Uptake and mobility of uranium in black oaks: implications for biomonitoring depleted uranium-contaminated groundwater

In a preliminary study, the uptake and the mobility of uranium (U) by black oak trees (Quercus velutina) were assessed by measuring the isotopic composition of tree rings in two mature oak trees in a heavy metal contaminated bog in Concord, MA. The bog is adjacent to a nuclear industrial facility that has been processing depleted uranium (DU) since 1959. Over the past 40 years, DU has been leaking from an onsite holding basin and cooling pond down gradient to the bog where the oaks are located. Because DU has no source outside the nuclear industry, contamination from the industrial facility is readily discernable from uptake of natural U by measuring isotopic compositions. Isotope ratio analysis confirms the occurrence of DU in bark, sapwood and heartwood tree rings dating back to 1937, pre-dating the introduction of DU at the site by at least 20 years. Isotope dilution analysis indicates high concentrations of U (>3 ppb) in sapwood that drop rapidly to relatively constant concentrations (0.3-0.4 ppb) in heartwood. These data indicate that once incorporated into tree cells, U is mobile, possibly by diffusion through the tree wood. Concentrations of U in sapwood are approximately equal to average U concentrations in groundwater onsite over the past 10 years, suggesting that oak trees can be used as present-day bioindicators of U-contaminated groundwater. We suggest that regional sampling of oak bark and sapwood is a reasonable, inexpensive alternative to drilling wells to monitor shallow groundwater U contamination.     

Can we predict uranium bioavailability based on soil parameters? Part 2: soil solution uranium concentration is not a good bioavailability index

The present study aimed to quantify the influence of soil parameters on uranium uptake by ryegrass. Ryegrass was established on eighteen distinct soils, spiked with (238)U. Uranium soil-to-plant transfer factors (TF) ranged from 0.0003 to 0.0340kgkg(-1). There was no significant relation between the U soil-to-plant transfer (or total U uptake or flux) and the uranium concentration in the soil solution or any other soil factor measured, nor with the U recovered following selective soil extractions. Multiple linear regression analysis resulted in a significant though complex model explaining up to 99% of variation in TF. The influence of uranium speciation on uranium uptake observed was featured: UO(2)(+2), uranyl carbonate complexes and UO(2)PO(4)(-) seem the U species being preferentially taken up by the roots and transferred to the shoots. Improved correlations were obtained when relating the uranium TF with the summed soil solution concentrations of mentioned uranium species.     

Lichens as biomonitors of uranium in the Balkan area

The contribution of the conflict of 1999 to the environmental levels of uranium in the Balkan area was evaluated by means of lichens used as biomonitors. The average U concentration found in lichens in the present study was in line with the values reported for lichens from other countries and well below the levels found in lichens collected in areas with natural or anthropogenic sources of U. Measurement of isotopic ratios 235U/238U allowed to exclude the presence of depleted uranium. According to these results, we could not detect widespread environmental contamination by depleted uranium in the Balkan area.     

Exposure of Chironomus riparius larvae to uranium: effects on survival, development time, growth, and mouthpart deformities

Among non-biologically essential metals, data concerning uranium effects on freshwater benthic macroinvertebrates are scarce. The effects of uranium on survival, development time, growth and mouthpart deformities of midge Chironomus riparius were investigated. A 10-day static laboratory bioassay was performed exposing first instar larvae to artificial sediment spiked with four concentrations of uranium (2.97; 6.07; 11.44; 23.84 microg U g(-1) dry wt). As uranium was released from the sediment to the overlying water during this bioassay, both the sediment and the water column act as contamination pathways in giving rise to the observed effects. Significant negative effects on survival, development time, and growth were detected at 6.07, 6.07 and 2.97 microg U g(-1) dry wt, respectively. An LC20 of 2.49 microg U g(-1) dry wt (95% CI=1.48-4.27), and an LC50 of 5.30 microg U g(-1) dry wt (95% CI=3.94-7.25) were estimated. With respect to effects of uranium on larvae mouthpart deformities, we found that the lower the concentrations, the higher the deformity rates. These results highlight the potential impact of uranium at population level in environmentally realistic concentrations.     

Can we predict uranium bioavailability based on soil parameters? Part 1: effect of soil parameters on soil solution uranium concentration

Present study aims to quantify the influence of soil parameters on soil solution uranium concentration for (238)U spiked soils. Eighteen soils collected under pasture were selected such that they covered a wide range for those parameters hypothesised as being potentially important in determining U sorption. Maximum soil solution uranium concentrations were observed at alkaline pH, high inorganic carbon content and low cation exchange capacity, organic matter content, clay content, amorphous Fe and phosphate levels. Except for the significant correlation between the solid-liquid distribution coefficients (K(d), L kg(-1)) and the organic matter content (R(2)=0.70) and amorphous Fe content (R(2)=0.63), there was no single soil parameter significantly explaining the soil solution uranium concentration (which varied 100-fold). Above pH=6, log(K(d)) was linearly related with pH [log(K(d))=-1.18 pH+10.8, R(2)=0.65]. Multiple linear regression analysis did result in improved predictions of the soil solution uranium concentration but the model was complex.     

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.     

Environmental distribution of uranium and other trace elements at selected Kosovo sites

This paper reports the results of a study using lichens as biomonitors to investigate the environmental distribution of uranium and other trace elements at selected Kosovo sites. The results suggested that the use of depleted uranium (DU) ammunitions in Kosovo did not cause a diffuse environmental contamination in such a way to have caused a detectable U enrichment in lichens. Also isotopic (235)U/(238)U measurements did not indicate the presence of DU particles in lichens. The present results also provided no indication of intense environmental contamination by the other trace elements analyzed, with the exception of Kosovska Mitrovica, where a diffuse environmental contamination by several heavy elements such as Pb, Zn, As and Cd was found.     

Levels of polybrominated diphenyl ethers and hexabromocyclododecane in the atmosphere and tree bark from Beijing, China

Air samples in four seasons at one site and tree bark samples from four districts were determined to investigate seasonal variation and regional distribution of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in Beijing, China. The total concentrations of PBDEs (∑PBDE) and HBCD (∑HBCD) were in the range of 57-470 and 20-1800 pg m⁻³ in the atmosphere, respectively. The ∑PBDE and ∑HBCD concentrations were significantly influenced by the total suspended particulate matter in atmosphere. The total concentrations of PBDEs and HBCD in tree bark samples were in the range of 99-3700 and 26-3400 ng g⁻¹ lipid weight. It was found that regional distribution of PBDEs and HBCD was related to the function of each district. In addition, the study found that weeping willow bark was an ideal atmospheric PBDEs and HBCD passive sampler. Finally, atmospheric levels of BDE-209 and HBCD at tree bark sampling districts were estimated via applying an established bark/air partitioning model, which had been verified by the measured concentrations in tree bark and atmosphere in Beijing.     

The ability of Helianthus annuus L. and Brassica juncea to uptake and translocate natural uranium and 226Ra under different milieu conditions

Seedlings of Helianthus annuus L. (HA) and Brassica juncea (BJ) were used to test the effect of the pH, the presence of phosphates, and the addition of ethylene-diamine-tetraacetic acid (EDTA) or citrate on the uptake and the translocation of uranium isotopes ((238)U, (235)U, and (234)U) and (226)Ra. The results indicated that the presence of phosphates generally reduces the uptake and transfer of uranium from the roots to the shoots of HA. In the case of BJ, while phosphate enhanced the retention of uranium by roots, the translocation was poorer. Likewise, for (226)Ra, the best translocation was in the absence of phosphates for both species. The addition of citrate increased the translocation of uranium for both species, but had no clear effect on the transfer of (226)Ra. The effect of EDTA was much more moderate both for uranium and for (226)Ra, and for both plant species. Only noticeable was a slightly better uptake of (226)Ra by BJ at neutral pH, although the translocation was lower.     

Uptake of 207Pb and 111Cd through bark of mature sugar maple,white ash and white pine: a field experiment

A field study was undertaken to determine whether 207Pb and 111Cd, applied to the exterior bark of sugar maple (Acer saccharum Marsh.), white ash (Fraxinus americana L.) and white pine (Pinus strobus L.), could enter xylem tissue. Stable isotope tracers (3 microg Pb ml(-1); 2 microg Cd ml(-1)) were applied separately to bark in simulated rainfall, acidified to pH 4.5, in multiple doses over a 4 month (July-October) period. Tree cores were extracted from the region of application in the following March, and Pb and Cd isotopes were measured in bark and the outer tree rings using inductively coupled plasma mass spectrometry. The majority of the applied stable isotope tracer recovered (over 94%) was present in bark tissue, although a small amount of each metal tracer entered the outer (1-3) tree rings in all trees. Despite high concentrations of excess 207Pb in bark (up to 50 microg g(-1)), the maximum concentration of excess 207Pb measured in tree rings was only around 50 ng g(-1), which represents less than 30% of the background Pb concentration in wood at the study site. High excess 111Cd concentrations in bark (up to 35 microg g(-1)) also resulted in small increases in 111Cd in wood (up to 50 ng g(-1)), but due to lower background Cd concentrations in wood, such increases more than doubled the amount of Cd in wood compared with background levels. However, at sites where such high bark Cd concentrations are found, uptake from Cd-contaminated soil would probably be much greater than found at our study site. It appears that Cd and Pb applied to bark can enter woody tissue, but that this route of uptake is likely to be a minor contributor to the metal burden in wood.     

Quantifying uranium complexation by groundwater dissolved organic carbon using asymmetrical flow field-flow fractionation

The long-term mobility of actinides in groundwaters is important for siting nuclear waste facilities and managing waste-rock piles at uranium mines. Dissolved organic carbon (DOC) may influence the mobility of uranium, but few field-based studies have been undertaken to examine this in typical groundwaters. In addition, few techniques are available to isolate DOC and directly quantify the metals complexed to it. Determination of U-organic matter association constants from analysis of field-collected samples compliments laboratory measurements, and these constants are needed for accurate transport calculations. The partitioning of U to DOC in a clay-rich aquitard was investigated in 10 groundwater samples collected between 2 and 30 m depths at one test site. A positive correlation was observed between the DOC (4-132 mg/L) and U concentrations (20-603 microg/L). The association of U and DOC was examined directly using on-line coupling of Asymmetrical Flow Field-Flow Fractionation (AsFlFFF) with UV absorbance (UVA) and inductively coupled plasma-mass spectrometer (ICP-MS) detectors. This method has the advantages of utilizing very small sample volumes (20-50 microL) as well as giving molecular weight information on U-organic matter complexes. AsFlFFF-UVA results showed that 47-98% of the DOC (4-136 mg C/L) was recovered in the AsFlFFF analysis, of which 25-64% occurred in the resolvable peak. This peak corresponded to a weight-average molecular weight of about 900-1400 Daltons (Da). In all cases, AsFlFFF-ICP-MS suggested that相似文献   

Tree bark as a passive air sampler to indicate atmospheric polybrominated diphenyl ethers (PBDEs) in southeastern China

The different barks were sampled to discuss the influence of the tree species, trunk circumference, and bark thickness on the accumulation processes of polybrominated diphenyl ethers (PBDEs) from air into the bark. The results of different PBDE concentrations indicated that barks with a thickness of 0–3 mm collected from weeping willow, Camphor tree, and Masson pine, the trunk circumferences of which were 100 to 150 cm, were better PBDEs passive samplers. Furthermore, tree bark and the corresponding air samples were collected at Anji (AJ), Hangzhou (HZ), Shanghai (SH), and Wenling (WL) to investigate the relationship between the PBDE concentrations in bark and those in air. In addition, the significant correlation (r ²?=?0.906; P?<?0.05) indicated that atmospheric PBDEs were the principle source for the accumulation of PBDEs in the barks. In this study, the log K _BA (bark–air partition coefficient) of individual PBDE congeners at the four sites were in the range from 5.69 to 6.79. Finally, the total PBDE concentration in WL was 5 to 20 times higher than in the other three cities. The result indicated that crude household workshops contributed a heavy amount of PBDEs pollution to the environment, which had been verified by the spatial distribution of PBDEs levels in barks collected at Wenling (range, 26.53–1317.68 ng/g dw). The good correlation between the PBDE concentrations in the barks and the air samples and the variations of the PBDE concentrations in tree barks collected from different sites reflected that the bark could be used as a passive sampler to indicate the atmospheric PBDEs.     

U(VI) adsorption on aquifer sediments at the Hanford Site

Aquifer sediments collected via split-spoon sampling in two new groundwater wells in the 200-UP-1 operable unit at the Hanford Site were characterized and showed typical Ringold Unit E Formation properties dominated by gravel and sand. High iron-oxide content in Fe oxide/clay coatings caused the highest U(VI) adsorption as quantified by batch K(d) values, indicating iron oxides are the key solid adsorbent in the 200-UP-1 sediments that affect U(VI) fate and mobility. Even though U(VI) adsorption on the gravel-sized fraction of the sediments is considered to be negligible, careful characterization should be conducted to determine U(VI) adsorption on gravel, because of presence of Fe oxides coatings and diffusion-controlled adsorption into the gravel particles' interior surfaces. A linear adsorption isotherm was observed up to 10(-6) M (238 microg/L) of total U(VI) concentration in batch U(VI) adsorption tests with varying total U(VI) concentrations in spiked groundwater. U(VI) adsorption decreased with increasing concentrations of dissolved carbonate, because strong anionic aqueous uranium-carbonate complexes formed at high pH and high alkalinity conditions. Noticeable uranium desorption hysteresis was observed in a flow-through column experiment, suggesting that desorption K(d) values for aged uranium-contaminated sediments at the Hanford Site can be larger than adsorption K(d) values determined in short-term laboratory experiments and slow uranium release from contaminated sediments into the groundwater is expected.     

Reduction in residential chromium following site remediation

The purpose of this study was to determine the influence of chromate production waste site remediation on residential Cr concentrations in house dust. Twenty-three homes in Jersey City, NJ, were identified as having had high (> 500 micrograms/gm, median 739 micrograms/gm), medium (100-400 micrograms/gm, median 245 micrograms/gm), or low (< 100 micrograms/gm, median 48 micrograms/gm) Cr in house dust during a study conducted in 1992-1993 prior to site remediation. House dust samples were collected on four visits from each home between November 1996 and February 1998, extracted with HNO3, and analyzed for Cr with an inductively coupled plasma-mass spectrometer. Homes that had low Cr concentrations in 1992-1993 continued to have low Cr concentrations (median 1 microgram/g). In contrast, substantial declines in Cr concentrations were found in the house dust collected from homes located near the remediated waste sites: previously high-level homes had a median of 50 micrograms/g and mid-level homes had a median of 34 micrograms/g. Site remediation had a beneficial effect on household loadings of Cr, since no differences in post-remediation house dust Cr concentrations were found among the three groups.     

Migration behavior of naturally occurring radionuclides at the Nopal I uranium deposit, Chihuahua, Mexico

Oxidation of pyrite at the Nopal I uranium deposit, Peña Blanca district, Chihuahua, Mexico has resulted in the formation of Fe-oxides/hydroxides. Anomalous U concentrations (i.e. several hundred to several thousand ppm) measured in goethite, hematite, and amorphous Fe-oxyhydroxides in a major fracture that crosscuts the deposit and the absence of U minerals in the fracture suggest that U was retained during secondary mineral growth or sorbed on mineral surfaces. Mobilization and transport of U away from the deposit is suggested by decreasing U concentrations in fracture-infilling materials and in goethite and hematite with distance from the deposit. Greater than unity ²³⁴U/²³⁸U activity ratios measured in fracture-infilling materials indicate relatively recent ( < 1 Ma) U uptake from fluids that carried excess ²³⁴U. Systematic decreases in ²³⁴U/²³⁸U activity ratios of fracture materials with distance from the deposit suggest a multistage mobilization process, such as remobilization of U from ²³⁴U-enriched infill minerals or differential or diminished transport of U-bearing solutions containing excess ²³⁴U.     

Metal contents of fish from cultureponds near scrap metal reclamation facilities

Milkfish (Chanos chanos) from four fish-culture ponds adjacent to different metal recovery facilities along the Er-Jen River area, Tainan, Taiwan, were sampled to determine their metal contents. Chemical analysis showed that fish tissue contained different concentrations of Cu: 0.71-6.37 micrograms/g, Pb: ND (not detectable) approximately 41.04 micrograms/g, Cd: ND approximately 0.41 microgram/g, Al: 6.75-64.11 micrograms/g, Ni: 0.062-0.504 microgram/g and Zn: 16.11-41.86 micrograms/g. The average concentrations of Cu, Al, Zn, Cd and Pb in fish samples from some of the ponds were significantly higher than those from the reference pond. In addition, there were variations in metal concentrations of fish collected from different ponds. Pond D had the highest mean values of Cu, Cd and Zn, and Pond B of Al and Pb. Further investigations are needed to determine the source of metal contamination in the fish.     

On the presence of enriched amounts of 235U in hot particles from the terrestrial area affected by the Palomares accident (Spain)

The characterisation by ICP-MS of an isolated Pu-U hot particle originating from the nuclear weapons accident in Palomares (Spain) shows, for the first time, that its uranium content is highly enriched in (235)U. The enrichment has been confirmed by independent analyses of two surface soil samples collected in a heavily contaminated area close to the impact point of one of the bombs. This finding clarifies better the composition of the weapons involved in the accident and is of importance when the inventory of U and Pu in the contaminated area are to be calculated.     

Oxidative dissolution of uraninite precipitated on Navajo sandstone

Column and batch experiments were conducted with sandstone and ground water samples to investigate oxidation of uraninite precipitated by microbially mediated reduction of U(VI), a contaminant in ground water beneath a uranium mill tailings site near Tuba City, AZ, USA. Uraninite precipitated together with mackinawite (FeS_0.9) because Fe(III) from the sandstone and sulfate, another contaminant in the water were reduced together with U(VI). After completion of U(VI) reduction, experiments were conducted to find out whether uraninite is protected by mackinawite against reoxidation. Uncontaminated ground water from the same site, containing 7 mg/l of dissolved oxygen, was passed through the columns or mixed with sandstone in batch experiments. The results showed that small masses of uraninite, 0.1 μg/g of sandstone, are protected by mackinawite from reoxidation. Uraninite masses on the order of 0.1 μg/g correspond to U(VI) concentrations of 0.5 mg/l, typically encountered in uranium contaminated ground waters. Mackinawite is an effective buffer and is formed in sufficient quantity to provide long-term protection of uraninite. Uranium concentrations in ground water passed through the columns are too low (4 μg/l) to distinguish between dissolution and oxidative dissolution of uraninite. However, batch experiments showed that uraninite oxidation takes place.     

Trees as bioindicator of heavy metal pollution in three European cities

Concentrations of four heavy metals were determined in tree leaves and bark collected from polluted and non-polluted areas of three European cities (Salzburg, Belgrade and Thessaloniki) for a comparative study. Platanus orientalis L. and Pinus nigra Arn., widespread in urban northern and southern Europe, were tested for their suitability for air quality biomonitoring. Leaves and barks were collected uniformly of an initial quantity of about 30 g of each sample. Analysis was accomplished by electrothermal atomic absorption spectrometry after total digestion. Site-dependent variations were found with the highest concentration level measured in Belgrade, followed by Thessaloniki and Salzburg. A higher accumulation of heavy metals was found in bark compared to leaves. Pine tree bark, accumulating higher concentrations of trace metals compared to plane tree bark, shows a higher efficiency as bioindicator for urban pollution. Both indicator species are suitable for comparative studies on bioindication of urban air pollution.