用黑麦幼苗法测定土壤中污染元素的生物有效性

本文对全国污灌区１２个土样中Ｃｄ形态与生物有效性的试验表明，Ｃｄ的交换态，吸附态，有机结合态均有效，且有机结合态最为有效，对紫阳县富硒土壤的试验表明：黑麦幼苗中的总Ｓｅ量与０．１ｍｏｌ／１ＫＨ２ＰＯ４的浸提量最为相关，从而推荐该法为酸性土壤有效Ｓｅ的浸提方法，对西安污水厂污水污泥在娄土上不同施用量的试验表明：幼苗中Ｎ，Ｐ随施用量增加而增加，Ｎ，Ｐ的有效率分别为５０－７０％及１５－２８％；黑麦幼苗中     

耕地土壤铜、镉、锌形态及生物有效性研究

土壤重金属总量常被用来评估土壤质量安全,但是大量事实说明单纯用土壤重金属总量并不能完全说明土壤重金属的生物有效性及其环境风险。相对于国内外常用的Tessier的五态方法,欧共体标准物质局提出的三步提取法（BCR法1,中国地质调查局地质连续提取法的七态标准少见报道。本研究选取河南平原耕地样品,采用中国地质调查局地质连续提取法（DD2005．03）进行耕地中重金属元素（Cu、Cd、Zn）的形态分布,结果表明：Cu、Zn主要以残渣态存在,其残渣态分别占全量的55．80％和67．35％。Cd以离子交换态为主,占全量的27．30％。Cu、Cd、Zn各态含量占全量比例的顺序是,Cu：残渣态〉弱有机结合交换态〉铁锰氧化态〉碳酸盐结合态〉强有机结合态〉水溶态〉离子交换态。Cd：离子交换态〉弱有机结合交换态〉强有机结合态〉残渣态〉碳酸盐结合态〉铁锰氧化态〉水溶态。Zn：残渣态〉铁锰氧化态〉弱有机盐结合态〉离子交换态〉强有机结合态〉碳酸盐态〉水溶态。从生物可利用性系数k来看,Cd主要以活动性较大的状态存在,很容易被作物吸收。     

广州城市水体沉积物中重金属形态分布研究

选取广州城市水体中的４ 个污染沉积物样品,采用连续提取法研究沉积物中重金属元素（ Ｐｂ 、 Ｚｎ 、 Ｃｕ 、 Ｎｉ 、 Ｃｒ 、 Ｍｎ） 的形态分布,结果表明：重金属元素主要以残渣态、有机结合态和氧化铁结合态存在,其中 Ｐｂ 、 Ｎｉ、 Ｍｎ 以残渣态和氧化铁结合为主, Ｚｎ 以残渣态和有机结合态为主, Ｃｕ 以有机态和氧化铁结合态为主, Ｃｒ 以氧化铁结合态为主。沉积物中固相组分对重金属的富集能力为：无定型氧化锰＞ ＞ 碳酸盐＞ 氧化铁＞ 有机质,而富集量则是后两者大于前两者。     

天津市蓟州区土壤硒的有效性及影响因素

以天津市蓟州富硒区土壤为研究对象,对土壤中硒含量、有效硒含量及硒的形态特征进行分析,并对土壤有效硒的影响因素进行研究.结果表明,蓟州富硒区土壤总硒的含量范围0.14—0.65 mg·kg~(-1),均值为0.37 mg·kg~(-1),高于蓟州区环境背景值0.23 mg·kg~(-1)和全国土壤硒元素的平均值0.29 mg·kg~(-1).土壤有效硒的均值为0.021 mg·kg~(-1),有效度为5.63%.研究区土壤硒元素以强有机结合态和残渣态为主,两种形态的平均含量分别为0.14 mg·kg~(-1)和0.11 mg·kg~(-1),占总硒的比例分别为44%和35%,水溶态、离子交换态和碳酸盐结合态的硒含量较少,仅占总硒含量的4.6%,1.7%和0.9%.土壤中有效硒的含量近似等于水溶态、离子交换态和碳酸盐结合态硒的含量之和,且两者的差异性检验结果显示并无显著性差异.土壤中有效硒与硒全量、pH和有机质均呈显著的正相关关系,偏分析结果表明有效硒主要受土壤硒含量和pH的影响.     

上海化学工业区土壤重金属元素形态分析

选取上海化学工业区土壤背景值样品，采用Tessier A连续提取法研究土壤中6种重金属元素的形态分布。研究结果表明，在该化工区土壤中，Cd主要以可交换态和铁锰氧化物结合态为主，分别占总量的41．5％和36．7％，说明元素Cd较活泼，具有潜在的环境影响能力，应该给予更多的关注；Cr、Cu、Ni和Zn等4种元素主要以有机结合态和残余态为主，两者分别占总量的41．4％、58．9％、31．4、32．5％和45．9％、31．5％、57．4％、52．3％；而Pb则主要以有机结合态形式存在，其占总量的87．8％；元素形态分析表明Cr、Cu、Ni、Zn和Pb这5种元素相对比较稳定。     

深圳湾红树林沉积物-植物体系汞的分布规律和形态分配特征

为了解重金属汞在非根际沉积物-根际沉积物-红树植物连续体系中的分布特征和迁移规律,以及沉积物中汞的化学形态特征,于深圳湾福田红树林实地采集红树植物幼苗样品及其林下沉积物样品,采用连续提取法对沉积物中汞的各种化学形态进行提取,通过冷原子荧光光谱仪进行定量分析。研究对象包括福田红树林3种常见红树植物,包括白骨壤(Avicennia marina)、桐花树(Aegiceras corniculatum)2个本土种和海桑(Sonneratia caseolaris)1个引进种,并以无植被覆盖的光滩作为空白对照。结果表明,在沉积物-红树植物体系中,根际和非根际沉积物中的总汞含量均高于红树植物幼苗。进入植物体后,汞在茎中的含量均小于根和叶。本土种植株表现出较强的汞积累能力。白骨壤幼苗汞积累量最高,质量分数达到45.32 ng·g-1,其次为桐花树幼苗,汞质量分数为23.49 ng·g-1。3种红树植物对汞的生物积累因子在0.02~0.35范围内,迁移因子处于0.4~0.99范围内,均低于1,表明它们从土壤吸收、并向地上部分运输汞的能力较弱,倾向于采取金属排斥策略,以实现植物体的自我保护。非根际沉积物中汞的各个化学形态质量百分比表现为有机结合态可挥发态残渣态可交换态碳酸盐结合态铁锰氧化物结合态,根际沉积物中汞表现为可挥发态机结合态残渣态铁锰氧化物结合态可交换态碳酸盐结合态,总体表现为生物可利用态和潜在可利用态质量分数较高,不可利用态较少。与本土种相比,引进种海桑能够将更多汞以稳定性相对较高的生物不可利用态和潜在可利用态形式固定于土壤中,表现出较好的治理汞污染能力。     

喀斯特深水湖泊富硒沉积物中Se的赋存特征

采用硒的循环提取技术,改进后对湖区沉积物中重金属元素硒进行地球化学形态分析.分析结果表明,红枫湖沉积物中Se的硫化物结合态平均含量最高,占总量的45.7%,其含量顺序为硫化物结合态>残渣态>有机结合态>可交换态>酸溶态>水溶态.并采用次生相富集系数法(SPEF)评价红枫湖沉积物中的Se,结果得KSPEF=2.58,即重金属元素Se可能存在某种人为污染.利用配备X射线能谱的电子显微镜进行微形貌的观察,结果表明,沉积物中除去土壤中常见的元素含量外,S的含量较高,约为0.61%(重量比),但并未发现自然Se的存在.应用X射线多晶衍射仪对沉积物中Se的晶型进行分析,红枫湖沉积物中MSe、MSeO4、MSeO3、MSe2O5和含Se的有机化合物是Se元素存在的主要晶型(其中M为金属离子).加之沉积物中有机质及Se的可利用态含量较高,故红枫湖沉积物经植物修复后,可用于富硒农作物的种植.     

渍水土壤中硒迁移行为的研究

用土柱模拟4种加硒处理的土壤还原淋溶过程，研究了硒在土壤中的迁移和积累。结果表明，未加硒处理（土壤背景硒）的溶液中硒的迁移以有机硒占优势，Se(Ⅵ）及Se（Ⅳ）占的比例很小；土壤富野酸硒由上层向下层迁移。外源蛋白硒的处理的溶液中硒迁移为有机硒，部分外源硒以富里酸硒积累在下层土壤。外源Se(Ⅵ）和Se（Ⅳ）处理的溶液中硒迁移量只占加入量的0．2％和0．4％，硒迁移的主要形态前者为有机硒，后者为Se(Ⅳ）和有机硒；外源Se（Ⅵ）和Se(Ⅳ）的绝大部分以富里酸硒的形态积累于土壤，其积累量Se（Ⅵ）处理高于Se(Ⅳ）处理，上层土壤高于下层土壤。     

粤东凤凰山茶区土壤氟化学形态特征及其影响因素

采用连续化学提取法对粤东凤凰山茶区12个较大型茶园共60份土壤样品氟的5种化学形态分布进行研究.结果发现,土壤中氟的5种化学形态分布的规律为残余态〉〉铁锰结合态〉有机态〉水溶态〉可交换态.水溶态氟含量与可交换态氟含量、残余态氟含量及总氟含量呈显著正相关性,而铁锰结合态含量与有机束缚态之间呈显著正相关性,残余态与总氟之间...     

水分条件对紫色土中铅形态转化的影响

以培养试验模拟3种水分条件（80％田间持水量、于湿交替及淹水）下,重金属铅（Pb）在紫色土中形态转化的动态过程,结果表明,外源Pb进入紫色土后,随着培养时间的增长由交换态向碳酸盐态、铁锰氧化物态、有机结合态转变,残渣态所占比例基本稳定．Elovieh方程可以拟合交换态Pb在紫色土中转化的动力学过程．交换态Pb在土壤中的...     

Speciation of heavy metals in sediments from the Scheldt estuary,Belgium

A simple three-step sequential extraction procedure was applied to study the speciation of heavy metals in sediment from Scheldt estuary, and their relationship to sediment grain size and organic matter content. The sedimentary metal content was fractionated into carbonate and exchangeable, metals bound to organic matter and residual fractions. Sedimentary total metal content was also determined using an industrial microwave (ETHOS 900) HF/HNO₃ extraction method. The extracts were analysed for metals using inductively coupled plasma atomic emission spectrometry. The bioavailable fraction (exchangeable and metals bound to organic matter) comprised less than the other forms. Residue metals were the dominant form of metals in almost all studied sites. The average total metal content for the studied sites decreased in the order Fe>Cr>Cu>Co>Zn>Pb>Cd. Based on average values for the studied sites, the highest bioavailable metals in sediments were Cd (38%) from Westkapelle, Zn (17%) from Yerseke, Co (12%) from Domburg, Cr (9%) from Vlissingen, Fe and Pb each (2%) from Yerseke, and Cu (1%) from Domburg. Metal recovery was good, with<10% difference between the total metal recovered through the extractant steps and the total metal determined using HF/HNO₃ extract.     

Spatial variation of phosphorus fractionation in the coral reef sediments of Lakshadweep Archipelago,Indian Ocean

Surface sediments were collected from the shore and lagoons of Kavaratti, Kadamat and Agatti islands of Lakshadweep Archipelago during May 2015 and analysed for the spatial distribution of the micronutrient element, phosphorus. Phosphorus was separated by sequential extraction procedure into five fractions – exchangeable (Ex-P), iron bound, (Fe-P), calcium bound (Ca-P), organic and residual fractions (OP) and total phosphorus (TP). The average relative contribution of each P species to TP was: OP?>?Ca –P?>?Ex – P?>?Fe – P. The high concentration of organic and residual phosphorus (87–96%) compared to inorganic phosphorus is particularly evident at stations characterised by higher total phosphorus concentrations. Among the three forms of IP in the sediments, Ca-P was dominant at all stations. The OC/OP ratio ranged from 3 to 163 in the sediments, suggesting that the organic matter in sediments had been subjected to degradation. Hence, the major contribution towards organic and residual phosphorus form is from the residual fraction comprising biologically resistant or non-available phosphorus form composed of refractory materials. The concentration of phosphorus reported in the present study is higher than that of the earlier studies in Lakshadweep, indicating a terrestrial and anthropogenic in?uence on the sediment.     

Heavy metals availability (Fe, Mn, Zn, Cu and Cr) in Aden Gulf sediments under aerobic and anaerobic conditions

The present study aims to analyse the chemical speciation of heavy metals in relation to aerobic and anaerobic conditions. Two sediment samples (from the Gulf of Aden, Yemen) were incubated under flooded conditions. In particular, the chemical forms of Fe, Mn, Zn, Cu and Cr under the experimental conditions were studied using a sequential chemical extraction method. The pH and Eh of the suspension were measured as critical parameters controlling the fate of the metals in the environment. The results showed that the metals concentration in the different forms varied with time incubation and affected by the variation of redox potential and pH value. Also, the changes in both redox potential (Eh) and pH values had evident effects on heavy metals transformation. It is obvious that the highest redox potential affected the amount of iron and manganese in the oxides form. When the redox potential decreased to-133 and-170 mV, it caused a significant transformation of the Fe-Mn oxide form to the water-soluble and exchangeable fractions. Under anaerobic conditions, the relative percentage of all five metals including the summation of four fractions (the water-soluble and exchangeable, carbonate, oxides and organic fractions) constituted 45-60% of the total amount of iron, 33-50% for manganese, 33-63% for Zn, 63-74% for Cu and 19-43% for Cr. Both zinc and copper among water-soluble and exchangeable fraction were high at the end of incubation period, this accompanied by a significant decrease in the content of the organically bound fraction. In general, the reducing conditions were more favorable for metal bound to water soluble and exchangeable fraction.     

耕地土壤铜、镉、锌形态及生物有效性研究

土壤重金属总量常被用来评估土壤质量安全,但是大量事实说明单纯用土壤重金属总量并不能完全说明土壤重金属的生物有效性及其环境风险。相对于国内外常用的Tessier的五态方法,欧共体标准物质局提出的三步提取法(BCR法),中国地质调查局地质连续提取法的七态标准少见报道。本研究选取河南平原耕地样品,采用中国地质调查局地质连续提取法(DD2005-03)进行耕地中重金属元素(Cu、Cd、Zn)的形态分布,结果表明:Cu、Zn主要以残渣态存在,其残渣态分别占全量的55.80%和67.35%。Cd以离子交换态为主,占全量的27.30%。Cu、Cd、Zn各态含量占全量比例的顺序是,Cu:残渣态弱有机结合交换态铁锰氧化态碳酸盐结合态强有机结合态水溶态离子交换态。Cd:离子交换态弱有机结合交换态强有机结合态残渣态碳酸盐结合态铁锰氧化态水溶态。Zn:残渣态铁锰氧化态弱有机盐结合态离子交换态强有机结合态碳酸盐态水溶态。从生物可利用性系数k来看,Cd主要以活动性较大的状态存在,很容易被作物吸收。     

Fractionation of trace metals (Mn,Zn, Cu,Pb) in Red Sea sediments,Gulf of Aden,Yemen

A sequential extraction technique was applied to estimate the chemical association of Mn, Zn, Cu and Pb in five chemical phases (exchangeable, carbonate, Fe–Mn oxides, organic matter and residual) in sediments of the Gulf of Aden, Yemen. The results indicated that a higher level of Mn was associated with the residual fraction (natural sources) than the non-residual fraction (anthropogenic sources). Zn fractionations revealed that it was associated more with Fe–Mn oxides and organic fractions than exchangeable and carbonate fractions. Most of the Cu was present in the residual form (60–72%) except for in the main port area (zone III), where it was associated with the organic phase (77% of the total Cu content, the organic matter content was 5%). Similarly, most Pb was bound in the residual fraction (56–71%) except the main port area where ～ 62% of the total Pb was bound in non-residual fractions. It was also found that the Pb concentration in the exchangeable fraction was very high compared with other metals. The risk assessment code for the metals showed a low risk for Zn and Cu, but low to medium risk for Mn. Fractionation of Pb showed medium risk at most of the regions except at the eastern area, which revealed a high risk for the aquatic environment.     

用连续提取法研究芘在鱼鳃表面的结合形态

建立了研究鱼鳃表面芘的结合状态的四步连续提取方法．分别用H2O、CaCl2、CH3OH和n-C6H14+CH2Cl2(1:1, v/v)混合液提取经暴露的鱼鳃．操作定义的前3步分别提取松散附着在鳃表的鱼鳃黏液中的芘,紧密附着在鳃表的鱼鳃黏液中的芘以及直接吸着在鱼鳃表皮上的芘,第4步则用来提取鱼鳃组织吸收的芘．其提取的芘分别占总量的 4．0％、12．1％、45．2％和38．7％．经3 h暴露,进入鳃组织的芘仅为总测定量的三分之一强,因此大部分芘并未进入鳃组织．单独进行的五步CH3OH连续提取实验结果证明,CH3OH提取步骤能有效地解吸鳃表吸着的芘,但不会导致鳃组织中芘的释放．动态实验结果表明,黏液结合态芘在暴露1h左右即达到平衡,而鳃表吸着态和鳃组织吸收态芘在暴露3h内含量迅速上升,3 h后显著趋缓．     

四环素类抗生素和铜复合污染对猪粪厌氧消化的影响

兽用抗生素和矿物元素添加剂可起到预防动物疾病、促进动物生长、提高饲料转化率等作用,因此被广泛应用于畜禽养殖业。本研究以猪粪中温厌氧消化为研究目标,采用全自动甲烷潜势测试系统,考察了一定浓度的四环素(TC:30 mg·kg~(-1)dry weight,DW)、土霉素(OTC:50 mg·kg~(-1)DW)和金霉素(CTC:15 mg·kg~(-1)DW)对厌氧累积产甲烷量和日产甲烷速率的影响。结果表明,TC、OTC和CTC对猪粪中温厌氧消化累积产甲烷量和日产甲烷速率均有促进作用(累积产甲烷总量提高比例分别为7.9%、0.4%和5.4%)。另外,采用超高效液相色谱-四极杆串联质谱对猪粪厌氧消化前后样品中四环素类抗生素及其代谢产物进行了分析。结果表明,液相中的四环素类抗生素在猪粪厌氧消化过程中得到了明显的去除,去除率达到90%~100%;而固相中只有金霉素和差向异构金霉素有明显的去除效果,去除率分别为41.69%和41.58%。采用Tessier连续提取法对猪粪厌氧消化前后样品中5种形态的铜包括可交换态、碳酸盐结合态、铁锰氧化结合态、有机物结合态、残渣态进行了分析,结果表明,猪粪厌氧消化后,可交换态、碳酸盐结合态和铁锰结合态的铜浓度比厌氧消化前分别降低了1%~9%、0.1%~3%、12%~19%,而有机态和残渣态的铜浓度却在厌氧消化后分别增加了15%~35%、1%~2%。厌氧消化后,70%~80%的铜都是以有机铜的形态存在。铜逐渐从不稳定态转化为相对稳定的有机态和残渣态铜,因此,厌氧消化过程使铜从可生物利用态转变为不可生物利用态,趋于稳定化。     

Comparison of three sequential extraction procedures for trace element partitioning in three contaminated Mediterranean soils

The sequential extraction procedures described by Tessier et al., McGrath and Cegarra, and Gimeno-García et al. were compared to investigate trace element (As, Cr, Cu, Pb, and Zn) partitioning patterns and extraction efficiency in three contaminated soils from Mediterranean regions of Spain. Soils were selected from Onda (Castellón) (S1), Aznalcóllar (Sevilla) (S2), and Silla (Valencia) (S3). S1 was a soil contaminated with Pb and Zn after dumping of wastes from the manufacture of ceramic tiles, S2 was polluted accidentally with a highly acid and As-concentrated sludge from mining activities, and S3 was a soil with a high Cr content from tannery sludge disposal. Trace element distribution in the soils—soluble, exchangeable, organically bound, precipitated with carbonates, bound to iron and manganese oxides, and precipitated with sulfides fractions—varied significantly according to the extraction procedure used. In addition, different extraction efficiencies were found for the three sequential extraction procedures compared. Finally, the trace elements studied showed different and specific distribution patterns between the various soil fractions examined.     

外加锌在土壤中形态的研究

本文采用化学逐级提取法对吸附锌后的土壤分别提取了交换态、CaCO_3结合态、氧化物结合态和有机质结合态的锌量,并讨论pH、温度和溶液中锌离子浓度对不同形态锌分布的影响。实验结果表明:外加锌被石灰性土壤吸附后,高pH值(7.5)时形态分布为:CaCO_3结合态≥交换态>氧化物结合态>有机质结合态;低pH值(5.5)时则为:交换态>CaCO_3结合态>氧化物结合态>有机质结合态。各形态锌的分配系数还受到吸附时的温度和溶液中锌离子浓度的影响。     

Metal speciation in sediments of polluted and non‐polluted lakes

A five‐step extraction procedure for metal speciation studies (copper, lead, nickel, manganese and zinc) was applied to the analysis of lake sediments characterised by different environmental features. A different partition of metals into the several metal forms was observed. Both the metal fraction sorbed or co‐precipitated on hydrous Mn‐oxides (especially lead and zinc) and that bound to organic matter (especially copper) are high in some samples. A prevalently anthropogenic origin of these metals may be hypothesised on the basis of existing knowledge of the equilibrium and change phenomena occurring among water, particulate and sediments. Conversely, the non‐solubilised forms of metals are abundant in the sediments of lakes that are certainly not polluted. The concentration of manganese is very high in the sediments of Antarctic lakes; sequential extractions show its lithogenic origin. In conclusion, a knowledge of the different types of metal associations in sediments and their percentage can facilitate understanding of both natural and anthropogenic metal enrichment of aquatic systems.