Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia Usneoides (L.) in an industrialized area in Rio de Janeiro state, south east Brazil--Part I: PCDD and PCDF

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic Bromeliad species as biomonitor and measuring total deposition rates on funnels covered with polyurethane foams. Samples were collected during 78 days in V.R. and 95 days in PNI in winter (dry season, June-August 2003) and during 114 days in both areas in summer (rainy season, December 2003-February 2004). The PCDD/PCDF deposition rates ranged from 0.10 to 1.9 pg WHO-TEQ/(m2 day) in winter and from 0.11 to 2.2 pg WHO-TEQ/(m2 day) in summer. Deposition rates found in V.R. in summer were four- to ninefold higher than those measured in PNI, while in winter deposition rates in both regions were in the same range. Deposition rates in V.R. in summer were about five fold lower than those measured in 1996. PCDD/PCDF levels in biomonitor samples were between 0.95 and 14.6 ng WHO-TEQ/kg d.m. in winter and between 2.2 and 5.2 ng WHO-TEQ/kg d.m. in summer. In winter, concentrations found in V.R. were up to 11 times higher than those found in PNI, while in summer the levels measured in both areas were comparable. The homologue and isomer profiles found in the deposition as well as in the biomonitor samples from V.R. indicate that steel production is the main source of contamination in the region, whereas in PNI, the long range transport of these pollutants is the predominant contamination pathway.     

Effect of nitrogenous air pollutants on changes in protein spectra with the onset of winter in the leaves and shoots of the bilberry (Vaccinium myrtillus L.)

Electrophoretic profiles of 0.1 m Tris-HCl (pH 9.0)-soluble proteins in the leaves and stems of the bilberry (Vaccinium myrtillus L.) were investigated in the latter part of the growing season (July-October), in a highly-polluted industrial area with serious forest damage (main emissions NO(2), SO(2), NH(3), urea and fertilizer dust) in Oulu, northern Finland, and in an unpolluted control forest with the same climatic and edaphic conditions. About ten protein components in the leaves and seven in the stems increased in concentration in SDS-PAGE towards the autumn, while one to four other components decreased in concentration. The pollutants in the industrial area caused a considerable decrease in the concentrations of soluble proteins, particularly in the leaves in August and September. A decrease was obtained in six components in the leaves and three components in the stems, while increases were observed in one component in the leaves (10 kDa) and four components in the stems (10, 43, 50 and 65 kDa). One reason for the lowered cold-resistance in the bilberry caused by air pollutants could thus be the lowered concentrations of certain soluble cytoplasmic proteins that protect the plant against winter conditions.     

Spatial and temporal variations of mercury levels in Okefenokee invertebrates: southeast Georgia

Accumulation of mercury in wetland ecosystems has raised concerns about impacts on wetland food webs. This study measured concentrations of mercury in invertebrates of the Okefenokee Swamp in Georgia, focusing on levels in amphipods, odonates, and crayfish. We collected and analyzed total mercury levels in these invertebrates from 32 sampling stations across commonly occurring sub-habitats. Sampling was conducted in December, May, and August over a two-year period. The highest levels of mercury were detected in amphipods, with total mercury levels often in excess of 20 ppm. Bioaccumulation pathways of mercury in invertebrates of the Okefenokee are probably complex; despite being larger and higher in the food chain, levels in odonates and crayfish were much lower than in amphipods. Mercury levels in invertebrates varied temporally with the highest levels detected in May. There was a lack of spatial variation in mercury levels which is consistent with aerial deposition of mercury.     

Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia usneoides (L.) in an industrialized area in Rio de Janeiro state, southeast Brazil--Part II: PCB and PAH

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic bromeliad species as biomonitor and measuring bulk deposition rates of polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH). For the sum of PCB, overall deposition rates were between 17 and 314 ng/(m2 day) in winter and between 43 and 81 ng/(m2 day) in summer, respectively. Deposition rates of dioxin-like PCBs ranged from 0.14 to 2.8 pg WHO-TEQ/(m2 day) in winter and from 0.90 to 4.3 pg WHO-TEQ/(m2 day) in summer. PCB deposition rates (total PCB and WHO-TEQ) were in the same range in winter in V.R. and PNI. In summer, contamination levels in V.R. were 6-10-folds higher than in PNI. PCB concentrations in biomonitor samples from V.R. and PNI were in the same range in summer and in winter. Concentrations of total PCB ranged from 14 to 95 microg/kg dry matter (d.m.) in winter and from 18 to 27 microg/kg d.m. in summer, respectively. The TEQ values were between 1.7 and 4.1 ng WHO-TEQ/kg d.m. in winter and between 1.9 and 2.9 ng WHO-TEQ/kg d.m. in summer. PCB concentrations of di-ortho PCB but not of non-ortho PCB were a factor of 2-4 lower in summer in both areas. PCB congener profiles resembled those from technical formulations. The profiles shifted to the higher chlorinated congeners in summer, probable due to revolatilisation of the lighter components at higher temperatures. PCB profiles in biomonitor resembled those from deposition samples and the shift to the heavier congeners in summer was even more pronounced. PAH deposition rates were in a similar range in both areas (131-2415 ng/(m2 day)). PAH levels in biomonitor samples from V.R. were about one order of magnitude higher than in samples from PNI indicating the impact of local sources. PAH profiles revealed stationary thermal processes as main source of contamination in V.R. whereas in PNI, biomass burning seems to be the main contamination source.     

A modified in-vitro method to assess bioavailable arsenic in pesticide-applied soils

An incubation study was designed to modify the existing in vitro methods to increase the accuracy in estimation of bioavailable arsenic in pesticide-applied soils. In addition to simulating arsenic dissolution in gastric and intestinal solutions, absorbtion by the intestinal membrane was also mimicked using iron-oxide coated filter paper strips inserted in nylon bags. The in vitro experiments were sequentially performed in two phases, namely, the stomach phase and the absorbed-intestinal phase. Arsenic extraction in the in vitro absorbed intestinal phase increased, thereby making it more comparable to the potential in vivo arsenic pool. While animal studies are needed to verify the in vitro results, preliminary data indicate that this modified method may be able to improve site-specific bioavailability predictions in arsenic-contaminated soils.     

An integrated assessment of estrogenic contamination and biological effects in the aquatic environment of The Netherlands

An extensive study was carried out in the Netherlands on the occurrence of a number of estrogenic compounds in surface water, sediment, biota, wastewater, rainwater and on the associated effects in fish. Compounds investigated included natural and synthetic hormones, phthalates, alkylphenol(ethoxylate)s and bisphenol-A. The results showed that almost all selected (xeno-)estrogens were present at low concentrations in the aquatic environment. Locally, they were found at higher levels. Hormones and nonylphenol(ethoxylate)s were present in concentrations that are reportedly high enough to cause estrogenic effects in fish. Field surveys did not disclose significant estrogenic effects in male flounder (Platichthys flesus) in the open sea and in Dutch estuaries. Minor to moderate estrogenic effects were observed in bream (Abramis brama) in major inland surface waters such as lowland rivers and a harbor area. The prevalence of feminizing effects in male fish is largest in small regional surface waters that are strongly influenced by sources of potential hormone-disrupting compounds. High concentrations of plasma vitellogenin and an increased prevalence of ovotestes occurred in wild male bream in a small river receiving a considerable load of effluent from a large sewage treatment plant. After employing in vitro and in vivo bioassays, both in situ and in the laboratory, we conclude that in this case hormones (especially 17 alpha-ethynylestradiol) and possibly also nonylphenol(ethoxylate)s are primarily responsible for these effects.     

Assessing the effect of climate oscillations and land-use changes on streamflow in the central Spanish Pyrenees

Plans to increase the amount of irrigated land in Mediterranean countries should consider how changes in climate and land-use affect water resources. In this study, both precipitation and temperature were used to analyze regional trends in discharge in the basins of the Central Spanish Pyrenees since the mid-20th century. Annual variations in the relationship between precipitation and discharge suggested that discharge was relatively lower in the second half of the study period, coinciding with major changes in land use. On a monthly scale, precipitation increased significantly in October, April, and July, and decreased in March, and temperature increased in January and February and decreased in April. Nevertheless, discharge has decreased significantly in most months in the past 50 years. Land-use and plant-cover changes are the only nonclimatic factor that can explain the loss of around 30% of the average annual discharge.     

酸化模型在国内的发展与应用进展

酸沉降与环境的酸化模型在国外已有较大进展,在我国尚属起步阶段。本文系统介绍了国内在酸化模型方面研究进展。这方面成果主要是适合于大尺度区域评估的指标评价模型的建立和将国外成熟的酸化模型应用于中国具体实践。希望尽快建立我国的酸化水化学研究体系。     

三垟湿地沉积物-间隙水-上覆水界面磷形态研究

沉积物与上覆水间营养物质交换,成为导致水体发生富营养化的首要化学变迁过程.分别在三垟湿地的柑橘林(S1)、景观用地(S2)和生活用地(S3)取样,研究了沉积物-间隙水-上覆水界面磷形态以及相互关系.结果表明:(1)沉积物TP增加时,间隙水PO3-4和可溶性总磷(TDP)也增加.要削减磷在上覆水中的含量,控制间隙水PO3-4或TDP是一良策.(2)随着沉积物铁磷、铝磷的增加,间隙水PO3-4也增加.在三垟湿地沉积物中,铁磷和铝磷含量都可作为间隙水PO34-含量的指示.(3)S1、S2和S3的沉积物活性磷、间隙水TDP和上覆水TDP存在明显的浓度梯度,沉积物活性磷＞间隙水TDP＞上覆水TDP.说明在三垟湿地中,沉积物活性磷是磷释放的关键因子,而沉积物-间隙水界面则是磷释放的关键界面.     

Comparison of particulate mass, chemical species for urban, suburban and rural areas in central Taiwan, Taichung

Aerosol samples for PM2.5, PM(2.5-10) and TSP were collected from June to September 1998 and from February to March 1999 in central Taiwan. Ion chromatography was used to analyze the acidic anions: sulfate, nitrate and chloride in the Universal samples. The ratios of fine particle concentrations to coarse particle concentrations displayed that the fine particle concentrations are almost greater than that of coarse particle concentrations in Taichung area. The average concentrations of PM2.5, PM(2.5-10) and TSP in urban sites are higher than in suburban and rural sites at both daytime and night-time. Chloride dominated in the coarse mode in daytime and in fine mode in night-time. Nitrate can be found in both the coarse and fine modes. Sulfate dominated in fine mode in both daytime and night-time.     

Warming and drought change trace element bioaccumulation patterns in a Mediterranean shrubland

A field experiment consisting of drought and warming manipulation was conducted in a Mediterranean shrubland dominated by the shrubs Erica multiflora and Globularia alypum. The aim was to investigate the effects of the climatic changes predicted by IPCC models for the coming decades on trace element concentration and accumulation in aboveground biomass, plant litter, and soil. Warming increased concentrations and aboveground accumulation of some trace elements related to plant root uptake, such as Al, As, Cr, Cu, and partially Pb. This effect was more general in E. multiflora than in G. alypum. The stronger effects were increases in Al leaf concentrations (42%) and aboveground accumulation (500gha(-1)) in E. multiflora, in As stem biomass accumulation (0.2gha(-1)) in E. multiflora, and in Cr leaf concentrations (51%) in G. alypum and stem aboveground accumulation in E. multiflora (1.1gha(-1)). These species-specific increases were related to greater retranslocation, photosynthetic capacity and growth in E. multiflora than in G. alypum. Warming decreased the concentrations of some trace elements in leaf litter, implying the existence of an increased leaf retranslocation. Drought increased As (40%) and Cd (55%) in E. multiflora stems, whereas it decreased Cu (50%) in leaves, Ni (28%) in stems and Pb (32%) in leaf litter of G. alypum. The increasing concentrations of some trace elements in E. multiflora and not in G. alypum were related to a greater growth reduction in E. multiflora than in G. alypum. Warming increased As soil solubility (67%) and decreased total soil As (21%). Those changes were related to a greater Fe mobilization in warming plot and to a greater plant capture. Drought increased Hg (350%) concentrations in soils but had no significant effects on trace element accumulation in aboveground biomass. The different response to warming and drought in the two dominant species implies uneven changes in the quality of the plant tissues that may have implications for herbivores. This may be specially important for the performance of the studied Mediterranean ecosystems under the warmer and drier conditions predicted by the next decades by the GCM and ecophysiological models.     

Dietary mercury exposure and bioaccumulation in amphibian larvae inhabiting Carolina bay wetlands

Inorganic mercury and methylmercury concentrations were measured both in guts and remaining carcasses of southern leopard frog (Rana sphenocephala) larvae from 10 Carolina bay wetlands in South Carolina, USA. Significant variation among bays in methylmercury and inorganic mercury concentrations existed both in guts and carcasses. There was a moderate negative correlation between dissolved organic carbon concentration in bays and mean inorganic mercury concentrations in guts. There was also a weak positive correlation between pH in bays and mean methylmercury concentrations in carcasses. The ratio of methylmercury to inorganic mercury decreased with increasing total mercury concentration in guts and in larvae, but the rate of decrease was highly variable among bays. Ratios of concentrations in carcasses to concentrations in guts were inversely related to gut concentration. Mercury concentrations in carcasses in some bays were within the range of concentrations at which adverse effects have been observed in laboratory studies of R. sphenocephala.     

Recent changes in levels of persistent organochlorines and mercury in eggs of seabirds from the Barents Sea

Eggs of ten seabird species were collected from six regions in North Norway, Svalbard and NW Russia in 1993, and were analyzed for organochlorines (OCs) and mercury. Significant declines in levels of PCBs, p,p'-DDE, HCB, beta-HCH, gamma-HCH and oxychlordane were documented in nearly half the data set since a similar study in 1983 in six of the seabird species breeding in North Norway. Only four of the 90 paired data sets increased significantly, and the remainder remained unchanged. There was very little change in mercury levels. The decline in OCs corresponds to similar declines found in Canada and the Baltic Sea, and to declines documented in marine fish in a Norwegian fjord. They can all be attributed to the reduction in use and spread of contaminants, both in Norway and internationally. No consistent regional differences in residue levels were found.     

Reproductive status, blood chemistry, gill histology and growth of perch (Perca fluviatilis) in three acidic lakes

Perch (Perca fluviatilis L.) were sampled soon after spawning in three small acidic lakes (pH 4.3-6.1, Al(lab) 5-106 microg litre(-1), Ca2+ 0.01-0.08 mmol litre(-1)) and in one circumneutral lake (pH 5.9-6.4, Al(lab) 4-12 microg litre(-1), Ca2+ 0.06-0.07 mmol litre(-1)) in southern Finland. Due to the delayed spawning of perch in the acidic lakes, sampling in those lakes was performed later than in the reference lake. In spite of that, the gonadosomatic index (GSI) of males in all the acidic lakes was significantly greater than in the reference lake. Of the two lakes with similar low water pH, the effects on reproduction were more prominent in the lake with higher water Al content. The plasma Ca2+ concentrations of females in the acidic lakes were significantly smaller than in the females of the reference lake. The low female:male plasma Ca2+ ratio (1.0-1.32) depicted delay of spawning. Stress in perch in acidic water was also seen in elevated blood haematocrit values, especially in females. On the other hand, a low plasma Cl- level, a common response to acidic water in salmonids, was not detected in perch in the most acidic lakes. The amount of Al accumulated in the gill epithelium was highest in the most acidified lake with high Al concentration, but was also pronounced in a lake with low pH and low Al concentration.     

Heavy metals in water, sediment and tissues of Leuciscus cephalus from a stream in southwestern Turkey

Concentrations of heavy metals (Cd, Cr, Cu, Pb and Zn) were measured in water, bottom sediment and tissues (muscle and gills) of Leuciscus cephalus from the Dipsiz stream in the Yatagan basin (southwestern Turkey), the site of a thermal power plant. Results for levels in water were compared with national and international water quality guidelines, as well as literature values were reported for streams and rivers. Comparisons were made of metal concentrations in water and sediment with those in the muscle and gills of L. cephalus caught from the Dipsiz stream. We found that there was metal accumulation in the gills compared to the muscle. Concentrations of Cd, Pb, Zn and Cr in the gills were higher than that in the muscle; however, Cu levels were higher in muscle than that in gills. Concentrations of heavy metals in L. cephalus muscle were below the legal limits for human consumption, although Cr, Pb and Zn levels in the gills were above the limits in the fish taken from the Dipsiz stream. On the other hand, no correlation was found between metal concentrations in water and sediment or between metal concentrations in water and muscle and gills of L. cephalus. A positive correlation was found between concentrations of Cu and Zn in the sediment and in fish tissue, whereas there was no relationship between other metal concentrations in the sediment and water, and muscle and gills of L. cephalus. As with water, Pb and Cd concentrations in particular were higher in sediment than that in background levels. The results show that the pollutants from the thermal power plant may be a source of these elements.     

Analysis of tree rings using inductively coupled plasma mass spectrometry to record fluctuations in a metal pollution episode

Analysis of Acer pseudoplatanus L. (sycamore) tree rings using ICP-MS was used to assess the impact of metal deposition on trees growing in the vicinity of a metal refinery at Prescot, north-west England compared to a reference site at Croxteth 6 km distant receiving minimal deposition. No difference in tree growth between sites was recorded. Large reductions in Cu and Cd deposition since the late 1970s was accompanied by a steep decline in Cd concentrations in the outer rings in trees close to the refinery. A similar reduction in Cu concentrations was less apparent due to a tendency for Cu to increase in the outer rings. Zinc and Ni were higher in xylem at Prescot compared to Croxteth. There was no trend in Zn concentrations at either site although Ni concentrations increased in trees close to the refinery after 1982. Manganese concentrations in xylem were much higher at Prescot; Mn levels declined until the late 1970s and then increased slightly in later years interspersed by large concentration peaks within individual years during the 1980s. There was little change in Mn concentrations in trees at Croxteth during this period. Calcium, Mg and Sr concentrations remained steady or declined slightly in rings formed since 1965 in trees at Croxteth. Concentrations of Ca, Mg and Sr were higher in rings formed prior to the mid 1970s in trees at Prescot, but declined steadily after this period, although peaks in concentrations of each element were recorded in individual years during the 1980s. Phosphorous concentrations in rings increased towards the cambium at Croxteth, although P levels decreased in rings formed after 1982 at Prescot. No difference in K concentrations between sites was recorded. Lead concentrations in xylem at both sites declined steadily in rings formed after 1970, although concentrations were higher at the reference site. Analysis of individual sycamore tree rings appears to record short-term changes in pollution episodes, with little lateral movement of elements occurring. It is suggested that changes in element concentrations in trees close to the refinery are a result of reduced metal deposition combined with increased soil acidity due to reduced buffering capacity of metal ions in rainfall.     

Different compensatory mechanisms in two metal-accumulating aquatic macrophytes exposed to acute cadmium stress in outdoor artificial lakes

Mechanisms underlying cadmium (Cd) detoxification were compared in two aquatic macrophytes commonly used in phytoremediation, namely Pistia stratiotes L. and Eichhornia crassipes (Mart.) Solms. To simulate Cd pollution in the open environment, plants growing in outdoor artificial lakes were exposed for 21d to either 25 or 100microM Cd, in two consecutive years. Toxicity symptoms were absent or mild in both species. Metal accumulation was much higher in the roots of P. stratiotes, whereas in E. crassipes a comparatively higher fraction was translocated to the leaves. In both species, Cd was neither included in phenolic polymers or Ca-oxalate crystals, nor altered the levels of Cd-complexing organic acids. Glutathione levels were constitutively remarkably higher and much more responsive to Cd exposure in P. stratiotes than in E. crassipes. Abundant phytochelatin synthesis occurred only in P. stratiotes, both in roots and in leaves. In E. crassipes, on the other side, the constitutive levels of some antioxidant enzymes and ascorbate were higher and more responsive to Cd than in P. stratiotes. Thus, in these two aquatic plants grown in the open, different detoxification mechanisms might come into play to counterbalance Cd acute stress.     

Chronic effects of mercuric chloride on the activities of some enzymes in certain tissues of the fresh water murrel, Channapunctatus

Alterations in the activities of some enzymes in the brain, gills, intestine, kidney, liver and muscles have been examined in the fresh water murrel, $\text{Channa}$$\text{punctatus}$, after exposure to a sublethal concentration of mercuric chloride (3 μg/1) for 15, 30 and 60 days. The results revealed that after 15 days of exposure amino acid oxidase activity was elevated in brain and liver and inhibited in intestine. The activity of xanthine oxidase was increased in gills, and inhibited in kidney. Thirty days exposure produced significant inhibition in the activities of malate dehydrogenase in liver, glutamate dehydrogenase in gills and brain, aminoacid oxidase in gills, and xanthine oxidase in liver and intestine. In contrast, glutamate dehydrogenase in intestine, kidney and liver and aminoacid oxidase in brain and liver were elevated. After 60 days of treatment, a decrease in the activity of glucose-6-phosphatase was recorded in gills, intestine, kidney and liver. Hexokinase activity in kidney and liver, and malate dehydrogenase in all the six tissues were inhibited. Glutamate dehydrogenase activity in intestine, kidney and liver remained higher than in control fish. In brain, kidney and liver the activity of aminoacid oxidase was elevated, but in gills the enzyme activity decreased. Xanthine oxidase activity was inhibited in intestine and liver.     

Metal accumulation in earthworms inhabiting floodplain soils

The main factors contributing to variation in metal concentrations in earthworms inhabiting floodplain soils were investigated in three floodplains differing in inundation frequency and vegetation type. Metal concentrations in epigeic earthworms showed larger seasonal variations than endogeic earthworms. Variation in internal levels between sampling intervals were largest in earthworms from floodplain sites frequently inundated. High and low frequency flooding did not result in consistent changes in internal metal concentrations. Vegetation types of the floodplains did not affect metal levels in Lumbricus rubellus, except for internal Cd levels, which were positively related to the presence of organic litter. Internal levels of most essential metals were higher in spring. In general, no clear patterns in metal uptake were found and repetition of the sampling campaign will probably yield different results.     

HCHs and DDTs in salt marsh plants (Scirpus) from the Yangtze estuary and nearby coastal areas, China

HCHs and DDTs in salt marsh plants taken from intertidal flats in the Yangtze estuary and coastal area in April and July 2002 were determined by GC-ECD. A significant seasonal effect was observed for HCHs and DDTs in sources and concentration levels in different sample types including above-ground tissues and roots as well as the whole plants and rhizospheric sediments. The results indicated that the concentration of t-HCH was higher in the above-ground tissues than in their roots in April; however, the partitioning of DDTs between contaminated sediments and the roots showed the higher concentrations of t-DDT in their roots. HCHs and DDTs concentration levels were higher in above-ground tissues than in roots in July. BCFs of HCHs and DDTs exhibited lower values with higher levels of contaminants in sediments, and higher values with lower levels in sediments.