Evidence for trans-cuticular uptake of HNO3 vapor by foliage of Eastern white pine (Pinus strobus L.)

Forest declines in Europe and the northeastern United States are widely believed to be associated with deposition of air pollutants, perhaps including nitric acid vapor. The experiments presented here, which were conducted in indoor chambers, involved measurement of steady-state rates of nitric acid deposition on foliage of seedlings of eastern white pine. Nitric acid concentrations ranged from 37 to 1260 ppb, but were mostly in the 130-180 ppb range. Between 130 and 180 ppb, much of the deposited nitric acid could be removed by washing leaf surfaces with water. Amounts of nitrate removed by washing increased with exposure duration to a maximum of 7.6 nmol cm(-2) after about 8 h. Although nitrate concentrations in the washings remained constant after 8 h, nitric acid deposition nonetheless continued at a steady-state rate. We have termed this steady-state deposition 'trans-cuticular' on the assumption that the nitric acid diffuses through the cuticle. Resistance to trans-cuticular uptake (69 m(2) s mol(-1)) far exceeded resistance to diffusion across the unstirred layer at the surface of the leaf (5 m(2) s mol(-1)). High concentrations used in these experiments preclude quantitative extrapolation to ambient conditions; however, we have demonstrated that the white pine cuticle is both a major storage pool and a major barrier to uptake of deposited nitric acid.     

Assessing the impact of weather events at mid-latitudes on the atmospheric transport of chemical pollutants using a 2-dimensional multimedia meteorological model

We investigate the long-range transport potential (LRTP) of five different classes of hypothetical chemical pollutants (volatile, multimedia, semivolatile, particle-associated and hydrophilic) during a low pressure weather event using a novel 2 (x- and z-axis)-Dimensional Multi-Media Meteorological Model (2D4M). The atmosphere (z-axis) is described by three atmospheric layers, where two layers constitute the boundary layer and the third layer the free troposphere. The 2D4M can describe distinct weather events on a regional scale and calculate the LRTP of chemicals as a function of time during these events. Four weather factors are used to model weather events and their influence on the atmospheric transport of chemicals: (1) temperature, (2) wind speed and mixing dynamics of the troposphere, (3) hydroxyl radical concentrations and (4) precipitation. We have modeled the impact of variability in each of these factors on LRTP of pollutants during a front event associated with a low pressure period that interrupts a dominant high pressure system. The physico-chemical properties of the pollutant determine which specific weather factors contribute most to variability in transport potential during the event. Volatile and multimedia chemicals are mainly affected by changing atmospheric mixing conditions, wind speeds and OH radical concentrations, while semivolatile substances are also affected by temperature. Low-vapor-pressure pollutants that are particle-associated, and water-soluble pollutants are most strongly affected by precipitation. Some chemical pollutants are efficiently transported from the boundary layer into the upper troposphere during the modeled low pressure event and are transported by much higher wind speeds than in the boundary layer. Our model experiments show that the transport potential of volatile, multimedia and semivolatile compounds is significantly increased during a front event as a result of efficient tropospheric mixing and fast wind speeds in the upper troposphere, whereas low-volatility and hydrophilic chemicals are largely scavenged from the atmosphere. In future LRTP assessment of chemical contaminants as required by the Stockholm Convention and the convention on long-range transboundary air pollution, it is therefore advised to prioritize volatile, multimedia and semivolatile chemicals that are identified in initial screening.     

Modelling the fate of organic chemicals in the soil plant environment: Model study of root uptake of pesticides

The fate of organic chemicals in the soil-plant-atmosphere environment and the governing processes were studied with a coupled dynamic soil transport and plant compartment model. Scenarios with applications of pesticides on sand and loam soils with chemical uptake in barley and wheat were used in the model calculations. Root uptake and concentrations in the plant compartments stem, leave and fruit were calculated for the pesticides terbuthylazine, isoproturon and carbofuran.

The effectivity of uptake from soils with different soil sorption coefficients had been shown for sand and loam soils. The processes degradation in plant and volatilization from leaves to atmosphere are especially effective for carbofuran and terbuthylazine. Although the concentrations in corn at harvest are lower than the maximum allowed concentrations, the peak concentrations in the course of the vegetation period are significantly higher (factor ≤ 200).     

Evaluation and comparison of multimedia mass balance models of chemical fate: application of EUSES and ChemCAN to 68 chemicals in Japan

The European Union System for Evaluation of Substances (EUSES) and the ChemCAN chemical fate model are applied to describe the fate of 68 chemicals on two spatial scales in Japan. Emission information on the chemicals has been obtained from Japan's Pollutant Release and Transfer Registry and available monitoring data gathered from government reports. Environmental concentrations calculated by the two models for the four primary environmental media of air, water, soil and sediment agree within a factor of 3 for over 70% of the data, and within a factor of 10 for over 87% of the data. Reasons for certain large discrepancies are discussed. Concentrations calculated by the models are generally consistent with the lower range of concentrations that are observed in the environment. Agreement between modeled and observed concentrations is considerably improved by including an estimate of the advective input of chemicals in air from outside Japan. The agreement between the EUSES and ChemCAN models suggests that results of individual chemical assessments are not likely to be significantly affected by the choice of chemical fate model. Primary sources of discrepancy between modeled and observed concentrations are believed to be uncertainties in emission rates, degradation half-lives, and the lack of data on advective inflow of contaminants in air.     

Modeling coupled interactions of carbon,water, and ozone exchange between terrestrial ecosystems and the atmosphere. I: model description

A new biophysical model (FORFLUX) is presented to study the simultaneous exchange of ozone, carbon dioxide, and water vapor between terrestrial ecosystems and the atmosphere. The model mechanistically couples all major processes controlling ecosystem flows trace gases and water implementing recent concepts in plant eco-physiology, micrometeorology, and soil hydrology. FORFLUX consists of four interconnected modules-a leaf photosynthesis model, a canopy flux model, a soil heat-, water- and CO2- transport model, and a snow pack model. Photosynthesis, water-vapor flux and ozone uptake at the leaf level are computed by the LEAFC3 sub-model. The canopy module scales leaf responses to a stand level by numerical integration of the LEAFC3model over canopy leaf area index (LAI). The integration takes into account (1) radiative transfer inside the canopy, (2) variation of foliage photosynthetic capacity with canopy depth, (3) wind speed attenuation throughout the canopy, and (4) rainfall interception by foliage elements. The soil module uses principles of the diffusion theory to predict temperature and moisture dynamics within the soil column, evaporation, and CO2 efflux from soil. The effect of soil heterogeneity on field-scale fluxes is simulated employing the Bresler-Dagan stochastic concept. The accumulation and melt of snow on the ground is predicted using an explicit energy balance approach. Ozone deposition is modeled as a sum of three fluxes- ozone uptake via plant stomata, deposition to non-transpiring plant surfaces, and ozone flux into the ground. All biophysical interactions are computed hourly while model projections are made at either hourly or daily time step. FORFLUX represents a comprehensive approach to studying ozone deposition and its link to carbon and water cycles in terrestrial ecosystems.     

BETR North America: a regionally segmented multimedia contaminant fate model for North America

We present the Berkeley-Trent North American contaminant fate model (BETR North America), a regionally segmented multimedia contaminant fate model based on the fugacity concept. The model is built on a framework that links contaminant fate models of individual regions, and is generally applicable to large, spatially heterogeneous areas. The North American environment is modeled as 24 ecological regions, within each region contaminant fate is described using a 7 compartment multimedia fugacity model including a vertically segmented atmosphere, freshwater, freshwater sediment, soil, coastal water and vegetation compartments. Inter-regional transport of contaminants in the atmosphere, freshwater and coastal water is described using a database of hydrological and meteorological data compiled with Geographical Information Systems (GIS) techniques. Steady-state and dynamic solutions to the 168 mass balance equations that make up the linked model for North America are discussed, and an illustrative case study of toxaphene transport from the southern United States to the Great Lakes Basin is presented. Regionally segmented models such as BETR North America can provide a critical link between evaluative models of long-range transport potential and contaminant concentrations observed in remote regions. The continent-scale mass balance calculated by the model provides a sound basis for evaluating long-range transport potential of organic pollutants, and formulation of continent-scale management and regulatory strategies for chemicals.     

Developing a multimedia model of chemical dynamics in an urban area.

A multimedia model has been developed to account for the movement of semi-volatile organic compounds (SOCs) in an urban environment. The model, based on a Level III fugacity model of D. Mackay (Multimedia Environmental Models: The Fugacity Approach, Lewis Publishers, Boca Raton, FL, 1991), consists of six compartments: air, surface water, sediment, soil, vegetation, and an organic film that coats impervious surfaces. The latter is a newly identified compartment into which gas-phase SOCs partition and particle-phase SOCs are believed to be efficiently captured (M.L. Diamond, S.E. Gingrich, K. Fertuck, B.E. McCarry, G.A. Stern, B. Billeck, B. Grift, D. Brooker, T.D. Yager, Environ. Sci. Technol., 34 (2000a), 2900-2908). The model, parameterized for downtown Toronto, Ontario, Canada, and run with an illustrative emission rate for selected polycyclic aromatic hydrocarbons and homologues of polychlorinated dibenzodioxins, indicates that the film achieves the highest concentrations among media but that soils are the greatest sink for all but the least hydrophobic chemicals. The film "reflects" the more volatile chemicals into air, facilitates removal to surface waters by wash-off, and provides a surface on which photolytic degradation can occur. As such, the film is a transient sink that increases chemical mobility in urban areas by increasing air concentrations and the cycling of these compounds between air and urban surfaces and increasing water concentrations. Vegetation also accumulates SOCs, a portion of which is transferred to soil that reduces chemical mobility.     

Strategies for including vegetation compartments in multimedia models

The incentives for including vegetation compartments in multimedia Level I, II and III fugacity calculations are discussed and equations and parameters for undertaking the calculations suggested. Model outputs with and without vegetation compartments are compared for 12 non-ionic organic chemicals with a wide variety of physical-chemical properties. Inclusion of vegetation compartments is shown to have a significant effect on two classes of chemicals: (1) those that are taken up by atmospheric deposition and (2) those that are taken up by transpiration through the plant roots. It is suggested that uptake from the atmosphere is important for chemicals with logK(OA) greater than 6 and a logK(AW) of greater than -6. Plant uptake by transpiration is important for chemicals with logK(OW) less than 2.5 and a logK(AW) of less than -1. At logK(OA) > 9 atmospheric uptake is dominated by particle-bound deposition and the importance of partitioning to vegetation is largely dependent on the relative magnitude of the particle deposition velocities to soil and vegetation. These property ranges can be used to determine if a chemical will significantly partition to vegetation. If the chemical falls outside the property ranges of the two classes it will probably be unnecessary to include vegetation in models for assessing environmental fate. The amount of chemical predicted to partition to vegetation compartments in the model is shown to be highly sensitive to certain model assumptions. Further experimental research is recommended to obtain more reliable equations describing equilibrium partitioning and uptake/depuration kinetics.     

Current issues and uncertainties in the measurement and modelling of air-vegetation exchange and within-plant processing of POPs

Air-vegetation exchange of POPs is an important process controlling the entry of POPs into terrestrial food chains, and may also have a significant effect on the global movement of these compounds. Many factors affect the air-vegetation transfer including: the physicochemical properties of the compounds of interest; environmental factors such as temperature, wind speed, humidity and light conditions; and plant characteristics such as functional type, leaf surface area, cuticular structure, and leaf longevity. The purpose of this review is to quantify the effects these differences might have on air/plant exchange of POPs, and to point out the major gaps in the knowledge of this subject that require further research. Uptake mechanisms are complicated, with the role of each factor in controlling partitioning, fate and behaviour process still not fully understood. Consequently, current models of air-vegetation exchange do not incorporate variability in these factors, with the exception of temperature. These models instead rely on using average values for a number of environmental factors (e.g. plant lipid content, surface area), ignoring the large variations in these values. The available models suggest that boundary layer conductance is of key importance in the uptake of POPs, although large uncertainties in the cuticular pathway prevents confirmation of this with any degree of certainty, and experimental data seems to show plant-side resistance to be important. Models are usually based on the assumption that POP uptake occurs through the lipophilic cuticle which covers aerial surfaces of plants. However, some authors have recently attached greater importance to the stomatal route of entry into the leaf for gas phase compounds. There is a need for greater mechanistic understanding of air-plant exchange and the 'scaling' of factors affecting it. The review also suggests a number of key variables that researchers should measure in their experiments to allow comparisons to be made between studies in order to improve our understanding of what causes any differences in measured data between sites.     

Revisiting old lessons from classic literature on persistent global pollutants: This article belongs to Ambio’s 50th Anniversary Collection. Theme: Environmental contaminants

Looking back 50 years at classic literature was a reminder of inspiring discoveries and clever theories that were formative to the field of environmental chemistry, but also of the irreparable costs that persistent global pollutants have had on ecosystems and human society. In my view, these three papers have greatly impacted contemporary science and influenced development of policies that have limited the spread of hazardous contaminants. At the same time, a sobering reality is that reversing decades of past pollution has proven impossible in our lifetime, and global trends are dire for both legacy and emerging contaminants. Lessons in these papers are clear to most environmental scientists, but I argue have not resulted in adequate investment in infrastructure or manpower to enable systematic unbiased searching for pollutants as proposed by Sören Jensen in 1972. Acknowledging that the costs of new global contaminants will be too high, we must incentivize safer chemicals and their sustainable use, increase international exchange of lists of chemicals in commerce, and coordinate international efforts in nontarget screening to identify new contaminants before they circulate the world.     

Modeling the mechanisms for uptake and translocation of dioxane in a soil-plant ecosystem with STELLA

Knowledge of mechanisms for uptake, translocation, and accumulation of soil contaminants in plants is essential to successful applications of the phytoremediation technique. Analysis and evaluation of these mechanisms would be greatly facilitated by the availability of a dynamic model that can predict soil contaminant uptake by roots, transport from roots through stems to leaves, and accumulation in plant during the transport process. In this study, a dynamic model for uptake and translocation of contaminants from a soil-plant ecosystem (UTCSP) was developed using the STELLA modeling tool. The structure of UTCSP consists of time-dependent simultaneous upward transport, accumulation, and transpiration of water and contaminants in the soil-plant-atmosphere continuum, which was driven by water potential gradients among soils, roots, stems, leaves, and atmosphere. The UTCSP model was calibrated using the experimental measurements and applied to predict phytoremediation of 1,4-dioxane from a sandy soil by a poplar tree. Simulation results showed that about 20% of 1,4-dioxane was removed from the soil by the poplar tree in 90 days. The simulations further revealed that while the mass of 1,4-dioxane in the poplar tree increased consecutively with time, the rates of water and 1,4-dioxane uptake and translocation in the roots, stems, and leaves have a typical diurnal distribution pattern: increasing during the day and decreasing during the night, resulting from daily variations of plant water potentials that were caused by leaf water transpiration. This study suggests that the UTCSP model is a useful tool for estimating phytoremediation of contaminants in the soil-plant ecosystems.     

A study of the adsorption of NH3 and SO2 on leaf surfaces

The adsorption of NH₃ and SO₂ on the external leaf surface of bean (Phaseolus vulgaris L.) and poplar (Populus euramericana L.) was studied. The adsorbed quantities increased strongly with increasing air humidity, indicating that water on the leaf surface plays a major role in the interaction of these gases with the leaf surface. On the other hand temperature in the range between 15 and 26°C had no significant influence. The adsorbed quantities of NH₃ at a specific air humidity appeared to be proportional to NH₃ concentration. This proportionality was less clear for SO₂. The affinity of SO₂ for the leaf surface was found to be approximately twice that of NH₃. A mixture of these gases in the air mutually stimulated their adsorption on the leaf. No significant desorption or uptake of these gases through the cuticle could be detected, indicating that the bulk of the adsorbed gases remains associated with the cuticle.     

What environmental fate processes have the strongest influence on a completely persistent organic chemical's accumulation in the Arctic?

Fate and transport models can be used to identify and classify chemicals that have the potential to undergo long-range transport and to accumulate in remote environments. For example, the Arctic contamination potential (ACP), calculated with the help of the zonally averaged global transport model Globo-POP, is a numerical indicator of an organic chemical's potential to be transported to polar latitudes and to accumulate in the Arctic ecosystem. It is important to evaluate how robust such model predictions are and in particular to appreciate to what extent they may depend on a specific choice of environmental model input parameters. Here, we employ a recently developed graphical method based on partitioning maps to comprehensively explore the sensitivity of ACP estimates to variations in environmental parameters. Specifically, the changes in the ACP of persistent organic contaminants to changes in each environmental input parameter are plotted as a function of the two-dimensional hypothetical “chemical space” defined by two of the three equilibrium partition coefficients between air, water and octanol. Based on the patterns obtained, this chemical space is then segmented into areas of similar parameter sensitivities and superimposed with areas of high default ACP and elevated environmental bioaccumulation potential within the Arctic. Sea ice cover, latitudinal temperature gradient, and macro-diffusive atmospheric transport coefficients, and to a lesser extent precipitation rate, display the largest influence on ACP-values for persistent organic contaminants, including those that may bioaccumulate within the polar marine ecosystems. These environmental characteristics are expected to be significantly impacted by global climate change processes, highlighting the need to explore more explicitly how climate change may affect the long-range transport and accumulation behavior of persistent organic pollutants.     

What Do the Hydrocarbons from Trees Contribute to Air Pollution?

Plant species release appreciable quantities of volatile organic substances to the atmosphere. The major compounds emitted are monoterpenes (C₁₀) like α-pinene, β-pinene, and limonene and the hemiterpene (C5) isoprene. The rate of emission of isoprene is light dependent and ranges between 0.04 to 2.4 ppb/cm²/min/l for oak, cottonwood, and eucalyptus foliage. The rate of emission of a- and/3-pinene and limonene is dependent on the rate of transpiration, structural integrity of the oil cells and resin glands, and temperature of the foliage. Rates of emission for conifer foliage range from 0.4 to 3.5 ppb/g/min/l. An inventory of North American forest regions for the frequency of occurrence of these chemicals released by different tree species showed that 15% was the lowest value for a specific forest-type that emitted terpenes to the atmosphere. More commonly 100% of the trees of a given forest-type emitted terpenes to the atmosphere. An average of 70% is typical of the United States forested regions as a whole. The annual contribution of forest hydrocarbon emissions to the air pollution problem on a global basis is reflected in the 175 × 10⁶ tons of reactive hydrocarbons from tree foliage sources compared to the 27 × 10⁶ tons from man’s activities; in other words, there is a 6.2-fold greater emission level from natural sources than from man made sources. The fate of these gaseous olefins in the atmosphere is undetermined.     

Food contamination control in European new Member States and associated candidate countries: Data collected within the SAFEFOODNET project

This paper reports the results obtained from the data collected within the European Commission funded project SAFEFOODNET regarding the state of the art in the control of chemical food contaminants in twelve European New Member States and one Associated Candidate Country (Turkey). Information has been gathered on institutions involved in food chemical contamination control, types of contaminants and matrices analyzed, procedures for data quality assurance, purposes of the analyses and accessibility of data in the participant countries. The resulting picture points out the general availability of adequate capabilities for the analysis of food contaminants in the laboratories in charge of control and the performance of the analysis of a large variety of chemicals (persistent organic pollutants, polycyclic aromatic hydrocarbons, pesticides, mycotoxins, heavy metals, radionuclides) in almost each country with few exceptions (dioxins in Bulgaria, Turkey, Latvia, persistent organic pollutants in Lithuania and Malta, polycyclic aromatic hydrocarbons in Malta). The application of validated analytical methods and the process of laboratory accreditation are partially fulfilled within the investigated countries, but still forthcoming for some countries, as in Romania, Turkey and Malta. Information collected on food controls is only partially available online and the language used is prevalently local and English to a lesser extent.     

The uptake of particulates by an urban woodland: site description and particulate composition

Woodlands may improve local air quality by increasing the uptake rates of gaseous, particulate and aerosol pollutants from the atmosphere and can also act as relatively permanent sinks for some pollutants. Rough Wood, Walsall was selected for a study of the material which accumulates on tree foliage because of its location in a densely populated urban area, and its proximity to a motorway with high traffic flow (the M6) and to other pollutant sources. Methods were developed for leaf washing to allow determination of the quantity of dust and the identification of the dust particles present on oak leaves. Elemental analysis of particles was also undertaken using scanning electron microscopy coupled with electron probe microanalysis. A large proportion of particles were organic in origin. Of the inorganic particles, the majority contained silicon and aluminium in varying proportions suggesting that they were soil derived. Some particles were clearly identified as the products of combustion, and sea or road salt was present on leaf surfaces. Some particles contained copper, tin and titanium which may reflect the proximity of Rough Wood to local metal workings. The number of particles counted on leaf surfaces decreased as distance from the motorway increased.     

Root versus canopy uptake of heavy metals by birch in an industrially polluted area: contrasting behaviour of nickel and copper

We investigated root versus canopy uptake of nickel and copper by mountain birch, Betula pubescens subsp. czerepanovi, close to a nickel-copper smelter on the Kola Peninsula, northwest Russia. To distinguish between aerial contamination of leaf surfaces by dust particles and root-derived contamination of leaves by soluble metals, we transplanted seedlings from a control site to clean and metal-contaminated soils and exposed these seedlings both in clean and polluted sites. Patterns of leaf surface contamination and root uptake were similar for nickel and copper; however, nickel but not copper was effectively translocated from roots to shoots and leaves. The majority (80-95%) of nickel and copper found in birch foliage in the heavily contaminated site was due to deposition of dust particles on leaf surfaces; 32-40% of foliar nickel and 9-19% of foliar copper were in water soluble forms. Washing of fresh leaves removed only a minor part of surface contaminants; boiling of unwashed leaves in distilled water for 15 min removed >90% of soluble nickel and copper.     

基于荧光素酶发光检测体系的几种工业污染物综合毒性评价

利用化工污染物能抑制荧光素酶催化发光反应这一特性,对水质中6种化工化合物分别进行毒性测试,建立一种快速检测水质中化工污染物毒性的生物学方法。实验结果表明,对苯二酚、4-氨基酚、苯胺、氯仿、盐酸邻联甲苯胺和硫柳汞的EC50值分别为:5.563、10.225、20.236、38.432、8.827和0.6 mg/L,6种污染物毒性大小依次为:硫柳汞>对苯二酚>盐酸邻联甲苯胺>4-氨基酚>苯胺>氯仿,相关系数>0.95。该方法为进一步研究基于荧光素酶反应体系检测水质中化工污染物综合毒性的生物传感器方法奠定基础。