Depleted uranium mobility and fractionation in contaminated soil (Southern Serbia)

GOAL, SCOPE AND BACKGROUND: During the Balkan conflict in 1999, soil in contaminated areas was enriched in depleted uranium (DU) isotopic signature, relative to the in-situ natural uranium present. After the military activities, most of kinetic DU penetrators or their fragments remained buried in the ground in certain geomorphological and geochemical environments exposed to local weathering conditions. The contamination distribution, mobility and/or fixation of DU in the contaminated soil profile at one hot spot were the subject of our study. The results should disclose what happened with released DU corrosion products in three years elapsed, given the scope of their geochemical fractionation, and mark out the most probable host substrates in investigated soil type. METHODS: Gamma-spectrometric analysis of soil samples taken in the DU penetrator impact-zone was done to obtain present contamination levels. Set of samples is subjected to five-step and three-step sequential extraction procedures, specifically selective to different physical/chemical associations in soil. The stable elements are determined in extracts by the atomic absorption spectroscopy. After the ion-exchange based uranium separation procedure, alpha-spectrometric analysis of obtained fractions was done and DU distribution in five extraction phases found from 235U/238U and 234U/238U isotopic ratios. RESULTS: Depleted uranium concentration falls down to the 1% of the initial value, at approximately 150 mm distance to the source. Carbonates and iron/manganese hydrous oxides are indicated as the most probable substrates for depleted uranium in the characterized soil type. Therefore, in the highly contaminated soil samples, depleted uranium is still weakly bonded and easy exchangeable. The significant levels of organic-bonded depleted uranium are found in surface soil only. DISCUSSION: Dependence of the fractionation on the contamination levels is evident. Samples with higher DU contents have shown a longer maintenance in the exchangeable phases, probably because adsorption/desorption mass transfer through the medium was not very fast. Organic-bonded, depleted uranium is present in surface soil samples due to its higher humus content. Considering geochemical composition of investigated soil, the indicating chemical associations as substrates are in agreement with some considerations based on the results for low-level waste unsaturated zones. CONCLUSIONS: The soil contamination with depleted uranium in investigated area is still 'spot' type and not widespread. Dependence of the fractionation on the contamination levels and presence of weakly bonded, depleted uranium in the hot spots areas is evident. RECOMMENDATIONS AND PERSPECTIVES: A detailed study may be undertaken with suitable extractive reagents to define a bio-available fraction of depleted uranium in soil. The comparison of results for different soil types investigated by the same methodology may be useful. An applied combination of physical/chemical procedures and analysis may help in the decision making on the remediation strategy for sites contaminated with depleted uranium used in military operations.     

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.     

Kinetics and equilibrium of adsorption of dissolved organic matter fractions from secondary effluent by fly ash

Fly ash was used as a low-cost adsorbent for removing dissolved organic matter (DOM) in secondary effluent. Batch experiments were conducted under various adsorbent dosages, pH, contact time, temperatures and DOM fractional characteristics. Under the optimum conditions of fly ash dosage of 15 g/L, temperature of 303 K and contact time of 180 min, a removal of 22.5% of the dissolved organic carbon (DOC), 23.7% of UV-254, 25.9% of the trihalomethanes precursors in secondary effluent was obtained. The adsorption of DOM fractions onto fly ash all followed the pseudo second-order kinetic model, and the hydrophilic fraction adsorption by fly ash also fitted the intraparticle diffusion model quite well. Freundlich and Langmuir models were applicable to the fly ash adsorption and their constants were evaluated. The maximum adsorption capacities of the adsorptions revealed that fly ash was more effective in adsorbing hydrophilic fraction than the acidic fractions. Structure changes of the DOM fractions after fly ash adsorption were also characterized via spectrum analyzing. Those mechanisms presented critical step toward improved efficiencies of fly ash adsorption via further surface-modification.     

非质量氧同位素分馏效应研究进展

非质量氧同位素分馏效应(mass independent oxygenisotope fractionation)研究为一些重大地质科学问题的解释开辟了一条新途径。在简要介绍非质量分馏理论后,重点评述了非质量氧同位素分馏效应的研究进展,包括非质量同位素分馏效应的成因机制、氧同位素组成分析方法建立及其在环境地学领域的应用。并对非质量氧同位素分馏领域未来研究趋势作了进一步探讨。     

Controlling various contaminants in wastewater effluent through membranes and engineered wetland

For effective wastewater reclamation and water recovery, the treatment of natural and effluent organic matters (NOM and EfOM), toxic anions, and micropollutants was considered in this work. Two different NOM (humic acid of the Suwannee River, and NOM of US and Youngsan River, Korea), and one EfOM from the Damyang wastewater treatment plant, Korea, were selected for investigating the removal efficiencies of tight nanofiltration (NF) and ultrafiltration (UF) membranes with different properties. Nitrate, bromate, and perchlorate were selected as target toxic anions due to their well known high toxicities. Tri-(2-chloroethyl)-phosphate (TCEP), oxybenzone, and caffeine, due to their different K _ow and pK _a values, were selected as target micropollutants. As expected, the NF membranes provided high removal efficiencies in terms of all the tested contaminants, and the UF membrane provided fairly high removal efficiencies for anions (except for nitrate) and the relatively hydrophobic micropollutant, oxybenzon. Through the wetlands, nitrate was successfully removed. Therefore, a fair process of combining membranes with an engineered wetland could be proposed for sustainable wastewater reclamation and optimum control of contaminats.     

Variations in expression of carbon isotope fractionation of chlorinated ethenes during biologically enhanced PCE dissolution close to a source zone

The stable carbon isotope values of tetrachloroethene (PCE) and its degradation products were monitored during studies of biologically enhanced dissolution of PCE dense nonaqueous phase liquid (DNAPL) to determine the effect of PCE dissolution on observed isotope values. The degradation of PCE was monitored in a 2-dimensional model aquifer and in a pilot test cell (PTC) at Dover Air Force Base, both with emplaced PCE DNAPL sources. Within the plume down gradient from the source, the isotopic fractionation of dissolved PCE and its degradation products were consistent with those observed in biodegradation laboratory studies. However, close to the source zone significant shifts in the isotope values of dissolved PCE were not observed in either the model aquifer or PTC due to the constant input of newly dissolved, non fractionated PCE, and the small isotopic fractionation associated with PCE reductive dechlorination by the mixed microbial culture used. Therefore the identification of reductive dechlorination in the presence of PCE DNAPL was based upon the appearance of daughter products and the isotope values of those daughter products. An isotope model was developed to simulate isotope values of PCE during the dissolution and degradation of PCE adjacent to a DNAPL source zone. With the exception of very high degradation rate constants (>1/day) stable carbon isotope values of PCE estimated by the model remained within error of the isotope value of the PCE DNAPL, consistent with measured isotope values in the model aquifer and in the PTC.     

东部平原湖区沉积物中溶解性有机氮分布特征

选择东部平原湖区11个湖泊进行水质和表层沉积物调查,采用综合营养状态指数（TLI）对各湖泊营养状态进行评价,研究了沉积物溶解性有机氮（DON）和游离氨基酸（FAA）的含量分布及DON分子质量分级特征,并探讨了不同湖泊沉积物有机质来源。结果表明：除固城湖和骆马湖处于中营养水平外,东部平原湖区其他湖泊均处于富营养化状态。沉积物DON浓度差异较大,在9.98~182.00 mg·kg-1之间波动,均值为57.25 mg·kg-1,太湖、滆湖、阳澄湖沉积物DON含量较高,均在140 mg·kg-1以上,其他湖泊沉积物DON含量均在50 mg·kg-1以下。区域内氨基酸（FAA）分布比较均匀,FAA浓度在3.58~13.28 mg·kg-1之间,平均值是8.14 mg·kg-1。沉积物DON和FAA含量与沉积物其他形态氮、溶解性有机碳（DOC）等污染指标均表现出显著正相关性。东部平原湖区沉积物分子质量分级结果表明：该湖区沉积物DON、DOC和SUV254基本都分布在 30 kDa 2个范围内。东部平原湖区C/N比的值介于2.31~89.02之间,除滆湖外其他湖泊沉积物C/N值均大于10,说明该地区湖泊沉积物有机质主要来自外源。     

中国南方砂(页)岩铜矿床硫同位素地球化学研究

以中国南方著名的滇中和会理盆地砂页岩铜矿床宏观地质特征和硫同位素分析数据为基础，系统地研究了我国南方砂页岩铜矿床硫同位素组成特征。首次用筛分模式、分馏效应对硫同位素总体进行评分，结果表明硫主要有三个来源：有机质分解或还原流酸盐，占11．3％；地下水，占42．5％；热卤水，占46．2％。本研究为该类型矿床的成因、成矿地球化学环境及指导区域找矿勘探等提供了重要依据。     

Disinfection byproduct precursor removal by enhanced coagulation and their distribution in chemical fractions

Raw water from the Songhua River was treated by four types of coagulants, ferric chloride(FeCl3), aluminum sulfate(Al2(SO4)3),polyaluminum chloride(PACl) and composite polyaluminum(HPAC), in order to remove dissolved organic matter(DOM). Considering the disinfection byproduct(DBP) precursor treatability, DOM was divided into five chemical fractions based on resin adsorption.Trihalomethane formation potential(THMFP) and haloacetic acid formation potential(HAAFP) were measured for each fraction. The results showed that hydrophobic acids(HoA), hydrophilic matter(HiM) and hydrophobic neutral(HoN) were the dominant fractions.Although both HoN and HoA were the main THM precursors, the contribution for THMFP changed after coagulation. Additionally,HoA and HiM were the main HAA precursors, while the contribution of HoN to HAAFP significantly increased after coagulation.HoM was more easily removed than HiM, no matter which coagulant was used, especially under enhanced coagulation conditions.DOC removal was highest for enhanced coagulation using FeCl3 while DBPFP was lowest using PACl. This could indicate that not all DOC fractions contained the precursors of DBPs. Reduction of THMFP and HAAFP by PACl under enhanced coagulation could reach51% and 59% respectively.     

Improvement of soil quality after "alperujo" compost application to two contaminated soils characterised by differing heavy metal solubility

Reclamation of trace element polluted soils often requires the improvement of the soil quality by using appropriate organic amendments. Low quality compost from municipal solid waste has been tested for reclamation of soils, but these materials can provide high amounts of heavy metals. Therefore, a high-quality compost, with low levels of heavy metals, produced from the main by-product of the Spanish olive oil extraction industry ("alperujo") was evaluated for remediation of soils affected by a pyritic mine sludge. Two contaminated soils were selected from the same area: they were characterised by differing pH values (4.6 and 7.3) and total metal concentrations, which greatly affected the fractionation of the metals. Compost was applied to soil at two rates (equivalent to 48 and 72 Tm ha(-1)) and compared with an inorganic fertiliser treatment. Compost acted as an available nutrient source (C, N and P) and showed a low mineralisation rate, suggesting a slow release of nutrients and thus favouring long term soil fertility. In addition, the liming effect of the compost led to a significant reduction of toxicity for soil microorganisms in the acidic soil and immobilisation of soil heavy metals (especially Mn and Zn), resulting in a clear increase in both soil microbial biomass and nitrification. Such positive effects were clearly greater than those provoked by the mineral fertiliser even at the lowest compost application rate, which indicates that this type of compost can be very useful for bioremediation programmes (reclamation and revegetation of polluted soils) based on phytostabilisation strategies.