Photochemical mobilization of dissolved hydrocarbon oxidation products from petroleum contaminated soil into a shallow aquifer activate human nuclear receptors.

Elevated non-volatile dissolved organic carbon (NVDOC) concentrations in groundwater (GW) monitoring wells under oil-contaminated hydrophobic soils originating from a pipeline rupture at the National Crude Oil Spill & Natural Attenuation Research Site near Bemidji, MN are documented. We hypothesized the elevated NVDOC is comprised of water-soluble photooxidation products transported from the surface to the aquifer. We use field and laboratory samples in combination with complementary analytical methods to test this hypothesis and determine the biological response to these products. Observations from optical spectroscopy and ultrahigh-resolution mass spectrometry reveal a significant correlation between the chemical composition of NVDOC leached from photochemically weathered soils and GW monitoring wells with high NVDOC concentrations measured in the aquifer beneath the contaminated soil. Conversely, the chemical composition from the uncontaminated soil photoleachate matches the NVDOC observed in the uncontaminated wells. Contaminated GW and photodissolution leachates from contaminated soil activated biological targets indicative of xenobiotic metabolism and exhibited potential for adverse effects. Newly formed hydrocarbon oxidation products (HOPs) from fresh oil could be distinguished from those downgradient. This study illustrates another pathway for dissolved HOPs to infiltrate GW and potentially affect human health and the environment.

Water availability modifies productivity response to biodiversity and nitrogen in long-term grassland experiments.

Diversity and nitrogen addition have positive relationships with plant productivity, yet climate-induced changes in water availability threaten to upend these established relationships. Using long-term data from three experiments in a mesic grassland (ranging from 17 to 34 yr of data), we tested how the effects of species richness and nitrogen addition on community-level plant productivity changed as a function of annual fluctuations in water availability using growing season precipitation and the Standardized Precipitation-Evapotranspiration Index (SPEI). While results varied across experiments, our findings demonstrate that water availability can magnify the positive effects of both biodiversity and nitrogen addition on productivity. These results suggest that productivity responses to anthropogenic species diversity loss and increasing nitrogen deposition could depend on precipitation regimes, highlighting the importance of testing interactions between multiple global change drivers.

Weathering of Oil in a Surficial Aquifer.

The composition of crude oil in a surficial aquifer was determined in two locations at the Bemidji, MN, spill site. The abundances of 71 individual hydrocarbons varied within 16 locations sampled. Little depletion of these hydrocarbons (relative to the pipeline oil) occurred in the first 10 years after the spill, whereas losses of 25% to 85% of the total measured hydrocarbons occurred after 30 years. The C6-30 n-alkanes, toluene, and o-xylene were the most depleted hydrocarbons. Some hydrocarbons, such as the n-C10-24 cyclohexanes, tri- and tetra- methylbenzenes, acyclic isoprenoids, and naphthalenes were the least depleted. Benzene was detected at every sampling location 30 years after the spill. Degradation of the oil led to increases in the percent organic carbon and in the δ 13 C of the oil. Another method of determining hydrocarbon loss was by normalizing the total measured hydrocarbon concentrations to that of the most conservative analytes. This method indicated that the total measured hydrocarbons were depleted by 47% to 77% and loss of the oil mass over 30 years was 18% to 31%. Differences in hydrocarbon depletion were related to the depth of the oil in the aquifer, local topography, amount of recharge reaching the oil, availability of electron acceptors, and the presence of less permeable soils above the oil. The results from this study indicate that once crude oil has been in the subsurface for a number of years there is no longer a "starting oil concentration" that can be used to understand processes that affect its fate and the transport of hydrocarbons in groundwater.

Plant diversity, CO2, and N influence inorganic and organic N leaching in grasslands.

In nitrogen (N)-limited systems, the potential to sequester carbon depends on the balance between N inputs and losses as well as on how efficiently N is used, yet little is known about responses of these processes to changes in plant species richness, atmospheric CO2 concentration ([CO2]), and N deposition. We examined how plant species richness (1 or 16 species), elevated [CO2] (ambient or 560 ppm), and inorganic N addition (0 or 4 g x m(-2) x yr(-1)) affected ecosystem N losses, specifically leaching of dissolved inorganic N (DIN) and organic N (DON) in a grassland field experiment in Minnesota, USA. We observed greater DIN leaching below 60 cm soil depth in the monoculture plots (on average 1.8 and 3.1 g N x m(-2) x yr(-1) for ambient N and N-fertilized plots respectively) than in the 16-species plots (0.2 g N x m(-2) x yr(-1) for both ambient N and N-fertilized plots), particularly when inorganic N was added. Most likely, loss of complementary resource use and reduced biological N demand in the monoculture plots caused the increase in DIN leaching relative to the high-diversity plots. Elevated [CO2] reduced DIN concentrations under conditions when DIN concentrations were high (i.e., in N-fertilized and monoculture plots). Contrary to the results for DIN, DON leaching was greater in the 16-species plots than in the monoculture plots (on average 0.4 g N x m(-2) x yr(-1) in 16-species plots and 0.2 g N x m(-2) x yr(-1) in monoculture plots). In fact, DON dominated N leaching in the 16-species plots (64% of total N leaching as DON), suggesting that, even with high biological demand for N, substantial amounts of N can be lost as DON. We found no significant main effects of elevated [CO2] on DIN or DON leaching; however, elevated [CO2] reduced the positive effect of inorganic N addition on DON leaching, especially during the second year of observation. Our results suggest that plant species richness, elevated [CO2], and N deposition alter DIN loss primarily through changes in biological N demand. DON losses can be as large as DIN loss but are more sensitive to organic matter production and turnover.

Nitrogen limitation constrains sustainability of ecosystem response to CO2.

Enhanced plant biomass accumulation in response to elevated atmospheric CO2 concentration could dampen the future rate of increase in CO2 levels and associated climate warming. However, it is unknown whether CO2-induced stimulation of plant growth and biomass accumulation will be sustained or whether limited nitrogen (N) availability constrains greater plant growth in a CO2-enriched world. Here we show, after a six-year field study of perennial grassland species grown under ambient and elevated levels of CO2 and N, that low availability of N progressively suppresses the positive response of plant biomass to elevated CO2. Initially, the stimulation of total plant biomass by elevated CO2 was no greater at enriched than at ambient N supply. After four to six years, however, elevated CO2 stimulated plant biomass much less under ambient than enriched N supply. This response was consistent with the temporally divergent effects of elevated CO2 on soil and plant N dynamics at differing levels of N supply. Our results indicate that variability in availability of soil N and deposition of atmospheric N are both likely to influence the response of plant biomass accumulation to elevated atmospheric CO2. Given that limitations to productivity resulting from the insufficient availability of N are widespread in both unmanaged and managed vegetation, soil N supply is probably an important constraint on global terrestrial responses to elevated CO2.

Species and functional group diversity independently influence biomass accumulation and its response to CO2 and N.

The characteristics of plant assemblages influence ecosystem processes such as biomass accumulation and modulate terrestrial responses to global change factors such as elevated atmospheric CO(2) and N deposition, but covariation between species richness (S) and functional group richness (F) among assemblages obscures the specific role of each in these ecosystem responses. In a 4-year study of grassland species grown under ambient and elevated CO(2) and N in Minnesota, we experimentally varied plant S and F to assess their independent effects. We show here that at all CO(2) and N levels, biomass increased with S, even with F constant at 1 or 4 groups. Likewise, with S at 4, biomass increased as F varied continuously from 1 to 4. The S and F effects were not dependent upon specific species or functional groups or combinations and resulted from complementarity. Biomass increases in response to CO(2) and N, moreover, varied with time but were generally larger with increasing S (with F constant) and with increasing F (with S constant). These results indicate that S and F independently influence biomass accumulation and its response to elevated CO(2) and N.