Speciation and the bioavailability of actinide elements

A good understanding of the quantitative uptake of actinide elements from foodstuffs, across the mucosal cell membranes of the gastrointestinal tract, into man is of great importance in setting intake limits and in assessing radiation doses to critical organs.

In the past, such knowledge has been gained from the extrapolation of animal models to man. Whilst this strategy has proved useful in a number of cases, it is, unfortunately, phenomenological and the results prone to perturbation from factors such as the fasting state of the animal and the initial chemical form of the actinide.

The application of computer simulation models which can calculate the chemical speciation of an element in a variety of foodstuffs under conditions pertinent to the gastrointestinal tract offers a non‐invasive and general method for predicting the uptake of exogenous elements, like the actinides.

This paper reviews the current state of chemical speciation analysis with respect to bioavailability highlighting areas requiring further consideration, presenting results amplifying the issues raised and showing that computer simulation has a rôle to play in predicting quantitative uptake of the actinides.     

Variations in the elemental compositions of plants,and computer‐aided sampling in ecosystems∗

To obtain comparable results of multi‐element analysis of plant materials by different laboratories, a harmonized sampling procedure for terrestrial and marine ecosystems is essential. The heterogeneous distribution of chemical elements in living organisms is influenced by different biological parameters. These parameters are mainly characterized by genetic predetermination, seasonal changes, edaphic and climatic conditions, and delocalization processes of chemical substances by metabolic activities.

The biological variations of the element content in plants were divided into 5 systematic levels, which are: 1. the plant species; 2. the population; 3. the stand (within an ecosystem); 4. the individual; and 5. the plant compartment. Each of these systematic levels can be related to: 1. genetic variabilities; 2. different climatic, edaphic and anthropogenic influences; 3. microclimatic or microedaphic conditions; 4. age of plants (stage of development), exposure to environmental influences (light, wind, pollution etc.), seasonal changes; and 5. transport and deposition of substances within the different plant compartments (organs, tissues, cells, organelles).

An expert system for random and systematic sampling for multi‐element analysis of environmental materials, such as plants, soils and precipitation is presented. After statistical division of the research area, the program provides advice for contamination‐free collection of environmental samples.     

Trace metals in fish,sediment and water from the south west coast of the Arabian sea,Pakistan

Concentrations of ten metals (As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn and Hg) in the edible muscle of Arius maculatus captured from eight different near‐shore and off‐shore sites off the south west coast of the Arabian Sea, Pakistan, were determined by atomic absorption spectrophotometry. Relevant water and sediment samples from the sites were also analysed for the metals. Zinc showed the highest metal concentration (6.763 μg/g, wet weight) in the muscle of the fish, while Mn and Hg showed lowest level (0.019 μg/g, wet weight). Of all the metals investigated, largest scatter (measured as σ) was observed for Zn (σ = 2.058 /μg/g) in fish muscle, for Fe and Mn in sediment (σ = 27481 and 44.50 μg/g) and for As in water (σ = 0.270 μg/L). The metal distribution data pertaining to water, fish and sediment were examined on the basis of simple metal correlations. The statistical study revealed that Ni, Cr, Pb and Cu had significant positive correlations (r > 0.830 at ρ = 0.01). The finding substantiated a trace metal concentration gradient in the area, thereby indicating that the local marine environment is contaminated by anthropogenic sources.     

煤矸石烧结砖厂废气凝结物的研究

采集煤矸石烧结砖厂隧道窑废气热交换器内壁的凝结物,利用XRF、XRD、IR、DTA-TG、SEM、EDS、ICP-MS和AFS等方法进行了研究。结果表明:凝结物主要为水合硫酸亚铁和水合硫酸铁,S含量为119.2 mg/g,且Se、As、Pb等微量元素在凝结物中富集。与煤矸石原料相比,凝结物中Se的富集程度最高,含量达到了0.637 mg/g,相对富集因子为467.52;S、Tl、Mo、As、Pb的相对富集因子从57.05依次减小到6.18,F及亲硫元素Sb、Cd、Zn、Ni、Cu、Co富集程度较低;Sr、Th、Be、Ba、U、V、Cr的相对富集因子小于0.5,显示在烧结砖制备过程中的挥发性很低。     

天津市某社区老年人PM2.5暴露痕量元素健康风险评估

为研究PM_2.5暴露特征,对天津市某社区101名老年人(平均年龄67岁)夏季(2011年6月13日—7月2日)和冬季(2011年11月30日—12月12日)的PM_2.5暴露水平进行了监测,并分析了PM_2.5载带痕量元素的含量及其健康风险. 结果表明,研究对象夏、冬两季PM_2.5个体暴露浓度分别为(124.2±75.2)、(170.8±126.6)μg/m3,室内暴露浓度分别为(120.0±48.9)、(164.9±125.7)μg/m3,环境暴露浓度分别为(98.6±33.3)、(140.0±87.7)μg/m3. 10种痕量元素中,ρ(Zn)最高,夏季为324.18~345.65ng/m3,占痕量元素总质量浓度的37%以上;冬季为148.36~362.00ng/m3,占痕量元素总质量浓度的35%以上. V、Cr、Mn、Cu、Zn和Pb的非致癌风险值均小于1,理论风险较小;但其中Cr和Mn风险值均超过0.1〔HQ(风险系数)分别为0.882和0.306〕,对于属于易感人群的老年人群体,仍有可能对其身体健康产生危害,需引起重视;As、Cd和总体致癌风险均超过10-6,对人体健康的危害不容忽视.      

Metal accumulation by three Tilapia spp. from some Egyptian inland waters

Five trace metals (Cu, Zn, Fe, Mn and Cd) were determined in different tissues and organs (muscle, liver, brain, gills, gonads and intestines) of some Tilapia spp. (Oreochromis spp. and Sarotherodon galilaues) collected from two Egyptian Lakes (Edku and Mariut, exposed to different types of pollutants), El-Umum Drain, and from the fishing farm El-Nozha Hydrodrome. Our results indicate that metal accumulation in different organs vary considerably between the same and among different Tilapia spp. There is a preferential accumulation of metals by different organs. Liver is a target organ for Cu accumulation, whereas the brain and flesh tissues clearly accumulate more levels of Zn than the other studied elements. Amongst the studied elements, Cd concentrations in the different organs are the lowest. It was found that edible parts of Tilapia spp. collected from Lake Mariut accumulate the highest levels of the studied elements (Fe, Zn, Mn and Cu for S. galilaues and Cd for Oreochromis niloticus), compared with those in the other studied areas. In general, the levels of Cd (0.0–0.11?ppm), Cu (0.25–1.85?ppm) and Zn (3.58–8.46?ppm) in the edible parts of studied fish cannot be considered as hazardous levels.     

Trace elements and vanadium in tissues and organs of five species of cetaceans from Italian coasts

Trace element concentrations (chromium, copper, zinc, iron, manganese and vanadium) were determined in organs of five species of cetaceans (Stenella coeruleoalba, Tursiops truncatus, Grampus griseus, Physeter macrocephalus, Ziphius cavirostris) that were found stranded along Italian coasts in the period 2000–2009. This dataset represents an important opportunity to verify and assess (particularly for V) patterns of incorporation of trace elements in different organs of cetaceans in a wide spectrum of species and related specimens distributed in all the age classes, and consequently determine the physiological and metabolic effects on the distribution modes of the same chemicals. In particular, Cu, Zn, and Fe accumulate preferentially in the liver of all studied specimens, while Mn and Cr values are found to be nearly constant in the analysed organs and tissues regardless of species. Comparable concentrations of trace elements, in different age classes, were measured for both specimens of S. coeruleoalba and T. truncatus (the most abundant dolphin species in the Mediterranean sea) in all analysed organs. On the other hand, unprecedented reported concentrations of V in tissues and organs of cetaceans from the Mediterranean show higher values when compared to levels measured in other marine mammals from the Atlantic Ocean.     

Comparison of sample digestion procedures for the determination of trace elements in antarctic krill by GF‐AAS

Two independent digestion procedures for Antarctic krill samples were compared. Dry ashing (DA) and microwave (MW) acid‐assisted digestion were tested for decomposing the samples to determine essential (Cu, Fe, Cr) and toxic elements (Cd, Pb) by graphite furnace‐atomic absorption spectrometry (GF‐AAS). A mixture of HNO₃ and H₂O₂ as digesting agent was used in the microwave procedure. For the dry ashing digestion, the organic matter was oxidated at 480°C in an open system. Both digestion methods were compared in terms of accuracy and applied to the analysis of a certified reference material: MURST‐ISS‐A2 (Antarctic krill).

The detection limits for the five elements analysed ranged from 3 to 150 ng g^‐1. Both digestion procedures are suitable for the decomposition of krill samples. However, dry ashing is not recommended to determine Pb and Cd because losses can occur.     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

Soils and geomedicine

Geomedicine is the science dealing with the influence of natural factors on the geographical distribution of problems in human and veterinary medicine. Discussions on potential harmful impacts on human and animal health related to soil chemistry are frequently focused on soil pollution. However, problems related to natural excess or deficiency of chemical substances may be even more important in a global perspective. Particularly problems related to trace element deficiencies in soils have been frequently reported in agricultural crops as well as in livestock. Deficiencies in plants are often observed for boron, copper, manganese, molybdenum, and zinc. In animals deficiency problems related to cobalt, copper, iodine, manganese, and selenium are well known. Toxicity problems in animals exposed to excess intake have also been reported, e.g., for copper, fluorine, and selenium. Humans are similar to mammals in their relations to trace elements and thus likely to develop corresponding problems as observed in domestic animals if their supply of food is local and dependent on soils providing trace element imbalances in food crops. In large parts of Africa, Asia, and Latin America, people depend on locally grown food, and geomedical problems are common in these parts of the world. Well-known examples are Keshan disease in China associated with selenium deficiency, large-scale arsenic poisoning in Bangladesh and adjacent parts of India, and iodine deficiency disorders in many countries. Not all essential elements are derived only from the soil minerals. Some trace elements such as boron, iodine, and selenium are supplied in significant amounts to soils by atmospheric transport from the marine environment, and deficiency problems associated with these elements are therefore generally less common in coastal areas than farther inland. For example, iodine deficiency disorders in humans are most common in areas situated far from the ocean. There is still a great need for further research on geomedical problems.