A comparison of two methods for the isolation of free and occluded particulate organic matter

Various methods exist for the isolation of particulate organic matter (POM), one of the soil‐organic‐matter (SOM) fractions reacting most sensitive on land‐use or soil‐management changes. A combination of density separation and ultrasonic treatment allows to isolate two types of POM: (1) free POM and (2) POM occluded in soil aggregates. POM fractions are closely linked to their biochemical function for the formation and stabilization of aggregates, therefore methods using different aggregate sizes may result in different POM fractions isolated. We evaluated two physical fractionation procedures to reveal whether they yield different POM fractions with respect to amount and composition, using grassland and arable soils with sandy‐loam to sandy–clay‐loam texture and thus low macroaggregate stability. Method I used air‐dried aggregates of <2.0 mm size and a low‐energy sonication for aggregate disruption, method II used field‐moist aggregates <6.3 mm and a high‐energy–sonication procedure for aggregate disruption. POM fractions were analyzed by elemental analysis (C, N) and CPMAS ¹³C‐NMR spectroscopy. With both methods, about similar proportions of the SOM are isolated as free or occluded POM, respectively. The free‐ and occluded‐POM fractions obtained with method I are also rather similar in C and N concentration and composition as shown by ¹³C‐NMR spectroscopy. Method II isolates a free‐ and occluded‐POM fraction with significantly different C and N concentrations. NMR spectra revealed significant differences in the chemical composition of both fractions from method II, with the occluded POM having lower amounts of O‐alkyl C and higher amounts of aryl C and alkyl C than the free POM. Due to the use of larger, field‐moist aggregates with minimized sample pretreatment, two distinctly different POM fractions are isolated with method II, likely to be more closely linked to their biochemical function for the formation and stabilization of aggregates. High‐energy sonication as in method II also disrupts small microaggregates <63 µm and releases fine intraaggregate POM. This fraction seems to be a significant component of occluded POM, that allows a differentiation between free and occluded POM in sandy soils with significant microaggregation. It can be concluded, that microaggregation in arable soils with sandy texture is responsible for the storage of a more degraded occluded POM, that conversely supports the stabilization of fine microaggregates.     

Extraction of organic compounds from airborne particulate matter

The extraction of organic compounds from airborne particulate matter, obtained by glass fiber filtration, has been studied with different solvents and has been followed as a function of time. For many compounds, almost quantitative extraction was obtained after S h. Polyaromatic hydrocarbons and polar compounds often yielded higher extraction efficiencies with methanol than with benzene. The gas chromatographic mass spectrometric determination of these compounds is somewhat simplified by a separation of the sample into neutral, acidic and basic fractions. The efficiency of this procedure was tested on a mixture of compounds representative for the actual aerosol composition. It was concluded that the basic fraction yielded poor results. The techniques for these measurements included quantitative gas chromatography with electronic integration for standard mixtures and quantitative mass chromatography for natural sample extracts.     

大型自然通风奶牛舍空气颗粒物浓度监测方法中采样间隔优化

规模化奶牛养殖产生的颗粒物会对人员和奶牛的呼吸道以及周边环境健康产生不利影响。对于奶牛舍空气颗粒物的实时连续监测,除了监测点数量和位置外,监测设备的采样间隔同样会影响监测结果的准确性。为确定合理的采样间隔,该研究采用环境物联网技术在大型自然通风奶牛舍内共计布置了17个采样点,对秋季至冬季舍内的总悬浮颗粒物（total suspended particulate, TSP）和细颗粒物（PM_2.5）浓度进行连续6个月的实时监测,计算舍内17个采样点的平均浓度（视为“真值”）。基于误差分析法,分别计算了30 min和1、2、3、6、1.2 h采样间隔下秋季和冬季的颗粒物浓度日均值,以及10、15、20、30 min和1 h采样间隔下白天、夜间与生产管理操作期间的颗粒物浓度小时均值及其与真值的相对误差（E_r）,统计了E_r在5%与10%范围内的占比情况,以66.7%作为可接受标准,确定了秋冬季节颗粒物浓度日均值和小时均值的最大可接受采样间隔。结果显示,在5%的相对误差允许范围内,秋冬季节TSP日均值的最大可接受采样间隔为2 h（秋季）和1 h（冬季）,PM_2.5为3 h（秋季）和1 h（冬季）;白天TSP小时均值的最大可接受采样间隔为20 min（秋季）和15 min（冬季）,夜间TSP为30 min（秋季）和15 min（冬季）,秋冬季节白天和夜间的PM_2.5的最大采样间隔均为30 min;当TSP和PM_2.5的最大可接受采样间隔为10 min和20 min时,测量数据可以较好地反映秋冬季节生产管理操作对舍内颗粒物浓度的影响。研究对于畜禽舍颗粒物监测中传感器采样频率的设定具有重要意义。     

Pesticide adsorptivity of aged particulate matter arising from crop residue burns

Particulates (ashes) arising from the burning of crop residues are potentially effective adsorbents for pesticides in agricultural soils. To determine the long-term adsorptive sustainability of ashes, a wheat (Triticum aestivum L.) ash was aged under environmentally relevant conditions (in CaCl(2) solution at room temperature and pH 7) in soil extract for 1 month and in a soil (1% ash) for a period of up to 12 months. The aged ash and ash-amended soil were used to sorb diuron from water. The diuron sorption was also measured in the presence of atrazine as a competing pesticide. There was no observed microbial impact on the stability of the wheat ash in soil. All isotherms with the ash were nonlinear type-I curves, suggestive of the surface adsorption. On a unit mass basis, the ash in soil extract was 600-10000 times more effective than the soil in sorbing diuron. Adsorption of dissolved soil organic matter (DOM) during aging on the ash surfaces reduced the diuron adsorption by 50-60%. Surface competition from the atrazine adsorption also reduced the ash adsorption of diuron by 10-30%. A total of 55-67% reduction in diuron sorption by the ash-amended soil was observed. Due to its high initial adsorptivity, the ash fraction of the aged ash-amended soil contributed >50% to the total diuron sorption. Thus, the wheat ash aged in the soil remained highly effective in adsorbing diuron. As crop residues are frequently burned in the field, pesticides in agricultural soils may be highly immobilized due to the presence of ashes.     

柴油机排放颗粒物中石墨烯结构分析

为了了解不同粒径的柴油机排放颗粒物中石墨烯结构,利用激光拉曼光谱仪和软X射线谱学显微光束线站分析了不同粒径的柴油机排放颗粒物中石墨烯结构和碳原子价态信息。结果表明,排放颗粒的D1峰(由无序石墨烯边缘和基底碳原子的A1g对称振动而产生的)与D2峰(无序石墨烯表面碳原子的E2g对称振动)的相对强度在3.34~4.01之间,石墨烯缺陷类型主要为边缘缺陷。随着排放颗粒粒径的增加,D1峰的半高宽分别增加了2.8和6.7 cm-1,化学异相性增加;D1峰与G峰(是理想石墨烯晶格E2g对称振动引起的)的相对强度分别降低了14.67%和27.17%,石墨化程度提高;D3峰(代表排放颗粒中的无定形碳,主要包括有机成分、碎片和官能团)的相对强度R3分别降低了13.73%和39.22%,无定形碳含量降低。石墨烯晶格内部C-C键长与粒径关系不大,晶格内部C-C键长约为0.142 nm;随着排放颗粒粒径的增加,石墨烯微晶尺寸分别增加了约0.412和0.821 nm,相邻石墨烯间距降低,排放颗粒活性增加;脂肪族C=C化学键、脂肪族C-H和羧基C=O化学键含量降低,"石墨烯性"C=C、酚类C-OH和酮类C=O化学键含量增加。该研究可为不同粒径柴油机排放颗粒形成机理的完善和排放颗粒净化装置的优化提供参考。     

Carbon and nitrogen mineralization of added particulate and macroorganic matter

Particulate organic matter (POM) is more sensitive than total SOM to changes in management practices and, accordingly, may indicate changes in soil quality. A soil incubation study was conducted to determine the effects of added POM (75 to 250 μm size fraction), or macroorganic matter (MOM, 250 to 2000 μm size fraction) on C and N mineralization and microbial C and N content. A 1 kg composite made from 16 predominantly silt loam soils was amended with 10 g of POM, MOM or MOM ground to a reduced size of 75 to 250 μm (GMOM). The MOM amendment equaled 4.55-fold and POM equaled 1.60-fold of total MOM and POM found in the composite soil. Carbon mineralization of MOM and POM after 8 weeks was approximately 9 and 4%, respectively of the total MOM and POM-C added. Reducing the size of MOM to 75 to 250 μm did not affect mineralization. Nitrogen mineralization was slightly greater in the amended soils after 8 weeks and equaled 5 to 6% of the MOM or POM-total N added. Contribution of POM to total mineralized N from soil organic matter (SOM) in the composite soil was proportional to the POM content in SOM or approximately 12%. Amended soils had 25 to 42% more biomass-C than the control soil 2 weeks after amendment application. After 8 weeks, the amended soils contained about 32% more biomass-C. This increase in biomass-C at 8 weeks accounted for approximately 2% of the added C. At 8 weeks, microbial biomass-N in GMOM-, MOM- and POM-amended soils was about 56, 46 and 14% higher, respectively, than in the control soil. These increases were approximately 8% of the MOM-N added and 2% of the POM-N added. Increases in POM resulted in increases in soil respiration and microbial biomass-C and N, which also are suggested indicators of soil quality. Therefore, POM may be a suitable soil quality indicator that provides similar information as soil respiration or microbial biomass determinations.     

柴油机燃烧甲醇/生物柴油尾气颗粒物热解特性分析

采集了甲醇/生物柴油(5%、10%、15%)混合燃料在柴油机燃烧的尾气颗粒。采用热重分析仪和切线法、Flynn-Wall-Ozawa(FWO)热解动力学方法,研究颗粒挥发及氧化规律,分析了颗粒热解特征温度和活化能。结果表明:随着甲醇掺混量的增加,颗粒中H_2O的质量分数由2.6%增加到3.5%,可溶有机物(soluble organic fraction,SOF)质量分数由26.1%增加到32.5%,SOF的质量变化速率增大,对应的峰值温度后移;在O_2氛围中,SOF挥发阶段与在N2氛围中的表现基本一致,但质量变化速率明显增大;碳烟(soot)质量减小,由70.3%减少到63.8%,soot质量变化率峰值增大;SOF析出温度变化较小,soot起始燃烧温度明显降低,由488℃降低到458℃,SOF起始燃烧温度与燃尽温度均有所降低,颗粒的热解总反应时间缩短;颗粒的热解反应活化能由140.3 k J/mol降低117.3 k J/mol,颗粒的热解性能增强,颗粒更易被氧化。研究结果可为甲醇/生物柴油燃烧颗粒的处理及柴油机颗粒捕集器(diesel particulate filter,DPF)再生提供依据。     

能量密度对低温等离子体辅助催化转化柴油机颗粒物和NOx的影响

为了研究低温等离子体辅助催化后处理技术对柴油机有害排放物的作用效果,基于介质阻挡放电理论设计了低温等离子体（NTP）发生器,研究了NTP发生器工作电压随能量密度的变化关系。以涂覆γ-Al2O3的蜂窝状陶瓷为载体,采用柠檬酸凝胶法制备了LaMnO3催化剂,建立了NTP辅助LaMnO3催化试验系统。在台架试验基础上,研究了能量密度变化对NTP辅助LaMnO3催化技术转化（颗粒物）PM和NOx的影响规律。试验结果表明：在相同频率作用下,NTP发生器的能量密度随着工作电压的升高而增加;与原机相比,NTP辅助LaMnO3催化技术作用后NO浓度显著降低,NO2浓度显著增加,NOx浓度降低;随着能量密度的增加,碳烟转化效果越明显,碳烟的不透光烟度最高降低约83%。结果表明NTP辅助LaMnO3催化技术可有效转化PM和NOx,在柴油机排气后处理领域有着广泛的研究前景。     

规模化笼养蛋鸡舍冬季氨气和颗粒物排放特征研究

畜禽养殖的氨气(NH3)和颗粒物(particulatematter,PM)排放已成为危害人畜健康,并可能造成环境风险的重大问题。该文选择北京郊区一典型规模化蛋鸡养殖舍,对典型冬季条件下蛋鸡舍的NH3和PM排放进行了连续8d的监测;并根据二氧化碳平衡原理,对NH3及PM的排放通量进行了估算。研究结果表明,蛋鸡舍出风口处NH3平均质量浓度为(4.58±3.29)mg/m3,每只鸡NH3排放通量为(32.2±12.5)mg/d。蛋鸡舍出风口处PM2.5、PM10和总悬浮颗粒物(total suspended particulates, TSP)质量浓度为(0.13±0.06)、(0.81±0.16)、(3.28±1.32)mg/m3,每只鸡PM2.5、PM10和TSP排放通量分别为(0.7±0.4)、(6.3±1.4)、(27.6±12.5)mg/d。氨气以及PM的排放均随着舍内1次/2 d的机械清粪频率呈现2 d的周期变化趋势。除清粪作业、鸡群日间活动等影响外,舍内PM2.5浓度一定程度上受舍外环境本底值影响。舍内PM2.5与PM10的比例在10.4%~20.4%之间。舍内PM2.5颗粒上所含的K+、Mg2+含量均显著高于舍外环境本底PM2.5(P0.05)。同时舍内及舍外PM2.5颗粒上解析出来的阳离子所带的电荷量均高于阴离子。研究结果可为畜禽养殖NH3和PM排放清单的编制提供基础参数;同时对畜禽舍PM的组分研究,可为后续开展二次无机气溶胶形成机理以及颗粒物源解析的研究提供支撑。     

Elements in water,suspended particulate matter and sediments of the Sava River

Purpose

River ecosystems are under pressure from several different stressors. Among these, inorganic pollutants contribute to multiple stressor situations and the overall degradation of the ecological status of the aquatic environments. The main sources of pollution include different industrial activities, untreated effluents from municipal waste waters and intensive agriculture. In the present study, water, suspended particulate matter (SPM) and sediments of the Sava River were studied in order to assess the pollution status of this river system.

Materials and methods

Sampling was performed during the first sampling campaign of the EU 7th FW funded GLOBAQUA project in September 2014, at 18 selected sampling sites along the Sava River. In 2014, floods predominated from spring to fall. Water samples were collected to determine the total element concentrations, the dissolved (0.45 μm) fraction and element concentrations in SPM. In order to assure comparative results with other river basins, the fraction below 63 μm was analysed in sediments. The extent of pollution was estimated by determination of the total element concentrations and by the identification of the most hazardous highly mobile element fractions (extraction 0.11 mol L^?1 acetic acid) and anthropogenic inputs of elements to sediments (normalization to aluminium (Al) concentration). Concentrations of selected elements were determined by inductively coupled plasma mass spectrometry (ICP-MS).

Results and discussion

Since during sampling campaign the water level was extremely high, water samples contained high amounts of SPM (in general between 80 and 100 mg L^?1). The data of chemical analysis revealed that concentrations of elements in water, SPM and sediments in general increase along the Sava River from its origin to the confluence with the Danube River. Elevated concentrations of chromium (Cr) and nickel (Ni) in SPM and sediments were observed at industrially exposed sites. Concentrations of Cr and Ni in sediments were up to 320 and 250 mg kg^?1, respectively. Nevertheless, these elements were present in sparingly soluble forms and hence did not represent an environmental threat. Phosphorus (P) was found in elevated concentrations (up to 1500 mg kg^?1) at regions with intensive agricultural activities and cities with dense population.

Conclusions

With respect to element concentrations, the pollution of the Sava River is similar to other moderately polluted European rivers. The data from the present study are beneficial for the water management authorities and can contribute to sustainable utilization, management and protection of the Sava River water resources.

     

Recovering decomposing plant residues from the particulate soil organic matter fraction: size versus density separation

 A detailed size separation of particulate organic matter (POM) from soils amended with straw from Hordeum vulgare or Vicia sativa revealed that the loss of C during the first 56 days of incubation mainly occurred from particles >2,000 μm, without a concomitant reduction in the size of these large particles. Preliminary studies of POM from non-amended soil had shown that the stable heavy (>1.4 g cm^–3) POM fraction was mainly (>80%) composed of particles <400 μm, whereas the light fraction was dominated by larger particles (>80%). Therefore we decided to compare the POM <1.4 g cm³ with POM >400 μm. There was a very close relationship between POM>400 μm and POM <1.4 g cm^–3 with regard to amounts of C and N, as well as the appearance of these fractions under the microscope. Similarly there was a close relationship between changes in the C content of the POM fractions and the CO₂ respired, and this was also the case when comparing changes in POM-N with net N mineralization. This indicated that the biological activity during decomposition was actually localized in the POM. Due to the lighter workload and lower expenditure for reagents in connection with size separation of POM, we recommend the size separation procedure in connection with studies of residue decomposition in arable systems. Received: 23 May 2000     

Investigation of the coagulation mechanism of the suspended particulate matter in coastal waters

The granulometry of the suspended matter in various coastal waters collected around the Patras city in Greece, together with the average particle diameters, have been determined during 12 mo by means of a simple, quick, inexpensive and relatively accurate photosedimentometer. The particle size distributions were found to be self-preserving and independent of time, hydrologic regime, nature and amount of particulate materials and particle mobility. The experimental results show that the Brownian diffusion is the factor dominant in the flocculation processes in coastal waters. The flocculation processes of the suspended particles taking place when river water meets sea water were also investigated.     

Sorption and desorption of non-ionic herbicides onto particulate organic matter from surface soils under different land uses

In vegetative filter strips used to intercept pesticides present in run‐off, particulate organic matter derived from the vegetation plays an important function in pesticide sorption processes, because it accumulates at the soil surface and quickly responds to changes in land use. Two herbicides with contrasted properties: isoproturon, moderately hydrophobic (log K_ow= 2.5), diflufenican, strongly hydrophobic (log K_ow= 4.9), and isopropylaniline, a metabolite of isoproturon, were used to characterize the sorption and desorption properties of POM originating from soils under three different land uses: a cropped plot under conventional wheat/maize rotation, an adjacent 10‐year‐old grassed strip and a nearby 80‐year‐old oak/chestnut forest. Chemical structural composition information obtained from solid‐state ¹³C CPMAS NMR and estimation of hydrophobicity from contact angle measurements were used to explain the different sorption capacities of POM according to their size and origins. Sorption of isoproturon and diflufenican increased with hydrophobicity of POM, which was greater in the forest soil. Aromaticity of POM was positively correlated to sorption coefficients (K_oc). Desorption of the more hydrophobic compounds, diflufenican and isopropylaniline was weak for all POM fractions, regardless of their origin and size. On the other hand, desorption of isoproturon depended on land use and POM characteristics. The sorption capacities of POM were not only controlled by their chemical composition, but also by their size, due to a greater number of sorptive sites related to a greater surface area with decreasing particle‐size.     

棉秆燃烧过程中的颗粒物排放特性

该文利用滴管炉结合DEKATI低压撞击采样器,研究燃烧温度和原料粒径对棉秆燃烧过程中颗粒物排放特性的影响,并结合扫描电镜和X射线光谱分析仪探讨了颗粒物的微观结构和元素组成.结果表明PM1排放量随燃烧温度升高而显著降低,从68.90 mg/m3降低至14.02 mg/m3;颗粒物总排放量从75.41 mg/m3降低至16.30 mg/m3;颗粒物分布峰值从0.609μm附近移至0.261μm附近;原料粒径减小使得PM1排放量下降,从39.84 mg/m3降低23.06 mg/m3,而PM1-10排放量增加,从5.18 mg/m3增至8.38 mg/m3.分析表明细颗粒物(0.028~0.261μm)主要由K、Cl及少量S元素组成,形成途径主要为碱金属化合物如KCl、KOH及K2SO4等的蒸发-凝集作用,并呈现较规则的微观结构,存在形式主要为KCl;粗颗粒物(1.590~9.860μm)主要由Ca、Mg及少量Si、P组成,主要通过大颗粒的破碎或富Ca、Mg和Si颗粒物的异质凝结转化形成,多呈较规则的球形结构;中间段颗粒物(0.261~1.590μm)属于过渡段,介于细颗粒物和粗颗粒物之间,微观结构较为复杂.     

Dry deposition loading of Lake Michigan by airborne particulate matter

A transport model as a function of particle size is presented which couples Chicago area meteorological data through the mixed layer with laboratory and field data on water surface dry deposition. The model is used to (a) estimate a minimum mass transfer efficiency by dry deposition from the Chicago area to Lake Michigan, (b) compare this minimum with the maximum wet deposition likely, and (c) estimate the transfer efficiency of trace metals. Dry deposition is found to cause 15% or more mass transfer efficiency of aerosols to the Lake. This value is considered to be equal to or greater than the efficiency of precipitation scavenging mass transfer. However, dry deposition as a function of particle size is such that the transfer of trace metals by this mechanism appears to be a few percent or less. Consequently, precipitation scavenging appears to be the dominant mechanism for trace metal transfer to Lake Michigan.     

柴油机排放颗粒物的热重特性分析

为了解不同粒径颗粒物在特定氛围下的氧化特性,该文利用MOUDI采样器收集到的柴油机颗粒物,在纯N2及纯O2环境下,对0.18～0.32、0.32～0.56、0.56～1.00和1.00～1.80 μm 4个粒径级颗粒分别进行热重分析试验。结果表明,随着粒径级的增大,颗粒物中水分和SOF（soluble organic fraction）的含量下降,而干碳烟（soot）和无机盐的含量增加。在纯N2氛围下,颗粒在SOF挥发阶段随着颗粒物粒径级减小,其SOF含量和失重峰值速率随之增加;但在soot热解阶段不同粒径级的失重速率趋同。程序升温终了时,各粒径级颗粒的热重曲线在纯N2氛围下缓滞停在不同位置,而在纯O2氛围下则渐趋归一。随着颗粒物粒径级的减小,热重曲线呈下降趋势,颗粒越细则越易升温（氧化）失重;而在纯O2氛围下,各粒径级在SOF挥发阶段表现出与纯N2氛围下一致的规律但失重速率峰值明显增加。在soot热解阶段,随着颗粒物粒度减小,比表面积增加使其吸附氧的能力增加,发生化学反应的活性增大,颗粒氧化的起燃温度降低,且起燃时刻对应的失重速率增加;各粒径级颗粒物的失重速率峰值出现在600～640℃之间,随着颗粒物粒径增大其soot所占含量随之增多,热解失重速率峰值亦显著增加。研究结果可为颗粒物处理的技术措施提供基础物性数据,有助于推动颗粒物处理装置的改进和优化。