Chemical response of lakes in the Adirondack Region of New York to declines in acidic deposition

Long-term changes in the chemistry of wet deposition and lake water were investigated in the Adirondack Region of New York. Marked decreases in concentrations of SO4(2-) and H+ in wet deposition have occurred at two sites since the late 1970s. These decreases are consistent with long-term declines in emissions of sulfur dioxide (SO2) in the eastern United States. Changes in wet NO3- deposition and nitrogen oxides (NOx) emissions have been minor over the same interval. Virtually all Adirondack Lakes have shown marked decreases in concentrations of SO4(2-), which coincide with decreases in atmospheric S deposition. Concentrations of NO3- have also decreased in several Adirondack lakes. As atmospheric N deposition has not changed over this period, the mechanism contributing to this apparent increase in lake/watershed N retention is not evident. Decreases in concentrations of SO4(2-) + NO3- have resulted in increases in acid-neutralizing capacity (ANC) and pH and resulted in a shift in the speciation of monomeric Al from toxic inorganic species toward less toxic organic forms in some lakes. Nevertheless, many lakes continue to exhibit pH values and concentrations of inorganic monomeric Al that are critical to aquatic biota. Extrapolation of rates of ANC increase suggests that the time frame of chemical recovery of Adirondack Lakes will be several decades if current decreases in acidic deposition are maintained.     

Factors affecting acid neutralizing capacity in the Adirondack region of New York: a solute mass balance approach

High rates of acidic deposition in the Adirondack region of New York have accelerated acidification of soils and surface waters. Annual input-output budgets for major solutes and acid-neutralizing capacity (ANC) were estimated for 43 drainage lake-watersheds in the Adirondacks from 1998 to 2000. Sulfate was the predominant anion on an equivalent basis in both precipitation and drainage export. Calcium ion had the largest cation drainage export, followed by Mg2+. While these watersheds showed net nitrogen (N) retention, the drainage losses of SO4(2-), Cl-, base cations, and ANC exceeded their respective inputs from precipitation. Land cover (forest type and wetlands) affected the export of SO4(2-), N solutes, and dissolved organic carbon (DOC). The relationships of solute export with elevation (negative for base cations and Cl-, positive for NO3- and H+) suggest the importance of the concomitant changes of biotic and abiotic watershed characteristics associated with elevational gradients. The surface water ANC increased with the sum of base cations and was greatest in the lakes with watersheds characterized by thick deposits of glacial till. The surface water ANC was also higher in the lake-watersheds with lower DOC export. Some variation in lake ANC was associated with variability in acidic deposition. Using a classification system previously developed for Adirondack lakes on the basis primarily of surficial geology, lake-watersheds were grouped into five classes. The calculated ANC fluxes based on the major sinks and sources of ANC were comparable with measured ANC for the thick-till (I) and the medium-till lake-watersheds with low DOC (II). The calculated ANC was overestimated for the medium-till with high DOC (III) and the thin-till with high DOC (V) lake-watersheds, suggesting the importance of naturally occurring organic acids as an ANC sink, which was not included in the calculations. The lower calculated estimates than the measured ANC for the thin-till lake-watersheds with low DOC (IV) were probably due to the mobilization of Al as an ANC source in these watersheds that were highly sensitive to strong acid inputs. Our analysis of various drainage lakes across the Adirondacks on the basis of solute mass balances, coupled with the use of a lake classification system and GIS data, demonstrates that the lake-watersheds characterized by shallow deposits of glacial till are highly sensitive to acidic deposition not only in the southwestern Adirondack region where previous field-based studies were intensively conducted but also across the entire Adirondack region. Moreover, the supply of organic acids and Al mobilization substantially modify the acid-base status of surface waters.     

Modeling the past atmospheric deposition of mercury using natural archives

Historical records of mercury (Hg) accumulation in lake sediments and peat bogs are often used to estimate human impacts on the biogeochemical cycling of mercury. On the basis of studies of lake sediments, modern atmospheric mercury deposition rates are estimated to have increased by a factor of 3-5 compared to background values: i.e., from about 3-3.5 microg Hg m(-2) yr(-1) to 10-20 microg Hg m(-2) yr(-1). However, recent studies of the historical mercury record in peat bogs suggest significantly higher increases (9-400 fold, median 40x), i.e., from about 0.6-1.7 microg Hg m(-2) yr(-1) to 8-184 microg Hg m(-2) yr(-1). We compared published data of background and modern mercury accumulation rates derived from globally distributed lake sediments and peat bogs and discuss reasons for the differences observed in absolute values and in the relative increase in the industrial age. Direct measurements of modern wet mercury deposition rates in remote areas are presently about 1-4 microg m(-2) yr(-1), but were possibly as high as 20 microg Hg m(-2) yr(-1) during the 1980s. These values are closer to the estimates of past deposition determined from lake sediments, which suggests that modern mercury accumulation rates derived from peat bogs tend to overestimate deposition. We suggest that smearing of 210Pb in the uppermost peat sections contributes to an underestimation of peat ages, which is the most important reason for the overestimation of mercury accumulation rates in many bogs. The lower background mercury accumulation rates in peat as compared to lake sediments we believe is the result of nonquantitative retention and loss of mercury during peat diagenesis. As many processes controlling time-resolved mercury accumulation in mires are still poorly understood, lake sediments appear to be the more reliable archive for estimating historical mercury accumulation rates.     

Influence of forest canopies on the deposition of methylmercury to boreal ecosystem watersheds

Although it has been previously shown that forest canopies significantly increase the total deposition of Hg to watersheds, sources and fates of atmospherically deposited MeHg in particular remain poorly understood. In this study, net loadings of MeHg to a watershed were quantified, and the retention and (photo)reduction of MeHg on foliage were measured using unique stable Hg isotope experiments. Annual loadings of MeHg in throughfall (0.34 ± 0.01 to 0.60 ± 0.16 mg ha?1 yr?1) and litterfall (0.77 ± 0.07 to 0.97 ± 0.34 mg ha?1 yr?1) were collectively 3-4 times higher under different forest canopies than loadings of MeHg in the open (0.41 mg ha?1 yr?1), suggesting dry deposition of MeHg to forest canopies. Using Me1??Hg, we found that a portion of MeHg wet deposited to forest canopies is retained on foliage over time, eventually contributing to MeHg in litterfall. Average half-lives (t?) of Me1??Hg on spruce, jack pine, and birch foliage were 204 ± 66, 187 ± 101, and 8 ± 3 days, respectively. We also found using Me1??Hg that following wet deposition, MeHg is rapidly (photo)reduced to 1??Hg(0) on canopy foliage, which then evades to the atmosphere. We were unable to quantify concentrations of particulate-bound MeHg (p-MeHg) in the air using vacuum pumps and quartz microfiber air sampling filters, despite the possibility that p-MeHg does exist in small quantities. As a result, the source of dry deposited MeHg remains partially elusive.     

Direct and indirect atmospheric deposition of PCBs to the Delaware River watershed

Atmospheric deposition can be an important source of PCBs to aquatic ecosystems. To develop the total maximum daily load (TMDL) for polychlorinated biphenyls (PCBs) for the tidal Delaware River (water-quality Zones 2-5), estimates of the loading of PCBs to the river from atmospheric deposition were generated from seven air-monitoring sites along the river. This paper presents the atmospheric PCB data from these sites, estimates direct atmospheric deposition fluxes, and assesses the importance of atmospheric deposition relative to other sources of PCBs to the river. Also, the relationship between indirect atmospheric deposition and PCB loads from minor tributaries to the Delaware River is discussed. Data from these sites revealed high atmospheric PCB concentrations in the Philadelphia/Camden urban area and lower regional background concentrations in the more remote areas. Wet, dry particle, and gaseous absorption deposition are estimated to contribute about 0.6, 1.8, and 6.5 kg year-(-1) sigmaPCBs to the River, respectively, exceeding the TMDL of 0.139 kg year(-1) by more than an order of magnitude. Penta-PCB watershed fluxes were obtained by dividing the tributary loads by the watershed area. The lowest of these watershed fluxes are less than approximately 1 ng m(-2) day(-1) for penta-PCB and probably indicates pristine watersheds in which PCB loads are dominated by atmospheric deposition. In these watersheds, the pass-through efficiency of PCBs is estimated to be on the order of 1%.     

Factors governing the atmospheric deposition of polycyclic aromatic hydrocarbons to remote areas

Polycyclic aromatic hydrocarbons (PAH) were measured in bulk atmospheric deposition collected in three remote areas of Europe during 1997-1998. Mean total PAH fluxes over a period of 18 months were 1560 +/- 750 and 1150 +/- 630 ng m(-2) mo(-1) in the Pyrenees and the Alps, respectively. In the Caledonian mountains (Scandinavia) the observed mean fluxes were 1900 +/- 940 ng m(-2) mo(-1) (6 month collection). Similar qualitative PAH compositions (p values <0.05) in the bulk atmospheric deposition have been observed between sites, which are dominated by the more volatile parent compounds. The main differences between lakes are related to the high molecular weight compounds. Atmospheric deposition of PAH to these remote sites appears to be independent of their concentrations in the atmosphere, which are similar between sites (in the range of 1.8-3.0 ng x m(-3)), being controlled mainly by particle deposition, followed by precipitation and air temperature. A multilevel regression model including these three variables accounted for 74% of the total variability in total PAH bulk deposition; however, the contribution of each variable in the model is compound and site-dependent. The deposition of high molecular weight PAH depends more on particle deposition and precipitation, whereas air temperature is the main factor controlling the deposition fluxes of the low molecular weight PAH.     

Impacts of the Canadian forest fires on atmospheric mercury and carbonaceous particles in Northern New York

The impact of Canadian forest fires in Quebec on May 31, 2010 on PM(2.5), carbonaceous species, and atmospheric mercury species was observed at three rural sites in northern New York. The results were compared with previous studies during a 2002 Quebec forest fire episode. MODIS satellite images showed transport of forest fire smoke from southern Quebec, Canada to northern New York on May 31, 2010. Back-trajectories were consistent with this regional transport. During the forest fire event, as much as an 18-fold increase in PM(2.5) concentration was observed. The concentrations of episode-related OC, EC, BC, UVBC, and their difference (Delta-C), reactive gaseous mercury (RGM), and particle-bound mercury (PBM) were also significantly higher than those under normal conditions, suggesting a high impact of Canadian forest fire emissions on air quality in northern New York. PBM, RGM, and Delta-C are all emitted from forest fires. The correlation coefficient between Delta-C and other carbonaceous species may serve as an indicator of forest fire smoke. Given the marked changes in PBM, it may serve as a more useful tracer of forest fires over distances of several hundred kilometers relative to GEM. However, the Delta-C concentration changes are more readily measured.     

Modeling the atmospheric transport and deposition of PCDD/F to the Great Lakes

Atmospheric deposition is a significant loading pathway for polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxin) to the Great Lakes. An innovative approach using NOAA's HYSPLIT atmospheric fate and transport model was developed to estimate the 1996 dioxin contribution to each lake from each of 5,700 point sources and 42,600 area sources in a U.S./Canadian air emissions inventory. These unusually detailed source-receptor modeling results show that deposition to each lake arises from a broad geographical region, with significant contributions from up to 2,000 km away. The source categories contributing most significantly to 1996 dioxin deposition appear to be municipal waste incineration, iron sintering, medical waste incineration, and cement kilns burning hazardous waste. Model-predicted air concentrations and deposition fluxes were consistent with ambient measurement data, within the uncertainties in each, but there may be a moderate tendency toward underestimation using midrange emissions estimates. The most likely reason for this tendency appears to be missing or underestimated emissions sources, but in-situ atmospheric formation of octachlorinated dibenzo-p-dioxin (OCDD) and heptachlorinated dibenzo-p-dioxin (HpCDD) may have also contributed. Despite uncertainties, the findings regarding the relative importance of different sources types and source regions appear to be relatively robust and may be useful in prioritizing pollution prevention efforts.     

Spectrofluorescence of sediment humic substances and historical changes of lacustrine organic matter provenance in response to atmospheric nutrient enrichment

Humic substances were extracted from the sediments of two small alpine lakes in the Colorado Front Range and characterized by three-dimensional fluorescence spectroscopy. The fluorescence index (FI), defined as the ratio of fluorescence emitted at 450 nm to that emitted at 500 nm from an excitation wavelength of 370 nm, was computed and thereafter compared to additional sediment proxies of recent environmental change. Stratigraphic changes in both sediment C:N ratios and diatom assemblages parallel those of Fl, together indicating pronounced increases in the contribution of autochthonous organic matter to lake sediments since the mid-20th century. This result is consistent with increased algal production attributable to nutrient enrichment, given thatthe region undergoes episodic nitrogen saturation in response to anthropogenic N emission. The validation of sediment Fl measurements through comparisons with independent methods demonstrates the utility of this technique for characterizing shifts in the provenance of lake sediment organic matter arising from changing environmental conditions.     

Contemporary trends in the acid-base status of two acid-sensitive streams in western Maryland

Recovery of streamwater acid neutralizing capacity (ANC) resulting from declines in regional acid deposition was examined using contemporary (1990-2005) data from two long-term monitoring stations located on the Appalachian Plateau in western Maryland, U.S. Two computational methods were used to estimate daily, monthly, and annual fluxes and discharge-weighted concentrations of ANC, sulfate, nitrate, and base cations over the period of record, and two statistical methods were used to evaluate long-term trends in fluxes and concentrations. The methods used to estimate concentrations, as well as the statistical techniques, produced very similar results, underlining the robustness of the identified trends. We found clear evidence that streamwater sulfate concentrations have declined at an average rate of about 3 microeq L(-1) yr(-1) at the two sites due to a 34% reduction in wet atmospheric sulfur deposition. Trends in nitrate concentrations appear to be related to other watershed factors, especially forest disturbance. The best evidence of recovery is based on a doubling of ANC (from 21 to 42 microeq L(-1)) at the more acid-sensitive site over the 16-year period. A slowing, or possible reversal, in the sulfate, nitrate, and SBC trends is evident in our data and may portend a decline in the rate of--or end to--further recovery.     

A quantitative and qualitative assessment of mung bean (Vigna mungo (L.) Wilczek) seed in response to elevated atmospheric carbon dioxide: potential changes in fatty acid composition

The effect of rising atmospheric carbon dioxide concentration ([CO₂]) on seed production and the fatty acid profiles of mung bean (Vigna mungo L. Wilczek) were studied under field conditions. Increased [CO₂] (ca 250 ppm above ambient) resulted in significant increases in pod number, pod weight and total seed weight, but also significantly increased the percentage of immature pods at harvest. Qualitatively, increased [CO₂] significantly decreased the percentages of palmitic and omega‐6 fatty acids, but increased the percentage of omega‐3 fatty acids and the relative proportion of omega‐3 to omega‐6 fatty acids in mature seed. Overall, increased carbon dioxide may significantly increase quantity and alter quality in mung bean seed, a recognized alternative source of fatty acids in the human diet. Copyright © 2007 Society of Chemical Industry     

Evaluating regional patterns in nitrate sources to watersheds in National Parks of the Rocky Mountains using nitrate isotopes

In the Rocky Mountains, there is uncertainty about the source areas and emission types that contribute to nitrate (NO3) deposition, which can adversely affect sensitive aquatic habitats of high-elevation watersheds. Regional patterns in NO3 deposition sources were evaluated using NO3 isotopes in five National Parks, including 37 lakes and 7 precipitation sites. Results indicate that lake NO3 ranged from detection limit to 38 microeq/L, delta18O (NO3) ranged from -5.7 to +21.3% per thousand, and delta15N (NO3) ranged from -6.6 to +4.6 per thousand. delta18O (NO3) in precipitation ranged from +71 to +78% per thousand. delta15N (NO3) in precipitation and lakes overlap; however, delta15N (NO3) in precipitation is more depleted than delta15N (NO3) in lakes, ranging from -5.5 to -2.0 per thousand. delta15N (NO3) values are significantly related (p < 0.05) to wet deposition of inorganic N, sulfate, and acidity, suggesting that spatial variability of delta15N (NO3) over the Rocky Mountains may be related to source areas of these solutes. Regional patterns show that NO3 and delta15N (NO3) are more enriched in lakes and precipitation from the southern Rockies and at higher elevations compared to the northern Rockies. The correspondence of high NO3 and enriched delta15N (NO3) in precipitation with high NO3 and enriched delta15N (NO3) in lakes, suggests that deposition of inorganic N in wetfall may affect the amount of NO3 in lakes through a combination of direct and indirect processes such as enhanced nitrification.     

Polycyclic aromatic hydrocarbons and other semivolatile organic compounds collected in New York City in response to the events of 9/11

Concentrations of over 60 nonpolar semivolatile and nonvolatile organic compounds were measured in Lower Manhattan, NY, using a high-capacity integrated organic gas and particle sampler after the initial destruction of the World Trade Center (WTC). The results indicate that the remaining air plumes from the disaster site were comprised of many pollutants and classes and represent a complex mixture of biogenic (wood-smoke) and anthropogenic sources. This mixture includes compounds that are typically associated with fossil fuel emissions and their combustion products. The molecular markers for these emissions include the high molecular weight PAHs, the n-alkanes, a Carbon Preference Index approximately 1 (odd carbon:even carbon approximately 1), as well as pristane and phytane as specific markers for fuel oil degradation. These results are not unexpected considering the large number of diesel generators and outsized vehicles used in the removal phases. The resulting air plume would also include emissions of burning and remnant materials from the WTC site. Only a small number of molecular markers for these emissions have been identified such as retene and 1,4a-dimethyl-7-(methylethyl)-1,2,3,4,9,10,10a,4a-octahydrophenanthrene that are typically biogenic in origin. In addition, the compound 1,3-diphenylpropane[1',1'-(1,3-propanediyl)bis-benzene] was observed, and to our knowledge, this species has not previously been reported from ambient sampling. It has been associated with polystyrene and other plastics, which are in abundance at the WTC site. These emissions lasted for at least 3 weeks (September 26-October 21, 2001) after the initial destruction of the WTC.     

Atmospheric concentrations and deposition of polycyclic aromatic hydrocarbons to the Mid-Atlantic East Coast region

Atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured at urban/industrial, suburban, coastal, and rural areas in New Jersey as part of the New Jersey Atmospheric Deposition Network. Concentrations of 36 PAH compounds were measured in the gas and particle phases in air and in precipitation at nine sites at regular intervals from October 1997 through May 2001. Gas-phase and particle-phase sigma36PAH concentrations ranged from 0.45 to 118 ng m(-3) and from 0.046 to 172 ng m(-3), respectively, and precipitation concentrations ranged from 11 to 16200 ng L(-1). PAH concentrations vary spatially across the region, with the highest concentrations occurring at the most heavily urban and industrial locations. Average gas absorption deposition ranged from 0.004 (naphthacene) to 5040 (methylphenanthrenes) ng m(-2) d(-1), and dry particle deposition PAH fluxes ranged from 0.11 (naphthacene) to 300 (benzo[b+k]fluoranthene) ng m(-2) d(-1) at the nine sites. Average atmospheric wet deposition PAH fluxes at the seven sites ranged from 0.40 (cyclopenta[cd]pyrene) to 140 (methylphenanthrenes) ng m(-2) d(-1). These represent the first comprehensive estimates of PAH deposition to New Jersey and the Mid-Atlantic East Coast.     

Plant-soil distribution of potentially toxic elements in response to elevated atmospheric CO2

The distribution of contaminant elements within ecosystems is an environmental concern because of these elements' potential toxicity to animals and plants and their ability to hinder microbial ecosystem services. As with nutrients, contaminants are cycled within and through ecosystems. Elevated atmospheric CO2 generally increases plant productivity and alters nutrient element cycling, but whether CO2 causes similar effects on the cycling of contaminant elements is unknown. Here we show that 11 years of experimental CO2 enrichment in a sandy soil with low organic matter content causes plants to accumulate contaminants in plant biomass, with declines in the extractable contaminant element pools in surface soils. These results indicate that CO2 alters the distribution of contaminant elements in ecosystems, with plant element accumulation and declining soil availability both likely explained by the CO2 stimulation of plant biomass. Our results highlight the interdependence of element cycles and the importance of taking a broad view of the periodic table when the effects of global environmental change on ecosystem biogeochemistry are considered.     

Influence of dietary calcium chloride on adaptive changes in acid-base status and mineral metabolism in lactating dairy cows fed a diet high in sodium bicarbonate

Eight mature, lactating Holstein cows were assigned to two treatments in a simple changeover design to examine physiological adaptations to dietary NaHCO3 over a 2-wk period. Treatments were diets containing, on a total diet DM basis, 1) 1.4% NaHCO3 and 2) 1.4% NaHCO3 with 1.3% CaCl2 substituted for limestone. Blood samples were collected hourly, and urine samples bihourly, for 8 h postfeeding on the 1st d of the experimental period and daily at 4 h post-feeding thereafter. Hourly analysis revealed that for most variables measured, the greatest response to dietary treatments occurred at or after 4 h post-feeding. Blood pH and blood HCO3- tended to be lower, and urinary excretion of chloride higher, on 1.4% NaHCO3 plus 1.3% CaCl2 throughout the trial. Blood HCO3- and blood partial pressure of CO2 fluctuated in response to the dietary treatments but functioned to maintain blood pH fairly constant. Plasma K concentration tended to increase during the experimental period on both treatments, but overall, plasma mineral concentration was relatively unresponsive to diet, and urinary mineral excretion was an excellent indicator of dietary mineral concentration. Inherent homeostatic mechanisms appear adequate to maintain a constant internal milieu when a high NaHCO3 diet is fed for 2 wk.     

Estimating the natural background atmospheric deposition rate of mercury utilizing ombrotrophic bogs in southern Sweden

A critical gap in the understanding of the global cycling of mercury is the limited data describing the natural background atmospheric deposition rate of mercury before the advent of pollution. Existing estimates of the natural deposition rate are typically about 2-5 microg of Hg m(-2) year(-1) (see, for example, Swain et al. Science 1992, 257, 784-787), based on studies that generally rely on short, 210Pb-dated lake sediment and peat cores that span the past 150 years. Analyses of mercury in long peat cores in southcentral Sweden indicate that natural mercury deposition rates in the period 4000-500 BP were lower, about 0.5-1 microg of Hg m(-2) year(-1). This suggests that recent mercury accumulation rates in the peat (15-25 microg of Hg m(-2) year(-1)) and measured atmospheric deposition rates of mercury in Sweden over the past 3 decades (5-30 microg of Hg m(-2) year(-1)) (Munthe et al. Water, Air, Soil Pollut.: Focus 2001, 1, 299-310) are at least an order of magnitude greater than the prepollution deposition rate, rather than representing only a 3-5-fold increase, as has generally been estimated.