Review: Technical and policy challenges in deep vadose zone remediation of metals and radionuclides.

Contamination in deep vadose zone environments is isolated from exposure so direct contact is not a factor in its risk to human health and the environment. Instead, movement of contamination to the groundwater creates the potential for exposure and risk to receptors. Limiting flux from contaminated vadose zone is key for protection of groundwater resources, thus the deep vadose zone is not necessarily considered a resource requiring restoration. Contaminant discharge to the groundwater must be maintained low enough by natural attenuation (e.g., adsorption processes or radioactive decay) or through remedial actions (e.g., contaminant mass reduction or mobility reduction) to meet the groundwater concentration goals. This paper reviews the major processes for deep vadose zone metal and radionuclide remediation that form the practical constraints on remedial actions. Remediation of metal and radionuclide contamination in the deep vadose zone is complicated by heterogeneous contaminant distribution and the saturation-dependent preferential flow in heterogeneous sediments. Thus, efforts to remove contaminants have generally been unsuccessful although partial removal may reduce downward flux. Contaminant mobility may be reduced through abiotic and biotic reactions or through physical encapsulation. Hydraulic controls may limit aqueous transport. Delivering amendments to the contaminated zone and verifying performance are challenges for remediation.

Isotopic tracking of Hanford 300 area derived uranium in the Columbia River.

Our objectives in this study are to quantify the discharge rate of uranium (U) to the Columbia River from the Hanford Site's 300 Area and to follow that U downriver to constrain its fate. Uranium from the Hanford Site has variable isotopic composition due to nuclear industrial processes carried out at the site. This characteristic makes it possible to use high-precision isotopic measurements of U in environmental samples to identify even trace levels of contaminant U, determine its sources, and estimate discharge rates. Our data on river water samples indicate that as much as 3.2 kg/day can enter the Columbia River from the 300 Area, which is only a small fraction of the total load of dissolved natural background U carried by the Columbia River. This very low level of Hanford-derived U can be discerned, despite dilution to <1% of natural background U, 400 km downstream from the Hanford Site. These results indicate that isotopic methods can allow the amounts of U from the 300 Area of the Hanford Site entering the Columbia River to be measured accurately to ascertain whether they are an environmental concern or insignificant relative to natural uranium background in the Columbia River.

Controls on species distribution and biogeochemical cycling in nitrate-contaminated groundwater and surface water, southeastern Australia.

A detailed study of groundwater and surface water nitrate over four seasons across an area of varied landuse provided insights into the mechanisms that underlie accumulation and transport of nitrate. High nitrate concentrations found in a significant percentage of surface water and shallow groundwater samples are due to anthropogenic contamination. Statistics (PCA, ANOVA, parsimonious model and general linear regression) were used to explore the relationship between NO3- and land use, and confirmed that areas of high NO3- concentration are associated with dairy pasture and horticulture. Seasonally, NO3- levels are greater during winter, the wettest part of the year. Values of δ15N showed that most nitrate is sourced from livestock waste, with a smaller contribution from synthetic fertilizer. Direct wash-off of animal waste from dairy farms results in higher NO3- concentrations in surface water than in groundwater. Denitrification is an important NO3- attenuation mechanism which reduces NO3- to NH4, as demonstrated by the PCA analysis, which showed positive correlation of NO3- concentrations with dissolved oxygen and negative correlations with NH4+, Fe2+and Mn2+; the latter two species may act as the electron donors necessary for reduction of NO3-. The often high NO3- concentrations in shallow groundwater are decreased by denitrification, which can occur at relatively shallow depths (<3 m). The relatively small NO3- concentrations in deeper groundwater are due partly to denitrification, but more to originally lower NO3- concentrations, as the age of deeper groundwater shows that it was recharged before agriculture was established in the study area. Overall, the study demonstrates the usefulness of hydrogeochemical characterisation and multivariate statistics in the evaluation of impacts of agricultural land-use on regional N cycling. In particular, the results show that efforts to mitigate NO3- pollution from farms should concentrate more on wash-off of animal waste than the contribution of nitrogenous synthetic fertilizer.

Pathways of aqueous Cr(VI) attenuation in a slightly alkaline oxic subsurface.

Column experiments combined with geochemical modeling, microscopic inspections, spectroscopic interrogations, and wet chemical extractions were used to study sediment-dependent Cr(VI) desorption, physical location, mineral association, and attenuation mechanism(s) in four freshly or naturally aged contaminated sediments exposed to concentrated Cr(VI) waste fluids. Results showed that majority of Cr(VI) mass was easily removed from the sediments (equilibrium site K(d) varied from 0 to 0.33 mL g(-1) and equilibrium site fraction was greater than 95%). Long tailings of time-dependent Cr(VI) concentrations above maximum contaminant level of 1.9 micromol L(-1) were also observed (kinetically controlled fraction K(d) and desorption reaction half-lives varied from 0 to 45 mL g(-1), and from 76.1 to 126 h, respectively). Microscopic and spectroscopic measurements confirmed that Cr was concentrated within fine-grained coatings in small areas mainly rich in phyllosilicates that contained both Cr(III) and Cr(VI). However, Cr(VI) reduction was neither significant nor complete. Under slightly alkaline and oxic conditions, contaminant Cr in the sediments occurred: (i) In the highly mobile pool (over 95% of total Cr); (ii) In the slow and time-dependent releasing pool, which served as long-term source of contamination; (iii) As reduced Cr(III) which most likely formed during Cr(VI) reaction with aqueous, sorbed, or structural Fe(II).

Measurement of helium isotopes in soil gas as an indicator of tritium groundwater contamination.

The focus of this study was to define the shape and extent of tritium groundwater contamination emanating from a legacy burial ground and to identify vadose zone sources of tritium using helium isotopes (3He and 4He) in soil gas. Helium isotopes were measured in soil-gas samples collected from 70 sampling points around the perimeter and downgradient of a burial ground that contains buried radioactive solid waste. The soil-gas samples were analyzed for helium isotopes using rare gas mass spectrometry. 3He/4He ratios, reported as normalized to the air ratio (RA), were used to locate the tritium groundwater plume emanating from the burial ground. The 3He (excess) suggested that the general location of the tritium source is within the burial ground. This study clearly demonstrated the efficacy of the 3He method for application to similar sites elsewhere within the DOE weapons complex.

Tracking sources of unsaturated zone and groundwater nitrate contamination using nitrogen and oxygen stable isotopes at the Hanford site, Washington.

The nitrogen and oxygen isotopic compositions of nitrate in pore water extracts from unsaturated zone (UZ) core samples and groundwater samples indicate at least four potential sources of nitrate in groundwaters at the U.S. DOE Hanford Site in south-central Washington. Natural sources of nitrate identified include microbially produced nitrate from the soil column (delta15N of 4 - 8 per thousand, delta18O of -9 to 2 per thousand) and nitrate in buried caliche layers (delta15N of 0-8 per thousand, delta 18O of -6to 42 per thousand). Isotopically distinctindustrial sources of nitrate include nitric acid in low-level disposal waters (delta15N approximately per thousand, delta 18O approximately 23%o) per thousandnd co-contaminant nitrate in high-level radioactive waste from plutonium processing (6'5delta1of 8-33 % o, per thousand18delta oO -9 to 7%0). per thousandThe isotopic compositions of nitrate from 97 groundwater wells with concentrations up to 1290 mg/L NO3- have been analyzed. Stable isotope analyses from this study site, which has natural and industrial nitrate sources, provide a tool to distinguish nitrate sources in an unconfined aquiferwhere concentrations alone do not. These data indicate that the most common sources of high nitrate concentrations in groundwater at Hanford are nitric acid and natural nitrate flushed out of the UZ during disposal of low-level wastewater. Nitrate associated with high-level radioactive UZ contamination does not appear to be a major source of groundwater nitrate at this time.

Identifying the sources of subsurface contamination at the Hanford Site in Washington using high-precision uranium isotopic measurements.

In the mid-1990s, a groundwater plume of uranium (U) was detected in monitoring wells in the B-BX-BY Waste Management Area at the Hanford Site in Washington. This area has been used since the late 1940s to store high-level radioactive waste and other products of U fuel-rod processing. Using multiple-collector ICP source magnetic sector mass spectrometry, high-precision uranium isotopic analyses were conducted of samples of vadose zone contamination and of groundwater. The isotope ratios 236U/238U, 234U/238U, and 238U/235U are used to distinguish contaminant sources. On the basis of the isotopic data, the source of the groundwater contamination appears to be related to a 1951 overflow event at tank BX-102 that spilled high-level U waste into the vadose zone. The U isotopic variation of the groundwater plume is a result of mixing between contaminant U from this spill and natural background U. Vadose zone U contamination at tank B-110 likely predates the recorded tank leak and can be ruled out as a significant source of groundwater contamination, based on the U isotopic composition. The locus of vadose zone contamination is displaced from the initial locus of groundwater contamination, indicating that lateral migration in the vadose zone was at least 8 times greater than vertical migration. The time evolution of the groundwater plume suggests an average U migration rate of approximately 0.7-0.8 m/day showing slight retardation relative to a groundwater flow of approximately 1 m/day.