Correction: Growth and survival relationships of 71 tree species with nitrogen and sulfur deposition across the conterminous U.S.

[This corrects the article DOI: 10.1371/journal.pone.0205296.].

Growth and survival relationships of 71 tree species with nitrogen and sulfur deposition across the conterminous U.S.

Atmospheric deposition of nitrogen (N) influences forest demographics and carbon (C) uptake through multiple mechanisms that vary among tree species. Prior studies have estimated the effects of atmospheric N deposition on temperate forests by leveraging forest inventory measurements across regional gradients in deposition. However, in the United States (U.S.), these previous studies were limited in the number of species and the spatial scale of analysis, and did not include sulfur (S) deposition as a potential covariate. Here, we present a comprehensive analysis of how tree growth and survival for 71 species vary with N and S deposition across the conterminous U.S. Our analysis of 1,423,455 trees from forest plots inventoried between 2000 and 2016 reveals that the growth and/or survival of the vast majority of species in the analysis (n = 66, or 93%) were significantly affected by atmospheric deposition. Species co-occurred across the conterminous U.S. that had decreasing and increasing relationships between growth (or survival) and N deposition, with just over half of species responding negatively in either growth or survival to increased N deposition somewhere in their range (42 out of 71). Averaged across species and conterminous U.S., however, we found that an increase in deposition above current rates of N deposition would coincide with a small net increase in tree growth (1.7% per Δ kg N ha-1 yr-1), and a small net decrease in tree survival (-0.22% per Δ kg N ha-1 yr-1), with substantial regional and among-species variation. Adding S as a predictor improved the overall model performance for 70% of the species in the analysis. Our findings have potential to help inform ecosystem management and air pollution policy across the conterminous U.S., and suggest that N and S deposition have likely altered forest demographics in the U.S.

Concentrations in human blood of petroleum hydrocarbons associated with the BP/Deepwater Horizon oil spill, Gulf of Mexico.

During/after the BP/Deepwater Horizon oil spill, cleanup workers, fisherpersons, SCUBA divers, and coastal residents were exposed to crude oil and dispersants. These people experienced acute physiological and behavioral symptoms and consulted a physician. They were diagnosed with petroleum hydrocarbon poisoning and had blood analyses analyzed for volatile organic compounds; samples were drawn 5-19 months after the spill had been capped. We examined the petroleum hydrocarbon concentrations in the blood. The aromatic compounds m,p-xylene, toluene, ethylbenzene, benzene, o-xylene, and styrene, and the alkanes hexane, 3-methylpentane, 2-methylpentane, and iso-octane were detected. Concentrations of the first four aromatics were not significantly different from US National Health and Nutritional Examination Survey/US National Institute of Standards and Technology 95th percentiles, indicating high concentrations of contaminants. The other two aromatics and the alkanes yielded equivocal results or significantly low concentrations. The data suggest that single-ring aromatic compounds are more persistent in the blood than alkanes and may be responsible for the observed symptoms. People should avoid exposure to crude oil through avoidance of the affected region, or utilizing hazardous materials suits if involved in cleanup, or wearing hazardous waste operations and emergency response suits if SCUBA diving. Concentrations of alkanes and PAHs in the blood of coastal residents and workers should be monitored through time well after the spill has been controlled.

Soil mercury and its response to atmospheric mercury deposition across the northeastern United States.

Terrestrial soil is a large reservoir of atmospherically deposited mercury (Hg). However, few studies have evaluated the accumulation of Hg in terrestrial ecosystems in the northeastern United States, a region which is sensitive to atmospheric Hg deposition. We characterized Hg and organic matter in soil profiles from 139 sampling sites for five subregions across the northeastern United States and estimated atmospheric Hg deposition to these sites by combining numerical modeling with experimental data from the literature. We did not observe any significant relationships between current net atmospheric Hg deposition and soil Hg concentrations or pools, even though soils are a net sink for Hg inputs. Soil Hg appears to be preserved relative to organic carbon (OC) and/or nitrogen (N) in the soil matrix, as a significant negative relationship was observed between the ratios of Hg/OC and OC/N (r = 0.54, P < 0.0001) that shapes the horizonal distribution patterns. We estimated that atmospheric Hg deposition since 1850 (3.97 mg/m2) accounts for 102% of the Hg pool in the organic horizons (3.88 mg/m2) and 19% of the total soil Hg pool (21.32 mg/m2), except for the southern New England (SNE) subregion. The mean residence time for soil Hg was estimated to be 1800 years, except SNE which was 800 years. These patterns suggest that in addition to atmospheric deposition, the accumulation of soil Hg is linked to the mineral diagenetic and soil development processes in the region.

Distribution and concentrations of petroleum hydrocarbons associated with the BP/Deepwater Horizon Oil Spill, Gulf of Mexico.

We examined the geographic extent of petroleum hydrocarbon contamination in sediment, seawater, biota, and seafood during/after the BP/Deepwater Horizon Oil Spill (April 20-July 15, 2010; 28.736667°N, -88.386944°W). TPH, PAHs, and 12 compound classes were examined, particularly C1-benzo(a)anthracenes/chrysenes, C-2-/C-4-phenanthrenes/anthracenes, and C3-naphthalenes. Sediment TPH, PAHs, and all classes peaked near Pensacola, Florida, and Galveston, Texas. Seawater TPH peaked off Pensacola; all of the above classes peaked off the Mississippi River, Louisiana and Galveston. Biota TPH and PAHs peaked near the Mississippi River; C-3 napthalenes peaked near the spill site. Seafood TPH peaked near the spill site, with PAHs and all classes peaking near Pensacola. We recommend that oil concentrations continued to be monitored in these media well after the spill has ceased to assist in defining re-opening dates for fisheries; closures should be maintained until hydrocarbon levels are deemed within appropriate limits.

Measuring environmental change in forest ecosystems by repeated soil sampling: a north american perspective.

Environmental change is monitored in North America through repeated measurements of weather, stream and river flow, air and water quality, and most recently, soil properties. Some skepticism remains, however, about whether repeated soil sampling can effectively distinguish between temporal and spatial variability, and efforts to document soil change in forest ecosystems through repeated measurements are largely nascent and uncoordinated. In eastern North America, repeated soil sampling has begun to provide valuable information on environmental problems such as air pollution. This review synthesizes the current state of the science to further the development and use of soil resampling as an integral method for recording and understanding environmental change in forested settings. The origins of soil resampling reach back to the 19th century in England and Russia. The concepts and methodologies involved in forest soil resampling are reviewed and evaluated through a discussion of how temporal and spatial variability can be addressed with a variety of sampling approaches. Key resampling studies demonstrate the type of results that can be obtained through differing approaches. Ongoing, large-scale issues such as recovery from acidification, long-term N deposition, C sequestration, effects of climate change, impacts from invasive species, and the increasing intensification of soil management all warrant the use of soil resampling as an essential tool for environmental monitoring and assessment. Furthermore, with better awareness of the value of soil resampling, studies can be designed with a long-term perspective so that information can be efficiently obtained well into the future to address problems that have not yet surfaced.

Changes in aluminum concentrations and speciation in lakes across the northeastern U.S. following reductions in acidic deposition.

We surveyed 113 lakes in the northeastern U.S. in 2001 that had previously been sampled in 1986 to evaluate the effects of reductions in acidic deposition on the concentrations and speciation of aluminum (Al). We found ubiquitous decreases in the concentrations of total Al and inorganic monomeric aluminum (Ali) across the region. Median total Al decreased from 1.45 to 1.01 micromol L(-1) across the region, with the largest decrease in the Adirondacks (4.60 micromol L(-1) to 2.59 micromol L(-1)). Organic monomeric aluminum (Alo) also decreased region-wide and in all the subregions except the Adirondacks. The speciation of Ali shifted from largely Al-F complexes in 1986 to largely Al-OH complexes in 2001 in ponds whose concentrations were above the detection limit (>0.7 micromol L(-1)). In 2001, only seven lakes studied, representing a population of 130 lakes in the region, had Al1 concentrations above a toxic limit of 2 micromol L(-1) compared with 20 sample lakes, representing 449 lakes, in 1986. Thus, we estimate that more than 300 lakes in the northeastern United States no longer have summer Ali concentrations at levels considered harmful to aquatic biota.

Chemical recovery of surface waters across the northeastern united states from reduced inputs of acidic deposition: 1984-2001.

Changes in lake water chemistry between 1984 and 2001 at 130 stratified random sites across the northeastern United States were studied to evaluate the population-level effects of decreases in acidic deposition. Surface-water S04(2-) concentrations decreased across the region at a median rate of -1.53 microequiv L(-1) year(-1). Calcium concentrations also decreased, with a median rate of -1.73 microequiv L(-1) year(-1). This decrease in Ca2+ retarded the recovery of surface water acid neutralizing capacity (Gran ANC), which increased at a median rate of 0.66 microequiv L(-1) year(-1). There were small increases in pH in all subregions except central New England and Maine, where the changes were not statistically significant. Median NO3- trends were not significant except in the Adirondacks, where NO3- concentrations increased at a rate of 0.53 microequiv L(-1) year(-1). A regionwide decrease in the concentration of total Al, especially in ponds with low ANC values (ANC < 25 microequiv L(-1)), was observed in the Adirondack subregion. These changes in Al were consistent with the general pattern of increasing pH and ANC. Despite the general pattern of chemical recovery, many ponds remain chronically acidic or are susceptible to episodic acidification. The continued chemical and biological recovery at sites in the northeastern United States will depend on further controls on S and N emissions.

Structural, Conformational, and Spectroscopic Studies of Primary Amine Complexes of Iron(II) Porphyrins.

Three novel bis(primary amine)iron(II) porphyrins [Fe(TPP)(RNH(2))(2)], where RNH(2) = 1-butylamine, benzylamine, and phenethylamine, have been synthesized and characterized by X-ray crystallography and IR, electronic, and Mössbauer spectroscopy. The compounds provide unprecedented structural data for the coordination of primary amines by iron(II) porphyrins. The Fe-N(ax) distances of [Fe(TPP)(1-BuNH(2))(2)], [Fe(TPP)(BzNH(2))(2)], and [Fe(TPP)(PhCH(2)CH(2)NH(2))(2)] are 2.039(3), 2.043(3), and 2.028(2) Å, respectively. The Fe-N(p) distances of the three complexes average 1.990(2) Å. The zero-field Mössbauer spectra (5-300 K) show comparable isomer shifts (0.393(1)-0.493(1) mm/s) and quadrupole splittings (1.144(6)-1.204(3) mm/s) that are consistent with an S = 0 iron(II) assignment in each case. The bis(primary amine) complexes are structurally and spectroscopically similar to [Fe(TPP)(Py)(2)] derivatives, where Py = an unsubstituted pyridine. Molecular mechanics (MM) calculations with a force field parametrized for primary and secondary amine complexes of iron(II) porphyrins show that stable conformations arise when the alpha-CH(2) and NH(2) protons of the coordinated ligands are staggered relative to the Fe-N(p) bonds of the porphyrin core. The lowest energy conformations of the three [Fe(TPP)(RNH(2))(2)] complexes therefore have the ligand alpha-carbons positioned directly over the Fe-N(p) bonds of the porphyrin core. The X-ray structure of [Fe(TPP)(PhCH(2)CH(2)NH(2))(2)] lies close to the global minimum (phi(1), phi(2) = 0, 180 degrees ) on the potential surface, while [Fe(TPP)(BzNH(2))(2)] and [Fe(TPP)(1-BuNH(2))(2)] show deviations that may be attributed to packing interactions in the solid and intrinsically low barriers to axial ligand rotation (<0.5 kcal/mol). Three types of minimum energy conformation are accessible for [Fe(TPP)(Pip)(2)]. The lowest energy conformation has an S(4)-ruffled porphyrin core. The conformation which matches the X-ray structure (Radonovich, L. J.; Bloom, A.; Hoard, J. L. J. Am. Chem. Soc. 1972, 94, 2073-2078) is a local minimum (1.6 kcal/mol higher in energy than the global minimum) with exact inversion symmetry. Higher in vacuo strain energy barriers ( approximately 2.2 kcal/mol) separate the potential minima of [Fe(TPP)(Pip)(2)], consistent with the increased bulk of the secondary amine axial ligands.