A conceptual framework: Redefining forest soil's critical acid loads under a changing climate

Federal agencies of several nations have or are currently developing guidelines for critical forest soil acid loads. These guidelines are used to establish regulations designed to maintain atmospheric acid inputs below levels shown to damage forests and streams. Traditionally, when the critical soil acid load exceeds the amount of acid that the ecosystem can absorb, it is believed to potentially impair forest health. The excess over the critical soil acid load is termed the exceedance, and the larger the exceedance, the greater the risk of ecosystem damage. This definition of critical soil acid load applies to exposure of the soil to a single, long-term pollutant (i.e., acidic deposition). However, ecosystems can be simultaneously under multiple ecosystem stresses and a single critical soil acid load level may not accurately reflect ecosystem health risk when subjected to multiple, episodic environmental stress. For example, the Appalachian Mountains of western North Carolina receive some of the highest rates of acidic deposition in the eastern United States, but these levels are considered to be below the critical acid load (CAL) that would cause forest damage. However, the area experienced a moderate three-year drought from 1999 to 2002, and in 2001 red spruce (Picea rubens Sarg.) trees in the area began to die in large numbers. The initial survey indicated that the affected trees were killed by the southern pine beetle (Dendroctonus frontalis Zimm.). This insect is not normally successful at colonizing these tree species because the trees produce large amounts of oleoresin that exclude the boring beetles. Subsequent investigations revealed that long-term acid deposition may have altered red spruce forest structure and function. There is some evidence that elevated acid deposition (particularly nitrogen) reduced tree water uptake potential, oleoresin production, and caused the trees to become more susceptible to insect colonization during the drought period. While the ecosystem was not in exceedance of the CAL, long-term nitrogen deposition pre-disposed the forest to other ecological stress. In combination, insects, drought, and nitrogen ultimately combined to cause the observed forest mortality. If any one of these factors were not present, the trees would likely not have died. This paper presents a conceptual framework of the ecosystem consequences of these interactions as well as limited plot level data to support this concept. Future assessments of the use of CAL studies need to account for multiple stress impacts to better understand ecosystem response.     

Effect of bone char application on Pb bioavailability in a Pb-contaminated soil

The effects of bone char (BC) application on the bioavailability of Pb in a polluted soil from Hunan Province, China were examined. The Pb-contaminated soil was treated with two types of bone char, one from the UK and the other from China. The bioavailability of Pb was determined in terms of the uptake by Chinese cabbage (Brassica chinensis L.), sequential extraction and X-ray diffraction analysis. The results indicate that the Pb concentrations in both shoots and roots decreased with increasing quantities of added bone char, and the application of BC from the UK at the rate of 1.6% (w:w) had the largest effect. Lead Pb concentrations in the shoots and roots decreased by 56.0% and 75.9%, respectively, whereas the application of BC from Zhejiang Province, China at the rate of 1.6% (w:w) reduced Pb concentrations in the shoots and roots to 2.04 mgkg(-1) and 8.42 mgkg(-1), respectively, only 45.8% and 30.2% compared to the control treatment. Sequential extraction results indicate that the addition of bone char, as a metal-immobilizing agent, substantially transforms soil Pb from non-residual fractions to the residual fraction. The transformation was further confirmed using X-ray diffraction studies.     

Assessment of Uncertainty in Long-Term Mass Balances for Acidification Assessments: A MAGIC Model Exercise

Long-term (1860–2010) catchment mass balance calculations rely on models and assumptions which are sources of uncertainty in acidification assessments. In this article, we report on an application of MAGIC to model acidification at the four Swedish IM forested catchments that have been subject to differing degrees of acidification stress. Uncertainties in the modeled mass balances were mainly associated with the deposition scenario and assumptions about sulfate adsorption and soil mass. Estimated base cation (BC) release rates (weathering) varied in a relatively narrow range of 47–62 or 42–47 meq m⁻² year⁻¹, depending on assumptions made about soil cation exchange capacity and base saturation. By varying aluminum solubility or introducing a dynamic weathering feedback that allowed BC release to increase at more acidic pHs, a systematic effect on predicted changes in acid neutralizing capacity (ΔANC ca. 10–41 μeq l⁻¹) and pH (ca. ΔpH = 0.1–0.6) at all sites was observed. More robust projections of future changes in pH and ANC are dependent on reducing uncertainties in BC release rates, the timing, and extent of natural acidification through BC uptake by plants, temporal changes in soil element pools, and fluxes of Al between compartments.     

Will PM control undermine China's efforts to reduce soil acidification?

China’s strategies to control acidifying pollutants and particulate matter (PM) may be in conflict for soil acidification abatement. Acidifying pollutant emissions are estimated for 2005 and 2020 with anticipated control policies. PM emissions including base cations (BCs) are evaluated with two scenarios, a base case applying existing policy to 2020, and a control case including anticipated tightened measures. Depositions of sulfur (S), nitrogen (N) and BCs are simulated and their acidification risks are evaluated with critical load (CL). In 2005, the area exceeding CL covered 15.6% of mainland China, with total exceedance of 2.2 Mt S. These values decrease in the base scenario 2020, implying partial recovery from acidification. Under more realistic PM control, the respective estimates are 17.9% and 2.4 Mt S, indicating increased acidification risks due to abatement of acid-neutralizing BCs. China’s anthropogenic PM abatement will have potentially stronger chemical implications for acidification than developed countries.     

Model and input uncertainty in multi-media fate modeling: benzo[a]pyrene concentrations in Europe

This paper evaluates the contribution of (i) uncertainty in substance properties, (ii) lack of spatial variability, (iii) intermodel differences and (iv) neglecting sorption to black carbon (BC) to the uncertainty of Benzo[a]pyrene (BaP) concentrations in European air, soil and fresh water predicted by the multi-media fate model Simplebox. Uncertainty in substance properties was quantified using probabilistic modeling. The influence of spatial variability was quantified by estimating variation in predicted concentrations with three spatially explicit fate models (Impact 2002, EVn BETR and BETR Global). Intermodel differences were quantified by comparing concentration estimates of Simplebox, Impact 2002, EVn BETR and the European part of BETR Global. Finally, predictions of a BC-inclusive version of Simplebox were compared with predictions of a BC-exclusive version. For air concentrations of BaP, the lack of spatial variability in emissions was most influential. For freshwater concentrations of BaP, intermodel differences and lack of spatial variability in dimensions of fresh water bodies were the dominant sources of uncertainty. For soil, all sources of uncertainty were of comparable magnitude. Our results indicate that uncertainty in Simplebox can be as large as three orders of magnitude for BaP concentrations in the environment and would be substantially underestimated by focusing on one source of uncertainty only.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

Soil sensitivity to acidification in Asia: status and prospects

Exceedance of steady-state critical loads for soil acidification is consistently found in southern China and parts of SE Asia, but there is no evidence of impacts outside of China. This study describes a methodology for calculating the time to effects for soils sensitive to acidic deposition in Asia under potential future sulfur (S), nitrogen (N), and calcium (Ca) emission scenarios. The calculations are matched to data availability in Asia to produce regional-scale maps that provide estimates of the time (y) it will take for soil base saturation to reach a critical limit of 20% in response to acidic inputs. The results show that sensitive soil types in areas of South, Southeast, and East Asia, including parts of southern China, Burma, Hainan, Laos, Thailand, Vietnam, and the Western Ghats of India, may acidify to a significant degree on a 0-50 y timescale, depending on individual site management and abiotic and biotic characteristics. To make a clearer assessment of risk, site-specific data are required for soil chemistry and deposition (especially base cation deposition); S and N retention in soils and ecosystems; and biomass harvesting and weathering rates from sites across Asia representative of different soil and vegetation types and management regimes. National and regional assessments of soils using the simple methods described in this paper can provide an appreciation of the time dimension of soil acidification-related impacts and should be useful in planning further studies and, possibly, implementing measures to reduce risks of acidification.     

Black carbon emissions in China

Black carbon (BC) is an important aerosol species because of its global and regional influence on radiative forcing and its local effects on the environment and human health. We have estimated the emissions of BC in China, where roughly one-fourth of global anthropogenic emissions is believed to originate. China's high rates of usage of coal and biofuels are primarily responsible for high BC emissions. This paper pays particular attention to the application of appropriate emission factors for China and the attenuation of these emissions where control devices are used. Nevertheless, because of the high degree of uncertainty associated with BC emission factors, we provide ranges of uncertainty for our emission estimates, which are approximately a factor of eight. In our central case, we calculate that BC emissions in China in 1995 were 1342 Gg, about 83% being generated by the residential combustion of coal and biofuels. We estimate that BC emissions could fall to 1224 Gg by 2020. This 9% decrease in BC emissions can be contrasted with the expected increase of 50% in energy use; the reduction will be obtained because of a transition to more advanced technology, including greater use of coal briquettes in place of raw coal in cities and towns. The increased use of diesel vehicles in the future will result in a greater share of the transport sector in total BC emissions. Spatially, BC emissions are predominantly distributed in an east–west swath across China's heartland, where the rural use of coal and biofuels for cooking and heating is widespread. This is in contrast to the emissions of most other anthropogenically derived air pollutants, which are closely tied to population and industrial centers.     

天然溶解性有机质对黑炭吸附萘和菲的抑制作用

研究了土壤天然溶解性有机质(富里酸或腐殖酸)对黑炭吸附萘和菲的影响.结果表明:增加天然溶解性有机质的负载量能够减弱黑炭对萘和菲的吸附能力;而同在100mg的负载量条件下,不同分子量的富里酸或腐殖酸的负载对黑炭吸附萘和菲的抑制作用没有明显差别;相对于富里酸或腐殖酸单独负载,金属离子(Al3+或Fe3+)和富里酸或腐殖酸联...     

Quantifying the role of forest soil and bedrock in the acid neutralization of surface water in steep hillslopes

The role of soil and bedrock in acid neutralizing processes has been difficult to quantify because of hydrological and biogeochemical uncertainties. To quantify those roles, hydrochemical observations were conducted at two hydrologically well-defined, steep granitic hillslopes in the Tanakami Mountains of Japan. These paired hillslopes are similar except for their soils; Fudoji is leached of base cations (base saturation <6%), while Rachidani is covered with fresh soil (base saturation >30%), because the erosion rate is 100-1000 times greater. The results showed that (1) soil solution pH at the soil-bedrock interface at Fudoji (4.3) was significantly lower than that of Rachidani (5.5), (2) the hillslope discharge pH in both hillslopes was similar (6.7-6.8), and (3) at Fudoji, 60% of the base cations leaching from the hillslope were derived from bedrock, whereas only 20% were derived from bedrock in Rachidani. Further, previously published results showed that the stream pH could not be predicted from the acid deposition rate and soil base saturation status. These results demonstrate that bedrock plays an especially important role when the overlying soil has been leached of base cations. These results indicate that while the status of soil acidification is a first-order control on vulnerability to surface water acidification, in some cases such as at Fudoji, subsurface interaction with the bedrock determines the sensitivity of surface water to acidic deposition.     

Carbon storage in northeast China as estimated from vegetation and soil inventories

We have estimated the stocks of carbon in vegetation and soil in northeast China based on data for 122 plots from the fourth national forest inventory, and for 388 soil profiles from the second national soil survey. The techniques of Geographic Information System (GIS) have been used to extrapolate site-specific estimates of vegetation and soil organic carbon to the entire area of northeast China. Our estimate indicates that the amount of carbon in vegetation and soil for the region are 2.81 PgC (10(15) g C) and 26.43 PgC, respectively, and that the area weighted average density of vegetation and soil organic carbon are 22.7 MgC/ha and 212.7 MgC/ha, respectively. The eastern and northern parts of the region show much higher carbon storage than the rest of the region. Substantial spatial variations in vegetation and soil organic carbon across northeast China suggest that regional estimates on carbon stocks and fluxes should take into account these spatial variations. We suggest that the methodology developed can be used for the entire nation of China as well as other regions of the world.     

Arsenic mobility in brownfield soils amended with green waste compost or biochar and planted with Miscanthus

Degraded land that is historically contaminated from different sources of industrial waste provides an opportunity for conversion to bioenergy fuel production and also to increase sequestration of carbon in soil through organic amendments. In pot experiments, As mobility was investigated in three different brownfield soils amended with green waste compost (GWC, 30% v/v) or biochar (BC, 20% v/v), planted with Miscanthus. Using GWC improved crop yield but had little effect on foliar As uptake, although the proportion of As transferred from roots to foliage differed considerably between the three soils. It also increased dissolved carbon concentrations in soil pore water that influenced Fe and As mobility. Effects of BC were less pronounced, but the impacts of both amendments on SOC, Fe, P and pH are likely to be critical in the context of As leaching to ground water. Growing Miscanthus had no measurable effect on As mobility.     

Acidification in developing countries: ecosystem sensitivity and the critical load approach on a global scale

Acidification represents a growing threat to certain developing country ecosystems in tropical and subtropical climates. A methodology investigating the extent of acidification risks from sulfur emissions on a global scale is presented. Atmospheric transfer models have been used to calculate transfer and deposition of sulfur (using emissions for 1990 and a projection for 2050) and alkaline soil dust. A method to derive the relative sensitivity of terrestrial ecosystems is explained and preliminary critical load values are assigned. A range of values for critical loads and base cation deposition have been used to investigate uncertainty in maps depicting the excess of deposition above critical loads. These show an increasing risk of acidification in 2050 in extended regions of southern and eastern Asia, as well as parts of southern Africa, in comparison to 1990. Certain areas, especially in Asia, are shown at risk even when high values of critical load and base cation deposition are used.     

Estimating historical anthropogenic global sulfur emission patterns for the period 1850–1990

It is important to establish a reliable regional emission inventory of sulfur as a function of time when assessing the possible effects of global change and acid rain. This study developed a database of annual estimates of national sulfur emissions from 1850 to 1990. A common methodology was applied across all years and countries allowing for global totals to be produced by adding estimates from all countries. The consistent approach facilitates the modification of the database and the observation of changes at national, regional, or global levels. The emission estimates were based on net production (i.e., production plus imports minus exports), sulfur content, and sulfur retention for each country's production activities. Because the emission estimates were based on the above considerations, our database offers an opportunity to independently compare our results with those estimates based on individual country estimates. Fine temporal resolution clearly shows emission changes associated with specific historical events (e.g., wars, depressions, etc.) on a regional, national, or global basis. The spatial pattern of emissions shows that the US, the USSR, and China were the main sulfur emitters (i.e., approximately 50% of the total) in the world in 1990. The USSR and the US appear to have stabilized their sulfur emissions over the past 20 yr, and the recent increases in global sulfur emissions are linked to the rapid increases in emissions from China. Sulfur emissions have been reduced in some cases by switching from high- to low-sulfur coals. Flue gas desulfurization (FGD) has apparently made important contributions to emission reductions in only a few countries, such as Germany.     

DNAPL distribution in the source zone: effect of soil structure and uncertainty reduction with increased sampling density

This paper focuses on parameters describing the distribution of dense nonaqueous phase liquid (DNAPL) contaminants and investigates the variability of these parameters that results from soil heterogeneity. In addition, it quantifies the uncertainty reduction that can be achieved with increased density of soil sampling. Numerical simulations of DNAPL releases were performed using stochastic realizations of hydraulic conductivity fields generated with the same geostatistical parameters and conditioning data at two sampling densities, thus generating two simulation ensembles of low and high density (three-fold increase) of soil sampling. The results showed that DNAPL plumes in aquifers identical in a statistical sense exhibit qualitatively different patterns, ranging from compact to finger-like. The corresponding quantitative differences were expressed by defining several alternative measures that describe the DNAPL plume and computing these measures for each simulation of the two ensembles. The uncertainty in the plume features under study was affected to different degrees by the variability of the soil, with coefficients of variation ranging from about 20% to 90%, for the low-density sampling. Meanwhile, the increased soil sampling frequency resulted in reductions of uncertainty varying from 7% to 69%, for low- and high-uncertainty variables, respectively. In view of the varying uncertainty in the characteristics of a DNAPL plume, remedial designs that require estimates of the less uncertain features of the plume may be preferred over others that need a more detailed characterization of the source zone architecture.     

Evaluation of PCB sources and releases for identifying priorities to reduce PCBs in Washington State (USA)

Polychlorinated biphenyls (PCBs) are ubiquitously distributed in the environment and produce multiple adverse effects in humans and wildlife. As a result, the purpose of our study was to characterize PCB sources in anthropogenic materials and releases to the environment in Washington State (USA) in order to formulate recommendations to reduce PCB exposures. Methods included review of relevant publications (e.g., open literature, industry studies and reports, federal and state government databases), scaling of PCB sources from national or county estimates to state estimates, and communication with industry associations and private and public utilities. Recognizing high associated uncertainty due to incomplete data, we strived to provide central tendency estimates for PCB sources. In terms of mass (high to low), PCB sources include lamp ballasts, caulk, small capacitors, large capacitors, and transformers. For perspective, these sources (200,000–500,000 kg) overwhelm PCBs estimated to reside in the Puget Sound ecosystem (1500 kg). Annual releases of PCBs to the environment (high to low) are attributed to lamp ballasts (400–1500 kg), inadvertent generation by industrial processes (900 kg), caulk (160 kg), small capacitors (3–150 kg), large capacitors (10–80 kg), pigments and dyes (0.02–31 kg), and transformers (<2 kg). Recommendations to characterize the extent of PCB distribution and decrease exposures include assessment of PCBs in buildings (e.g., schools) and replacement of these materials, development of Best Management Practices (BMPs) to contain PCBs, reduction of inadvertent generation of PCBs in consumer products, expansion of environmental monitoring and public education, and research to identify specific PCB congener profiles in human tissues.     

Inverse modeling to estimate LNAPL plume release timing

Methodologies are presented for dating releases of light nonaqueous phase liquids (LNAPLs) using an inverse modeling approach with simple analytical models. Models for LNAPL plume migration are presented to predict LNAPL plume velocity in the unsaturated and saturated zones as a function of basic soil and fluid properties. A relative mobility factor is introduced for LNAPL movement at the water table that depends primarily on the van Genuchten n parameter (related to the breadth of the soil pore size distribution) and the magnitude of water table fluctuations. Estimated LNAPL plume velocities compare reasonably with more rigorous numerical models, which may be used in cases where data availability warrant the greater effort entailed.Two methods of estimating release timing and its uncertainty are investigated. A direct estimation method is described that determines travel time for a single observed travel distance based on estimated soil and fluid properties. Release date uncertainty may be determined using the first order (FO) or Monte Carlo (MC) methods. The second method for estimating release date involves nonlinear parameter estimation utilizing distance vs. time measurements and other data.A case study is presented for a field site where independent estimates of release timing were obtained from a numerical modeling analysis. Release timing estimates based on direct inversion of the analytical timing model agree well with the numerical analysis. Results for a second field site indicate that release date confidence limits estimated by the FO method, assuming log-normally distributed travel times, are close to values determined by the MC method, which makes no assumption regarding the form of the travel time probability distribution.Results for a hypothetical problem indicate that LNAPL velocity and travel time may be accurately estimated if sufficient data on travel distance vs. time are available. Incorporating prior information on relevant soil and fluid properties into the objective function reduces the uncertainty in release date if prior estimates are accurate. However, biased prior estimates may lead to over- or underestimation of release date uncertainty. Simultaneous estimation of soil and fluid properties and release date is possible if prior information is available to condition the parameter estimates.     

Black carbon-dominated PCDD/Fs sorption to soils at a former wood impregnation site

The influence of black carbon (BC) on the sorption of 17 native polychlorinated-p-dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was studied in five soil samples from a sawmill site where wood used to be impregnated with chlorophenol preservatives. The presence of BC caused measured total organic carbon (TOC)-water distribution ratios (K(TOC)) to be a median factor of 51 (interquartile range 18-68, n=85) higher than modeled amorphous organic carbon (AOC)-water distribution ratios (K(AOC)). K(TOC) was a factor of 73+/-27 above K(AOC) for PCDFs (n=10) and a factor of 20+/-13 (n=7) for PCDDs. The reason for this difference is probably that attaining a planar configuration after sorption to BC is less thermodynamically favorable for PCDDs than for PCDFs. BC-water distribution ratios were calculated from K(TOC), K(AOC) and BC contents, and ranged from 10(9.9) (2,3,7,8-Tetra-CDD) to 10(11.5) l kg(-1) (Octa-CDF). More than 90% of the PCDD/Fs in the soil was calculated to be BC-sorbed. Dissolved organic carbon (DOC)-water distribution ratios were measured to be in the same order of magnitude as K(AOC). This study shows that strong sorption to BC should be included when assessing ecotoxicological risk or modeling transport to groundwater of PCDD/Fs in soil.     

Extension of coupled multispecies metal transport and speciation (TRANSPEC) model to soil

Atmospheric deposition of metals emitted from mining operations has raised metal concentrations in the surrounding soils. This repository may be remobilized and act as a source of metals to nearby surface aquatic systems. It is important to understand metal dynamics and the impact of various chemistry and fate parameters on metal movement in the soil environment in order to evaluate risk associated with metals in terrestrial ecosystems and accurately establish critical discharge limits that are protective of aquatic biota. Here we extend our previously developed coupled multispecies metal fate-TRANsport and SPECiation/complexation (TRANSPEC) model, which was applicable to surface aquatic systems. The extended TRANSPEC, termed TRANSPEC-II, estimates the partition coefficient, K(d), between the soil-solid and -soluble phases using site-specific data and a semi-empirical regression model obtained from literature. A geochemical model calculates metal and species fractions in the dissolved and colloidal phases of the soil solution. The multispecies fugacity/aquivalence based fate-transport model then estimates inter-media transport rates such as leaching from soil, soil runoff, and water-sediment exchanges of each metal species. The model is illustratively applied to Ni in the Kelly Lake watershed (Sudbury, Ontario, Canada), where several mining operations are located. The model results suggest that the current atmospheric fallout supplies only 4% of Ni removed from soil through soil runoff and leaching. Soil runoff contributes about 20% of Ni entering into Kelly Lake with the rest coming from other sources. Leaching to groundwater, apart from runoff, is also a major loss process for Ni in the soil. A sensitivity analysis indicates that raising soil pH to above 6 may substantially reduce metal runoff and improve water quality of nearby water bodies that are impacted by runoff.     

Adaptation, validation and application of the chemo-thermal oxidation method to quantify black carbon in soils

The chemo-thermal oxidation method at 375 °C (CTO-375) has been widely used to quantify black carbon (BC) in sediments. In the present study, CTO-375 was tested and adapted for application to soil, accounting for some matrix specific properties like high organic carbon (≤39%) and carbonate (≤37%) content. Average recoveries of standard reference material SRM-2975 ranged from 25 to 86% for nine representative Swiss and Indian samples, which is similar to literature data for sediments. The adapted method was applied to selected samples of the Swiss soil monitoring network (NABO). BC content exhibited different patterns in three soil profiles while contribution of BC to TOC was found maximum below the topsoil at all three sites, however at different depths (60-130 cm). Six different NABO sites exhibited largely constant BC concentrations over the last 25 years, with short-term (6 months) prevailing over long-term (5 years) temporal fluctuations.