Distribution and migration of 239,240Pu in soil profiles in North China.

The source, vertical distribution and migration behavior of plutonium in five soil profiles (from forest, grassland and desert areas) in northern China were investigated. The average 240Pu/239Pu atomic ratio of 0.184 ± 0.022 observed in these samples is in good agreement with the reported value of global fallout, suggesting that the global fallout is the major source of plutonium in northern China. The 239,240Pu inventories in five soil profiles ranges from 43.3 Bq/m2 to 175 Bq/m2, lying in the reported range for global fallout in the similar latitude band. The effective convection velocity (0.04-0.16 cm/y) and effective dispersion coefficient (0.13-0.41cm2/y) of plutonium in different soil profiles derived using the CDE model varies significantly, attributed to multi-factors including location, topography, climate and soil types. The results showed that the migration of plutonium in grassland soil is significantly slow compared to other type of soil, especially desert soil.

Level, distribution and sources of plutonium in the northeast and north China.

Concentrations of 239Pu and 240Pu in 163 surface soil samples and five soil cores collected from the northeast and north China were analyzed using the radiochemical separation combined with inductively coupled plasma mass spectrometry measurement. The average 240Pu/239Pu atomic ratios (0.185 ± 0.018) for all surface soil samples indicated that the global fallout is the major source of plutonium in the studied region. The 239,240Pu concentrations of the surface soil ranged from 0.002 mBq/g to 4.82 mBq/g, lying in the range of the reported results in the areas with similar latitude, except for a few samples. The distribution of 239,240Pu in this region is controlled by the deposition of plutonium in the atmosphere and its preservation in the soil, which were affects by multi-factors such as topography, climate, utilization of the land and vegetation coverage. The analytical results could be used as the baseline data for the assessment of the impact of nuclear activities in the past and the future.

Determination of ultra-trace level plutonium isotopes in soil samples by triple-quadrupole inductively coupled plasma-mass spectrometry with mass-shift mode combined with UTEVA chromatographic separation.

Although triple-quadrupole inductively coupled plasma-mass spectrometry (ICP-MS/MS) has become an attractive technique for the measurement of long-lived radionuclides, the abundance sensitivity, isobaric and polyatomic ions interferences seriously restrict the application. The spectral peak tailing and uranium hydrides (UH+, UH2+) from 238U have a serious influence on the accurate measurement of 239Pu and 240Pu, especially for the ultra-trace level plutonium isotopes in the higher uranium sample. A new method was developed using ICP-MS/MS measurement in mass-shift mode with collision-reaction gas combined with a chemical separation procedure. As O2 readily converted Pu+ ion to PuO2+, while disassociated the interfering diatomic ions of interfering elements (U, Pb, Hg, Tl, etc.), the interferences from these elements were completely eliminated if plutonium was detected as PuO2+ at the m/z more than 270. By the mass filter in MS/MS mode combined with O2 as reaction gas the lower peak tailing of 238U+ (<5 × 10-12) was significantly suppressed. By this way, the 238UO2H+/238UO2+ atomic ratio was reduced to 4.82 × 10-9, which is significantly lower than that of other collision-reaction gas modes. Interferences from Pb, Hg and Tl polyatomic ions were also completely eliminated. Thus, accurate measurement of ultra-trace level 239Pu in high uranium sample solutions with the 239Pu/238U concentration ratio of 10-10 was achieved by the mass-shift mode with 0.15 mL/min O2/He + 12.0 mL/min He as collision-reaction gas, and high elimination efficiency of uranium interferences up to 1014 can be obtained by combination with the chemical separation using a single UTEVA resin column. The developed method can be applied to accurately determine the fg level 239Pu in high uranium samples, such as large-size deep seawater, deep soil and sediment, uranium debris of nuclear fuel.

The level, distribution and source of artificial radionuclides in surface soil from Inner Mongolia, China.

Mid- and long-half-life artificial radioisotopes in the earth's surface environment are of great concern to the environmental radiation risk assessment. As nuclear fuel and fission products, 239Pu, 240Pu, 241Am, 90Sr and 137Cs in soils from Inner Mongolia of China were analyzed with a modified systematic separation procedure combined with ICP-MS and LSC measurements, to study the level, distribution and source of artificial radionuclides in the region. The radioactivity and inventory of 137Cs (0.26-28.3 Bq/kg, 0.5-5.4 kBq/m2), 239+240Pu (0.05-1.26 Bq/kg, 20-229 Bq/m2), 241Am (0.036-0.35 Bq/kg, 11-81 Bq/m2) and 90Sr (1.2-7.6 Bq/kg, 0.39-1.7 kBq/m2) all lie in the range of the global fallout. Vertical distributions of these radionuclides were examined for two soil core samples SC14025 and SC14038, and great differences were observed between these two sample locations. For SC14025 where little human disturbance to soil occurred, both 137Cs and 239+240Pu have a subsurface activity maximum followed by an exponential decay. Fittings base on CDE model gives a small downward migration velocity of about 0.097 cm/y for both Pu and 137Cs. Source identification for SC14025 and SC14038 soil cores with 240Pu/239Pu (average of 0.180 ± 0.017 and 0.164 ± 0.035, respectively), 137Cs/239+240Pu (average of 25.3 ± 0.6 and 25.6 ± 3.0, respectively) and 241Am/239+240Pu (average of 0.56 ± 0.08 and 0.60 ± 0.09, respectively) ratios consistently indicated that anthropogenic radionuclides in Xilingol region are mostly from the global fallout of atmospheric nuclear weapons tests in the last century. According to the geographical distribution of the radioactivity level, the high radioactivity level in the east of Inner Mongolia probably results from enhanced deposition by the blocking of the Great Khingan Range.

The speciation, transformation kinetics and fate of spiked Pu (IV) in highly saline groundwater.

The mobility of plutonium (Pu) in groundwater is dependent of its speciation distribution and transformation. The speciation and transformation kinetics of Pu(IV) and its colloids in highly saline groundwater have, however, been rarely studied. In the present study, groundwater (Ionic strength 1 M) from Dunhuang region, NW China, was collected for investigating the speciation, transformation kinetics and fate of spiked Pu (IV) with aging time. The results showed that ~99% of the spiked Pu (IV) (over initial concentration c0 range 2.5 × 10-10-7.8 × 10-7 mol·L-1) was easily associated with the natural colloids and transformed into relatively unstable Pu pseudo-colloids in 1 day, which then gradually deposited and/or adsorbed on the container walls with aging. The suspended Pu pseudo-colloids decreased in similar exponential models, with rate equations r(t) = -3.1 × 10-10e- t/4 and -1.3 × 10-8e-/3 for c0 = 1.25 × 10-9 mol·L-1and 4.17 × 10-8 mol·L-1, respectively. The chemical speciation of the suspended colloidal Pu was dominated by "Fe/Mn Oxides" at the early time, while "Carbonates" with slower depositing rate (r(t) = -6.9 × 10-12e- 0.149t) dominated it (~82%) at equilibrium state. Whatever the c0 was, the concentration of dissolved Pu (i.e., the apparent solubility of Pu) kept at 0.7 × 10-11 mol·L-1 over aging. The valence of dissolved Pu was dominated by Pu(IV) at early time, while Pu(V + VI) would become dominant (~95%) at equilibrium state with transformation rate of r(t) = -92.9e- t/16.6 + 96.9. The equilibrium times of Pu deposition (and/or adsorption), speciation transformation of the suspended colloidal Pu, and valence change of the dissolved Pu were 30 d, 80 d and 120 d, respectively. The kinetic process for each Pu species could be well fitted with exponential model. These results suggest that the majority of released Pu(IV) into highly saline groundwater will be easily associated with natural aquatic colloids and then become immobile in short time due to deposition (and/or adsorption) onto the environmental medium, but potential migration risk caused by stable suspended Pu colloids cannot be ignored.

Plutonium partitioning in water-granite and water-α-FeOOH systems: from a viewpoint of a three-phase system.

Traditional sorption experiments commonly treat the colloidal species of low-solubility contaminants as immobile species when separated by centrifugation or ultrafiltration. This study shows that, from a viewpoint of a three-phase system, the mobile Pu species, especially the colloidal species, play an important role in Pu partitioning in water-granite and water-α-FeOOH systems. A new distribution coefficient term Ks/(d+c) was defined to take the mobile colloidal species into consideration, and it differs to the traditional distribution coefficient Ks/d by orders of magnitude in the water-granite and water-α-FeOOH systems. This term, Ks/(d+c), can quantitatively describe Pu partitioning in the suspension, in particular the fraction of mobile species that dominate Pu migration in the environment. The effects of ionic strength (I) and pH on the Pu partitioning in water-granite and water-α-FeOOH systems are well interpreted with respect to the zeta potential change of granite grains, α-FeOOH colloid particles and polymeric Pu. It is concluded that the presence of the α-FeOOH colloid with a low concentration (<10 mg L(-1)) is favorable for the stability of colloidal Pu and leads to large proportion of mobile Pu, especially colloid-associated Pu, which will migrate much faster than dissolved Pu in groundwater.

Goethite colloid enhanced Pu transport through a single saturated fracture in granite.

α-FeOOH, a stable iron oxide in nature, can strongly absorb the low-solubility plutonium (Pu) in aquifers. However, whether Pu transports though a single saturated fracture can be enhanced in the presence of α-FeOOH colloids remains unknown. Experimental studies were carried out to evaluate Pu mobilization at different water flow velocity, as affected by goethite colloids with various concentrations. Goethite nanorods were used to prepare (α-FeOOH)-associated Pu suspensions with α-FeOOH concentration of (0-150) mgL(-1). The work experimentally evidenced that α-FeOOH colloid does enhance transport of Pu through fractured granites. The fraction of mobile (239)Pu (RPu, m=41.5%) associated with the α-FeOOH of an extremely low colloid concentration (0.2mgL(-1)) is much larger than that in absence of α-FeOOH (RPu, m=6.98%). However, plutonium mobility began to decrease when α-FeOOH concentration was increased to 1.0mgL(-1). On the other hand, the fraction of mobile Pu increased gradually with the water flow velocity. Based on the experimental data, the mechanisms underlying the (α-FeOOH)-associated plutonium transport are comprehensively discussed in view of its dynamic deposition onto the granite surfaces, which is decided mainly by the relative interaction between the colloid particle and the immobile surface. This interaction is a balance of electrostatic force (may be repulsive or attractive), the van der Walls force, and the shear stress of flow.