Growth responses of birch and Sitka spruce exposed to acidified rain

Seedlings of birch and Sitka spruce were grown on a range of British soils for 2 years and exposed to simulated acid rainfall treatments of pHs 5.6, 4.5, 3.5 and 2.5. Both species developed visible leaf injury patterns when exposed to the pH 2.5 treatment. In Sitka spruce this leaf injury was followed by high needle loss during the first winter and greater mortality. Generally, height growth of Sitka spruce was unaffected by treatments, but acid rainfall at pH 2.5 increased the height of birch. Mean height of both species was strongly affected by soil type. Significant soils x treatment effects on the heights of both species indicated that on some soils plant growth responses to the treatments did not fit the general pattern. Hence, while the results indicate that generally ambient acidities of rainfall in the UK are unlikely to adversely affect the growth of birch or Sitka spruce, plants growing on some soils may be susceptible to injury.     

Responses of field-grown Medicago sativa L. to acidic fog and ambient ozone

The relationship between pollutant-induced leaf drop or reductions in foliar pigment concentrations and yield was determined for field-grown alfalfa (Medicago sativa L. 'Moapa') exposed to simulated fogs of pH 7.24, 2.69 and 1.68 singly, and in combination with ambient ozone (O3) over an 11-week period. Highly acidic fog (pH 1.68) or ambient O3 significantly reduced totalseason dry yield and foliar pigment concentrations, and increased leaf drop. Significant interactive effects between acidic fog and O3 were observed for the leaf parameters, but not for yield. Thus, multiple exposures to acidic fog at current ambient levels of acidity (i.e. pH 2.69) could effect leaf quality in the absence of significant effects on yield. Alternatively, O3-induced effects on leaves may have utility as bioindicators of potential yield losses.     

Effects of acidic fog on seedlings of Pinus ponderosa and Abies concolor: foliar injury, physiological and biochemical responses

Seedlings of Pinus ponderosa (ponderosa pine) and Abies concolor (white fir) were exposed to acidic fog (pH 2.0, 3.0 or 4.0) in open-field plots for six weeks. The two species exhibited dissimilar injury responses; neither current year nor previous year needles of ponderosa pine were injured by pH 2.0 fog, but current year needles exhibited higher membrane permeability responses (i.e. needle extract conductivity, K+ concentration). In comparison, both needle age classes in white fir were significantly injured by pH 2.0 fog, but no significant effects on membrane permeability were observed. For both species, whole-study average rates of net photosynthesis in previous year needles were lower in plants exposed to pH 2.0 fog than in plants treated with pH 4.0 fog. While decreased process rates coincided with leaf necrosis in white fir, stomatal closure appeared to be the mechanism of inhibition in ponderosa pine with pH 2.0 fog (i.e. no visible injury). The findings of the present study provide evidence that frequent applications of highly acidic fog (i.e. pH 2.0-3.0) can cause temporal alterations in membrane permeability and gas exchange rates in western conifer seedlings, in the presence or absence of visible injury. However, because incipient effects on other measures of foliage health were species-specific (i.e. concentrations of starch, photosynthetic pigments, inorganic nutrients), a general mechanism of phytotoxicity could not be identified.     

Effects of acid mist on needles from mature Sitka spruce grafts. Part II. Influence of developmental stage, age and needle morphology on visible damage

Mature grafts of five Sitka spruce (Picea sitchensis (Bong.) Carr.) clones were exposed to simulated acid mist comprising an equimolar mixture of H(2)SO(4) and NH(4)NO(3) (1.6 and 0.01 mol m(-3)) at pH 2.5 and 5.0. Mist was applied to potted plants growing in open-top chambers on consecutive days, four times a week, at a precipitation equivalent of 1 mm per day. The total exposure to polluted mist was equivalent to three times that measured at an upland forest in SE Scotland. The aim of the experiment was to characterize the response of juvenile foliage produced by physiologically mature grafts (on seedling root stock) and compare it with the behaviour of juvenile foliage on seedlings. Development of visible foliar damage was followed through the growing season. Measurements of needle length, diameter, weight, surface area, surface was weight and wettability were made on current year needles to determine whether particular foliar characteristics increased susceptibility to injury. Significant amounts (> 10%) of visible needle damage was observed on only one of the five clones. Damage was most severe on the clone with the most horizontal branch and needle habit, but over the five clones there was no relationship between angle of branch display and damage. Likewise no combination of needle characteristics (length, width, area, amount of wax) was indicative of potential susceptibility. A comparison with previous acid misting experiments using seedlings suggests that juvenile foliage on physiologically mature trees is equally susceptible to visible injury as juvenile seedling foliage. Data of budburst differed among clones, and in this experiment exerted the over-riding influence on development of injury symptoms. Foliage exposed to a combination of strong acidity and high sulphate concentrations over the few weeks immediately following budburst suffered most visible injury. The absence of significant amounts of visible damage in UK forests probably reflects the general low susceptibility to visible injury of Sitka spruce exposed to acid mist.     

The effects of simulated acid rain on the growth of three herbaceous species grown on a range of British soils

Seedlings of winter barley, perennial ryegrass and white clover were grown on a range of British soils for 21-24 weeks and exposed to simulated acid rainfall treatments of pHs 5.6, 4.5, 3.5 and 2.5. Whilst leaves of white clover developed leaf lesions after 18 weeks of exposure to the pH 2.5 treatments, there were no signs of visible injury to the other two species. At harvest, it was noted, for all species, that there was a large amount of variation in the sizes of individual plants and this made it difficult to detect differences between the treatments for plants on an individual soil. However, in combined analyses for all soils, it was found that the treatments had substantial effects on the yields of plants. The yields of both winter barley and clover were highly correlated with rainfall pH, showing substantial reductions in the more acid rains as compared to the pH 5.6 (control) treatment. In contrast, plants of perennial ryegrass produced higher yields of shoots at the most acid (pH 2.5) as compared to the other treatments. It was noted that the pH 2.5 treatment resulted in a generally lower soil pH at the termination of the experiment.     

Exposure of two upland plant species to acidic fogs

A system is described for exposing large numbers of plants to acidic fogs. The system allows low volumes of treatment solutions to be provided at particle sizes chiefly in the 5-30 microm range (equivalent to fog/cloud droplets). Plants of Poa alpina L. and Epilobium brunnescens were propagated from material collected in Snowdonia, North Wales and exposed to fog treatments at pH values of 2.5, 3.5, 4.5 and 5.6. There were 3 x 4 h exposures per week which provided a total of 6 mm deposition. Supplementary watering was with pH 4.5 simulated acid rain (24 mm per week). After 21 weeks, there was increased lowering and a greater dry weight for plants of E. brunnescens exposed to the pH 2.5 fog in comparison with other treatments. Also, the plants used assimilated material to form shoots rather than roots. A similar increase in dry weight accumulation in the pH 2.5 treatment was found in P. alpina after 63 weeks but this was not associated with changes in assimilate partitioning.     

Seasonal trends in reduced leaf gas exchange and ozone-induced foliar injury in three ozone sensitive woody plant species

Seasonal trends in leaf gas exchange and ozone-induced visible foliar injury were investigated for three ozone sensitive woody plant species. Seedlings of Populus nigra L., Viburnum lantana L., and Fraxinus excelsior L. were grown in charcoal-filtered chambers, non-filtered chambers and open plots. Injury assessments and leaf gas exchange measurements were conducted from June to October during 2002. All species developed typical ozone-induced foliar injury. For plants exposed to non-filtered air as compared to the charcoal-filtered air, mean net photosynthesis was reduced by 25%, 21%, and 18% and mean stomatal conductance was reduced by 25%, 16%, and 8% for P. nigra, V. lantana, and F. excelsior, respectively. The timing and severity of the reductions in leaf gas exchange were species specific and corresponded to the onset of visible foliar injury.     

Effects of ozone on the foliar histology of the mastic plant (Pistacia lentiscus L.)

An open-top chamber study was conducted to investigate the tissue and cellular-level foliar effects of ozone (O3) on a Mediterranean evergreen species, the mastic plant (Pistacia lentiscus L.). Plants were exposed at three different O3 levels, and leaf samples were collected periodically from the beginning of the exposure. Although no visible foliar injury was evident, alterations of the plastids and vacuoles in the mesophyll were observed. Senescence processes were accelerated with an anomalous stacking of tannin vacuoles, and a reduction in the size and number of the chloroplasts. Overall, most of the modifications induced by O3 were consistent with previously reported observations on deciduous broadleaf species, with the exception of alterations in the cells covering the secretory channels, reported here as a new finding. Comments on the feasibility of using microscopy to validate O3 related field observations and subtle foliar injury are also given.     

Ozone exposure thresholds and foliar injury on forest plants in Switzerland

Canton Ticino in southern Switzerland is exposed to some of the highest concentrations of tropospheric ozone in Europe. During recent field surveys in Canton Ticino, foliar symptoms identical to those caused by ozone have been documented on native tree and shrub species. In Europe, the critical ozone level for forest trees has been defined at an AOT40 of 10 ppm.h O3 (10 ppm.h accumulated exposure of ozone over a threshold of 40 ppb) during daylight hours over a six-month growing season. The objective of this study was to determine the amount of ambient ozone required to induce visible foliar symptoms on various forest plant species in southern Switzerland. Species were grown within eight open-top chambers and four open plots at the Vivaio Lattecaldo Cantonal Forest Nursery in Ticino, Switzerland. Species differed significantly in terms of the ppb.h exposures needed to cause visible symptoms. The most to least symptomatic species grown within open-plots in this study rank as Prunus serotina, Salix viminalis, Vibrnum lantana, Rhamnus cathartica, Betula pendula, Rumex obtusifolius, Sambucus racemosa, Morus nigra, Prunus avium, Fraxinus excelsior, Rhamnus frangula, Alnus viridis, Fagus sylvatica and Acer pseudoplatanus. Similar rankings were obtained in the non-filtered chamber plots. The ranking of species sensitivity closely follows AOT values for the occurrence of initial symptoms and symptom progression across the remainder of the exposure season. Species that first showed evidence of foliar injury also demonstrated the most sensitivity throughout the growing season, with symptoms rapidly advancing over ca. 25-30% of the total plant leaf surfaces by the end of the observation period. Conversely, those species that developed symptoms later in the season had far less total injury to plant foliage by the end of the observation period (1.5 to < 5% total leaf area injured). The current European ambient ozone standard may be insufficient to protect native plant species from visible foliar injury, and many more native species may be sensitive to ozone-induced foliar injury than are currently known.     

Ozone air pollution and foliar injury development on native plants of Switzerland

The objectives of this study were to examine the foliar sensitivity to ozone exposure of 12 tree, shrub, and herbaceous species native to southern Switzerland and determine the seasonal cumulative ozone exposures required to induce visible foliar injury. The study was conducted from the beginning of May through the end of August during 2000 and 2001 using an open-top chamber research facility located within the Lattecaldo Cantonal Forest Nursery in Canton Ticino, southern Switzerland (600 m asl). Plants were examined daily and dates of initial foliar injury were recorded in order to determine the cumulative AOT40 ppb h ozone exposure required to cause visible foliar injury. Plant responses to ozone varied significantly among species; 11 species exhibited visible symptoms typical of exposures to ambient ozone. The symptomatic species (from most to least sensitive) were Populus nigra, Viburnum lantana, Salix alba, Crataegus monogyna, Viburnum opulus, Tilia platyphyllos, Cornus alba, Prunus avium, Fraxinus excelsior, Ribes alpinum, and Tilia cordata; Clematis spp. did not show foliar symptoms. Of the 11 symptomatic species, five showed initial injury below the critical level AOT40 10 ppmh O3 in the 2001 season.     

Growth responses of three legume species exposed to simulated acid rain

Seedlings of Vicia faba L., Phaseolus multiflorus L. and Pisum sativum L. were raised during exposure to simulated acid rainfall treatments of pHs 5.6, 4.5, 3.5 and 2.5 at a rate of 30 mm per week. All three species were found to be adversely affected by the more acid pH 3.5 and pH 2.5 treatments after 7-8 weeks of exposure. There were total plant dry weight reductions of 40% for V. faba, 31% for P. sativum and 28% for P. multiflorus exposed to the pH 2.5 treatment, as compared to those grown in the control (pH 5.6 treatment). In addition, V. faba was found to be sensitive to the pH 4.5 treatment with an 18% reduction in total plant weights (compared to plants grown in the pH 5.6 treatment). In P. multiflorus, reduction in the dry weights of shoots in response to increasing acidity of rain was not accompanied by reduction in root weights, indicating an interference in the partitioning of assimilates. It is concluded that these three species, and V. faba in particular, may be growing below their potential in much of the UK.     

The individual and combined effects of ozone and simulated acid rain on growth, gas exchange rate and water-use efficiency of Pinus armandi Franch

The seedlings of Pinus armandi Franch. were exposed to ozone (O(3)) at 300 ppb for 8 h a day, 6 days a week, and simulated acid rain of pH 3.0 or 2.3, 6 times a week, alone or in combination, for 14 weeks from 15 June to 20 September 1993. The control seedlings were exposed to charcoal-filtered air and simulated rain of pH 6.8 during the same period. Significant interactive effects of O(3) and simulated acid rain on whole plant net photosynthetic rate were observed, but not on other determined parameters. The exposure of the seedlings to O(3) caused the reductions in the dry weight growth, root dry weight relative to the whole plant dry weight, net photosynthetic rate, transpiration rate in light, water-use efficiency and root respiration activity, and increases in shoot/root ratio, and leaf dry weight relative to the whole plant dry weight without an appearance of acute visible foliar injury, but did not affect the dark respiration rate and transpiration rate in the darkness. The decreased net photosynthetic rate was considered to be the major cause for the growth reduction of the seedlings exposed to O(3). On the other hand, the exposure of the seedlings to simulated acid rain reduced the net photosynthetic rate per unit chlorophyll a + b content, but did not induce the significant change in other determined parameters.     

Effects of acid mist on mature grafts of Sitka spruce. Part I. Frost hardiness and foliar nutrient concentrations

Mature grafts of five clones of Sitka spruce (Picea sitchensis Bong. Sarg.) were exposed to simulated acid mist composed of an equimolar mixture of sulphuric acid and ammonium nitrate at pH 2.5 and pH 5.0 in open-top chambers from May to November 1991. Treatments were applied on consecutive days, four times a week. The pH 2.5 treatment provided an overall dose three times higher than that received by forests in upland areas of Britain. Frost hardiness was assessed in November by freezing detached current year shoots at a range of temperatures and assessing the rate of electrolyte leakage Foliar nutrient concentrations were determined on the same shoots. Acid mist at pH 2.5 significantly reduced frost hardiness in four of the five clones; the temperature causing 50% shoot death (LT50) was increased by 0 to 7 degrees C. The clones varied in their level of hardiness, one clone being exceptionally frost sensitive. The frost hardiness of the frost sensitive clone was found to be less perturbed by acid mist than the hardiness of the more frost resistant clones. Mature grafts showed a smaller reduction in hardiness at an equivalent dose than that found previously with Sitka spruce seedlings. Compared with seedlings, grafts had lower absolute concentrations of foliar sulphur. Exposure to acid mist at pH 2.5 increased %S in current year foliage by <0.05% compared with absolute increases of more than 0.10% in current year foliage of seedlings. We conclude that the effect of acid mist on frost hardiness is likely to be less on mature trees than on seedlings and that the increased frost risk to mature trees of Sitka spruce from occult deposition alone is small.     

Size-mediated foliar response to ozone in black cherry trees

Local ozone concentration and visible foliar injury were measured over the 1994 growing season on open-grown black cherry (Prunus serotina Ehrh.) trees of varying size (age) within forest stands and adjacent openings at a site in north-central Pennsylvania. Relationships were determined between visible ozone injury and ozone exposure, as well as calculated between injury and ozone uptake expressed as the product of stomatal conductance and ozone concentration. In addition, simultaneous measurements of visible symptoms and leaf gas exchange were also conducted to determine the correlation between visible and physiological injury and ozone exposure. By September, the amount of leaf area affected by visible foliar ozone injury was greatest for seedlings (46%), followed by canopy trees (20%) and saplings (15%). A large amount of variability in foliar ozone symptom expression was observed among trees within a size class. Sum40 and Sum60 (ozone concentration > 40 and > 60 nl liter(-1)) cumulative exposure statistics were the most meaningful indices for interpretation of foliar injury response. Seedlings were apparently more sensitive to ozone injury than larger trees because their higher rates of stomatal conductance resulted in higher rates of ozone uptake. Seedlings also had higher rates of early leaf abscission than larger trees with an average of nearly 30% of the leaves on a shoot abscised by 1 September compared to approximately 5% for larger trees. However, per unit ozone uptake into the leaf, larger trees exhibited larger amounts of foliar injury. The amount of visible foliar injury was negatively correlated (r(2) = 0.82) with net photosynthetic rates, but was not related to stomatal conductance. Net photosynthesis and stomatal conductance thus became uncoupled at high levels of visible foliar injury.     

The role of arginine decarboxylase in modulating the sensitivity of barley to ozone

Polyamines (PA) are known to be involved in the areas of plant physiology and biochemistry which are related to the response of a plant to air pollution. This study examines the role of arginine decarboxylase (ADC), an important rate-limiting enzyme in polyamine synthesis, in barley plants exposed to ozone (O(3)). The activity of ADC increased significantly in O(3)-treated leaves when visible injury was hardly apparent. The increase in ADC activity may be a mechanism to increase the PA levels in O(3)-treated leaves and so minimize the damaging effects of O(3). Supporting this, foliar applications of DL-alpha-difluoromethylarginine (DFMA), a specific inhibitor of ADC, prevented the rise in ADC activity and visible injury was considerable on exposure to O(3). This damage was not due to the foliar sprays, as little visible injury was seen in leaves in the O(3)-free controls. The results are discussed in terms of the roles of PA in conferring O(3) resistance in plants.     

Effects of ethylenediurea and ozone on the antioxidative systems in beans (Phaseolus vulgaris L.)

To study the biochemical mechanism of EDU protection against ozone injury, peroxidase, ascorbate-dependent peroxidase, and catalase activities, and the contents of ascorbic acid, dehydroascorbic acid, malondialdehyde and soluble protein were measured in Phaseolus vulgaris L. cv. Lit exposed to ozone and ethylenediurea (EDU) in open-top chambers. Plants not treated with EDU showed foliar bronzing due to ozone, while EDU-treated plants were not affected. EDU application modified the reaction of biochemical parameters to ozone. Soluble protein content was elevated by EDU. Peroxidase activity increased with ozone exposure in untreated plants only, while ascorbate-dependent peroxidase activity was lower in EDU treated plants. Catalase activity decreased in EDU-untreated plants. The ratio of ascorbic acid to dehydroascorbic acid was significantly increased in EDU treated plants. These results suggest that EDU might induce ascorbic acid synthesis and therefore provide the plant with a very potent antioxidant. Or the content of hydrogen peroxide was reduced due to other unknown processes and caused a delay in foliar senescence, regardless of whether these processes were ozone-induced or due to natural aging processes.     

Direct damage to vegetation caused by acid rain and polluted cloud: definition of critical levels for forest trees

The concept of critical levels was developed in order to define short-term and long-term average concentrations of gaseous pollutants above which plants may be damaged. Although the usual way in which pollutants in precipitation (wet deposition) influence vegetation is by affecting soil processes, plant foliage exposed to fog and cloud, which often contain much greater concentrations of pollutant ions than rain, may be damaged directly. The idea of a critical level has been extended to define concentrations of pollutants in wet deposition above which direct damage to plants is likely. Concentrations of acidity and sulphate measured in mountain and coastal cloud are summarised. Vegetation at risk of injury is identified as montane forest growing close to the cloud base, where ion concentrations are highest. The direct effects of acidic precipitation on trees are reviewed, based on experimental exposure of plants to simulated acidic rain, fog or mist. Although most experiments have reported results in terms of pH (H(+) concentration), the accompanying anion is important, with sulphate being more damaging than nitrate. Both conifers and broadleaved tree seedlings showing subtle changes in the structural characteristics of leaf surfaces after exposure to mist or rain at or about pH 3.5, or sulphate concentration of 150 micromol litre(-1). Visible lesions on leaf surfaces occur at around pH 3 (500 micromol litre(-1) sulphate), broadleaved species tending to be more sensitive than conifers. Effects on photosynthesis and water relations, and interactions with other stresses (e.g. frost), have usually been observed only for treatments which have also caused visible injury to the leaf surface. Few experiments on the direct effects of polluted cloud have been conducted under field conditions with mature trees, which unlike seedlings in controlled conditions, may suffer a growth reduction in the absence of visible injury. Although leaching of cations (Ca(2+), Mg(2+), K(+)) is stimulated by acidic precipitation, amounts leached are small compared with root uptake, unless soils have been impoverished. This aspect of the potential effects of acidic precipitation is best considered in terms of the long-term critical-load of pollutants to the soil. Given the practical difficulties in monitoring cloud water composition, a method for defining critical levels is proposed, which uses climatological average data to identify the duration and frequency of hill cloud, and combines this information with measured or modelled concentrations of particulate sulphate in the atmosphere, to derive cloud water concentrations as a function of cloud liquid water content. For forests within 100 m of the cloud base the critical levels of particulate sulphate, corresponding to solution concentrations in the range 150-500 micromol litre(-1), are in the range 1-3.3 microg S m(-3). These concentrations are observed over much of central Europe, suggesting that many montane forests are at risk of direct effects of fossil-fuel-derived pollutants in cloud.     

Ozone injury on cutleaf coneflower (Rudbeckia laciniata) and crown-beard (Verbesina occidentalis) in Great Smoky Mountains National Park

Incidence and severity of visible foliar ozone injury on cutleaf coneflower (Rudbeckia laciniata L.) and crown-beard (Verbesina occidentalis Walt.) were determined along selected trails at three locations in Great Smoky Mountains National Park during the summers of 2000 and 2001: Clingmans Dome, Cherokee Orchard Road and Purchase Knob. Cutleaf coneflower exhibited a greater amount of foliar injury than crown-beard each year of the 2-year study. Incidence and severity of injury was significantly greater for cutleaf coneflower growing near the edge of the Clingmans Dome trail than in the interior of the stand. Injury was greater at Clingmans Dome than Purchase Knob (70% vs. 40% ozone-injured plants, respectively), coincident with greater ozone exposures. In contrast to Clingmans Dome, there were no differences in injury between plants growing near- and off-trail at Purchase Knob. Differences in sensitivity to ozone were not observed for crown-beard growing near the edge compared with the interior of the stand adjacent to the Cherokee Orchard Road Loop. Ozone injury was greatest on the lower leaves for both species sampled with over 95% of the injured leaves occurring on the lower 50% of the plant. This is the first report of foliar ozone injury on these plant species in situ, in the Park, illustrating the great variability in symptom expression with time, and within and between populations.     

Interactions between the Encelia leaf beetle and its host plant, Encelia farinosa: The influence of acidic fog on insect growth and plant chemistry

The impact of acidic deposition on interactions between the plant Encelia farinosa and the herbivorous beetle Trirhabda geminata (Chrysomelidae) was determined under greenhouse conditions. Acidic fogs (pH 2.75) did not significantly affect the overall foliar concentrations of water or soluble protein as compared with control fogs (pH 5.6). Nonetheless, E. farinosa foliage was altered by exposure to three 3-h acidic fogs such that growth and biomass gain by T. geminata increased by more than 30% as compared to beetles feeding on control-fogged plants. Thus, previous indications that changes in soluble proteins or water content were responsible for increased biomass gain and growth of T. geminata cannot be substantiated by this study. Additionally, changes in the plant defensive chemistry were not responsible for increased herbivore growth, as farinosin, encecalin, and euparin foliar concentrations did not vary significantly between fog treatments. Significant increases in CO2 assimilation rates of E. farinosa exposed to acidic fogs were documented at 3, 7, and 21 days following treatment, suggesting that carbohydrate-based products of increased plant metabolism may have played a role (e.g. soluble carbohydrates). However, the key factors responsible for increasing herbivore performance on acidic-fogged E. farinosa remain largely unknown.     

Internal acid buffering in San Joaquin Valley fog drops and its influence on aerosol processing

Although several chemical pathways exist for S(IV) oxidation in fogs and clouds, many are self-limiting: as sulfuric acid is produced and the drop pH declines, the rates of these pathways also decline. Some of the acid that is produced can be buffered by uptake of gaseous ammonia. Additional internal buffering can result from protonation of weak and strong bases present in solution. Acid titrations of high pH fog samples (median pH=6.49) collected in California's San Joaquin Valley reveal the presence of considerable internal acid buffering. In samples collected at a rural location, the observed internal buffering could be nearly accounted for based on concentrations of ammonia and bicarbonate present in solution. In samples collected in the cities of Fresno and Bakersfield, however, significant additional, unexplained buffering was present over a pH range extending from approximately four to seven. The additional buffering was found to be associated with dissolved compounds in the fogwater. It could not be accounted for by measured concentrations of low molecular weight (C₁–C₃) carboxylic acids, S(IV), phosphate, or nitrophenols. The amount of unexplained buffering in individual fog samples was found to correlate strongly with the sum of sample acetate and formate concentrations, suggesting that unmeasured organic species may be important contributors. Simulation of a Bakersfield fog episode with and without the additional, unexplained buffering revealed a significant impact on the fog chemistry. When the additional buffering was included, the simulated fog pH remained 0.3–0.7 pH units higher and the amount of sulfate present after the fog evaporated was increased by 50%. Including the additional buffering in the model simulation did not affect fogwater nitrate concentrations and was found to slightly decrease ammonium concentrations. The magnitude of the buffering effect on aqueous sulfate production is sensitive to the amount of ozone present to oxidize S(IV) in these high pH fogs.