Interaction between ozone and winter stress

In some countries, ozone (O3) is primarily a summer pollutant, but in much of Europe, elevated concentrations occur outside the growing season so perennials and over-wintering annuals may be subjected to the combined stresses of pollution, plus chilling, freezing, and winter desiccation. It is recognised that some air pollutants modify the response of plants to environmental stress, but little is known of interactions involving O3. This paper is part of a programme concerned with the effects of O3 on resistance to chilling, freezing, and winter desiccation. Pea (Pisum sativum L.) was used as a convenient model to confirm that O3 affects freezing resistance. The experiment also served as a further evaluation of the use of induced chlorophyll fluorescence kinetics to detect latent O3 injury. Two cultivars, 'Feltham First' and 'Conquest', were fumigated for 7 days, 7 h day(-1). Diffusive resistance and induced fluorescence were recorded daily during the period, then the plants were hardened at 4 degrees C day/2 degrees C night before exposure to 0, -2, -4, -6 and -8 degrees C. Ozone (0.075 ppm; 150 microg O3 m(-3)) caused stomatal closure in both cultivars, but the response was more rapid in 'Conquest'. There were also rapid effects on fluorescence kinetics, and it was concluded that FR, the rate of rise of induced fluorescence, is a useful parameter for indicating latent injury and for distinguishing between cultivars of different sensitivity. Exposure to O3 increased freezing injury and led to greater electrolyte leakage. The freezing resistance of 'Feltham First' was more affected than that of 'Conquest', probably because of the slower stomatal response to the pollutant leading to greater flux of O3 to the internal tissues. It is concluded that interactions involving pollutants and winter stress have implications for crop loss assessment. Perennials and over-wintering annuals should be exposed to the full range of environmental stresses.     

A theory on the mechanisms regulating the bioavailability of mercury in natural waters

A number of quantifiable properties of natural waters have been used by various scientists to 'explain' the Hg content in fish (e.g. pH, level of bioproduction, humosity, conductivity, calcium content, oxygen conditions, zinc and selenium content). This work presents a theory aimed at providing an explanation of the chemical mechanisms behind many established statistical relationships. The theory focuses on some equilibrium reactions and the causal relationships behind these reactions. The basic concept of the theory is that the activity of Hg(2+) in natural waters is essentially regulated by the activity of S(2-), which, in turn, is strongly affected by pH and redox conditions. Due to protonisation reactions, the S(2-) activity is very low at natural pH levels. The equilibrium between Hg(2+) and HgS(s) is given by the solubility constant Ks = 10(-52). This is an extremely low constant, which indicates that, in the presence of sulphide, essentially all Hg will appear as HgS(s). The Hg(2+) activity, and the Hg content in fish, can be increased if the S(2-) activity is decreased by lowering the pH and/or increasing the redox potential. Besides sulphide there are two other elements with a similar relationship towards Hg; namely, Se and Te (Ks = 10(-58) and Ks = 10(-70), respectively). The Hg(2+) concentration in natural waters varies quite widely, but is often about 5 ng litre(-1). This is a high concentration in these contexts. Such as high concentration can prevail only if the S(2-) (and/or the Se(2-)) activity is very small. In waters where the S(2-) and/or the Se(2-)) activity is high, e.g. from sulphide rocks in the drainage area, or if S(2-) and/or Se(2-) are added to the water, the Hg(2+) activity, and the Hg content in fish, will be effectively reduced.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, -thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².

The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Variation in CO2 assimilation rate induced by simulated dew waters with different sources of hydroxyl radical (*OH) on the needle surfaces of Japanese red pine (Pinus densifora Sieb. et Zucc.)

The hydroxyl radical (*OH) is generated in polluted dew on the needle surfaces of Japanese red pine (Pinus densiflora Sieb. et Zucc.). This free radical, which is a potent oxidant, is assumed to be a cause of ecophysiological disorders of declining trees on the urban-facing side of Mt. Gokurakuji, western Japan. Mists of *OH-generating N(III) (HNO2 and NO2-) and HOOH + Fe + oxalate solutions (50 and 100 microM, pH 5.1-5.4) simulating the dew water were applied to the foliage of pine seedlings grown in open-top chambers in the early morning. Needles treated with 100 microM N(III) tended to have a greater maximum CO2 assimilation rate (Amax), a greater stomatal conductance (g(s)) and a greater needle nitrogen content (Nneedle), suggesting that N(III) mist acts as a fertilizer rather than as a phytotoxin. On the other hand, needles treated with 100 microM HOOH + Fe + oxalate solution showed the smallest Amax, g(s), and Nneedle, suggesting that the combination of HOOH + Fe + oxalate caused a decrease in needle productivity. The effects of HOOH + Fe + oxalate mist on pine needles were very similar to the symptoms of declining trees at Mt. Gokurakuji.     

Levels and tissue-dependent distribution of dioxin in Japanese domestic leafy vegetables--from the 1999 national investigation

In 1999, Japanese domestic leafy vegetables were successively investigated for levels of dioxins, including 17 dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), four non-ortho co-planar PCBs (co-PCBs) and eight mono-ortho co-PCBs, all of which had been assigned toxic equivalency factors (TEFs) by WHO in 1997. The mean levels of dioxins in the edible portions were 0.07 (0.09) pg TEQ/g in spinach, 0.13 (0.14) pgTEQ/g in garland chrysanthemum, 0.01 (0.04) pg TEQ/g in mitsuba (marsh parsley) and 0.01 (0.03) pg TEQ/g in chingentsuai (Brassica Campestris var. chinesis), when non-detects were set to zero (and set to half the limit of detection). In order to understand the dioxin pollution of leafy vegetables in detail, a further investigation of dioxin levels in the tissues of spinach was conducted. As a result, the dioxin levels in the leaves were found to be higher than those in the stem and red collar, but they were much lower than those found in the primary and secondary roots, which are considerably affected by the soil, which is recognized as a sink of airborne dioxins. The dioxin levels in edible portions (leaves, stem and red collar) were obviously lower than those in non-edible portions (primary and secondary roots). In addition, from the finding that several lower-chlorinated PCDD/Fs and co-PCBs, namely 2,3,7,8-TCDD/F, 1,2,3,7,8-PeCDD, 1,2,3,7,8/2,3,4,7,8-PeCDFs, 1,2,3,7,8,9-HxCDD, 1,2,3,4,7,8-/1,2,3,6,7,8-HxCDFs, 3,3',4,4'-TCB, 2,3,3',4,4'-/2,3',4,4',5-PeCBs, and 2,3',4,4',5,5'-HxCB, were more highly represented in the dioxins in the leaves than in those in the secondary roots, it was suggested that in leafy vegetables the deposition of gaseous, presumably moderately volatile dioxins in leaf wax is another pollution pathway in addition to the adhesion of dioxin-contaminated particles including soil.     

Exchange of sulfur pollution between Bulgaria and Greece

The EMAP model (Eulerian Model for Air Pollution) is applied for calculating the sulfur concentration and deposition fields for 1995 as based upon Bulgarian and Greek sources. The country-to-country budgets show that about 4% of the sulfur oxides emitted by Bulgaria are deposited over Greek territory, estimated at 28 kt S. Only 2% of sulfur compounds emitted by Greece are deposited over Bulgaria, estimated at 6.2 kt S for 1995. This data is in agreement with EMEP/MSC-W estimates and provides more details concerning time and space. The results can be used in decision-making, negotiating and the development of contamination strategies.     

Photocatalytic degradation of gaseous perchloroethylene: products and pathway

Batch photocatalytic degradation of 1000-ppm gaseous perchloroethylene (PCE) was conducted with UV irradiation such that nearly 100% was decomposed within 10 min. The main intermediate and final product were identified as trichloroacetylchloride (TCAC) and hydrogen chloride (HCl), respectively, and minor ones as dichloroacetic acid (DCAC), monochloroacetic acid (MCAC), carbon tetrachloride, chloroform, and phosgene. More than 90% of Cl- equivalent, i.e., the sum of the chlorine number in PCE, intermediates, and HCl, was compensated for during the time of PCE degradation; a result indicating that no other major chlorinated intermediates are present during the time of PCE degradation. In a similar experiment, 500 ppm of gaseous TCAC degraded into HCl within 3 h without producing DCAC or MCAC, where like PCE, more than 90% of Cl- equivalent, i.e., the sum of the chlorine number in TCAC and HCl, was compensated for during time of TCAC degradation. Accordingly, gaseous PCE is concluded to predominantly follow a degradation pathway of PCE --> TCAC --> HCl.     

Accumulation of silver in the liver of three species of pinnipeds

Silver in the three species of pinnipeds [northern fur seal (Callorhinus ursinus), Steller sea lion (Eumetopias jubatus), and harbor seal (Phoca vitulina)] caught in the North Pacific Ocean were analyzed using inductively coupled plasma-mass spectrometry, in order to understand accumulation and distribution of silver in pinnipeds. In northern fur seals, relatively high concentrations of silver were observed in the liver and body hair. Some 70% of the silver burden was concentrated in the liver. Hepatic silver concentrations were significantly correlated to age in northern fur seals (r = 0.766, P < 0.001, n = 49) and Steller sea lions (r = 0.496, P < 0.01, n = 28). Levels of silver concentrations per wet weight (microgram g-1) in the three pinnipeds ranged from 0.04 to 0.55 for northern fur seals, from 0.1 to 1.04 for Steller sea lions and from 0.03 to 0.83 for harbor seals. Silver concentrations in liver for all pinnipeds were significantly correlated with mercury, and selenium (P < 0.001). Molar ratios between silver to selenium approximated 1:180 in northern fur seals, 1:120 in Steller sea lions, and 1:60 in harbor seals. The silver-mercury molar ratios were approximately 1:170 in northern fur seals, and 1:80 both in the other species. Increase in silver accumulation in the liver was caused by the retention in nuclei and mitochondria fraction together with mercury and selenium in the cells of northern fur seals.     

The use of amino compounds for binding 2,4,6-trinitrotoluene in water

Sites polluted with 2,4,6-trinitrotoluene (TNT) constitute a worldwide problem. In this work, chemical reactions for binding TNT to amino-compounds are proposed as an initial step for developing new remediation techniques to clean-up groundwater and soils contaminated with TNT. Indeed, addition of aniline and an amino acid-like cysteine caused a decrease in free TNT of 86% and 68-100%, respectively. Using 13C-NMR spectroscopy, it was shown that TNT chemically forms a Meisenheimer complex with cysteine and aniline in 1/1 (by vol.) H2O/d6-acetone.     

Oxidation of triphenylarsine to triphenylarsineoxide by Trichoderma harzianum and other fungi

Arsenic resistant strains of bacteria and fungi were isolated from soil contaminated by chemical warfare agents. Until now, no metabolic products of microbial attack against the phenyl residues of the model substrate triphenylarsine (TP) were found if it was incubated together with these strains in liquid culture assays. However, one of the isolated fungi, Trichoderma harzianum As 11, was found to oxidize TP to triphenylarsineoxide (TPO). The yeast Trichosporon mucoides SBUG 801 and the white-rot fungus Phanerochaete chrysosporium were also able to oxidize the As(III) in TP. In addition, P. chrysosporium transformed phenylarsineoxide (PAO) to phenylarsonic acid (PAA) under O2-atmosphere. By means of a respirometer system, the oxidation of TP by T. harzianum As 11 was confirmed by a significantly higher consumption of oxygen in the presence of these compounds. HPLC analysis of the oxidation products TPO and PAA in the medium of the assays provided evidence for the transfer reaction of As(III) to As(V) in organic bonds. The oxidation products TPO and PAA are more hydrophilic than TP and PAO. Therefore, it was concluded that particular fungi contribute to the mobilization of arsenic in soil contaminated by chemical warfare agents.