Levels and speciation of heavy metals in soils of industrial Southern Nigeria

A knowledge of the total content of trace metals is not enoughto fully assess the environmental impact of polluted soils. Forthis reason, the determination of metal species in solution isimportant to evaluate their behaviour in the environment andtheir mobilization capacity. Sequential extraction procedure wasused to speciate five heavy metals (Cd, Pb, Cu, Ni and Zn) fromfour contaminated soils of Southern Nigeria into sixoperationally defined geochemical species: water soluble,enchangeable, carbonates, Fe-Mn oxide, organic and residual.Metal recoveries were within ± 10% of the independentlydetermined total Cd, Pb, Cu, Ni and Zn concentrations. The highest amount of Cd (avg. 30%) in the nonresidual fractionswas found in the exchangeable fraction, while Cu and Zn weresignificantly associated with the organic fraction. Thecarbonate fraction contained on average 14, 18.6, 12.6, 13 and11% and the residual fraction contained on average 47, 18, 33,50 and 25% of Cd, Pb, Cu, Ni and Zn respectively. Assuming thatmobility and bioavailability of these metals are related to thesolubility of the geochemical form of the metals, and that theydecrease in the order of extraction sequence, the apparentmobility and potential bioavailability for these five metals inthe soil were: Pb > Zn > Cu > Ni > Cd. The mobility indexes ofcopper and nickel correlated positively and significantly withthe total content of metals, while mobility indexes of cadmiumand zinc correlated negatively and significantly with the totalcontent of metals.     

序贯高斯法模拟新沂、东海农业区土壤砷空间变异性

采用序贯高斯条件模拟值法,研究了江苏省新沂、东海农业区土壤砷含量空间变异性.结果表明,研究区土壤砷为正偏态分布,经高斯非线性转化后,符合二阶平稳假设.其经验半变异函数表现为各向同性.采用加权多项式法,对经验半变异函数拟合结果进行评价,并根据结果选择了带块金效应的高斯模型作为拟合模型.对研究区砷分布情况进行了100次模拟,模拟结果平稳.根据模拟数据与实际监测数据的关系,采用相关系数法选择最终模拟结果.研究区西北部土壤砷含量最高,中北部最低.     

Accident modelling and analysis in process industries

Accident modelling is a methodology used to relate the causes and effects of events that lead to accidents. This modelling effectively seeks to answer two main questions: (i) Why does an accident occur, and (ii) How does it occur. This paper presents a review of accident models that have been developed for the chemical process industry with in-depth analyses of a class of models known as dynamic sequential accident models (DSAMs). DSAMs are sequential models with a systematic procedure to utilise precursor data to estimate the posterior risk profile quantitatively. DSAM also offers updates on the failure probabilities of accident barriers and the prediction of future end states. Following a close scrutiny of these methodologies, several limitations are noted and discussed, and based on these insights, future work is suggested to enhance and improve this category of models further.     

利用稳定同位素202Hg稀释技术判定不同来源有机肥施用对外源汞在土壤中形态分布的影响

有机肥施入土壤后,是否会对土壤重金属的活性及植物吸收造成影响是人们关心的问题.本研究应用稳定同位素²⁰²Hg稀释技术,通过培养实验和改进的Tessier连续提取法,探索不同来源有机肥(秸秆、杨树叶、油枯、酒糟、猪粪、鸡粪)施用对外源汞在天津潮土中形态分布及有效性的影响.结果表明,在连续提取法中结合同位素²⁰²Hg稀释技术,通过同位素比值R_Hg(²⁰²Hg/²⁰⁰Hg)的变化对Hg进行形态分析,相比传统的对Hg形态直接进行含量测定,可以更精确直观地反映出Hg形态分布的变化.在潮土中加入外源²⁰²Hg和有机肥后,同位素比值R_Hg最为显著的变化集中在交换态(含水溶态)、胡敏酸结合态、富里酸结合态及有机质结合态,且不同来源有机肥对Hg形态的影响也主要集中在这部分形态,对碳酸盐结合态、铁锰氧化物结合态和残渣态的影响较小.与未加入有机肥的对照处理相比,猪粪及鸡粪的施用使外源示踪²⁰²Hg显著向活性较强的交换态(含水溶态)、富里酸结合态转移,而在胡敏酸结合态中比例降低,下降幅度约为55%(猪粪)和58%(鸡粪).油枯及酒糟的施用,使外源示踪²⁰²Hg显著向活性较低的胡敏酸结合态转移,其同位素比值R_Hg分别增长了约90%(酒糟)和85%(油枯),而在活性较高的交换态(含水溶态)和富里酸结合态中分布比例降低.秸秆和杨树叶对于污染土壤Hg形态分布的影响并不显著.研究结果表明,不同来源的有机肥对Hg污染潮土中Hg的形态分布有显著影响,因此,在Hg污染农田土壤上施用有机肥料需要格外谨慎.     

不同含量外源镉在红壤中的变化特征

为探讨外源离子态镉（Cd）进入红壤后随时间的变化特征,在农田土壤中添加不同含量的Cd （0、0.3、2.0、5.0、10、30、60和100 mg ·kg^-1）,分别于第3、7、14、28、42、56、70和84 d时取样,采用BCR分级提取法分析农田土壤Cd的赋存形态,使用3种动力学模型模拟农田土壤Cd的稳定化和分布特征.结果表明：①外源Cd进入土壤后,土壤Cd的形态会重新进行分配,趋向于供试土壤Cd原始形态分布特征,Cd与土壤的结合强度会随时间的增加而增加,并且总再分配系数会逐渐趋于1.②红壤中外源Cd的稳定化是一个较为长期的过程.弱酸可提取态会逐渐向其他3种形态转换,最终转换为残渣态.在84d内,可氧化态在0.3 mg ·kg^-1时,会随时间逐渐减小,其余形态则相反.在84 d内,可还原态在30 mg ·kg^-1以下时,会随时间逐渐减小,其余形态则相反.③在红壤中,外源Cd的稳定化过程主要是多个反应机制共同控制的扩散过程.当外源Cd添加量越高时,会导致其残渣态的变化速率越高.研究结果可为以外源Cd为基础的相关研究以及重金属污染土壤风险管控与修复提供理论依据.     

Fish forewarning of comprehensive toxicity in water environment based on Bayesian sequential method

Environmental impact of pollutants can be analyzed effectively by acquiring fish behavioral signals in water with biological behavior sensors. However, a variety of factors, such as the complexity of biological organisms themselves, the device error and the environmental noise, may compromise the accuracy and timeliness of model predictions. The current methods lack prior knowledge about the fish behavioral signals corresponding to characteristic pollutants, and in the event of a pollutant invasion, the fish behavioral signals are poorly discriminated. Therefore, we propose a novel method based on Bayesian sequential, which utilizes multi-channel prior knowledge to calculate the outlier sequence based on wavelet feature followed by calculating the anomaly probability of observed values. Furthermore, the relationship between the anomaly probability and toxicity is analyzed in order to achieve forewarning effectively. At last, our algorithm for fish toxicity detection is verified by integrating the data on laboratory acceptance of characteristic pollutants. The results show that only one false positive occurred in the six experiments, the present algorithm is effective in suppressing false positives and negatives, which increases the reliability of toxicity detections, and thereby has certain applicability and universality in engineering applications.     

宣威肺癌高发区燃煤排放颗粒物中铁的价态及其氧化性

云南宣威地区的高肺癌死亡率被认为是与居民室内燃烧烟煤有关.为探明宣威地区高肺癌死亡率的原因,在宣威4个不同区域采集了原煤样品并在室内利用一套自行设计的烟气采集装置对所采集的原煤样品模拟当地燃烧条件进行了燃烧,获取燃煤排放颗粒物样品.使用BCR连续提取法(community bureau of reference,BCR)获取原煤、底灰和燃煤排放颗粒物中铁的赋存形态及分布特征,用高效液相色谱(HPLC)检测燃煤颗粒物在替代肺液(surrogate lung fluid,SLF)中产生·OH水平的变化.结果显示,原煤中存在大量的可氧化态铁,经过燃烧后,飞灰颗粒物中生物可利用的铁(酸可提取态、可还原态、可氧化态)占了很大的比重(46%~78%);燃煤颗粒物24 h所产生·OH的量在不同粒径颗粒物之间存在一定差异,在细粒径段(1μm、1.1~2μm、2~3.3μm)和粗粒径段(3.3~7μm、7μm)均表现为·OH的量随粒径减小而增加;同时,燃煤颗粒物中可氧化态Fe的含量与产生·OH能力具有一定的线性相关性(R2=0.32).     

蠡湖沉积物重金属形态及稳定性研究

以蠡湖及其入湖河口为研究对象,采用连续分级提取法研究了表层沉积物中Cr、Ni、Cu、Zn、As、Cd、Hg和Pb形态的空间赋存特征,同时结合各金属在间隙水体中的空间分布,探讨了各形态金属的稳定度及其生物有效性.结果表明,间隙水体及表层沉积物可提取态金属分布都具有明显的空间异质性,Cr、Cu、Zn、Pb的高值区沿宝界桥和蠡湖大桥呈"带状"分布,Ni、As、Cd、Hg的高值区沿河口向湖区扩展,呈"扇形"分布,并且含量都在退渔还湖区较低.沉积物中Cd、Cu、Ni的可提取态占总量的质量分数较高,分别达到71.02%、54.79%和50.62%,其余金属则主要以残渣态为主.8种金属稳定性顺序为Cr>Pb>Hg>As>Cu>Ni>Zn>Cd,Cd和Zn在大部分点位处于不稳定状态,快速解吸释放的风险较大.间隙水体毒性评估表明,各金属不会对水生生态系统产生急性毒性,但部分区域尤其是入湖河口的Hg和Pb可能会对底栖生物产生慢性毒性.     

寨上金矿矿区河流沉积物中砷的形态分析

在野外调查和样品采集的基础上,对寨上金矿矿区河流沉积物中砷的质量分数进行了测定,并采用Tessier连续提取法对砷在沉积物中的存在形态进行了提取分析。结果表明,砷在该区水系沉积物中质量分数较高（55.0~189.0μg.g-1）,说明金矿的开采已经对该区的环境造成了影响。运用Tessier连续提取法研究发现,沉积物样品中砷的提取率为89.87%~110.54%,样品沉积物中砷的形态分布基本一致,以残渣态为主,占其总量的85%以上,其他各形态相对含量较少,但相对活泼形态（水溶态、离子交换态和碳酸盐结合态）绝对质量分数较高（2.029~4.942μg.g-1）,说明该区水系沉积物中大部分砷在自然条件下相对比较稳定,小部分砷（1.10%~5.55%）易释放至环境中,但由于其绝对质量分数较高,将对环境产生较大危害。