Steady-state Mass Balance Model Research Articles

Intake fraction of nonreactive vehicle emissions in US urban areas

Abstract Intake fraction, which is the fraction of emissions that are inhaled by people, quantifies the “exposure efficiency” of an emission source. We use three methods to estimate intake fractions for vehicle emissions in US urban areas. First, we use a one-compartment steady-state mass-balance model, incorporating meteorological and demographic data. Second, we use an empirical emissions-to-concentration relationship for vehicle carbon monoxide developed for 15 US urban areas. Third, we analyze model results for benzene and diesel particulate matter from the US Environmental Protection Agency's National-scale Air Toxics Assessment (NATA). The population-weighted mean intraurban intake fraction for nonreactive gaseous vehicle emissions in US urban areas is estimated to be in the range 7–21 per million, with a best estimate of 14 per million. The intake fraction for diesel particles is 4 per million, based on NATA results. An intake fraction of 4 per million means that 4 mg of pollution are inhaled per kg emitted. Intake fraction values for urban vehicle emissions are usually higher in winter than in summer because of seasonal variability in the atmospheric mixing height. The results presented in this work can be used in health risk assessments, cost–benefit analyses, and other investigations that require a summary of the emission-to-intake relationship.

Towards Consistent Evaluation of the Persistence of Organic, Inorganic and Metallic Substances

Several criteria, including persistence (P), bioaccumulation (B), its related factor bioavailability, toxicity (T), and potential for long range transport (LRT) are currently applied when assessing the environmental hazard and risk associated with the use of chemicals of commerce. Whereas information on B and T criteria may be obtained by experimental measurement using standard tests or by the use of mass balance models, in the case of P and LRT no such standard tests exist, except for certain degradation rates in single media. Nor can these properties be measured in the environment at large. Here we focus on the criterion of persistence and its evaluation using steady-state multimedia mass balance models. It is concluded that it is possible to assess the persistence of all chemical substances including organics, inorganics, and metals using a common methodology in which mass balance models are applied to describe the substance's behavior in a specified environment or “unit world.” This avoids inconsistent evaluation and excessive regulatory fragmentation, which is likely if assessment procedures are specific to classes of chemicals. It is essential that persistence be recognized as only one of several factors influencing hazard and risk. Regulatory actions must also thus reflect other attributes such as toxicity, bioaccumulation, quantities used, and the societal value of the substances.

210Pbex depth distribution in soil and calibration models for assessment of soil erosion rates from210Pbex measurements

Three soil cores collected from China and UK show the210Pbex and137Cs depth distribution on uncultivated and cultivated land. Depth distributions of the two nuclides are very similar. Those nuclide concentrations are higher in the top horizon and decrease exponentially with depth on uncultivated land while the concentrations are almost uniform throughout the plough layer as a result of mixing associated with cultivation on cultivated land.210Pbex reference inventory in the Loess Plateau is 573 mBq▪cm−2, a little higher than 520.0 mBq▪cm−2 in UK. Distribution of artificial fallout137Cs, produced during the nuclear testing period of the late 1950s and 1960s, is in an unsteady state. In contrast, distribution of natural fallout210Pbex is in a steady state under constant conditions of land environment and erosion processes for a long term, e.g. >100 years. Therefore, mass balances of137Cs and210Pbex in soil are different. According to its processes of continues deposition from the atmosphere, nature decay and losses with soil losses,210Pbex steady state mass balance models for cultivated land as well as for uncultivated land are developed to estimate soil erosion rates in this paper. Besides, the proportion of freshly deposited210Pbex fallout removed by erosion on cultivated land can also be calculated from210Pbex depth distribution at a reference site of uneroded permanent grass land.

Variation in iron, aluminum and dissolved organic carbon mass transfer coefficients in lakes

Steady-state mass balance models have been successfully used to predict annual loads and concentrations of numerous substances in lakes. A major limitation of the model is that the value of the mass transfer coefficient, ν X , for some substance, X, is assumed constant and is taken as a mean value of a set of calibration lakes. The range in mean values between lakes for ν X is typically two- to three-fold. Thus, there is some potential for error in model predictions if the true but unknown value for a given lake differs from the mean, calibration value. Moreover, the use of a region-specific value for ν X for all lakes in a region means that when environmental conditions change, the model will have to be re-calibrated requiring many more years of monitoring. In this study, mass balances for two substances, total iron and aluminum, are presented along with simple empirical relationships that predict mass transfer coefficients for iron as a function of dissolved organic carbon (DOC) concentration and aluminum as a function of DOC and pH. The relationships, which are consistent with current understanding of iron and aluminum behavior, account for >90% of the variation in ν X . Improvements in mass balance model predictions are expected when these coefficients are used in place of constant values.

How Can Local Environmental Planning Affect Forest Soil Acidity? A Case Study in Stockholm, Sweden

The objective of this study is to assess how local planning can influence the acidity in the upper forest soil layer. Exceedance of soil acidity was determined by a steady-state mass balance model approach in relation to both present and future deposition. Future deposition scenarios were derived for Stockholm County based on transportation planning. Europe-wide scenarios were derived using the RAINS (Regional Air Pollution Information and Simulation) model. The deposition changes were assessed in relation to two different types of forest harvesting practices: whole-tree harvesting; and stem harvesting. The results demonstrate that local emission reductions combined with tree stem harvesting give the greatest remediation of soil acidity. This implies that forest soil acidity can be introduced as an indicator in local environmental planning.

Estimation of Critical Loads of. Sulfur and Nitrogen for the Korean Ecosystem

The critical loads of sulfur and nitrogen and their exceedances by the sulfur and nitrogen deposition of 1994-1998 were mapped for South Korea for the first time with a spatial resolution of 11km×14km (0.12 5° Long.×0.125° Lat.) using the steady-state mass balance model. The Korean soil and geological maps with the map scale of 1: 250, 000 and the Korean forestry statistical yearbooks were used as basis for the estimations of weathering rate of base cations, critical alkalinity leaching, denitrification fraction and uptakes of base cation and nitrogen. Wet depositions of sulfur, nitrogen and non-sea-salt base cations were derived from measured concentrations in precipitation and precipitation rates using optimum regression equations while dry depositions of sulfur and base cations were estimated using the inferential method. However, dry deposition of nitrogen due to NO, NO2, NH3 and NH4+ species was estimated using the MM5 numerical model, a modified Regional Acid deposition Model (RADM) and the K-mean clustering technique using three consecutive days of gridded daily mean 850 hPa geopotential height fields without precipitation on the last day over South Korea for 5 years. The predominant ranges of base cation deposition, weathering and uptake were estimated to be 300-500 eq ha-1 yr-1, 200-500 eq ha-1 yr-1 and 200-400 eq ha-1 yr-1, respectively. Critical alkalinity leaching was mainly in the range of 1, 0002, 000 eq ha-1 yr-1. Consequently, a large percentage of the maximum critical load of sulfur was found to be in the range of 1, 0002, 000 eq ha-1 yr-1. The estimated predominant ranges of nitrogen immobilization and uptake were 120-180 eq ha-1 yr-1 and 300-400 eq ha-1 yr-1, respectively, indicating low values of the minimum critical load of nitrogen. The maximum critical load of nitrogen was found to be relatively high (predominantly 2, 0004, 000 eq ha-1 yr-1) while the critical load of nutrient nitrogen was low (predominantly 400-800 eq ha-1 yr-1). Exceedance of the maximum critical load of sulfur was found at 85% of the Korean ecosystems considered mainly in the southeastern part of Korea, whereas that of the critical load of nutrient nitrogen was found in the whole Korean ecosystems. This implies that Korean ecosystems are very susceptible to the combined loadings of sulfur and nitrogen.

Steady-State and Dynamic Assessment of Forest Soil Acidification in Switzerland

The European steady-state Simple Mass Balance (SMB) model and the dynamic soil acidification model SAFE were used to assess the risk of future forest soil acidification in Switzerland. 2010 deposition forecasts on a 150x150 km grid resolution as well as corresponding ecosystem protection levels were obtained from RAINS model runs based on the 1999 Gothenburg Protocol obligations under the UN/ECE LRTAP Convention. Deposition values for 2010 on the national resolution were derived by scaling down present l x l km deposition values according to the deposition trends at the 150x150 km grid resolution. Meeting the Protocol obligations will reduce the percentage of Swiss forest ecosystems not protected against acidification between 1990 and 2010 from 41 to 4% according to the RAINS assessment and from 63 to 16% according to the assessment with the SMB at the lxl km resolution. The dynamic approach indicates, however, that soil conditions may not improve as much as these steady-state models suggest. By 2010, 39% of the sites considered will still have soil solution Bc/Al molar ratios below 1 at least in one soil layer. Nevertheless, deposition reductions obtained from the implementation of the new protocol will prevent the major part of Swiss forest soils from further acidification. Aiming at recovery of the more sensitive forest ecosystems would require emission reductions beyond the Protocol’s obligations.

Testing the validity of a critical sulfur and nitrogen load model in southern Ontario, Canada, using soil chemistry data from MARYP.

The validity of a steady-state mass balance model (Arp et al., 1996; referred to as ARP) was tested using physicochemical soil data from the Monitoring Acid Rain Youth Program (MARYP). Four ARP sites were matched with ten MARYP sites according to proximity, bedrock type and subsoil pH to test the validity of the ARP model for critical load exceedances. Soil solution pH, base concentration and A1 concentration from MARYP sites, which were well matched to ARP sites, validated the modelled critical load exceedances. Higher exceedance areas were associated with more acidic pH and lower base and higher A1 concentrations from matched MARYP sites and vice versa. One ARP site was inappropriately matched with MARYP sites and could not be validated using base and A1 concentrations. This study also confirmed the southern limit of the zero critical load exceedance isopleth from the model. However, variability of the other exceedance isopleths was noted due to the limited number of sites used in the model. The validation of these sites in the ARP model and the zero critical load exceedance isopleth nonetheless allows greater confidence in using this model as a management tool for acidic deposition.

高気密住宅における室内ホルムアルデヒド濃度の挙動に関する考察

Field-measurements of indoor formaldehyde (HCHO) concentrations were conducted in newly developed apartment houses in Japan. We found the time courses of HCHO concentrations did not follow theoretical curves described from the present steady-state mass balance model in air-tight houses with less than 0.2/h of air-change rate. Then, we introduced a concept of equilibrium concentration into the model and evaluated. The predicted time courses of HCHO concentration calculated from the proposed model showed good agreement to experimental values even when air-cleaners were operated in the air-tight houses.

Towards a complete mass balance and model for PCBs and PAHs in a small rural lake, Cumbria U.K.

This paper summarizes the processes of exchange/fluxes for polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in a small well‐studied rural lake, Esthwaite Water in northwest England. Measurements of PCB and PAH concentrations have been made in rain, air, water, dated sediment cores, and sediment trap samples over a 2‐yr study period and used to determine fluxes to and from the lake. A steady state mass balance model was used to construct an input‐output budget for the chemicals and to investigate the relative importance of transport into and out of the lake. The hydraulic transport from the lake was the most important loss mechanism for both PCBs and PAHs. Volatilization, not sedimentation, is currently the dominant loss process for PCBs in the water column, whereas, sedimentation exceeds volatilization for PAHs. The data further suggest that the current sediment‐water flux is upward for PCBs and downwards for PAHs, indicating that the sediments might be acting as a secondary source for PCBs but continue to act as a sink for PAHs. Riverine, catchment runoff, or both are believed to be the most important input for PCBs and PAHs to the lake although direct aerial deposition to the lake is also important for PCBs. Differences in the mixtures of compounds in the various compartments suggests significant fractionation of PCBs and PAHs in the air‐water‐sediment system in the lake.

Screening Chemicals for Persistence in the Environment

A method is suggested for rapid screening of chemicals for persistence in the environment. Physical−chemical equilibrium partitioning information between air, water, and octanol are used as a first screen to identify the media for which degradation half-lives are required and those for which half-lives may be unnecessary. An overall persistence under equilibrium conditions is then estimated using half-lives in air, water, soil, and sediment using a steady-state mass balance model. A graphical technique to identify the key half-lives is demonstrated using 233 chemicals. For chemicals of more extreme partitioning properties, some half-lives may not be needed.

Evaluation of different approaches for modeling effects of acid rain on soils in China

Acid deposition is an environmental problem of increasing concern in China. Acidic soils are common in the southern part of the country and soil acidification caused by acid deposition is expected to occur. Here we test and apply two different approaches for modeling effects of acid deposition and compare results with observed data from sites throughout southern China. The dynamic model MAGIC indicates that, during the last few decades, soil acidification rates have increased considerably due to acid deposition. This acidification will continue if sulfur deposition is not reduced, and if reduced more rapidly than base cation deposition. With the Steady State Mass Balance model (SSMB), and assuming that a molar ratio of Ca 2+/Al 3+<1 in soil water is harmful to vegetation, we estimate a slight probability for exceedance of the critical load for present deposition rates. Results from both modeling approaches show a strong dependence with deposition of base cations as well as sulfur. Hence, according to the models, changes in emission control of alkaline particulate matter prior to sulfur dioxide will be detrimental to the environment. Model calculations are, however, uncertain, particularly because available data on base cation deposition fluxes are scarce, and that model formulation of aluminum chemistry does not fully reproduce observations. An effort should be made to improve our present knowledge regarding deposition fluxes. Improvements to the model are suggested. Our work indicates that the critical loads presented in the regional acid deposition assessment model RAINS-Asia are too stringent. We find weaknesses in the SSMB approach, developed for northern European conditions, when applying it to Chinese conditions. We suggest an improved effort to revise the risk parameters for use in critical load estimates in China.

A Modeling Strategy for Planning the Virtual Elimination of Persistent Toxic Chemicals from the Great Lakes: An Illustration of Four Contaminants in Lake Ontario

A systematic seven-step process is proposed as a strategy for planning “virtual elimination” of persistent toxic contaminants in the Great Lakes. The strategy involves (i) estimating loadings, (ii) gathering prevailing concentration data, (iii) obtaining physical-chemical property data for the chemicals of interest, (iv) obtaining data concerning conditions in the lake, (v) applying a relatively simple steady-state mass balance model incorporating an appropriate treatment of variability and uncertainty to reconcile the range of estimated concentrations with the range of monitoring data, (vi) identifying reasonable targets for loading reductions, and finally (vii) applying the model in dynamic form to estimate how future concentrations will respond to suggested loading reductions thus providing a set of targets for virtual elimination. The uncertainties in these estimates are quantified to convey an impression of their perceived accuracy. The strategy is illustrated for four contaminants (polychlorinated biphenyls, benzo(b)fluoranthene, arsenic, and lead) in Lake Ontario.

Modeling potentially sustainable biomass productivity in jack pine forest stands

A steady-state mass balance model (ForSust), developed to simulate potentially sustainable levels of tree biomass growth and related nutrient uptake dynamics, was applied to 17 jack pine sites across Canada. The model simulates potential tree biomass growth based on nutrient inputs from estimated atmospheric deposition (N, Ca, Mg, K) and soil weathering (Ca, Mg, K), and matches the resulting nutrient supply rates with calculated nutrient demand. Nutrient demand calculations are based on nutrient concentrations in wood, bark, branches, and foliage. Specifically, the model simulates sustainable annual increment (SAI) of biomass growth for stem-only and whole-tree (aboveground biomass) harvesting, and for recurring forest fire conditions. Calculated SAI levels were compared with field-estimated mean annual increments for aboveground forest biomass (MAI). For recurring forest fires, it was found that SAI values, as simulated, corresponded with the MAI field estimates in general. For whole-tree harvesting, SAI was lower than MAI for most but not all sites. For stem-only harvesting, SAI corresponded with MAI, but there was a greater scatter between SAI and MAI values than what appeared to be the case for the recurring forest fire scenario. Key words: Jack pine; whole-tree, stem-only harvesting; steady-state mass balance; forest biomass; N, Ca, Mg, K growth limitations; atmospheric deposition

Colour - mass balances and colour - dissolved organic carbon relationships in lakes and streams in central Ontario

Colour and dissolved organic carbon (DOC) concentrations and mass balances were measured for seven unproductive lakes and 20 tributary streams between June 1980 and May 1992. Individual observations of colour, which measures an unknown DOC fraction assumed to be principally humic, were not good predictors of discrete DOC concentrations for any of the study sites. Long-term mean colour was, however, strongly correlated with long-term mean DOC concentrations in streams and lakes. Colour behaved differently from the total DOC pool in lakes. Lake retention and loss coefficients for colour were always higher than corresponding values for the total DOC pool, and the mean annual colour/DOC ratios in lake outflows were always less than the corresponding ratios in lake inputs, indicating that the coloured fraction was preferentially removed or photooxidized. A steady-state mass balance model was used to estimate the upper bound for the average coloured fraction of DOC in each lake. The upper bound for the seven lakes ranged from 34 to 88%, increasing with increasing colour, DOC, and total phosphorus.

Dissolved organic and inorganic carbon mass balances in central Ontario lakes

Mass balances of dissolved organic carbon (DOC) and dissolvedinorganic carbon (DIC) based on stream and precipitation inputs andoutflows were measured for seven unproductive lakes in central Ontariobetween 1981 and 1989. Net annual CO2 evasion occurred in sixof the seven study lakes with minor net invasion in the seventh. Atmosphericinvasion might have been significant at certain times of the year, particularlyduring the growing season. Net evasion rates were greater than DIC loadingrates, indicating partial mineralization of the terrestrially-derived DOC in thelakes. A steady state mass balance model adequately described the variationin DOC retention between lakes. Net annual carbon accumulation of forestcommunities based on estimates of net ecosystem production may beoverestimated because of significant export of carbon to lakes via streamsand groundwater, particularly in catchments with extensive peatlands.

Long-term phosphorus budgets and an examination of a steady-state mass balance model for central Ontario lakes

The objective of this study was to evaluate, modify if necessary, and calibrate a mass balance steady-state total phosphorus (TP) model for use in the Precambrian Shield area of Ontario. Hydrologic data, TP mass balances and lake concentrations data were collected between June 1978 and May 1992 from seven oligotrophic and oligomesotrophic lakes located on the Precambrian Shield in central Ontario. Two of the lakes (Dickie and Harp) had substantial shoreline development; four lakes had alkalinities <25 μ eql −1. The gross settling or loss coefficient, v, was underestimated when internal load was ignored. Long-term mean v ranged about three-fold, from 4.7 m yr −1 in Plastic Lake to 13.7 m yr −1 in Dickie Lake with an average for six lakes of 7.9 m yr −1. The exception was Harp Lake where v was 23.2 m yr −1. The difference in v between heavily developed Dickie and Harp Lakes may have been due to the unusually thick glacial tills in the Harp catchment and their likely ability to retain at least some of the TP from septic effluent. The current inability to predict septic TP retention rates by soils/tills, the highly variable nature of soils/tills, and the decades required to reach equilibrium after installation leave environmental managers with little choice but to apply the “precautionary principle” to ensure adequate protection of inland recreational waters and assume that soils do not retain septic TP. There was no evidence that enhanced sedimentation of TP (“oligotrophication”) occurred in any of the three most acidic lakes. In fact, losses via sedimentation were lowest in these lakes. Average retention, R ((input-output)/input) of TP during the ice-free months of May to November was much higher than average R in winter (December–April) in all lakes. Lack of wind-induced mixing, low biological activity and thermal stratification caused by ice cover make it more likely that stream loads are discharged directly from lakes during winter. Seasonal variation in retention suggests that R and v should be higher in warmer climatic zones. There may be no globally valid v, although the data presented here suggest that a regionally applicable estimate of v may be appropriate. The model should only be calibrated with a long-term data set and should be only used to predict long-term, average responses to changes in average TP loading.

Calculating critical S and N loads and current exceedances for upland forests in southern Ontario, Canada

A steady-state mass-balance model was used to calculate critical loads of S and N deposition for maintaining acceptable long-term acidity levels within upland forests in southern Ontario. Preliminary estimates about critical S and N loads were obtained using existing information about soils, vegetation and atmospheric ion deposition from 12 forest sites, all located within provincial parks or conservation areas. The following were considered: wet atmospheric deposition of all major cations and anions; availability for plant uptake of N, Ca, Mg, and K in the rooting space of each soil; nutrient uptake and storage in the growing woody biomass of the forest stands; estimates of soil weathering; and mean annual air temperature, precipitation, and evapotranspiration. From this, regional isopleth maps were generated to depict the following: (1) current deposition patterns; (2) critical acidification loads and their current exceedances (or nonexceedances) for two acidification effects criteria for soil solutions, namely (i) acceptable Al concentrations ([Al]leach,crit) and (ii) acceptable Al to base cation concentration ratios ([Al]/[BC]leach,crit); (3) critical N-eutrophication loads and their current exceedances for acceptable levels of NO3-N concentrations in soil solutions ([NO3-N]leach,crit). It was found that the northern part of the study area (part of the Canadian Shield) is currently subjected to atmospheric S and N deposition in excess of critical loads, with [Al]leach,crit set at 0.02 mequiv./L or [Al]/[BC]leach,crirt set at 0.15 equiv./equiv. This sensitivity to acid precipitation is, as calculated, primarily due to shallow and weathering-resistant soils and soil parent materials (mostly granitic). The middle portion of the study area is calculated to receive N slightly in excess of the N eutrophication limit, when [NO3-N]leach,crit is set at 0.1 mequiv./L. Considerable co-deposition of base cations (Ca, Mg, K) in the middle and southern part of the study area alleviates some of the atmospheric acidification stress. This stress is further neutralized by the soils and bedrock of this region (predominantly calcareous).

Methyl bromide: ocean sources, ocean sinks, and climate sensitivity.

The oceans play an important role in the geochemical cycle of methyl bromide (CH3Br), the major carrier of O3-destroying bromine to the stratosphere. The quantity of CH3Br produced annually in seawater is comparable to the amount entering the atmosphere each year from natural and anthropogenic sources. The production mechanism is unknown but may be biological. Most of this CH3Br is consumed in situ by hydrolysis or reaction with chloride. The size of the fraction which escapes to the atmosphere is poorly constrained; measurements in seawater and the atmosphere have been used to justify both a large oceanic CH3Br flux to the atmosphere and a small net ocean sink. Since the consumption reactions are extremely temperature-sensitive, small temperature variations have large effects on the CH3Br concentration in seawater, and therefore on the exchange between the atmosphere and the ocean. The net CH3Br flux is also sensitive to variations in the rate of CH3Br production. We have quantified these effects using a simple steady state mass balance model. When CH3Br production rates are linearly scaled with seawater chlorophyll content, this model reproduces the latitudinal variations in marine CH3Br concentrations observed in the east Pacific Ocean by Singh et al. [1983] and by Lobert et al. [1995]. The apparent correlation of CH3Br production with primary production explains the discrepancies between the two observational studies, strengthening recent suggestions that the open ocean is a small net sink for atmospheric CH3Br, rather than a large net source. The Southern Ocean is implicated as a possible large net source of CH3Br to the atmosphere. Since our model indicates that both the direction and magnitude of CH3Br exchange between the atmosphere and ocean are extremely sensitive to temperature and marine productivity, and since the rate of CH3Br production in the oceans is comparable to the rate at which this compound is introduced to the atmosphere, even small perturbations to temperature or productivity can modify atmospheric CH3Br. Therefore atmospheric CH3Br should be sensitive to climate conditions. Our modeling indicates that climate-induced CH3Br variations can be larger than those resulting from small (+/- 25%) changes in the anthropogenic source, assuming that this source comprises less than half of all inputs. Future measurements of marine CH3Br, temperature, and primary production should be combined with such models to determine the relationship between marine biological activity and CH3Br production. Better understanding of the biological term is especially important to assess the importance of non-anthropogenic sources to stratospheric ozone loss and the sensitivity of these sources to global climate change.

Evaluation of estimation methods and base data uncertainties for critical loads of acid deposition in Japan

Simplified steady state mass balance model for critical load (CL) estimation was applied to a test area in Japan to evaluate applicability of the model. Three different criteria for acidification limits (1: [Al3+]<0.2 eq. m−3, 2: Al/BC<1.0 mol mol−1, 3:Al depletion criterion) were used. Mean values and spatial distribution patterns of CL values calculated by these criteria were extremely different from each other. The first criterion produced much higher CL than the second criterion in the Japanese condition with high annual precipitation. Improvements including definition of the criterion were considered necessary. As quantitative data of the base cation weathering rate (BCw) was lacking, the rate was specified based on surface geology and the soil type of each site. To evaluate uncertainty of BCw used for CL calculation, ion content and particle-size distribution were measured for the soils collected from the test area, and BCw was estimated with PROFILE model based on these measurements. It appeared that BCw estimates by surface geology were adequate as a mean value, but they had uncertainty of about 50% of the average values due to variability of ion contents within the same surface geology group.