南方土壤酸沉降敏感性研究 Ⅵ.固相组成与酸缓冲性能

通过连续提取方法研究了土壤固相组成对酸沉降敏感性的影响。结果表明，不同土壤质子缓冲反应的类型不同，因此，缓冲容量及缓冲强度等指标也有较大差异。有机质对酸缓冲反应存在双重影响。取决于土壤原始ＰＨ值及盐基组成状态。     

南方土壤酸沉降敏感性研究Ⅶ——盐基淋溶与缓冲机理

研究了模拟酸雨对我国南方主要土壤类型盐基离子淋溶的影响,结果表明,ＰＨ低于３．０或３．５时,盐基离子淋溶总量明显增加,但ＰＨ高于３．５时,则影响不明显。     

铁锰双金属材料在不同pH条件下对土壤As和重金属的稳定化作用

pH是影响土壤As和重金属赋存形态及稳定化过程的重要因素,本文以人工合成的铁锰双金属材料(FMBO)为研究对象,研究了其在不同pH条件下对3种As和重金属复合污染土壤的稳定化作用,同时探讨了材料添加对土壤pH和酸碱缓冲性的影响.结果表明,As、Pb元素分别在土壤pH 3~9的中性偏酸性条件、pH 5~10的中性偏碱性条件下较为稳定,Cd、Zn、Cu在pH为7~11的碱性条件下浸出浓度较低.在碱性条件下,FMBO材料自身稳定性及稳定化作用均优于酸性条件,在As和重金属稳定的最适pH范围内,随着材料添加量增加,稳定化效率逐渐升高,其对As、Pb、Cd、Zn、Cu的稳定化效率最高分别能达到92.7%、100%、97.0%、88.7%、82.7%.添加FMBO材料可使土壤pH值升高,并能够提高土壤的酸缓冲能力,对As和重金属的长期稳定性有促进作用,而对土壤碱缓冲作用影响较小.从浸出元素的相关关系可以看出,Fe元素对土壤中As的稳定性有重要作用,Pb、Cd、Zn、Cu的稳定性受土壤pH影响较大.     

香港的酸雨和地表水酸度

 通过对香港新界小流域水文过程中pH值的监测,结果表明,在研究的5年期间,降雨pH值的中位数年变化为4.5～4.7,而溪流的pH值接近中性,其中位数年变化为6.6～6.8.研究表明,陆地生态系统的植被和土壤对地表水的酸度调节起着关键的作用,但不同的植被和植物种类组成对陆地生态系统的酸缓冲能力有重要影响.     

Effects of simulated acid rain on cation release in soils of South China

This paper deals with the release of base cations and Al3+ at the treatment with simulated acid rain (SAR) in main soil types collected from South China. Results showed that the amounts of base cations increased obviously when the pH value of simulated acid rain was lower than 3.0 or 3.5. Compared with the leaching of K+ and Na+, the leaching of Ca2+ and Mg2+ was affected by the pH value of SAR. Only when the amounts of base cations leached from soils exceeded the cation exchange capacity, the pH value of leaching solutions decreased sharply and the amounts of released Al3+ increased. The H+ buffering mechanisms, which were affected notonly by the pH values of SAR, but also by the types and solid components of soils, were proposed for the main soils studied.     

Effects of simulated acid rain on cation release in soils of South China

This paper deals with the release of base cations and Al3+ at the treatment with simulated acid rain (SAR) in main soil types collected from South China. Results showed that the amounts of base cations increased obviously when the pH value of simulated acid rain was lower than 3.0 or 3.5. Compared with the leaching of K+ and Na+, the leaching of Ca2+ and Mg2+ was affected by the pH value of SAR. Only when the amounts of base cations leached from soils exceeded the cation exchange capacity, the pH value of leaching solutions decreased sharply and the amounts of released Al3+ increased. The H+ buffering mechanisms, which were affected notonly by the pH values of SAR, but also by the types and solid components of soils, were proposed for the main soils studied.     

模拟氮沉降对土壤酸化及土壤酸缓冲能力的影响

为探讨N沉降对酸雨区森林土壤酸化和土壤酸缓冲能力的影响,于2012年4—12月在重庆缙云山地区选取针阔混交林和常绿阔叶林2种典型林分进行模拟N沉降试验,设N0、N1、N2、N3 4个处理,施N量(模拟N沉降量)分别为0、60、120、240 kg/(hm2·a),每月月初将NH₄NO₃溶液均匀喷洒在所选样方内,8个月后进行取样分析. 结果表明:①不同pH下2种林分土壤的酸缓冲能力存在较大差异,pH越低土壤酸缓冲能力越高. ②2种林分的土壤酸缓冲能力随N沉降量的增加而降低. 在相同的N沉降量下,常绿阔叶林土壤酸缓冲能力略高于针阔混交林. ③N沉降会加快土壤酸化速率. 与N0处理相比,N1、N2、N3处理常绿阔叶林土壤pH分别下降了0.03、0.06、0.16,而针阔混交林则分别下降了0.08、0.10、0.26. ④2种林分土壤中盐基离子含量均随N沉降量的增加而降低,交换性Al3+含量则相反. 与N0处理相比,常绿阔叶林N1、N2、N3处理盐基离子含量分别下降了55.76%、66.00%、70.38%,交换性Al3+含量分别增加了16.03%、21.37%、31.81%;针阔混交林盐基离子含量分别下降了24.12%、43.38%、62.24%,交换性Al3+含量分别增加了19.19%、23.48%、34.85%. 研究表明,氮沉降会降低森林土壤酸缓冲能力,加快酸化速率,并且常绿阔叶林土壤对N沉降的敏感性高于针阔混交林.      

Arsenite oxidation by three types of manganese oxides

Oxidation of As（Ⅲ） by three types of manganese oxides and the effects ofpH, ion strength and tartaric acid on the oxidation were investigated by means of chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Three synthesized Mn oxide minerals, bimessite, cryptomelane, and hausmannite, which widely occur in soil and sediments, could actively oxidize As（Ⅲ） to As（Ⅴ）. However, their ability in As（Ⅲ）-oxidation varied greatly depending on their structure, composition and surface properties. Tunnel structured cryptomelane exhibited the highest ability of As （Ⅲ） oxidation, followed by the layer structured birnessite and the lower oxide hausmannite. The maximum amount of As （Ⅴ） produced by the oxidation was in the order （mmol/kg） of cryptomelane （824.2） 〉 bimessite （480.4） 〉 hausmannite （117.9）, As pH increased from the very low value（pH 2.5）, the amount of As（Ⅲ） oxidized by the tested Mn oxides was firstly decreased, then negatively peaked in pH 3.0 6.5, and eventually increased remarkably. Oxidation of As（Ⅲ） by the Mn oxides had a buffering effects on the pH variation in the solution. It is proposed that the oxidative reaction processes between As （Ⅲ） and biruessite（or cryptomelane） are as follows： （1） at lower pH condition： （MnO2）x＋ H3AsO3 ＋ 0.5H^＋=0.5H2AsO4^- ＋ 0.5HAsO4^2- ＋Mn〉^2＋ （MnO2）x-1 ＋ H2O; （2） at higher pH condition： （MnO2）x ＋ H3AsO3 = 0.5H2AsO4^- ＋ 0.5HAsO4^2- ＋ 1.5H^＋ ＋ （MnO2）x-1. MnO. With increase of ion strength, the As（Ⅲ） oxidized by bimessite and cryptomelane decreased and was negatively correlated with ion strength. However, ion strength had little influence on As （Ⅲ） oxidation by the hausmarmite. The presence of tartaric acid promoted oxidation of As（Ⅲ） by birnessite. As for cryptomelane and hansmannite, the same effect was observed when the concentration of tartaric acid was below 4 mmol/L, otherwise the oxidized As（Ⅲ） decreased. These findings are of great significance in improving our understanding of As geochemical cycling and controlling As contamination.     

重庆电厂炉前煤及飞灰中As元素在有机酸作用下的淋滤行为

采用模拟酸雨手段，突出有机酸对Ａｓ元素的淋出作用。分别配置ｐＨ＝４．４７的硝酸、乙酸及硝酸与乙酸的混酸三种淋滤液，对重庆电厂炉前煤及飞灰中的Ａｓ元素进行４０ｈ的淋滤实验，以探讨有机酸淋滤条件下Ａｓ元素的淋出行为。结果表明：有机酸淋滤液对炉前煤及飞灰中的Ａｓ元素具有较强的淋出作用，有机酸中Ｈ＾＋的缓冲释放作用是导致Ａｓ元素较强淋出率的主要因素。     

碱性改良剂对富铝化淋溶土酸缓冲性能影响研究

研究区２种酸缓冲能力较弱的富铝化酸性淋溶土施用不同剂量ＣａＣＯ３和电厂粉煤灰后，土壤ｐＨ值和酸化缓冲容量均有不同程度增高，施ＣａＣＯ３处理尤为显，表明土壤抗酸化性能有明显改善，实验结果同时表明，施用改良剂后，土壤胶体表面正电荷量减少，负电荷量增加，后对介中阴离子的斥力增大，故对酸雨中主成份离子－ＳＯ４＾２－的吸附量降低，虽然对其固定能力未明显减弱，但也说明将有较多的ＳＯ４＾２－在土体中移动和     

中国酸雨成因研究

根据大气颗粒物酸化缓冲能力、土壤的碱金属及碱土金属含量、土壤的酸碱性质、酸雨前体物排放强度和酸性物雨洗能力等闸明了我国酸雨成因及其地理分布,并指出其它一些敏感地区,如云南东南部、东北东部和北部、山东半岛东部等地区可能出现酸性降水。根据前体物排放量预测,２０２０年前我国酸雨仍将继续发展。     

土壤酸沉降缓冲机制的探讨

选取南方主要酸沉降区土壤作模拟酸雨淋溶实验,分析在酸雨作用下各土壤盐基离子的淋溶特性,硅、铝元素的释放规律及淋出液的 pH值变化特点。在此基础上,对土壤酸沉降的缓冲机制进行了探讨。      

土壤pH和Cd全量对伴矿景天修复效率的影响

修复效率是影响植物修复周期和技术推广的主要因素之一.采用不同pH和不同程度Cd污染农田土壤进行盆栽试验,其中,重度Cd污染土壤（简称"SKS处理"）中w（Cd）（Cd全量）高于GB 15618-2018《土壤环境质量农用地土壤污染风险管控标准（试行）》中的风险管控值,中度Cd污染土壤（通过人为调节并稳定其pH为3.97、4.97、6.03、6.90和7.93）中w（Cd）介于GB 15618-2018风险筛选值和管控值之间,轻度Cd污染土壤（简称"YH处理"）中w（Cd）略高于GB 15618-2018风险筛选值;比较修复前后不同pH和不同程度Cd污染对土壤Cd有效性、形态分配及w（Cd）的影响,并结合PCA（主成分分析）和Pearson相关性分析等方法深入研究影响植物修复效率的主控因素.结果表明:①与修复前相比,不同pH处理修复后土壤中w（有效态Cd）、w（弱酸提取态Cd）、w（可还原态Cd）、w（可氧化态Cd）和w（Cd）的减少量均随pH的降低而增加,土壤pH ≤ 6.0时,伴矿景天修复效率显著高于土壤pH>6.0的处理（P <0.05）.②修复后,轻度Cd污染土壤中w（Cd）降至GB 15618-2018风险筛选值以下,中度Cd污染土壤pH ≤ 6.0的处理中w（Cd）降至0.60 mg/kg左右,而pH>6.0的处理中w（Cd）仍高于1.00 mg/kg.③重度Cd污染土壤中w（有效态Cd）最高,其伴矿景天生物量与轻度Cd污染土壤处理无显著差异,w（Cd）达681.5 mg/kg,但修复效率显著低于其他处理（P <0.05）.综合PCA和Pearson相关性分析发现,影响伴矿景天修复效率的主控因素除土壤pH、Cd有效性和伴矿景天生物量外,伴矿景天的BCF（富集系数）对修复效率也具有重要作用.因此,伴矿景天更适用于弱酸性、中度Cd污染和轻度Cd污染土壤;而对碱性或重度Cd污染土壤进行植物修复时,可适当延长修复周期或联合修复以提高其修复效率.      

Speciation and fractionation of heavy metals in soil experimentally contaminated with Pb,Cd, Cu and Zn together and effects on soil negative surface charge

Speciation and fractionation of heavy metals in soil subsamples experimentally loaded with Pb, Cd, Cu and Zn in orthogonal design was investigated by sequential extraction, and operationally defined as water-soluble and exchangeable(SE), weakly specific adsorbed( WSA),Fe and Mn oxides-bound(OX) and organic-bound( ORG). The results showed that fractions of heavy metals in the soil subsamples depended on their speciation. About 90% of Cd and 75% of Zn existed in soil subsamples in the SE fraction. Lead and Cu existed in soil subsamples as SE, WSA and OX fractions simultaneously, although SE was still the major fraction. Organic-bound heavy metals were not clearly apparent in all the soil subsamples. The concentration of some heavy metal fractions in soil subsamples showed the good correlation with ionic impulsion of soil, especially for the SE fraction. Continuous saturation of soil subsamples with 0.20 mol/L NH4CI, which is the first step for determination of the negative surface charge of soil by the ion retention method, resulted in desorption of certain heavy metals from the soil. It was found that the percentage desorption of heavy metals from soil subsamples depended greatly on pH, the composition and original heavy metal content of the soil subsamples. However, most of the heavy metals in the soil subsamples were still be retained after multiple saturation. Compared with the parent soil, the negative surface charge of soil subsamples loaded with heavy metals did not show difference significantly from that of the parent one by statistical analysis. Heavy metals existed in the soil subsamples mainly as exchangeable and precipitated simultaneously.     

碳酸钙与生物炭对酸化菜地土壤持氮能力的影响

针对太湖地区稻田改种菜地后带来的土壤酸化现象,以碳酸钙与生物炭作为酸化改良剂,开展室内培养及多次淋洗模拟试验,比较两种改良剂对酸化菜地土壤持氮能力及酸化修复效果的影响.结果表明,基于碱缓冲曲线法,本试验用酸化菜地土壤每提高1个p H单位需向土壤中添加碳酸钙3.92×10-2mol·kg~(-1)或生物炭27.73 g·kg~(-1).无外源氮条件下碳酸钙添加使土壤氮矿化速率显著提高了37%,对土壤铵态氮、硝态氮含量影响不显著;生物炭添加使土壤氮矿化速率显著提高了35%~44%,且显著增加了土壤硝态氮含量42%~58%.模拟淋洗下,生物炭添加显著消减渗漏液体积24%,渗漏液氮浓度45%,显著减少氮淋失量42%~57%,而碳酸钙添加对渗漏液体积没有影响,增加了渗漏液中氮浓度,氮淋失量增加了12%~76%.淋洗后,各处理土壤p H值发生不同程度的降低,无外源氮条件下添加碳酸钙处理土壤p H值降幅最低,外源氮添加条件下生物炭添加处理降幅最低.由此可见,碳酸钙对酸化土壤修复效率较高,但在外源氮添加条件下降低了土壤持氮能力,更适用于酸化严重且需要休耕改良的菜地土壤;生物炭在维持土壤p H值的同时可以有效提高土壤矿质氮留存量,降低氮淋失,更适用于仍在高强度种植的菜地土壤.     

畜禽粪便有机肥中Cu、Zn在不同农田土壤中的形态归趋和有效性动态变化

通过土壤培养试验,研究了不同畜禽粪便有机肥中重金属Cu、Zn在不同农田土壤中的形态归趋和有效性动态变化过程,为合理确定由畜禽粪便有机肥带入农田土壤的重金属负荷,科学评价畜禽粪便有机肥中重金属进入土壤后的生态风险提供理论依据.结果表明,土壤中施用畜禽粪便有机肥后,酸性土壤p H值升高,而石灰性土壤p H值降低.施用鸡粪后6个月内,有效态Cu含量在2种土壤中显著低于等量Cu无机盐处理,而有效态Zn含量则与等量Zn无机盐处理无显著差异;施用猪粪后6个月内,有效态Cu和Zn含量在2种土壤中均与等量Cu和Zn无机盐处理无显著差异.形态归趋研究表明,通过畜禽粪便有机肥进入土壤中的Cu和Zn在土壤中主要以交换态、碳酸盐结合态、铁锰氧化物结合态以及有机结合态的形式存在,且畜禽粪便有机肥的来源不同,各形态Cu和Zn在不同土壤中所占比例不同.土壤中施用畜禽粪便有机肥6个月时,Cu和Zn交换态以及铁锰氧化物结合态所占比例低于等量Cu和Zn无机盐处理,而有机结合态所占比例高于等量Cu和Zn无机盐处理,其它形态与无机盐处理无显著差异.     

pH对镉在土水系统中的迁移和形态的影响

研究了４种红壤和水体系中ｐＨ对镉的迁移影响．结果表明：镉在土水体系中的迁移是一快反应过程，４种土壤对镉的吸附量随土水系统中ｐＨ的变化，可分为３个区域，即低吸附量区、中等吸附区，以及强吸附和沉淀区，在中等吸附区镉吸附量与ｐＨ呈正相关；ｐＨ６以下被吸附的镉中生物有效态镉量随ｐＨ的升高而增加，ｐＨ６以上被吸附的镉中生物有效态镉量随ｐＨ升高而降低．石灰导致镉毒性降低的主要原因是ｐＨ＞７５时镉主要以粘土矿物和氧化物结合态及残留态形式存在．     

地层介质对垃圾渗滤液的pH缓冲性能研究

通过一维土柱穿透实验和静态实验,分别从空间和时间2方面研究了不同天然地层介质对垃圾渗滤液的PH缓冲性能.结果表明,细砂、粉砂和粘土的本底pH缓冲容量分别为79.9·pH-1 mmol/kg、207.5·pH-1 mmol/kg、456.4·PH-1 mmol/kg.受垃圾渗滤液污染后,除细砂外,随着时间的延长、离污染源距离的减小,每种介质总的pH缓冲容量都逐渐减小;其中碳酸钙缓冲体系的缓冲容量均逐渐增大;硅酸盐、阳离子交换缓冲体系的缓冲容量无明显变化;铝、氧化铁缓冲体系的缓冲容量逐渐减少,但土壤铝缓冲体系的缓冲容量则呈现出先增大后减少的趋势.细砂各个缓冲体系的缓冲容量随时、空变化均呈现出略微增大的趋势.4种介质对渗滤液的pH缓冲能力的顺序是:细砂<粉砂<粘土<土壤.土壤、粘土对垃圾渗滤液有较好的pH缓冲性能,同时对渗滤液中各种污染物的迁移,扩散也有较好的控制作用.     

pH值对海陆交互相土壤镉纵向迁移转化的影响

为揭示土壤pH值影响下海陆交互相土壤镉(Cd)纵向迁移转化规律,共布设18组土壤剖面,测定90组海陆交互相不同深度土壤中的pH值及重金属镉含量,运用地质累积指数和潜在生态风险指数法对Cd污染程度进行评价,采用相关分析识别土壤pH值对土壤Cd迁移转化的影响程度.结果表明:广州市南沙区土壤多属于中度-强污染,具有高潜在生态...     

红壤中质子化及铝的溶解与质子缓冲之间的关系

 用平衡实验及动力学实验研究了我国南方4种红壤的表面质子化及铝的溶解与质子缓冲之间的关系.结果表明,由于游离氧化铁的含量、活性及对铝溶解反应位的掩盖程度等与质子化密切相关因素的不同影响,4种红壤的总H⁺消耗量和铝溶解量不同,宁海红壤和嵊县红壤的质子化程度及H⁺的总消耗量大于永春红壤和屯溪红壤;屯溪红壤铝的溶解量最大,宁海红壤铝的溶解量最小.尽管屯溪红壤铝的溶解量最大,但H⁺的总消耗量却最小.当红壤中氧化铁含量较高时,铝的溶解在H⁺消耗中只起次要作用,质子化过程是H⁺消耗的主要途径.