城市土壤中黑碳的特征與溯源及其環(huán)境意義
發(fā)布時間：2018-07-29 08:49
【摘要】：本論文以鞍山城市土壤為研究對象,對城市土壤中黑碳的濃度、空間分布以及溯源等進行了研究。研究采集115個城市表土和4個土壤剖面樣本,利用化學(xué)氧化法測定城市土壤中的黑碳(BC)和總碳(TC)濃度,并分析了它們的空間分布規(guī)律和來源。結(jié)果表明鞍山城市表土中黑碳的濃度介于1.86～346.46g/kg之間,平均濃度為33.86g/kg,黑碳占土壤中總碳比例的平均值為75.73%。土壤剖面中BC和TC的濃度隨著深度的增加而減少,而BC/TC比值隨剖面深度的變化不明顯。城市土壤BC濃度的空間分布圖表明,高濃度的黑碳區(qū)位于城市北部,系該市鋼鐵生產(chǎn)企業(yè)分布區(qū)。表土中BC的富集系數(shù)(EF)介于0.28和37.23之間,平均值為5.11,表明城市表層土壤中BC呈中等或嚴重的累積。土壤顆粒中BC的粒級分布表明,BC的分布系數(shù)(DF)以1000-500μm粒級最高,50-2μm粒級最低。而250-50μm和50-2μm這兩級BC的質(zhì)量負荷系數(shù)(GSF)占76.2%,表明BC容易在這兩級土壤粒級中累積。土壤中BC和重金屬負荷污染指數(shù)(PLI)之間具有很強的相關(guān)性,表明土壤中BC和重金屬具有相同的來源。土壤中BC/TC比在0.45～0.97之間,平均值為0.75。BC/TC的比值可以用來識別BC的來源。鋼鐵工業(yè)區(qū)采集的土壤樣品中,BC/TC比值的平均值為0.88,表明BC主要來源于煤炭的燃燒。土壤中BC濃度和BC/TC比值可以反映城市土壤中人類活動的影響程度和污染源,可作為指示土壤中人為污染的指標。黑碳(BC)是參與許多地質(zhì)和環(huán)境過程的一種關(guān)鍵碳。利用元素分析、掃描電子顯微鏡和能散x射線能譜(SEM/EDS)、傅里葉變換紅外光譜(FTIR)、熱重分析(TGA)、X射線衍射(XRD)和穩(wěn)定碳同位素(δ13C)等方法對城市土壤中BC的化學(xué)成分、形貌、分子結(jié)構(gòu)和碳穩(wěn)定同位素進行了研究。元素分析結(jié)果表明,黑碳中碳元素含量平均超過70%,H/C和O/C摩爾原子比的平均值分別為0.73和0.18。BC顆粒的顯微圖像顯示了 BC的不同形態(tài),主要有多孔球形,不規(guī)則多孔碎塊以及塊狀顆粒。其中,多孔球形BC顆粒的O/C摩爾原子比范圍在0.04和0.37之間,表明這些BC顆粒主要來源于煤炭的燃燒。BC的XRD結(jié)果顯示,BC結(jié)合的礦物主要有赤鐵礦(Fe2O3),高嶺石(Al2Si2O5(OH)4),石英(SiO2)和方解石(CaCO3)。傅里葉紅外光譜顯示BC的主要化學(xué)鍵為:3400cm-1的O-H鍵,2920 cm-1的 C=H 鍵,1600 cm-1的 C=C 鍵,1230 cm-1 的 C=O 鍵以及 1070 cm-1 的 C=O 鍵。BC的穩(wěn)定碳同位素(δ13C)值范圍為-24.48‰～-23.18‰,平均值為-23.79‰±0.39。BC中O/C摩爾原子比和碳同位素(δ13C)表明,它們主要來自化石燃料燃燒。因此,城市土壤中黑碳的濃度可以記錄大氣污染的歷史,可作為區(qū)分城市環(huán)境污染源指標。圍繞BC與重金屬的相關(guān)性,研究了城市土壤黑碳中的重金屬分布、遷移性和潛在環(huán)境風(fēng)險。以10個代表性土壤的黑碳顆粒為材料,按照顆粒大小將BC分為三級,測定了重金屬(Cd、Cr、Cu、Pb、Zn和Ni)的濃度,并利用毒性淋溶試驗(TCLP)和EDTA浸提法評價了黑碳中重金屬的生物有效性和淋溶性。結(jié)果表明,黑碳中重金屬的濃度隨著顆粒粒徑的減小而增加,尤其以50μm粒徑的BC中重金屬濃度最高,重金屬的富集系數(shù)(EFs)隨著黑碳粒級的減小而增大,尤其以Cd和Zn富集最為嚴重。表明細顆粒黑碳積累較多的重金屬,具有較大的重金屬污染風(fēng)險。細粒黑碳顆粒中重金屬的分布系數(shù)(DFs)為Zn(3.22)Cu(2.84)Pb(2.61)Cr(2.19)Cd(2.05)。同時,根據(jù) TCLP 和 EDTA 的淋溶性測定表明Cd和Zn比其他重金屬有較高的淋溶性和生物有效性。根據(jù)上述研究,可以認為細黑碳顆粒是潛在有毒金屬的重要來源,而不同粒級黑碳中重金屬含量的變化在環(huán)境評估中也應(yīng)該被考慮。為了進一步理解不同生物質(zhì)燃燒源BC的特性,采集了21種不同的生物質(zhì)原料,開展了不同熱解溫度和時間條件下生物質(zhì)燃燒源BC特性的研究。生物質(zhì)燃燒源BC特性的表征包括元素分析(C、H、O、N)、灰分、產(chǎn)量、pH值、EC、總碳、陽離子交換量、官能團(酸、堿、酚和羧基)和表面負電荷等。結(jié)果表明,黑碳中C含量、pH值和EC隨著熱解溫度的增加而增加;而H、O、N含量、總碳(TC)、陽離子交換量(CEC)、黑碳產(chǎn)率和表面負電荷則隨著裂解溫度下降而降低。含氧官能團中,酸性官能團隨著熱解溫度的升高而增加,而其他三種官能團則隨著熱解溫度的增加而降低。對黑碳的基本性質(zhì)進行相關(guān)性分析、主成分分析和聚類分析,結(jié)果發(fā)現(xiàn)黑碳的pH值同總碳含量,灰分含量,EC,羧基以及表面負電荷呈顯著相關(guān);主成分分析表明黑碳的性質(zhì)可以分成四個主成分。根據(jù)聚類分析,21種黑碳可以分為四類。研究結(jié)果表明,生物質(zhì)燃燒源黑碳的理化性質(zhì)在很大程度上依賴于原料,黑碳理化性質(zhì)的差異有助于理解土壤中BC的來源。城市土壤中黑碳的來源很廣泛,我們研究了六種黑碳顆粒的基本性質(zhì)以及黑碳與土壤礦物的相互作用。其中,利用元素分析、SEM/EDS、FTIR、XRD等對不同來源黑碳的基本性質(zhì)進行研究。結(jié)果表明,除了污泥黑碳的碳含量較低,大約36%外,其余五種黑碳的碳含量均大約50%。黑碳的傅里葉紅外光譜顯示主要化學(xué)鍵的位置,其中,具體為3400cm-1的O-H鍵,1600cm-1的C=C鍵,1230 cm-1的C=O鍵以及1070 cm-1的C=O鍵。XRD分析表明,六種黑碳顆粒的礦物組成差異明顯,尤其ASBC樣品更為特殊,僅它含有赤鐵礦以及2920 cm-1處的C=H鍵。SEM圖像顯示不同來源的黑碳顆粒具有不同的形態(tài),其中生物黑碳孔隙規(guī)律,邊緣鋒利,幾乎沒有球形結(jié)構(gòu),而煤質(zhì)黑碳呈孔隙不規(guī)律,多孔球形或者塊狀結(jié)構(gòu)。SEM觀察發(fā)現(xiàn)黑碳顆粒和土壤礦物的相互作用方式有表面接觸,表面嵌入以及內(nèi)部結(jié)合。土壤中黑碳與礦物的相互作用是理解BC在環(huán)境中的持久性、環(huán)境行為和對土壤性質(zhì)影響的重要內(nèi)容。
[Abstract]:In this paper, the concentration, spatial distribution and traceability of black carbon in urban soil were studied in Anshan city soil. 115 urban topsoil and 4 soil profile samples were collected, and chemical oxidation method was used to determine the concentration of black carbon (BC) and total carbon (TC) in urban soil, and their spatial distribution and distribution were analyzed. The results show that the concentration of black carbon in the urban topsoil of Anshan is between 1.86 and 346.46g/kg, the average concentration is 33.86g/kg, the average ratio of black carbon to the total carbon in the soil decreases with the depth of BC and TC in the 75.73%. soil profile, but the BC/TC ratio is not obvious with the depth of the section. The space of BC concentration in urban soil is in space. The distribution map shows that the high concentration of black carbon area is located in the northern part of the city. The concentration coefficient (EF) of BC in the topsoil is between 0.28 and 37.23, with an average of 5.11, indicating that the BC in the surface soil of the city is medium or serious. The distribution of BC in the soil particles indicates that the BC distribution coefficient (DF) is 1000-500 mu m particles. At the highest level, the grain level of 50-2 mu m is the lowest. The mass load coefficient (GSF) of 250-50 m and 50-2 micron BC (GSF) accounts for 76.2%, indicating that BC is easy to accumulate in the grain grade of the two grade soil. The BC and heavy metal load pollution index (PLI) in the soil have a strong correlation, indicating that the soil BC and heavy metals have the same source. The BC/TC ratio in the soil is 0.45. To 0.97, the ratio of the average value of 0.75.BC/TC can be used to identify the source of BC. The average value of the BC/TC ratio in the soil samples collected in the iron and steel industrial area is 0.88, indicating that the BC mainly originates from the combustion of coal. The BC concentration and BC/TC ratio in the soil can reflect the degree of influence of human activity in the urban soil and the source of pollution, which can be used as an indication. Black carbon (BC) is a key carbon that participates in many geological and environmental processes. Using elemental analysis, scanning electron microscopy and energy dispersive X ray spectroscopy (SEM/EDS), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X ray diffraction (XRD) and stable carbon isotope (delta 13C), and other methods for BC in urban soil Chemical composition, morphology, molecular structure and carbon stable isotopes have been studied. Elemental analysis shows that the average content of carbon in black carbon is more than 70%, the average value of H/C and O/C molar ratio is 0.73 and 0.18.BC particles, respectively, showing different shapes of BC, which are mainly porous, irregular, porous and lumpy. Among them, the O/C molar ratio range of the porous spherical BC particles is between 0.04 and 0.37, indicating that these BC particles are mainly derived from the XRD results of coal combustion.BC, and that the BC binding minerals are mainly hematite (Fe2O3), kaolinite (Al2Si2O5 (OH) 4), quartz (SiO2) and calcite (CaCO3). Fourier infrared spectroscopy shows the main chemistry of BC. The key is: the O-H key of 3400cm-1, the C=H key of 2920 cm-1, the C=C key of the 1600 cm-1, the C=O key of 1230 cm-1, and the.BC stable carbon isotope (delta 13C) of 1070 cm-1 C=O key range from per thousand to per thousand, and the average value is shown by the molar ratio of molar atoms and carbon isotopes (delta), which are mainly from the combustion of fossil fuels. Therefore, the concentration of black carbon in urban soil can record the history of atmospheric pollution and can be used as an indicator of urban environmental pollution. Around the correlation between BC and heavy metals, the distribution, mobility and potential environmental risk of heavy metals in urban soil black carbon are studied. The black carbon particles in 10 representative soils are used as the material and BC according to the size of the particles. The concentration of heavy metals (Cd, Cr, Cu, Pb, Zn and Ni) was measured, and the bioavailability and leaching of heavy metals in black carbon were evaluated by toxic leaching test (TCLP) and EDTA leaching. The results showed that the concentration of heavy metals in black carbon was increased with the decrease of particle size, especially the heavy metal concentration in BC of 50 micron diameter. The concentration coefficient (EFs) of metal increases with the decrease of the black carbon particle size, especially in Cd and Zn. It shows that the heavy metals with more heavy black carbon accumulation have greater heavy metal pollution risk. The distribution coefficient of heavy metals in fine black carbon particles (DFs) is Zn (3.22) Cu (2.84) Pb (2.61) Cr (2.19) Cd (2.05). At the same time, it is based on TCLP and E. The leaching of DTA shows that Cd and Zn have higher leaching and bioavailability than other heavy metals. According to these studies, it is considered that fine black carbon particles are an important source of potential toxic metals, and the changes of heavy metals in different granular black carbon should be considered in environmental assessment. In order to further understand different biomass, the different biomass can be further understood. The characteristics of the combustion source BC were collected and 21 different biomass materials were collected. The BC characteristics of the biomass combustion source were carried out under different pyrolysis temperatures and time conditions. The characterization of the BC characteristics of the biomass combustion source included element analysis (C, H, O, N), ash, yield, pH, EC, total carbon, cation exchange, functional group (acid, alkali, phenol and carboxyl) and surface negative electricity. The results show that C content, pH value and EC in black carbon increase with the increase of pyrolysis temperature, while H, O, N content, total carbon (TC), cation exchange (CEC), black carbon yield and surface negative charge decrease with the decrease of pyrolysis temperature. In oxygen functional groups, the acidic group increases with the increase of pyrolysis temperature, while the other three functional groups The correlation analysis of the basic properties of black carbon, principal component analysis and cluster analysis showed that the pH value of black carbon was significantly correlated with the total carbon content, ash content, EC, carboxyl and surface negative charges, and the principal component analysis showed that the properties of black carbon could be divided into four main components. According to cluster analysis, 2 1 kinds of black carbon can be divided into four types. The results show that the physical and chemical properties of black carbon are largely dependent on the raw materials, the differences in physical and chemical properties of black carbon are helpful to understand the source of BC in the soil. The sources of black carbon in urban soil are very wide, and we have studied the basic properties of six kinds of black carbon particles and the black carbon and soil minerals. The basic properties of black carbon from different sources were studied by element analysis, SEM/EDS, FTIR, XRD and so on. The results showed that, in addition to the low carbon content of the sludge black carbon, about 36% outside, the other five kinds of black carbon content of about 50%. black carbon showed the position of the main chemical bonds in the Fourier infrared spectrum of the black carbon, which was specifically 3400cm The O-H key of -1, the C=C bond of 1600cm-1, the C=O key of 1230 cm-1 and the C=O bond.XRD analysis of the 1070 cm-1 show that the mineral composition of the six black carbon particles is distinct, especially the ASBC sample is more special. Only it contains hematite and the C=H key of 2920 cm-1 shows the different forms of black carbon particles from different sources, of which the biological black carbon pores are found. There is a regular gap, edge sharp, almost no spherical structure, but coal black carbon is irregular in pore, porous spherical or massive structure.SEM observation found that the interaction of black carbon particles and soil minerals has surface contact, surface embedding and internal binding. The interaction of black carbon and mineral in soil is to understand the persistence of BC in the environment, Environmental behavior and its impact on soil properties are important.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：S153
本文編號：2152142
[Abstract]:In this paper, the concentration, spatial distribution and traceability of black carbon in urban soil were studied in Anshan city soil. 115 urban topsoil and 4 soil profile samples were collected, and chemical oxidation method was used to determine the concentration of black carbon (BC) and total carbon (TC) in urban soil, and their spatial distribution and distribution were analyzed. The results show that the concentration of black carbon in the urban topsoil of Anshan is between 1.86 and 346.46g/kg, the average concentration is 33.86g/kg, the average ratio of black carbon to the total carbon in the soil decreases with the depth of BC and TC in the 75.73%. soil profile, but the BC/TC ratio is not obvious with the depth of the section. The space of BC concentration in urban soil is in space. The distribution map shows that the high concentration of black carbon area is located in the northern part of the city. The concentration coefficient (EF) of BC in the topsoil is between 0.28 and 37.23, with an average of 5.11, indicating that the BC in the surface soil of the city is medium or serious. The distribution of BC in the soil particles indicates that the BC distribution coefficient (DF) is 1000-500 mu m particles. At the highest level, the grain level of 50-2 mu m is the lowest. The mass load coefficient (GSF) of 250-50 m and 50-2 micron BC (GSF) accounts for 76.2%, indicating that BC is easy to accumulate in the grain grade of the two grade soil. The BC and heavy metal load pollution index (PLI) in the soil have a strong correlation, indicating that the soil BC and heavy metals have the same source. The BC/TC ratio in the soil is 0.45. To 0.97, the ratio of the average value of 0.75.BC/TC can be used to identify the source of BC. The average value of the BC/TC ratio in the soil samples collected in the iron and steel industrial area is 0.88, indicating that the BC mainly originates from the combustion of coal. The BC concentration and BC/TC ratio in the soil can reflect the degree of influence of human activity in the urban soil and the source of pollution, which can be used as an indication. Black carbon (BC) is a key carbon that participates in many geological and environmental processes. Using elemental analysis, scanning electron microscopy and energy dispersive X ray spectroscopy (SEM/EDS), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X ray diffraction (XRD) and stable carbon isotope (delta 13C), and other methods for BC in urban soil Chemical composition, morphology, molecular structure and carbon stable isotopes have been studied. Elemental analysis shows that the average content of carbon in black carbon is more than 70%, the average value of H/C and O/C molar ratio is 0.73 and 0.18.BC particles, respectively, showing different shapes of BC, which are mainly porous, irregular, porous and lumpy. Among them, the O/C molar ratio range of the porous spherical BC particles is between 0.04 and 0.37, indicating that these BC particles are mainly derived from the XRD results of coal combustion.BC, and that the BC binding minerals are mainly hematite (Fe2O3), kaolinite (Al2Si2O5 (OH) 4), quartz (SiO2) and calcite (CaCO3). Fourier infrared spectroscopy shows the main chemistry of BC. The key is: the O-H key of 3400cm-1, the C=H key of 2920 cm-1, the C=C key of the 1600 cm-1, the C=O key of 1230 cm-1, and the.BC stable carbon isotope (delta 13C) of 1070 cm-1 C=O key range from per thousand to per thousand, and the average value is shown by the molar ratio of molar atoms and carbon isotopes (delta), which are mainly from the combustion of fossil fuels. Therefore, the concentration of black carbon in urban soil can record the history of atmospheric pollution and can be used as an indicator of urban environmental pollution. Around the correlation between BC and heavy metals, the distribution, mobility and potential environmental risk of heavy metals in urban soil black carbon are studied. The black carbon particles in 10 representative soils are used as the material and BC according to the size of the particles. The concentration of heavy metals (Cd, Cr, Cu, Pb, Zn and Ni) was measured, and the bioavailability and leaching of heavy metals in black carbon were evaluated by toxic leaching test (TCLP) and EDTA leaching. The results showed that the concentration of heavy metals in black carbon was increased with the decrease of particle size, especially the heavy metal concentration in BC of 50 micron diameter. The concentration coefficient (EFs) of metal increases with the decrease of the black carbon particle size, especially in Cd and Zn. It shows that the heavy metals with more heavy black carbon accumulation have greater heavy metal pollution risk. The distribution coefficient of heavy metals in fine black carbon particles (DFs) is Zn (3.22) Cu (2.84) Pb (2.61) Cr (2.19) Cd (2.05). At the same time, it is based on TCLP and E. The leaching of DTA shows that Cd and Zn have higher leaching and bioavailability than other heavy metals. According to these studies, it is considered that fine black carbon particles are an important source of potential toxic metals, and the changes of heavy metals in different granular black carbon should be considered in environmental assessment. In order to further understand different biomass, the different biomass can be further understood. The characteristics of the combustion source BC were collected and 21 different biomass materials were collected. The BC characteristics of the biomass combustion source were carried out under different pyrolysis temperatures and time conditions. The characterization of the BC characteristics of the biomass combustion source included element analysis (C, H, O, N), ash, yield, pH, EC, total carbon, cation exchange, functional group (acid, alkali, phenol and carboxyl) and surface negative electricity. The results show that C content, pH value and EC in black carbon increase with the increase of pyrolysis temperature, while H, O, N content, total carbon (TC), cation exchange (CEC), black carbon yield and surface negative charge decrease with the decrease of pyrolysis temperature. In oxygen functional groups, the acidic group increases with the increase of pyrolysis temperature, while the other three functional groups The correlation analysis of the basic properties of black carbon, principal component analysis and cluster analysis showed that the pH value of black carbon was significantly correlated with the total carbon content, ash content, EC, carboxyl and surface negative charges, and the principal component analysis showed that the properties of black carbon could be divided into four main components. According to cluster analysis, 2 1 kinds of black carbon can be divided into four types. The results show that the physical and chemical properties of black carbon are largely dependent on the raw materials, the differences in physical and chemical properties of black carbon are helpful to understand the source of BC in the soil. The sources of black carbon in urban soil are very wide, and we have studied the basic properties of six kinds of black carbon particles and the black carbon and soil minerals. The basic properties of black carbon from different sources were studied by element analysis, SEM/EDS, FTIR, XRD and so on. The results showed that, in addition to the low carbon content of the sludge black carbon, about 36% outside, the other five kinds of black carbon content of about 50%. black carbon showed the position of the main chemical bonds in the Fourier infrared spectrum of the black carbon, which was specifically 3400cm The O-H key of -1, the C=C bond of 1600cm-1, the C=O key of 1230 cm-1 and the C=O bond.XRD analysis of the 1070 cm-1 show that the mineral composition of the six black carbon particles is distinct, especially the ASBC sample is more special. Only it contains hematite and the C=H key of 2920 cm-1 shows the different forms of black carbon particles from different sources, of which the biological black carbon pores are found. There is a regular gap, edge sharp, almost no spherical structure, but coal black carbon is irregular in pore, porous spherical or massive structure.SEM observation found that the interaction of black carbon particles and soil minerals has surface contact, surface embedding and internal binding. The interaction of black carbon and mineral in soil is to understand the persistence of BC in the environment, Environmental behavior and its impact on soil properties are important.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：S153
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