Analysis of the Major Fe Bearing Mineral Phases in Recent Lake Sediments by EXAFS Spectroscopy

Extended X-ray absorption fine structure (EXAFS) spectroscopy and chemical analyses were combined to determine the Fe bearing minerals in recent lake sediments from Baldeggersee (Switzerland). The upper section of a laminated sediment core, deposited under eutrophic conditions, was compared to the lower part from an oligotrophic period. Qualitative analysis of FeK EXAFS agreed well with chemical data: In the oligotrophic section Fe(II)–O and Fe(III)–O specieswere present, whereas a significant fraction of Fe(II)–S sulfides was strongly indicated in the eutrophic part. A statistical analysis was performed by least square fitting of normalized reference spectra. The set of reference minerals included Fe(III) oxides and Fe(II) sulfides, carbonates and phosphates. In the oligotrophic regime no satisfying fit was obtained using the set of reference spectra, indicating that siderite (FeCO₃) was not present in a significant amount in these carbonate-rich sediments. Simulated EXAFS spectra for a(Ca_x, Fe_1-x)CO₃solid solution allowed reconstructing the specificfeatures of the experimental spectra, suggesting that this phase was the dominant Fe carrier in the oligotrophic section of the core. In the eutrophic part, mackinawite was positively identified and represented the dominant Fe(II) sulfide phase. This finding agreed with chemical extraction, which indicated that18–40 mol% of Fe was contained in the acid volatile iron sulfide fraction. EXAFS spectra of the eutrophic section were best fitted by considering the admixture of mackinawite and the Fe–Ca carbonate phase inferred to be predominant in the oligotrophic regime.     

水环境及水产品中汞的测定与形态分析进展

概要总结了世界各地对水环境及水产品中汞的测定与形态分析的研究成果,涵盖样品采集、储存、传递与处理,各种色谱(薄层色谱、气相色谱、液相色谱、电色谱和离子色谱)分离分析方法及其联用技术,以及分光光度法、电化学法、原子吸收光谱和原子荧光光谱的应用等。并对未来发展提出了改进建议。     

典型工业城市土壤重金属元素形态特征及生态风险评估

城市工业化发展易造成土壤重金属污染等环境问题。已有研究表明, 土壤重金属对生态环境的危害不仅与其总量有关,更大程度上取决于重金属的赋存形态。为查明河套平原某典型工业城市城区土壤重金属的含量特征、赋存状态和风险状况,本文在该市不同功能区采集土壤样品52件,利用电感耦合等离子体质谱法(ICP-MS)、原子荧光光谱法(AFS)等分析技术测定土壤重金属元素含量和赋存形态状况的基础上,采用风险评价编码法(RAC)对城区土壤重金属的生态风险进行评价。结果表明: ①表层土壤重金属元素含量(除As外)均不同程度地高于河套平原背景值,Pb、Cr、Mn、Cd、Zn的变异系数较大,空间分布不均匀,受人类活动影响显著;工业区重金属含量超过背景值程度最重,尤其是Cd(背景值的5.83倍)和Pb(背景值的3.58倍);道路重金属含量也明显高于背景值,Cd是背景值的近4倍。②重金属Cr、Mn、Ni、Cu、Zn、Pb、As元素形态以残渣态为主;Cr、Ni、Cu和As的残渣态平均占比都大于70%,Cd的残渣态在各功能区约占30%。③RAC风险评价结果显示各功能区的Cd和工业区的Pb达到高风险等级,生态风险较大。研究结果可为城区土壤重金属潜在生态风险防范提供科学依据。     

4l0哌啶树脂分离富集－原子吸收测定化探样品中痕量镉

研究了４１０哌啶树脂对Ｃｄ的吸附行为,在２％～２０％ＨＣＩ介质中［ＣｄＣｌ＿３］￣－被树脂吸附,采用４％～３０／ＨＮＯ＿３溶液可以解脱Ｃｄ,回收率在９６％以上。测定了Ｃｄ在该树脂上的分配系数为５４９０,对含Ｃｄ０．０６７μｇ／ｇ的标样ＧＳＲ－３平行测定６次,相对标准偏差为９．５％。方法用于化探样品中０．０Ｘ×１０￣－６级Ｃｄ的测定,结果满意。     

江西省鄱阳湖流域根系土硒形态分析及其迁移富集规律

对江西省鄱阳湖流域根系土中硒的形态分析表明,根系土中Se的强有机态、腐植酸结合态约占Se全量的66.23%,残渣态占12.32%,3种形态均与根系土Se全量呈极显著的线性正相关.根系土Se全量受pH值的影响不明显,但受有机质含量的影响很大,线性回归关系极显著,说明岩石风化、土壤发育过程中,有机质吸附Se,致使Se较其他元素流失比例少,造成根系土中Se相对富集.同时,提出了利用全量Se推导Se各形态值的方法,建立了土壤Se全量与各形态间的关系模型和决定土壤有效态Se的公式,建议在评价土壤Se时只用考虑有机结合态Se、残渣态Se、水溶态Se和全量Se.     

Fate of aluminium released by sacrificial anodes – Contamination of marine sediments by environmentally available compounds

To protect their steel structures from corrosion by cathodic protection, many harbours use aluminium sacrificial anodes, which induces aluminium release and potential contamination of the surrounding waters and sediments. To study the impact on Al mobility, a natural marine sediment was artificially contaminated with aluminium from different sources: sulphate or chloride salts, or sacrificial anodes. To estimate Al mobility in sediments, single (HCl) and sequential (F6) extractions were performed; they highlighted that aluminium is poorly mobile in natural sediment (HCl-leachable: 2% and F6-leachable: 9%). Contamination by aluminium salts inhibits HCl-leachability (≤ 2%), whereas the Al F6-leachability is intensified up to 18%, suggesting that the additional aluminium is scavenged in a mobile fraction that HCl is not able to solubilise. In case of aluminium anode contamination, sediments present surging Al HCl-leachable (15%) and F6-leachable (32%) fractions, which are related to aluminium mineralogical speciation. Indeed, contrary to the Al naturally present or introduced by salts, Al released by anodes is partly bound to the acid-soluble fraction, probably because of the integration of the released Al into the calcareous deposit produced at the anodes surfaces that finally comes away and gets mixed up with the sediment. The presence of aluminium in the acid-soluble fraction of sediments could have an important environmental impact as this fraction is easily available. Indeed, Al scavenged in the acid-soluble fraction of sediments participates in enhancing Al lability near the sacrificial anodes and may affect the surrounding ecosystems.     

液态乳及乳粉中硝酸盐的污染分析

采用固相萃取-离子色谱法和国家标准中化学法(镉柱还原光度法)分析石家庄市售110份液态乳及奶粉中硝酸盐含量.离子色谱法中将制备好的样品加入适量乙酸沉淀蛋白,离心取上清液,通过固相萃取柱去除脂肪等疏水性化合物,采用AS1 1-HC型阴离子色谱柱进行分析,同时对液态乳样品采用镉柱还原法进行比对实验.两种方法测得液态乳中硝酸盐的平均含量分别为10.05 mg/kg和9.95 mg/kg,奶粉中硝酸盐的平均含量分别为25.74 mg/kg和25.66 mg/kg.经t检验分析,显示=0.07,P＞0.05,即无显著性差异,研究结果证实了离子色谱法的准确性,实验过程也进一步验证了离子色谱法的简易性.依据我国目前对乳粉中硝酸盐的限量要求,所测乳粉中的硝酸盐均在限量规定范围内,对食用的安全性不产生负面影响;而液态乳中的硝酸盐进行污染评价发现,超标率大约为14％.     

水稻吸收Cd的地球化学控制因素研究——以苏锡常典型区为例

对苏锡常地区416套稻米-耕层土样品Cd等元素含量的解剖研究,证实了土壤Cd、Zn、Se、p H、OM、CEC等是控制稻米Cd的重要地球化学因素。相关统计分析结果显示:1)酸性土壤环境中当稻米Cd的BCF值大于10%时,稻米Cd与土壤Cd、Zn呈显著正相关,相关系数大于0.67。土壤Cd的生物有效量普遍较高,土壤中酸可溶态Cd与稻米Cd含量的相关系数大于0.7,接近或稍高于稻米与土壤Cd的相关性;2)土壤Se、OM、CEC均能抑制水稻对土壤Cd的吸收,在一定条件下稻米Cd与土壤Se、OM、CEC之间显著负相关,相关系数均小于-0.5;3)土壤酸化可促进稻米对土壤Cd的吸收,当土壤Cd0.2 mg/kg、OM变化于2.5%~6.5%时,稻米Cd与土壤p H呈显著负相关,相关系数为-0.6;4)水稻不同器官中Cd含量不同,从根部→地上部→稻米Cd含量渐次降低,指示根部水稻器官在稻米从土壤吸收Cd的过程中发挥了更大作用、水稻根系吸收的Cd多积聚于根部。     

胁迫时间和胁迫浓度对超积累植物印度芥菜细胞中镉分布的影响

超积累植物对重金属的区隔化作用能有效降低细胞质内金属离子的浓度,是对重金属重要的解毒机制之一,而细胞内各组织的区隔化作用大小并未取得一致性结论。本文研究了胁迫浓度和胁迫时间对超积累植物印度芥菜(Brassica juncea)细胞及亚细胞中镉分布的影响。印度芥菜幼苗分别用0.5、1.0、2.0、3.0、5.0mg/L镉胁迫1、5、7、10、14天后收获,采用电感耦合等离子体质谱法测定印度芥菜根系和叶片亚细胞中镉的含量。结果表明:镉在细胞壁中的比例占50%~64%,细胞液占22%~38%,细胞器占7%~17%,镉在细胞壁中所占比例显著高于细胞液和细胞器,证明细胞壁区隔化在镉的解毒机制中具有重要的作用。随着胁迫时间和胁迫浓度的增加,根系和叶片中亚细胞各组织中镉含量持续增加,超过7天,镉含量显著升高,说明镉对植物的危害是一个缓慢过程。印度芥菜对镉胁迫浓度的最大耐受量为1.0 mg/L,超过此浓度,植物细胞的破坏症状加重;细胞超微结构研究也表明,镉胁迫浓度超过1.0 mg/L后,细胞结构发生了不同程度的损坏,出现质壁分离、液泡增大甚至空泡化、质膜粗糙等现象,继而影响到细胞的正常功能。因此,在考察重金属对植物的危害时,要充分考虑时间和浓度梯度两个参数的协同作用。     

四种浸提剂对果园与菜地土壤有效硒浸提效果的对比研究

有效硒是评价土壤中硒对植物供给能力的重要指标,我国目前尚无测试有效硒的国家标准方法。浸提剂的选择对于准确测定有效硒的含量至关重要,本文根据浸提的有效硒与硒形态的关联性来确定最优浸提剂种类。实验中选取了碳酸氢钠、磷酸二氢钾、硝酸和盐酸四种浸提剂,对天津果园和菜地的土壤进行有效硒浸提,采用原子荧光光谱法测定各形态硒的含量,并分别对浸提的有效硒与水溶态+离子交换态+碳酸盐结合态硒的最小值、25%处数据值、中位数、75%处数据值和最大值进行比较分析和差异性检验。结果表明:采用碳酸氢钠和磷酸二氢钾提取菜地土壤有效硒的平均含量均约为0.039mg/kg,高于硝酸和盐酸的提取量;采用碳酸氢钠、磷酸二氢钾、硝酸和盐酸提取果园土壤有效硒的含量依次降低。两种土壤中,磷酸二氢钾浸提有效硒的最小值、25%处数据值、中位数、75%处数据值和最大值与水溶态+离子交换态+碳酸盐结合态硒的含量最为接近,而且无显著差异性。研究认为,0.1mol/L磷酸二氢钾适合作为天津果园和菜地土壤有效硒的浸提剂。