Environmentally significant photochemistry of chlorinated benzenes and their derivatives in aquatic systems†

The pollution of soil and aquatic environments by chlorinated aromatic pollutants (CAPs) such as polychlorobenzenes (PCBzs), polychlorophenols (PCPs), polychloro‐diphenyl ethers (PCDPEs), phenoxyacetic acids, etc., creates growing public anxiety. Phototransformation is an important process for pollutants in aquatic systems. This article extensively reviews the environmentally significant solution phase photochemistry of PCBzs as well as other CAPs derived therefrom. The paper includes photochemical fate of these CAPs at wavelengths >285 nm on the one hand and their photolysis in solution in aquatic systems on the other. In this article, photolytic reductive dechlorination and isomerization of PCBzs are reviewed together with the photoformation of several products including polychlorobiphenyls (PCBs) from PCBzs. Recently developed phenomena of photoincorporation of PCBzs into humic model monomers is also described. This review also describes the environmental photochemistry of chlorobenzene derivatives, namely, α‐substituted p‐chlorotoluenes of the general structure p‐ClC₆H₄CH₂‐X (X = H, Cl, CN, COOH and OH), di‐through pentachlorophenols, PCDPEs (having Cl_1–5 contents) with and without o‐OH substituents, and 2,4‐di‐ and 2,4,5‐trichlorophenoxyacetic acid (2,4‐D and 2,4,5‐T, respectively) as well as their esters and some formulations.     

Occupational exposure to airborne aromatic amines in rubber manufacturing: Determination by gas chromatography‐mass spectrometry

Aromatic amines (AAs) are used in a variety of chemical industries and consequently they are the object of great attention in occupational hygiene owing to the carcinogenic effects that many of them have shown. This work outlines a procedure for the determination of occupational exposure to airborne AAs in the rubber industry and the application of this method in a tyre manufacturing plant using p‐phenylenediamines as antiozonants. Samples were collected on a glass fibre filter followed by a silica gel tube and analyzed by GC‐MS/SIM using a capillary column coated with methyl silicone. p‐Phenylendiamines and other AAs probably formed as thermodegradation products were found in concentrations of up to 10 μg/m³ during rubber vulcanization.     

A chemical mechanism for dry deposition—the role of biogenic hydrocarbon (Terpene) emissions in the dry deposition of O3, SO2 and NOx in forest areas

Terpenes react quite rapidly with ambient ozone and lead via ozonides to highly oxidizing radicals and consecutive products forming aerosols. In the presence of SO₂ sulphur containing compounds, mainly as sulphate, are formed. By means of gas chromatography/mass spectrometry and by comparison with known spectra the main products of the reaction of ß‐pinene (as a model compound) with ozone and sulphur dioxide could be identified.

Reaction of terpenes with NO₃‐radicals, which build up in the atmosphere at night‐time, leads to the formation of organic nitrates that form aerosols. The kinetics as well as the products of the reaction between NO₃‐radicals and ß‐pinene have been studied by FTIR and MS.     

Using Coral Disease Prevalence to Assess the Effects of Concentrating Tourism Activities on Offshore Reefs in a Tropical Marine Park

Abstract: Concentrating tourism activities can be an effective way to closely manage high‐use parks and minimize the extent of the effects of visitors on plants and animals, although considerable investment in permanent tourism facilities may be required. On coral reefs, a variety of human‐related disturbances have been associated with elevated levels of coral disease, but the effects of reef‐based tourist facilities (e.g., permanent offshore visitor platforms) on coral health have not been assessed. In partnership with reef managers and the tourism industry, we tested the effectiveness of concentrating tourism activities as a strategy for managing tourism on coral reefs. We compared prevalence of brown band disease, white syndromes, black band disease, skeletal eroding band, and growth anomalies among reefs with and without permanent tourism platforms within the Great Barrier Reef Marine Park. Coral diseases were 15 times more prevalent at reefs with offshore tourism platforms than at nearby reefs without platforms. The maximum prevalence and maximum number of cases of each disease type were recorded at reefs with permanently moored tourism platforms. Diseases affected 10 coral genera from 7 families at reefs with platforms and 4 coral genera from 3 families at reefs without platforms. The greatest number of disease cases occurred within the spatially dominant acroporid corals, which exhibited 18‐fold greater disease prevalence at reefs with platforms than at reefs without platforms. Neither the percent cover of acroporids nor overall coral cover differed significantly between reefs with and without platforms, which suggests that neither factor was responsible for the elevated levels of disease. Identifying how tourism activities and platforms facilitate coral disease in marine parks will help ensure ongoing conservation of coral assemblages and tourism.     

Trace analysis of airborne toluene diisocyanate as a pentafluorobenzyl derivative by gas chromatography with electron capture detection

Trace analysis of airborne toluene diisocyanate (TDI) vapor was accomplished by measuring the derivative using gas chromatography with electron‐capture detector after collecting gas samples with a microimpinger containing 2 ml toluene, 1 μl pentafluorobenzyl alcohol, and 1 μl triethylamine. The sampling efficiency was determined to be 99.4% for short‐term exposure level of TDI and the 2,4‐ and 2,6‐isomers of TDI were well separated. The derivative was identified to be a new compound with a molecular weight of 570 by mass spectrometry in fast atomic bombardment mode and nuclear magnetic resonance spectrometry. This method is convenient and can be applied in the field where airborne TDI is in vapor form.     

Dissipation and effect of chlorophenoxy herbicide on plant pigments and carbohydrates of sunflower (Helianthus annuus L.)

The dissipation pattern of the chlorophenoxy herbicides (2,4‐D and 2,4,5‐T) residues in sunflower plants (Helianthus annuus L.) has been studied along with its effect on the changes of plant pigments (chlorophyll‐a,b, total chlorophyll, carotene and anthocyanin), sugar and starch in different parts of the plant. The residues of 2,4‐D and 2,4,5‐T remained for larger period of time (10 days) at higher concentrations than the lower concentration. The concentrations of chlorophylls and carotene were found to be reduced with the application of both 2,4‐D and 2,4,5‐T. But the chlorophyll concentrations were slowly normalized accompanied with the reduction of the herbicide residues. For anthocyanin, there was no significant effect. In case of carbohydrate, the sugar concentration was found to be raised by all doses in leaf and stem. The change in starch content in different plant parts did not follow an uniform pattern at different doses of herbicides.     

Chromosome damage in individuals exposed to heavy metals†

Testing the mutagenic activity of environmental pollutants has become an important area of modern environmental science and prophylactic medicine. The most suitable method for short‐term mutagenicity testing on man, at present, are chromosome studies on somatic cells of exposed individuals. Mutation types analyzed by such studies are of high practical relevance as indicator system of genetic damage induced in man under in vivo conditions. A rather large series of such studies has been dedicated to the action of heavy metals on individuals contacted with these metals under therapeutic, ecological or occupational conditions or by intoxication. Lead, cadmium, chromium, nickel, mercury, zinc and other metals as well as their compounds have been under study. Analyses of that kind, of course, are hampered by difficulties with the distinct estimation of the actual load as well as unclear conditions of exposition, e.g. simultaneous exposition to different metals.

Results obtained till now arouse some suspicion of a direct or indirect mutagenic activity in man by certain chromium and platinum compounds, arsenic, mercury, and combinations of lead with other heavy metals (cadmium, zinc, arsenic, antimony, etc.). Life style, above all smoking habits, well may act comutagenic. In most cases, however, mutagenic activity of metals and metal compounds apparently is clearly superposed by their toxic activity. In specific cases, chromosome studies also may contribute to discover sources of ecological exposition and to monitor occupational load by heavy metals.     

Synthesis of 2,5‐diaryl‐2,4‐pentadienenitriles and their spectral,fluorescence and mutagenic properties

The condensation of substituted cinnamaldehydes and arylacetonitriles using sodium ethoxide in ethanol at room temperature afforded 2,5‐diaryl‐2,4‐pentadienenitriles in good yield. The structure of the reaction products was established on the basis of their infrared, nuclear magnetic resonance and elemental analysis data. Two representative compounds were studied for their mutagenic activity. One of them showed a weak mutagenicity while the second showed a high mutagenic activity in TA97a Salmonella strain. Both were negative in TA100. Some of these pentadienenitriles showed fluorescence in solutions.     

Photodegradation of pesticides .1. Photolysis rates and half‐life of acylanilides and their major metabolites in water

The photolysis in water solution of three fungicides (Metalaxyl, Benalaxyl, and Furalaxyl) was studied under artificial light. At λ = 254 Benalaxyl and Furalaxyl underwent fast degradation with rearrangement reactions less complex than those of Metalaxyl. Under A = 254–290 the photolysis was very fast and Benalaxyl and Furalaxyl show a common behaviour. This was found to be a kinetic consecutive process leading, at first, to N‐2,6‐xylyl‐D,L‐alaninate (II), which was degraded to 2,6‐dimethylaniline (IV). This amine gives unknown products. Metalaxyl underwent a parallel/consecutive photodegradtion to give (II) and N‐(methoxyacetyl)‐2,6‐dimethylaniline (VI). While (II) was easily converted to (IV) as earlier, (VI) was more stable to photolysis. Under λ > 290 all the fungicides shown very slow degradation with pseudo first order rate constants. The photoproducts were degraded faster than the parent compounds by factors from 13 to 1800. The presence of photosensitizer in water (humic acids or acetone) resulted in total decomposition of fungicides and of their photoproducts.     

Negative Effects of Habitat Loss on Survival of Migrant Warblers in a Forest Mosaic

Abstract: Habitat loss and fragmentation in forested landscapes often negatively affect animal abundance; however, whether these factors also affect fitness is not well known. We hypothesized that observed decreases in bird occurrence and abundance in landscapes with harvested forests are associated with reduced apparent survival of adults. We defined apparent survival as an estimate of survival that accounts for an imperfect resighting probability, but not permanent emigration (i.e., dispersal). We examined the association between spatially extensive habitat loss and apparent survival of males of 2 Neotropical migrant species, Blackburnian Warbler (Dendroica fusca) and Black‐Throated Green Warbler (D. virens), over 7 years in the Greater Fundy Ecosystem, New Brunswick, Canada. We estimated apparent survival among and within breeding seasons. We quantified amount of habitat in the context of individual species. In this landscape, boundaries between land‐cover types are gradual rather than clearly identifiable and abrupt. Estimated apparent within‐season survival of both species decreased as a function of amount of habitat within a 2000‐m radius; survival was approximately 12 times (95% CI 3.43–14) greater in landscapes with 85% habitat than in landscapes with 10% habitat. Apparent annual survival also decreased as a function of amount of habitat within a 100‐m radius. Over the range of habitat amount, apparent annual survival decreased 15% (95% CI 7–29%) as the amount of habitat decreased. Our results suggest that reduced species occurrence in landscapes with low proportions of habitat is due partly to lower apparent survival at these sites. This mechanism operates both directly (i.e., via effects on mortality or dispersal during breeding) and possibly through indirect effects during the nonbreeding season. Habitat loss was associated not only with a lower number of individuals, but also with lower survival of those individuals.     

Glutathione S-transferase in the branchiopod<Emphasis Type="Italic"> Artemia salina</Emphasis>

The glutathione S-transferase enzyme system, which belongs in phase II of detoxification, has been studied in developmental stages of the branchiopod Artemia salina. The highest total activity and specific activity towards 1-chloro-2,4-dinitrobenzene was observed 48 h after hatching. The number of isoenzymes present in A. salina varies between three and four, depending on the developmental stage. The two major isoenzymes, with corresponding isoelectric points of 8.5 and 7.2, were present in all developmental stages, but at a varying rate: as the organism grew older, the alkaline isoenzyme was expressed at a higher rate. The kinetic and molecular characteristics of the enzyme were similar to those of other aquatic organisms. With regards to the kinetic characteristics, significant differences were observed between the two major isoenzymes, and, since the rate of their expression changes as the organism grows, the detoxification potential of the organism varies according to developmental stage.Communicated by O. Kinne, Oldendorf/Luhe     

Effects of herbicides on Odonata communities in a rice agroecosystem

The effects of the five herbicides propanil, quinclorac, molinate/propanil, 2,4-D amine, and bensulfuron on Odonata diversity and abundance at the experimental rice plots was investigated. A total of 13 Odonata morphospecies belonging to two families have been identified. Treated plots exhibited higher species richness (up to 12 species) than the control plot (8 species). Ishnura spp. was the most abundant species in the treated plots with a mean density of 194.2 individuals per m², (ind m^?2) followed by Brachythemis contaminata (152 ind m^?2) and Agriocnemis spp. (124 ind m^?2). In the control plots, Agrocnemis spp. was the dominant species (153 ind m^?2) followed by Ishnura spp. (143 ind m^?2) and Neurothemis fluctuans (59 ind m^?2). In the propanil-treated plot, the highest number of odonate species (10 species) was recorded followed by the plots treated with quinclorax and molinate/propanil (9 species). On the 2,4-D amine or bensulfuron-treated plots as well as the control plot, only eight odonate species were recorded. This study revealed that herbicide application had a positive effect on Odonata diversity. This seems reasonable as Odonata are non-target organisms for herbicides. Furthermore, the decomposed weeds resulting from herbicide application would enrich the water with necessary organic matter.     

Acute nitrate poisoning in two cattle

Abstract

The rate and product composition during photooxidation of aromatic hydrocarbons (toluene, o‐, m‐, p‐xylene and cumene) dissolved in n‐hexane and spread as a liquid film on water is reported. The photo degradability of these chemicals is 10–20%. The products identified are oxygenated aromatic compounds. It is observed that the absorption bands of the compounds under investigation depend upon the partial pressure of dissolved oxygen and these bands extend up to 290 nm. The new absorption band around 290 nm is probably due to broadening of ¹L_b bands which is responsible for direct photolysis.

stream. We have been especially interested in investigating the rate of disappearance and distribution of main oxidation products in two phases. Besides that an attempt has been made to throw some light on the reaction mechanism.     

Impact of a Community‐Based Payment for Environmental Services Intervention on Forest Use in Menabe,Madagascar

Abstract: Despite the growing interest in conservation approaches that include payments for environmental services (PES), few evaluations of the influence of such interventions on behaviors of individuals have been conducted. We used self‐reported changes in six legal and illegal forest‐use behaviors to investigate the way in which a PES for biodiversity conservation intervention in Menabe, Madagascar, influenced behavior. Individuals (n =864) from eight intervention communities and five control communities answered questions on their forest‐use behaviors before and after the intervention began, as well as on their reasons for changing and their attitudes to various institutions. The payments had little impact on individuals’ reported decisions to change behaviors, but it had a strong impact on individuals’ attitudes. Payments appeared to legitimize monitoring of behaviors by the implementing nongovernmental organization (NGO), but did not act as a behavioral driver in their own right. Although there were no clear differences between changes in behaviors in the intervention and control communities, the intervention did influence motivations for change. Fear of local forest associations and the implementing NGO were strong motivators for changing behavior in communities with the PES intervention, whereas fear of the national government was the main reason given for change in control communities. Behavioral changes were most stable where fear of local organizations motivated the change. Our results highlight the interactions between different incentives people face when making behavioral decisions and the importance of considering the full range of incentives when designing community‐based PES interventions.     

Chlorophenol tolerant and degradative bacteria isolated from a river receiving pulp mill discharges

A screening was carried out in a river receiving pulp mill discharges (BioBio river, central Chile) to study the bacterial population able to tolerate and degrade chlorophenols. In four selected stations and at different seasons, water samples were taken from the river. Total bacterial population and the number of chlorophenol tolerant bacteria were counted. Bacterial tolerance to 25, 50, 100, 200 and 400 μg/ml of 2,4‐dichlorophenol (DCP), 2,4,6‐trichlorophenol (TCP) and pentachlorophenol (PCP) was determined. Strains able to tolerate at least 400 μg/ml chlorophenols were found. Eighteen bacterial strains able to use chlorophenols as the sole carbon source were isolated: five of them were Pseudomonas fluorescens, two Alcaligenes sp., one Citrobacter freundii, one Aeromonas sp. and nine unidentified Gram negative bacilli. A good correlation (r ² = 0.758) between the logarithm of DCP tolerant bacteria and the content of adsorbable organic halogen (AOX) at low dilution in the river water was established. Four groups of tolerant bacteria were found: growing on PCP and DCP, growing on PCP and TCP, growing only on PCP and growing only on TCP.     

Microbiological degradation of polycyclic aromatic hydrocarbons: Anthracene,benzo(K)fluoranthene,dibenzothiophene, benzo(H) quinoline and 2‐nitronaphthalene

Biodegradation experiments of various polycyclic aromatic hydrocarbons were studied with mixed bacteria culture under aerobic conditions. An easy‐to‐handle clean‐up procedure was developed for PAH and their metabolites simultaneously as well as a gc‐ms‐method to identify and quantify these compounds.

Anthracene and dibenzothiophene are completely degradable in an aqeous system, whereas biodegradation of benzo(k)fluoranthene and benzo(h)quinoline is possible only in an oil‐in‐water‐system with dodecane as cosubstrate. No degradation of nitronaphthalene was observed in aqueous systems. New metabolites are 2,3‐dihydroxybenzothiophene, hydroxybenzothiophenecarbonic acid and benzothiophenequinone for dibenzothiophene and hydroxyfluoranthenic acid for benzo(k)flouranthene. Whereas the former metabolites are degradable under the experimental conditions, the latter accumulates during the degradation experiment.

The results are important for microbiological wastewater treatment, since knowledge of biodegradation processes is indespensable for the successful treatment of PAH‐containing wastewater.     

Photolytic decomposition of uc‐54229, a Proinsecticide of the Carbamate group

Phototransformation of UC‐54229 (1) [2,3‐dihydro‐2,2‐dimethyl‐7‐benzofuranyl‐N‐(trimethylamino acetyl)‐N‐methyl carbamate chloride] was studied under UV and visible light conditions. Photoirradiation of 1 with UV‐light resulted in the formation of five degradation products which on the basis of their mass and ¹H Nmr spectral analysis were characterised as 2, 3, 4, 5 and 6. It was observed that under the influence of light, UC‐54229 was degraded to acetyl‐carbofuran which under similar conditions underwent further transformation to the actual toxicant carbofuran. The degradation products or impurities present in 100% water soluble powder formulation were identified as carbofuran phenol and triethylamine hydrochloride.     

Evidences showing 2,4-D ethyl ester and pencycuron-induced DNA damage in cyanobacteria and detection by PCR

The impact of 2,4-D ethyl ester and pencycuron in inducing DNA damage in three species of cyanobacteria-Anabaena fertilissima, Aulosira fertilissima, and Westiellopsis prolifica as evidenced by PCR-based assays: RAPD and 16S rRNA amplification was examined. Exposure of genomic DNA (in vitro) to pencycuron for 4 days did not produce severe damage in DNA fragments of all three cyanobacterial species whereas exposure to 2,4-D ethyl ester markedly inhibited the template activity of genomic DNA compared to untreated cultures of A. fertilissima. In A. fertilissima a single band of approximately 1000?bp was observed even after 16 days of exposure to 60?ppm pencycuron which suggests that certain segments of DNA are resistant to pencycuron DNA damaging effects. However, a significant effect was observed in the case of W. prolifica for 2,4-D ethyl ester and pencycuron where complete disappearance of fragments was not recorded even after 16 days of incubation and interestingly some new DNA bands were induced. Similar to the effects with RAPD profile, amplification of rRNA was significantly inhibited following exposure of genomic DNA to 2,4-D ethyl ester and pencycuron. Our findings clearly demonstrate that pesticide concentrations affected cyanobacterial DNA and lethality of these microbes might be due to irreversible DNA damage. Thus, it is postulated that PCR assays may be conveniently used for screening DNA damage produced by 2,4-D ethyl ester and pencycuron in all three cyanobacteria examined in this study.     

Functional nonredundancy of elephants in a disturbed tropical forest

Conservation efforts are often motivated by the threat of global extinction. Yet if conservationists had more information suggesting that extirpation of individual species could lead to undesirable ecological effects, they might more frequently attempt to protect or restore such species across their ranges even if they were not globally endangered. Scientists have seldom measured or quantitatively predicted the functional consequences of species loss, even for large, extinction‐prone species that theory suggests should be functionally unique. We measured the contribution of Asian elephants (Elephas maximus) to the dispersal of 3 large‐fruited species in a disturbed tropical moist forest and predicted the extent to which alternative dispersers could compensate for elephants in their absence. We created an empirical probability model with data on frugivory and seed dispersal from Buxa Tiger Reserve, India. These data were used to estimate the proportion of seeds consumed by elephants and other frugivores that survive handling and density‐dependent processes (Janzen‐Connell effects and conspecific intradung competition) and germinate. Without compensation, the number of seeds dispersed and surviving density‐dependent effects decreased 26% (Artocarpus chaplasha), 42% (Careya arborea), and 72% (Dillenia indica) when elephants were absent from the ecosystem. Compensatory fruit removal by other animals substantially ameliorated these losses. For instance, reductions in successful dispersal of D. indica were as low as 23% when gaur (Bos gaurus) persisted, but median dispersal distance still declined from 30% (C. arborea) to 90% (A. chaplasha) without elephants. Our results support the theory that the largest animal species in an ecosystem have nonredundant ecological functionality and that their extirpation is likely to lead to the deterioration of ecosystem processes such as seed dispersal. This effect is likely accentuated by the overall defaunation of many tropical systems.     

Contrasts in Livelihoods and Protein Intake between Commercial and Subsistence Bushmeat Hunters in Two Villages on Bioko Island,Equatorial Guinea

Across West and Central Africa, wildlife provides a source of food and income. We investigated the relation between bushmeat hunting and household wealth and protein consumption in 2 rural communities in Bioko Island, Equatorial Guinea. One village was dedicated to commercial hunting, the other trapped game primarily for food. We tested whether commercial‐hunter households were nutritionally advantaged over subsistence‐hunter households due to their higher income from the bushmeat trade and greater access to wild‐animal protein. We conducted bushmeat‐offtake surveys in both villages (captures by hunters and carcasses arriving to each village). Mammals (including threatened primates: black colobus [Colobus satanas], Preussi's guenon [Allochrocebus preussi], and russet‐eared guenon [Cercopithecus erythrotis]), birds, and reptiles were hunted. The blue duiker (Philantomba monticola), giant pouched rat (Cricetomys emini), and brush‐tailed porcupine (Atherurus africanus) contributed almost all the animal biomass hunted, consumed, or sold in both villages. Monkeys and Ogilbyi's duikers (Cephalophus ogilbyi) were hunted only by commercial hunters. Commercial hunters generated a mean of US$2000/year from bushmeat sales. Households with commercial hunters were on average wealthier, generated more income, spent more money on nonessential goods, and bought more products they did not grow. By contrast, households with subsistence hunters spent less on market items, spent more on essential products, and grew more of their own food. Despite these differences, average consumption of vegetable protein and domestic meat and bushmeat protein did not differ between villages. Our results highlight the importance of understanding the socioeconomic and nutritional context of commercial and subsistence bushmeat hunting to correctly interpret ways of reducing their effects on threatened species and to enable the sustainable offtake of more productive taxa. Contrastes en el Sustento y la Ingesta de Proteínas entre Carne de Caza de Subsistencia y Comercial en Dos Aldeas en Isla Bioko, Guinea Ecuatorial