土壤性质对重金属铅镉稳定化过程的影响研究
摘要
随着城市化、工业化的快速发展和化肥、农药的大量施用,大量重金属污染物直接或间接的进入农田土壤。外源重金属铅(Pb)、镉(Cd)污染物进入土壤后,随时间的延长,在土壤中的有效性降低,有效态含量趋于稳定。这一过程受到土壤质地、阳离子交换量(CEC)、有机质、pH等因素的影响。对于单一因素的影响机理前人已有研究,但土壤是一个复杂的多相体系,各种因素并存且相互作用,因此对自然状态下,各种因素对重金属污染物在土壤中稳定化过程的综合作用研究,将更有实际意义。
本研究利用室内培养实验,在27个土样中人为加入Pb.Cd盐溶液,于污染后的第2、7、15、30、60、90、180、270、360天采样,用0.5mol·L-1MgCl2提取有效态,通过动力学方程模拟单一及复合污染条件下土壤中外源Pb、Cd的稳定化过程,选取最优模型,并得到表征土壤中Pb、Cd稳定化过程的参数；通过回归分析、通径分析研究了不同土壤性质(CEC、有机质含量、颗粒组成、pH)对重金属稳定化过程的影响的大小,并确定主要影响因子。得出以下结果：
1)加入500 mg·kg-1 Pb、1.0 mg·kg-1 Cd或1.0 mg·kg-1 Cd+500 mg·kg-1 Pb条件下,有效Pb、Cd含量在培养前期迅速减少,随后减少速率变缓,培养30天后趋于平衡。培养360天时,有效态铅、镉含量约为培养2天时的30%-70%。不同土壤中有效态Pb、Cd含量差异很大,一般在pH较低的红壤中,有效态Pb、Cd含量较高；在pH较高的潮土、褐土、黑色石灰土等土壤中,有效态Pb、Cd含量较低。取自长期定位实验点的红壤、潮土、黑土等19个土样,施有机肥处理的NPKM、1.5NPKM等土样,由于pH较高,有机质含量较高,有效Pb、Cd含量一般都低于施化肥的N、NP和NPK等土样。
2)利用一阶指数衰减函数、Elovich方程、二级动力学方程和双常数方程模拟外源Pb、Cd在土壤中的稳定化过程。27个土样的有效态Pb、Cd随培养时间变化都以二级动力学方程和一阶指数方程的模拟结果较好,模拟方程的决定系数均达到极限显著水平(R2>0.90),其中,二级动力学方程模拟的决定系数最高,为最优模型。双常数方程模拟的决定系数在0.53-0.93之间,也都达到显著水平。Elovich方程模拟的结果相对较差,尤以对红壤NPK、砂岩红壤、赤红壤、黑土PK、黑土NPKM上Pb稳定化过程的模拟结果最差。
3)通过二级动力学方程模拟得出的平衡浓度y0值可知,Pb单一污染中以花岗岩红壤的y0值最高(239 mg·kg-1),黑色石灰土最低(0.360 mg·kg-1). Cd单一污染中,以红壤NP的y0值最高(0.554 mg·kg-1),黑色石灰土最低(0.093 mg·kg-1)。Pb-Cd复合污染中,除了黑土NPK、黑土1.5NPKM和砂岩红壤外,外源Pb的加入提高了土壤中有效Cd的含量,增加了其环境危害。外源Cd的加入对土壤Pb的浓度没有显著的影响,这与Cd的竞争力弱于Pb,以及Cd的加入浓度(lmgCd/kg土)非常低有关。
4)双常数方程得出的速率常数B值反映了土壤重金属污染物随时间延长而降低得快慢,B值越大,稳定化进程越快,反之则越慢。Pb稳定化过程的B值以黑色石灰土最高(0.482),红壤N最低(0.051)；Cd稳定化过程的B值也以黑色石灰土最高(0.216),红壤N最低(0.055)。在Pb或Cd单一污染下,红壤的稳定化速率总体比黑土、潮土较慢。Pb-Cd复合污染下,Pb或Cd稳定化速率受离子间交互作用的影响,在不同土壤有很大的差异。
5)不同土壤性质影响了Cd、Pb稳定化过程的速率和平衡浓度。通径分析表明,土壤pH是影响稳定化过程中Cd、Pb平衡浓度的主要因素,表现为土壤pH增加可以有效地降低Cd、Pb的活性,使其环境的毒害作用减小。阳离子交换量和粘粒含量对Cd、Pb平衡浓度也有一定影响,但都是通过pH变化实现的。土壤有机质和pH是影响Cd、Pb稳定化速率的主要因素。随着有机质和pH的提高,土壤Cd、Pb稳定化速率不断加快。阳离子交换量的增加也能够在一定程度上加快Cd、Pb稳定化的进程,而粘粒含量对稳定化速率影响较小。
With the rapid development of urbanization and industrialization, a large number of chemical fertilizer and pesticide application and many heavy metal pollutants were carried into the farmland soil directly or indirectly. The availability of lead (Pb) or cadmium (Cd) would decreased with the time after the polllutants of Pb or Cd was added into the soil, this process was affected by soil mechanical composition, cation exchange capacity(CEC), organic matter, pH, and so on. Some research about the single factor have been done, but the soil as a complicated heterogeneous system with various factors existing and interacting, it would have more practical significance to research the effect of soil properties on the stabilization processes of Cd and Pb in the natural conditions.
The stabilization processes of Cd and Pb in single and combined metal-contaminated soil of China were studied. MgCl2 extraction was employed to examine the available speciation of Cd, Pb in soils. Cd, Pb or their mixture were added into twenty-seven soil samples respectively. Each treatment were sampled at 2rd,7th,15th,30th,60th,90th,180th, and 360th day after pollution and then extracted using 0.5 mol·L-1 MgCl2. Four kinds of dynamical equations were used to simulate the stabilization process of Cd or Pb, then, the optimum fitting equation was selected, the parameters modeled by dynamical equations about the stabilization processes of Cd and Pb were gained. By means of regression analysis and path analysis, the effect of different soil properties (CEC, organic matter, soil mechanical composition and pH) on the stabilization processes of Cd and Pb was researched, the most important factor was confirmed. The results had been drawn as follows:
1) After 500 mg·kg-1 Pb,1.0 mg·kg-1 Cd or 500 mg·kg-1 Pb+1.0 mg·kg-1 Cd were added in soil, soil availability of Pb and Cd were decreased rapidly during the first some days, then, decreased slowly, and stabilized after 30 day's incubation. The differences of content of available Pb or Cd in the 27 soil samples were very significant, generally, in the red soil with low pH, the content of available Pb or Cd was higher, while, in the soil samples with high pH, such as fluvo-aquic soils, cinnamon soil, black limestone soil and so on, the content of available Pb or Cd was lower. In the red soil, black soil and fluvo-aquic soil, which taken from the long-term positioning sites, the content of available Pb or Cd in the NPKM and 1.5NPKM treatment with the high pH and high organic matter content were lower than that in the N, NP, and NPK treatment.
2) The stabilization process of Cd and Pb in the soil were simulated by first-order exponential decay function, second-order equation, Elovich equation, and two-constant equation. The second-order equation and first-order exponential decay function perfectly described the changes of available Pb and Cd with incubation time in the 27 soil samples, the correlation coefficients of the equations came up to the most significant standard (r>0.90), and the second-order equation was the optimum model, because its correlation coefficients was the highest. Then, the correlation coefficients of two-constant were between 0.53 to 0.93, all reached the significant standard. Elovich equation was the worse model than other models, especially, in red soil NPK treatment, Red sandstone, lateritic red earths, black soil PK treatment and NPKM treatment, the equation describing stabilization process of Pb in these soils were worst.
3) The equilibrium concentration (y0) can be gained by the second-order equation. In the group of single Pb contaminated soils, the value of yo was highest in granitization red soil (239 mg·kg-1),while it was lowest in black limestone soil(0.360 mg·kg-1). In the group of single Cd contaminated soils, the value of yo was highest in red soil NP treatment (0.554 mg·kg-1), while it was lowest in black limestone soil (0.093 mg·kg-1). In the Pb-Cd combined metal-contaminated soils, the existing of Pb increased the content of availability of Cd, except in black soil NPK treatment, black soil 1.5NPKM treatment and red sandstone, this would increase the harmfulness of Cd in the environmental. Whereas these had no significant effect of Cd on the availability of Pb, perhaps, it was because that the competitiveness of Cd was weaker than Pb and it had some related to the low concentration of added Cd.
4) The stabilization velocity (B), which obtained from the two-constant equation, reflected the rate of content of available heavy metal decreasing with the time. The value of B was larger, the velocity of stabilization process was faster; if not, the velocity of stabilization process would lower. In the group of Pb, the value of B was largest in black limestone soil(0.482), while it is least in the red soil N treatment (0.051), In the group of Cd, the value of B also was largest in black limestone soil(0.216), while it was least in the red soil N treatment (0.055). In the single Pb or Cd contaminated soils, generally, the stabilization velocity was slower in the red soils than that was in the black soils and fluvo-aquic soils. In the Pb-Cd combined contaminated soils, the stabilization velocity of Pb or Cd was affected by the interaction of ions, so it had large diversity between different soils.
5) The stabilization velocity and equilibrium concentration of Cd or Pb were influenced by soil properties. Path analysis indicated that pH contributed greatly to affect the equilibrium concentration of Cd or Pb in the stabilization process, showed that the increase of pH could reduce effectiveness of Cd or Pb, reduced the risk of environmental pollution in agricultural production. CEC and clay content also had some effect on the equilibrium concentration of Cd and Pb, but it were realized by the pH. The organic matter and pH were the major factors of affecting the stabilization velocity of Cd and Pb, with the increasing content of organic matter and pH, the stabilization velocity of Cd and Pb accelerated. To some extent, the increasing of CEC also could quickened the stabilization process of Cd and Pb, but the clay content had little effect on the stabilization velocity.
本研究利用室内培养实验,在27个土样中人为加入Pb.Cd盐溶液,于污染后的第2、7、15、30、60、90、180、270、360天采样,用0.5mol·L-1MgCl2提取有效态,通过动力学方程模拟单一及复合污染条件下土壤中外源Pb、Cd的稳定化过程,选取最优模型,并得到表征土壤中Pb、Cd稳定化过程的参数；通过回归分析、通径分析研究了不同土壤性质(CEC、有机质含量、颗粒组成、pH)对重金属稳定化过程的影响的大小,并确定主要影响因子。得出以下结果：
1)加入500 mg·kg-1 Pb、1.0 mg·kg-1 Cd或1.0 mg·kg-1 Cd+500 mg·kg-1 Pb条件下,有效Pb、Cd含量在培养前期迅速减少,随后减少速率变缓,培养30天后趋于平衡。培养360天时,有效态铅、镉含量约为培养2天时的30%-70%。不同土壤中有效态Pb、Cd含量差异很大,一般在pH较低的红壤中,有效态Pb、Cd含量较高；在pH较高的潮土、褐土、黑色石灰土等土壤中,有效态Pb、Cd含量较低。取自长期定位实验点的红壤、潮土、黑土等19个土样,施有机肥处理的NPKM、1.5NPKM等土样,由于pH较高,有机质含量较高,有效Pb、Cd含量一般都低于施化肥的N、NP和NPK等土样。
2)利用一阶指数衰减函数、Elovich方程、二级动力学方程和双常数方程模拟外源Pb、Cd在土壤中的稳定化过程。27个土样的有效态Pb、Cd随培养时间变化都以二级动力学方程和一阶指数方程的模拟结果较好,模拟方程的决定系数均达到极限显著水平(R2>0.90),其中,二级动力学方程模拟的决定系数最高,为最优模型。双常数方程模拟的决定系数在0.53-0.93之间,也都达到显著水平。Elovich方程模拟的结果相对较差,尤以对红壤NPK、砂岩红壤、赤红壤、黑土PK、黑土NPKM上Pb稳定化过程的模拟结果最差。
3)通过二级动力学方程模拟得出的平衡浓度y0值可知,Pb单一污染中以花岗岩红壤的y0值最高(239 mg·kg-1),黑色石灰土最低(0.360 mg·kg-1). Cd单一污染中,以红壤NP的y0值最高(0.554 mg·kg-1),黑色石灰土最低(0.093 mg·kg-1)。Pb-Cd复合污染中,除了黑土NPK、黑土1.5NPKM和砂岩红壤外,外源Pb的加入提高了土壤中有效Cd的含量,增加了其环境危害。外源Cd的加入对土壤Pb的浓度没有显著的影响,这与Cd的竞争力弱于Pb,以及Cd的加入浓度(lmgCd/kg土)非常低有关。
4)双常数方程得出的速率常数B值反映了土壤重金属污染物随时间延长而降低得快慢,B值越大,稳定化进程越快,反之则越慢。Pb稳定化过程的B值以黑色石灰土最高(0.482),红壤N最低(0.051)；Cd稳定化过程的B值也以黑色石灰土最高(0.216),红壤N最低(0.055)。在Pb或Cd单一污染下,红壤的稳定化速率总体比黑土、潮土较慢。Pb-Cd复合污染下,Pb或Cd稳定化速率受离子间交互作用的影响,在不同土壤有很大的差异。
5)不同土壤性质影响了Cd、Pb稳定化过程的速率和平衡浓度。通径分析表明,土壤pH是影响稳定化过程中Cd、Pb平衡浓度的主要因素,表现为土壤pH增加可以有效地降低Cd、Pb的活性,使其环境的毒害作用减小。阳离子交换量和粘粒含量对Cd、Pb平衡浓度也有一定影响,但都是通过pH变化实现的。土壤有机质和pH是影响Cd、Pb稳定化速率的主要因素。随着有机质和pH的提高,土壤Cd、Pb稳定化速率不断加快。阳离子交换量的增加也能够在一定程度上加快Cd、Pb稳定化的进程,而粘粒含量对稳定化速率影响较小。
With the rapid development of urbanization and industrialization, a large number of chemical fertilizer and pesticide application and many heavy metal pollutants were carried into the farmland soil directly or indirectly. The availability of lead (Pb) or cadmium (Cd) would decreased with the time after the polllutants of Pb or Cd was added into the soil, this process was affected by soil mechanical composition, cation exchange capacity(CEC), organic matter, pH, and so on. Some research about the single factor have been done, but the soil as a complicated heterogeneous system with various factors existing and interacting, it would have more practical significance to research the effect of soil properties on the stabilization processes of Cd and Pb in the natural conditions.
The stabilization processes of Cd and Pb in single and combined metal-contaminated soil of China were studied. MgCl2 extraction was employed to examine the available speciation of Cd, Pb in soils. Cd, Pb or their mixture were added into twenty-seven soil samples respectively. Each treatment were sampled at 2rd,7th,15th,30th,60th,90th,180th, and 360th day after pollution and then extracted using 0.5 mol·L-1 MgCl2. Four kinds of dynamical equations were used to simulate the stabilization process of Cd or Pb, then, the optimum fitting equation was selected, the parameters modeled by dynamical equations about the stabilization processes of Cd and Pb were gained. By means of regression analysis and path analysis, the effect of different soil properties (CEC, organic matter, soil mechanical composition and pH) on the stabilization processes of Cd and Pb was researched, the most important factor was confirmed. The results had been drawn as follows:
1) After 500 mg·kg-1 Pb,1.0 mg·kg-1 Cd or 500 mg·kg-1 Pb+1.0 mg·kg-1 Cd were added in soil, soil availability of Pb and Cd were decreased rapidly during the first some days, then, decreased slowly, and stabilized after 30 day's incubation. The differences of content of available Pb or Cd in the 27 soil samples were very significant, generally, in the red soil with low pH, the content of available Pb or Cd was higher, while, in the soil samples with high pH, such as fluvo-aquic soils, cinnamon soil, black limestone soil and so on, the content of available Pb or Cd was lower. In the red soil, black soil and fluvo-aquic soil, which taken from the long-term positioning sites, the content of available Pb or Cd in the NPKM and 1.5NPKM treatment with the high pH and high organic matter content were lower than that in the N, NP, and NPK treatment.
2) The stabilization process of Cd and Pb in the soil were simulated by first-order exponential decay function, second-order equation, Elovich equation, and two-constant equation. The second-order equation and first-order exponential decay function perfectly described the changes of available Pb and Cd with incubation time in the 27 soil samples, the correlation coefficients of the equations came up to the most significant standard (r>0.90), and the second-order equation was the optimum model, because its correlation coefficients was the highest. Then, the correlation coefficients of two-constant were between 0.53 to 0.93, all reached the significant standard. Elovich equation was the worse model than other models, especially, in red soil NPK treatment, Red sandstone, lateritic red earths, black soil PK treatment and NPKM treatment, the equation describing stabilization process of Pb in these soils were worst.
3) The equilibrium concentration (y0) can be gained by the second-order equation. In the group of single Pb contaminated soils, the value of yo was highest in granitization red soil (239 mg·kg-1),while it was lowest in black limestone soil(0.360 mg·kg-1). In the group of single Cd contaminated soils, the value of yo was highest in red soil NP treatment (0.554 mg·kg-1), while it was lowest in black limestone soil (0.093 mg·kg-1). In the Pb-Cd combined metal-contaminated soils, the existing of Pb increased the content of availability of Cd, except in black soil NPK treatment, black soil 1.5NPKM treatment and red sandstone, this would increase the harmfulness of Cd in the environmental. Whereas these had no significant effect of Cd on the availability of Pb, perhaps, it was because that the competitiveness of Cd was weaker than Pb and it had some related to the low concentration of added Cd.
4) The stabilization velocity (B), which obtained from the two-constant equation, reflected the rate of content of available heavy metal decreasing with the time. The value of B was larger, the velocity of stabilization process was faster; if not, the velocity of stabilization process would lower. In the group of Pb, the value of B was largest in black limestone soil(0.482), while it is least in the red soil N treatment (0.051), In the group of Cd, the value of B also was largest in black limestone soil(0.216), while it was least in the red soil N treatment (0.055). In the single Pb or Cd contaminated soils, generally, the stabilization velocity was slower in the red soils than that was in the black soils and fluvo-aquic soils. In the Pb-Cd combined contaminated soils, the stabilization velocity of Pb or Cd was affected by the interaction of ions, so it had large diversity between different soils.
5) The stabilization velocity and equilibrium concentration of Cd or Pb were influenced by soil properties. Path analysis indicated that pH contributed greatly to affect the equilibrium concentration of Cd or Pb in the stabilization process, showed that the increase of pH could reduce effectiveness of Cd or Pb, reduced the risk of environmental pollution in agricultural production. CEC and clay content also had some effect on the equilibrium concentration of Cd and Pb, but it were realized by the pH. The organic matter and pH were the major factors of affecting the stabilization velocity of Cd and Pb, with the increasing content of organic matter and pH, the stabilization velocity of Cd and Pb accelerated. To some extent, the increasing of CEC also could quickened the stabilization process of Cd and Pb, but the clay content had little effect on the stabilization velocity.
引文
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