土壤和植物中镉的污染及防治

阐述了镉在土壤中的含量与形态,镉对植物的毒害效应,各种植物对镉富集能力,以及植物对镉的吸收和在不同器官的积累差异,还综述了镉对植物叶细胞超微结构的影响,提出了防治农业生态系统中镉污染的方法。     

不同活化剂对镉、铅单一及复合污染土壤的修复效果影响

选取柠檬酸(CA)、木醋液(WV)、聚天冬氨酸(PASP)、羟基乙叉二磷酸(HEDP)和FeCl3作为活化剂,以镉、铅单一和复合污染土壤为研究对象,采用振荡淋洗法结合形态分析技术研究活化剂对重金属污染土壤的修复效果。结果表明:(1)重金属单一污染时,5种活化剂对镉、铅均有一定的淋出效果,淋出效率均随活化剂浓度的增大而增大。活化剂通过淋洗实验主要淋出酸溶态和可还原态重金属。(2)重金属复合污染时,金属离子间的竞争作用会不同程度地影响重金属在土壤中的存在形态,进而影响重金属的淋出效率,多数情况下,铅的存在会促进镉的淋出,但镉的存在会抑制土壤铅的释放。     

氮对镉胁迫下东南景天根系形态及镉积累的影响

通过水培试验,研究了供氮(尿素)对镉胁迫下两种生态型东南景天根系形态及镉积累的影响.实验结果表明,当供氮水平为4～16 mmol/L时,能明显促进东南景天的根系生长;当供氮水平为32～64 mmol/L时,与对照相比,东南景天的根系长度、根系表面积和根系体积等指标明显受到抑制.不同供氮水平对两种生态型东南景天0＜D≤0.2 mm的根系生长影响最大,而对D＞0.2 mm的根系影响较小.不同供氮水平下,两种生态型东南景天均以0＜D≤0.4 mm的根系为主,其中根系长度、根系表面积和根系体积分别占总根系长度、总根系表面积和总根系体积的66.3%～81.2%、68.5%～80.3%和62.1%～79.8%.氮素对东南景天的镉积累有一定的促进作用,随着氮素用量的增加,镉积累逐渐升高,与根系形态不同的是,镉积累量在供氮水平为32 mmol/L 时达到最大.适当提高营养液氮素用量有利于提高东南景天的各项根系形态指标和镉积累量.     

氮素形态对烟草根际镉的有效性及镉吸收的影响

采用盆栽实验,研究了不同氮素形态对酸性紫色土和中性紫色土中烟草根际有效镉含量及烟草吸收镉的影响。结果表明,氮素形态对烟草根际有效镉含量的影响不显著,但铵态氮(AN)和铵态氮+硝化抑制剂双氰胺(AN+DCD)使非根际有效镉含量显著提高。2种土壤中,烟草的生物量均以AN+DCD处理最高;烟草地上部镉含量在酸性紫色土中以硝态氮(NN)处理最高,中性紫色土中则以AN+DCD处理最高;烟草地上部镉累积量均以AN+DCD和AN+NN处理最高。从植物修复角度,2种土壤宜以铵态氮与硝态氮混合或铵态氮与双氰胺混合方式施用。     

添加天然沸石和石灰对土壤镉形态转化的影响

采用土壤培养实验,研究镉污染土壤中添加沸石、石灰及两者配施对土壤pH值和土壤镉形态变化的影响。结果表明,土壤pH值随沸石用量的增加而增加,随培养时间呈现先增加后下降并逐渐趋于稳定的趋势,但均高于对照。高剂量石灰的处理对土壤pH的影响最大,与对照相比土壤pH提高了3.33个单位。在土壤5~50 d培养过程中,石灰处理的土壤交换态镉含量呈现先逐渐降低而后略有升高的趋势,其余处理均呈下降趋势。培养50 d后,高剂量的沸石、石灰及高剂量沸石与石灰配施处理的土壤交换态镉含量从5 d时的67.54、61.95和55.56 mg/kg降低至54.65、49.93和45.96mg/kg。相关分析表明,不同培养时期交换态镉含量与土壤pH值呈负相关关系。在10个处理中,L2Z3(石灰2 g/kg土和沸石60 g/kg土)组合处理效果最好,使土壤交换态镉含量下降了34.68%,碳酸盐结合态镉含量上升了4.30%,铁锰氧化结合态镉含量上升了16.97%,有机结合态镉含量上升了1.31%,残渣态镉含量上升了12.11%。     

菜籽饼施加对镉-铜污染土壤中重金属形态转化及其植物有效性的影响

选择菜籽饼作为有机物料,模拟水田条件,研究菜籽饼施用后重金属污染土壤中镉-铜的赋存形态的变化及其有效性的影响。结果表明,菜籽饼施加后,土壤pH波动在0.5内,变化较小。但在一定程度促进土壤中镉、铜由弱酸提取态向可还原态转化,残渣态占比变化均较小。经培养一定时间,植物有效态DTPA-Cd由1.26±0.03下降至0.69±0.03,下降幅度约为45.2%,DTPA-Cu由82.9±0.09下降至48.7±0.09,最大下降幅度约为41.3%,下降较为明显。同时,土壤溶液中可溶性碳（DOC）和可溶性氮（DON）的含量显著增加,分别增加约4.14倍和6.48倍,因此,菜籽饼应用于重金属污染水稻土改良,可以间接降低水稻中重金属的含量。     

黔中地区不同污染风险等级黄壤镉形态分布特征

为探究喀斯特地区地带性黄壤的镉形态分布特征,在中国南方喀斯特中心区域——黔中地区进行了农田黄壤样品采集,并对其化学成分进行了定量分析,通过对土壤镉形态及pH、钙、镁的分析测定,探究了喀斯特背景对黄壤中镉形态分布的影响。结果表明,黔中地区黄壤全镉为0.184～3.316mg/kg,具有较大的空间差异,各形态镉含量随污染风险等级的提高而显著增加(p<0.01)。黄壤中的镉主要以残渣态及可还原态存在,可交换态镉占全镉的17.52%(质量分数,下同)～22.83%,且随着风险等级的提高,可交换态镉向更为稳定的形态转变。可交换态镉与全镁、可交换态镁均显著负相关(p<0.05),镁组分可在一定程度上降低黄壤中可交换态镉含量,对镉的生物有效性具有一定的调控作用。     

污泥焚烧中Cd形态转化的热力学平衡模拟

采用热力学平衡分析方法,结合典型污泥成分和焚烧条件预测了污泥焚烧过程中重金属Cd的转化和迁移规律。模拟计算中考虑了主量矿物质与Cl、S对Cd的形态转化的影响。研究结果表明,污泥焚烧过程中,在低温的条件下Cd主要以固体碳酸盐形式存在,随着温度升高,碳酸盐分解为固态CdO,随后有气态Cd(OH)2、Cd和CdO生成,并且在较高温度主要以气态Cd存在。焚烧体系中,矿物质SiO2对Cd的形态转化影响大于其他矿物质,SiO2能与Cd结合生成稳定的CdSiO3,从而可有效抑制含Cd气态污染物的排放。焚烧体系中Cl较易与Cd结合形成CdCl2而导致Cd的挥发,Cl含量的增加促进了Cd在焚烧体系中的挥发。在低温阶段,Cd易与S结合形成固态硫酸盐,抑制了金属的挥发;在高温阶段,金属的形态转化基本不受S的影响,但是可以影响气态金属Cd的生成温度。根据污泥在不同焚烧温度、Cl含量、S含量条件下Cd的不同产物形态,可以对Cd的污染进行有效控制。     

公路两侧土壤中铅和镉污染以及存在形态分布的分析

测定了土壤中铅、镉总量,并采用五级连续浸提法和石墨炉原子吸收分光光度法对北京市3条典型公路两侧的土壤样品中铅和镉的存在形态分布进行了测定.结果表明,所选3条公路出京方向右侧的土壤铅和镉污染严重,其铅、镉总量分别是北京地区土壤铅和镉含量背景值的1.62～6.69、5.97～18.74倍.土壤中铅主要以铁锰氧化物结合态、碳酸盐结合态、有机结合态和残渣态等形式存在,镉主要以铁锰氧化物结合态和残渣态形式存在,而活性强的离子交换态浓度均较低.不容忽视的是,铅和镉的碳酸盐结合态在碱性条件下稳定,但是具有遇酸释放的隐患.     

冻融循环对含铁材料稳定砷污染土壤的影响

为分析冻融循环对污染土壤砷（As）的稳定化性能的影响,投加4种含铁材料（FeSO4、FeS、Fe2（SO4）3和Fe0）对土壤中的As进行稳定化处理,并通过实验室模拟冻融过程,研究4种含铁材料稳定化处理后土壤中无定形氧化铁含量、氧化铁活化度、pH和As的浸出毒性随冻融循环的变化。结果表明：4种含铁材料稳定化土壤无定形氧化铁含量与氧化铁活化度随冻融循环的变化趋势基本一致;冻融循环降低了无定形氧化铁的含量,促进了铁氧化物的结晶老化。与未冻融土壤相比,冻融循环增加了稳定化土壤As的浸出毒性,但在冻融后期,As浸出毒性的增加量呈降低的趋势。4种含铁材料稳定化土壤As的浸出毒性随冻融循环表现出不同的变化趋势。1% Fe0稳定化土壤经过冻融循环As的稳定性最高,1% FeSO4和1% Fe2（SO4）3稳定化土壤次之,而1% FeS稳定化土壤最低。因此,冻融循环增加了稳定化土壤As再释放的环境风险,Fe0用做冻融地区As污染土壤稳定化药剂较为合适。     

中国商品有机肥重金属分析

测定了来自10个地区不同生产原料的118个商品有机肥样品的重金属含量.结果表明:(1)商品有机肥样品中的Cd、Hg、Pb、Cr、As、Zn、Cu、Ni的平均值分别为0.600、0.120、7.34、84.30、9.45、202.91、91.06、11.01 mg/kg.(2)河南、湖北、上海的商品有机肥中8种重金属平均值均较高;内蒙古的商品有机肥中Cr平均值为20.32 mg/kg,广西的商品有机肥中Zn平均值为51.36mg/kg,远低于所有样品中Cr和Zn平均值.(3)以猪粪为主要生产原料的商品有机肥中重金属平均值最高.(4)Cr超过中国商品有机肥重金属限量标准、欧盟生态标志法的重金属限量标准、加拿大堆肥重金属限量标准(A级)和加拿大堆肥重金属限量标准(B级);As、Cd超过中国商品有机肥重金属限量标准、欧盟生态标志法的重金属限量标准和加拿大堆肥重金属限量标准(A级);Cu、Zn超过欧盟生态标志法的重金属限量标准和加拿大堆肥重金属限量标准(A级);Hg超过加拿大堆肥重金属限量标准(A级);Pb超过中国商品有机肥重金属限量标准;Ni均未超标.     

生物菌肥与石灰配施对水稻吸收积累Cd的影响

采用田间随机区组试验的方法,研究了基施生物菌肥(Bi处理)与追施石灰(L处理)及其配合施用(Bi+L处理)对晚稻湘晚籼12号生物量、水稻对土壤Cd的富集情况、4个生育期内各部位间转运系数以及各部位中Cd含量的影响。结果表明,水稻各部位间Cd含量从大到小依次为根部、茎鞘、穗部、叶片,随不同生育期对营养物质的需求而改变,各处理不会影响水稻生物量及转运系数,并能降低水稻各部位富集Cd能力,使水稻糙米中Cd含量显著降低,其中以生物菌肥与石灰配施的降Cd效果最佳。     

土壤中Pb、Cd的稳定化修复技术研究进展

在众多重金属修复技术当中,稳定化技术具有花费少、环境损失小等诸多优势。综述了国内外土壤中Pb、Cd稳定化修复的研究进展;分析了稳定剂的作用机制、土壤中Pb、Cd的赋存形态;探讨了土壤中Pb、Cd稳定化修复的主要影响因素。最后,还提出了稳定化修复技术在土壤中Pb、Cd污染治理应用中尚存在的问题。     

Relationships between organic matter, black carbon and persistent organic pollutants in European background soils: Implications for sources and environmental fate

Black carbon (BC) and total organic carbon (TOC) contents of UK and Norwegian background soils were determined and their relationships with persistent organic pollutants (HCB, PAHs, PCBs, co-planar PCBs, PBDEs and PCDD/Fs) investigated by correlation and regression analyses, to assess their roles in influencing compound partitioning/retention in soils. The 52 soils used were high in TOC (range 54-460 mg/g (mean 256)), while BC only constituted 0.24-1.8% (0.88%) of the TOC. TOC was strongly correlated (p < 0.001) with HCB, PCBs, co-PCBs and PBDEs, but less so with PCDD/Fs (p < 0.05) and PAHs. TOC explained variability in soil content, as follows: HCB, 80%; PCBs, 44%; co-PCBs, 40%; PBDEs, 27%. BC also gave statistically significant correlations with PBDEs (p < 0.001), co-PCBs (p < 0.01) and PCBs, HCB, PCDD/F (p < 0.05); TOC and BC were correlated with each other (p < 0.01). Inferences are made about possible combustion-derived sources, atmospheric transport and air-surface exchange processes for these compounds.     

Biodegradation of Kupferschiefer black shale organic matter (Fore-Sudetic Monocline, Poland) by indigenous microorganisms

This study provides the first evidence for the direct biodegradation of persistent organic matter extracted from the organic-rich polymetallic black shale ore Kupferschiefer, one of the most important sources of metals in the world. It was demonstrated that an enriched community of indigenous heterotrophic microorganisms isolated from black shale grown under aerobic conditions could utilize shale organic matter as the sole carbon and energy source. Colonization of shale organic matter was observed. The main biodegradation intermediates and products such as phosphonic acid dioctadecyl ester and isoindole-1,3 were detected in the aqueous phase of cultures. The bacterial community showed the ability to PAH biodegradation, assimilation of organic acids and esters as well as lipase activity. The intracellular accumulation of phosphorus by bacteria during growth on organic matter was confirmed. Strains within the genus Pseudomonas were found to dominate the bacterial population at the end of the experiment. The results of this study confirm that indigenous bacteria are likely to play a role in the biotransformation of black shale and can influence the geochemical cycles of ancient organic carbon in the deep terrestrial subsurface. This process may also occur in tailings ponds containing black shale, and cause the mobilization of potentially toxic compounds to the soil and groundwater.     

Pollution characteristics of 23 veterinary antibiotics in livestock manure and manure-amended soils in Jiangsu province,China

The aim of this study was to investigate the pollution characteristics of typical veterinary antibiotics in manure and soil of livestock farms in Jiangsu province. This investigation employed solid-phase extraction (SPE) coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). A total of 53 manure and 50 amended soil samples from 16 livestock farms in Jiangsu province were collected for analysis. In the manure samples, the highest detected frequencies and concentrations were those of tetracyclines (TCs, 54.1 ± 5775.6 μgkg^?1), followed by fluoroquinolones (FQs, 8.4 ± 435.6 μgkg^?1), sulphonamides (SAs, 3.2 ± 5.2 μgkg^?1) and macrolides (MACs, 0.4 ± 110.5 μgkg^?1). Statistical analysis was used to illuminate the pollution characteristics of 23 veterinary antibiotics for various animal types and different regions in Jiangsu province. The results showed that the pollution level in cow manure was relatively lower compared with pig and chicken manure due to the relative restriction of medication. Furthermore, contamination was serious in amended soil from chicken farms. The pollution level in manure among different regions was higher to the south and north compared with the centre of the region. The same outcome was found for soil. Antibiotic residues in organic fertilizer were also investigated in this study. We found that although the detected concentration was lower in organic fertilizer than in fresh manure, detection frequencies (10–90%) were high, especially for roxithromycin (90%) in MACs (30–90%). This finding suggests attention should be paid to the pollution levels in organic fertilizer. This study is the first extensive investigation of the occurrence and distribution of many kinds of typical veterinary antibiotics in manure and soil from livestock farms of Jiangsu province. This investigation systematically assesses veterinary antibiotics usage and related emissions in southeast China.     

The effects of chemical remediation treatments on the extractability and speciation of cadmium and lead in contaminated soils

Two rural soils contaminated by cadmium (Cd) and lead (Pb) were used to evaluate the effect of different chemical treatments on changes in speciation and extractability of Cd and Pb, and in phytoavailability to wheat. Triplicates of seven chemical treatments were tested to compare and evaluate the remediation techniques for contaminated soils using pot experiments. Treatments applied were calcium carbonate, a high quantity of phosphate salt, hog composts, iron oxide, manganese oxide, zeolite, and unamended control. Wheat (Triticum aestivum) was planted in the different amended soils for a further one month to evaluate the effectiveness of treatments on uptake of Cd and Pb by the wheat shoots. Results indicated that addition of calcium carbonate, manganese oxide, or zeolite reduces the extractability of Cd or Pb in both soils, and significantly reduce the uptake of Cd and Pb by wheat shoots. Changes in the extractability and metal sequential fractionations indicate that the exchangeable (or available) form of Cd and Pb in two soils can be transformed into unavailable forms after these amendments.     

Effect of arsenic and mercury speciation on inhibition of respiration rate in activated sludge systems

The inhibition effect of arsenite, As(III), arsenate, As(V), inorganic mercury, Hg(II) and methylmercury, MeHg, on the respiration rate of activated heterotrophic sludge microorganisms was evaluated. As(III) and MeHg were much more toxic to activated sludge than As(V) and Hg(II) respectively. The effect of various experimental parameters on the toxicity, such as sludge age, concentration of suspended solids and exposure time, was investigated. An increase of sludge age or the concentration of suspended solids reduces the observed inhibition. Longer exposure seems to dramatically increase the inhibition of As(III), MeHg and Hg(II) during the first hours of exposure, while the later inhibition increases at a slower rate. On the contrary, in the presence of As(V), 24 hours after exposure, the respiration rate was similar to that of the control biomass.     

Effect of clay and organic matter type on the ecotoxicity of zinc and cadmium to the potworm Enchytraeus albidus

Clay and organic matter are considered as important parameters influencing bioavailability and ecotoxicity of metals in soils. As there exists a large variation in the type of clay and organic matter in field soils, the quantity of these variables alone may not be good indicators of metal bioavailability. To test this hypothesis, toxicity experiments with the potworm Enchytraeus albidus were conducted in artificial soils with three types of clay and seven types of organic matter, while the soil pH was kept constant. The 14d LC₅₀ of zinc and cadmium varied from 83.0 to 1140 mg Zn/kg D.W. and from 55.2 to 704 mg Cd/kg D.W., respectively, depending on the type of clay and organic matter that were used. Simultaneous measurements of the cation exchange capacity showed that this soil parameter is a better indicator of the bioavailability as it takes into account the type of clay and organic matter as well as other adsorption phases such as metal oxyhydroxides.     

Effect of four experimental insecticides on enzyme activities and levels of adenosine triphosphate in mineral and organic soils

Abstract

A laboratory study was conducted to determine the effect of four experimental insecticides, DOWCO429X, DPX43898, tefluthrin and trimethacarb, on enzyme activities and levels of adenosine 5'‐triphosphate (ATP) in mineral and organic soils. DOWCO429X decreased urease activity in organic soil after 7 days while a stimulatory effect was observed with most treatments after 14 days. No inhibition on acetylene (C₂H₂) reduction by nitrogenase was evident with any of the insecticides in either soil. With the exception of DOWCO429X and tefluthrin at 7 days in organic soil, none of the insecticide treatments inhibited dehydrogenase activity in either soil. Dehydrogenase activity, measured by formazan formation, was greater in many samples in sandy loam than the control throughout the experiment. No inhibitory effect was observed on amylase activity after 2 or 3 days in sandy soil. A stimulatory effect was apparent in many samples after 2 days in organic soil. All insecticide treatments in sandy soil reduced invertase activity at 2 days. However, none of the experimental insecticides inhibited invertase activity after 3 days. A stimulatory effect in invertase activity was apparent in most cases at 2 days in organic soil and no difference was observed after 3 days. Phosphatase activity in insecticide treated samples was equal to or greater than that of control in sandy soil after 2 h. With the exception of DPX43898, the insecticides depressed phosphatase activity in most organic soil samples. The insecticides did not affect ATP levels in either soil. Results indicated that the chemical treatments at the levels tested did not significantly affect activities of enzymes or level of ATP in both soils.