Deposition of semivolatile organic compounds to spruce needles

The accumulation of atmospheric HCB, Lindane, DDT, DDE and the PCB congeners 52, 101, 138, 153 and 180 in spruce needles (Picea abies) was investigated at outdoor locations and in greenhouses supplied with ambient air. The air supply of the greenhouses was modified to dinstinguish between gaseous and particle-associated deposition of the compounds. Accumulation of the compounds occurred in all spruce except those grown in the greenhouse where the gaseous concentration of the compounds was reduced. Spruce grown in the greenhouse supplied with particle-free ambient air behaved similarity to those grown outdoors. Protecting the spruce located outdoors from rain did not affect the accumulation. The results show that under spring and summer conditions at a typical central European rural environment dry gaseous deposition is the dominant pathway of these compounds to needles. For Part I “Calculation of Dry and Wet Fluxes” see issue 3, pp. 146–150.     

Passive air sampling theory for semivolatile organic compounds

The mathematical modelling underlying passive air sampling theory can be based on mass transfer coefficients or rate constants. Generally, these models have not been inter-related. Starting with basic models, the exchange of chemicals between the gaseous phase and the sampler is developed using mass transfer coefficients and rate constants. Importantly, the inter-relationships between the approaches are demonstrated by relating uptake rate constants and loss rate constants to mass transfer coefficients when either sampler-side or air-side resistance is dominating chemical exchange. The influence of sampler area and sampler volume on chemical exchange is discussed in general terms and as they relate to frequently used parameters such as sampling rates and time to equilibrium. Where air-side or sampler-side resistance dominates, an increase in the surface area of the sampler will increase sampling rates. Sampling rates are not related to the sampler/air partition coefficient (K(SV)) when air-side resistance dominates and increase with K(SV) when sampler-side resistance dominates.     

Thermal degradation products of spruce needles

Spruce needles are analysed by in-source pyrolysis (Py)-field ionization (FI) mass spectrography and Curie-point Py-gas chromatography/electron ionization mass spectrometry. The identified thermal degradation products allow the interpretation of the FI mass signals. It could be shown that Py-FI mass spectra of plant materials are representative fingerprints which consist primarily of molecular ions of Py products derived from the thermal degradation of the main constituents of spruce needles such as carbohydrates, lignin, lipids and proteins. Primary building blocks of these biopolymers form characteristic Py products of spruce needles. Furthermore, over 500 different molecular ion species of volatilized, thermostable plant constituents are recorded using FI as soft ionization method. The present study shows that Py-FIMS is suitable for the rapid and comprehensive characterization of complex biological materials, without pretreatment of the sample except of drying and milling. The presented results contribute to the basic knowledge for the evaluation of the causes of the present tree damage.     

Nonvolatile,semivolatile, or volatile: Redefining volatile for volatile organic compounds

Although widely used in air quality regulatory frameworks, the term “volatile organic compound” (VOC) is poorly defined. Numerous standardized tests are currently used in regulations to determine VOC content (and thus volatility), but in many cases the tests do not agree with each other, nor do they always accurately represent actual evaporation rates under ambient conditions. The parameters (time, temperature, reference material, column polarity, etc.) used in the definitions and the associated test methods were created without a significant evaluation of volatilization characteristics in real world settings. Not only do these differences lead to varying VOC content results, but occasionally they conflict with one another. An ambient evaporation study of selected compounds and a few formulated products was conducted and the results were compared to several current VOC test methodologies: SCAQMD Method 313 (M313), ASTM Standard Test Method E 1868-10 (E1868), and U.S. EPA Reference Method 24 (M24). The ambient evaporation study showed a definite distinction between nonvolatile, semivolatile, and volatile compounds. Some low vapor pressure (LVP) solvents, currently considered exempt as VOCs by some methods, volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents they are meant to replace. Conversely, bio-based and heavy hydrocarbons did not readily volatilize, though they often are calculated as VOCs in some traditional test methods. The study suggests that regulatory standards should be reevaluated to more accurately reflect real-world emission from the use of VOC containing products.

Implications:The definition of VOC in current test methods may lead to regulations that exclude otherwise viable alternatives or allow substitutions of chemicals that may limit the environmental benefits sought in the regulation. A study was conducted to examine volatility of several compounds and a few formulated products under several current VOC test methodologies and ambient evaporation. This paper provides ample evidence to warrant a reevaluation of regulatory standards and provides a framework for progressive developments based on reasonable and scientifically justifiable definitions of VOCs.     

Prediction of octanol--air partition coefficients of semivolatile organic compounds based on molecular connectivity index

A new method has been developed to describe the quantitative relationship between the octanol-air partition coefficients and molecular connectivity indexes of semivolatile organic compounds such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated naphthalenes (PCNs), polycyclic aromatic hydrocarbons (PAHs), chlorobenzenes (CBs), polybrominated diphenyl ethers (PBDEs). The stepwise multiple linear regression was used to derive six equations with correlation coefficients greater than 0.99 except for PBDEs' (0.96). The largest relative error is 4.6%, and the standard deviation is less than 1.83 log units. Compared with the data obtained from the relevant experiments, the results of prediction are very accurate.     

Structural changes in spruce and fir needles

Needles from spruce and fir trees were analyzed for histological changes induced by long-term exposure in open-top chambers to SO(2) and/or O(3) combined with acid rain. Light and electron microscopical evaluation revealed initial structural changes in the vascular bundle of fir needles, with an increased number of crushed sieve cells in the phloem. In addition the walls of young, adaxial sieve cells lacked the typical thickening usually observed in naturally aged needles. These findings may indicate restricted assimilate translocation. The presence of SO(2) in any treatment led to thylakoidal swellings and membrane reductions in the chloroplasts of mesophyll cells near the vascular bundle. This damage pattern resembled alterations caused by nutrient deficiency rather than by the direct action of gaseous pollutants. In general, fir appears to be more sensitive to environmental stress than spruce; this substantiates the findings of previous studies.     

Testing of a sampling system and analytical method for determination of semivolatile organic compounds in ambient air

A sampling system and analytical procedure for determining PCDD/Fs, PCBs, HCB, and PAHs in ambient air was tested. The reproducibility of the concentrations and the gas/particle partitioning was ± 10% for most compounds. The removal of gaseous compounds on the XAD resin trap was greater than 99%. The adsorption of gaseous substances on the glass fiber filter was negligible for compounds primarily found in the gas phase, but could not be ruled out for compounds found mainly on particles.     

Regional aspects and statistical characterisation of the load with semivolatile organic compounds at remote Austrian forest sites

Spruce needles and humus layer of 25 remote forest sites spread all over Austria were investigated for their concentrations of PCDD/F, PCB, HCH, HCB, PCP, DDX and PAH. Influences of the sites' location on the detected concentrations have been identified: The north of Austria was characterised by a comparably higher overall pollutant load. In addition, altitudinal aspects were addressed. Between several compounds significant positive correlations have been identified, which were more pronounced for compounds with a stronger causal relationship. Pattern analyses allowed to identify--even for the remote sites--differences between the relative PCDD/F, HCH, DDX and PAH patterns of the sites. Partly, these different patterns were related to significantly higher or lower corresponding absolute concentrations of the sites.     

Analysis of volatile and semivolatile organic compounds in municipal wastewater using headspace solid-phase microextraction and gas chromatography.

The aim of this work was to develop a simple and fast analytical method for the determination of a wide range of organic compounds (volatile and semivolatile compounds) in municipal wastewater. The headspace-solid-phase microextraction (HS-SPME) and gas chromatography (with mass spectroscopy) was used for determination of the organic compounds. In this study, 39 organic compounds were determined, including 3 sulfur compounds, 28 substituted benzenes, and 8 substituted phenols. The extraction parameters, such as types of SPME fiber, extraction temperature, extraction time, desorption time, salt effect, and magnetic stirring, were investigated. The method had very good repeatability, because the relative standard deviations ranged from 0.5 to 12%. The detection limit of each compound was at or below the microgram-per-liter level. This method was applied for determination of the organic compounds in raw wastewater, primary effluent, secondary effluent, and chlorinated secondary effluent samples from the Chania Municipal Wastewater Treatment Plant (Crete, Greece).     

Energy and redox status, and carbon allocation in one- to three-year-old spruce needles

Metabolite pools were determined in lyophilized homogenates of one- to three-year-old needles from 13-year-old spruce trees. These were exposed in open-chambers for five consecutive years to SO(2) (30 microg m(-3)) and O(3) (50 to 180 microg m(-3)), singly and in combination. The samples were taken shortly before bud break (mid-March). The energy (ATP/ADP) and redox status (NAD(P)H/NAD(P)) increased with needle age. This increase was most pronounced in needles exposed to both pollutant gases. To evaluate carbohydrate metabolism, levels of starch, sugars (sucrose, fructose, glucose), sugar phosphates (dihydroxyacetone phosphate, glyceraldehyde 3-phosphate (triose phosphates, TP), fructose 6-phosphate, fructose 2,6-bisphosphate: F2,6BP) and 3-phosphoglyceric acid (PGA) were measured. The concentrations of starch, glucose, fructose and TP on a dry weight basis increased with needle age, while those of sucrose and F2,6BP decreased. Interestingly, the total amount of soluble sugars remained constant in needles from control chambers and large fluctuations mainly occurred after a single application of the pollutants. Needles from fumigated trees generally showed somewhat lower starch and sugar, and fructose 6-phosphate levels. The content of TP increased with needle age while that of sucrose and F2,6BP decreased. This inverse behavior was even more prominent in the presence of both pollutants and is discussed in the context of recent knowledge on the regulation of carbon partitioning. There was a significant increase in the ratio of TP/PGA in samples from the combined exposure treatments. This also indicates an increase in the redox charge and corroborates the data on both the redox status of the pyridine nucleotide system and the significantly increased ATP/ADP ratio. The results are indicative of a switch in metabolism, from anabolic to predominantly catabolic reactions, which is most pronounced in the samples fumigated with both O(3) and SO(2). The data are compared to those obtained from naturally exposed trees in the southern Black Forest (K?lbelescheuer/Haldenhof, near Freiburg, Germany).     

Deposition of ozone to a mature spruce forest: measurements and comparison to models

Removal of ozone at terrestrial surfaces provides a major sink for tropospheric ozone and, therefore, a constraint on the peak concentrations achieved during photochemical episodes. This study reports results from 5 years of almost continuous measurements of vertical profiles of ozone and related meteorological variables over a mature spruce forest in Bavaria. Deposition velocities calculated from flux/gradient and eddy correlation flux measurements have been compared with estimates based on a resistance model and yield satisfactory agreement during fine weather conditions. The results also suggest that biogenic emissions of reactive hydrocarbons from the forest influence the vertical profile of ozone.     

New passive samplers for chlorinated semivolatile organic pollutants in ambient air

Two new types of passive samplers were designed and tested on semivolatile organic compounds. The first type (a spiral-rod sampler) consists of a low-density polyethylene membrane acting as a permeation film and a silicone elastomer as the receiving material; the second (a stir-bar sampler) has the same membrane material but a polydimethylsiloxane-coated stir bar acting as the collector phase and installed radially symmetrically in the sampler. The advantages of the new samplers are their simple design, low costs, and their easy processing via thermodesorption coupled with capillary gas chromatography and mass selective detection. In both samplers, the uptake of selected analytes was integrative over exposure periods of up to 384 h. The sampling rates calculated from a laboratory calibration study using the chlorinated semivolatiles hexachlorobenzene, hexachlorocyclohexane isomers and polychlorinated biphenyls ranged from 88.1 ml h-1 for delta-hexachlorocyclohexane to 3443 ml h-1 for 2,2',5,5'-tetrachlorobiphenyl. A field trial at a hazardous waste dump near Bitterfeld, Germany, for up to 21 days combined with periodical determinations of air concentrations using low-volume sampling indicated that the new samplers can in principle be used in the field, although the sampling rates derived from the field results differed considerably from the laboratory findings. Nevertheless the preliminary results suggest that the new sampler types are promising for the long-term air monitoring of semivolatiles.     

Long-range transport potential of semivolatile organic chemicals in coupled air-water systems

Ongoing deliberations on the regulation of semivolatile organic chemicals require the assessment of chemical transport in atmospheric and marine systems. The characteristic travel distance was proposed as a measure for the transport potential in air and water. However, the existing definition treats the transport processes separately. It is shown that combined transport in coupled air-ocean systems can accelerate the overall transport into remote regions. Concentration ratios in air and water change with distance from sources depending on the initial concentration ratio and on the difference between the transport velocities. A measure is suggested facilitating the chemical screening with respect to transport potentials in such air-ocean systems. A case study for alpha and gamma-hexachlorocyclohexane shows that the suggested measure qualitatively reveals the transport potentials of these chemicals and exemplifies possible concentration patterns.     

The use of light and electron microscopy to assess the impact of ozone on Norway spruce needles

Light (LM) and transmission electron (TEM) microscopy were used to study previously specified ozone symptoms in the foliage of Norway spruce. The three youngest green needle generations from twenty mature trees in two stands on sites of different soil fertility at Asa, southern Sweden, were sampled in 1999. The critical dose of ozone, expressed as AOT40, was 6,362 ppb.h. LM showed ozone-specific symptoms: decreased chloroplast size with electron dense stroma advancing gradually from the outer to the inner cell layers, being most severe in the needle side facing the sky. The symptoms were expressed as ozone syndrome indices at the needle generation, tree and stand levels. The index had higher values at the low fertility site. TEM was used to confirm the LM results. The study shows that LM can be used for diagnosis of the impact of ozone on conifers in the field.     

Regional variation in surface properties of Norway spruce and scots pine needles in relation to forest decline

Measurements of leaf wettability (contact angle), amounts of epicuticular wax and of surface dust are reported for Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L) Karst) trees growing at 12 sites in Europe from SW Germany to NE Scotland. At each site, three year classes (current year, 1 and 2-year-old) of needles were sampled from the mid-crown of up to 12 trees. Trees were selected at random from two strata, those showing visible decline symptoms (i.e. loss of needles or discoloration) and those apparently healthy. Needles for analysis were taken from apparently healthy (green) shoots in both cases. There were no significant differences between 'declining' and 'healthy' trees within sites, suggesting that leaf surface properties reflect environmental exposure rather than plant response. There were significant differences between sites, particularly for Norway spruce, which may be related to environmental factors including air pollution. Contact angles were consistently smaller at low-altitude sites in Britain and The Netherlands than at high-altitude sites in Germany where forests show decline symptoms. Leaf wettability decreased (contact angles increased) with wax amount and increased with dust amount. Leaf surface properties integrate environmental influences over long periods, and may be useful in identifying sites 'at risk' of developing decline symptoms, but causal relationships cannot be deduced without further direct experimentation.     

Cytological observations on spruce needles after prolonged treatment with ozone and acid mist

Light and electron microscopic studies of four clones of 5-year-old Picea abies trees subjected to ozone and acid mist treatment showed, that: (1) Clones respond differently to the treatment, with clone 14 the most sensitive clone. (2) Main effects were observed in the mesophyll; the vascular strand showed minor cellular changes. (3) Needle shape and ratio of intercellular area to cross section was clone- age-dependent, with a clear increase in intercellular space associated with the treatment (clone 14 and 11 only). (4) Accumulation of tannins in vacuoles was clone-specific. (5) Strong starch formation was found in all samples; in clones 14 and 133 this formation was enhanced by the treatment in older needles, if number of starch grains per cell was calculated. (6) The accumulation of plastoglobules in plastids depended on clone and age, with the older needles containing more globules. In clones 11 and 133, the treatment led to an increase in the number of plastoglobules. (7) Grana stacking in all clones and both needle ages subjected to ozone and acid mist was significantly reduced. The observed changes in the ultrastructure of needle tissue are comparable to those found in field investigations with similar conditions, or phytotron studies evaluating pollution effects on spruce trees.     

The Missoula Valley semivolatile and volatile organic compound study: seasonal average concentrations

The city of Missoula is located in a high mountain valley (elevation 3200 ft.) in western Montana and contains one of the largest populations in the entire Rocky Mountain Region completely enclosed by mountains. During the 2000/2001 Missoula Valley Sampling Program, ambient levels of 61 semivolatile organic compounds (SVOCs) and 54 volatile organic compounds (VOCs) were originally quantified before refining the analytical program to 28 of the most prominent SVOCs and VOCs found in the Missoula Valley airshed. These compounds were measured over 24-hr periods at two locations throughout an entire year. This study provides the first, comprehensive appraisal of the levels of SVOCs and VOCs measured simultaneously throughout all four seasons at two locations in the Missoula Valley, including those levels measured during the 2000 Montana wildfire season. Generally, SVOC levels were comparable between both sides of the Missoula Valley. However, there were nearly double the amount of VOCs measured at the more urban Boyd Park site compared with the rural Frenchtown sampling site, a result of the greater number of automobiles on the eastern side of the Valley. SVOCs and VOCs were measured at their highest levels of the sampling program during the winter. Forest fire smoke samples collected during the summer of 2000 showed significant increases in SVOC phenolic compounds, including phenol, 2-methylphenol, 4-methylphenol, and 2,4-dimethylphenol. Although there were modest increases in some of the other SVOCs and VOCs measured during the fire season, none of the increases were as dramatic as the phenolics.     

Removal of volatile and semivolatile organic contamination from soil by air and steam flushing

A soil core, obtained from a contaminated field site, contaminated with a mixture of volatile and semivolatile organic compounds (VOC and SVOC) was subjected to air and steam flushing. Removal rates of volatile and semivolatile organic compounds were monitored during flushing. Air flushing removed a significant portion of the VOC present in the soil, but a significant decline in removal rate occurred due to decreasing VOC concentrations in the soil gas phase. Application of steam flushing after air flushing produced a significant increase in contaminant removal rate for the first 4 to 5 pore volumes of steam condensate. Subsequently, contaminant concentrations decreased slowly with additional pore volumes of steam flushing. The passage of a steam volume corresponding to 11 pore volumes of steam condensate reduced the total VOC concentration in the soil gas (at 20 degrees C) by a factor of 20 to 0.07 mg/l. The corresponding total SVOC concentration in the condensate declined from 11 to 3 mg/l. Declines in contaminant removal rates during both air and steam flushing indicated rate-limited removal consistent with the persistence of a residual organic phase, rate-limited desorption, or channeling. Pressure gradients were much higher for steam flushing than for air flushing. The magnitude of the pressure gradients encountered during steam flushing for this soil indicates that, in addition to rate-limited contaminant removal, the soil permeability (2.1 x 10(-9) cm2) would be a limiting factor in the effectiveness of steam flushing.     

Occurrence and distribution of atmospheric organic micropollutants in conifer needles

The distribution of some chlorinated hydrocarbons(p,p′-DDT, p,p′-DDE,α-HCH,γ-HCH,HCB) in spruce (Picea abies) needles was investigated. A comparision of concentrations in the wax with that of the remaining needle and time-resolved washing of the needle-surface shows the distribution behaviour of these substances.