植物多酚物质原位钝化污染土壤重金属的研究Ⅱ.对土壤Cu环境行为和生物活性的影响动态

通过室内好气培养和生物盆栽试验研究了缩合类植物多酚L和Y以及 8 羟基喹啉在污染红壤和潮土中的降解动态及其对土壤Cu环境行为的影响 .结果表明植物多酚在两周内降解相对较快 ,而 8 羟基喹啉则难以降解 .与空白相比 ,Cu污染土壤中施用植物多酚后土壤水溶性Cu显著下降 ,钝化Cu的效果次序为 :8 羟基喹啉 >多酚Y >多酚L .随着植物多酚的降解 ,土壤Cu被释出 ,其水溶性Cu浓度与残留在土壤中多酚浓度 (以DOC浓度表示 )呈负相关关系 ,尤其在潮土上更为明显 ,而pH与水溶性Cu没有相关性 .试验还发现 ,钝化剂施用后 ,小麦体内的Cu含量降低 ,因此 ,植物多酚是钝化重金属污染土壤的良好选择     

pH和水溶性有机质对苏打盐碱土壤吸附解吸汞的影响

苏打盐碱土壤是一种具有特殊理化性质的土壤。采用1次平衡法,研究不同pH和水溶性有机质(DOM)含量对苏打盐碱土壤吸附解吸Hg的动力学特征。结果表明:随着平衡溶液pH的增加,苏打盐碱土对Hg的吸附量呈现先升高后降低的趋势,其中最大吸附量出现在pH为3.5~5.5;对Hg的解吸量呈现先降低后升高的趋势,最小解吸量出现在pH为4.5~6.0。DOM对不同浓度Hg的吸附、解吸特征影响不一,当平衡溶液Hg浓度低于10 mg/L,DOM的增加显著降低土壤对Hg的吸附量;而当平衡溶液Hg浓度升高,DOM的增加反而促进Hg的吸附。当平衡溶液ρ(DOM)<100 mg/L时,DOM的增加对土壤中Hg的解吸起促进作用。苏打盐碱地土壤具有强碱性、低有机质的特性,不利于Hg在土壤中的存留。     

腐殖酸对土壤吸附四溴双酚A 的影响

采用批量平衡实验方法,研究了腐殖酸(HA)对3 种土壤吸附四溴双酚A(TBBPA)的影响,并且采用增溶法探讨了HA 与TBBPA 在溶液中的结合作用.结果表明,TBBPA 的表观溶解度随HA 加入浓度的增加而增加,二者在供试浓度范围内(以DOC 计,0~90mg/L)有较好的线性关系,计算得到的TBBPA 与HA 结合系数为8807L/kg.HA 的加入增加了TBBPA 在土壤中的吸附,增加的程度受土壤类型和HA 添加浓度的影响.分析发现,HA 对土壤吸附TBBPA 的影响主要与HA 和TBBPA 在溶液中的结合作用、在土壤中的累积吸附效应以及溶液pH 值等有关.     

施用有机物料对污染土壤水溶性有机物和铜活性的动态影响

采用黑麦草盆栽研究施用绿肥、污泥和猪粪后，对Cu污染土壤水溶性有机物(DOM)和土壤Cu环境行为动态的影响．施用有机物料后土壤DOM含量比对照增加0.4—7.5倍，尤以绿肥和猪粪最明显．但随时间延长DOM降解明显，尤其在第一周内．污染土壤中水溶性Cu浓度随DOM的降解而相应减少研究发现，施用污泥有利于降低污染土壤中水溶性Cu浓度和黑麦草对Cu的吸收量，这是污泥固相有机质对Cu吸持使其活性降低和污泥DOM使Cu活性提高二者综合作用的结果．与此相反，施用绿肥和猪粪后，黑麦草体内的Cu含量却明显提高，其中潮土上提高1．4～2．1倍，红壤上提高1．4-1．6倍．因此．施用有机物料改良重金属污染地需格外谨慎。     

耐铅、铜微生物的筛选及吸附性能研究

采用浓度梯度筛选的方法,从重金属污染土壤中分离筛选到两株耐受和吸附铅、铜的细菌G、Y。用单因素的方法得到G最适的培养条件为．T=30℃;pH=6．O;NaCl浓度为0．5％;Y的最适培养条件分别为：T=37℃;pH=8．5;NaCl浓度为0．5％。用原子吸收分光光度法测得,G、Y的冻干菌体对Pb2＋、Cu2＋的吸附量分别为：G铅 126．42mg／g,G铜75mg／g,Y钢61．08mg／g,Y钢45．86mg／g。G湿菌体对铅、铜的吸附率分别为：G铅94．66％,G铜92．84％;Y湿菌体对铅、铜的吸附率分别为：Y铅99．74％,Y铜97．96％。经检测,其遗传性状稳定。可进一步开发为重金属吸附剂。     

钙硼复合对土壤锌吸附-解吸热力学和动力学的影响

酸性紫色土对锌的等温吸附 -解吸和动力学试验表明 :锌的等温吸附符合 L angmuir方程 ,最大吸附量为15 3.8mg/kg土。钙、硼与锌复合 ,均降低土壤锌的最大吸附量及结合常数 K。所吸持的锌的解吸量和解吸率小 ,钙和硼均降低了锌的解吸率。土壤吸附锌的动力学以 Elovich方程 (Ct=a+blnt)描述最佳 ,反映土壤对锌吸附速率大小的方程参数 b值以 Zn>Zn+Ca+B>Zn+B>Zn+Ca。     

啤酒糟对活性染料的吸附特性研究

通过批式实验考察了不同条件对啤酒糟吸附活性黑31和活性蓝49的影响。结果表明：在较宽的溶液初始pH值范围内（2～9）,啤酒糟投加量为10g/L时,4h内啤酒糟能有效地对100mg／L活性黑31和300mg／L活性蓝49溶液吸附脱色。啤酒糟对活性黑31和活性蓝49的吸附率都随NaCl浓度的增加而降低。吸附率随时间的增加逐渐增大,8h内吸附基本达到平衡。染料初始浓度越高,吸附率越低。由该批式实验得到的最佳吸附脱色条件为：pH2．0,啤酒糟投加量15g／L,吸附时间8h。     

有机配体EDTA对土壤吸附和解吸稀土元素行为的影响

研究了有机配体EDTA对土壤吸附和解吸稀土元素La、Gd、Y的影响．结果表明,吸附作用在加入有机配体和稀土元素后0.5h便达到平衡,当存在单一稀土元素时,土壤对La、Gd、Y吸附量随EDTA浓度增加而减少,而在混合稀土元素条件下,土壤对各稀土元素的吸附与稀土－EDTA配合物稳定常数呈负相关,并且观察到竞争吸附现象．EDTA可促进稀土元素从土壤中解吸下来,解吸量与EDTA配体浓度呈正相关,其相关方程可用 1nX＝n 1n c＋1nK来描述     

柠檬酸对土壤吸附五氯酚的影响

采用批量平衡试验方法,研究了柠檬酸对黄棕壤、棕红壤和红壤吸附五氯酚(PCP)的影响.结果表明,供试3种土样对PCP的等温吸附曲线均可用Freundlich吸附等温方程描述,对PCP的吸附容量大小为黄棕壤>棕红壤3红壤,与其有机质含量大小顺序一致.实验条件下,随着柠檬酸加入浓度的提高(0~100mmol/L),棕红壤和红壤对PCP的吸附容量和吸附强度表现为先升高后下降的趋势,较低浓度(￡50mmol/L)的柠檬酸处理显著促进了它们对PCP的吸附,而较高浓度柠檬酸处理则抑制其吸附.供试浓度范围内,柠檬酸对PCP在黄棕壤中的吸附容量和吸附强度均表现为促进作用,但较高浓度柠檬酸处理下促进作用减弱.加入柠檬酸后,土壤吸附PCP的平衡溶液的pH值显著降低,这可促进PCP在土壤中的吸附,同时土壤固相有机质的释放和溶液中溶解性有机质(DOM)浓度的增加则可减少土壤对PCP的吸附.     

青霉菌GX2对蒽醌染料的吸附作用

GX2生长菌体对 4种蒽醌染料均表现出优良的吸附性能 ,但由于染料分子的结构不同 ,吸附速率和吸附率也表现出一定的差异 .染料对菌体的生长具有一定的抑制作用 ,但即使在很高的染料浓度下 ,GX2生长菌体仍表现出很强的吸附性能 .对 250mg/L活性艳蓝KN-R的吸附率高达 100% ,对 400mg/LKN R的吸附率也可达91.4% .在 0～2%范围内 ,随着盐度 (NaCl)的增加 ,菌体干重增加 ;颗粒状菌团的直径却随之减小 ,比表面积增大 ,对GX2生长菌体的染料吸附表现出较为明显的促进作用 .碳源浓度通过影响菌体的生长而影响染料吸附 ,当培养基中的葡萄糖浓度大于 2.5g/L时 ,即可使浓度为 120mg/L的活性艳蓝KN R溶液完全脱色 .生长菌体具有比静止活体和死体更好的吸附性能 .     

水溶性有机物在土壤剖面中的分馏及对Cu迁移的作用

通过室内土柱试验研究了DOM在土壤剖面中的“分馏”作用,DOM在纵向运移过程中的穿透行为及对污染的红壤和潮土中重金属Cu溶出效果的影响.结果表明,绿肥和猪粪DOM经过土柱后极性都有所降低,在潮土上的降低幅度较大,分别为11.4%和10.72%;DOM能够明显地增加污染土壤中Cu的溶出,且这种作用效果与DOM及土壤的性质有关,绿肥DOM的作用效果比猪粪DOM的强,整个淋洗过程中潮土上Cu的平均溶出量是红壤上的4.37倍(绿肥DOM)和3.03倍(猪粪DOM);由于微生物对DOM的分解作用,降低了DOM对土壤中Cu的溶出效果.     

水溶性有机物在土壤中的吸附及对Cu沉淀的抑制作用

通过室内序批试验研究了来自绿肥(GM)和猪粪(PM)的水溶性有机物(DOM)在潮土和红壤中的吸附行为以及来自绿肥和猪粪堆肥(PMC)的DOM对Cu在高pH下沉淀的影响.结果表明,当没有外源DOM加入时,潮土、红壤中存在DOM的净释放,分别为33.58mg·L^-1和17.17mg·L^-1.随外源DOM加入量的增加土壤净释放量减小,存在土壤对DOM的吸附作用.与绿肥DOM相比,土壤对猪粪DOM的吸附能力更强,m、K_d分别为0.424 1、2.946(红壤),0.284 6、1.58(潮土).比绿肥对应高出32.9%、57.1%(红壤),67%、93.7%(潮土).红壤由于Fe、Al、Mn等氧化物含量较高及低pH值,使其对DOM的亲和力比潮土强.试验结果还表明绿肥和猪粪堆肥DOM能够明显地抑制Cu的沉淀,在pH6～10范围内效果明显,其中Cu的沉淀率分别降低了43.6%(Cu+GM),22.6%(Cu+PMC).     

Impacts of soil organic matter, pH and exogenous copper on sorption behavior of norfloxacin in three soils

Norfloxacin (Nor) sorption and the factors (soil organic matter (SOM), pH, and exogenous copper (Cu) influencing the sorption were investigated in a black soil (soil B), a fluvo-aquic soil (soil F), and a red soil (soil R). With increasing of Nor concentrations, sorption amount of norfloxacin increased in both the bulk soils and their SOM-removed soils, but the sorption capacity in SOM-removed soils was higher than that of their corresponding bulk soils, indicating that the process of norfloxacin sorption in soil was influenced by the soil properties including SOM. The sorption data in all bulk soils and SOM-removed soils were fitted to Freundlich and Langmuir models. The correlation coefficients suggested that the experimental data fitted better to Freundlich equation than to Langmuir equation. Furthermore, the data from soil F and SOM-removed F could not be described by Langmuir equation. The norfloxacin sorption amount decreased in soil B and soil F, whereas it increased in soil R as solution pH increased. The maximum KD and KOC were achieved in soil R when the equilibrium solution pH was 6. And the norfloxacin sorption was also influenced by the exogenous Cu2+ ions, which depended on the soil types and Cu2+ concentrations. With increasing of Cu2+ concentrations in solution, generally, sorption amount, KD and KOC for norfloxacin in soils increased and were up to a peak at 100 mg/L Cu2+, and then the sorption amount decreased regardless of norfloxacin levels.     

熟污泥改性黄土对铜的吸附解吸特征

为探明熟污泥改性黄土对重金属的容纳能力,以熟污泥改性黄土为供试土样,采用序批实验法研究了供试土样对铜(Cu)的吸附解吸特征,并分析了供试土样对铜的固定能力及影响因素.供试土样对铜的吸附量在铜添加浓度小于100mg/L时急剧增加,在铜添加浓度大于100mg/L时增加缓慢,而解吸量的变化趋势则恰恰相反.Langmuir型吸附等温式是描述供试土样对铜的吸附过程的最佳模型,而吸附量与解吸量的关系可以很好的用指数函数来描述.供试土样对铜的固定吸附量随熟污泥含量的增加而增加,有机质含量是决定性因素.     

垃圾渗滤液水溶性有机物对土壤吸附重金属Cd2+、Pb2+的影响

采用序批次吸附试验,研究了不同填埋年限(0、4～5、12a)垃圾渗滤液中的DOM对土壤吸持重金属Cd2 、Pb2 的影响.结果表明,垃圾渗滤液中的DOM能促进土壤对重金属Cd2 、Pb2 的吸附.在有垃圾渗滤液DOM存在的条件下,Cd2 、Pb2 的吸附等温线可用Freundlich方程拟合(R2＞0.94),土壤对Cd2 、Pb2 的吸附量比对照处理(无垃圾渗滤液DOM)分别高1.13～1.42倍和1.09～1.84倍,填埋年限长的垃圾渗滤液较之填埋年限短的渗滤液对土壤吸附Cd2 、Pb2 的影响强烈.在Cd2 、Pb2 初始浓度相同时,潮土较红壤具有更高的吸持能力,并且随体系pH的增高,其吸持量增加.     

Release behavior of copper and zinc from sandy soils

The concentrations and chemical forms of copper(Cu) and zinc(Zn) in surface soils directly influence the movement of Cu and Zn. In this study, thirteen sandy soil samples with a wide range of total Cu and Zn concentrations were collected for evaluating the relationships between Cu and Zn release and extraction time, ratio of soil to water, pH and electro;yte types. The results indicated that Cu released in batch extraction that represents long-term leaching was mainly from exchangeable, and carbonate bound Cu fractions, and Zn released in the batch extraction was mainly from its carbonate bound fraction. However, the Cu and Zn leached from the soils using the column leaching that represents short-term leaching were mainly from their exchangeable fractions. Soil column leaching at different pH values indicated that the amounts of leached Zn and Cu were greatly affected by pH. The Cu and Zn release experiments with varying extraction times and ratio of soil to water suggest that long-term water-logging in the soils after rain may increase contact time of the soils with water and the release of Cu and Zn to water from the soils, and total amounts of Cu or Zn released from the soils increase, but the Cu or Zn concentration in the surface runoff decrease with increasing rainfall intensity. The increased Ca concentration in soil solution increased stability of organic matter-mineral complexes and might decrease the dissolution of organic matter, and thus decreased the release of Cu-binding component of organic matter. However, high concentration of Na in the soil solution increased the dispersion of the organic matter-mineral complexes and increased dissolution of organic matter and the release of Cu from the soils.     

水溶性有机物对草萘胺在土壤中吸附与迁移的影响

采用批次吸附试验和土柱淋洗试验,研究了绿肥和污泥中水溶性有机物(DOM)对除草剂草萘胺在黄棕壤和石灰性潮土上吸附和迁移影响.结果表明,供试DOM均能明显降低草萘胺在2种土壤上的吸附,促进草萘胺的迁移,在黄棕壤上效果更明显.在所研究的草萘胺和DOM浓度范围内,绿肥DOM(GM)都比污泥DOM(SS)作用显著.草萘胺的吸附等温线可用Freundlich方程定量描述.绿肥DOM和污泥DOM可分别使黄棕壤中草萘胺吸附量比对照处理(不加DOM)减少22.9%和11.3%,使迁移出土体的草萘胺总量提高了73.42%和26.87%,而使潮土中草萘胺的吸附量减少了9.5%和6.5%,迁移出土体的草萘胺总量增加了43.54%和28.29%.因此,农业土壤中溶解性有机物对农药环境行为有一定影响.     

Changes in the sorption, desorption, distribution, and availability of copper, induced by application of sewage sludge on Chilean soils contaminated by mine tailings

The effect of mine tailings and sewage sludge was evaluated on sorption, desorption, availability and distribution of copper in two soils, one high (sandy soil) and one low in copper (clay soil). In both soils contaminated by mine tailings the copper sorption capacity and the affinity of the substrate for the metal decreased substantially compared to the uncontaminated soils, however, the sorption remained always high in the clay soil substrates. In the substrates with sandy soil, the high Cu content and lower clay content were determining factors in the lower magnitude of the sorption. Similarly, metal desorption was closely related to these two parameters, and it was higher in clay soil with lower pH. In general, the application of sewage sludge favored the sorption of Cu in soils contaminated and uncontaminated with mine tailings, and in all cases desorption decreased, an effect that remained for at least 30 days. Simple extraction of Cu with CaCl2 and diethylenetriaminepentaacetic acid gave contradictory results, so a careful choice of the procedure is required, depending on the level of metal in the soil and on the acting principle of the extracting agent. In that relation, more complete information on the changes in the metal forms was obtained by application of the sequential extraction procedure proposed by the European Community Bureau of Reference.     

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.