Given the tendency of heavy metals to accumulate in soil and plants, the purpose of this study was to determine the contamination levels of Cd, Ni, Pb, and Zn on peppers (leaves and fruit) grown in contaminated soils in industrial centers. For this purpose, we measured the uptake of the four heavy metals by peppers grown in the heavy metal contaminated soils throughout the four growth stages: two-leaf, growth, flowering, and fruiting, and calculated various vegetation indices to evaluate the heavy metal contamination potentials. Electromagnetic waves were also applied for analyzing the responses of the target plants to various heavy metals. Based on the relevant spectral bands identified by principal component analysis (PCA) and random search methods, a regression method was then employed to determine the most optimal spectral bands for estimating the target hazard quotient (THQ). The THQ was found to be the highest in the plants contaminated by Pb (THQ= 62) and Zn (THQ= 5.07). The results of PCA and random search indicated that the spectra at the bands of b₅₇₀, b₆₅₀, and b₇₆₀ for Pb, b₄₀₀ and b₁₀₃₀ for Ni, b₄₀₀ and b₈₈₀ for Cd, and b₅₆₀, b₉₁₀, and b₁₀₅₀ for Zn were the most optimal spectra for assessing THQ. Therefore, in future studies, instead of examining the amount of heavy metals in plants by chemical analysis in the laboratory, the responses of the plants to the electromagnetic waves in the identified bands can be readily investigated in the field based on the established correlations.     

Abundance and distribution of ammonia-oxidizing archaea in Tibetan and Yunnan plateau agricultural soils of China

As low oxygen and high ultraviolet （UV） exposure might significantly affect the microbial existence in plateau, it could lead to a specialized microbial community. To determine the abundance and distribution of ammonia-oxidizing archaea （AOA） in agricultural soil of plateau, seven soil samples were collected respectively from farmlands in Tibet and Yunnan cultivating the wheat, highland-barley, and colza, which are located at altitudes of 3200-3800 m above sea level. Quantitative PCR （q-PCR） and clone library targeting on amoA gene were used to quantify the abundances of AOA and ammonia-oxidizing bacteria （AOB）, and characterize the community structures of AOA in the samples. The number of AOA cells （9.34 × 10^7-2.32× 10^8 g^-1 soil） was 3.86-21.84 times greater than that of AOB cells （6.91 × 10^6-1.24 × 10^8 g^-1 soil） in most of the samples, except a soil sample cultivating highland- barley with an AOA/AOB ratio of 0.90. Based Kendall＇s correlation coefficient, no remarkable correlation between AOA abundance and the environmental factor was observed. Additionally, the diversities of AOA community were affected by total nitrogen and organic matter concentration in soils, suggesting that AOA was probably sensitive to several environmental factors, and could adjust its community structure to adapt to the environmental variation while maintaining its abundance.     

Radioactivity Monitored From Moored Oceanographic Buoys

The principles and operation of a gamma radiation sensor mounted on oceanographic buoys are described. the sensor has proved rugged in severe weather conditions and has satisfactory detection limits and accuracy. Continuous monitoring of artificially produced γ-emitters such as ¹³⁷Cs, ¹³⁴Cs, ¹³¹I, ¹³³I, ¹³²Te, naturally occuring emitters such as ⁴⁰k and ²¹⁴Bi in open sea conditions can provide important information in critical situations.     

Heavy-metal adsorption by non-living biomass

The adsorption of some heavy metals onto the walls of harvested, washed, and dried non-living biomass cells of different Pseudomonas strains was studied at optimum experimental conditions using a simplified single component system. The Langmuir adsorption model was found to be a suitable approach to describe the system via multi-step processes. Isotherms measured at 30.0°C and pH 5.5 with [M]_total = 10-100 mM for tight, reversible Cr⁶⁺(aq), Ni²⁺(aq), Cu²⁺(aq) and Cd²⁺(aq) binding by the cell walls of the investigated biomass fit the Langmuir model and give the pH-independent stoichiometric site capacities ν_i and equilibrium constants K_i for metal binding at specific biomass sites i = A, B, C, and D. Tight binding sites A, B, and D of the non-living biomass are occupied by Cr^VI, sites A and C by Ni^II, sites A and D by Cd^II, and only site B by Cu^II. It is concluded that ν_i is a stoichiometric parameter that is independent of the magnitude of K_i for binding site i and that the studied heavy metals selectively and tightly bind at different biomass sites.     

Microbial communities biostimulated by ethanol during uranium (VI) bioremediation in contaminated sediment as shown by stable isotope probing

Stable isotope probing (SIP) was used to identify microbes stimulated by ethanol addition in microcosms containing two sediments collected from the bioremediation test zone at the US Department of Energy Oak Ridge site, TN, USA. One sample was highly bioreduced with ethanol while another was less reduced. Microcosms with the respective sediments were amended with ¹³C labeled ethanol and incubated for 7 days for SIP. Ethanol was rapidly converted to acetate within 24 h accompanied with the reduction of nitrate and sulfate. The accumulation of acetate persisted beyond the 7 d period. Aqueous U did not decline in the microcosm with the reduced sediment due to desorption of U but continuously declined in the less reduced sample. Microbial growth and concomitant ¹³C-DNA production was detected when ethanol was exhausted and abundant acetate had accumulated in both microcosms. This coincided with U(VI) reduction in the less reduced sample. ¹³C originating from ethanol was ultimately utilized for growth, either directly or indirectly, by the dominant microbial community members within 7 days of incubation. The microbial community was comprised predominantly of known denitrifiers, sulfate-reducing bacteria and iron (III) reducing bacteria including Desulfovibrio, Sphingomonas, Ferribacterium, Rhodanobacter, Geothrix, Thiobacillus and others, including the known U(VI)-reducing bacteria Acidovorax, Anaeromyxobacter, Desulfovibrio, Geobacter and Desulfosporosinus. The findings suggest that ethanol biostimulates the U(VI)-reducing microbial community by first serving as an electron donor for nitrate, sulfate, iron (III) and U(VI) reduction, and acetate which then functions as electron donor for U(VI) reduction and carbon source for microbial growth.     

The Relationship Between Iodine, Chlorinity, Ph, Reactive Phosphate, Nitrite and Organic Matter in the Coastal Water of Alexandria

Water samples were taken from 12 stations at El-Dikheila Harbour, El-Mex Bay, Western Harbour, Qayet Bey outfall, Eastern Harbour, El-Ibrahemiya, Gleem, Sidi Bishr and Mandara, during January, April, August and November 1995. the area lies between latitude 31˚ 8' and 31˚ 17' North and longitude 29˚ 47' and 30˚ East. the annual mean of chlorinity (11.69-20.5%₀), pH (7.9-8.3), reactive phosphate (0.31-2.24 μM), nitrite (0.18-1.98 μM), oxidizable organic matter (1.97-8.95 mgO₂ 1^-1), iodide (21.14-46.74 μg 1^-1) and iodate (4.61-2.04 μg 1^-1) were measured. Iodide content in water is three times higher than iodate. Iodide is positively correlated with chlorinity (r=0.65) and iodate (r=0.45), while it is negatively correlated with nitrite (r= -0.72), oxidizable organic matter (r= -0.55) and pH (r= -0.4).     

Inventories and Distribution of Radiocaesium in Arctic Marine Sediments: Influence of Biological and Physical Processes

Extensive surveys of sediment burdens of radiocaesium, specifically ¹³⁷Cs, and other radioactive contaminants in the Arctic during the 1990's, indicate that almost all anthropogenic radionuclides buried on continental shelves adjacent to Alaska are derived from global bomb fallout. the ¹³⁷Cs (half-life: 30.2y) activities observed in surface (0-4 cm) marine sediments however, vary widely, albeit much less than the expected current inventory resulting from bomb fallout at this latitude (∼100mBq cm^-2). This observed geographical variation provided the opportunity to evaluate physical and biological mechanisms that may affect caesium biogeochemistry on Arctic continental shelves. We investigated whether high biological productivity in portions of the Bering and Chukchi Seas is effective in removing dissolved radiocaesium from the water column, and whether biological production in overlying water affects total radiocaesium inventories in sediments. Based upon C/N ratios in the organic fraction of shallow sediments, we found no evidence that higher inventories or surface activities of radiocaesium are present in areas with higher deposition of particulate organic matter. Based upon stable carbon isotope ratios of organic matter in sediments, we found no evidence that terrestrial runoff contributes proportionally to higher surface activities, although terrestrial runoff may affect total inventories of the radionuclide. Radiocaesium content of surface sediments was significantly correlated with total organic carbon content of sediments and the proportion of sediments in the finest sediment fractions. Because high current flow can also be expected to influence distributions of those sedimentary parameters, we conclude that re-distribution of     

Enhanced enzymatic removal of anthracene by the mangrove soil-derived fungus, Aspergillus sydowii BPOI

• A. sydowii strain bpo1 exhibited 99.8% anthracene degradation efficiency. • Four unique metabolic products were obtained after anthracene degradation. • Ligninolytic enzymes induction played vital roles in the removal of anthracene. • Laccase played a crucial role in comparison with other enzymes induced. The present study investigated the efficiency of Aspergillus sydowii strain bpo1 (GenBank Accession Number: MK373021) in the removal of anthracene (100 mg/L). Optimal degradation efficiency (98.7%) was observed at neutral pH, temperature (30℃), biomass weight (2 g) and salinity (0.2% w/v) within 72 h. The enzyme analyses revealed 131%, 107%, and 89% induction in laccase, lignin peroxidase, and manganese peroxidase respectively during anthracene degradation. Furthermore, the degradation efficiency (99.8%) and enzyme induction were significantly enhanced with the addition of 100 mg/L of citric acid and glucose to the culture. At varying anthracene concentrations (100–500 mg/L), the degradation rate constants (k₁) peaked with increasing concentration of anthracene while the half-life (t_1/2) decreases with increase in anthracene concentration. Goodness of fit (R² = 0.976 and 0.982) was observed when the experimental data were subjected to Langmuir and Temkin models respectively which affirmed the monolayer and heterogeneous nature exhibited by A. sydwoii cells during degradation. Four distinct metabolites; anthracene-1,8,9 (2H,8aH,9aH)-trione, 2,4a-dihydronaphthalene-1,5-dione, 1,3,3a,7a-tetrahydro-2-benzofuran-4,7-dione and 2-hydroxybenzoic acid was obtained through Gas Chromatography-Mass spectrometry (GC-MS). A. sydowii exhibited promising potentials in the removal of PAHs.     

Polychlorinated Biphenyls (Pcbs) Pollution in Sea of Japan

Deep waters of the Sea of Japan and surface waters of the Pacific Coast of Honshu and the northeast Sea of Japan were analysed for polychlorinated biphenyls (PCBs) pollution. the ΣPCB concentrations in solution in the Sea of Japan (50-3000 m) were between 140 and 1230 fg dm_-3. the space-integrated surface water concentration near the Pacific coast of northern Honshu was 140 fg dm_-3and for the surface water of the Sea of Japan was 230 fg dm_-3. Based on these analyses four water masses were deduced in the Sea of Japan during the summer months. It is shown for the first time in the Sea of Japan that polychlorinated biphenyls are excellent chemical indicators of not only the anthropogenic pollution, but also water masses.     

电子垃圾拆解区土壤中典型手性PCBs分布及对映体特征

龙塘镇位于广东省清远市,是国内最大的进口电子垃圾集中处理处置地之一.通过对龙塘镇土壤中7种手性PCBs对映体浓度和对映体百分数(enantiomer fractions,EF)值的测定,发现龙塘镇土壤样品除PCB45和PCB174外,其余5种手性PCBs在土壤中均有不同程度的检出.土壤中5种目标手性PCBs(PCB91、PCB95、PCB132、PCB136和PCB149)的总浓度为145.4—286.7 ng·g^-1,这与先前文献中测定清远市土壤中手性PCBs污染水平基本一致.5种同系物的含量排序为PCB95>PCB132>PCB136>PCB149>PCB91.在距离电子垃圾拆解区10km以外的区域也检测到手性PCBs,证实这些污染物已经迁移到周边地区.土壤中手性PCB91、PCB95、PCB132、PCB136和PCB149的EFs值分别为0.519±0.005、0.4443±0.006、0.427±0.003、0.379±0.016和0.494±0.008,其中PCB149具有双向选择性.在全部检出样品中26%的PCB91、78%的PCB95、100%的PCB132、86%的PCB136和53%的PCB149具有非外消旋特征,表明该地区土壤中手性对映体选择性降解的显著性.     

Do mucilage events influence pico- and nanoplankton size and structure in the Adriatic sea?

Temporal changes in abundance and biomass of picophytoplankton, heterotrophic pico-eukaryotes, and nanoplankton assemblages were investigated along a transect crossing the Adriatic Sea, from the Italian to the Croatian coast. This 15-months (June 1999-August 2000) investigation allowed comparing microbial parameters during summer 1999 (year without mucilage) and summer 2000 when a major mucilage event occurred. Pico- and nanoplankton assemblages displayed significant differences between the 2 summer periods. The main differences can be summarized as: (i) presence of cyanobacterial blooms (up to 10⁸ cells l^-1) in summer 2000, absent in summer 1999; (ii) an increasing fraction of heterotrophic pico-eukaryotes (up to 5.0 × 10⁶ cells l^-1) and heterotrophic nanoplankton (size 2-5 µm) during mucilage event; (iii) a reduced abundance of small-sized (2-3 µm) phototrophic nanoplankton in summer 2000. Changes in community structure were signals of changes in trophic condition of the system, which resulted in a competitive advantage for small sized pico- and nanoheterotrophs. Data presented here indicated that mucilage events are associated with changes in microbial community structure and functioning in ambient water and induced the amplification of 3-step microbial food chain. The potential use of the heterotrophic pico-eukaryotes for describing alterations of the trophic pathways during mucilage events is discussed.     

Tailoring the simultaneous abatement of methanol and NOx on Sb-Ce-Zr catalysts via copper modification

● Cu addition enhances CH₃OH oxidation and alleviates its inhibitory effect on SCR. ● Cu addition improves the activation of SCR reactants in the presence of methanol. ● Damaged structure by more Cu addition decreases specific surface area and acidity. ● Excessive Cu addition would lead to the narrowing of SCR temperature window. Simultaneously removal of NO_x and VOCs over NH₃-SCR catalysts have attracted lots of attention recently. However, the presence of VOCs would have negative effect on deNO_x efficiency especially at low temperature. In this study, copper modification onto Sb_0.5CeZr₂O_x (SCZ) catalyst were performed to enhance the catalytic performance for simultaneous control of NO_x and methanol. It was obtained that copper addition could improve the low-temperature activity of both NO_x conversion and methanol oxidation, where the optimal catalyst (Cu_0.05SCZ) exhibited a deNO_x activity of 96% and a mineralization rate of 97% at 250 °C, which are around 10% higher than that of Cu free sample. The characterization results showed that copper addition could obviously enhance the redox capacity of the catalysts. As such, the inhibition effect of methanol incomplete oxidation on NO adsorption and NH₃ activation were then lessened and the conversion of surface formamide species were also accelerated, resulting in the rising of NO_x conversion at low temperature. However, excessive copper addition would damage the Sb-Ce-Zr oxides solid solution structure owing to Cu-Ce strong interactions, decreasing the surface area and acidity. Meanwhile, due to easier over-oxidation of NH₃ with more Cu addition, the temperature window for NO_x conversion would become quite narrow. These findings could provide useful guidelines for the synergistic removal of VOCs over SCR catalyst in real application.     

In situ electron-induced reduction of NOx via CNTs activated by DBD at low temperature

• An in situ electron-induced deNO_x process with CNT activated by DBD was achieved. • Carbon atoms on CNT surface were verified to be excited by plasma in DBD-CNT system. • Reactions between NO_x and excited C result in synergistic effect of DBD-CNT system. In this study, a new in situ electron-induced process is presented with carbon nanotubes (CNTs) as a reduction agent activated by dielectric barrier discharge (DBD) for nitrogen oxide (NO_x) abatement at low temperature (<407 K). Compared with a single DBD system and a DBD system with activated carbon (DBD-AC), a DBD system with carbon nanotubes (DBD-CNT) showed a significant promotion of NO_x removal efficiency and N₂ selectivity. Although the O₂ content was 10%, the NO_x conversion and N₂ selectivity in the DBD-CNT system still reached 64.9% and 81.9% at a specific input energy (SIE) of 1424 J/L, and these values decreased to 16.8%, 31.9% and 43.2%, 62.3% in the single DBD system and the DBD-AC system, respectively. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were utilized to investigate surface changes in the CNTs after activation by DBD to explore the NO_x reduction abatement mechanism of this new process. Furthermore, the outlet gas components were also observed via Fourier transform infrared spectroscopy (FTIR) to help reveal the NO_x reduction mechanism. Experimental results verified that carbon atoms excited by DBD and the structure of CNTs contributed to the synergistic activity of the DBD-CNT system. The new deNO_x process was accomplished through in situ heterogenetic reduction reactions between the NO_x and carbon atoms activated by the plasma on the CNTs. In addition, further results indicated that the new deNO_x process exhibited acceptable SO₂ tolerance and water resistance.