Arsenic Speciation in Lichens and in Coarse and Fine Airborne Particulate Matter by HPLC–UV–HG–AFS

A three-step sequential extraction procedure with Milli-Q, CaCl₂ and H₃PO₄ was applied for extraction of arsenic species in lichen transplants and airborne particulate matter (fine and coarse fractions). The samples used in this work were collected in 1994–1995 near coal-fired power plants. Both transplant lichens and airborne particulate matter were submitted to the same environment simultaneously. Arsenic species identification and quantification was performed by HPLC–UV–HG–AFS. Inorganic forms of arsenic (arsenite and arsenate) were present in significant amounts in most of the samples. Only in lichens also organic forms of arsenic (monomethyl arsonic acid and dimethyl arsinic acid) were identified which may indicate biotransformation of inorganic arsenic.     

Mapping Lichen Diversity as a First Step for Air Quality Assessment

The evaluation of air quality is an important topic. It is well known that lichens have a set of characteristics that make them well suited for biomonitoring purposes. Sampling lichen diversity is not as expensive as chemical analysis, allowing a dense sampling grid and reducing the costs. Lichen diversity can be used to identify more disturbed areas, resulting from pollution, land use or ecological variables. In recent years, in order to enable extended use of lichens and to reduce ambiguities, i.e., variations due to unwanted environmental variables, efforts have been made to develop a feasible protocol for lichen sampling for biomonitoring purposes. This work aims at providing the information needed a priori for an air quality assessment study, in the form of a map showing areas where lichen diversity and abundance is lower. This study was done by sampling foliose and fruticulose lichen diversity and frequency, in a region in southwest Portugal (Sines) with large industrial facilities. A long-term study has been underway in the same area since the 1970s using lichens as bioindicators to evaluate air quality. In this work, we used a standard protocol to determine a lichen diversity value (LDV), to be used as an indicator of environmental quality. In order to reduce uncertainty concerning the type of disturbance affecting lichens, sampling sites were restricted using well-defined criteria. Whenever possible, sampling site variables were quantified. This method allowed us to reduce the many sources of variability affecting lichen diversity.     

Lichens as bioindicators of atmospheric heavy metal deposition in Valencia, Spain

The lichens due to their symbiotic nature have unique characteristics that confer them a key role as bioindicators of the environmental contamination. Many investigations have been done using epiphytic lichens as bioindicators, but only a few of these studies have used epilithic-crustose lichens. Three different epilithic-crustose lichens species: Candelariella sp., Lecanora sp. and Caloplaca sp. were studied as bioindicators of V, Cr, Mn, Co, Ni, Cu, Zn, As, Rb, Sr, Mo, Cd, Sb, Ba, Pb, Bi and U trace elements. Inductively Coupled Plasma Mass Spectrometry routine procedure is used to determining these element concentrations. Two sites were selected for lichens sampling according to environmental contamination. The lichens were collected on the facade of the Santos Juanes church in an urban area of Valencia; and on the rural area of Albarracin. The main aim of this work is showing the efficacy of the epilithic-crustose lichens as bioindicators of the air pollution. This study shows that the city of Valencia, compared with the rural area has high levels of Cu and Pb as detected using lichens as bioindicators. Therefore on the basis of these results, it can be hypothesized that Candelariella sp., Lecanora sp. and Caloplaca sp. are good accumulators of air borne heavy metals.     

Measurements of H2S and SO2 over the Atlantic Ocean

Concentrations of sulfur gases H₂S and SO₂ have been measured in the marine atmosphere over the Atlantic Ocean at various sites. Mean values of 40 ng H₂S m^-3 STP and 209 ng SO₂ m^-3 STP are the results of the measurements. A diurnal variation of H₂S concentration was detected on the west coast of Ireland with nighttime concentrations of up to 200 ng H₂S m^-3 STP and values below detection limit (15 ng H₂S m^-3 STP) during daytime.     

Monitoring of Short-Term Heavy Metal Deposition by Accumulation in Epiphytic Lichens (Hypogymnia Physodes (L.) Nyl.)

Many lichens are very sensitive to air pollution due to their symbiotic nature. However, they are generally less sensitive to toxic effects of trace elements; therefore they can be used as accumulator organisms for estimating concentrations of these elements in the environment. Heavy metal accumulation in lichens is a commonly used bioindication method for assessing heavy metal ambient levels. An active biomonitoring method was used for the determination of short-term accumulation of zinc, lead, arsenic and cadmium by epiphytic lichens transplanted at different localities in Slovenia polluted by heavy metals. The atomic absorption spectrophotometry method was used for the determination of heavy metal content in lichen thalli. The content of heavy metals in lichens collected in the background area with clean air (Rogla, Pohorje Mountains) was used as the reference value. Lichens were transplanted from Rogla using the branch transplantation technique for a period of 6 months in the surroundings of Slovenian thermal power plants (Velenje, otanj, Zavodnje, Veliki Vrh, Vnajnarje, and Dobovec) and close to the lead and zinc ore smelter at erjav. The monthly accumulation of heavy metals was comparable within years at selected locations. Heavy metal pollution was the highest at erjav despite of remediation of lead and zinc ore smelter. The monthly accumulation of all four heavy metals was statistically significantly higher in lichens exposed at erjav than at other localities.     

Polyamine Production in Lichens Under Metal Pollution Stress

In the present study, thalli of the lichen species Pseudevernia furfuracea Zopf. and Evernia prunastri (L.) Ach. transplanted around an oil-fired power station. Following an exposure of 4 months, trace element concentrations (Al, Cd, Cr, Cu, Fe, Ni, Pb, V and Zn) and polyamine (PA) content [putrescine (Put), spermidine (Spd) and spermine (Spm)] of thalli were measured to study the polyamines production in lichens under metal pollution stress. The polyamine production was not significantly different for the two species but two types of statistically significant relationships were revealed between polyamines production and metals concentration in lichen thalli: a positive linear relationship for the pairs total PAs–Cd (P. furfuracea), total PAs–Cu (E. prunastri), Put–Pb (E. prunastri), Spm–Pb (E. prunastri) and a second-order polynomial relationship for the pairs Put–Cd (P. furfuracea), Spm–Cr (E. prunastri) and total PAs–V (E. prunastri). A possible involvement of polyamines in metal pollution stress response of lichens is discussed.     

Impact of UV-B, Heat and Chemicals on Ethylene-Production of Lichens

To assess the impact of UV-B radiation combined with NaHSO₃ in solution under laboratory conditions, we compared the amounts of stress-ethylene produced by two lichen species of the same genus. Ramalina lacera, an epiphytic Mediterranean lichen, was found to be rather sensitive to UV-B combined with NaHSO₃, relative to the epilithic desert lichen R. maciformis. The impact of high temperatures with FeCl₂ in solution, measured by amounts of stress ethylene accentuated the adaptability of R. maciformis to desert conditions, whereas R. lacera appeared to be rather sensitive to extreme temperatures especially in the case of chemical contamination. The adaptability of R. maciformis to UV-B appears to be related to the photoprotective capabilities of lichen substances.     

Shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide in the Caribbean and Gulf of Mexico

Simultaneous shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide were made on three cruises in the Gulf of Mexico and the Caribbean. The cruise tracks include both oligotrophic and coastal waters and the air masses sampled include both remote marine air and air masses heavily influenced by terrestrial or coastal inputs. Using samples from two north-south Caribbean transects which are thought to represent remote subtropical Atlantic air, mean concentrations of DMS and H₂S were found to be 57 pptv (74 ng S m^-3, =29 pptv, n=48) and 8.5 pptv (11 ng S m^-3, =5.3 pptv, n=36), respectively. The ranges of measured concentrations for all samples were 0–800 pptv DMS and 0–260 pptv H₂S. Elevated concentrations were found in coastal regions and over some shallow waters. Statistical analysis reveals slight nighttime maxima in the concentrations of both DMS and H₂S in the remote marine atmosphere. The diurnal nature of the H₂S data is only apparent after correcting the measurements for interference due to carbonyl sulfide. Calculations using the measured ratio of H₂S to DMS in remote marine air suggest that the oxidation of H₂S contributes only about 11% to the excess (non-seasalt) sulfate in the marine boundary layer.     

Uranium Isotopes, Metals and Other Elements in Lichens and Tree Barks Collected in Bosnia–Herzegovina

The United Nations Environment Programme (UNEP) performed field surveys at 15 sites in Bosnia–Herzegovina where depleted uranium (DU) ammunition was used by the North Atlantic Treaty Organization (NATO) during the Balkans conflict (1994–1995). During the field missions, the Italian Environmental Protection Agency (APAT) evaluated airborne contamination due to DU dusts or aerosol particles, generated at the time of the conflict by the impact of DU ammunition on hard targets, using lichens and tree barks as biomonitors. Each sample was analyzed by alpha-spectrometry for DU determination. The ²³⁴U/²³⁸U activity concentration ratios were used to distinguish natural from anthropogenic uranium. This paper reports the data obtained by the UNEP investigation, including (non-radioactive) metal and other element concentrations in lichen and tree bark samples measured by instrumental neutron activation analysis (INAA). The results indicated: (i) lichens and tree barks are sensitive bio-accumulators of past airborne contamination by depleted uranium dusts; (ii) 8 years after the conflict, environmental DU contamination is still present at some of the target sites; and (iii) the highest concentrations of most non-radioactive elements were found at sites used for ammunition destruction.     

Biogenic hydrogen sulphide emissions and non-sea sulfate aerosols over the Indian Sundarban mangrove forest

Temporal variations in atmospheric hydrogen sulphide concentrations and its biosphere-atmosphere exchanges were studied in the World’s largest mangrove ecosystem, Sundarbans, India. The results were used to understand the possible contribution of H₂S fluxes in the formation of atmospheric aerosol of different size classes (e.g. accumulation, nucleation and coarse mode). The mixing ratio of hydrogen sulphide (H₂S) over the Sundarban mangrove atmosphere was found maximum during the post-monsoon season (October to January) with a mean value of 0.59?±?0.02 ppb and the minimum during pre-monsoon (February to May) with a mean value of 0.26?±?0.01 ppb. This forest acted as a perennial source of H₂S and the sediment-air emission flux ranged between 1213?±?276 μg S m^?2 d^?1(December) and 457?±?114 μg S m^?2 d^?1 (August) with an annual mean of 768?±?240 μg S m^?2d^?1. The total annual emissions of H₂S from the Indian Sundarban were estimated to be 1.2?±?0.6 Tg S. The accumulation mode of aerosols was found to be more enriched with non-sea salt sulfate with an average loading of 5.74 μg m^?3 followed by the coarse mode (5.18 μg m^?3) and nucleation mode (1.18 μg m^?3). However, the relative contribution of Non-sea salt sulfate aerosol to total sulfate aerosol was highest in the nucleation mode (83%) followed by the accumulation (73%) and coarse mode (58%). Significant positive relations between H₂S flux and different modes of NSS indicated the likely link between H₂S, a dominant precursor for the non-sea salt sulfate, and non-sea sulfate aerosol particles. An increase in H₂S emissions from the mangrove could result in an increase in enhanced NSS in aerosol and associated cloud albedo, and a decrease in the amount of incoming solar radiation reaching the Sundarban mangrove forest.     

Element-Enrichment Factors in Lichens from Terceira, Santa Maria and Madeira Islands (Azores and Madeira Archipelagoes)

In this study, more than 20 minor and trace elements have been determined by INAA (instrumental neutron activation analysis), in different species of lichens in three Portuguese islands of the Central North Atlantic (Santa Maria, Terceira, and Madeira Islands). The foliose species Parmotrema bangii, Parmotrema robustum, Parmotrema crinitum, Flavoparmelia caperata, Platismatia glauca, and the fruiticose species Ramalina canariensis, Ramalina farinacea, Ramalina implectens, Ramalina pusilla, Cladonia furcata, Cladonia coniocraea, Usnea dasaea, Usnea esperantiana, were the collected species. Samples of superficial soils were also collected and the fraction below 64 m was analysed. The enrichment factors relative to this fraction using Al as the normalising element were calculated. Fruiticose and foliose lichens displayed different EF values concerning bromine and potassium. The first was more enriched in the foliose species while the latter was more enriched in the fruiticose species and was assigned to the physiological response. Enrichment was found for Mg, Cs, As, Hg, Na, Zn, and Cl, in all the species. Lichen-based concentration patterns were shown for Na, Al, Cl, Br, Sb, Ce, and Hg and compared to similar patterns in Portugal mainland. In general, the patterns compared well except for Cl, Na, and Br. Background levels of the epiphytic lichens collected in the islands were obtained.     

Lichens as Biomonitors of Depleted Uranium in Kosovo

This paper reports the results of a study using lichens as biomonitors to investigate the environmental distribution of depleted uranium (DU) at selected Kosovo sites as a consequence of the use of DU ordnance during the conflict of 1999. The results suggested that the use of DU ammunitions did not cause a diffuse environmental contamination in such a way to have caused a detectable U enrichment in lichens. Also isotopic ²³⁵U/²³⁸U measurements did not indicate the presence of DU particles in lichens, except for some samples at a heavily shelled site, which resulted contaminated by DU.     

Sorption Characteristics of Inorganic, Methyl and Elemental Mercury on Lichens and Mosses: Implication in Biogeochemical Cycling of Mercury

The sorption studies of Hg²⁺, CH₃Hg⁺ and elemental mercury (Hg⁰) were carried out on lichen (Parmelia sulcata) and moss (Funaria hygrometrica) samples under laboratory conditions. Desorption studies with HCl indicate that inorganic mercury (Hg⁺²) and methyl mercury could be completely desorbed with 1 M HCl and 0.5 M HCl, respectively. Samples loaded with elemental mercury, however, needed 4–5 M HCl concentration for complete desorption of the adsorbed elemental mercury. When similar desorption studies were carried out with field samples collected around a thermometer factory with elevated levels of mercury (8 mg/kg), it was found that only about 10–15% of total mercury was desorbed with 1M HCl, while 4–5 M acid was required for complete desorption. We have tried to correlate this information to understand the transformations of mercury species that may occur either in the atmosphere or on the biomonitors. The results indicated that the elemental mercury, the principal form of mercury contamination around the thermometer factory, is converted into a strongly held form by some chemical binding agents on the surface of lichen/moss, or elemental mercury could diffuse into the cells of the lichen/moss, which then needs the stronger acid to release it. Sorption capacity studies suggest that the lichens and mosses can also be used as sorbent material for the decontamination of inorganic and methyl mercury from aqueous solutions.     

Rapid change in nitrate and sulfate concentrations observed in early stage of precipitation and their deposition processes

The concentrations of H⁺, nitrate (NO₃ ^-), and sulfate (SO₄ ^2-) in rainwater and their temporal changes were analyzed on the basis of continuous observation from 1 July 1991 to 30 June 1992 at a suburb of Nagoya, Japan. The yearly average for pH was 4.4. In general, an increasing pH with increase in precipitation amount was observed for rain events. Relatively high pH rainwater was sometimes observed at the beginning of rainfall, even though high concentrations of NO₃ ^- and SO₄ ^2- were involved. The high pH values were considered to be caused by the neutralization process with particulate matter containing cations. The yearly averaged ratio of equivalent concentration of nitrate to sulfate (N/S) in rainwater was 0.58. In the early stage of rain, the N/S value was usually more than 1.0 due to the difference of scavenging process between NO₃ ^- and SO₄ ^2-. High values of N/S ranging from 5 to 10 were found under the atmospheric conditions of calm winds and low humidity, during which it is possible that atmospheric particles float for a long time in the air before a rain event. The adsorption of NO₃ ^- in the early stage of rainfall by particulate matter was suggested from the difference in scavenging processes of NO₃ ^- and SO₄ ^2-. A possible scavenging process, called limb cloud scavenging, is presented to explain the interaction of particles and nitrate ions at the early stage of rain. In limb cloud scavenging, the repeated migration of cloud particles or raindrops between the inside and outside of clouds increases the absorption of ions to a highly condensed level, thus increasing the N/S value of rainwater. The influence of global scale seasonal phenomena with large amounts of particulates, such as typhoons or Asian dust storms, was also studied.     

Estimation of fog deposition on epiphytic bryophytes in a subtropical montane forest ecosystem in northeastern Taiwan

The fog meteorology, fog chemistry and fog deposition on epiphytic bryophytes were investigated from July 2000 to June 2001 in the Yuanyang Lake forest ecosystem. The elevation of the site ranges from 1650 to 2420 m, at which the high frequency of fog occurrence throughout the year has been thought to be of benefit to the establishment of the primary Taiwan yellow cypress forest [Chamaecyparis obtusa var. formosana (Hayata) Rehder] and to the extensive growth of the epiphytic bryophytes. A weather station including a visibility sensor and an active fog collector was installed for fog meteorological and chemical study. The fog deposition rate on epiphytic bryophytes was estimated by measuring the increase rate in plant weight when exposed to fog. Average fog duration of 4.7 and 11.0 h per day was measured in summer months (June to August) and the rest of the year, respectively. November 2000 was the foggiest month in which the average fog duration reached 14.9 h per day. The ionic composition of fog water revealed that the area was less polluted than expected from literature data. The in situ exposure experiments done with the dominant epiphytic bryophytes showed an average fog deposition rate of 0.63 g H₂O g⁻¹ d. w. h⁻¹, which approximated 0.17 mm h⁻¹ at the stand scale. The nutrient fluxes estimated for February 2001 showed that for all ions, more than 50% of the ecosystem input was through fog deposition. These results demonstrate the importance of epiphytic bryophytes and fog deposition in nutrient cycling of this subtropical montane forest ecosystem. The incorporation of fog study in the long-term ecosystem research projects is necessary in this area.     

Metabolised Tritium and Radiocarbon in Lichens and Their Use as Biomonitors

Lichens are now well known for their potential as bio-indicators of environmental pollution, but less is known about their suitability as quantitative biomonitors for atmospheric emissions of tritium (mainly as tritiated water, HTO) and radiocarbon (as ¹⁴CO₂) from nuclear facilities, although both radionuclides could result in non-trivial individual or collective radiation doses due to their high environmental mobility and their long half-lives. ³H and ¹⁴C are fixed in lichens mainly by the photosynthesis of the algal partner and then stored in the organic molecules of both alga and fungus. They have the advantage of allowing the monitoring of atmospheric water vapour without interference of soil water or soil organic substances as long as soil-inhabiting species are avoided. Lichens were collected in the surroundings of (military and civil) nuclear facilities, in areas away from any direct source of contamination and some were transplanted from a contaminated area to a non-contaminated one. The influence of the nuclear facilities can be clearly traced, sometimes in a spectacular way and the first results of analyses after transplants give a base for estimating the effective half-life of ³H in lichens.     

Pollutant concentrations in fog and low cloud water at selected sites of the Czech Republic

In this paper, the basic composition of fog and low cloud water are presented, resulting from the analyses of water samples from 111 fog/cloud events. The samples were collected at five sites located in various regions of the Czech Republic. Two sampling sites are in mountainous regions and three sites represent various urban areas. The mountain stations are located in two regions of the Czech Republic with different industry types. At all the sites, active fog collectors were employed. In the water samples, the conductivity, acidity (pH), cations (H⁺, Na⁺, K⁺, NH₄⁺, Mg²⁺, Ca²⁺) and anions (F⁻, Cl⁻, NO₃⁻, SO₄²⁻) were determined.A mean pH value of about 4.5 was obtained at mountain sites whereas the measurements in urban areas showed mean pH values from 4.9 to 6.4. The mean conductivity values in the samples from the two mountain stations were 137 and 191.5 μS cm⁻¹. The samples from urban sites showed mean values between 127.7 and 654.4 μS cm⁻¹. The maximum concentration means for the three dominant pollutants (expressed by the ratio mountain sites/urban sites) are 32.9/99.6 mg l⁻¹ for NO₃⁻, 32.5/192.9 mg l⁻¹ for SO₄²⁻ and 18.5/52.7 mg l⁻¹ for NH₄⁺. As expected, we found higher ion concentrations in the northern part of the Czech Republic where larger numbers of lignite-burning power plants, chemical factories and opencast lignite mines are located. A decrease in ion concentrations was observed at higher altitude sites, probably reflecting at least in part higher liquid water contents at these locations.     

A comparison of the enzyme fluorometric and the peroxyoxalate chemiluminescence methods for measuring H2O2

During September 25 to October 28, 1985, the enzyme fluorometric (Lazrus et al., 1985) and the peroxyoxalate chemiluminescence (Klockow and Jacob, 1986; Jaeschke, 1986) techniques for analyzing H₂O₂ were compared in laboratory studies at the National Center for Atmospheric Research in Boulder, Colorado, U.S.A. and under field conditions at the Whiteface Mt. field station of the Atmospheric Sciences Research Center, Albany, New York, U.S.A. Both methods showed excellent agreement, with a maximum deviation of ±5%. Only at unusually high concentrations of some potential atmospheric species could slight interferences be observed. During the experiments the detection limits were 1.3×10^-8 mol/l (0.44 ppbm) of H₂O₂ for the fluorometric instrument and 4×10^-8 mol/l (1.36 ppbm) of H₂O₂ for the chemiluminescence instrument. For the chemiluminescence technique, the response to methylhydroperoxide was approximately 80-fold less than that to an equivalent concentration of H₂O₂.     

Laboratory Study of O(1S) Formation Process in the Photolysis of O3 and its Atmospheric Implications

A high-sensitive technique to detect O(¹S) atoms using vacuum ultraviolet laser-induced fluorescence (VUV-LIF) spectroscopy has been applied to study the O(¹S) production process from the UV photodissociation of O₃, N₂O, and H₂O₂. The quantum yields for O(¹S) formation from O₃ photolysis at 215 and 220 nm are determined to be (1.4 ± 0.4) × 10⁻⁴ and (5 ± 3) × 10⁻⁵, respectively. Based on thermochemical considerations, the O(¹S) formation from O₃ photolysis at 215 and 220 nm is attributed to a spin-forbidden process of O(¹S)+O₂(X³Σ_g ⁻). Analysis of the Doppler profile of O(¹S) produced from O₃ photolysis at 193 nm also indicates that the O(¹S) atoms are produced from the spin-forbidden process. In the photolysis of N₂O and H₂O₂ at 193 nm, no discernible signal of O(¹S) atoms has been detected. The upper limit values of the quantum yields for O(¹S) production from N₂O and H₂O₂ photolysis at 193 nm are estimated to be 8 × 10⁻⁵ and 3 × 10⁻⁵, respectively. Using the experimental results, the impact of the O(¹S) formation from O₃ photolysis on the atmospheric OH radical formation through the reaction of O(¹S)+H₂O has been estimated. The calculated results show that the contribution of the O(¹S)+H₂O reaction to the OH production rate is ∼2% of that of the O(¹D)+H₂O reaction at 30 km altitude in mid-latitude. Implications of the present laboratory experimental results for the terrestrial airglow of O(¹S) at 557.7 nm have also been discussed.     

Lichen as quantitative biomonitors of atmospheric heavy metals deposition in Central India

Three different growth forms of lichens belonging to six species; Phaeophyscia hispidula, Parmotrema praesorediosum (foliose); Caloplaca subsoluta, Diploschistes candidissmus (crustose) and Peltula euploca, Phylliscum indicum (squamulose) were studied comparatively for the biomonitoring of Al, Cd, Cr, Cu, Fe, Ni and Zn in Mandav city in central India. Based on the anthropogenic activities three sites were selected for lichen collection. To identify the sources of heavy metal pollution, their concentration was analyzed in thallus as well as in their respective substrates. The thallus of studied lichens showed higher concentration of metals such as Cd, Cr, Ni and Zn, while most of the metals were absent or present in negligible amount in substrates (Fe, Al, Cu), which proves that the accumulated metals were air borne. The foliose lichens (P. hispidula and P. praesorediosum) found highly significant in metal accumulation at each sites followed by crustose and squamulose forms. Lichen samples collected from site 2, adjacent to road side accumulated maximum quantities of Zn, Ni, Cd and Cr whereas the city centre (Site 1) had maximum concentrations of Fe, Cu and Al. The site 3 situated away from the city had lowest amount of all the metals. The analysis of variance and LSD indicated that the metal concentrations among lichen species as well as between substratum is significant at p < 0.05% and P < 0.01% level respectively.