臺灣博碩士論文加值系統

台灣有些農田受重金屬污染，農耕中施入之磷肥可能會影響重金屬移動的宿命。許多學者提出重金屬連續萃取法 (sequential chemical extractions, SCE)研究重金屬存在型態大多忽略和磷酸鹽之相關性，本研究擬提出適當的連續萃取步驟，探討中性及鹼性污染土壤中重金屬與磷存在型態的分佈及其相關性，並探討用鹽酸清洗此等土壤時，其可能移除重金屬之型態及部份植物養分成份被移除的程度。
試驗土壤採自受重金屬污染的農田，有一中性的彰化市荊桐段土壤(Soil A)與兩個污染程度不同的鹼性高雄縣海埔段土壤(較高污染程度之Soil B1、較低污染程度之Soil B2)。本試驗共分三部分：第一部分利用常用於分析有效性磷的方法，測定同時萃取的磷與重金屬含量。第二部分依試驗土壤的特性修改SCE法，將重金屬型態區分為：交換及碳酸鹽結合型態(EC)、醋酸萃取態(AE)、無定型鐵錳氧化物結合型態(AmFe)、結晶型鐵錳氧化物結合型態(CyFe)、有機物結合型態(OM)及殘留物型態(Res)。第三部分以土液比(S/L)較低的方式加入不同濃度的鹽酸，模擬重金屬污染土的酸洗復育法，壤土之S/L為1:2 (w/v)，砂質土之S/L為1:1 (w/v)，洗出液以ICP-AES分析P、Fe、Mn、Al、Cu、Zn、Cd、Cr、Ni、Pb、K、Ca、及Mg的濃度。
試驗結果顯示，在中性土壤利用Olsen試劑僅能萃取出少量重金屬，推測磷與此土壤之重金屬結合而存在於可交換部份的比例很低；在鹼性土壤，Olsen試劑能萃取出大量的Pb(47.4%)、Cd(10.8%)及Cu(10.0%)，故Pb、Cd及Cu與磷酸根的結合可能會輕微的吸附於土壤表面，故容易以交換性的試劑抽出。
在SCE試驗中，鹼性土壤達污染之重金屬主要存在於EC型態，而未污染之重金屬主要存在於AmFe型態。中性土壤達污染之重金屬以AmFe型態的比例為最高，EC型態次之，CyFe型態再次之，未達污染之重金屬則CyFe抽出型態最高。抽出與鐵錳氧化物結合型態重金屬的同時有大量的磷被抽出，且在磷含量高的土壤中，重金屬的型態分佈與磷的抽出量有顯著的相關性，故在探討重金屬型態時重金屬與磷的結合型態是不容忽視。在酸洗試驗中重金屬被酸溶出的效果符合其型態分佈，主要抽出EC型態，與無定型鐵錳氧化物結合的重金屬有少部份會在高濃度鹽酸酸洗時被釋放。在Pb及Cd高污染的土壤中(Soil B1)，當酸洗液濃度提高時Pb與Cd的抽出量反而有下降的趨勢，顯示在酸洗過程中重金屬可能與磷產生再沉澱的現象。用鹽酸移除重金屬之同時有大量的Ca被溶出（中性土壤大於42％; 鹼性土壤大於63%），而K與Mg的抽出率較低(皆低於總量的10%)。在決定酸洗液的濃度時若能同時考慮養分元素的抽出情況則有利於土壤復育後肥力的管理。

There are some agricultural lands polluted by heavy metals in Taiwan .The over use of phosphate fertilizer may affect the fate of the heavy metals in soil, such as the precipitation of heavy metals as phosphates. The purposes of this study were to develop a sequential chemical extractions (SCE) scheme suitable to fractionate the forms of heavy metals associated with phosphate in neutral and alkali soils contaminated with heavy metals. In order to investigate the forms and fractions of heavy metals and nutrients removed as heavy metals polluted soil washed with HCl solution in remediation process.
In this study, Ching-Tung neutral soil (Soil A) in Changhua city and two Hai-pu alkali soils in Kaohsiung county, (Soil B1, high polluted; Soil B2, media polluted) were collected, air dried, and passed through a 2 mm sieve. This was conducted in three parts: First, contaminated soils were extracted by the common available phosphate analysis methods to analyse both of phosphorus and heavy metals to know how much fraction of heavy metals combined. Second, a new SCE scheme was set in this study, the sequential fractionations were exchangeable and carbonate-bound(EC), acid-extractable (AE), amorphous Fe/Mn oxyhydroxide (AmFe), crystalline Fe/Mn oxyhydroxide (CyFe), organic matter (OM) and residual (Res). Third, soils were washed with HCl solution by low soil/liquid ratio(S/L), Soil A was 1:2(w/v), and Soil B1 and B2 were 1:1(w/v).The concentration of the heavy metals, phosphorus and other nutrient elements were measure by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES).
The results show that the portion of heavy metals combined with phosphate in exchangeable fraction is very low. In alkaline contaminated soils, the polluted metals were mainly remained in the EC fraction, while the unpolluted metals in the AmFe fraction. In neutral contaminated soil, the polluted metals were distributed in the order : AmFe >EC>CyFe, while unpolluted metals were remained mainly in the AmFe fraction. The phosphorus was mainly remained in the AmFe and CyFe fractions. The correlations between the concentrations of phosphorus and heavy metals in different fractions extracted by this SCE were significant in soil A. In study on fate of heavy metals in agricultural land(and shall take phosphorus in account, especially the presence of phosphorus at high levels.) In acid-washing study, part of the AmFe form of heavy metals could be extracted by concentrated HCl solutions, but it was hardly to destroy the crystalline Fe/Mn oxyhydroxide so that the heavy metals with CyFe form could not be released by the HCl solution. In the high Pb and Cd contaminated soil (Soil B1), the amount of Pb and Cd in acid leachates did not show the increase with increasing the strength acid. This may indicate that a reprecipitation with phosphate happened during prolonging the extraction period. In the acid washing, a large amount of Ca (neutral soil>42%; alkali soils>63%) was removed, but the part of Mg and K removed were quite low (i.e., less the 10% of the total content). The informations were be worth for remediation of heavy metal polluted soil washed by HCl in fertility management.

摘要 i
Abstract iii
目錄 v
表次 vii
圖次 viii
附錄 x
壹、前言 1
貳、前人研究 2
一、重金屬在土壤的分佈 2
二、重金屬連續萃取法 3
三、土壤中磷酸鹽的型態 6
四、磷酸鹽與重金屬的結合 7
五、 本研究擬定SCE之萃取藥劑的選擇 8
参、材料與方法 10
一、試驗土壤基本物理及化學性質分析 10
二、重金屬之連續萃取 14
三、酸洗液的濃度測試 17
肆、結果與討論 18
一、試驗土壤的基本理化性質 18
二、中鹼性污染土的重金屬型態分佈 26
三、0.1 M HCL 抽出與連續萃取法抽出之有效性濃度的比較 32
四、磷的抽出量與重金屬型態分佈的相關性 34
五、重金屬及磷的酸洗情況及其相關 37
六、鹽酸酸洗對土壤養分的影響 63
伍、結論 69
陸、參考文獻 71
柒、附錄 76

表次
表 一、供試土壤之基本物理及化學性質 13
表 二、供試土壤分別以0.1 M 鹽酸及以王水萃取之重金屬含量 21
表 三、試驗土壤以Olsen法及Bray NO.1法抽出之磷與重金屬的抽出量 23
表 四、連續萃取海埔較低污染土壤(Soil B2)之交換及碳酸鹽結合型態(EC) 25
表 五、連續萃取荊桐段土壤(A)之交換及碳酸鹽結合型態(EC) 25
表 六、SCE試驗中磷抽出量與重金屬抽出量的相關係數(R) 36
表 七、SCE試驗中Fe抽出量與重金屬抽出量的相關係數(R) 36
表 八、比較不同抽出法對重金屬抽出的效果(Soil A) 56
表 九、比較不同抽出法對重金屬抽出的效果(Soil B1) 57
表 十、比較不同抽出法對重金屬抽出的效果(Soil B2) 58
表 十一、酸洗試驗中磷抽出量與重金屬抽出量的相關係數(R) 62


圖次
圖 一、試驗流程圖 12
圖 二、修改式SCE之流程圖 16
圖 三、荊桐段土壤(Soil A)各金屬元素連續抽出的分佈 29
圖 四、海埔段高污染土壤(Soil B1)各金屬元素連續抽出的分佈 30
圖 五、海埔段較低污染土壤(Soil B2)各金屬元素連續抽出的分佈 31
圖 六、荊桐段土壤(A)加入不同濃度HCl溶液於不同平衡時間後溶液pH之變化 38
圖 七、海埔段高污染土壤(B1) 加入不同濃度HCl溶液於不同平衡時間後溶液pH之變化 38
圖 八、海埔段較低污染土壤(B2)加入不同濃度HCl溶液於不同平衡時間後溶液pH之變化 39
圖 九、試驗土壤之酸洗液的pH變化情況 40
圖 十、試驗土壤之酸洗液的Fe變化情況 43
圖 十一、試驗土壤之酸洗液的Mn變化情況 44
圖 十二、試驗土壤之酸洗液的Al變化情況 45
圖 十三、試驗土壤之酸洗液中P的變化情況 46
圖 十四、試驗土壤之酸洗液的Cu變化情況 48
圖 十五、試驗土壤之酸洗液的Zn變化情況 49
圖 十六、試驗土壤之酸洗液的Cd變化情況 50
圖 十七、試驗土壤之酸洗液的Cr變化情況 51
圖 十八、試驗土壤之酸洗液的Ni變化情況 52
圖 十九、試驗土壤之酸洗液的Pb變化情況 53
圖 二十、供試土壤各養分元素連續抽出的比例 65
圖 二十一、試驗土壤之酸洗液的K變化情況 66
圖 二十二、試驗土壤之酸洗液的Ca變化情況 67
圖 二十三、試驗土壤之酸洗液的Mg變化情況 68

初建、王敏昭。1999。重金屬於其污染土壤之固相型態。中國農業化學會誌。37(1):32-41。
戴佳如。2003。蔬菜在重金屬地復育的角色。中興大學土壤環境科學研究所碩士論文。
Aklil, A., M. Mouflih, and S. Sebti. 2004. Removal of heavy metal ions from water by using calcined phosphate as a new adsorbent. J. Hazard. Mater. 112:183-190.
Baker, D.E., and M.C. Amacher. 1982. Nickel, copper, zinc and cadmium. p. 323-336. In A.L. Page et al. (ed.) Methods of soil analysis. Part 2. 2nd ed. Agron. Monogr. 9. ASA and SSSA, Madison, WI.
Barrow, N.J. 1987. The effects of phosphate on zinc sorption by a soil. Soil Sci. 38:453-459.
Beckett, P.H.T. 1989. The use of extractants in studies on trace metals in soils, sewage sludges, and sludge-treated soils. Adv. Soil Sci. 9:143-176.
Bray, R.H., and L.T. Kurtz. 1945. Determination of total, organic, and available forms of P in soils. Soil Sci. 59:39-45.
Bremner, J.M., and C.S. Mulvaney. 1982. Nitrogen-total. p. 595-624 In A.L. Page et al. (ed.) Methods of soil analysis. Part 2. 2nd ed. Agron. Monogr. 9. ASA and SSSA, Madison, WI.
Calmano, W., U. Foerstner, and M. Kersten. 1986. Metal associations in anoxic sediments and changes following upland disposal. Toxicol. Environ. Chem. 12:313-321.
Cao, X., L.Q. Ma, D.R. Rhue, and C.S. Appel. 2004. Mechanisms of lead, copper, and zinc retention by phosphate rock. Environ. Pollut. 131: 435-444.
Chao, T.T., and L. Zhou. 1983. Extraction techniques for selective dissolution of amorphous iron oxides from soils and sediments. Soil Sci. Sec. Am. J. 47:225-232.
Chen, X., J.V. Wright, J.L. Conca, and L.M. Peurrung. 1997. Evaluation of heavy metal remediation using mineral apatite. Water Air Soil Pollut. 98:57-78.
Crannell, B.S., T.T. Eighmy, J.E. Krzanowski, J.D. Eusden,Jr., E.L. Shaw, and C.A. Francis. 2000. Heavy metal stabilization in municipal solid waste combustion bottom ash using soluble phosphate. Waste Manage. 20:135-148
Davies, B.E. 1980. Heavy metals in soils. p. 287-351. In B.J. Alloway (ed.) Lead. John Wiley & Sons, New York.
Doll, E.C., and R.E. Lucas. 1973. Testing soil for potassium, calcium and magnesium. p. 133-152. In L.M. Walsh and J.B. Beaton (ed.) Soil Testing and Plant Analysis. SSSA, Madison, WI.
Elliott, H.A., M.R. Liberti, and C.P. Huang. 1986. Competitive adsorption of heavy metals by soils. J. Environ. Qual. 15:214-219.
Foerstner, U. 1993. Metal speciation - general concepts and applications. Int. J. Environ. Anal. Chem. 51:5-23.
Freeman, J.S., and D.L. Rowell. 1981. The adsorption and precipitation of phosphate onto calcite. Soil Sci. 32:75-84.
Gee, G.W., and J.W. Bauder. 1986. Particle-size analysis. p. 383-411. In A. Klute (ed.) Methods of soil analysis. Part 1. 2nd ed. Agron. Monogr. 9. ASA and SSSA, Madison, WI.
Gleyzes, C., S. Tellier, R. Sabrier, and M. Astruc. 2001. Arsenic characterisation in industrial soils by chemical extractions. Environ. Technol. 22:27-38.
Gruebel, K.A., J.A. Davis, and J.O. Leckie. 1988. The feasibility of using sequential extraction techniques for arsenic and selenium in soil and sediments. Soil Sci. Soc. Am. J. 52:390-397.
Hertz, J., C. Angehrn-Bettinazzi, and H. Stockli. 1990. Distribution of heavy metals in various litter horizons and forest soils. Int. J. Environ. Anal. Chem. 39:91-99.
Iyengar, S.S., D.C. Martens, and W.P. Miller. 1981. Distribution and plant availability of soil zinc fractions. Soil Sci. Soc. Am. J. 45:735-739.
Karczewska, A., L. Szerszen, and C. Kabala. 1998. Forms of selected heavy metals and their transformation in soils polluted by the emissions from copper smelters. Adv. GeoEcol. 31:705-712.
Keller, C., and J.C. Vedy. 1994. Distribution of copper and cadmium fractions in two forest soils. J. Environ. Qual. 23:987-999.
Lo, I.M.-C., and X.-Y. Yang. 1998. Removal and redistribution of metals from contaminated soils by a sequential extraction method. Waste Manage. 18:1-7.
Luoma, S.N., and E.A. Jenne. 1976. Estimating bioavailability of sediment-bound trace metals with chemical extractants. Trace Subst. Environ. Health. 10:343-351.
Ma, L.Q., and G.N. Rao. 1997. Chemical fractionation of cadmium, copper, nickel and zinc in contaminated soils. J. Environ. Qual. 26:259-264.
Ma, Q.Y., S.J. Traina, T.J. Logan, and J.A. Ryan. 1993. In situ lead immobilization by apatite. Environ. Sci. Technol. 27:1803-1810.
McLean, E.O. 1982. Soil pH and lime requirement. p. 199-223. In A.L. Page et al. (ed.) Methods of soil analysis. Part 2. 2nd ed. Agron. Monogr. 9. ASA and SSSA, Madison, WI.
Miller, W.P., D.C. Martens, and L.W. Zelazny. 1986. Effect of sequence in extraction of trace metals from soils. Soil Sci. Soc. Am. J. 50:598-601.
Narwal, R.P., B.R. Singh, and B. Salbu. 1999. Association of cadmium, zinc, copper, and nickel with components in naturally heavy metal-rich soils studied by parallel and sequential extractions. Commun. Soil. Sci. Plant Anal. 30:1209-1230.
Nelson, D.W., and L.E. Sommers. 1982. Total carbon, organic carbon, and organic matter. p. 539-579. In A.L. Page et al. (ed.) Methods of soil analysis. Part 2. 2nd ed. Agron. Monogr. 9. ASA and SSSA, Madison, WI.
Nriagu, J.O. 1972. Solubility equilibrium constant of strengite. Am. J. Sci. 272:476-484.
Obrador, A., M.I. Rico, J.I. Mingot, and J.M. Alvarez. 1997. Metal mobility and potential bioavailability in organic matter-rich soil-sludge mixtures: effect of soil type and contact time. Sci. Total Environ. 206:117-126.
Olsen, S.R., and L.E. Sommers. 1982. Phosphorus. p. 403-430. In A.L. Page et al. (ed.) Methods of soil analysis. Part 2. 2nd ed. Agron. Monogr. 9. ASA and SSSA, Madison, WI.
Orsini, L., and A. Bermond. 1993. Application of a sequential extraction procedure to calcareous soil samples: preliminary studies. Int. J. Environ. Anal. Chem. 51:97-108.
Prudent, P., M. Domeizel, and C. Massiani. 1996. Chemical sequential extraction as decision-making tool: application to municipal solid waste and its individual constituents. Sci. Total Environ. 178:55-61.
Quevauviller, P., A. Ure, H. Muntau, and B. Griepink, 1993. Improvement of analytical measurements within the BCR program: single and sequential extraction procedures applied to soil and sediment analysis. Int. J. Environ. Anal. Chem. 51:129-134.
Ramos, L., L.M. Hernandez, and M.J. Gonzalez. 1994. Sequential fractionation of copper, lead, cadmium and zinc in soils from or near Donana National Park. J. Environ. Qual. 23:50-57.
Rhoades, J.D. 1982. Cation exchange capacity. p. 149-157. In A. Page, R.H. Miller and D.R. Keeney (ed.) Methods of Soil Analysis. Part 2. 2nd ed. Agron. Monogr. 9. ASA and SSSA, Madison, WI.
Ruby, M.V., A. Davis, and A. Nicholson. 1994. In situ formation of lead phosphates in soils as a method to immobilize lead. Environ. Sci. Technol. 28:646-654.
Salbu, B., T. Krekling, and D.H. Oughton. 1998. Characterization of radioactive particles in the environment. Analyst 123:843-849.
Salomons, W., and U. Foerstner. 1984. Metals in the Hydrocycle. Springer-Verlag, Berlin.
Shiowatana, J., R.G. McLaren, N. Chanmekha, and A. Samphao. 2001. Fractionation of arsenic in soil by a continuous-flow sequential extraction method. J. Environ. Qual. 30: 1940-1949.
Shuman, L.M. 1985. Fractionation method for soil microelements. Soil Sci. 140:11-22.
Sidhu, P.S., R.J. Gilkes, R.M. Cornell, A.M. Pasner, and J.P. Quirk. 1981. Dissolution of iron oxides and oxyhydroxides in hydrochloric and perchloric acids. Clays Clay Miner. 29:269-276.
Soon, Y.K., and T.E. Bates. 1982. Chemical pools of cadmium, nickel and zinc in polluted soils and some preliminary indications of their availability to plants. Soil Sci. 33:477-488.
Sulkowski, M., and A.V. Hirner. 2006. Element fractionation by sequential extraction in a soil with high carbonate content. App. Geochem. 21:16-28.
Suzuki, T., K. Ishigaki, and M. Miyake. 1984. Synthetic hydroxyapatites as inorganic cation exchangers. Part 3. Exchange characteristics of lead dications. J. Chem. Soc., Faraday Trans. I. 80:3157-3165.
Tessier, A., P.G.C. Campbell, and M. Bisson. 1979. Sequential extraction procdure for the speciation of particulate trace metals. Anal. Chem. 51:844-851.
Ton, S., J.J. Delfino, and H.T. Odum. 1993. Wetland retention of lead from a hazardous site. Bull. Environ. Contam. Toxicol. 51:430-437.
Turner, B.L., and A.B. Leytem. 2004. Phosphorus compounds in sequential extracts of animal manures: chemical speciation and a novel fractionation procedure. Environ. Sci. Technol. 38:6101-6108.
Xu, Y., and F.W. Schwartz. 1994. Lead immobilization by hydroxyapatite in aqueous solutions. J. Contam. Hydrol. 15:187-206.